Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING ANTIBODY
CONTROLLED CELLULOLYTIC ACTIVITY
FIELD of the INVENTION
The present invention relates to laundry detergent compositions
comprising a cellulase-directed antibody and a cellulase in order to prevent
potential tensile strength loss related to the hydrolytic activity of cellulase on
cell~llose s~ sl,ates while maintaining the desired benefits from the use of
cell~ se.
BACKGROUND of the INVENTION
An important part of the system which protects ve, lebrales against
infections 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 a
micro- or macromolecu'c foreign to that body and bind the body-foreign structureinitialin~ its destruction. Such a body-foreign molec~lle is called an antigen. The
antibody is c~i(ected against the antigenic determinant or hapten of the anligene.g. an amino acid sequence, parts of oligos~ccharides, polysaccharides,
lipopolysaccharides, glycoproteins, lipoproteins, lipoteichoinic acids.
The specific antibodies generated in this manner can combine with the
a-)ligen which elicited their fo""dtion to form an antigen-antibody complex.
Antibody molecules have binding sites that are very specific for and
complementary to the structural features of the antigen that induced their
formation.
... ..
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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 in
various domains such as analytical chemistry, therapeutic treatment, 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 l~alment compositions for topical application containing
micro~ps~ ~les which enclose a beneficial agent at a target location, the
microcapsules having an antibody or antibody fragment specific to the target
location or a lectin.
W092/04380 describes reshaped human antibody or reshaped human
antibody f~a~~.nents having specificity for human polymorphic epithelial mucin to
be used in the treatment or diagnosis of cancer. The use of Epstein-Barr virus
specific polypeptides for the prod~ction of antibodies and the diagnostic and
treatment of said dise~se is disclosed in W094/06470.
Oral compositions comprising a~ Itibodies as anti-caries or periodontal
~lise~ses treatment have been extensively described 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 rlisclose hair cosmetic compositions
containing an a.,libody to hair or hair extract, obtained from egg yolk or poultry
immunised with the hair or hair extract and a polymer emulsion to provide
redlJc~d hair damage, softness, moistened feel and smoothness, said
co",position being adsorbed only onto a specified part of the hair.
Comrosi(ions containing antagonists (tyrphostins or al,liho~iqs) against
epidermal and transforming growth factors, suitable for use in treatment of acneare described in WO9~/24896.
The use of antibodies in the overall detergency context has been
sugyested in Unilever Researchprijs "Molecule zoekt partner" 1992 wherein
modified antibodies directed to specific stains are proposed to be used in
bleaching process.
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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 ~reparing vaccine composition for dental caries
in nasal drops comprising an antigen produced by integraling a protein antigen-
expressing gene into the chromosomal gene of a streptococcus mutants GS-5
strain. W094/25591 discloses the prod~lr,tion of antibodies or functionalised
fragments thereof derived from heavy chain immunoglobulins of camelidae.
Detergent compositions include nowadays a complex combination of
active ingredients which fulfill certain specific needs: a su~raclant system,
enzymes providing cleaning and fabric care benefits, bleaching agents, a buildersystem, suds su,upressors, soil-suspending agents, soil-release agents, optical
brighteners, softening agents, dispersants, dye transfer inhibition col"pounds,
abrasives, bactericides, perfumes, and their overall ,I)e~ro~ ance has indeed
improved over the years.
In particular, current detergent formulations generally include dete,genl
enzymes and more specifically cell~ ses
The activity of cellulase is one in which cellulosic fibres or suL,slrales are
~tl~cked by the eellul~se and depending on the particular function of the
cellulase, which can be endo-or exo cellulase and the respective hemicell~l~ ses.
The cellulose structures are depolymerized or cleaved into smaller and thereby
more soluble or dispersible fractions. This activity in particular on fabrics
provides a cleaning, rejuvenalion, softening and generally improved handfeel
chara.,t~ri~lics to the fabric structure.
In the detergenl field cellul~ses ,~e,ro~",i.~g in a typical deterge"l wash
environ",ent are available with an activity at which the desired cellul~se
pelror",al1ce is reached prior to the end of a wash-cycle. However, since the
cellulase continues to react, even after having provided the desired performance,
cleavage of the cellulose will continue. Therefore, there is a potential risk oftensile slre"glh loss.
It should be noted however, that tensile strength loss of fabric is also an
unavoidable result of mechanical action due to use/wearing and may further
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result from damage by a bleaching component in the laundry process especially
if the fabric is contaminated with metal compounds.
It has now been surprisingly found that the application of antibodies
raised against the cellulolytic enzyme prevents the occurrence of undesirable
residual cellulolytic activity. The cellulolytic activity can be fully controlled during
the cleaning process so that the negative effects due to overexposure to the
cellulolytic enzyme can now be avoided.
It is therefore an object of the present invention to provide a cellulase-
containing laundry detergent composition preventing potential tensile s(lellyltlloss related to the hydrolytic activity of cellulase on cellulose substrates while
maintaining the desired benefits from the use of cellulase.
The above need has been met by specific laundry detergent co"~positions
comprising a cellulase and an antibody directed against said cellulolytic enzyme.
Cellulase exhibiting exceptionally high activity have been discloseJ in the
context of compact detergents in W0-92-13057 in the context of quaternary
an""onium softening compounds in EP-A~95 554 and in the context of softening
clay in a deterge,-t composition in EP-A495 258 and EP-A-177 165. Cellulase
as such with exceptionally high activity has been disclosed in WO 91/17243.
