CA2152620C - Dispersing agent - Google Patents
Dispersing agent Download PDFInfo
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- CA2152620C CA2152620C CA002152620A CA2152620A CA2152620C CA 2152620 C CA2152620 C CA 2152620C CA 002152620 A CA002152620 A CA 002152620A CA 2152620 A CA2152620 A CA 2152620A CA 2152620 C CA2152620 C CA 2152620C
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- poly
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- amino acid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3719—Polyamides or polyimides
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- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Detergent Compositions (AREA)
- Colloid Chemistry (AREA)
- Materials For Medical Uses (AREA)
Abstract
A cleaning composition contains (a) a detersive surfractant and (b) a poly(amino acid) compound or a precursor thereof, the said component (b) being protected from contact wito a level of alkalinity as would cause degradation toereof. The component (b) may be stabilised by, for example, coating it with an organic acid compound or with a film-forming polymer; by agglomerating it with a controlled level of alkaline or alkaline-reacting compound (e.g. sodium carbonate); by spray-granulating it in admixture wito a nonionic surfractant by encapsulating it with a silicon-based resin; or by incorporating it in a composition that is non-alkaline. The storage stability of the composition is thereby improved.
Description
W094/14939 2 i 5 ~ ~ ~ Q PCT~S93/12090 DTSPF~T~G AGFNT
Field of the Tnvent;on The present invention relates to the U8Q of poly(amino acids) and derivatives thereof as di~persing agent~, espQeially in cl~Aning eompositions, for example in laundry detergent eompositions.
Backaround to the Invention Polyaerylates and aerylate/maleate eopolymers are widely used a~ dispersing agents, speeifieally a~ soil-suspending and/or anti-reA~rQ~ition agents, in detergent eompositions and eonfer important eleaning benefits thereon.
However, the~e polymers and eopolymer~ are not readily biodegradable, thereby po~ing potential environmental probl~m~. Ca.Lox~methyl eellulose i~ biodegradable at a de~aaof substitution (DS) of 1-88 than 0.7 but, al~h~7h it eonfers ~ome whitenes~-main~enAnce benefit to-detergent eompositions, it is defieient with regard to soil-~uspension properties.
In EP-A-0,454,126, it i~ diselo~ed that eertain poly(amino aeids) and derivatives thereof ean be used as 2S builder~ or eo-builders in the formulation of detergent eompo~itions. The ~aid polymer~, e~peeially tho~e derived from aspartie aeid, glutamie aeid and mi~ e3 thereof, are de~eribed a~ effeetive agents for the eomplexing of ealeium and for ~L~el.~ing the formation of ealeium earbonate erystals. The said polymers are ~tated to have further advantages, in that they are re~ifitant to heat, stable to pH, non-toxie, non-irritant and entirely biodegradable.
However, ~ ch by the ~ ent Applieant has revealed that polya~partate or other salt~ of poly(amino aeids) ineorporated in a granular detergent eomposition will degrade over a period of time, espeeially under eonditions of elevated temperature and/or high humidity (e.g.
eonditions of 90F (32.2C) and 80% relative humidity), sueh WO94/14939 PCT~S93/12090 ~S~ 6~ 2 as are typical of Southern European and other Mediterranean countries (and which may obtain even in warehouses elsewhere). Such degradation, which i8 irrever~ible, may give rise to a significant 108s in dispQrsant activity within the storage periods (typically up to 8 weeks) that may occur in practice. Thi~ degradation was unexpected in view of the relative ~trength of the amide linkages pre~ent in poly(amino acids).
10 ~marv of the Invent~on The present invention provides a cleaning composition containing a poly(amino acid) com~oul~d or a ~rc_~L~or thereof and a detersive surfactant, characteri~ed in that the poly(amino acid) compound or ~Le~ or thereof is protected from contact with a level of alkalinity a8 would cau~Q degradation thereof.
The ~L~ 7Qnt invention al~o provides a poly(amino acid) com~oul.d or a ~Le_u.~or thereof, characterised in that it is provided with a coating, is encAp~ ated or is mixed, in the form of an agglomerate or granulate, with at lea~t one other material.
The ~L~7ent invention also provides a poly(amino acid) compound or a ~Le~ or thereof, characterised in that it is in the for~ of an agglomerate with an alkaline or alkaline-reacting ~aterial.
The ~rc~ent invention further provides a ~oce~s for producing a poly(amino acid) com~o~.~ in the form of an agglomerate suitable for incoL ~GL ation into a cleaning composition, which comprise~ agglomerating the alkaline or alkaline-reacting material with a compound that is converted into the poly(amino acid) com~-o,-,-l in alkaline conditions, the agglomeration being effected in the ~L~-~n~e of sufficient moisture for the conversion into the poly(amino acid) com~ou~-d to proceed.
DescriDtion of ~YemDlary Embodiments W094/14939 2 1 5 2 6 2 0 PCT~S93/12090 The exprQssion "poly(amino acid)~ compound includes herein not only a poly(amino acid) as ~uch but also a derivative thereof, such as an amide, an ester or a salt.
The poly(amino acid) may be a homopolymer or may be copolymer of two or more amino acids. The a~ino acid may be a D-amino acid, an L-amino acid or a mixture, e.g. a racemic mixture, thereof. The amino acids include, for instancQ, alanine, glycine, tyrosine, serine and lysine, although glutamic, carboxyglutamic and aspartic acida are preferred.
Of these, aspartic acid is particularly preferred.
Normally, for the ~ Q~ of formulating a cleaning composition, in particular a laundry detergent compo~ition, the poly(amino acid) will be u~ed in the for~ of a salt thereof, preferably an alkali metal salt and more preferably lS the sodium salt.
It will b~ under~tood that the poly(amino acid) compound ~ay be constituted by a ~ixture of two or more com~o~ of the a~ iate description.
Al~o contemplated herein i~ the uae of a ~C~rsor of a poly(amino acid) compound, suitable y~ G~ being com~o~.~s that will undergo convQrsion into a poly(amino acid) or derivative thereof when exposed to alkaline conditions. Thus, a preferred ~e~ or herein is polysuccinimide, which hydrolysQs to polyaspartic acid at a pH greater than 9, the hydroly~i~ being particularly rapid at pH value~ Or lO or higher. Thia opens up the possibility of for~ing the poly(amino acid) or derivative thereof in situ in the wash liquor formed by the addition of the 1 A~ detQrgent or other cleaning compo~ition to water;
such wash liquors typically have a pH value of lO.S or ther~h~t~.
The molecular weight of the poly(amino acid) compound or its ~L e_Ul aor may be varied within wide limits.
Preferably, the molecular weight is fro~ 500 to 200,000, more preferably 2000 to 20,000.
According to the ~ ?nt invention, a poly(amino acid) com~ou~.d or precursor thereof is atabili~ed -g~in~t degradation sufficiently to render it acceptably storage-2 ~5 PCT~S93/12090 stable. This i~ effected, in particular, by protecting thesaid com~ound or precursor from contact with a level of alkalinity as would cause unacceptable degradation thereof.
The stabilisation or protection should be such that the amount of degradation of the poly(amino acid) co~u..d or precursor thereof is less than 50% over an 8 week storage period under ~ 7e~ conditions (90-F(32.2-C) and 80%
relative humidity), preferably less than 30~ and most preferably le~s than 5%.
A preferred method for stabllislng the poly(amino acid) com~o~.d against degradation is to apply a ~tabilising coating thereon. The coating material, which should be compatible with other components of the cleaning composition, may be selected from a wide variety of biodegradable and non-biodegr~dable comF~nd~. or ~Ou~
the coating may comprise a mixture Or two or more suitable materials.
In certain preferred embodiments, the coating material is an organic acid compound, in particular such a com~our.d that is solid at ambient temperatures; thus, the organic compounds should in general have a melting point of at least 30C and will preferably have a melting point Or at least 40C and, more preferably, a melting point in ~x_ T - - of 50C. The organic acid com~G~.d ~o~l~ also be highly ~5 soluble in water at ambient t-mperatures, "highly soluble"
being defined for the purposes Or the pre~ent invention as at -l-a~t 5g Or the acid dissolving in lOOg of distilled wat-r at 20-C. PrefQrably, th- organic acid compound ha~ a solubility of at lQast 20g/lOOg of water at 20C and most pref~rably the organic acid compound will dissolve in its own weight of water at 20C.
Organic acid com~ suitable as coating agents for the pu.~_-e~ of the ~ -ent invention include aliphatic or aromatic, monomeric or oligomeric carboxylic acids, preferably the monomeric aliphatic carboxylic acids.
Examples of such aliphatic acid COm~O~ln~ are glycolic, glutamic, succinic, l-lactic, malonic, glutaric, adipic, maleic, malic, tartaric, diglycolic, carboxymethyl W094/14939 PCT~S93/~090 21S26'2~
succinic, citric, citraconic, itA~oniC and ~esaconic acids;
and copolymers for~ed from an unsaturated polyca~Lo~ylic acid (e g maleic, citraconic, it~ro~ic or mesaconic acid) as one monomer and an unsaturated monocarboxylic acid such a~ acrylic acid or an alpha-Cl-C4 alkyl acrylic acid ~8 the r- n~1 ~ono~er, suitable copolymers being available fro~
BASF under the trade na~e- ~c~alAn- CP5 and CP45 The organic acid com~o~ d may be used in ad~ixture with another material suitable rOr U5~ in the cleAn~ng composition thus, for example, a coating which will impart an acid environment around the poly(a~ino acid) co~pound nay comprise citric acid or the like di-solved in a nonionic surfactant The use of gelatine a- an ad ixture is also possiblQ The use Or a coating of a poly(~ino acid) to protect a poly(amino acid) derivative also com 8 into consideration The acid- are applied at levels of, in general, frou 2% to 20% by weight Or th- coated substrate, preferably fro~
2% to 15~, more preferably from 3~ to ~2Yo and most preferably fro~ 3~0to 10% by weight Or the coated ub~trate Glycolic acid at a level of a~Loximat-ly 5% by weight of the coated substrate is a part~ rly preferred coating agent The organic acid compound may be sprayed on as a molten mat-rial or as a solution or di-p~rsion in a olvent/
carrier liquid uhich is subsequently r~oved by ~ tion The organic acid compound can also be applied as a powder coating although this is 1~88 preferred as the provi~ion of a uniforu layer of coating material is le88 easy and therefore le~ effective Molten coating i~ a preferred tec~n~que for organic acid compound~ of melting point less than 80 C, ~uch a~
glycolic and l-lactic acids, but is le88 convenient for higher melting point acids (e g higher than lOO C) such as citric acid For organic acid com~o~ of melting point higher than 80 C spraying-on a~ a ~olution or dispersion is preferred Organic solvent~ such as ethyl and is~Lo~yl alcohol can be used to form the solution- or dispersions, wo 94/l49392~52 62 ~ PCT~S93/12090 although this will r~c--~itate a solvent ~e_ovcry stage in order to make their uQe economic. However, the use of organic solvent~ also gives rise to safety problems such as flammability and operator safety and thus aqueous solution~
or dispersions are preferred.
Aqueous solutions are particularly advantageous where the organic acid com~ou--d has a high agueous solubility (e.g. citric acid) and the solution ha~ a sufficiently low visco~ity to enable it to be ~ d. Preferably a 0 ~Q~ "L.ation of at least 25% by weight of the organic acid com~o~.d in the solvent i~ used in order to reduce the drying/evaporation load after coating has taken place. The coating apparatus can be any of those norm~lly used for this purpose, such a~ inclined rotary pans, rotary drums and fluidised beds.
