Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING ANTIBODY
CONTROLLED LIPOLYTIC ACTIVITY
FIELD of the INVENTION
The present invention relates to detergent co",posilions including laundry
dishwashing and hard surface cleaning compositions comprising a lipolytic
enzyme and a lipolytic enzyme-directed anlil,ody in order to prevent potential
malodour fon~,ation related to the hydrolytic activity of lipolytic enzyme whilemaintaining excellent wash perfor",ance.
BACKGROUND of the INVENTION
An important part of the system which protects vertebrates against
infe~;tions by bacteria and viruses is the humoral immune system. Specialised
cells present in bone marrow Iymphoid tissues and blood produce
immunoglobulins (antibody) which appear in response to the introduction of
micro- or ",aclo",ol~cule foreign to that body and bind the body-foreign structure
initiating its destruction. Such a body-foreign molecule is called an antigen. The
a,ltiboJy is di,~cted against the antigenic determinant or hapten of the antigene.g. an amino acid sequence parts of oligosaccharides polysaccharides
lipopolysaccharides glycoproteins lipoproteins lipoteichoinic acids.
The speciric alllil-odies generated in this manner can combine with the
antigen which elicited their formation to form an antigen-antibody complex.
- Antibody mol ~ ~u'es have binding sites that are very specific for and
coi"plementary to the structural features of the antigen that induced their
~UI 11 IdliOI I .
, . , _ , _
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This highly specific antigen-antibody recognition and binding has found
several applications such as recognition agent binding agent or carrier agent invarious domains such as analytical che~ y therapeutictreatment health and
beauty care.
EP 479 600 EP 453 097 and EP 450 800 relate to the use of antibodies
or fragments thereof for the delivery of active ingredients to a target site. EP 481
701 discloses treatment compositions for topical application containing
microcapsules which enclose a belleficial agent at a target location the
"~iclocapsules having an antibody or antibody fragment specific to the target
location or a lectin.
W092/04380 describes reshaped human antibody or reshaped human
antibody frag")enl~ having speci~city for human polymorphic epithelial mucin to
be used in the l,adt"~ent or diagnosis of cancer. The use of Epstein-Barr virus
specific polypeptides for the production of antihodies and the diagnostic and
treatment of said disease is disclosed in W094/06470.
Oral compositions comprising antibodies as anti-caries or periodontal
dise~ses treatment have been extensively clesc,iLed in WO95/01155
WO95/00110 WO95/10612 EP 140 498 GB 2 151 923 GB 2 176 400 GB 2
167 299 DE 4324859 US 5 401 723 and EP 280 576.
EP 673 683 and EP 542 309 disclose hair cosr"elic compositions
containing an anlil.ody to hair or hair extract obtained from egg yolk or poultry
immunised with the hair or hair extract and a polymer emulsion to provide
reduced hair dar"a~e softness moistened feel and sr"ooll,ness said
composition being adsorbed only onto a specified part of the hair.
Cor"posilions co,)lailling antagollists (tyrpl,osli"s or anti~odies) against
epidermal and transforming growth factors suitable for use in treatment of acne
are described in W095/24896.
The use of al lliL,odies in the overall detergency context has been
suggested in Unilever Researchprijs Molecule zoekt partner 1992 wherein
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modified antibodies directed to specific stains are proposed to be used in
bleaching process.
The production of antibodies by hyperimmunisation of mammals such as a
cow with a vaccine derived from E. coli bacteria is described in EP 102 831. EP
400 569 discloses a method for preparing vaccine composition for dental caries
in nasal drops comprising an a"li~en produced by integrating a protein antigen-
expressing gene into the chnj",osomal gene of a s~ ptococcl)s mutants GS-5
strain. WO94/25591 disclQses the production of antibodies or functionalised
fragments thereof derived from heavy chain immunoglobulins of camelidae.
Deteryent co"~positions include nowadays a complex combination of
active ingredients which fulfill certain specific needs: a sur~actant system,
enzymes providing cleaning and fabric care benefits, bleaching agents, a buildersystem, suds Supple:ssors~ soil-suspending agents, soil-release agents, optical
b-iyhteners, softening agents, dispersants, dye transfer inhibition compounds,
abrasives, bactericides, perfumes, and their overall pe,fi.l",auce has indeed
improved over the years.
In particular, current laundry detergent formulations generally include
detergent enzymes and more specifically lipolytic enzymes.
However, overe~l~osure of the substrate to the lipolytic activity and/or
transfer of the lipolytic activity to the post mainwash part of the washing cycle
such as rinse, spinning and/or drying steps can lead to unwanted effects e.g.
malodour for,ndtion. It is well known that detergent lipolytic enzymes can undercertain circ--",:,ta,lces lead to unattractive odor. It is bel.~ved that lipolytic
enzymes which are adsorbed in the wash cycle onto re~idu~l lipid stains / soils,continues to function thereafter, especia!~y in the rinse and drying cycles. Wlthout
meaning to be bound by theory, it is believed that this malodor is stei"",i"g from
the post mainwash hydrolysis of residual lipid soils/ stains.
It has now been surprisingly found that the applicalion of antil,Gdies raised
aga.nsl lipolytic enzyme prevents the occurrence of undesirable residual lipolytic
activity. The lipolytic activity can be fully controlled during the cleaning process
so that the potential negative effects, i.e. malodor fon"ation due to the
overexposure of the sul~sl,ale to the active lipolytic enzyme can now be avoided.
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It is therefore an object of the present invention to provide a lipase-
containing detergent composition delivering excellent cleaning performance such
as stain and/or soil removal, dingy cieaning and which has improved odor
characteristics.
The above need has been met by specific detergent compositions
including laundry, dishwashing and hard surface cleaning, Co"",,i~il,y a lipolytic
enzyme and an antibody directed to the lipolytic enzyme.
SUMMARY of the INVENTION
The present invention relates to detergent cGI~positions including laundry,
dishwashing and hard surface cleaning compositions colnp,ising a lipolytic
enzyme and a lipolytic enzyme-dir~cted antibody in order to prevent potential
malodor fo.",aliol) related to the hydrolytic activity of lipolytic enzyme whilemainl~ ing exce"ent wash performance.
DETAILED DESCRIPTION of the INVENTION
ANTIBODY
An essenlial element of the deler~ent compositions of the present
invention is an antiboJy.
The immunoglol~ ins are classified into 5 cl -sses, respectively: IgM, IgG,
IgA, IgD and IgE. rl~f~ndd types of immunoglobulins are IgG and IgA. Secretory
slgA which are found into human excreted body fluids such as milk, saliva,
respiratory and i"teslinal fluids are especially designed to survive in said
secretio"s, they have enhanced binding characteristics and are resistant to
proteolytic hydrolysis.
The anlibG.Jy which may be monoclonal or polyclonal or an antibody
~,a!Jr"enl, may be generated by techniques conventional in the art, for example
by using recombinant DNA techniques allowing to produce ar,liL.od;es variants
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with new properties: reduced immunogenecity, enhanced affinity, altered size, ...
Specific binding may also be used. Preferred for the purpose of the present
invention is a monoclonal antibody, more preferred is a fragment thereof. These
fragments may be si~ nilcirly generated by conventional techniques such as
enzymatic digestion by papain or pepsin, or using recombinant DNA techniques.
Antibody fldgn,ents may also be generated by conventional recombinant DNA
techniques. Antibodies and antibodies' f~dyl"e~ may be humanised, such as
described in Meded. - Fac. Landbouwkd. Toegepast Biol. Wet. (Univ. Gent)
(1995), 60(4a, Forum forApplied Biotechnology, 1995, Part 1), 2057-63.
Heavy and light chains are indeed co"~posed of consla,)l and variable
domains. In the organisms producing immunoglobulins in their natural state the
constant domains are very important for a number of ful)~tiGns, but for many
applications in industrial proGesses and products their variable domains are
sufficient. Consequently many methods have been described to produce
antibody f,dgme"t~.
Antibody f,dy-"ents which are used may be a Fab, a Fv, a scFv or any
other fragment having similar binding plope,lies. Preferred routes to antibodiesfrasiments are through ~co"lbinant DNA technology, so that the fragment is
expressed by a genatically l,~nsformed organism.
Antibodies and antibody fragments produced by l~:con,binant DNA
techn~logy do not need to be identical to fragment of antibodies produced in
vertebrates, having neve,lî,eless the same binding properties eval~ tecl by their
Km, Ki and Kcat. For insta. ~ce they may include sequences of amino acids and/orglycosyl.llions which differ from those found in antibodies produced in other
ways, especially sequences at the end of fidgl"ent~. Somewhat analogously,
antibody r,ay,nel1ts produced through recol"bi.)al)l DNA technology may include
extra amino acid sequences at their termini which have no counterpart in
antibodies produced in other ways.
A related possibility is that a binding agent for use in this invention is a
natural or sy,ltl,~lic polymer which mimics the specific b.nding activity of a natural
antibody's complel"eillairy region(s). Such a polymer is for exa.nple a
.. , , .. , . , . . ~ ..
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polypeptide or a polymer imprinting (Angew. Chem. Int. Ed. Engl. 1995, 34,
1812-1832).
The usual method for the production of antibodies may be adopted in
immunising mam~llals or poultry with the cGr~esponding antigens. As mammals to
be immunised, mice, rabbits, goats, sheep, horses, cows, etc. may be used. The
antibody (immunoglobulin fraction) may be separated from the antiserum, the
milk or the eggs according to the ordinary antibody pu,ificalion ~elhod including
salting-out n~elhod, Polson extraction, gel-fillldtiGn chro",alography, ion-
exchange chro",a~ography, afffinity chromalography and the like, the salting-outmethod using ammo~ m sulfate to produce the prec;~.itdtes, followed by
dialysing the pr~c;~vilates against physiological saline to obtain the purified
precipitates as the antibody.
Plants are also capable of synthesising and assernbling every kind o
antibody molecule and allow a large scale of production of antibodies as
described in Tibtech. Dec 1995, Vol 13, pp 522-527; Plant Mol. Biol., 26, pp
1701-1710, 1994 and Biotechnol. proj. 1991, 7, pp 455461 and in US patent 5,
202,422. Antibodies can also ~e produced into microorganisms such as E. coli
or S. cerevisiae via b.orelll)entation process as illusl,aled in the EP patent 667
394.
Techniques for the production of antibody rldy",e"ts are well known in the
literature: Saiki et al. Science 230 1350-54 (1985); Orlandi et al. PNAS USA 86
3833-7 (1989); W089/09825; EP 368 684; WO 91/08482 and WO94/25591.
The drawbacks due to plolonged activity of the enzyme can be avoided by
an effective control of the enzymatic activity trough the introduction of the
specifically wr,~:spo"Jing antibody. Such antibodies can be either polyclonal -
directed to the whole enzyme structure - or mol1oclonal - directed to specific
epitopes of the enzyme activity controlling regions of the enzyme structure.
Antibodies raised against specific enzyme can effectively deactivate the enzyme
by the antibody-antigen binding in or very near the active site. The fo""dlion of
such compl_x leads to the enzyme deactivation and could be explained by the
distortion of the 3-di,-~e"sional structure and/or steric hindrance at the substrate
- cleft. The deactivation of the enzyme can also be achieved by the precipitation of
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the complex antibody-antigen from the washing solution. Due to very high
specificity and efficiency of the antibody-antigen interaction, no other detergent
active is thereby affected.
The lipolytic enzyme-directed antibodies are pref~rdbly comprised in the
detergent compositions of the ~resenl invention at a level of from 10E-6% to
10E+1% by weight of total cG"~rosition. In some instances, antibodies raised
against a specific lipolytic enzyme have the capability of binding other lipolytic
enzymes of high structural similarity, providing cross-reactivity. Typically, a
mo'ecul~r ratio of lipolytic enzyme-directed antibody to lipolytic enzyme will be of
100:1 or lower, p,t:ferably of 50:1 or lower. For monoclonal antibodies or
fragments thereof, the molecu~r ratio of lipolytic enzyme-directed antibody to
lipolytic enzyme will be generally of 50:1 or lower, preferably of 20:1 or lower.
The antibodies raised against the lipolytic enzyme are rclw-.cd in the
wash solution after a lag-period allowing to deliver exc~ nl benefits to be
achieved by the end of the wash process.
Therefore, the antiL,ocl.~s are pr~:reral~ly incG,,uoraled into a release agent
in order to control their release timing and rate in the wash solution. The physical
form of the antibody-containing release agent is adapted to the. physical form of
the corresponding detergent or additive.
For granular and powder detergent and cleaning products, the antibodies
and release agents can be conlained in a granulate. Said a,ltil,oJy granulate can
suitably contain various granulation aids, binders, fillers, plaslici~e,s, lubricants,
cores and the like. Examples ll,ereof include cellulose (e.g. cellulosic fibers or in
microcrystalline form), cel' ~ose derivatives (CMC, MC, HPC, HPMC), gelatin,
starch, dextrins, sugars, polyvinylpyrrolidone, PVA, PEG, salts (e.g. sodium
sulfate, calcium sulfate), titanium dioxide, talc, clays (kaolin or bentonite)and
nonioni~ su~ rdclarils. Other materials of relevance for incorporation in the
granulate are described in EP 304 331.