Recognition of the potential tensile strength loss of cellulase has been repG,ted
in several p! IhliC~t;l:~ils. For example Japanese application J~2-310754
discloses particular cellul~ses having a specific so-called non-de~rading index.Japanese arpli.~~tion J~3-134830 discloses deterge"~ compositions for clothing
containing a cellulase which has a non-destructive index and US 4 978470
discloses a detergeot composition for closing containing cellul-lse enzyme with a
"non-degrading index" of less than 500.
SUMMARY of the INVENTION
The present invention relates to the use of laundry deterge. ,t
compositions in household fabric treatment machines and handwash treatments.
The laundry detergent composition comprises a cell~ se enzyme and an
antibody raised against the cellulolytic enzyme in order to prevent potential
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tensile strength loss related to the hydrolytic activity of cellulase on cellulose
substrates while maintaining the desired benefits from the use of cellulase.
DETAILED DESCRIPTION of the INVENTION
ANTIBODY
An essential element of the detergel)l coi),positions of the presenl
invention is an antibody.
The immunoglobulins are classified into 5 cl~sses, respectively: IgM, IgG,
IgA, IgD and IgE. Preferred cl~sses of immunoglobulins are the IgG and IgA.
Secretory slgA which are found into human excreted body fluids such as milk,
saliva, respiratory and intestinal fluids are especi?'ly designed to survive in said
secretions, they have enhanced binding characteristics and are resistant to
proteolytic hydrolysis.
The antibody which may be monoclonal or polyclonal or an antib~Jy
fragment, may be generated by techniques conventional in the art, for example
by using reco",binant DNA techniques allowing to produce antibodies vciriants
with new prope, lies: reduced immunogenecity, enhanced affinity, altered size, ...
Specific binding may also be used. Prefer.ed for the purpose of the present
invention is a ,.,Gnoclonal alltibody, more prefe"ed is a fragment thereof. These
r, ag,n~n~s may be similarly generated by conventional techniques such as
enzymatic digestion by papain or pepsin, or using recoi"l~inant DNA techniques.
Antibody r,ag,nenls may also be ~yerlerated by conventional recombinant DNA
techniques. Antibodies and antibodies' r,ay,ne,)ls may be humanised, such as
described in Meded. - Fac. Landbouwkd. Toegepast Biol. Wet. (Univ. Gent)
(1995), 60(4a, ForumforApplied Bioteel.nology, 1995, Part 1), 2057-63.
Heavy and light chains are indeed composed of constant and variable
domains. In the organis.ns producing immunoglobulins in their natural state the
co,)stant doi"ains are very important for a number of functions, but for many
~ppli~tions in industrial processes and products their variable domains are
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sufficient. Consequently many methods have been described to produce
antibody fragments.
Antibody fragments which are used may be a Fab, a Fv, a scFv or any
other fragment having similar binding properties. Preferred routes to antibodiesfragments are through recombinant DNA technology, so that the fragment is
expressed by a genetically transformed organism.
Antibodies and antibody frayments produced by recombinant DNA
technology do not need to be identical to fragment of antibodies produced in
vertebrates, having nevertheless the same binding properties evaluated by their
Krn, Ki and Kcat. For instance they may include sequences of amino acids
andlor glycosylations which differ from those found in antibodies produced in
other ways, especi?'ly sequences at the end of fragments. Somewhat
ana'Qgo~ ~sly, antibody fragments produced through recombinant DNA tecl " lologymay 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 synthetic polymer which mimics the specific binding activity of a
natural antibody's complementary region(s). Such a polymer is for example a
polypeptide or a polymer i",p,i-,ling (Angew. Chem. Int. Ed. Engl. 1995, 34,
1812-1832).
The usual method for the production of antibodies may be adopted in
immunising ",a,n,)~als or poultry with the corresponding antigens. As "~ammals to
be immunised, mice, rabbits, goats, sheep, horses, cows, etc. may be used. The
antibody (imm~,noglobulin r,action) may be separated from the antiserum, the
milk or the eggs according to the ordinary antibody purification method including
salting-out method, polson extraction, gel-filtration chromatography, ion-
e~.cl,a"ge chromatog~apl,y, affinity chromatography and the like, the salting-out
method using a,nmonium sulfate to produce the precipitates, followed by
dialysing the ~,recipilates againsl physiological saline to obtain the purified
precipitates as the antibody.
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Plants are also capable of synthesising and assembling every kind of
antibody molecule and allow a large scale of production of antibodies as
~ described in Tibtech. Dec 19g5, 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 be produced into microorganisms such as E. coli
or S. cerevisiae via biofermentation process as illustrated in the EP patent 667394.
Techniques for the production of anlibGdy fragments 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 W094125591.
The drawbacks due to prolonged activity of the enzyme can be avoided by
an effective control of the enzymatic activity through the introduction of the
specirically conesponding antibody. Such antibodies can be either polyclonal -
directed to the whole enzyme structure - or ",onoclonal - directed to specific
epitopes of the enzyme activity controling regions of the enzyme structure of the
enzyme core or s-6sl,ate binding domain. Antibodies raised against specific
enzyme can effectively deactivate the enzyme by the antibody-antigen binding in
or very near the active site. The formation of such complex leads to the enzyme
deactivation and could be explained by the distortion of the 3-dimensional
structure and/or steric hindla,)ce at the substrate clefl. The deactivation of the
enzyme can also be achieved by the precipitation of the complex anlibody-
antigen from the wasl,ing solution. Due to very high specificity and efficiency of
the ~nti~GJy-antigen interaction, no other cJetergent active is thereby affected.