The poly(~mino acid) compound ~ay alternatively be s~h~ ed by means of a coating for~ed fro~ a water-soluble film-forming poly~er. Such poly~ers include water-soluble cellulose ethQr~, for exa~ple ~ethyl cellulose, ethyl cellulose, hy~Lo~yethyl cellulose, ~ethyll,y~Lo~y-ethyl cellulose, methyl hydLo~y~LG~yl cellulosQ, carboxymethyl cellulo~e (in particular a~ -the sodium salt) and methylearboxy methyl eQllulose (in par~ Ar as the sodium salt); water-soluble starehes, for example maize stareh or depolyoerised stareh; stareh ethers, for example earboxy-ethyl stareh,l.~d~ox~eLhyl stareh and methyl stareh;
an~ mix-u~__ of any two or more of these. Sodium e~ ~ethyl eellulose (CMC) is preferred.
Suitable film-forming polymers also inelude homopolymers or eopolymers of carboxylie aeids, such as polyaerylie aeid, polymethaerylie aeid and polymaleie aeid;
eopolymers of aerylie aeid or methaerylie aeid with maleic aeid, or a eopolymer of maleie aeid with vinylmethyl ether;
and the salts, in particular the sodium salts, of such polymeric aeids. Preferred film-forming agents from this group are sodium polyaerylate and the sodium salts of aerylie aeid/maleie aeid copolymers with a weight ratio of aerylie aeid: maleie aeid of 10:1 to 1:1, preferably 7:1 to W094/14939 PCT~S93/12090 7 21 ~2620 2:1. These compounds may have a molecular weight of 3000 to 150,000, preferably 5000 to 10,000.
A further clas~ of film-forming polymers are the carbon-chain polymers with nonionic hyd~o~l,ilic ~-u~_ as well as polyether group~, example~ of which include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone, polyacrylamide and polyethylene glycol ether.
Suitable mixture~ of film-forming polym rs include, for example, a mixture of CMC or methyl cellulose with polyacrylate or with an acrylic/maleic acid copolymer, or a mixture of polyethylene glycol ether with polyacrylate or an acrylic acid/maleic acid copolymer.
Another, and particularly preferred, method of stabilising the poly(amino acid) com~o~.d i8 to formulate it as an agglomerate with an alkaline or alkaline-reacting - com~o~ . An alkali as ~uch, e.g. sodium or potassium hyd~oxide, al~o~gh not precluded, may not be ~uitable for many cle~ning compositions and it is preferred to U8Q an alkaline salt, for example a carbonate, bicarbonate or silicate. Preferred salts are the alkali metal salts, especially sodium salts. Naturally, a mixture of two or more alkaline or alkaline-reacting com~o~ may be used.
Moreover, the alkaline or alkaline-reacting com~ou..d may be used in admixture with one or more other suitable materials, for example an anionic surfactant such as alkyl ethoxy sulfonate (AES).
Bearing in mind that polyaspartate or the like is -urc~ptible to alkaline hydrolysis, it i~ particularly surpri~ing that poly(amino acid) comlo~ can be rendered storage-stable by agglomerating them with an alkaline or alkaline-reacting compound. However, in accordance with one aspect of this invention, the degradation of the poly(amino acid) com~ou..d can be inhibited by cG..~lolling the level of alkaline or alkaline-reactive com~ou..d in the agglomerate:
in certain preferred embodiments, there i~ no more than 1 mole of alkaline or alkaline-reacting compo~nA per mole of monomeric unit in the poly(amino acid) compound.
W094/14939 PCT~S93/12090 6~ 8 In a preferred emhc~iment of this invention, the alkaline or alkaline-reacting comro~A is mixed initially with a precursor of the poly(amino acid) compound, in particular such a ~.e_~L~or that converts into a poly(amino acid) com~-d under alkaline condition~. The agglomeration stage is normally effected in the presence of ~ufficient water to allow such conversion to take place and, even after drying, the agglomerate~ will normally contain sufficient residual moi~ture to permit the conver~ion to ~L~_ eeA to completion if it has not already done 80 by then. Suitable precursors are, for example, the imides of those poly(amino acids) that form such imides. Thus, storAgc _~able poly(aspartic acid) or a salt thereof, in particular sodium polyaspartate, can be readily prepared by agglomerating polysuccinimide with an alkaline or alkali-~lYaacting com~o~ , the polysuccinimide being co..~LLed into the polyaspartic acid or polyaspartate in s~tu. This method is particularly advantageous in that the poly~uccinimide is markedly cheaper than the commercially available polyaspartate and yet this method provides the latter com~ou~.d in a storage-stable form that i~ suitable for incorporation into a granular~ (which term includes pulverulent) cle~ninq composition, for example a laundry detergent composition.
The preferred alkaline or alkaline-reacting material i~ sodium carbonate, which salt is a worthwhile component in cl~-n~ng compositions in its own right, since it acts as an effective dissolution aid. Normally, the carbonate is included in laundry detergent composition~ in the form of a micronized powder; however, the use of carbonate having a larger particle size, or carbonates having different particle sizes, comes into consideration, since this will reduce the surface area per unit mass and thereby will --- reduce the rate of reaction between the poly(amino acid) com~ou..d and the carbonate.
In certain preferred embodiments there is no more than 1 mole of alkaline or alkaline-reacting compo~n~, e.g.
carbonate, per mole of monomeric unit in the ~e_u~or, e.g.
W094/14939 21 PCT~S93112090 the ~uccinimide moiety in polysuccinimide.
Another preferred embodiment consists in forming agglomerates from polyaspartic acid (or other poly(amino acid)) and sufficient carbonate (or other alkaline or alkaline reacting com~ou..~) to effect neutralisation but not degradation. The poly(amino acid) may be formed in s~tu from a suitable PL e~ Or~ e.g. polysuccinimide. Other components may, of course, be included in ~uch ~gglomerate~.
The agglomeration of the poly(amino acid) compound, or its precursor, and the alkaline or alkaline-reacting com~vund may be carried out using any suitable agglomeration tec~nique and apparatus, if appropriate with compatible agglomeration auxiliaries. Such technique~, apparatu~ and auxiliaries are well-known in the detergent-formulating art.
Once the agglomerates are formed, they may be dried, if required, by conventional mean~.
Agglomeration of the poly(amino acid) compound or ~,e_~or thereof can be conveniently carried out in variou~
type~ of high ~ r mixer~, for exa~ple a Z-blade mixer, an Eirich mixer or a L~dige mixer.
The agglomerates according to thi~ invention may contain, for example, the following: 20-40% of anionic surfactant, 0-30~ of sodium carbonate, 0-50% of zeolite, O-15% of the poly(amino acid) com~o~-d or ~Le_~.~or thereof, 0-10% of CMC, with the balance being water. In a typical dure the agglomeration mixer i~ charged with the inorganic ~aterials and the CMC, together with the poly(~ino acid) CO~O~ld or precur~or thereof, the resultant mixture being agglomerated with a high-active anionic ~urfactant (typically from 50-85% active by weight), suitable anionic ~urfactant~ being, for ex~mple, C45AS, LAS
or TAS. Typically, the paste addition i~ effected at 50-80C and the agglomeration time will typically be from 1 to 15 minutes. The agglomeration may be followed by an optional drying and cooling step. Typical physical properties of the resultant agglomerates are a density in the range of 500-9OOg/l, a mean particle size of 200-800 ~m, a coL~z~ronAing low cake strength and good free-flowing W094/14935 ~6~ PCTtUS93tl2090 properties.
It is, of course, also possible to agglomerate the poly(amino acid) compo~n~ with a non-A 1 ~A 1; ne material, e.g.
a nonionic surfactant, zeolite, bicarbonate, or a mixture of S two or more of thesQ and/or other non-alkaline materials.
A further method according to this invention of stabilising the poly(amino acid) compound is to spray-granulate it in admixturs with, for ~xample, a nonionic ~urfactant. Yet another method according to the invention is to encapsulate the poly(amino acid) compound, for example using a silicone-based resin.
Yet another method of stabilising the poly(amino acid) com~o~.d against alkaline hydrolysis and hence degradation consists in i-- oL~o~ating the said compound as a dispQrsing lS agent in a cleaninq composition, in particular a laundry detergent composition, that is 80 formulated as to be essentially neutral in terms of it~ pH. In this emho~iment, the detergent matrix itself is acting, a~ it were, as the stabilising medium and it i~ not therefore neces~ary to coat, agglomerate, spray-granulate or ~ncap~ulate the dispersing agent as described above, al~o-~g~ this is not precluded.
. ~ L L~ ~atment of the poly(a~ino acid) compound or precur~or thereof may be carried out if a~. O~L iate. For example, the said com~o~.d or ~LL_~r~lor may bQ premixed with a surfactant paste prior to agglomeration, coating, spray-granulating, enr~rsulation or the like, or it may be mixed in the form of an aqueous ~olution with the surfactant, followed by drying to remove moisture. The latter ~.o~ ke permit~ a predetermined moisture le~el to be achieved.
By suitable adjustment of the ~.~L.c~tmQnt, e.g. via premixing of the poly(amino acid) com~o~.~ or a ~c_u~or thereof with surfactant pa~te, it is possible to obtain agglomerates cont~ining an exces~ of carbonate or other 3S alkaline or alkaline-reacting compound.
As demonstrated in Example 2 hereinafter, degradation of a poly(amino acid) com~oul.d may also be caused by the ~ qnce of a bleach, in particular a source of hyd~G~en W094/14939 PCT~S93/12090 peroxide. Accordingly, it is a further aspect of this invention to provide a eleAni~g eomposition containing a poly(amino aeid) com~o~.d or a precursor thereof and a detersive ~urfaetant, characteri~ed in that the poly(amino acid) compound or precursor thersof is protected from contact with a level of bleach as would cause degradation thereof. The poly(amino acid) eompound or its precursor may be stabili~ed or proteeted against unaeeeptable degradation (a~ defined above) by eoating, by ene~p~ulation or by mixing, in the form of an agglomerate or granulate, with at least one other material, by means analogous to those de~eribed above. In certain preferred emhoAiments~ the poly(amino acid) eomro~nA or ~e~ or thereof is included in a detergent or other eleaning eomposition that eontains no, or substantially no, bleaeh; in ~ueh a ease, depenAin~
upon the level of alkaline or alkaline-reaeting material, it may not be ne_-~s?ry to further Qtabili~e the poly(amino aeid) eompound or it6 ~e~ or by means of eoating, ene~r~ulation, agglomerating, granulating or the like, although this i8 not preeluded.
The stabili~ed poly(aspartie aeid) eompound aeeording to the present invention may be usQd a~ a dispersing agent (whieh term herein ineludes a elay-~oil-suspenA~ng agent and/or an anti-re~ero~ition agent) in solid (e.g. grA~ Ar or other partieulate) eleaning eomposition~ and will g~nerally be employed therein at a level of from 0.1% to 50%, usually at least 0.4%, preferably 1 to 15%, more pref~rably 2.5 to 10% and moct preferably 3 to 6%, by weight. The eleAning eompositions will generally contain one or more detersive surfaetant~, the total amount of such ~urfaetant being in general up to 70%, typieally 1% to 50%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20%, by weight of the total eomposition.