The lelease agent may be, for example, a cOdtillg. Said coali"g protects
said granulates in the wash environment for a certain period of time. The codling
will normally be app' ed to said granulates in an amount in the range of 1% to
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50% by weight (calcul~ted on the basis of the weight of the uncoated, dry
granulate), preferably in the range of 5 % to 40 % by weight The amount of
coating to be applied to said granulates will depend to a considerable extent onthe nature and composition of the desired coating, and to the kind of protectionsaid coating should offer to said granulates. For example, the thickness of saidcoating or a multi-layered coating applied onto any of the above granulates may
determine the period in which the content of said granulates is released. A
possible multi-layered coating may be a coati~g in which, for example, a fast
release coating is applied over a slow release coating.
Also co-granulates can be constructed containing in the outer layer the
detergent enzyme and a fast releasing agent and in the inner core, the antibody
and a slow releasing agent.
Suitable release coalings are coali"~s which give rise to release of the
contents of antibody-containing granulates under the cor,.litions prevailing during
the use thereof. Thus, for example, when a prepardliGn of the invention is to beintroduced into a washing liquor containing a washing detergent (normally
comprising, e.g. one or more types of surfactants), the coating should be one
which ensures the release of the contents of said granulates from the release
agent when it is introduced into the washing medium.
Fr~ft:r,ed rel2asc coating are codlings which are sul,sl~nt;a"y insoluble in
water. Release coalinys which are appropriate in washing media may suitably
co,nprise substances s~lected from the following: cellulose and cellulase
derivatives, F~VA, PVP, tallow; hydrogenated tallow; partially hydrolyzed tallow;
fatty acids and fatty alcohols of natural and sy~ltl,elic origin; long-chain fatty acid
mono-, di- and l,iest~r~ of glycerol (e.g. glycerol monostearate); ethoxylated fatty
alcohols; I~P~eS; hydrocarbons of melting point in the range of 50-80~C; and
waxes. Melt-co~li"g agents are a preferred class of fast or slow l~lease coatingagents which can be used without dilution with water. Reference may be made to
Controlled Release Systems: Fabricalion Technology, Vol. I, CRC Press, 1988,
for further info""dlion on slow release coating.
Codli"gs may suitably further comprise substdnces such as clays (e.g. kaolin),
titanium ~ioxide, pigments, salts (such as calcium carbonate) and the like. The
person skilled in the art will be aware of further codling constituents of relevance
in the present invention.
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In liquid detergent compositions, the antibody can be incorporated as a
dispersion of particles containing in addition to the antibody, a release agent. The
antibody can be present in a liquid or solid form. Suitable particles consist of a
porous hydrophobic material (e.g., silica with an average pore diameter of 500
Angstrom or higher) containing into the pores a solution of antibodies and a
surfactant as described in EP 583 512 of Surukidis A. et al.
The release agent might be a coali"g which protects said particles in the wash
cycle for a certain period of time. The coating is pr~ferably a hydrophobic coating
,naterial such as a hydrophibic liquid polymer. Said polymer can be an organo
polysi'3xal1e oil, alternatively a high olecula weight hydrocarbon or water
illsolu~lc but water permeable polymeric material such as
carboxymethylcellulose, PVA, PVP. The polymer properties are selected to
achieve a suitable release profile of the antibody in the wash solution.
THE LIPOLYTIC ENZYME
Suitable specific lipolytic enzymes for use herein include those of bacterial
and fungal origin.Origin can further be mesophilic or extremophilic (psychrophilic,
psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.).
Purified or non-purified forms of these enzymes may be used. Also included by
def",ilio", are mutants of native enzymes. Mutants can be obtained e.g. by
protein and/or genetic engineering, chemical and/or physical modir,~dliGns of
native enzymes. Co""nGn practice as well is the expression of the enzyme via
host o~ani_."s in which the genetic malerial responsible for the pro~uction of the
enzyme has been cloned.
In the presel)t contexl, the term "lipolytic enzyme" is inlended to i"clicale
an enzyme exhibiting a lipid deg~acling capability, such as a c~p~hility of
degrading a triglyceride, a phospholipid, a wax-ester or cutin. The lipolytic
enzyme may, e.g., be a lipase, a phospholipase, an esterase or a cutinase.
An essential ele."eilt of the present invention is carboxylic ester
hydrolase EC 3.1.1 and especi~ly a lipase EC 1.1.1.3. Said lipolytic enzyme is
incorporated at a level of from 0.0001 to 2%, preferably from 0.0002% to 1%,
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more preferably from 0.0005% to 0.1 % pure enzyme by weight of total
composition.
Suitable lipase enzymes for detergent usage include those produced by
microorganisms of the Pseudomonas group, such as Pseudomonas stukeri
ATCC 19.154, as dis-~losed in British Patent 1,372,034. Suitable lipases includethose which show a positive immunological cross-reaction with the antibody of
the lipase, produced by the microorganism Pseudomonas fluorescent IAM 1057.
This lipase is available from Amano Phar")aceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter r~fer~J to as "Amano-P".
Other s~lit~le co""ner~,ial lipases include Amano-CES, lipases ex Chromobacter
viscosvm, e.g. Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo
Jozo Co., Tagata, Japan; Chrcmobacter viscosvm lipases from ~J.S. Biochemical
Corp., U.S.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas
gladioli. Especially suitable lipases are lipases such as M1 LipaseR and
LipomaxR (Gist-Br(,cades) and LipolaseR and Lipolase UltraR(Novo) which have
found to be very effective when used in cGillbi.ldlion with the compositions of the
present invention. Also suitables are the lipolytic enzymes described in EP 258
068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578,
WO 95/35381 and WO 96/00292 by Unilever.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a
spsci-' kind of lipase, nan,ely lipases which do not require interfacial activation.
Suitable cutinases are described in WO 94/14963 and WO 94/14964. Addition of
culinases to deter~enl compositions have been described in e.g. WO-A-
88/09367 (Gel)encor) and WO 90/09446 (Plant Genetic System).
The cutinases are normally incol~ordted in the deleryenl composition at levels
from 0.0001 % to 2% of active enzyme by weight of the detergent composition.
Deter~ent ~."~,onents
The detergent compositions of the invention may also contain additional
detergent components. The precise nature of these additional components, and
levels of incorporation thereof will depend on the physical forrn of the
co,,,,uosilion, and the nature of the cleaning operation for which it is to be used.
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The detergent compositions according to the invention can be liquid
paste gels bars. tablets powder or granular forms. Granular compositions can
also be in "compact " form the liquid compositions can also be in a
"concentrated" form.
The co",positions of the invention may for example be formulated as hard
surface cleaner hand and machine dishwashing c~i "positi~ns hand and
machine laundry detergent compositions including laundry additive compositions
and compositions suitable for use in the soalcing and/or pr~t,eat",eilt of sldi"ed
fabrics rinse added fabric softener CGIllpositions.
When formulated as compositions for use in manual dishwashing methods
the compositions of the invention p~eferably contain a surfactant and preferablyother detergent compounds seJected from organic polymeric cG~Ipounds suds
enhancing agents group 11 metal ions solvents hydrotropes and additional
enzymes.
When formulated as cGr"positions suitable for use in a laundry machine
washing method the cGIlll~ositiGl)s of the invention p~rerdbly contain both a
surfactant and a buiider compound and additiG"ally one or more detergent
components preferably s~lected from organic polymeric compounds bleaching
agents additional enzymes suds suppressor~ disper~.anls lime-soap
disper~ants soil suspension and anti-~edeposition agents and corrosion
inhibitors. Laundry c~",,~ositions can also conlain sorlenL)g agents as additional
detergent components.
The cG"~positions of the invention can also be used as deteryent additive
products CGIIIp~iSillg a lipolytic enzyme-directed allliLody and will be added to
conventional deteryent lipolytic enzyme-containing compositiGns. The detergent
additives can also cGmprise a lipolytic enzyme and a lipolytic enzyme-directed
antibody. Such additive products are intended to supplement or boost the
perfor",ance of convenliGnal detergent co~positions prererably comprise up to
50% antibodies by weight of total c~l"position.
. .
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If needed the density of the granular laundry detergent compositions
herein ranges from 400 to 1200 g/litre, preferably 600 to 950 g/litre of
composition measured at 20~C.
The "compact" form of the granular laundry detergent compositions herein
is best reflected by density and, in terms of composition, by the amount of
inorga"ic filler salt; inorganic filler salts are conventional ingredients of detergent
compositions in powder form; in conventional detergent compositions, the filler
salts are present in subst~rltial amounts, typically 17-35% by weight of the total
composition.
In the compact compositions, the filler salt is present in amounts not
exceecling 15% of the total composition, preferably not exceeding 10%, most
preferably not exceeding 5% by weight of the cG"".osition.
The inGrgan.c hller salts, such as meant in the present compositions are
selected from the alkali and alkaline-earth-metal salts of sul~hales and chlorides.
A prefer,ed filler salt is sodium sulphate.
Liquid detergent compositions according to the present invention can also
be in a "col1ce"t~dted form", in such case, the liquid detergenl cGmpositions
according the present invention will contain a lower amount of water, compared
to conventional liquid detergents.
Typically the water contenl of the conce, ILlaled liquid detergent is
p~eferdbly less than 50%, more preferably less than 40%, most preferably less
than 30% by weight of the detergent composition.
Surfactant s~t~.,.
The detergent co"~positions according to the present invention comprise a
surfactant system wherein the surfactant can be selected from nonionic and/or
anionic and/or cdlioni~ and/or a",pholytic and/or zwitlerionic and/or semi-polarsurfactants.
The surfactant is typically present at a level of from 0.1% to 60% by weight.
More preferred levels of incorporation are 1% to 35% by weight, most preferably
from 1% to 30% by weight of detergent compositions in accord with the invention.
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The surfactant is preferably formulated to be compatible with enzyme
components present in the composition. In liquid or gel compositions the
surfactant is most preferably formulated such that it promotes, or at least doesnot degrade, the stability of any enzyme in these compositions.
Preferred surfactant systems to be used according to the present invention
comprise as a surfactant one or more of the nonionic and/or anionic surfactants
described herein.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suitable for use as the nonionic surfactant of the surfactant systems
of the present invention, with the polyethylene oxide condensates being
preferred. These compounds include the condensation products of alkyl phenols
having an alkyl group co"tai"ing from about 6 to about 14 carbon atoms,
preferably from about 8 to about 14 carbon atoms, in either a straight-chain or
branched-chain configuration with the alkylene oxide. In a preferred embodiment,the ethylene oxide is present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of ethylene oxide per
mole of alkyl phenol. Com",ercially available nonionic surfactants of this type
include IgepalTM C0-630. marketed by the GAF Corporation; and TritonTM X-
45, X-114, X-100 and X-102, all marketed bythe Rohm & Haas Cornpany. These
surfactants ar c~-lllllonly referred to as alkylphenol alkoxylates (e.g., alkyl
phenol ethoxylat~).
The condensdlion products of primary and secondary aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use as the
nGni~ni~ surfactant of the nonionic surractant systems of the present invention.The alkyl chain of the aliphatic alcohol can either be straight or branched, primary
or seco"~ary, and generally contains from about 8 to about 22 carbon atoms.
P,efer,~:d are the condensation products of alcohols having an alkyl group
containing from about 8 to about 20 carbon atoms, more preferably from about
10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene
oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most
preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in
said condensation products. Examples of co"""ercially available nonionic
surfactants of this type include TergitolTM 1 5-S-9 (the condensation product of
.,
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C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW
(the condensation product of C12-C14 primary alcohol with 6 moles ethylene
oxide with a narrow molec~ r weight distribution), both marketed by Union
Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C1s
linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation
product of C12-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM
45-7 (the condensation product of C14-C1~ linear alcohol with 7 moles of
ethylene oxide), NeodolTM 4~-5 (the condensation product of C14-C1s iinear
alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company,
KyroTM EOB (the condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA
030 or 050 (the condensation product of C12-C14 alcohol with 3 or 5 moles of
ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products
is from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the surfactant systems of the present
invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group conlaini"~ from
about 6 to about 30 carbon atoms, preferdbly from about 10 to about 16 carbon
atoms and a polysaccl,aride, e.g. a polyglycoside, hydrophilic group containing
from about 1.3 to about 10, preferably from about 1.3 to about 3, most prererably
from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing5 or 6 carbon atoms can be used, e.g., glucose, galactose and g~l~Gtosyl
moieties can be substituted for the glucosyl moieties (o,uliGnally the hydrophobic
group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or
galactose as opposed to a glucoside or g~l~ctosiç!e). The intersaccharide bonds
can be, e.g., between the one position of the additiona! saccharide units and the
2-, 3-, 4-, and/or 6- posilio"s on the preceding saccharide units.