The cell~ se~i, ected antibodies are preferably co,)~prised in the
detergent composition of the present invention at a level of from 10E~% to
10E+1% by weight of total co",position. In some instances, antibodies raised
against a specific cellulase have the capability of binding other cellulases of high
structural similarily, providing cross-reactivity. Typically, a molecular ratio of
cellulase-directed antibody to cellulase will be of 100:1 or lower, pr~rerably of
50:1 or lower. For ",o"oclor,al antibodies or r,aS~",e-)ts thereof, the molecular
ratio of cellulase-directed antibody to cellulase will be generally of 50:1 or lower,
preferal~ly of 20:1 or lower.
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The antibodies raised against the cellulase are released in the wash
solution after a lag-period aliowing to deliver excellent performance benefits to
be achieved by the end of the wash process.
Therefore, the antibodies are preferably incorporated 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 ofths corresponding detergent or additive.
For granular and powder detergent and cleaning products, the antibodies
and release agents can be contained in a granulate. Said antibody granulate can
suitably contain various granulation aids, binders, fillers, plasticizers, lubricants,
cores and the like. Examples thereof include cellulose (e.g. cellulosic fibers or in
microcrystalline form), cellulose 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
nonionic surfactants. Other materials of relevance for incor,l~oraliol, in the
granulate are described in EP 304 331.
The release agent may be, for example, a cGaliog. Said coali"g protects
said granulates in the wash environment for a certain period of time. The coaling
will normally be arplied to said granulates in an amount in the range of 1% to
50% by weight (c~'c~ ted on the basis of the weight of the unco~led, 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 co,n~osilion of the desired coatil-g, and to the kind of protection
said coati-,y should offer to said granul~tes. For example, the thickness of said
coati. ~y 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 coating 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 coatings are coatings which give rise to release of the
contents of antibody-containing granulates under the conditions prevailing during
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the use thereof. Thus, for e~ample, when a preparation 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.
Preferred release coating are coatings which are subst~rltially insoluble in
water. Release coatings which are appropriate in washing media may suitably
comprise 5!lhSPrlCeS selected from the following: cellulose and cellulase
derivatives, PVA, PVP, tallow; hydrogenated tallow; partially hydrolyzed tallow;fatty acids and fatty alcohols of natural and synthetic origin; long-chain fatty acid
mono-, di- and triesters of glycerol (e.g. glycerol monostearate); ethoxylated fatty
alcohols; latexes; hydrocarbons of melting point in the range of 50~0~C; and
waxes. Melt-coating agents are a p~efer.ed class of fast or slow release coatingagents which can be used without dilution with water. Reference may be made to
Controlled Release Systems: Fabrication Technology, Vol. I, CRC Press, 1988,
for further information on slow release coating.
- Coatings may suitably further comprise s~ ~hsl~nces such as clays (e.g. kaolin),
titanium dioxide, pign,enls, salts (such as calcium carbonate) and the like. Theperson skilled in the art will be aware of further coating constituents of relevance
in the present invention.
In liquid ~etergent coi"rssilions, the antibody can be incor,uoraled as a
dispersio., of pallicl~s containing in A.tditioll to the antibo.ly, a release agent.
The a~tiboJy can be present in a liquid or solid form. Suitable particles co"sisl of
a porous hyJ~upl,obic material (e.g., silica with an average pore diameter of 500
A.)g~lroi" or higher) containing into the pores a solution of antibodies and a
su,raclant as described in EP 583 512 of Surutzidis A. et al.
The release agent might be a coatiny which prolects said particles in the wash
cycle for a certain period of time. The coating is preferably a hydlophobic coating
material such as a hydrophibic liquid polymer. Said polymer can be an organo
polysiloxane oil, aller"alively a high oleou~ weight hydroca, L,on or water
insoluble 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.
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THE CELLULASE ENZYME
The cellulases usable in the present invention include both bacterial or
fungal cell~ se. Origin can further be mesophilic or extremophilic (psyohro~c hilic,
psychrotlophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.).
Purified or non-purified forms of these enzymes may be used. Also included by
definition, are mutants of native enzymes. Mutants can be obtained e.g. by
protein and/or genetic engineering, chemical and/or physical modifications of
native enzymes. Common practice as well is the expression of the enzyme via
host organisms in which the genetic material responsible for the production of
the enzyme has been cloned.
Preferably, they will have a pH optimum of between 5 and 12 and an
activity above 50 CEVU (Cellulose Viscosity Unit). Suitable cellulases are
~isclosed in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and
W096/02653 which discloses fungal cellulase produced respectively from
Humicola insolens, Tricoderma, Thielavia and Sporotrichum. Suitable cellul~ses
are also disclosed in GB-A-2.075.028; GB-A-2.095.275, GB-A-2.095.275, DE-
OS-2.247.832 and W095/26398.