Although the poly(amino aeid) eom~o~.d may be included in a wide variety of eleaning eompositions, for example ha~ rfaee and other household eleaner~ and dishwashing compositions, they are particularly suitable for use in laundry detergent eompositions, e.g. general~ o~? or 2~2~o W094tl4939 PCT~S93/12090 heavy-duty grAnl~lAr laundry detergent compositions. These will contain not only the stabilised poly(amino acid) compound dispersing agent and detersive surfactant but al~o, optionally, one or more further components conventional in the art; these may be selQcted from, for example, a detergent builder, a bleach (in pArticular a source of hyd~Gyen peroxide, Q .g. sodium perborate or sodium percarbonate), a bleach activator (e.g. TAED), an enzyme, a polymeric soil-releasQ agent, a chelating agent, a conventional dispersing agent, a brightener, a suds su~e_sor, a pH-buffering agent, a dye, a dye transfer inhibition agent or a pigment. It will be under~tood that any of the above-mentioned components, whether essential or optional, may be con tituted, if desired, by a mixture of two or more com~o~ of the a~Lo~iate dQscription.
A wide range of surfactants can be used in the clqAn~g compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic clas~es, and specie~
of these surfactants, is given in US-A-3,664,961 ~ to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable herein, especially mix~les of sulfonate and sulfate 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 sulfonates include alkyl benzene sulfonates having from 9 to 15, especially 11 to 13, carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid e~ters in which the fatty acid is derived from a C12-C18 fatty source, preferably from a C16-Cl8 fatty source. In each instance the cation is, in general, an alkali metal, preferably sodium. Preferred sulfate surfactants are alkyl sulfates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulfates 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 sulfates are tallow alkyl sulfate, coconut alkyl sulfate, and Cl4_l5 alkyl sulfates.
The cation in each instance is again, in general, an alkali WO94/14939 2 I 5 2 6~a PCT~S93/12090 metal cation, preferably sodium.
one class of nonionic surfactants particularly useful in the ~ ent invention are conA~n~Ates of ethylene oxide, with a hy~ko~hobic moiety to provide a surfactant having an average hydrophilic~ op~ilic 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 poly~e~hylene group which is ~o~ with any particular h~d~G~hobic group can be readily ad~usted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
E~pecially preferred nonionic surfactants of this type are the Cg-Cl5 primary alcohol ethoxylates cont~i ni ng 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcQhols con~ in~ 6-8 mole8 of ethylene oxide per mole of alcohol, the C12-C15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, and mi~u~ ~3 thereo~.
Another suitable class of nonionic surfactants comprising alkyl polyglucoside com~o~ Or general formula RO (CnH2nO)tzs wherein Z i8 moiety derived from glucose; R is a saturated ~y~.G~hobic alkyl group that contains from 12 to 18 carbon atoms; t is from O to lO and n i8 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 detergents are disclosed in EP-A-O, 070, 077, EP-A-O, 075, 996 and EP-A-0,094, 118 .
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 _ C - N - Z, wherein Rl is H, Il 11 , , or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_3l hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly ~ol-~.ccted to the chain, W094/14939 ~S ~6~Q 14 PCT~S93112090 or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight Cl1_15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z iB derived from a reducing sugar such as glucose, fructo~e, maltose, lacto~e, in a reductive amination reaction.
A further class of surfactants-are the semi-polar surfactants such a~ ~mine OY~ . Suitable amine oxide~ are selectQd from mono C8-C20, preferably C10-Cl4, N-alkyl or alkenyl amine oxides and propylone-1,3-diaminQ dioxides wherein the remaining N position~ are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Another class of surfactants are amphoteric surfactants, such as polyamine-based species.
Cationic surfactant~ can also be used in the detergent compositions herein and suitable guaternary ammonium surfactants are selected from mono C8-C16, preferably Clo-C14, N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hyd~o~ v~yl ~.ou~s.
~ixLu~e_ of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic-cationic mixtures. Particularly preferred mixtures are described in GB-A-2,040,987 and EP-A-0,087,914.
Builder materials will typically be ~ nt at from 5% to 60% of the elsaning eompositions herein. The eomposition~ herein preferably are 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 consi~ts of water-soluble builders, water-insoluble builders, or mi~Lu~e_ thereof.
Water-insoluble builders can be an inorganic ion-PYchange material, commonly an inorganic hydrated aluminosilieate material, more partieularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B or HS.
Preferred aluminosilicate i~ Y~h~nge materials have the unit cell formula Mz [(A102)z (SiO2)y] xH20 W094/14939 PCT~S93/12090 2I 5~620 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 and are preferably crystalline, containing from 10% to 28%, more preferably from 18~ to 22%, water.-The above aluminosilicate ion eYrhAn~e materials maybe further characterised by a particle size diameter of from 0.1 to 10 micromQtQrs, preferably from 0.2 to 4 micrometers.
The term ~particle size diameter~ herein represents the average particle size diameter of a given ion ~YchAnge material as determined by conventional analytical tochniques such as, for example, mi~ opic determination utilizing a ~cAnning electron mi~-o-cope. The aluminosilicate ion ~YrhAnge materials may be further characterised by their calcium ion ~Y~h-n~e capacity, which i~ at least 200 mg equivalent of CaC03 water hardne~s/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 ~Ychange material~ herein may be still further characterised by their calcium ion eY~hange rate which i~ described in detail in GB-A-1,429 143.
Alumino~ilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally oc~lLing materials, but are preferably ~ynthetically derived. A method for producing alu~inosilicate ion ex~hAnge material~ is Ai~c~^e~ in US-A-3,98S,669. Preferred synthetic cry~talline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mix~e_ thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion eYchAnge material is Zeolite A and has the formula Nal2[ (A12)12 (sio2)l2] xH20 wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 ~(Al2)g6(si2)106]
.276H20 is also suitable, as well as Zeolite HS of formula W094/14939 ~ 16 PCT~S93/l2090 Na6~(Al02)6(siO2)6~ 7 5 2 ) Another suitable water-soluble, inorganic builder material is layered silicate, e.g. SKS-6 (H~e~hst). SKS-6 is a crystalline layered silicate con~isting of sodium silicate (Na2Si205). The high Ca+'/Mg++ binding capacity is mainly a cation exchange mech~nism. In hot water, the material become~ more solublQ.
The water-~oluble 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 BE-A-831,368, BE-A-821,369 and BE-A-821,370. Polycarboxylates containing two carboxy ~ uups include the water-solubl~ salts of succinic acid, malonic acid, (ethylQnedioxy) diacetic acid, maleic acid, diglycollic acid, tartartic acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in DE-A-2,446,686, DE-A-2,446,687 and US-A-3,935,257, and the sulfinyl carboxylates dQscribed in BE-A-840,623.
Polycarboxylates containing thr-e carboxy ~rou~s include, in particular, water-soluble citrates, aconitrates and citraconate~ as well as succinate derivatives ~uch as the carboxy~ethyloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in NQtherlands Patent Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.
Polycarboxylates containing four carboxy ~LOU~-include oxydisuccinates disclosed in GB-A-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 sulfosuccinate derivatives disclosed in GB-A-1,398,421 and GB-A-1,398,422 and in US-A-3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,082,179, while polycarboxylates containing phosphone substituents are disclosed in GB-A-1,439,000.
Alicyclic and heterocyclic polycarboxylates include WO94/14939 PCT~S93/12090 17 2I~2620 cyclopentane-cis, cis, 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 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclo~ed in G~-A-1,425,343.
Of the above, the preferred polycarboxylates arehydroxycarboxylatea containing up to three carboxy 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 a water-soluble carboxylate chelating agent such as citric acid.
Other builder materials that can form part of the builder system include inorganic material~ such a~ alkali metal carbonates, bicarbonates, silicates and organic phosphonates, amino polyalkylene pho~rhonate~ and amino polycarboxylates.
The cleaning compositions or detergent additives herein may contain a further soil antireAero~ition or soil-suspension agent, in addition to the poly(amino acid) comFo~l~A~ herein. Such antire~eFo~ition and soil-suspension ag~nts suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulo~e and hydroxycellulose, homo- or co-polymeric polycarboxylic acids or their salts and polyamino compounds. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers disclosed in detail in EP-A-0,137,669, as well as copolymers of maleic anhydride with ethylene, methyvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.025%
to 5% by weight, of the compositions herein.
WO94/14939 ~0 18 PCT~S93/12090 EP-A-311,342 discloses certain modified polyesters which act as soil-release agents on polyester fabrics; thQse modified polyesters also come into consideration herein.
The cleaning compocitions, in particular the detergent composition~, are preferably in granular form and more preferably in a "compact" form, i.e. having a density, which is higher than the density of conventional detergent compositions. The preferred den~ity of the compositions herein ranges from 550 to 950g/litre, preferably 650 to 850g/litre of compo~ition, measured at 20-C.
The pre~ent invention is illustrated in and by the following examples.
E~nle 1 Three formulations containing sodium polyaspartate were prepared, having the composition.
LAS 9.52 parts by weight TAS 0.49 25E3 3.26 TAEll 1.11 Zeolite A 19.5 Citrate 6.56 Polyaspartate, sodium 3.19 Silicate (2.0 ratio) 3.5 Carbonate 14.52 TAED 5.0 ~L ~ ate 16.0 DETPMP 0.38 MgS04 0.40 Enzyme 1.4 CMC 0.48 Brightener 0.24 Photobleach 0.002 Suds ~ essor 0.54 Perfume 0.43 The first formulation contained the polyaspartate W094/14939 21 5 ~ 6 2 ~ PCT~S93/12090 added directly by dry addition. The second formulation contained the polyaspartate added in the form of an agglomerate with sodium zeolite, sodium carbonate, anionic surfactant and CMC. The third formulation contained the s polyaspartate added in the form of an agglomerate with sodium zeolite, anionic sUrfaCtant and CMC (i.e. with no carbonate).
The agglomerates added to the sQcond and third compositions had the following, respective, constituents Second Thi r~
Anionic surfactant 31 31 Carbonate 21 o Zeolite 28 40 Polyaspartate 10 10 CMC
Each of the three formulations was placed in a L~rective, s~nAArd cardboard detergent carton and left open to the atmc-rh~~e under conditions of stress storage (90F (32.2-C) and 80% relative humidity) for a period of 8 weeks. Samples of each formulation were removed after given intervals of time during that storage period and were analysed by both quantitative and qualitative method~, using the stan~a~d analytical techn~que of capillary zone el~_Ll~horesis (CZE) and also by a s~an~ard detergent for ulation performance test method.
CZ~ traces (ele_LLG~h~.u~ams) were taken on samples of each of the three formulations removed from the respQctiYe stored products after intervals of 2, 4, 6 and 8 weeks. A reference sample of polyaspartate that had not been ~ub~ected to storage was also analy~ed by CZE. The ele_~ l.eLo~Lams showed degradation of the polyaspartate over the storage period in the cases of the first formulation (direct addition of polya~partate) and the ~e~on~ formulation (addition by means of agglomerates containing carbonate).
From both the qualitative and quantitative analysis Wo94/14939 PCT~S93/12090 ,6~ 20 of the polyaspartate performance over the 8-week storage period, it could be concluded that the polyaspartate is degraded when eYpo~e~ to high levels of alkalinity.