The pre~r,e~ alkylpolyglycosicles have the formula
R20(CnH2nO)t(91Yc~syl)x
wl ,erei., R2 is selected from the group consisting of alkyl, alkylphenyl,
hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which the alkyl groupscontain from about 10 to about 18, preferably from about 12 to about t4, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, pr~rerably 0; and x is from
CA 0226343~ 1999-02-ll
W O98/06810 15 PCTAUS97/14287
about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To
prepare these compounds, the alcohol or alkylpolyethoxy alcohol is formed first
and then reacted with glucose, or a source of glucose, to form the glucoside
(allacl~")ent at the 1-position). The additional glycosyl units can then be attached
between their 1-position and the preceding glycosyl units 2-, 3-, 4- and/or 6-
position, preferably predominately the 2-position.
The condensation products of ethylene oxide with a hydrophobic base formed
by the cGnde,lsdlion of propylene oxide with propylene glycol are also suitable for
use as the additional nonionic su,ractant systems of the present invention. The
hydrophobic portion of these compounds will preferably have a molecular weight
of from about 1500 to about 1800 and will exhibit water insolubility. The addition
of polyoxyethylene moieties to this hydrophobic portion tends to increase the
water solubility of the molecule as a whole, and the liquid character of the
product is retained up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product, which corresponds to
condensation with up to about 40 moles of ethylene oxide. ExanlFles of
compounds of this type include certain of the commercially-available PlurafacTM
LF404 and PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the "oni3"ic surfactant
system of the present invention, are the conde"saliGn products of ethylene oxidewith the product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists of th
reaction product of ethyle.)ediai,line and excess propylene oxide, and generallyhas a molecular weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that the condensation
product contains from about 40% to about 80% by weight of polyoxyethylene and
has a nl~lBCUI~r weight of from about 5,000 to about 11,000. Examples of this
type of nonionic SUI ractant include certain of the cGrr,r"er~,ially available
TetronicTM col"pounds, marketed by BASF.
r~t:rer,ed for use as the nonionic su,racldl~t of the su,r~ctant systems of the
present invention are polyethylene oxide condensates of alkyl phenols,
condensation products of primary and seconddly aliphatic alcohols with from
.
CA 0226343~ 1999-02-11
WO 98/06810 16 PCT~US97/14287
about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures
thereof. Most preferred are Cg-C14 alkyl phenol ethoxylates having from 3 to 15
ethoxy groups and Cg-C1g alcohol ethoxylates (preferably C10 avg.) having from
2 to 10 ethoxy groups, and mixtures thereof.
Highly preferred nonionic su~ ractdnls are polyhydroxy fatty acid amide
surfactants of the formula.
R2 C-N-Z,
Il I
o R1
wherein R1 is H, or R1 is C1 4 hydrocarbyl, 2-hydroxy ethyl, 2-hydroxy propyl ora mixture thereof, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative thereof. Pleferably, R1 is methyl, R2 is a
straight C11 15 alkyl or C16 18 alkyl or alkenyl chain such as coconut alkyl or
mixtures thereof, and Z is derived from a reducing sugar such as glucose,
fructose, maltose, l~ctose, in a reductive an~ lion ,eactiGn.
Suitable anionic surfactants to be used are linear alkyl benzene sulfonate,
alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic
acids (i.e., fatty acids) which are sulfonated with ~seolJs SO3 according to "The
Joumal of the American Oil Cl~e~ t~ Society", 52 (1975), pp. 323-329. Suitable
starting ~,aterials would include natural fatty substances as derived from tallow,
palm oil, etc.
The prefer,ed alkyl ester sulrur~ate surfactant, especi~ly for laundry applications,
comprise alkyl ester sulfonate surfactants of the structural formula:
o
Il
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or combination thereof,R4 is a C1-C6 hydloca~byl, preferably an alkyl, or combination thereof, and M isa cation which forms a water soluble salt with the alkyl ester sulfonate. Suitable
salt-forming cations include metals such as sodium, poPssium, and lithium, and
CA 0226343~ 1999-02-11
W O 98106810 17 PCTrUS97/14287
substituted or unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is C10-c16 alkyl, and R4 is
methyl, ethyl or isopropyl. Especially pr~re:r,ecl are the methyl ester sulfonates
wherein R3 is C10-C16 alkyl.
Other suitable anioniC surfactants include the alkyl sulfate surfactants which
are water soluble salts or acids of the formula ROS03M wherein R pr~f~::,ably isa C10-C24 hydrocarbyl, p~efer~bly an alkyl or hydroxyalkyl having a C10-C20
alkyl component, more preferably a C12-C1g alkyl or hydroxyalkyl, and M is H or
a cation, e.g., an alkali metal cation (e.g. sodium, pot~ssium, lithium), or
ammonium or s~bstituted amn,ol,ium (e.g. methyl-, di~ thyl-, and l,i.netl,yl
ammonium cations and quaternary ammonium cations such as tel,arnetl,yl-
a"""onium and di",etl,yl piperdinium catio"s and quaternary ammonium calions
derived from alkylamines such as ethylamine, diethylamine, triethylamine, and
mixtures thereof, and the like). Typically, alkyl chains of C12-C16 are preferred
for lower wash te""~erdlures (e.g. below about 50~C) and C16 18 alkyl chains
are preferred for higher wash temperatures (e.g. above about 50~C).
Other anionic surfactants useful for detersive purposes can also be included in
the detergent compositions of the present invention. These can include salts
(including, for example, sodium, potassium, ammonium, and substituted
ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22
primary of secondary alkanesulrunales, Cg-C24 olefinsulrùnates, sulru"d~ed
polycarboxylic acids pfepared by sulfonation of the pyrolyzed product of alkaline
earth metal citlat~s, e.g., as desc~ibed in British patent specificalion No.
1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl
glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, pararrin sulfonates,
alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates,
alkyl succi"a",ates and sulfosuccinales, monoesters of sulfosucc;nales
(especially saturated and unsaturated C12-C18 monoesLer~) and diesters of
sulfosucci"ates (especially saturated and unsaturated C6-C12 diesters), acyl
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds being described below),
branched primary alkyl sulfates, and alkyl polyethoxy carboxylates such as thoseof the formula RO(CH2CH20)k-CH2COO-M+ wherein R is a Cg-C22 alkyl, k is
.. ..
CA 0226343~ 1999-02-ll
W O98/06810 18 PCTrUS97/14287
an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids andhydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin,
and resin acids and hydrogenated resin acids present in or derived from tall oil.
Further e~ ples are described in "Surface Active A~ents and Detergents"
(Vol. I and ll by Schwartz, Perry and Berch). A variety of such surfactants are
also generally disclosed in U.S. Patent 3,929,678, issued December 30, 1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein
incorporated by reference).
When included therein, the laundry detergent co~positions of the present
invention typically comprise from about 1% to about 40%, preferably from about
3% to about 20% by weight of such anionic su, ra~;tdnts.
Highly preferred anionic SIJ~ ractar,l~ include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M
wherein R is an unsubstitl~ted C10-C24 alkyl or hydroxyalkyl group having a C10-C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
greater than zero, typically ~et.veEn about 0.5 and about 6, more p~ferably
between about 0.5 and about 3, and M is H or a cation which can be, for
example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium,
etc.), ammonium or suhstitl~ted-a,l,monium cation. Alkyl ethoxylated sulfates aswell as alkyl propoxylated sulfates are col)te,l.,~lated herein. Specific examples
of substituted ammonium caliol)s include methyl-, dilllelllyl, Iril"ell~yl-am"~ollium
cations and quaternary an)mG~Iium cations such as tetldmetl,yl-ammonium and
diln~tl.yl piperdi~ lm cdtions and those derived from alkylamines such as
ethylall,i,)e, diethylamine, triethylamine, mixtures thereof, and the like. Exer"pla,y
surfactants are C12-C1g alkyl polyethoxylate (1.0) sulfate (C12-C1gE(1.0)M),
C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-C1gE(2.25)M), C12-C1g alkyl
polyethoxylate (3.0) sulfate (C12-C1gE(3.0)M), and C12-C1g alkyl polyethoxylate
(4.0) sulfate (C12-C1gE(4.0)M), wherein M is conveniently selected from sodium
and potassium.
The detergent compositions of the present invention may also conlai" cationic,
ampholytic, z~itle,iol-ic, and semi-polar surfactants, as well as the nonionic
and/or anionic surr~Ctanls other than those already described herein.
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W O 98tO6810 PCTnUS97/14287
19
Cationic detersive surfactants suitable for use in the detergent compositions ofthe present invention are those having one long-chain hydrocarbyl group.
Exar"plss of such cationic surfactants include the ammonium surfactants such as
alkyltrimethylarrlillolliUm halogenides, and those surfactants having the formula:
[R2(oR3)y][R4(0R3)y]2R5N+X-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the alkyl chain, each R3 is selected from the group consisting of
-CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is select~d from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures ron"ed by joining the two R4 groups, -
CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
polymer having a "~o'e~.ul~r weight less than about 1000, and hydrogen when y
is not 0; R5 is the same as R4 or is an alkyl chain wherein the total number of
carbon atoms of R2 plus R5 is not more than about 18; each y is from 0 to about
10 and the sum of the y values is from 0 to about 1~; and X is any compatible
anion.
Quaternary ammonium surfactant suitable for the present invention has
the formula (I):
Rl~o~ ~R,
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the
formula (Il):
N~
Formula ll
y is 2-4, preferably 3.
CA 0226343~ 1999-02-11
W O98/06810 20 PCTrUS97/14287
whereby R2 is H or a C1-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and RS are either the same or different and can be either a shortchain alkyl (C1-C3) or alkoxylated alkyl of the formula lll,
whereby X- is a counterion, preferably a halide, e.g. chloride or methylsulfate.
R6
H
Formula lll
R6 is C1-C4 and z is 1 or2.
Pr~fer~ed quat ammonium surfactants are those as defined in formula I
whereby
R1 is Cg, C10 or mixtures thereof, x=o,
R3, R4 = CH3 and R~ = CH2CH2~H
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the formula:
R1 R2R3R4N+X- (i)
wherein R1 is Cg-C16 alkyl, each of R2, R3 and R4 is independently C1-C4
alkyl, C1-C4 hydroxy alkyl, benzyl, and -(C2H40)XH where x has a value from 2
to 5, and X is an anion. Not more than one of R2, R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C1s particularly where the alkyl
group is a mixture of chain le"!Jths derived from coconut or palm kernel fat or is
derived synthetically by olefin build up or OXO alcohols synthesis. Prefer~t:d
groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and phosphate ions.
Exanlples of suitable quaternary ammonium compounds of formulae (i) for use
herein are:
coconut l,i,neU,yl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12 15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
CA 02263435 1999-02-ll
WO 98/06810 21 PCTnUS97/14287
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-O-C-C12 14 alkyl and R2R3R4 are methyl).
Il
o
di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also descril,ed in U.S. Patent
4,228,044, Cambre, issued October 14, 1980 and in European Patent
Application EP 000,224.
When included therein, the deteryent compositions of the present invention
typically co",prise from 0.2% to about 25%, plef~r~bly from about 1% to about
8% by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in the detergent con,positions
of the present invention. These surfactants can be broadly described as aliphatic
derivatives of secondary or tertialy amines, or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical can be strai~ht- orbranched-chain. One of the aliphatic substituents contains at least about 8
carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one
contains an anionic water-solubilizing group, e.g. carboxy, sulfonate, sulfate. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued Dece",ber 30, 1975 at
column 19, lines 18-35, for examples of ampholytic sulractdnts.
When inchlded therein, the deteryent co",rositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by weight of such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in detergent compositions.
These sul~ddd~ can be broadly described as derivatives of seconda~y and
tertiary amines, derivatives of heterocyclic secondaly and tertialy amines, or
derivatives of quate"~aly ammonium, quaternary phosphonium or tertialy
sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
CA 0226343~ 1999-02-ll
W O98/06810 22 PCTrUS97/14287
December 30, 1975 at column 19, line 38 through column 22, line 48, for
examples of zwitterionic surfactants.
When included therein, the detergent compositions of the present invention
typically cGn,l rise from 0.2% to about 15%, pref~r~bly from about 1% to about
10% by weight of such zwitterionic surfactants.
Semi-polar nonionic surFactants are a special calegory of nonionic surfactants
which include water-soluble amine oxides containing one alkyl moiety of from
about 10 to about 18 carbon atoms and 2 ~oielies selected from the group
consisting of alkyl groups and hydroxyalkyl groups conlain;"g from about 1 to
about 3 carbon atoms; water-soluble phosphine oxides cGntaini"g one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from
the group consisli"g of alkyl groups and hydroxyalkyl groups containing from
about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected
from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide su,rdctanla
having the formula
o
R3(oR4)xN(R5)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures therof
containing from about 8 to about 22 carbon atoms; R4 is an alkylene or
hydroxyalkylene group containing from about 2 to about 3 carbon atoms or
mixtures ll,ereof, x is from 0 to about 3; and each R5 is an alkyl or hydroxyalkyl
group containing from about 1 to about 3 carbon atoms or a polyethylene oxide
group containing from about 1 to about 3 ethylene oxide groups. The R5 groups
can be attached to each other, e.g., through an oxygen or nitrogen atom, to forma ring structure.