Examples of cell~ se components which may be usable in the present
invention are:
A cello~ichydrolase component which is immu.)oreactive with an a"tiboJy raised
against a highly purified 70kD cellobiohydrolase (EC 3.2.1.91) derived from
Hulll.c~l~ insolens, DSM 1800, or which is a homolQgue or derivative of the
70kD cqllobiohydrolase exhibiting cellulase activity, or an endoglucanase
co"~ponent which is immunoreactive with an antibody raised against a highly
purified 50kD endoglu~nase derived from Humicola insolens, DSM 1800, or
which is a ~,o",clo~ue or derivative of the -50kD e"doglucanase exhibiting
cellulase activity; a prefened el,doglucanase cGIoponel)l has the amino acid
sequence disolosed in PCT Patent Application No. W091/17244, or an
endoglucanase component which is immunoreactive with an antibody raised
against a highly purified -SOkD (appa,ent molecular weight, the amino acid
col"posilion cor,aspol)ds to 45kD with 2n glycosylation sites) endoglucanase
derived from Fusarium oxysporum, DSM 2672, or which is a homologue or
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11
derivative of the -50kD endoglucanase exhibiting cellulase activity; a preferredendoglucanase component has the amino scid sequence disclosed in PCT
Patent Application No. WO91/17244, or any of the cellulases disclosed in the
published European Patent Application No. EP-A2-271 004, the cellulases
having a non-degrading index (NDI) of not less than 500 and being alkalophilic
cellulases having an optimum pH not less than 7 or whose relative activity at a
pH of not less than 8 is 50% or over of the activity under optimum conditions
when carboxy methyl cellulose (CMC) is used as a substrate, or an
endoglucanase component which is immunoreactive with an antibody raised
against a highly purified -43kD endoglucanase derived from Humicola insolens,
DSM 1800, or which is a homologue or derivative of the -43kD endoglucanase
exhibiting cellulase activity; a preferred endoglucanase component has the
amino acid sequence disclosed in PCT Patent Application No. WO 91/17243, or
an endoglucanase component which is immunoreactive with an antibody raised
against a highly purified -60kD endoglu~-~nase derived from Bacillus lautus,
NCIMB 40250, or which is a homologue or derivative of the -60kD
endoglucanase exhibiting cellulase activity; a preferred endoglucanase
component has the amino acid seguence disclosed in PCT Patent Application
No. WO 91110732. See also the celllJIases described in W091/21081. Other
suitable cellulases for fabric care and/or cleaning ,l~r~pe~ties are desc,ibed in
W096/34092, WO96117994 and WO95124471.
Other suitable celllll~ces are the EGIII cellulases from Trichoderma
longibrachiatum described in WO94/21801, Genencor, published Septe"ll,er 29,
1994. Fspeci~'ly suitablQ cellul~ses are the cell~ ses having color care benefits.
Examples of such cellulases are cellulases described in European patent
application No. 91202879.2, filed November6, 1991 (Novo).
According to the present invention, prerer,ed cellulases are those as
described in Danish Patent Application 1159/90 or PCT patent application
WO91/17243 which is also known as Carezyme(TM) available from Novo
Nordisk A/S in Bagsvaerd, in Denmark. The cellulase preparation described in
these p~Jhli~liG"s and the Carezyme(TM) consistent with this description, can
consist essenlially of a î ,o,.,ogeneous endoglucanase component, which is
immunoreactive with an anti-body raised against a highly purified 43 kD cellulase
derived from Hulll ~cl~ Insulens, DSM 1800, or which is homologous to said 43
kD endoglucanase. An alternative screening for appro~riale cell~ ses for use in
.
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12
the laundry detergent composition accGrding to the present invention is the
method specified in EP-A495 258 or more specifically in EP-A-350 098.
For industrial production of the cellulase preparation herein, however, it is
prerer,ed to employ recombinant DNA techniques or other techniques involving
adjustments of fermentations or mutation of the microorganisms involved to
ensure overprodllction of the desired enzymatic activities. Such methods and
techniques are known in the art and may readily be carried out by persons
skilled in the art. common practice as well is the expression of the enzyme in
host organisms in which the genetic material responsible for the production of
the enzyme has been cloned.
Deterqent components
The detergent compositions of the invention may also contain additional
deteryer,t components. The precise nature of these additional components, and
levels of incorporation thereof will depend on the physical form of the
composition, and the nature of the cleaning operation for which it is to be used.
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
"concer,llated" form.
The con,~osilions of the invention may be formulated as hand and
machine laundry detergent compositions including Jaundry additive comrositions
and co""~ositions suitable for use in the soaking and/or pretreatment of stainedfabrics, rinse added fabric softener compositions. Such compositions can providefabric cleaning, stain removal, whiteness maintenance, softening, color
a~,pearance and dye t~a,)sfer inhibition.
When formulated as compositions suitable for use in a laundry machine
washing method, the compositions of the invention preferably contain both a
surfactant and a builder compound and additionally one or more detergent
cG")~,o"ents l~referably selected from organic polymeric compounds, bleaching
agents, additional enzymes, suds suppressors, dispersants, lime-soap
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13
dispersants soil suspension and anti-redeposition agents and corrosion
inhibitors. Laundry compositions can also contain softening agents as
additional detergent components.
The compositions of the invention can also be used as detergent additive
products comprising a cellulase-directed antibody and will be added to a
conventional detergent cellu~qse-containing composition. The detergent
additives can also comprise both the cellulase and cell~ se-directed antibody.
Such additive products are intended to supplement or boost the peiror",ance of
conventional detergent compositions preferably comprise up to 50% antibodies
by weight of total composition.
If needed the density of the 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 compositions herein is best reflected by density and
in terms of composition by the amount of inorganic filler salt; i"organic filler salts
are conventional ingredients of detergent compositions in powder form; in
conventional detergent compositions the filler salts are present in s~bst~ntial
amounts typically 17-35% by weight of the total composition.
In the co",pal;t compositions the filler salt is ,t~resenl in amounts not
exceeding 15% of the total composition preferably not exceeding 10% most
prert:rably not exceeding 5% by weight of the composition.
The inorganic filler salts such as meant in the present co"~positions are
selecte~ from the alkali and alkaline-earth-metal salts of sulphates and chlorides.
A prefer,ed filler salt is sodium sulphate.
Liquid detergent compositions according to the presenl invention can also
be in a "concer,lraled form" in such case the liquid deterge"t compositions
accordi.)g the present invention will contain a lower amount of water co"~pared
to conventional liquid detergents.