~Y~mDle 2 Tests wer~ c~rried out in order to a~certain which of the detQrgcnt components were rQsponsiblQ for the degradation of polyaspartate.
A series of open-top, plastics bQakers (500ml capacity) were prepared, each containing sodium polyaspartate and one of the following components: (a) ~odium zeolite, (b) sodium percarbonate plus TAED, (c) sodiu~ perborate tetrahydrate plus TAED, (d) a proteolytic enzyme and (e) ~odium carbonat~.
The amount~ u~ed in the beaker~ were as follows (% by weight) Zeolite 80% 65% 55% 3s%
Carbonate - - 25%
Enzyme - 15%
Powdered polyaspartate 20% 20% 20% 20%
Bleach/TAED - - - 3~*
All were dry mixes.
The h~Aker~ were subjected, with their tops left open, to conditions of stress storage (90F (32.2C); 80% relative hu~idity). The polyaspartatQ content in each ca~e wa~
qu~ntitatively analysed by CZE and the rQsults showed that there was no significant degradation in the case of the composition (d) containing the enzyme and only a low level of degradation in the composition (a) containing the zeolite (~uch minimal degradation being, it is tho~yht, due to trace alkalinity in the zeolite material); there was, however, substantial degradation of the polyaspartate in the compositions (b) and (c) containing a bleach and a bleach activator, and substantial degradation also occurred in the composition (e) containing the carbonate.
WO94/14939 PCT~S93/12090 Example 3 A ~eries of compositions were prepared in the form of agglomerates, each containing four parts by weight of poly~uccinimide and, respectively, 0, 1, 2, 3, 4, 5, or 10 part~ by weight of sodium carbonate. The agglomerates were added to respQctivQ samples of a conventional laundry detergQnt matrix containing surfactant, builder, bleach, chelant, enzyme and ~uch minor ingredient~ as perfume and colouring ~atter. The agglomerates were added at a level customary for the addition of dispersant to laundry detergent compositions.
The resultant di~persant-contAining compositions were maintained over an 8-week storage period under conditions of ~LL~-- storage. During that period samples were analysed quantitatively using CZE.
The CZE traces indicated that, where the level of carbonate was less than or equal to equimolar with re~pect to the monomeric units in the polysuccinimide, the latter had been CG..~e~ Led partially or wholly into polyaspartate but that no significant degradation of the latter occurred over the te~t period. (In the experiment in which carbonate Wa8 absent there was no ~..v~L.ion of the polysuccinimide into polyaspartatic acid.) In contrast, where the level of carbonate was in ~ r ~ of equimolar with respect to the monomeric units in the polysuccinimide, the latter had been ..~Led into polyaspartate but this had in turn, undergone signl~icant degradation; inA~-A, in the composition containing an extremely high level (10 parts) of carbonate, complete degradation of the polyaspartate had occurred within two weeks.
E~nle 4 The following laundry detergent products can be prepared (amounts are in parts by weight) using polyaspartic acid, its sodium salt or polysuccinimide as the dispersant.
WO94/14939 PCT~S93/12090 ~,~5~6~ 22 1~ C
LAS 7.71 7.71 7.71 7.71 TAS 2.43 2.43 2.43 2.43 TAE11 1.10 1.10 1.10 1.10 25E3 3.26 3.26 3.26 3.26 Zeolite A 19.5 19.5 19.5 19.5 Citrate 6.5 6.5 6.5 6.5 Disper~ant 4.25 4.25 4.25 4.25 Carbonate 11.14 11.14 11.14 11.14 10 Perborate 16.0 16.0 16.0 16.0 TAED 5.0 5.0 5.0 5.0 EDTA 0.38 - - -DETPMP - 0.38 EDDS - - 0.38 0.22 15 CMC 0.48 0.48 0.48 0.48 Sud~ Su~ or 0.5 0.5 0.5 0.5 Brightener 0.24 0.24 0.24 0.24 Photoactivated bleach 0.002 0.002 0.002 0.002 Enzyme 1.4 1.4 1.4 1.4 20 Silicate (2.0 ratio) 4.38 4.38 4.38 4.38 MgS04 0.43 0.43 0.43 0.43 Perfume 0.43 0.43 0.43 0.43 Sulphate 4.10 4.10 4.10 4.10 Water and miscellaneou~ to balance It will of cour~e be under~tood that the pre~ent in~ention ha~ been de~cribed above purely by way of example and that ~odifications of detail can be made within the scope of the invention.
W094/14939 PCT~S93/12090 23 21526~0 In the detergent compositions, the abbreviated component identifications have the following mean~n~:
LAS : Sodium liner C12 alkyl benzene ~ulphonate TAS : Sodium tallow alcohol sulfate TAEn : Tallow alcohol ethoxylated with n moles of ethyleno oxide per mole of alcohol 25E3 : A Cl2_lsprimary alcohol conA-n~^~ with an average of 3 moles of ethylene oxide TAED : Tetraacetyl ethylene diamine Silieate : Amorphous Sodiu~ Silicate (SiO2:Na20 ratio normally follow~) Carbonate : AnhydLv~s sodium earbonate CMC : Sodium ea.~o~Jethyl eellulo~e Zeolite A : Hydrated Sodium Alumino~ilieate of formUla Nal2(AlO2sio2)l2 27H20 having a primary particle ~ize in the range from l to lO micromQtQrs Citrate : Tri-sodium citrate dihydrate Photobleach : Tetra sulfonated Zinc phthalocyanine MA/AA : Copolymer of 1:4 maleic/acrylic acid, average moleeular weight about 80,000 Enzyme : Miye~ proteolytie and amylolytic enzyme sold by Novo Industries AS
Brightener : Disodium 4,4'-bi~(2-morpholino-4-anilino-s-triazin-6-ylamino)~ ne-2:2'-disulphonate DETPMP : Diethylene triamine penta (Methylene phosp~onieacid), marketed by Moncanto under the Trade name Dequest 2060 M~Y~ Suds : 25% paraffin wax Mpt 50C, 17%
Suppres~or : hydrophobic silica, 58% paraffin oil
Field of the Tnvent;on The present invention relates to the U8Q of poly(amino acids) and derivatives thereof as di~persing agent~, espQeially in cl~Aning eompositions, for example in laundry detergent eompositions.
Backaround to the Invention Polyaerylates and aerylate/maleate eopolymers are widely used a~ dispersing agents, speeifieally a~ soil-suspending and/or anti-reA~rQ~ition agents, in detergent eompositions and eonfer important eleaning benefits thereon.
However, the~e polymers and eopolymer~ are not readily biodegradable, thereby po~ing potential environmental probl~m~. Ca.Lox~methyl eellulose i~ biodegradable at a de~aaof substitution (DS) of 1-88 than 0.7 but, al~h~7h it eonfers ~ome whitenes~-main~enAnce benefit to-detergent eompositions, it is defieient with regard to soil-~uspension properties.
In EP-A-0,454,126, it i~ diselo~ed that eertain poly(amino aeids) and derivatives thereof ean be used as 2S builder~ or eo-builders in the formulation of detergent eompo~itions. The ~aid polymer~, e~peeially tho~e derived from aspartie aeid, glutamie aeid and mi~ e3 thereof, are de~eribed a~ effeetive agents for the eomplexing of ealeium and for ~L~el.~ing the formation of ealeium earbonate erystals. The said polymers are ~tated to have further advantages, in that they are re~ifitant to heat, stable to pH, non-toxie, non-irritant and entirely biodegradable.
However, ~ ch by the ~ ent Applieant has revealed that polya~partate or other salt~ of poly(amino aeids) ineorporated in a granular detergent eomposition will degrade over a period of time, espeeially under eonditions of elevated temperature and/or high humidity (e.g.
eonditions of 90F (32.2C) and 80% relative humidity), sueh WO94/14939 PCT~S93/12090 ~S~ 6~ 2 as are typical of Southern European and other Mediterranean countries (and which may obtain even in warehouses elsewhere). Such degradation, which i8 irrever~ible, may give rise to a significant 108s in dispQrsant activity within the storage periods (typically up to 8 weeks) that may occur in practice. Thi~ degradation was unexpected in view of the relative ~trength of the amide linkages pre~ent in poly(amino acids).
10 ~marv of the Invent~on The present invention provides a cleaning composition containing a poly(amino acid) com~oul~d or a ~rc_~L~or thereof and a detersive surfactant, characteri~ed in that the poly(amino acid) compound or ~Le~ or thereof is protected from contact with a level of alkalinity a8 would cau~Q degradation thereof.
The ~L~ 7Qnt invention al~o provides a poly(amino acid) com~oul.d or a ~Le_u.~or thereof, characterised in that it is provided with a coating, is encAp~ ated or is mixed, in the form of an agglomerate or granulate, with at lea~t one other material.
The ~L~7ent invention also provides a poly(amino acid) compound or a ~Le~ or thereof, characterised in that it is in the for~ of an agglomerate with an alkaline or alkaline-reacting ~aterial.
The ~rc~ent invention further provides a ~oce~s for producing a poly(amino acid) com~o~.~ in the form of an agglomerate suitable for incoL ~GL ation into a cleaning composition, which comprise~ agglomerating the alkaline or alkaline-reacting material with a compound that is converted into the poly(amino acid) com~-o,-,-l in alkaline conditions, the agglomeration being effected in the ~L~-~n~e of sufficient moisture for the conversion into the poly(amino acid) com~ou~-d to proceed.
DescriDtion of ~YemDlary Embodiments W094/14939 2 1 5 2 6 2 0 PCT~S93/12090 The exprQssion "poly(amino acid)~ compound includes herein not only a poly(amino acid) as ~uch but also a derivative thereof, such as an amide, an ester or a salt.
The poly(amino acid) may be a homopolymer or may be copolymer of two or more amino acids. The a~ino acid may be a D-amino acid, an L-amino acid or a mixture, e.g. a racemic mixture, thereof. The amino acids include, for instancQ, alanine, glycine, tyrosine, serine and lysine, although glutamic, carboxyglutamic and aspartic acida are preferred.
Of these, aspartic acid is particularly preferred.
Normally, for the ~ Q~ of formulating a cleaning composition, in particular a laundry detergent compo~ition, the poly(amino acid) will be u~ed in the for~ of a salt thereof, preferably an alkali metal salt and more preferably lS the sodium salt.
It will b~ under~tood that the poly(amino acid) compound ~ay be constituted by a ~ixture of two or more com~o~ of the a~ iate description.
Al~o contemplated herein i~ the uae of a ~C~rsor of a poly(amino acid) compound, suitable y~ G~ being com~o~.~s that will undergo convQrsion into a poly(amino acid) or derivative thereof when exposed to alkaline conditions. Thus, a preferred ~e~ or herein is polysuccinimide, which hydrolysQs to polyaspartic acid at a pH greater than 9, the hydroly~i~ being particularly rapid at pH value~ Or lO or higher. Thia opens up the possibility of for~ing the poly(amino acid) or derivative thereof in situ in the wash liquor formed by the addition of the 1 A~ detQrgent or other cleaning compo~ition to water;
such wash liquors typically have a pH value of lO.S or ther~h~t~.
The molecular weight of the poly(amino acid) compound or its ~L e_Ul aor may be varied within wide limits.
Preferably, the molecular weight is fro~ 500 to 200,000, more preferably 2000 to 20,000.