These amine oxide surfactants in particular include C10-c18 alkyl dimethyl
amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
CA 0226343~ 1999-02-11
W O 98/06810 23 rcTrusg7/14287
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by weight of such semi-polar nonionic surfactants.
The deteryent composition of the present invention may further comprise
a cosurfactant selected from the group of primary or tertiary amines.
Suitable primary ai"ines for use herein include amines according to the formula
R1NH2 wherein R1 is a C6-C12, preferably C6-C10 alkyl chain or R4X(CH2)n, X
is -O-,-C(O)NH- or-NH-, R4 is a C6-C12 alkyl chain n is between 1 to 5,
preferably 3. R1 alkyl chains may be straight or branched and may be
interrupted with up to 12, preferably less than 5 ethylene oxide ",oieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein may be seiected from 1-hexylamine, 1-
octylamine, 1-decylamine and laurylamine. Other preferred primary amines
include C8-C10 oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido propylamine.
Suitable tertiary amines for use herein include tertiary amines having the
formula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or
R5
- (CH2- CH - O ~H
R3 is either a C6-C12, preferably C6-C10 alkyl chain, or R3 is R4X(CH2)n,
whereby X is -O-, -C(O)NH- or -NH-,R4 is a C4-C12, n is between 1 to 5,
prererably 2-3. Rs is H or C1-C2 alkyl and x is between 1 to 6 .
R3 and R4 may be linear or branched; R3 alkyl chains may be interrupted with
up to 12, p~3f~rably less than 5, ethylene oxide moieties.
Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain,
R2 and R3 are C1-C3 alkyl or
R5
- (CH2- CH - O ~H
where R5 is H or CH3 and x = 1-2.
~,. ... . . .. .
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WO 98/06810 PCT~US97/14287
24
Also preferred are the amidoamines of the formula:
ll
Rl--C--NH--~ CH2 )--N--( R2 )
wherein R1 is C6-C12 alkyl; n is 24,
preferably n is 3; R2 and R3 is C1-C4
Most pr~rerre:d amines of the present invention include 1-octylamine, 1-
hexylamine, 1-decylamine, 1 -dodecylamine,C8-1 Ooxypropylamine, N coco 1-
3dia",i"o~,ropane, coconutalkyldimetllylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lau~yl
amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10
amidopropyldi",etl ,ylamine.
The most plef~ned amines for use in the compositions herein are 1-hexylamine,
1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-
dodecylJ;,netl"~lamine and bishydroxyethylcoconutalkylamine and oleylamine 7
times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
C~ .,tional detergent ~ ".es
The detergent co"l~ositions can further co~,prise one or more enzymes
which provide deterye"t pe, ror",ance and/or fabric care benefits.
Said enzymes include enzymes selected from hemicellulnses, peroxidases,
proteases, gluco-amylases, amylases, xylanases, pectinases, keratanases,
reducPses, oxid~ses, phencl~xid~ses, lipoxygenases, lig"i,lases, pullulanases,
tannases, pentosanases, malanases, r~-glucanases, arabinosid~ses,
hyaluronidase, chondroitinase, l~cc~se or mixtures thereof.
A preferred combination is a detergent composition having cocktail of
conventional app'i~~~le enzymes like protease, amylase, lipase, cutinase and/or
cellulase in conjunction with one or more plant cell wall degrading enzymes.
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WO 98/06810 25 PCT~US97/14287
The cellulases usable in the present invention include both bacterial or
fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola insolens. Suitable
cellul~-ses are also disclosed in GB-A-2.07~.028; GB-A-2.095.275 and DE-OS-
2.247.832.
Exa,nples of such cellu~ases are cellulases produced by a strain of
Humicola illsolel)s (Humicola grisea var. ther,llcidea), particularly the Humicola
strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens havina molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415
amino acids and a -43kD endoglucanase derived from Humicola insolens, DSM
1800, exhibiting cellulase activity; a preferred endoglucanase component has theamino acid sequence cliscl~sed in PCT Patent Application No. WO 91/17243.
Also suitable cellulases are the EGIII cell~ llases from Trichoderma
longibracl,iatum described in WO94/21801, Genencor, published September 29,
1994. Fspecially suitahle cellulases are the cellul~ses having color care benefits.
Examples of such cellulases are cellulases described in European patent
applicalion No. 91202879.2, filed November 6, 1991 (Novo).
Peroxid~se enzymes are used in combination with oxygen sources, e.g.
percar6Onate, perborate, persù1fate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed from
su~sl,~te3 during wash operations to other su~sl~ates in the wash solution.
PerOxid~sç enzymes are known in the art, and include, for exa",ple, horseradish
peroxld~se, ligninase, and haloperoxid~se such as chloro- and bromo-
peroxldase.
Peroxidase-containing detergent cG",positions are dicclosed, for example,
in PCT Intel-,atiol)al Application WO 89/099813 and in European Patent
applic~lioll EP No. 91202882.6, filed on November 6, 1991.
Other suitable oxkl~ses is the laccase enzyme, using oxugen, hydrogen
peroxide as primary sul/slldtes.
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W O 98/06810 26 PCTAUS97/14287
Said cellulases and/or peroxidases are normally incorporated in the
detergent composition at levels from 0.0001% to 2% of active enzyme by weight
of the detergent composition.
Suitable proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. Iicheniformis (subtilisin BPN and BPN'). One suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, dcvelo,~ed and sold as ESPERASE~) by Novo
Industries AIS of Denri,arh, hereinafter "Novo". The preparation of this enzyme
and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable
proteases include ALCALASE~), DURAZYM~) and SAVINASE~) from Novo and
MAXATASE~), MA)(ACAL~, PROPERASE~g) and MA~(APEM~ (protein
engineered Maxacal) from Gist-Brocades. Proteolytic enzymes also enco",pass
modified bacterial serine proteAses, such as those cJescribed in European PatentApplication Serial Number 87 303761.8, filed April 28, 1987 (particularly pages
17, 24 and 98), and which is called herein "P~otease B", and in European Patent
Application 199,404, Venegas, published October 29, 1986, which refers to a
modi~ied bacterial serine protealytic enzyme which is calied "P~o~ease A" herein.
More preferred is what is called herein "P~otease C", which is a variant of an
alkaline serine protease from Ri9c~ s in which Iysine replaced arginine at
position 27, tyrosine replaced valine at position 104, serine replaced asparagine
at position 123, and alanine replaced threonine at position 274. P,otease C is
described in EP 90915958:4, cor,esl onding to WO 91/06637, Published May 16,
1991. Genetically modified variants, particularly of Plotease C, are also included
herein. See also a high pH p,otease from R~ci'lus sp. NCIMB 40338 descri6ed in
WO 93/18140 A to Novo. Enzymatic detergcnts comprisi"g protease, one or
more other enzymes, and a reversible protease inhibitor are described in WO
92/03529 A to Novo. When desired, a protease having decreased adsor~tiGn
and increased hydrolysis is available as described in WO 95/07791 to P~o-;ter &
Gamble. A recombinant trypsin-like protease for detergents suitable herein is
described in WO 94/25583 to Novo.
In more detail, plotease referred to as "Protease D" is a carbonyi
hydrolase variant having an amino acid sequence not found in nature, which is
derived from a precursor carbonyl hydrolase by substitllting a different amino
acid for a plurality of amino acid residues at a position in said carbonyl hydrolase
equivalent to position +76, preferably also in combination with one or more amino
CA 02263435 1999-02-11
WO 98/06810 2 7 PCT/US97/14287
acid residue positions equivalent to those selected from the group consisting of+99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,
+166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265,
and/or +274 according to the nu-,lberi,)g of Bacillus amyloliq~Jefaciens subtilisin,
as described in W095/10591 and in the patent application of C. Ghosh, et al,
"Bleaching Compositions Comprising Protease Enzymes" having US Serial No.
08/322,677, filed October 13, 1994. Also suitable for the present invention are
proteAses desc~iLed in patent ap~licdtiGns EP 251 446 and WO91/06637 and
pr~tease BLAP~) desc.i~ed in W091/02792. The proteolytic enzymes are
incorporated in the detergent compositions of the present invention a level of
from 0.0001% to 2%, pr~rer~bly from 0.001% to 0.2%, more pl~:r~r~bly from
0.005% to 0.1% pure enzyme by weight of the cG,.,position.
Amylases (a and/or ~) can be included for removal of carbohydrate-based
stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes
deterge,)t compositions which incG~,uorale mutant amylases. See also
WO94/18314, Genencor, published August 18, 1994 and WO95/10603, Novo
Nordisk A/S, published April 20, 1995 . Other amylases known for use in
detergent cornrositions include both a- and ~-amylases. a-Amylases are known
in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666;
WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British
Patent specificdtion no. 1,296,839 (Novo). Other suit~hlc amylase are stability-enhanced amylases including Purafact Ox AmR dascribed in WO 94/18314,
pulished August 18, 1994; W096/05295, Genencor, published February 22,
1996 and amylase variants having ad~ilional mo-lificdlion in the immediate
parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published
April 95. Exam~les of comloercial a-amylases products are Te,man~yl~,Ban(~)
Fungamyl~) and Duramyl~l9, all available from Novo Nordisk A~S Denmark.
W095/26397 descril es other s!~it~ble amylases: a-amylases characterised by
having a specific activity at least 25% higher than the specific activity of
Termamyl(~ at a te"".erdl.lre range of 25~C to 55~C and at a pH value in the
range of 8 to 10, measured by the Phadebas~ a-amylase activity assay. Other
amylolytic enzymes with improved properties with respect to the activity level and
the combination of thermostability and a higher activity level are described in
W095l35382.
_ . , .
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W O 98/06810 28 PCT~US97/14287
The above-mentioned enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Origin can further be
mesophilic or ex~ lophilic (psychrophilic, psyc~,rol~ophic, thermophilic,
barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms
of these enzymes may be used. Also included by definition, are mutants of nativeenzymes. Mutants can be obtained e.g. by protein and/or genetic engineering,
chemical and/or physical modificaliG"s of native enzymes. Common practice as
well is the expression of the enzyme via host organism in which the genetic
Il,aterial responsible for the production of the enzyme has been cloned. Said
enzymes are normally incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent co",position. The
enzymes can be added as separate single ingredients (prills, granulates,
stabilized liquids, etc., containing one enzyme) or as mixtures of two or more
enzymes (e.g., cogranulates).
Other suitable detergent ingredients that can be added are enzyme
oxidation scavengers which are described in Co-pending European Patent
application 92870018.6 filed on January 31, 1992. Examples of such enzyme
oxidaliG~I scavengers are ethoxylated tetraethylene polya,l,ines.
A range of enzyme n~aterials and means for their incorporation into
synthetic detergent compositions is also disclosed in WO 9307263 A and WO
9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.
3,553,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in
U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,21g, Hughes,
March 26, 1985. Enzyme materials useful for liquid detergen~ formulations, and
their incor~,oration into such forrnulations, are disclosed in U.S. 4,261,868, Hora
et al, April 14, 19.81. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme stabilisation techniques are disclosed and exemplified in
U.S. 3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586,
October 29, 1986, Venegas. Enzyme stabilisation systems are also described,
for example, in U.S. 3,519,570. A useful R~c~ us~ sp. AC13 giving proteases,
xylanases and cell~'a,es. is described in WO 9401532 A to Novo.
Color care benefts
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Technologies which provide a type of color care benefit can also be
included.- Examples of these technologies are metallo catalysts for color
maintenance. Such ",ete"o catalysts are described in co-pending European
PatentApplication No. 92870181.2.
The Bleaching agent
The detergent composiliGns of the present invention can further include
bleaching agents such as hydrogen peroxide, PB1, PB4 and percarbonate with a
pa-licle size of 400-800 microns. These bleaching agent components can
include one or more oxygen bleaching agents and, depending upon the
bleaching agent chosen~ one or more bleach activators. When present oxygen
bleaching compounds will typically be present at levels of from about 1 % to about
25%..
The bleaching agent co, nponent for use herein can be any of the
bleaching agents useful for detergent cGmpositions including oxygen bleaches as
well as others known in the art. The bleachi~,g agent suitable for the present
invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encon,p~sses
percarboxylic acid bleaching agents and salts thereof. Suitable examples of thisclass of agents include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of meta-chloro perbenzoic acid, 4-nonylamino~-
oxopero~ybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446,
European Patent Arp'~~tion 0,133,354 and U.S. Patent 4,412,934. Highly
pr~f-e,led bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid
as desc,il.ed in U.S. Patent 4,634,551.