Typically the water coi ,te"t of the concer,t~ ated liquid detergen~ is
~,rbterably less than 40% more preferal~ly less than 30% most preferably less
than 20% by weight of the detersJen~ composition.
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WO 98/07823 PCTAUS97/11544 14
SL~rfactant system
The detergent compositions according to the present invention comprise a
surfactant system wherein the surfactant can be selected from nonionic and/or
anionic and/or cationic andlor ampholytic and/or zwitterionic and/or semi-polar
surfactants.
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.
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 does
not degrade the stability of any enzyme in these compositions.
Prefer,ed surfactant systems to be used accordi"g to the present invention
comprise as a surfactant one or more of the nonionic and/or anionic sul~acta"ls
described herein.
Polyethylene polypropylene and polybutylene oxide condensales of alkyl
phenols are suitable for use as the nonionic s- l ~actant 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 conlai"i,1-J from about 6 to about 14 carbon atoms
preferably from about 8 to about 14 carbon atoms in either a straight-chain or
~ra"~;l,ed chain configuration with the alkylene oxide. In a preferled embodiment
the ethylene oxide is present in an amount equal to from about 2 to about 25
moles more preferal,ly from about 3 to about 15 moles of ethylene oxide per
mole of alkyl phenol. Co"""ercially available nonionic surfactants of this type
include lgepalTM C0~30 marketed by the GAF CGr~,oralion; and TritonTM X-
45 X-1 14 X-100 and X-102 all marketed by the Rohm & Haas Company. These
surfactants are commonly referred to as alkylphenol alkoxylates (e.g. alkyl
phenol ethoxylates).
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The condensation products of primary and secondary aliphatic alcohols with
from about 1 to about 25 moles of ethylene oxide are suitable for use as the
nonionic surfactant of the nonionic surfactant systems of the present invention.The alkyl chain of the aliphatic alcohol can either be straight or branched,
primary or secondary, and generally contains from about 8 to about 22 carbon
atoms. Preferred are the condensation products of alcohois 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 slcohol are
present in said condensation products. Examples of co,nr,lercially available
nonionic surfactants of this type include TergitolTM 15-S-9 (the condensation
product of C1 1 -C1 s 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 molQc~ r weight distribution), both marketed by
Union Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-
C1~ 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-C1s linear alcohol with
7 moles of ethylene oxide), NeodolTM 45-5 (the condensation product of C14-
C1s linear alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical
CGIIIPanY, KYrOTM EOB (the conJensation product of C13-C1s alcohol with
moles ethylene oxide), marketed by The Procter & Gamble Col-"~any, and
Genapol LA 030 or 050 (the cGndensdlion product of C12-C14 alcohol with 3
or ~ moles of ethylene oxide) marketed by Hoechst. Preferred range of HLB in
these products is from 8-1 1 and most preferred from 8-10.
Also useful as the nonionic su. raclant of the su. ractant systems of the present
invention are the alkylpolysaccharides disclosed in l:l.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hycJ,opl,obic group containing from
about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon
atoms and a polysaccharide, e.g. a polyglycoside, hydrophilic group containing
from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably
from about 1.3 to about 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon atoms can be used, e.g., glucose, g~-ctose and
gal~ctosyl moieties can be substituted for the glucosyl moieties (optionally the
.. ..... . ~ .. ~
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16
hydrophobic group is attached at the 2-, 3-, 4-, etc. positions thus giving a
glucose or g~l~ctose as opposed to a glucoside or galactoside). The
intersaccharide bonds can be, e.g., between the one position of the additional
saccharids units and the 2-, 3-, 4-, and/or 6- positions on the preceding
saccharide units.
The preferred alkylpolyglycosides have the formula
R20(CnH2nO)t(9lycosyl)x
wherein 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 14, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from
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
(attach" ,el ,t 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, prefera~ly predominately the 2-position.
The condensation products of ethylene oxide with a hydrophobic base for",ecl
by the condensation of propylene oxide with propylene glycol are also suitable
for use as the addilio,)al nonionic surfactant systems of the present invention.The hydl-ophobic portion of these co",pounds will preferably have a molecular
weight of from about 1500 to about 1800 and will exhibit water insolubility. Theaddition of polyoxyethylene moieties to this hydrophobic portion tends to
increase the water soluhility 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~/0 of the total weight of the conde"sation product, which corresponds to
condensation with up to about 40 moles of ethylene oxide. Examples of
co",pounds of this type include certain of the commercially-available PlurafacTMLF404 and PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of the nonionic sulractant
system of the present invention, are the condensation products of ethylene oxide
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17
with the product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and generally
has 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 molecular weight of from about 5,000 to about 11,000. Examples of this
type of nonionic surfactant include certain of the commercially available
TetronicTM compounds, marketed by BASF.
Prefer~ed for use as the nonionic surfactant of the surfactant systems of the
present invention are polyethylene oxide condensates of alkyl phenols,
condensation products of primary and secondary aliphatic alcohols with from
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 surfactants are polyhydroxy fatty acid amide
SIJI ract~nts of the formula.
R2 - C - N - Z,
Il I
o R1
wherein R~ is H, or R1 is C1~ hydrocdrl~yl, 2-hydroxy ethyl, 2-hydroxy propyl ora mixture thereof, R2 is Cs 31 hyJrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hy~JIocdrL.yl chain with at least 3 hydroxyls directly connected to
the chain, or an alkoxylated derivative thereof. rreferably, 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 amination reaction.
Suit~hle anionic su~racta"ts to be used are linear alkyl benzene sulfonate,
alkyl ester sulfonate s~l,ractai)ts including linear esters of Cg-C20 carboxylicacids (i.e., fatty acids) which are sulfonated with g~seous SO3 according to '~he
Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable
. . .