According to the ~ ?nt invention, a poly(amino acid) com~ou~.d or precursor thereof is atabili~ed -g~in~t degradation sufficiently to render it acceptably storage-2 ~5 PCT~S93/12090 stable. This i~ effected, in particular, by protecting thesaid com~ound or precursor from contact with a level of alkalinity as would cause unacceptable degradation thereof.
The stabilisation or protection should be such that the amount of degradation of the poly(amino acid) co~u..d or precursor thereof is less than 50% over an 8 week storage period under ~ 7e~ conditions (90-F(32.2-C) and 80%
relative humidity), preferably less than 30~ and most preferably le~s than 5%.
A preferred method for stabllislng the poly(amino acid) com~o~.d against degradation is to apply a ~tabilising coating thereon. The coating material, which should be compatible with other components of the cleaning composition, may be selected from a wide variety of biodegradable and non-biodegr~dable comF~nd~. or ~Ou~
the coating may comprise a mixture Or two or more suitable materials.
In certain preferred embodiments, the coating material is an organic acid compound, in particular such a com~our.d that is solid at ambient temperatures; thus, the organic compounds should in general have a melting point of at least 30C and will preferably have a melting point Or at least 40C and, more preferably, a melting point in ~x_ T - - of 50C. The organic acid com~G~.d ~o~l~ also be highly ~5 soluble in water at ambient t-mperatures, "highly soluble"
being defined for the purposes Or the pre~ent invention as at -l-a~t 5g Or the acid dissolving in lOOg of distilled wat-r at 20-C. PrefQrably, th- organic acid compound ha~ a solubility of at lQast 20g/lOOg of water at 20C and most pref~rably the organic acid compound will dissolve in its own weight of water at 20C.
Organic acid com~ suitable as coating agents for the pu.~_-e~ of the ~ -ent invention include aliphatic or aromatic, monomeric or oligomeric carboxylic acids, preferably the monomeric aliphatic carboxylic acids.
Examples of such aliphatic acid COm~O~ln~ are glycolic, glutamic, succinic, l-lactic, malonic, glutaric, adipic, maleic, malic, tartaric, diglycolic, carboxymethyl W094/14939 PCT~S93/~090 21S26'2~
succinic, citric, citraconic, itA~oniC and ~esaconic acids;
and copolymers for~ed from an unsaturated polyca~Lo~ylic acid (e g maleic, citraconic, it~ro~ic or mesaconic acid) as one monomer and an unsaturated monocarboxylic acid such a~ acrylic acid or an alpha-Cl-C4 alkyl acrylic acid ~8 the r- n~1 ~ono~er, suitable copolymers being available fro~
BASF under the trade na~e- ~c~alAn- CP5 and CP45 The organic acid com~o~ d may be used in ad~ixture with another material suitable rOr U5~ in the cleAn~ng composition thus, for example, a coating which will impart an acid environment around the poly(a~ino acid) co~pound nay comprise citric acid or the like di-solved in a nonionic surfactant The use of gelatine a- an ad ixture is also possiblQ The use Or a coating of a poly(~ino acid) to protect a poly(amino acid) derivative also com 8 into consideration The acid- are applied at levels of, in general, frou 2% to 20% by weight Or th- coated substrate, preferably fro~
2% to 15~, more preferably from 3~ to ~2Yo and most preferably fro~ 3~0to 10% by weight Or the coated ub~trate Glycolic acid at a level of a~Loximat-ly 5% by weight of the coated substrate is a part~ rly preferred coating agent The organic acid compound may be sprayed on as a molten mat-rial or as a solution or di-p~rsion in a olvent/
carrier liquid uhich is subsequently r~oved by ~ tion The organic acid compound can also be applied as a powder coating although this is 1~88 preferred as the provi~ion of a uniforu layer of coating material is le88 easy and therefore le~ effective Molten coating i~ a preferred tec~n~que for organic acid compound~ of melting point less than 80 C, ~uch a~
glycolic and l-lactic acids, but is le88 convenient for higher melting point acids (e g higher than lOO C) such as citric acid For organic acid com~o~ of melting point higher than 80 C spraying-on a~ a ~olution or dispersion is preferred Organic solvent~ such as ethyl and is~Lo~yl alcohol can be used to form the solution- or dispersions, wo 94/l49392~52 62 ~ PCT~S93/12090 although this will r~c--~itate a solvent ~e_ovcry stage in order to make their uQe economic. However, the use of organic solvent~ also gives rise to safety problems such as flammability and operator safety and thus aqueous solution~
or dispersions are preferred.
Aqueous solutions are particularly advantageous where the organic acid com~ou--d has a high agueous solubility (e.g. citric acid) and the solution ha~ a sufficiently low visco~ity to enable it to be ~ d. Preferably a 0 ~Q~ "L.ation of at least 25% by weight of the organic acid com~o~.d in the solvent i~ used in order to reduce the drying/evaporation load after coating has taken place. The coating apparatus can be any of those norm~lly used for this purpose, such a~ inclined rotary pans, rotary drums and fluidised beds.
The poly(~mino acid) compound ~ay alternatively be s~h~ ed by means of a coating for~ed fro~ a water-soluble film-forming poly~er. Such poly~ers include water-soluble cellulose ethQr~, for exa~ple ~ethyl cellulose, ethyl cellulose, hy~Lo~yethyl cellulose, ~ethyll,y~Lo~y-ethyl cellulose, methyl hydLo~y~LG~yl cellulosQ, carboxymethyl cellulo~e (in particular a~ -the sodium salt) and methylearboxy methyl eQllulose (in par~ Ar as the sodium salt); water-soluble starehes, for example maize stareh or depolyoerised stareh; stareh ethers, for example earboxy-ethyl stareh,l.~d~ox~eLhyl stareh and methyl stareh;
an~ mix-u~__ of any two or more of these. Sodium e~ ~ethyl eellulose (CMC) is preferred.
Suitable film-forming polymers also inelude homopolymers or eopolymers of carboxylie aeids, such as polyaerylie aeid, polymethaerylie aeid and polymaleie aeid;
eopolymers of aerylie aeid or methaerylie aeid with maleic aeid, or a eopolymer of maleie aeid with vinylmethyl ether;
and the salts, in particular the sodium salts, of such polymeric aeids. Preferred film-forming agents from this group are sodium polyaerylate and the sodium salts of aerylie aeid/maleie aeid copolymers with a weight ratio of aerylie aeid: maleie aeid of 10:1 to 1:1, preferably 7:1 to W094/14939 PCT~S93/12090 7 21 ~2620 2:1. These compounds may have a molecular weight of 3000 to 150,000, preferably 5000 to 10,000.
A further clas~ of film-forming polymers are the carbon-chain polymers with nonionic hyd~o~l,ilic ~-u~_ as well as polyether group~, example~ of which include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone, polyacrylamide and polyethylene glycol ether.
Suitable mixture~ of film-forming polym rs include, for example, a mixture of CMC or methyl cellulose with polyacrylate or with an acrylic/maleic acid copolymer, or a mixture of polyethylene glycol ether with polyacrylate or an acrylic acid/maleic acid copolymer.
Another, and particularly preferred, method of stabilising the poly(amino acid) com~o~.d i8 to formulate it as an agglomerate with an alkaline or alkaline-reacting - com~o~ . An alkali as ~uch, e.g. sodium or potassium hyd~oxide, al~o~gh not precluded, may not be ~uitable for many cle~ning compositions and it is preferred to U8Q an alkaline salt, for example a carbonate, bicarbonate or silicate. Preferred salts are the alkali metal salts, especially sodium salts. Naturally, a mixture of two or more alkaline or alkaline-reacting com~o~ may be used.
Moreover, the alkaline or alkaline-reacting com~ou..d may be used in admixture with one or more other suitable materials, for example an anionic surfactant such as alkyl ethoxy sulfonate (AES).
Bearing in mind that polyaspartate or the like is -urc~ptible to alkaline hydrolysis, it i~ particularly surpri~ing that poly(amino acid) comlo~ can be rendered storage-stable by agglomerating them with an alkaline or alkaline-reacting compound. However, in accordance with one aspect of this invention, the degradation of the poly(amino acid) com~ou..d can be inhibited by cG..~lolling the level of alkaline or alkaline-reactive com~ou..d in the agglomerate:
in certain preferred embodiments, there i~ no more than 1 mole of alkaline or alkaline-reacting compo~nA per mole of monomeric unit in the poly(amino acid) compound.
W094/14939 PCT~S93/12090 6~ 8 In a preferred emhc~iment of this invention, the alkaline or alkaline-reacting comro~A is mixed initially with a precursor of the poly(amino acid) compound, in particular such a ~.e_~L~or that converts into a poly(amino acid) com~-d under alkaline condition~. The agglomeration stage is normally effected in the presence of ~ufficient water to allow such conversion to take place and, even after drying, the agglomerate~ will normally contain sufficient residual moi~ture to permit the conver~ion to ~L~_ eeA to completion if it has not already done 80 by then. Suitable precursors are, for example, the imides of those poly(amino acids) that form such imides. Thus, storAgc _~able poly(aspartic acid) or a salt thereof, in particular sodium polyaspartate, can be readily prepared by agglomerating polysuccinimide with an alkaline or alkali-~lYaacting com~o~ , the polysuccinimide being co..~LLed into the polyaspartic acid or polyaspartate in s~tu. This method is particularly advantageous in that the poly~uccinimide is markedly cheaper than the commercially available polyaspartate and yet this method provides the latter com~ou~.d in a storage-stable form that i~ suitable for incorporation into a granular~ (which term includes pulverulent) cle~ninq composition, for example a laundry detergent composition.
The preferred alkaline or alkaline-reacting material i~ sodium carbonate, which salt is a worthwhile component in cl~-n~ng compositions in its own right, since it acts as an effective dissolution aid. Normally, the carbonate is included in laundry detergent composition~ in the form of a micronized powder; however, the use of carbonate having a larger particle size, or carbonates having different particle sizes, comes into consideration, since this will reduce the surface area per unit mass and thereby will --- reduce the rate of reaction between the poly(amino acid) com~ou..d and the carbonate.
In certain preferred embodiments there is no more than 1 mole of alkaline or alkaline-reacting compo~n~, e.g.
carbonate, per mole of monomeric unit in the ~e_u~or, e.g.
W094/14939 21 PCT~S93112090 the ~uccinimide moiety in polysuccinimide.
Another preferred embodiment consists in forming agglomerates from polyaspartic acid (or other poly(amino acid)) and sufficient carbonate (or other alkaline or alkaline reacting com~ou..~) to effect neutralisation but not degradation. The poly(amino acid) may be formed in s~tu from a suitable PL e~ Or~ e.g. polysuccinimide. Other components may, of course, be included in ~uch ~gglomerate~.
The agglomeration of the poly(amino acid) compound, or its precursor, and the alkaline or alkaline-reacting com~vund may be carried out using any suitable agglomeration tec~nique and apparatus, if appropriate with compatible agglomeration auxiliaries. Such technique~, apparatu~ and auxiliaries are well-known in the detergent-formulating art.
Once the agglomerates are formed, they may be dried, if required, by conventional mean~.
Agglomeration of the poly(amino acid) compound or ~,e_~or thereof can be conveniently carried out in variou~
type~ of high ~ r mixer~, for exa~ple a Z-blade mixer, an Eirich mixer or a L~dige mixer.