Another category of bleachi"g agents that can be used enco,npasses the
halogen bleaching agents. Exampl_s of hypohalite bleaching agents, for
exal"pl~, include trichloro isocyanuric acid and the sodium and potassium
dichloroisocyanurates and N-chloro and N-bromo alkane sulphona",ides. Such
materials are normally added at 0.5-10% by weight of the finished product,
prêferably 1-5% by weight.
.
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WO 98/06810 30 PCTrUS97/14287
The hydrogen peroxide releasing agents can be used in combination with
bleach activators such as tetraacetylethylenediamine (TAED),
nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or
pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6-
aminocaproic acid (NACA-OBS, described in WO94/28106), which are
perhydrolyzed to form a peracid as the active bleaching species, leading to
improved bleaching effect. Also suitable activators are acylated citrate esters
such as discloserl in Co-pending European Patent Application No. 91870207.7.
Useful bleaching agents, including peroxyacids and bleaching systems
col"prising bleach activators and peroxygen bleaching compounds for use in
detergent compositions according to the invention are described in our co-
pendi"g applicaliol Is USSN 08/136,626, PCT/US95/07823, W095/27772,
W095/27773, W095/27774 and W095/27775.
The hydrogen peroxide may also be present by adding an enzymatic
system (i.e., an enzyme and a subsll ate therefore) which is capable of
ge~,eraling hydrogen peroxide at the beginning or during the washing and/or
rinsing process. Such enzymatic systems are disclosed in EP Patent Application
91202655.6 filed October 9, 1991.
Metal-containing catalysts for use in bleach composiliGns, include cobalt-
containing catalysts such as Pentaamine ~cet~te cobalt(lll) salts and
",angallese-containing catalysts such as those described in EPA 549 271; EPA
549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US
5,114,611. Bleaching composition co",prising a peroxy compound, a
manganese-containing bleach catalyst and a chelating agent is described in the
patent application No 94870206.3.
Bleaching agents other than oxygen bleaching agents are also known in
the art and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. These r"aleridls can be
deposited upon the substldte during the washing process. Upon irradiation with
light, in the presence of oxygen, such as by hanging cloll,es out to dry in the
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daylight, the sulfonated zinc phthalocyanine is activated and, consequently, thesubstrate is bleached. Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033,718. Typically, detergent
compositions will contain about 0.025% to about 1.25%, by weightl of sulfonated
zinc phthalocyanine.
Bu~lder system
The composilions accGrdiny to the present invention may further cG")p,ise a
builder system. Any conventional builder system is suitable for use herein
including aluminosilicate materials, silicates, polycarl,oxylates, alkyl- or alkenyl-
succinic acid and fatty acids, materials such as ethylenediamine tetraacetate,
diethylene triamine penlamethyleneacetate, metal ion sequesl,anls such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene
phosphonic acid and diethylene triamine pentamethyle-,ephosphonic acid.
Phosphate builders can also be used herein.
Suitable builders can be an inor~an c ion exchange material, commonly an
inorganic hydrated aluminosilicate material, more particularly a hydrated
sy"ll,elic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6
(I loechst). SKS-6 is a crystalline layered silicate consislillg of sodium silicate
(Na2Si2~5)
Suitable polycarboxylates containing one carboxy group include lactic
acid, glycolic acid and ether derivatives thereof as disclQsed in Belgian PatentNos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy
groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) di~etic acid, maleic acid, diglycollic acid, tartaric acid, tartronic
acid and fumaric acid, as well as the ether carboxylates described in German
Orrer,!s3enschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and
the sulfinyl carl,oxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble citlales, aconitrates and citraconates as well as succ,i"ate derivativessuch as the carboxymethyloxysucc,i"ates described in British Patent No.
1,379,241, lactoxysuccil~ates described in Netheriands ApplicaliGn 7205873, and
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the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisucci"ales
disclosed in British Patent No. 1,261,829, 1,1,2,2-ethane tetracarboxylates,
1,1,3,3-propane tetracarboxylates and 1,1,2,3-propane tetracarboxylates.
Polycarboxylates containing sulfo substituents include the sulfosuccinate
derivatives disclosed in British Patent Nos. 1,3~8,421 and 1,398,422 and in U.S.Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in BritishPatent No. 1,082,179, while polycarl,oxylates containing phosphone substituents
are disclosed in British Patent No.1,439,000.
Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclo,l~enladienide pentacarboxylates, 2,3,4,5-
tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis -
dicarboxylates, 2,2,5,5-tetrahydrofuran - tetracarboxylates, 1,2,3,4,5,6-hexane -
hex~c~r-boxylates and and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. A-o",atic poly-carboxylates include mellitic
acid, pyromellitic acid and the phthalic acid derivatives disclosed in British Patent
No. 1,425,343.
Of the above, the p,erer-ad polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly cit,ates.
Preferred builder systems for use in the present compositions include a
mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a
layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as
citric acid. pr~fer.ed builder systems for use in liquid dekr~ent co".positions of
the present invention are soaps and polycarboxylates.
A suitable chelant for inclusion in the deteryent compositions in
accGr~Jance with the invention is ethylenediamine-N,N'-disuccinic acid (EDDS) orthe alkali metal, alkaiine earth metal, ammonium, or substituted a,."-,onium salts
thereof, or mixtures ~hereof. P,~rened EDDS compounds are the free acid forrn
and the sodium or ma~nesium salt thereof. Exa",pl-s of such prerer,ed sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium
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salts are the most preferred for inclusion in compositions in accordance with the
invention.
Preferred builder systems include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, and a watersoluble carboxylate
chelating agent such as citric acid.
Other builder materials that can form part of the builder system for use in
granular compositions include inorganic n~aterials such as alkali metal
carbonates, bicarbonates, silicates, and organic nldterials such as the organic
phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
Other suitable water-soluble organic salts are the homo- or co-polymeric
acids or their salts, in which the polycarboxylic acid comprises at least two
carboxyl radicals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,7~6. Examples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such copolymers having a molecular weight of from 20,000 to 70,000, especially
about 40,000.
Detergency builder salts are normally inctuded in amounts of from 5% to
80% by weight of the composition preferably from 10% to 70% and most usually
from 30% to 60% by weight.
Suds suppressor
Another G~JtiGnal ingredient is a suds suppressor, exemplified by silicones,
and silic~ si'icone mixtures. Silicones can be generally represented by alkylated
polysiloxane materials while siiica is nGm~ally used in finely divided forms
exemplified by silica aer(,gels and xerogels and hydrophobic silicas of various
types. These materials can be incorporated as particul~tes in which the suds
suppressor is advantageously rele~s~hly incorporated in a water-soluble or
water-dispersible, subst~utially non-surface-active detergent imperrneable
carrier. Alternatively the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of the other components.
A p,efer,~7d silicone suds controlling agent is disclosed in Bartollota et al.
U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-
,,, , " , . ~
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W 0 98/06810 PCTAUS97/14287
emulsifying silicone suds suppressors, described in German Patent Application
DTOS 2 646 126 published April 28, 1977. An example of such a compound is
DC-544, com-nercially available from Dow Corning, which is a siloxane-glycol
copolymer. Especially preferred suds controlling agent are the suds suppressor
system comprising a mixture of silicone oiis and 2-alkyl-alcanols. Suitable 2-alkyl-
alkanols are 2-butyl-octanol which are c~ mercially available under the trade
name Isofol 12 R.
Such suds suppressor system is described in Co-pending European Patent
application N 92870174.7 filed 10 November, 1992.
Especially preferled silicone suds controlling agents are described in Co-
pending European Patent arp'.c~tion N~92201649.8. Said compositions can
con,prise a silicone/silica mixture in combination with fumed nonporous silica
such as AerosilR.
The suds suppr~ssGr~ described above are normally employed at levels of
from 0.001 % to 2% by weight of the coi,-position, preferably from 0.01 % to 1 % by
weight.
Others
Other components used in detergent compositions may be employed,
such as soil-suspe,-Ji--g agents, soil-release agents, optical brighteners,
abrasives, ba~:teric;des, tarnish inhibitors, coloring agents, and/or encapsulated
or non-encapsulated perfumes.
rS~eci~lly suitable el,cal~s~ ting ~,-aleri.ls are water soluble capsules
which co"si:,l of a matrix of polysaccha, ide and polyhydroxy compounds such as
desc,il,ed in GB 1,464,616.
Other suitable water soluble encapsulating materials cor"~.rise dextrins
derived from ungelatinized starch acid-esters of substituted dicarboxylic acids
such as described in US 3,45~,838. These acid-ester dextrins are, preferably,
prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and
potato. Suitable exar.,ples of said encapsulating materials include N-Lok
manufactured by National Starch. The N-Lok encapsulating material consists of a
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W O98/06810 PCTAUS97/14287_
modified maize starch and glucose. The starch is modified by adding
monofunctional substituted groups such as octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents s~ ~itahl_ herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their
sa,ts. Polymers of this type include the polyacrylates and maleic anhydride-
acrylic acid copolymers previously mentioned as builders, as well as copolymers
of maleic anhydride with ethylene, methylvinyl ether or m~::ll,a~;rylic acid, the
maleic anhydride constituting at least 20 mole percent of the copolymer. These
n,dlerials are normally used at levels of from 0.5% to 10% by weight, more
preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the
c~" lpositioi ~.
Preferred optical brighteners are anionic in character, examples of which
are disodium 4,4'-bis-(2-diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-
2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino4-anilino-s-triazin-6-ylamino-
stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-
ylamino)stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri-
azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyî-N-
2-hydroxyethylarr,;,~o)-s-triazin-6-ylamino)stilbene-2,2' - disulphonate, di-sodium
4,4' -bis-(4-phenyl-2,1,3-triazol-2-yl)-stilbene-2,2' disulphonate, di-so-dium
4,4'bis(2-anilino4-(1-methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no)stilbene-
2,2'disulphonate, sodium 2(stilbyl 4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-
sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred brighteners are
the sp~ific brightel)er~ of copending European Patent applica~ion No.
95201943.8.
Other useful polymeric materials are the polyethylene glycols, particularly
those of ,,,olec~ weight 1000-10000, more particularly 2000 to 8000 and most
pr~rably about 4000. These are used at levels of from 0.20% to 5% more
preferably from 0.25% to 2.5% by weight. These polymers and the previously
mentioned homo- or co-polymeric polycarboxylate salts are valuable for
improving whiteness maintenance, fabric ash deposition, and cleaning
performance on clay, proteinaceous and oxidizable soils in the presence of
transition metal impurities.
.. . . . . ..
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WO 98/06810 36 PCT~US97/14287
Soil release agents useful in compositions of the present invention are
conventionally copolymers or terpolymers of terephthalic acid with ethylene
glycol and/or propylene glycol units in various arrangements. Examples of such
polymers are disclosed in the commonly assigned lJS Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272 033. A patticular
preferred polymer in accordance with EP-A-0 272 033 has the formula
(CH3(PEG)43)0.75(PoH)o.25[T-po)2.8(T-pEG)o-4]T(
H)o.25((pEG)43cH3~o.75
where PEG is -(OC2H4)0-,PO is (OC3tl60) and T is (pcOC6H4CO).
Also very useful are modified polyesters as random copolymers of
dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2
propane diol, the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or propane-diol. The target isto obtain a polymer capped at both end by sulphobenzoate groups, ",~rimarilyl', in
the present context most of said copolymers herein will be end-capped by
sulphobenzoate groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of monoester of ethylene
glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The s~lected polyesters herein contain about 46% by weight of dimethyl
terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weightethylene glycol about 13% by weight of dimethyl sulruberl oic acid and about
15% by weight of sulfoisophthalic acid, and have a molecu~~ weight of about
3.000. The polyesters and their method of preparation are desclibed in detail inEPA 311 342.
It is well known in the art that free chlorine in tap water rapidly deactivates
the enzymes comprised in detergent compositions. Therefore, using chlorine
scavenger such as perborate, a, l ,monium sulfate, sodium sulphite or
polyethyleneimine at a level above 0.1% by weight of total composition, in the
formulas will provide improved through the wash stability of the detergent
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enzymes. Compositions comprising chlorine scavenger are described in the
European patent application 92870018.6 filed January 31, 1992.
Alkoxylated polycarboxylates such as those prepared from polyacrylates
are useful herein to provide additiQnal grease removal peiro,-.,ar,ce. Such
n,aterials are described in WO 91/08281 and PCT gO/01815 at p. 4 et seq.7
incorporated herein by referel)ce. Chemically, these materials com~,rise
polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The
side-chains are o~ the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n
is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to
provide a "comb" polymer type structure. The mo'ec llar weight can vary, but is
typically in the range of about 2000 to about 50,000. Such alkoxylated
polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
Softening agents
Fabric softening agents can also be incorporated into laundry detergent
compositions in accor~a,~ce with the present invention. These agents may be
inorganic or organic in type. InGrya,)ic softening agents are exemplified by thesmeclil~ clays disclosed in GB-A-1 400 898 and in USP 5,019,292 Organic
fabric softening agents include the water insoluble tertiary amines as disclosed in
GB-A1 514 276 and EP-B0 011 340 and their cGmbi,)alion with mono C12-C14
quaternary ammonium salts are disclosed in EP-B-0 026 527 and EP-B-0 026
528 and di-long-chain ami.l~s as disclosed in EP-B-0 242 919. Other useful
organic ingredients of fabric softening systems include high molecular weight
polyethylene oxide materials as ~isclose~ in EP-A-0 299 575 and 0 313146.