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18
starting materials would include natural fatty substances as derived from tallow,
palm oil, etc.
The preferred alkyl ester sulfonate surfactant, especially for laundry applications,
comprise alkyl ester sulfonate surfactants of the structural formula
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydloca,Lyl, preferably an alkyl, or combination thereof,R4 is a C1-C6 hydrocarbyl, 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, potassium, and lithium, and
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 preferred are the methyl ester sulfonateswherein R3 is C10-C16 alkyl.
Other suitable anionic surfactants include the alkyl sulfate su,ra~;ta"ts which
are water soluble salts or acids of the formula ROSO3M wherein R preferably is
a C10-C24 hydrocarbyl, preferab~y an alkyl or hydroxyalkyl having a C10-C20
alkyl co,npo-)ent, 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~ssi~ ~m, lithium), or
ammonium or substituted ar"moi-ium (e.g. methyl-, di",ett,yl-, and trimethyl
ammonium cations and quaternary ammonium cations such as tetramethyl-
ammonium and dimethyl piperdinium cations and qua~erna,y ammonium cations
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 temperatures (e.g. below about 50~C) and C16 18 alkyl chains
are prefer, ed for higher wash temperatures (e.g. above about 50~C).
Other anionic su,racla"ts useful for detersive purposes can also be included
in the detergent ccsn,l,ositions of the present invention. These can include salts
(including, for example, sodium, potassium, a",monium, and substituted
amrnonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22
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19
primary of secondary alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline
earth metal citrates, e.g., as described in British patent specification 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, paraffin
sulfonates, alkyl phosphates, isethionates such as the acyl isethionates, N-acyltaurates, alkyl succ;namates and sulfosuccinates, monoesters of sulfosuccinates
(especially saturated and unsaturated C12-C18 monoesters) and diesters of
sulfosuccinates (especi~lly 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 carl,oxylates suchas those of the formula RO~CH2CH20)k-CH2C00-M+ wherein R is a Cg-C22
alkyl, k is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin
acids and hydrogenated 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 exa",ples are described in "SurFace Active Agents and Delerg~nts"
(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
incor~,orated by reference).
When incl~Jde~ r~in, the laundry ~etergenl compositions of the present
invention typically cu,-",rise from about 1% to about 40%, ,~)referably from about
3% to about 20% by weight of such a"ionic Sl" ractanls.
Highly ~r~fer-ed anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof ars water soluble salts or acids of the formula RO(A)mS03M
wherein R is an uns~Jhstihlted C10-C24 alkyl or hydroxyalkyl group having a
C10-C24 alkyl co,nponent, ~re~rably a C12-C20 alkyl or hydroxyalkyl, more
~referably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
grealer than zero, typicaîly between about 0.5 and about 6, more prefer~bly
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,
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W O 98/07823 PCTAUS97/11544
etc.), ammonium or substituted-ammonium cation. Alkyl ethoxylated sulfates as
well as alkyl propoxylated sulfates are contemplated herein. Specific examples
of substituted ammonium cations include methyl-, dimethyl, trimethyl-ammonium
cations and quaternary ammonium cations such as tetramethyl-ammonium and
dimethyl piperdinium cations and those derived from alkylamines such as
ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary
surfactants are C12-C18 alkyl polyethoxylate (1.0) sulfate (C12-C18E(1.o)M)l
C12-C1g alkyl polyethoxylate (2.25) sùlfate (C12-C18E(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 contain
cationic, ampholytic, zwitterionic, and semi-polar surfactants, as well as the
nonionic and/or anionic surfactants other than those already described herein.
Cationic detersive surfactants suitable for use in the detergent compositions ofthe present invention are those having one long-chain hydrocarb~l group.
Examples of such cationic s~" ra~:tants include the ammonium surfactants such asalkyltrimethylar"r"onium 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 ftom 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 selected from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -
CH2CHOH-CHOHCOR6CHOHCH2OH wherein R6 is any hexose or hexose
polymer having a molec~ 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 15; and X is any compatible
anion.
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21
Quaternary ammonium surfactant suitable for the present invention has
the formula (I):
R~
Formula I
whereby R1 is a short chainlength alkyl (C6-C10) or alkylamidoalkyl of the
formula (Il):
C6~¢N~ ~
Formula ll
y is 2~, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
whereby x is 04, prererably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a
short chain 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.
Preferred quat a,nmonium surfactants are those as defined in formula I
whereby
R1 is Cg, C10 or mixtures thereof, x=o,
R3, R4 = CH3 and R5 = CH2CH2~H
Highly IJreferred cationic surfactants are the water-soluble quatemary
ammonium compounds useful in the present composition having the formula:
R1 R2R3R4N+X- (i)
.
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WO ~ ID23 PCT~US97/11544
22
wherein R1 is C8-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 prefer,e~ alkyl chain length for R1 is C~2-C1s particularly where the alkyl
group is a mixture of chain lengths derived from coconut or palm kernel fat or is
derived synthetically by olefin build up or OXO alcohols synthesis. Preferred
groups for R2R3 and R4 are methyl and hydroxyethyl groups and the anion X
may be selected from halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of formulae (i) for use
herein are:
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl a",monium chloride or bromide;
decyl triethyl ai"r"ol,ium chloride;
decyl dimethyl hydroxyethyl a""l,o,lium chloride or bromide;
C12 15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut dimethyl hydroxyethyl ammonium chloride or bromide;
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 a",mGnium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-~-C-C12_14 alkyl and R2R3R4 are methyl).