The agglomerates according to thi~ invention may contain, for example, the following: 20-40% of anionic surfactant, 0-30~ of sodium carbonate, 0-50% of zeolite, O-15% of the poly(amino acid) com~o~-d or ~Le_~.~or thereof, 0-10% of CMC, with the balance being water. In a typical dure the agglomeration mixer i~ charged with the inorganic ~aterials and the CMC, together with the poly(~ino acid) CO~O~ld or precur~or thereof, the resultant mixture being agglomerated with a high-active anionic ~urfactant (typically from 50-85% active by weight), suitable anionic ~urfactant~ being, for ex~mple, C45AS, LAS
or TAS. Typically, the paste addition i~ effected at 50-80C and the agglomeration time will typically be from 1 to 15 minutes. The agglomeration may be followed by an optional drying and cooling step. Typical physical properties of the resultant agglomerates are a density in the range of 500-9OOg/l, a mean particle size of 200-800 ~m, a coL~z~ronAing low cake strength and good free-flowing W094/14935 ~6~ PCTtUS93tl2090 properties.
It is, of course, also possible to agglomerate the poly(amino acid) compo~n~ with a non-A 1 ~A 1; ne material, e.g.
a nonionic surfactant, zeolite, bicarbonate, or a mixture of S two or more of thesQ and/or other non-alkaline materials.
A further method according to this invention of stabilising the poly(amino acid) compound is to spray-granulate it in admixturs with, for ~xample, a nonionic ~urfactant. Yet another method according to the invention is to encapsulate the poly(amino acid) compound, for example using a silicone-based resin.
Yet another method of stabilising the poly(amino acid) com~o~.d against alkaline hydrolysis and hence degradation consists in i-- oL~o~ating the said compound as a dispQrsing lS agent in a cleaninq composition, in particular a laundry detergent composition, that is 80 formulated as to be essentially neutral in terms of it~ pH. In this emho~iment, the detergent matrix itself is acting, a~ it were, as the stabilising medium and it i~ not therefore neces~ary to coat, agglomerate, spray-granulate or ~ncap~ulate the dispersing agent as described above, al~o-~g~ this is not precluded.
. ~ L L~ ~atment of the poly(a~ino acid) compound or precur~or thereof may be carried out if a~. O~L iate. For example, the said com~o~.d or ~LL_~r~lor may bQ premixed with a surfactant paste prior to agglomeration, coating, spray-granulating, enr~rsulation or the like, or it may be mixed in the form of an aqueous ~olution with the surfactant, followed by drying to remove moisture. The latter ~.o~ ke permit~ a predetermined moisture le~el to be achieved.
By suitable adjustment of the ~.~L.c~tmQnt, e.g. via premixing of the poly(amino acid) com~o~.~ or a ~c_u~or thereof with surfactant pa~te, it is possible to obtain agglomerates cont~ining an exces~ of carbonate or other 3S alkaline or alkaline-reacting compound.
As demonstrated in Example 2 hereinafter, degradation of a poly(amino acid) com~oul.d may also be caused by the ~ qnce of a bleach, in particular a source of hyd~G~en W094/14939 PCT~S93/12090 peroxide. Accordingly, it is a further aspect of this invention to provide a eleAni~g eomposition containing a poly(amino aeid) com~o~.d or a precursor thereof and a detersive ~urfaetant, characteri~ed in that the poly(amino acid) compound or precursor thersof is protected from contact with a level of bleach as would cause degradation thereof. The poly(amino acid) eompound or its precursor may be stabili~ed or proteeted against unaeeeptable degradation (a~ defined above) by eoating, by ene~p~ulation or by mixing, in the form of an agglomerate or granulate, with at least one other material, by means analogous to those de~eribed above. In certain preferred emhoAiments~ the poly(amino acid) eomro~nA or ~e~ or thereof is included in a detergent or other eleaning eomposition that eontains no, or substantially no, bleaeh; in ~ueh a ease, depenAin~
upon the level of alkaline or alkaline-reaeting material, it may not be ne_-~s?ry to further Qtabili~e the poly(amino aeid) eompound or it6 ~e~ or by means of eoating, ene~r~ulation, agglomerating, granulating or the like, although this i8 not preeluded.
The stabili~ed poly(aspartie aeid) eompound aeeording to the present invention may be usQd a~ a dispersing agent (whieh term herein ineludes a elay-~oil-suspenA~ng agent and/or an anti-re~ero~ition agent) in solid (e.g. grA~ Ar or other partieulate) eleaning eomposition~ and will g~nerally be employed therein at a level of from 0.1% to 50%, usually at least 0.4%, preferably 1 to 15%, more pref~rably 2.5 to 10% and moct preferably 3 to 6%, by weight. The eleAning eompositions will generally contain one or more detersive surfaetant~, the total amount of such ~urfaetant being in general up to 70%, typieally 1% to 50%, preferably 1 to 30%, more preferably 5 to 25% and especially 10 to 20%, by weight of the total eomposition.
Although the poly(amino aeid) eom~o~.d may be included in a wide variety of eleaning eompositions, for example ha~ rfaee and other household eleaner~ and dishwashing compositions, they are particularly suitable for use in laundry detergent eompositions, e.g. general~ o~? or 2~2~o W094tl4939 PCT~S93/12090 heavy-duty grAnl~lAr laundry detergent compositions. These will contain not only the stabilised poly(amino acid) compound dispersing agent and detersive surfactant but al~o, optionally, one or more further components conventional in the art; these may be selQcted from, for example, a detergent builder, a bleach (in pArticular a source of hyd~Gyen peroxide, Q .g. sodium perborate or sodium percarbonate), a bleach activator (e.g. TAED), an enzyme, a polymeric soil-releasQ agent, a chelating agent, a conventional dispersing agent, a brightener, a suds su~e_sor, a pH-buffering agent, a dye, a dye transfer inhibition agent or a pigment. It will be under~tood that any of the above-mentioned components, whether essential or optional, may be con tituted, if desired, by a mixture of two or more com~o~ of the a~Lo~iate dQscription.
A wide range of surfactants can be used in the clqAn~g compositions. A typical listing of anionic, nonionic, ampholytic and zwitterionic clas~es, and specie~
of these surfactants, is given in US-A-3,664,961 ~ to Norris on May 23, 1972.
Mixtures of anionic surfactants are particularly suitable herein, especially mix~les of sulfonate and sulfate 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 sulfonates include alkyl benzene sulfonates having from 9 to 15, especially 11 to 13, carbon atoms in the alkyl radical, and alpha-sulphonated methyl fatty acid e~ters in which the fatty acid is derived from a C12-C18 fatty source, preferably from a C16-Cl8 fatty source. In each instance the cation is, in general, an alkali metal, preferably sodium. Preferred sulfate surfactants are alkyl sulfates having from 12 to 18 carbon atoms in the alkyl radical, optionally in admixture with ethoxy sulfates 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 sulfates are tallow alkyl sulfate, coconut alkyl sulfate, and Cl4_l5 alkyl sulfates.
The cation in each instance is again, in general, an alkali WO94/14939 2 I 5 2 6~a PCT~S93/12090 metal cation, preferably sodium.
one class of nonionic surfactants particularly useful in the ~ ent invention are conA~n~Ates of ethylene oxide, with a hy~ko~hobic moiety to provide a surfactant having an average hydrophilic~ op~ilic 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 poly~e~hylene group which is ~o~ with any particular h~d~G~hobic group can be readily ad~usted to yield a water-soluble compound having the desired degree of balance between hydrophilic and hydrophobic elements.
E~pecially preferred nonionic surfactants of this type are the Cg-Cl5 primary alcohol ethoxylates cont~i ni ng 3-8 moles of ethylene oxide per mole of alcohol, particularly the C14-C15 primary alcQhols con~ in~ 6-8 mole8 of ethylene oxide per mole of alcohol, the C12-C15 primary alcohols containing 3-5 moles of ethylene oxide per mole of alcohol, and mi~u~ ~3 thereo~.
Another suitable class of nonionic surfactants comprising alkyl polyglucoside com~o~ Or general formula RO (CnH2nO)tzs wherein Z i8 moiety derived from glucose; R is a saturated ~y~.G~hobic alkyl group that contains from 12 to 18 carbon atoms; t is from O to lO and n i8 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 detergents are disclosed in EP-A-O, 070, 077, EP-A-O, 075, 996 and EP-A-0,094, 118 .
Also suitable as nonionic surfactants are poly hydroxy fatty acid amide surfactants of the formula R2 _ C - N - Z, wherein Rl is H, Il 11 , , or Rl is C1_4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl or a mixture thereof, R2 is C5_3l hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly ~ol-~.ccted to the chain, W094/14939 ~S ~6~Q 14 PCT~S93112090 or an alkoxylated derivative thereof. Preferably, Rl is methyl, R2 is a straight Cl1_15 alkyl or alkenyl chain such as coconut alkyl or mixtures thereof, and Z iB derived from a reducing sugar such as glucose, fructo~e, maltose, lacto~e, in a reductive amination reaction.
A further class of surfactants-are the semi-polar surfactants such a~ ~mine OY~ . Suitable amine oxide~ are selectQd from mono C8-C20, preferably C10-Cl4, N-alkyl or alkenyl amine oxides and propylone-1,3-diaminQ dioxides wherein the remaining N position~ are substituted by methyl, hydroxyethyl or hydroxypropyl groups.
Another class of surfactants are amphoteric surfactants, such as polyamine-based species.
Cationic surfactant~ can also be used in the detergent compositions herein and suitable guaternary ammonium surfactants are selected from mono C8-C16, preferably Clo-C14, N-alkyl or alkenyl ammonium surfactants wherein the remaining N positions are substituted by methyl, hydroxyethyl or hyd~o~ v~yl ~.ou~s.
~ixLu~e_ of surfactant types are preferred, more especially anionic-nonionic and also anionic-nonionic-cationic mixtures. Particularly preferred mixtures are described in GB-A-2,040,987 and EP-A-0,087,914.
Builder materials will typically be ~ nt at from 5% to 60% of the elsaning eompositions herein. The eomposition~ herein preferably are 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 consi~ts of water-soluble builders, water-insoluble builders, or mi~Lu~e_ thereof.
Water-insoluble builders can be an inorganic ion-PYchange material, commonly an inorganic hydrated aluminosilieate material, more partieularly a hydrated synthetic zeolite such as hydrated Zeolite A, X, B or HS.
Preferred aluminosilicate i~ Y~h~nge materials have the unit cell formula Mz [(A102)z (SiO2)y] xH20 W094/14939 PCT~S93/12090 2I 5~620 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 and are preferably crystalline, containing from 10% to 28%, more preferably from 18~ to 22%, water.-The above aluminosilicate ion eYrhAn~e materials maybe further characterised by a particle size diameter of from 0.1 to 10 micromQtQrs, preferably from 0.2 to 4 micrometers.
The term ~particle size diameter~ herein represents the average particle size diameter of a given ion ~YchAnge material as determined by conventional analytical tochniques such as, for example, mi~ opic determination utilizing a ~cAnning electron mi~-o-cope. The aluminosilicate ion ~YrhAnge materials may be further characterised by their calcium ion ~Y~h-n~e capacity, which i~ at least 200 mg equivalent of CaC03 water hardne~s/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 ~Ychange material~ herein may be still further characterised by their calcium ion eY~hange rate which i~ described in detail in GB-A-1,429 143.