Levels of smectite clay are normally in the range from 2% to 20%, more
preferably from 5% to 15% by weight, with the material being added as a dry
mixed component to the remainder of the formulation. Organic fabric softening
agents such as the water-insoluble tertiary amines or dilong chain amide
n,dler;als are incorporated at le\~els of from 0.5% to 5% by weight, normally from
1% to 3% by weight whilst the high molecular weight polyethylene oxide
materials and the water soluble cationic materials are added at levels of from
0.1% to 2%, normally from 0.15% to 1.5% by weight These l"aterials are
~ .
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W O 98/06810 38 PCTrUS97/14287
normally added to the spray dried portion of the composition, although in some
instances it may be more convenient to add them as a dry mixed particulate, or
spray them as molten liquid on to other solid components of the composition.
Dispersants
The detergent composition of the present invention can also contain
dispersants: Suitable water-soluble organic salts are the homo- or co-polymeric
acids or their salts, in which the polycarboxylic acid comprises at least two
carboxyl r~cals separated from each other by not more than two carbon atoms.
Polymers of this type are disclosed in GB-A-1,596,756. Exalllples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such copolymers having a molecular weight of from 1,000 to 100,000.
Especially, copolymer of acrylate and methylacrylate such as the 480N
having a molecular weight of 4000, at a level from 0.5-20% by weight of
composition can be added in the detergent compositions of the present
invention.
The colll~,osiliG"s of the invention may contain a lime soap peptiser
compound, which has a lime soap dispersing power (LSDP), as defined
hereinafter of no more than 8, pr~ferably no more than 7, most preferably no
more than 6. The lime soap peptiser compound is preferably present at a level
from 0% to 20% by weight.
A nu"~erical measure of the effectiveness of a lime soap peptiser is given
by the lime soap dispersant power (LSDP) which is determined using the lime
soap dispersant test as described in an article by H.C. Borghetty and C.A.
Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime
soap dispersion test Ill~thod is widely used by practitioners in this art field being
referred to, for exa"~p'e, in the following review articles; W.N. Linfield, Surfactant
science Series, Volume 7, page 3; W.N. Linfield, Tenside surf. det., volume 27,
pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and
Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of
dispersing agent to sodium oleate required to disperse the lime soap deposits
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W O 98tO6810 39 PCTAUS97/14287
formed by 0.0259 of sodium oleate in 30ml of water of 333ppm CaCo3
(Ca:Mg=3:2) equivalent hardness.
Surfactants having good lime soap peptiser capability will include certain
amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord
with the present invention include C16-C1g dimethyl amine oxide, C12-C1g alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly
C12-C1s alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3(LSDP=4), and the C14-C1s ethoxylated alcohols with an average degree of
ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol
A012 and Lutensol A030 respectively, by BASF GmbH.
Polymeric lime soap pepliser~ suitable for use herein are described in the
article by M.K. Nagar~jan, W.F. Masler, to be found in Cosmetics and To.!et,ies,volume 104, pages 71-73, (1989).
Hydrophobic bleaches such as 4-[N-octanoyl-6-aminohexanoyllbenzene
sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
aminohexanoyl]~e, I,ene sulfonate and mixtures thereof; and nonanoyloxy
benzene sulfonate to~~ll,er with hydrophilic / hyd,ophobic bleach formulations
can also be used as lime soap peptisers compounds.
Dye transfer inhibiffon
The detergent cornpositions of the present invention can also include
compounds for inhibiting dye t,ansfer from one fabric to another of solubilized
and suspended dyes encountered during fabric laundering operations involving
colored fabrics.
Polymeric dye transfer inhibiting agents
The detergent compositions according to the present invention also
co.nprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably
, . . . . . . .
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WO 98/06810 4 o PCT/US97114287
from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally incorporated into detergent
compositions in order to inhibit the transfer of dyes from colored fabrics onto
fabrics washed therewith. These polymers have the ability to complex or adsorb
the fugitive dyes washed out of dyed fabrics before the dyes have the opportunity
to become attached to other articles in the wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole,
polyvinylpyllolidolne polymers, polyvinylox?~oliclones and polyvinylimid~7oles or
mixtures thereof.
Addition of such polymers also enhances the performance of the enzymes
according the invention.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having the
following structure formula:
p
I
(I) Ax
R
wherein P is a poly",erisable unit, whereto the R-N-O group can be attached to
or wherein the R-N-O group forms part of the polymerisable unit or a
co",l~ dtion of both.
O O O
Il 11 11
AisNC, CO,C,-O-,-S-,-N-;xisOor1;
R are aliphatic, ethoxylated aliphatics, alu",alic, heterocyclic or
alicyclic groups or any co",bindlion thereof whereto the nitrogen of the
N-O group can be attached or wherein the nitrogen of the N-O group
is part of these groups.
The N-O group can be represented by the following general structures:
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W O98/06810 41 PCT~US97/14287
~ O
(R1)x -N- (R2)y =N- (R1)x
I
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aromatic, heterocyclic or alicyclic groups or combinations lhereof, x or/and y or/and z is 0 or 1 and
wherein the nitrogen of the N-O group can be attached or wherein the
nitrogen of the N-O group forms part of these groups.
The N-O group can be part of the poly~erisable unit (P) or can be
attached to the polymeric backbone or a combination of both.
Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selectecl from
aliphatic, aromatic, alicyclic or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of polyamine N-
oxides wherein the nitrogen of the N-O group forms part of the R-group.
Preferred polyamine N-oxides are those wherein R is a heterocyclic group such
as pyrridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and
derivatives thereof.
Another class of said polyamine N-oxides co"~prises the group of polyamine N-
oxides wherein the nitrogen of the N-O group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine oxides whereto the
N-O group is attacl,ed to the poly",erisable unit.
P,efer,ed class of these polyamine N-oxides are the polyamine N-oxides having
the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic groups
wherein the llilloye" of the N-0 functional group is part of said R group.
Examples of these cl-~sses are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another prerer,ed class of polyamine N-oxides are the polyamine oxides having
the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groupswherein the nit,ogen of the N-0 functional group is dllached to said R groups.
Examples of these c~-sses are polyamine oxides wherein R groups can be
ar~." ,dlic such as phenyl.
. .
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WO 98/06810 PCTAJS97/14287 42
Any polymer backbone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiting properties. Examples of
suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and mixtures thereof.
The amine N-oxide polymers of the present invention typically have a ratio
of amine to the amine N-oxide of 10:1 to 1:1000000. However the amount of
amine oxide groups pr~senl in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-oxkl~tion. Pleferably,
the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More preferably
from 1:4 to 1:1000000, most preferdbly from 1:7 to 1:1000000. The polymers of
the present invention actually encompass random or block copolymers where
one monomer type is an amine N-oxide and the other monomer type is either an
amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa
< 10, preferably PKa < 7, more preferred PKa ~ 6.
The polyamine oxides can be oLldi"ed in almost any degree of polyme,i~aliG,).
The degree of poly-"eris~liol- is not critical provided the material has the desired
water-solubility and dye-suspending power.
Typically, the average molecular weight is within the range of 500 to 1000,000;
preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, most
preferably from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimid~-21e
The N-vinylimidazole N-vinylpyrrolidone polymers used in the present
invention have an average ",c'ecul~r weight range from 5,000-1,000,000,
p,t:fera~ly from 5,000-200,000.
Highly prefer,ed polymers for use in detergent com~ositions according to
the pr~:sent invention co"~rise a polymer selected from N-vinylimidazole N-
vinylpyrrolidone copolymers wherein said polymer has an average molecular
weight range from 5,000 to 50,000 more preferably from 8,000 to 30,000, most
p~feldbly from 10,000 to 20,000.
The average molecular weight range was determined by light scalleri"g as
descriled in Barth H.G. and Mays J.W. Chemical Analysis Vol 113,"Modern
Methods of Polymer Characte,i~aliGn".
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Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
average molec~llar weight range from 5,000 to 50,000; more preferably from
8,000 to 30,000; most preferably from 10,000 to 20,000.
The N-vinylimid~le N-vinylpyrrolidone copolymers characterized by
having said average ",c'erl~'qr weight range provide excellent dye transfer
inhibiting properties while not adversely drrecti"g the cleaning pe,rur-"ance ofdetergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has amolar ratio of N-vinyli-~ z~ to N-vinylpyrrolidone from 1 to 0.2, more
preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
The deter5Jent composilions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having an average molecular weight of from about
2,500 to about 400,000, p,eferably from about 5,000 to about 200,000, more
preferably from about 5,000 to about 50,000, and most p,~ferdbly from about
5,000 to about 15,000. Suitable polyvinylpyrrolidones are commercially vailable
from ISP Corporation, New York, NY and Montreal, Canada under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average mlo'ecul-r weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are cG")n,ercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to
persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-
256,696).
d) Polyvinylox~ol done:
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinylox~-~l dones have an average molecular weight of from about 2,500 to
about 400,000, preferably from about 5,000 to about 200,000, more preferably
from about 5,000 to about 50,000, and most preferably from about 5,000 to about
1 5,000.
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e) Polyvinylimidazole:
The detergent compositions of the present invention may also utilize
polyvinylimida~clc as poiymeric dye transfer inhibiting agent. Said
polyvinylimi ~7c'es have an average about 2,500 to about 400,000, preferably
from about 5,000 to about 200,000, more preferdbly from about 5,000 to about
50,000, and most ~ r~rably from about 5,000 to about 15,000.
f) Cross-linked polymers:
Cross-linked polymers are polymers whose backbone are interconnected to a
certain degree; these links can be of chemical or physical nature, possibly withactive groups n the backbone or on branches; cross-linked polymers have been
desc,ibed in the Journal of Polymer Science, volume 22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made in such a way that
they form a three-di."ellsional rigid structure, which can entrap dyes in the pores
formed by the three-dimensional structure. In another embocli,~ent, the cross-
linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-pending patent application
948702 1 3.9
Method of washin~
The co""~ositio,-s of the invention may be used in essentially any washing
or cleaning Ill~thods, including soaking methods, pretreatment methods and
Illelllods with rinsing steps for which a separate rinse aid cGr"position may beadded.
The process described herein comprises contacting fabrics with a
laundering sohltion in the usual manner and exel"p!;fied hereunder.
The process of the invention is conveniently carried out in the course of
the cleaning process. The method of cleaning is preferably carried out at ~ ~C to
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W O98/06810 PCT~US97/14287
95 ~C, especially between 10~C and 60~C. The pH of the treatment solution is
preferably from 7 to 11.
A preferred machine dishwashing method comprises treating soiled
articles with an aqueous solution of the machine dishwashing or rinsing
composition. A conventional effective amount of the machine dishwashing
composition means from 8-60 9 of product dissolved or dispersed in a wash
volume from 3-10 litres.
According to a manual dishwashing method, soiled dishes are contacted with an
effective amount of the diswashing cG,-",osition, typically from 0.5-209 (per 25dishes being treated). Preferred manual dishwashing methods include the
application of a concenlraled solution to the surfaces of the dishes or the soaking
in large volume of dilute solution of the detergent composition.
The compositions of the invention may also be formulated as hard surface
cleaner compositions.
The f~ g examples are meant to exemplify compositions of the
present invention, but are not necess~rily meant to limit or otherwise define the
scope of the invention.
In the delt:rgent cG,n~ositions, the level of the enzymes are expressed in
pure enzyme by weight of total composition and the abbreviated component
ide,~tiricdtions have the fc'lo~u;.,g meanings:
LAS : Sodium linear C12 alkyl ben~ene sulphonate
TAS : Sodium tallow alkyl sulphate
CXYAS : Sodium C1x - C1y alkyl sulfate
25EY : A C12 C1s predominantly linear primary alcohol
condensed with an average of Y moles of ethylene
oxide
. .
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CXYEZ : A C1x - C1y predominantly linear primary alcohol
condensed with an average of Z moles of ethylene
oxide
XYEZS : C1X - C1y sodium alkyl sulfate condensed with an
average of Z moles of ethylene oxide per mole
QAS : R2 N+(cH3)2(c2H4oH) with R2 = C12-C14
Soap : Sodium linear alkyl carboxylate derived from a 80/20
mixture of tallow and coconut oils.
Nonionic : C13-C1smixedethoxylated/propoxylated fattyalcohol
with an average degree of ethoxylation of 3.8 and an
average degree of propoxylation of 4.5 sold under the
tradename Plurafac LF404 by BASF Gmbh.
CFAA : C12-C14 alkyl N-methyl glucamide
TFAA : C16-C1g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
DEQA : Di-(tallow-oxy-ethyl)dimethyl ammonium chloride.
SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed stearic
acid.
Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by
Shell Cher"ical CO.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si2Os
Carbonate : Anhydrous sodium carbonate with a particle size
between 200 ~lm and 900~1m.
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WO98/06810 47 PCTrUS97/14287
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
behNeen 400 llm and 1200~m.
STPP : Anhydrous sodium tripolyphosphate
MA/M : Copolymer of 1:4 maleic/acrylic acid, average
mc'Qcl~lar weight about 80,000
PA30 : Polyacrylic acid of average molecular weight of
approxi")ately 8,000.
Terpolymer : Terpolymer of average "~ole~ 4r weight approx.
7,000, coln~rising acrylic:maleic:ethylacrylic acid
",onor"er units at a weight ratio of 60:20:20
480N : Random copolymer of 3:7 acrylic/methacrylic acid,
average mol~cul~r weight about 3,500.
Polyacrylate : Polyacrylate homopolymerwith an average ",c'ecul-~
weight of 8,000 sold under the tradename PA30 by
BASF GmbH
Zeolite A : Hydrated Sodium Aluminosilicate of formula
Na12(A1~2Si~2)12 27H2o having a primary particle
size in the range from 0.1 to 10 ",icru",eter~
Citrate : Tri-sodium citrate dihydrate of activity 86,4% with a
particle size distribution uetvlecn 425 ~m and 850 ~m.
Citric : Anhydrous citric acid
PB1 : Anhydrous sodium perborate monohydrate bleach,
empirical formula NaBo2.H2o2
PB4 : Anhydrous sodium perborate tetrahydrate
. .
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W O98/06810 48 PCTrUS97/14287
Percarbonate : Anhydrous sodium percarbonate bleach of empirical
formula 2Na2co3.3H2o2
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
Photoactivated : Sulfonated zinc phtlocyanine encarsu~ted in dextrin
Bleach soluble polymer.
PMC : Penldaloine acetate cobalt(lll) salt.
Pararfi" : Paraffin oil sold under the tradename Winog 70 by
Wintershall.
BzP : Benzoyl Peroxide.
Antibody : Anti-Lipolase antibody LAJR 009-012, available from
Novo Nordisk A/S.
Lipolytic enzyme : Lipolytic enzymes sold under the tradename Lipolase,
Lipolase Ultra by Novo Nordisk A/S.
Protease : Proteolytic enzyme sold under the tradename
Savinase, Alc~l~se, Durazym by Novo Nordisk A/S,
M~Y~C~I, Maxapem sold by Gist-Brocades and
p~oteases described in pdlenls WO91/06637 and/or
WO95/10591 and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the tradename Purafact
Ox AmR described in WO 94/18314,WO96/05295 sold
by Genencor; Termamyl~, Fungamyl(~) and Duramyl~g),
all availabl~ from Novo Nordisk A/S and those
desc,iL.ed in W095/26397.
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WO 98/06810 PCT/US97tl4287
Cellulase : Cellulytic enzyme sold under the tradename
Carezyme, Celluzyme and/or Endolase by Novo
Nordisk A/S.
CMC : Sodium carboxymethylcellulose.
I IEDP ~ hydroxyethane diphosphonic acid.
DETPMP Diethylene triamine penta (methylene phosphonic
acid), marketed by Monsa,)to under the Trade name
Dequest 2060.
PVNO : Poly(4-vinylpyridine)-N-Oxide.
PVPVI : Poly (4-vinylpyridine)-N-oxide/copolymer of vinyl-
imidazole and vinyl-pyrrolidone.
B~iyhtener 1 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
B,ightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-
2-yl) stilbene-2:2'-disulfonate.
Silicone antiroail, : Polydi~nelhylsiloxane foam controller with siloxane-
oxyalkylene copolymer as dispersing agent with a ratio
of said foam controller to said dispersing agent of 10:1
to 100:1.
Granular Suds : 12% Silicone/silica, 18% stearyl alcohol,70% starch in
Suppressor granular form
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy
and terephtaloyl backbone.
SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short
block polymer.
Sulphate : Anhydroussodium sulphate.
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HMWPEO : High molecular weight polyethylene oxide
PEG : Polyethylene glycol.
BTA : Ben~ol, ~_ole
Bismuth nitrate : Bismuth nitratesalt
NaDCC : Sodium dichloroisocyanurate
Encapsulated : Insoluble fragrance delivery technology utilising zeolite
perfume particles 13x, perfume and a dextrose/glycerin agglomerating
binder.
KOH : 100% Active solution of Potassium Hydroxide
pH : Measured as a 1% solution in distilled water at 20~C.
Exa,nple 1:
Antibodies' production:
Chickens were injected in the breast muscle with 1 ml of a 1 mg/ml Lipolase~
emulsion. The lipolytic emulsion was prepared with a Freunds completed
adjuvants (Freund and McDermott, 1942; Freund 1956) by intensively mixing an
equal amount of the Lipolase~) solution (2 mg/ml)and Freunds co,l,pletc
adjuvant.
The immunisation scheme was completed with injections using a Freunds
uncomplete adjuvant and after a 4 weeks period, the eggs were collected during
one week. The e~l,action of the antibodies from the eggs yolks was done
accorJi.~g to the Polson extraction method as described in Immunological
Inve:~tiy~iGn 19, 1990, pp 253-258.
Lipase enzymatic inactivation:
A I ipol~se~l9 stock solution was prepar~d in a Tris Buffer (5x10-2M Tris, 25 mMNaCI, pH= 7 and 10) at a concentration of 0.3% active enzyme. A Phosphate
Buffer (0.05M KH2PO4, pH 6.8) contained the antibody (0.18 mglml). The
interaction lipolytic enzyme (Final conce~ llralion of 0.08%) / antibody was
achieved Tris buffers and co",-,lercially available detergent solutions comprising
Ariel liquid (0.8% in city water, pH 8.5) and Ariel Color Futur (0.8% in city water,
pH 9.5) during 5 minutes at 40~C.
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51 _
The lipolytic residual activity was measured according the method based on the
butyric acid 4 nitrophenol ester hydrolysis. Within 5 minutes the enzymatic
activity of the lipase was successfully blocked as shown in the table below.
Residual lipolytic activity
(in % after 5 minutes)
Tris PH=7Tris DH=10 Ariel liquid Ariel Color Futur
2 5 3 4
ExamPle 2
The following laundry detergent compositions were prepared in accord with the
invention:
11 111 lV V Vl
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.118.1 18.1 18.1 18.1 18.1
Carbonate 13.013.0 13.0 27.0 27.0 27.0
Sj'jG~te 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
t~EDP 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.00260.0026 0.0026 0.0026 0.0026 0.0026
Amylase 0.00150.0015 0.0015 0.0015 0.0015 0.0015
Antibody 10E-1 10E-3 10E-3 10E+1 10E-2 10E-1
Lipolytic enzyme 0.04 0.002 0.001 0.2 0.005 0.01
MA/M 0.3 0.3 0.3 0.3 0.3 0.3
CMC 0.2 0.2 0.2 0.2 0.2 0.2
Photoactivated 15 15 15 15 15 15
bleach (ppm)
.
.
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Brightener 1 0.09 0.09 0.09 0.09 0.090.09
Perfume 0.3 0.3 0.3 0.3 03 03
Silicone antifoam 0.5 0.5 0.5 0 5 0 5 0 5
Misc/minors to 100%
Densityin g/litre 850 850 850 850 850 850
ExamPle 3
The following granular laundry detergent compositions of bulk density 750 g/litre
were prepared in accord with the invention:
ll lll
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5
QAS 0.8 2.0 2.0
STPP 19.7
Zeolite A - 19.5 19.5
NaSKS-6/citric acid (79:21) - 10.6 10.6
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8
Sodium sulfate 39.8 -. 14.3
PB4 5.0 12.7
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Antibody 1 OE-1 1 OE-2 1 OE-3
Lipolytic enzyme 0.03 0.003 0.001
Protease 0.0026 0.0085 0.045
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Cellulase 0.0006 0.0006 0.0006
Amylase 0.0009 0 0009 0 0009
MA/M 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.8
particles
Silicone a~ltiroa"~ 0.5 2.4 2.4
Minors/miscto 100%
ExamDle 4
The following detergent formulations, according to the presenl invention were
prepared, where I is a phosphorus-containing detergent composition, ll is a
zeolite-containing deteryent composition and lll is a compacl deteryent
composition:
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45AS 9.0 6.0 13.0
MA/M 2.0 4.0 2.0
LAS 6.0 8.0 11.0
TAS 2.0
~ilic~t~ 7.0 3.0 3 ~
CMC 1.0 1.0 0.5
Brightener 2 0.2 0.2 0.2
Soap 1.0 1.0 1.0
DETPMP 0.4 0.4 0.2
Spray On
, .. . ..... .
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WO 98106810 PCTIUS97/14287
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone a"liroam 0.3 0.3 0.3
Perfume 0.3 0.3 0.3
Dry additives
Carbonate 6.0 13.0 15.0
PB4 18.0 18.0 10.0
PB1 4.0 4.0 ~
TAED 3.0 3.0 1.0
Photoa.:ti~/ated bleach 0.02 0.02 0.02
Protease 0.01 0.01 0.01
Amylase 0.002 0.003 0.001
Lipolytic enzyme 0.04 0.002 0.001
Antibody 1 OE-1 0.002 1 OE-3
Dry mixed sodium sulfate 3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscel~aneous)
Density~g/litre) 630 670 670
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W O98106810 55 PCTrUS97/14287
Example 5
The following nil bleach-containing detergent formulations of particular use in the
washing of colored clothin~, accordi~8 to the present invention were prepared:
. 1
Blown Powder
Zeolite A 15.0 15.0
Sodiumsulfate 0.0 5.0
LAS 3.0 3 0
DETPMP 0.4 0.5
CMC 0.4 0.4
MA/M 4.0 4.0
Agglo,ner..tes
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - - 0.5
MA/M - - 2.0
Ca, Lol .ate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
C25E3 2.0 2.0 2.0
Dry additives
MA/M - - 3.0
NaSKS-6 - - 12.0
Cltrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Protease 0.026 0.016 0.047
Amylase 0.005 0 005 0.005
Cellulase 0.006 0.006 0.006
. ~
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W O 98106810 56 PCTnUS97/14287
Lipolytic enzyme 0.02 0.001 0.005
Antibody 1 OE-1 1 OE-3 1 OE-2
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodiumsulfate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 700 700 700
ExamPle 6
The following detergent formulations, according to the present invention were
prepared:
11 111 lV
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFM - 1.0 - -
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicar~onale - 7.5
DETPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/M 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.008 0.01 0.025 0.025
Amylase 0.007 0.004 - 0.002
Cellulase 0.0015 0.0005
Lipolytic enzyme 0.04 0.01 0.004 0.002
Antibody 10E-1 10E-1 10E-2 10E-2
Photoactivated 70ppm 45ppm - 1 Oppm
bleach (ppm)
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Brightener 1 0.2 0.2 0.08 0.2
P B1 6.0 2.0
NOBS 2.0 1.0
Balance (Moisture100 100 100 100
and Miscellaneous)
Example 7
The f~llDw;ng deter~ent formulations, according to the present invention were
prepared:
11 111 lV
Blown Powder
Zeolite A 30.0 22.0 6.0 6.7
Na SkS-6 - - - 3.3
Polycarboxylate - - - 7.1
Sodium sulfate 19 0 5.0 7.0
MA/~4~ 3.0 3.0 6.0
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - - - 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0
Bri~l)tener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 o 4
Spray On
C45E7 1.0 1.0 . 1.0 3.2
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Antibody 1 OE-1 1 OE-1 1 O E-3
Lipolytic enzyme 0.009 0.002 0.0005 0 009
Protease 0.053 0.001 0.001 0.001
Amylase 0.0008 0.0008 0.0008 0.0008
Cellulase 0.0002 0.0002 0.0002 0.0002
.. . ... ....