1~
o
di-alkyl imi~ olines [compounds of formula (i)].
Other cationic surfactants useful herein are also described in U.S. Patent
4,228,044, Cambre, issued October 14, 1980 and in European Patent
Arrlic~tion EP 000,224.
When incll~ded therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 25%, preferably from about 1% to about
8% by weight of such cationic sL-, rdctants.
Ampholytic surfactants are also suitable for use in the detergent compositions
of the present invention. These su"~clants can be broadly described as aliphaticderivatives of secondary or tertiary amines, or aliphatic derivatives of
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23
heterocyclic secondary and tertiary amines in which the aliphatic radical can bestraight- or branched-chain. One of the aliphatic substituents contains at leastabout 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 December 30,
1975 at column 19, lines 18-35, for examples of alllpholytic surfactants.
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 ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in detergent compositions.
These surfactants can be broadly described as derivatives of secondary and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatives of quale,~,ary a"""o"ium, quaternary phosphonium or tertiary
sulfonium compounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
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 comprise from 0.2% to about 15%, preferably from about 1% to about
10% by weight of such zwillerio,)ic surfactants.
Semi-polar nonionic su-ractan~s are a special category of nonionic surfactants
which include water-soluble amine oxides containing one alkyl moiety of from
about 10 to about 18 carbon atoms and 2 moieties selected from the group
consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to
about 3 carbon atoms; water-solubl~ phosphine oxides contai"ing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from
the group consisting of alkyl groups and hydroxyalkyl groups contai"ing 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 deters~ent surfactants include the amine oxide surfactants
having the formula
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24
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 thereof; 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 su,ractants in particular include C10-C18 alkyl dimethyl
amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included therein, the detergent compositions of the present invention
typically comprise from 0.2% to about 1~%, ,~referably from about 1% to about
10% by weight of such semi-polar nonionic surfactants.
The detergent composition of the present invention may further
comprise a cosurfactant selected from the group of primary or tertiary amines.
Suitable primary amines for use herein include amines according to the formula
R1NH2 wherein R1 is a C6-C12 prere.dbly 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 ~,
prereral~ly 3. R1 alkyl chains may be straight or br~nc~,ed and may be
interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are n-alkyl amines.
Suitable amines for use herein may be selected 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 -C8 alkylchains or
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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,
preferably 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, preferably 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
- (CH2- CH--~D ~ H
where R5 is H or CH3 and x = 1-2.
Also prefer,ad are the amidoamines of the formula:
o
Rl--C--NH~ CH2 ~,--N~ R2 )2
wherein R1 is C6-C12 alkyl; n is 24,
prefer~bly n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine, 1-
hexylamine, 1 ~ecylamine, 1 -dodecylamine,C8-1 Ooxypropylamine, N coco 1-
3diaminopropane, coconutalkyldimethylamine, lauryldimethylamine, lauryl
bis(hydroxyethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2 moles
propoxylated, octyl amine 2 moles propoxylated, lauryl
~"~idopropyldimethylamine, C8-10 amidopropyldimethylamine and C10
amidopropyldi",etl ,ylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine,
1-octylamine, 1-decylamine, 1-dodecylamine. Fspeci~lly desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7
times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
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26
Conventional detergent enzymes
The detergent compositions of the present invention can further comprise
one or more enzymes which provide detergent performance and/or fabric care
benefits.
Said enzymes include enzymes selected from peroxidases, proteases, gluco-
amylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases,
pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases,
ligninases, pullulanases, tannases, pentosanases, malanases, 13-glucanases,
arabinosidases, hyaluronidase, chondroitinase, l~sc~-se or mixtures thereof.
A preferred combination is a detergent composition having cocktail of
conventional applicable enzymes like protease, amylase, lipase, cutinase and/or
cellulase in conjunction with one or more plant cell wall degrading enzymes.
Peroxidase enzymes are used in combination with oxygen sources, e.g.
percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes or pigments removed from
substrates during wash operations to other substrates in the wash solution.
Peroxid~se enzymes arë known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase. Peroxid~se-containing detergent compositions are disclosed, for
example, in PCT l~,terl,alional Application WO 89/099813, WO89109813 and in
European Patent application EP No. 91202882.6, filed on November 6, 1991 and
EP No. 96870013.8, filed February 20, 1996.
Other suitable oxidases are l~c~se enzyme using oxygen, hydrogen peroxide
as primary substrate.
rl efer, ed enhancers are 1 0-Phenothiazinepropionicacid (PPT), 10-
ethylphenothiazine-4-carboxylic acid (EPC), 1 0-plle,~oxa~inepropionic acid
(POP) and 1 0-methylphenoxazine (described in WO 94/1 2621). Sodium
percarbonate or perborate are preferred sources of hy-llogen peroxide.
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27
Said peroxidases are normally incorporated in the detergent composition
at levels hom 0.0001% to 2% of active enzyme by weight of the detergent
composition.
Other preferred enzymes that can be included in the detergent
compositions of the present invention include lipases. Suitable lipase enzymes
for detergent usage include those produced by microorganisms of the
Pseudomonas group, such as PseudG"~o,1as stutzeri ATCC 19.154, as disclosed
in British Patent 1,372,034. Suitable lipases include those 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 Pharmaceutical Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hereinafter referred to as "Amano-P". Other suitable commercial
lir~ses include Amano-CES, lipases ex Ch~omobacter viscosum, e.g.
Chromobacter vjscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co.,
- Tagata, Japan; Chromobacter viscosum lipases from U.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-Brocades) and LipolaseR and Lipolase UltraR(Novo) which have
found to be very effective when used in combination with the compositions of thepresent invention.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special
kind of lipase, namely lipases which do not require interfacial activation. Addition
of culinases to detergent cG,npositions have been described in e.g. WO-A-
88/09367 (Genencor).