Alumino~ilicate ion-exchange materials useful in the practice of this invention are commercially available and can be naturally oc~lLing materials, but are preferably ~ynthetically derived. A method for producing alu~inosilicate ion ex~hAnge material~ is Ai~c~^e~ in US-A-3,98S,669. Preferred synthetic cry~talline aluminosilicate ion exchange materials useful herein are available under the designation Zeolite A, Zeolite B, Zeolite X, Zeolite HS and mix~e_ thereof. In an especially preferred embodiment, the crystalline aluminosilicate ion eYchAnge material is Zeolite A and has the formula Nal2[ (A12)12 (sio2)l2] xH20 wherein x is from 20 to 30, especially 27. Zeolite X of formula Na86 ~(Al2)g6(si2)106]
.276H20 is also suitable, as well as Zeolite HS of formula W094/14939 ~ 16 PCT~S93/l2090 Na6~(Al02)6(siO2)6~ 7 5 2 ) Another suitable water-soluble, inorganic builder material is layered silicate, e.g. SKS-6 (H~e~hst). SKS-6 is a crystalline layered silicate con~isting of sodium silicate (Na2Si205). The high Ca+'/Mg++ binding capacity is mainly a cation exchange mech~nism. In hot water, the material become~ more solublQ.
The water-~oluble 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 BE-A-831,368, BE-A-821,369 and BE-A-821,370. Polycarboxylates containing two carboxy ~ uups include the water-solubl~ salts of succinic acid, malonic acid, (ethylQnedioxy) diacetic acid, maleic acid, diglycollic acid, tartartic acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in DE-A-2,446,686, DE-A-2,446,687 and US-A-3,935,257, and the sulfinyl carboxylates dQscribed in BE-A-840,623.
Polycarboxylates containing thr-e carboxy ~rou~s include, in particular, water-soluble citrates, aconitrates and citraconate~ as well as succinate derivatives ~uch as the carboxy~ethyloxysuccinates described in GB-A-1,379,241, lactoxysuccinates described in NQtherlands Patent Application 7205873, and the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in GB-A-1,387,447.
Polycarboxylates containing four carboxy ~LOU~-include oxydisuccinates disclosed in GB-A-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 sulfosuccinate derivatives disclosed in GB-A-1,398,421 and GB-A-1,398,422 and in US-A-3,936,448, and the sulfonated pyrolysed citrates described in GB-A-1,082,179, while polycarboxylates containing phosphone substituents are disclosed in GB-A-1,439,000.
Alicyclic and heterocyclic polycarboxylates include WO94/14939 PCT~S93/12090 17 2I~2620 cyclopentane-cis, cis, 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 carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include mellitic acid, pyromellitic acid and the phthalic acid derivatives disclo~ed in G~-A-1,425,343.
Of the above, the preferred polycarboxylates arehydroxycarboxylatea containing up to three carboxy 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 a water-soluble carboxylate chelating agent such as citric acid.
Other builder materials that can form part of the builder system include inorganic material~ such a~ alkali metal carbonates, bicarbonates, silicates and organic phosphonates, amino polyalkylene pho~rhonate~ and amino polycarboxylates.
The cleaning compositions or detergent additives herein may contain a further soil antireAero~ition or soil-suspension agent, in addition to the poly(amino acid) comFo~l~A~ herein. Such antire~eFo~ition and soil-suspension ag~nts suitable herein include cellulose derivatives such as methylcellulose, carboxymethylcellulo~e and hydroxycellulose, homo- or co-polymeric polycarboxylic acids or their salts and polyamino compounds. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers disclosed in detail in EP-A-0,137,669, as well as copolymers of maleic anhydride with ethylene, methyvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer.
These materials are normally used at levels of from 0.025%
to 5% by weight, of the compositions herein.
WO94/14939 ~0 18 PCT~S93/12090 EP-A-311,342 discloses certain modified polyesters which act as soil-release agents on polyester fabrics; thQse modified polyesters also come into consideration herein.
The cleaning compocitions, in particular the detergent composition~, are preferably in granular form and more preferably in a "compact" form, i.e. having a density, which is higher than the density of conventional detergent compositions. The preferred den~ity of the compositions herein ranges from 550 to 950g/litre, preferably 650 to 850g/litre of compo~ition, measured at 20-C.
The pre~ent invention is illustrated in and by the following examples.
E~nle 1 Three formulations containing sodium polyaspartate were prepared, having the composition.
LAS 9.52 parts by weight TAS 0.49 25E3 3.26 TAEll 1.11 Zeolite A 19.5 Citrate 6.56 Polyaspartate, sodium 3.19 Silicate (2.0 ratio) 3.5 Carbonate 14.52 TAED 5.0 ~L ~ ate 16.0 DETPMP 0.38 MgS04 0.40 Enzyme 1.4 CMC 0.48 Brightener 0.24 Photobleach 0.002 Suds ~ essor 0.54 Perfume 0.43 The first formulation contained the polyaspartate W094/14939 21 5 ~ 6 2 ~ PCT~S93/12090 added directly by dry addition. The second formulation contained the polyaspartate added in the form of an agglomerate with sodium zeolite, sodium carbonate, anionic surfactant and CMC. The third formulation contained the s polyaspartate added in the form of an agglomerate with sodium zeolite, anionic sUrfaCtant and CMC (i.e. with no carbonate).
The agglomerates added to the sQcond and third compositions had the following, respective, constituents Second Thi r~
Anionic surfactant 31 31 Carbonate 21 o Zeolite 28 40 Polyaspartate 10 10 CMC
Each of the three formulations was placed in a L~rective, s~nAArd cardboard detergent carton and left open to the atmc-rh~~e under conditions of stress storage (90F (32.2-C) and 80% relative humidity) for a period of 8 weeks. Samples of each formulation were removed after given intervals of time during that storage period and were analysed by both quantitative and qualitative method~, using the stan~a~d analytical techn~que of capillary zone el~_Ll~horesis (CZE) and also by a s~an~ard detergent for ulation performance test method.
CZ~ traces (ele_LLG~h~.u~ams) were taken on samples of each of the three formulations removed from the respQctiYe stored products after intervals of 2, 4, 6 and 8 weeks. A reference sample of polyaspartate that had not been ~ub~ected to storage was also analy~ed by CZE. The ele_~ l.eLo~Lams showed degradation of the polyaspartate over the storage period in the cases of the first formulation (direct addition of polya~partate) and the ~e~on~ formulation (addition by means of agglomerates containing carbonate).
From both the qualitative and quantitative analysis Wo94/14939 PCT~S93/12090 ,6~ 20 of the polyaspartate performance over the 8-week storage period, it could be concluded that the polyaspartate is degraded when eYpo~e~ to high levels of alkalinity.
~Y~mDle 2 Tests wer~ c~rried out in order to a~certain which of the detQrgcnt components were rQsponsiblQ for the degradation of polyaspartate.
A series of open-top, plastics bQakers (500ml capacity) were prepared, each containing sodium polyaspartate and one of the following components: (a) ~odium zeolite, (b) sodium percarbonate plus TAED, (c) sodiu~ perborate tetrahydrate plus TAED, (d) a proteolytic enzyme and (e) ~odium carbonat~.
The amount~ u~ed in the beaker~ were as follows (% by weight) Zeolite 80% 65% 55% 3s%
Carbonate - - 25%
Enzyme - 15%
Powdered polyaspartate 20% 20% 20% 20%
Bleach/TAED - - - 3~*
All were dry mixes.
The h~Aker~ were subjected, with their tops left open, to conditions of stress storage (90F (32.2C); 80% relative hu~idity). The polyaspartatQ content in each ca~e wa~
qu~ntitatively analysed by CZE and the rQsults showed that there was no significant degradation in the case of the composition (d) containing the enzyme and only a low level of degradation in the composition (a) containing the zeolite (~uch minimal degradation being, it is tho~yht, due to trace alkalinity in the zeolite material); there was, however, substantial degradation of the polyaspartate in the compositions (b) and (c) containing a bleach and a bleach activator, and substantial degradation also occurred in the composition (e) containing the carbonate.
WO94/14939 PCT~S93/12090 Example 3 A ~eries of compositions were prepared in the form of agglomerates, each containing four parts by weight of poly~uccinimide and, respectively, 0, 1, 2, 3, 4, 5, or 10 part~ by weight of sodium carbonate. The agglomerates were added to respQctivQ samples of a conventional laundry detergQnt matrix containing surfactant, builder, bleach, chelant, enzyme and ~uch minor ingredient~ as perfume and colouring ~atter. The agglomerates were added at a level customary for the addition of dispersant to laundry detergent compositions.
The resultant di~persant-contAining compositions were maintained over an 8-week storage period under conditions of ~LL~-- storage. During that period samples were analysed quantitatively using CZE.
The CZE traces indicated that, where the level of carbonate was less than or equal to equimolar with re~pect to the monomeric units in the polysuccinimide, the latter had been CG..~e~ Led partially or wholly into polyaspartate but that no significant degradation of the latter occurred over the te~t period. (In the experiment in which carbonate Wa8 absent there was no ~..v~L.ion of the polysuccinimide into polyaspartatic acid.) In contrast, where the level of carbonate was in ~ r ~ of equimolar with respect to the monomeric units in the polysuccinimide, the latter had been ..~Led into polyaspartate but this had in turn, undergone signl~icant degradation; inA~-A, in the composition containing an extremely high level (10 parts) of carbonate, complete degradation of the polyaspartate had occurred within two weeks.
E~nle 4 The following laundry detergent products can be prepared (amounts are in parts by weight) using polyaspartic acid, its sodium salt or polysuccinimide as the dispersant.
WO94/14939 PCT~S93/12090 ~,~5~6~ 22 1~ C
LAS 7.71 7.71 7.71 7.71 TAS 2.43 2.43 2.43 2.43 TAE11 1.10 1.10 1.10 1.10 25E3 3.26 3.26 3.26 3.26 Zeolite A 19.5 19.5 19.5 19.5 Citrate 6.5 6.5 6.5 6.5 Disper~ant 4.25 4.25 4.25 4.25 Carbonate 11.14 11.14 11.14 11.14 10 Perborate 16.0 16.0 16.0 16.0 TAED 5.0 5.0 5.0 5.0 EDTA 0.38 - - -DETPMP - 0.38 EDDS - - 0.38 0.22 15 CMC 0.48 0.48 0.48 0.48 Sud~ Su~ or 0.5 0.5 0.5 0.5 Brightener 0.24 0.24 0.24 0.24 Photoactivated bleach 0.002 0.002 0.002 0.002 Enzyme 1.4 1.4 1.4 1.4 20 Silicate (2.0 ratio) 4.38 4.38 4.38 4.38 MgS04 0.43 0.43 0.43 0.43 Perfume 0.43 0.43 0.43 0.43 Sulphate 4.10 4.10 4.10 4.10 Water and miscellaneou~ to balance It will of cour~e be under~tood that the pre~ent in~ention ha~ been de~cribed above purely by way of example and that ~odifications of detail can be made within the scope of the invention.