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NOBS - 6.1 4.5 3.2
PB1 1.0 5.0 6.0 3.9
Sodium sulfate - 6.0 -to balance
Balance (Moisture and 100 100 100
Misc~ neous)
Example 8
The following high density and bleach-contai"ing detergent formulations,
according to the present invention were prepared:
1. Il 111
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodiumsulfate 0.0 5.0 0.0
LAS 3.0 3.0 3.0
QAS - 1.5 1.5
DETPMP 0.4 0.4 0.4
CMC 0.4 04 0.4
MA/M 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
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PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Antibody 1 OE-3 1 1 OE-2
Lipolytic enzyme 0.001 0.05 0.006
Protease 0.01 0.01 0.01
Amylase 0.005 0.005 0.005
Cellulase 0.0014 0.00140.0014
Silicone a"liroar" 5.0 5.0 5.0
Dry additives
Sodiumsulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
Example 9
The following high density detergent formulations, accordh~g to the present
invention were prepared:
11
AgglG",er~e
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/M 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0 4
Spray On
C25E5 5.0 5.0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 03
SKS 6 13.0 10.0
Citrate 3.0 1.0
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TAED 5.0 70
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Antibody 0.09 0.006
Lipolytic enzyme 0.02 0.001
P,oteasa 0.014 0.014
Cellulase 0.0014 0.0014
Amylase 0.005 0.005
Silicone a"liroar, 5.0 5.0
Brightener 1 0.2 0.2
B,i~htener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density(g/litre) 850 850
Example 10
The follaw;ng granular detergent formulations, accordi"g to the present invention
were prepared:
11 111 lV V
LAS 21.0 25.0 18.0 18.0
Coco C12-14 AS - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decyl dimethyl hydroxyethyl - 0.4 0.7 0.7 0.8
NH4+CI
Nonionic 1.2 - 0.9 0.5
Coco C12-14 Fatty Alcohol - - - - 1.0
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
MAIM ~ ~ 09 09
SRP1 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 13.0 15.0
Silicate 2.0 - 7.6 7.9
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Antibody 0.01 0.001 0.1 0.01 1.0
Lipolytic enzyme 0.003 0.001 0.01 0.003 0.04
r, otease .007 .007 .007 .007 .007
Amylase - 0.004 0.004 - .004
Cellulase - 0.001 0.001 .001 .001
NOBS - - - 1.2 1.0
PB1 - - - 2.4 1.2
Diethylene triamine penta - - - 0.7 1.0
acetic acid
Diethylene triamine penta - - 0.6
methyl phosphonic acid
Mg Sulfate - - 0.8 - -
Pl,otoacti~ated bleach 45 50 ppm 15 45 ppm 42
ppm ppm ppm
Brightener 1 0.05 - 0.04 0.04 0.04
Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to 100%
Example 11
The following liquid detergent formulations, according to the present invention
were prepared:
11 111 lV V Vl Vll Vlll
LAS 10.0 13.0 9.0 - 25.0 - - -
C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0
C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0
TFM - - - 4.5 - 6.0 8.0 8.0
QAS - - - - 3.0 1.0
TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0
Rapeseed fatty - - - 5.0 - - 4.0 4.0
aclds
Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
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Dodecenyl/ 12.0 10.0 - - 15.0
tetradecenyl
succinic acid
Oleic acid 4.0 2.0 1.0 - 1.0 - - -
Ethanol 4.0 4.0 7.0 2.0 7.0 2.0 3.0 2.0
1,2 Propanediol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Mono Ethanol - - - 5 0 - - g 0 9 0Amine
Tri Ethanol - - 8
Amine
NaOH (pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2
Ethoxylated 0.5 - 0.5 0.2 - - 0.4 0.3
tetraethylene
pentamine
DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1.0
S R P 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
Antibody 1 OE- 1 OE+ 1 OE- 1 OE-2 1 OE-2 1 OE-2 1 OE-3 1 OE-1
2 1 3
Lipolytic enzyme 0.02 0.15 .001 0.01 .005 .003 .001 .003
P,otease .016 .016 .013 .008 .048 .016 0.01 .019
Amylase - .002 - .004 .005 .005
Cellulase - - - .001 - - .002 .001Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na foi",dte - - 1.0
Ca chloride - 0.015 - 0.01
Bentonite clay - - - - 4.0 4.0
Suspending clay - - - - 0.6 0.3
S D 3
Balance moisture and miscellaneous: Up to 100%
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Example 12
Granular fabric cleaning compositions which provide "softening through the
wash" capability were prepared in accord with the present invention:
45AS - 10.0
LAS 7.6
68AS 1.3
45E7 4.0
25E3 - 5.0
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3 0
Na-SKS-6 - 11.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
PB1 1 5.0
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - 0.1
Antibody 0.9 1 OE-4
Lipolytic enzyme 0.02 0.002
P,otease 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
.. ... ... ... .. . ..
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Example 13
The following rinse added fabric softener composition was prepared in
accord with the present invention:
Softener active 20.0
Antibody 1 OE-2
lipolytic enzyme 0.003
Cellul~se 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaC12 0.20
Perfume 0.90
Water / minors Up to 100%
Exam~le 14
The fo'l~.i,)g fabric softener composition was prepared in accord with the
present invention:
ll lll
D~QA 2.60 19.00
SDASA - - 70.00
Stearic acid of IV=O 0.30
Neodol 45-13 - - 13.00
Hydrochloride acid 0.02 0.02
Ethanol - - 1.00
PEG - 0.60
Antibody 0.09 0.009 0.01
Lipolytic enzyme 0.01 0.001 0.005
Perfume 1.00 1.00 0.75
Digeranyl Succi,idte - - 0.38
Silicone ar,lifioa", 0.01 0.01
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Electrolyte - 600ppm
Dye 1 OOppm 50ppm 0.01
Water and minors 100% 100%
Example 15
Syndet bar fabric cleaning con)positions were prepared in accord with the
present invention:
11 111 lV
C26 AS 20.00 20.00 20.00 20.00
CFM 5.0 50 50 50
LAS (C11-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
STPP 70 70 70
Zeolite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (MW 1400) 0.2 0.2 0.2 0.2
Coconut monethanolamide 5.0 5.0 5.0 5.0
Antibody 0.01 0.1 0.1 0.01
Lipolytic enzyme 0.003 0.05 0.1 0.005
Amylase 0.01 0.02 - -
r~tease 0.3 - 0.5 0.05
Brightel)er, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgSO4 1.0 1.0 1.0 1.0
Water 40 40 40 40
Filler*: balal)ce to 100%
*Can be s~l~cte~ from convenient ~aterials such as CaC03, talc, clay (Kaolinite,S",e~;tite), silicates, and the like.
~, . .. . ... ..
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66
Example 16
The following compact high density (0.96Kg/l) dishwashing detergent
compositions I to Vl were prepared in accord with the present invention:
11 111 lV V Vl
STPP - - 49.0 38.0
Citrate 33.0 17.5 - - 54.0 25.4
Carbonate - 17.5 - 20.0 14.0 25.4
Silicate 33.0 14.8 20.4 14.8 14.8
Metasilicate - 2.5 2.5
PB1 1.9 9.7 7.8 14.3 7.8
PB4 8.6
Percarbonate - - - - - 6.7
Nonionic 1.5 2.0 1.5 1.5 1.5 2.6
TAED 4.8 2.4 2.4 - 2.4 4.0
HEDP 0.8 1.0 0.5 - - -
DETPMP 0.6 0.6 - - - -
PMC - - - 0.2
BzP - - - 4.4
Pararfi" 0.5 0.5 0.5 0.5 0.5 0.2
Antibody 1 OE-1 1 OE-2 1 OE-3 1 OE-1 1 OE-6 1 OE-3
Lipolytic enzyme 0.02 0.01 0.001 0.06 0.002 0.001
P,otease 0.075 0.05 0.1 0.1 0.08 0.01
Amylase 0.01 0.005 0.015 0.015 0.01 0.0025
BTA 0.3 0.3 0.3 0.3 03
Bismuth Nitrate - 0.3
PA30 4.0
Terpolymer - - - 4.0
480N - 6.0 2.8
Sulphate 7.1 20.8 8.4 - 0.5 1.0
pH (1% solution) 10.8 11.0 10.9 10.8 10.9 9.6
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Example 17
The following granular dishwashing detergent compositions examples I to
IV of bulk density 1.02Kg/L were prepared in accord with the present invention:
11 111 lV V Vl
STPP 30.0 30.0 30.0 27.9 34.5 26.7
Carbonate 30.5 30.5 30.5 23.0 30.5 2.80
Silicate 7.4 7.4 7.4 12.0 8.0 20.3
PB 1 4.4 4.4 4.4 4.4
NaDCC - - - 2.0 - 1.5
Nonionic 0.75 0.75 0.75 1.9 1.2 0.5
TAED 1.0 1.0 - - 1.0
PMC - ~ 0-004
BzP - 1.4
Paraffin 0.25 0.25 0.25
Antibody 0.4 0.1 0.005 0.08 0.007 0.2
Lipolytic enzyme0.06 0.02 0.001 0.008 0.002 0.005
Protease 0.05 0.05 0.05 - 0.1
Amylase - - 0.01 0.02 0.01
BTA 0.15 - 0.15
Sulphate 23.9 23.9 23.9 31.4 17.4
pH (1% solution)10.8 10.8 10.8 10.7 10.7 12.3
Example 18
The following detergent composition tablets of 25g weight were prepared
in accord with the present invention by compression of a granular dishwashing
detergent co",position at a pressure of 13KN/cm2 using a standard 12 head
rotary press:
ll lll
STPP - 48.8 47.5
Citrate 26.4
Carbonate - 5.0
.. , . , . _ . .
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Silicate 26.4 14.8 25.0
Antibody 0.06 0.015 0.009
Lipolytic enzyme0.01 0.005 0.002
Protease 0.03 0.075 0 01
Amylase 0.01 - 0.001
PB1 1.6 7.8
PB4 6.9 - 11.4
Nonionic 1.2 2.0 1.1
TAED 4.3 2.4 0.8
HEDP 0.7 - -
DETPMP 0.65
Paraffn 0 4 0 5
BTA 0.2 0.3
PA30 3.2
Sulphate 25.0 14.7 3.2
pH (1% sc'~ltion)10.6 10.6 11.0
EXd~ ~ IPIe 19
The following liquid dishwashing detergent compositions were prepared in
accord with the present invention I to ll, of density 1.40Kg/L:
ll
STPP 33.3 20.0
Carbonate 2.7 2.0
.Sil~c:lt~
NaDCC 1.1 1.15
Nonionic 2.5 1.0
Paraffin 2.2
Antibody 0.1 0.006
Lipolytic enzyme 0.04 0.001
Plotease 0.03 0.02
Amylase 0.005
480N 0 50 4.00
KOH - 6.00
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Sulphate 1.6
pH (1% solution) 9.1 10.0
Exam~le 20
The following liquid dish~,vashing compositions were prepared according to the
present invention:
11 111 lV V
C17ES 28.5 27.4 19.2 34.1 34.1
Amineoxide 2.6 5.0 2.0 3.0 3.0
C12 glucose amide - - 6.0 - -
Betaine 0.9 - - 2.0 2.0
Xylene sulfonate 2.0 4.0 - 2.0
Neodol C11E9 - - 5.0
Polyhydroxy fatty acid amide - - - 6.5 6.5
Sodium diethylene penta acetdte - - 0.03
(40%)
TAED - - - 0.06 0.06
Sucrose - - - 1.5 1.5
Ethanol 4.0 5.5 5.5 9.1 9.1
Alkyl diphenyl oxide disulronal~ - - - - 2.
Ca fo""dte - - - 0.5 1.1
Ammonium citrate 0.06 0.1
Na chloride - 1.0 - - -
Mg chloride 3.3 - 0.7
Ca chloride - - 0.4
Na sulfate - - 0.06
Mg sulfate 0.08
Mg hydroxide - - - 2.2 2.2
Na hydroxide - - - 1.1 1.1
Hydrogen peroxide 200ppm 0.16 0.006
Lipolytic enzyme 0.004 0.01 0.008 0.02 0.002
Antibody 1 OE-3 1 OE-2 1 OE-1 1 OE-2 1 OE4
Perfume 0.18 0.09 0.09 0.2 0.2
Water and minors Up to 100%
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Example 21
The following liquid hard surface cleaning compositions were prepared in
accord with the present invention:
11 111 lV V Vl
Antibody 0.007 0.05 0.1 0.3 0.6 0.5
Lipolytic enzyme 0.001 0.005 0.005 0.01 0.01 0.07
Amylase - - 0.005 0.02 - 0.005
Protease 0.05 0.01 0.02 0.03 0.005 0.005
EDTA* - - 2.90 2.90
Citrate - - - - 2.90 2.90
LAS 1.95 - 1.95 - 1.95
C12 AS - 2.20 - 2.20 - 2.20
NaC12(ethoxy) - 2.20 - 2.20 - 2.20
**sulfate
C12 Dimethylamine - 0.50 - 0.50 - 0.50
oxide
SCS 1.30 - 1.30 - 1.30
Hexyl Carbitol** 6.30 6.30 6.30 6.30 6.30 6.30
Water Balance to 100%
*Na4 ethylenediarnine cl~cetic acid
**Diethylene glycol ".G"ohexyl ether
***AII formulas adjusted to pH 7
ExamPle 22
The following spray composition for cleaning of hard surfaces and
removing household mildew was prepared in accord with the present invention:
Antibody 0.05
Lipolytic enzyme 0.005
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Protease 0.01
Sodium octyl sulfate 2.00
Sodium dodecyl sulfate 4.00
Sodium hydroxide 0.80
Silicate (Na) 0.04
Perfume 0.35
Water/minors up to 100%
Ex~",~le 23
Deteryenl additives were prepared in accord with the present invention:
LAS
STPP 30 30
Zeolite A 35
PB1 20 20 15
TAED 10 10 8
r, otease - 0.3
Lipolytic enzyme 0.5 - 0.2
Antibody 10 10 2