W094/14939 PCT~S93/12090 23 21526~0 In the detergent compositions, the abbreviated component identifications have the following mean~n~:
LAS : Sodium liner C12 alkyl benzene ~ulphonate TAS : Sodium tallow alcohol sulfate TAEn : Tallow alcohol ethoxylated with n moles of ethyleno oxide per mole of alcohol 25E3 : A Cl2_lsprimary alcohol conA-n~^~ with an average of 3 moles of ethylene oxide TAED : Tetraacetyl ethylene diamine Silieate : Amorphous Sodiu~ Silicate (SiO2:Na20 ratio normally follow~) Carbonate : AnhydLv~s sodium earbonate CMC : Sodium ea.~o~Jethyl eellulo~e Zeolite A : Hydrated Sodium Alumino~ilieate of formUla Nal2(AlO2sio2)l2 27H20 having a primary particle ~ize in the range from l to lO micromQtQrs Citrate : Tri-sodium citrate dihydrate Photobleach : Tetra sulfonated Zinc phthalocyanine MA/AA : Copolymer of 1:4 maleic/acrylic acid, average moleeular weight about 80,000 Enzyme : Miye~ proteolytie and amylolytic enzyme sold by Novo Industries AS
Brightener : Disodium 4,4'-bi~(2-morpholino-4-anilino-s-triazin-6-ylamino)~ ne-2:2'-disulphonate DETPMP : Diethylene triamine penta (Methylene phosp~onieacid), marketed by Moncanto under the Trade name Dequest 2060 M~Y~ Suds : 25% paraffin wax Mpt 50C, 17%
Suppres~or : hydrophobic silica, 58% paraffin oil
Claims (21)
1. A cleaning composition containing a poly(amino acid) compound or a precursor thereof and a detersive surfactant, characterized in that the poly(amino acid) compound or precursor thereof is protected from contact with a level of alkalinity as would cause degradation thereof.
2. A composition according to claim 1, in which the poly(amino acid) compound or precursor thereof is provided with a coating.
3. A composition according to claim 2, in which the coating comprises an organic acid compound, a polymeric film-forming material or a mixture thereof.
4. A composition according to claim 1, in which the poly(amino acid) compound or precursor thereof is in the form of a spray granulate with a nonionic surfactant, or is in encapsulated form, or is formulated as part of a cleaning composition that is non-alkaline.
5. A cleaning composition according to claim 1, in which the poly(amino acid) compound or precursor thereof is in the form of an agglomerate with an alkaline or alkaline-reacting compound.
6. A composition according to claim 5 in which the alkaline or alkaline-reacting compound is present in an amount that is equimolar or less, with respect to the poly(amino acid) constituent monomer units or precursor thereof.
7. A cleaning composition according to claim 5, in which the alkaline or alkaline-reacting material is a salt.
8. A cleaning composition according to claim 7, in which said salt is a carbonate, bicarbonate or silicate.
9. A cleaning composition according to claim 1, which contains a poly(amino acid) compound selected from polyaspartic acid and its salts, polyglutamic acid and its salts and mixtures of two or more of these.
10. A cleaning composition containing a poly(amino acid) compound or a precursor thereof and a detersive surfactant, characterised in that it contains no, or substantially no, bleach.
11. A poly(amino acid) or compound or a precursor thereof, characterised in that it is provided with a coating, is encapsulated or is mixed, in the form of an agglomerate or granulate, with at least one other material.
12. A poly(amino acid) compound or a precursor thereof, characterised in that it is in the form of an agglomerate with an alkaline or alkaline-reacting material.
13. A poly(amino acid) compound or a precursor thereof according to claim 12, wherein said alkaline-reacting material is an alkaline-reacting salt.
14. A poly(amino acid) compound or a precursor thereof according to claim 12, wherein said salt is a carbonate, bicarbonate, or silicate.
15. A poly(amino acid) compound or a precursor thereof according to claim 12, in which the alkaline or alkaline-reacting material is present in an amount that is equimolar or less, with respect to the monomeric units of the poly(amino acid) compound or its precursor.
16. A process for producing a poly(amino acid) compound in the form of an agglomerate according to claim 12, which comprises agglomerating the alkaline or alkaline-reacting material with a compound that is converted into the poly(amino acid) compound in alkaline conditions, the agglomeration being effected in the presence of sufficient moisture for the conversion into the poly(amino acid) compound to proceed.
17. A method according to claim 16, in which the poly(amino acid) compound is polyaspartic acid or a salt thereof and in which the alkaline or alkaline-reacting material is agglomerated with polysuccinimide.
18. An agglomerate that contains, or is prepared from, a poly(amino acid) compound or a precursor thereof, an alkaline or alkaline-reacting compound and optionally one or more other materials wherein the alkaline or alkaline-reacting material is present in an amount sufficient to effect complete neutralisation of the said poly(amino acid) or of poly(amino acid) derived from its precursor, without causing degradation thereof.
19. An agglomerate according to claim 18, wherein said alkaline-reacting compound is a carbonate.
20. An agglomerate that contains a poly(amino acid) compound or a precursor thereof, which agglomerate is essentially non-alkaline.
21. An agglomerate according to claim 20, in which the poly(amino acid) compound or precursor thereof is agglomerated with a nonionic surfactant, zeolite and bicarbonate.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| GB9226942.2 | 1992-12-24 | ||
| GB929226942A GB9226942D0 (en) | 1992-12-24 | 1992-12-24 | Dispersing agent |
| PCT/US1993/012090 WO1994014939A1 (en) | 1992-12-24 | 1993-12-13 | Dipsersing agent |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2152620A1 CA2152620A1 (en) | 1994-07-07 |
| CA2152620C true CA2152620C (en) | 2000-01-11 |
Family
ID=10727209
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002152620A Expired - Fee Related CA2152620C (en) | 1992-12-24 | 1993-12-13 | Dispersing agent |
Country Status (12)
| Country | Link |
|---|---|
| EP (1) | EP0677096B2 (en) |
| JP (1) | JP3553063B2 (en) |
| CN (1) | CN1049241C (en) |
| AT (1) | ATE193053T1 (en) |
| AU (1) | AU5827394A (en) |
| CA (1) | CA2152620C (en) |
| DE (1) | DE69328688T3 (en) |
| ES (1) | ES2145121T3 (en) |
| GB (1) | GB9226942D0 (en) |
| IN (1) | IN188267B (en) |
| MX (1) | MX9400083A (en) |
| WO (1) | WO1994014939A1 (en) |
Families Citing this family (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5288783A (en) * | 1992-05-14 | 1994-02-22 | Srchem Incorporated | Preparation of salt of polyaspartic acid by high temperature reaction |
| US5610267A (en) * | 1992-05-14 | 1997-03-11 | Bayer Ag | Process for preparing polysuccinimide by high temperature reaction |
| US5389303A (en) * | 1993-09-10 | 1995-02-14 | Srchem Incorporated | Mixtures of polyamino acids and citrate |
| ATE188497T1 (en) * | 1993-11-02 | 2000-01-15 | Bayer Ag | METHOD FOR PRODUCING POLYMERS CONTAINING ASPARAGIC ACID |
| DE4408478A1 (en) * | 1994-03-14 | 1995-09-21 | Bayer Ag | Water treatment agents |
| US5531934A (en) * | 1994-09-12 | 1996-07-02 | Rohm & Haas Company | Method of inhibiting corrosion in aqueous systems using poly(amino acids) |
| US5902782A (en) * | 1995-01-20 | 1999-05-11 | Procter & Gamble Company | Detergent compositions comprising stabilised polyamino acid compounds |
| DE19532717A1 (en) * | 1995-09-05 | 1997-03-06 | Basf Ag | Use of modified polyaspartic acids in detergents |
| EP1133550B1 (en) * | 1998-11-25 | 2002-10-23 | The Procter & Gamble Company | Process for forming an agglomerated particle |
| US6514929B1 (en) | 1998-11-25 | 2003-02-04 | The Procter & Gamble Company | Process for forming an agglomerated particle |
| DE19907014A1 (en) * | 1999-02-18 | 2000-08-24 | Bayer Ag | Formulation of spray-dried polyaspartic acid and/or iminodisuccinates into preformed compositions for use in detergents by agglomeration, compacting or extrusion |
Family Cites Families (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JPS5425277A (en) * | 1977-07-27 | 1979-02-26 | Fuji Photo Film Co Ltd | Method of producing microcapsule |
| US4587033A (en) * | 1984-07-02 | 1986-05-06 | Monsanto Company | Polymeric acetal carboxylate compositions |
| US4566980A (en) * | 1985-01-16 | 1986-01-28 | Creative Products Resource Associates, Ltd. | Carpet treating composition |
| KR940003701B1 (en) † | 1990-04-25 | 1994-04-27 | 샤프 가부시끼가이샤 | Method of character image generation on computer |
| IT1240684B (en) * | 1990-04-26 | 1993-12-17 | Tecnopart Srl | POLYAMINO ACIDS SUCH AS BUILDERS FOR DETERGENT FORMULATIONS |
| FR2675153B1 (en) † | 1991-04-15 | 1994-07-22 | Rhone Poulenc Chimie | DETERGENT COMPOSITION CONTAINING A POLYIMIDE BIOPOLYMER HYDROLYSABLE IN A WASHING MEDIUM. |
| US5266237A (en) * | 1992-07-31 | 1993-11-30 | Rohm And Haas Company | Enhancing detergent performance with polysuccinimide |
-
1992
- 1992-12-24 GB GB929226942A patent/GB9226942D0/en active Pending
-
1993
- 1993-12-13 WO PCT/US1993/012090 patent/WO1994014939A1/en active IP Right Grant
- 1993-12-13 AU AU58273/94A patent/AU5827394A/en not_active Abandoned
- 1993-12-13 JP JP51523994A patent/JP3553063B2/en not_active Expired - Fee Related
- 1993-12-13 AT AT94904076T patent/ATE193053T1/en not_active IP Right Cessation
- 1993-12-13 DE DE69328688T patent/DE69328688T3/en not_active Expired - Fee Related
- 1993-12-13 CA CA002152620A patent/CA2152620C/en not_active Expired - Fee Related
- 1993-12-13 ES ES94904076T patent/ES2145121T3/en not_active Expired - Lifetime
- 1993-12-13 EP EP94904076A patent/EP0677096B2/en not_active Expired - Lifetime
- 1993-12-22 IN IN1441DE1993 patent/IN188267B/en unknown
- 1993-12-24 CN CN93119978A patent/CN1049241C/en not_active Expired - Fee Related
-
1994
- 1994-01-03 MX MX9400083A patent/MX9400083A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| CN1090598A (en) | 1994-08-10 |
| ES2145121T3 (en) | 2000-07-01 |
| GB9226942D0 (en) | 1993-02-17 |
| EP0677096A1 (en) | 1995-10-18 |
| DE69328688T3 (en) | 2004-06-17 |
| EP0677096B2 (en) | 2003-08-20 |
| IN188267B (en) | 2002-08-31 |
| DE69328688D1 (en) | 2000-06-21 |
| WO1994014939A1 (en) | 1994-07-07 |
| CN1049241C (en) | 2000-02-09 |
| CA2152620A1 (en) | 1994-07-07 |
| DE69328688T2 (en) | 2001-01-11 |
| ATE193053T1 (en) | 2000-06-15 |
| JP3553063B2 (en) | 2004-08-11 |
| AU5827394A (en) | 1994-07-19 |
| EP0677096A4 (en) | 1998-04-29 |
| JPH08505173A (en) | 1996-06-04 |
| MX9400083A (en) | 1994-07-29 |
| EP0677096B1 (en) | 2000-05-17 |
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| Date | Code | Title | Description |
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| EEER | Examination request | ||
| MKLA | Lapsed |