The lir~ses andlor cutinases are normally incol~oraled in the detergent
coi,~position at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
Suitable prote~ses are the sl~btilisins which are obtained from particular
strains of B. subtilis and B. Iicheniformis (subtilisin BPN and BPN'). One suitahle
prolease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold as ESPERASE~) by Novo
Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme
and an~'ogo!~s enzymes is described in GB 1,243,784 to Novo. Other suitable
proteases include ALCALASE~9, DURAZYM~ and SAVIN~SE~) from Novo and
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28
MAXATASE~. MAXACAL~, PROPERASE~) and MAXAPEM~ (protein
engineered M~Y~C~I) from Gist-Brocades. Proteolytic enzymes also encompass
modified bacterial serine proteases, such as those described in European Patent
Application Serial Number 87 303761.8, filed April 28, 1987 (particularly pages
17, 24 and 98), and which is called herein "Protease B", and in European Patent
Application 199,404, Venegas, published October 29, 1986, which refers to a
modified bacterial serine protealytic enzyme which is called "Protease A" herein.
More preferred is what is called herein "Protease C", which is a variant of an
alkaline serine protease from Bacillus 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. Protease C is
described in EP 90915958:4, corresponding to WO 91/06637, Published May 16,
1991. Genetically modified variants, particularly of Protease C, are also included
herein. See also a high pH protease from Bacillus sp. NCIMB 40338 described in
WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or
more other enzymes, and a reversible protease inhibitor are described in WO
92103529 A to Novo. When desired, a protease having decreased adsorption
and increased hydrolysis is available as described in WO 95/07791 to Procter &
Gamble. A recol"binant trypsin-like protease for detergents suitable herein is
described in WO 94/25583 to Novo.
- In more detail, protease referred to as "Protease D" is a carbonyl
hydrolase variant having an amino acid sequence not found in nature, which is
derived from a precursor carbonyl hydrolase by substituting a different amino
acid for a plurality of amino acid residues at a pssition in said carbonyl hydrolase
equivalent to position +76, preferably also in combination with one or more
amino acid residue positions equivalent to those selected from the group
consisting of +99, +t01, +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 numbering of Bacillus
amyloliquefaciens subtilisin, as described in WO95/10591 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 described in patent applications
EP 251 446 and WO91/06637 and protease BLAP~19 Jesc~ibed in WO91/02792.
Protease enzyme may be incorporated into the co~,positions in accordarlce with
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29
the invention at a level of from 0.0001% to 2% active enzyme by weight of the
composition.
Amylases (a and/or 13) can be included for removal of carbohydrate-based
stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes
detergent compositions which incorporate mutant amylases. See also
WO94/18314, Genencor, published August 18, 1994 and W095/10603, Novo
Nordisk A/S, published April 20, 1995. Other amylases known for use in
detergent compositions include both a- and ,B-amylases. a-Amylases are known
in the art and include those disclosed in US Pat. no. 5,003,257; EP 252,666;
WOI91/00353; FR 2,676,456; EP 285,123; EP 525,610; EP 368,341; and British
Patent specification no. 1,296,839 (Novo). Other suitable amylase are stability-enhanced amylases including Purafact Ox AmR described in WO 94/18314,
published August 18l 1994; W096/05295, Genencor, published February 22,
1995 and amylase variants having additional modification in the immediate
parent available from Novo Nordisk A/S, disclosed in WO 95/10603, published
April 95. Examples of commercial a-amylases products are Termamyl~), Ban
(~) ,Fungamyl(~) and Duramyl~), all available from Novo Nordisk AIS Denmark.
W095/26397 describes other suitable amylases: a-amylases characterised by
having a specific activity at least 25% higher than the specific activity of
Ter,ndmyl(~) at a temperature range of 25~C to 55~C and at a pH value in the
range of 8 to 10, measured by the Ph~deb~s(~) a-amylase activity assay. Other
amylolytic enzymes with improved properties with respect to the activity level and
the combination of ll,er,nostability and a higher activity level are described in
W095/35382.
The above-mentioned enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal andyeastorigin. Origin can further be
mesophilic or exl~mopl,ilic (ps~ct)r~plliiic, psycl~rolrophic, ther",opl,ilic,
barophilic, alkalophilic, acidophilic, halophilic, etc. ). Purified or non-purified
forms of these enzymes may be used. Also included by definition, are mutants of
native enzymes. Mutants can be obtained e.g. by protein and/or genetic
engineering, chemical and/or physical modifications of native enzymes. Cor",non
practice as well is the expression of the enzyme via host organism in which the
genetic material responsible for the production of the enzyme has been cloned.
Said enzymes are normally incorporated in the detergent coi"position at levels
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from 0.0001% to 2% of active enzyme by weight of the detergent composition.
The enzymes can be added as separate single ingredients (prills, granulates,
stabiiized 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
oxidation scavengers are ethoxylated tetraethylene polyamines.
A range of enzyme materials 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 disrlssed in
U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes,
March 26, 1985. Enzyme ma~erials useful for liquid detergent formulations, and
their incorporation into such formulations, are clisclosed in U.S. 4,261,868, Hora
et al, April 14, 1981. 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 Bacillus, sp. AC13 giving proteases,
xylanases and cellulases, is described in WO 9401532 A to Novo.
Co/or care benefits
Technologies which provide a type of color care benefit can also be
includqd Examples of these technologies are metallo catalysts for color
maintenance. Such metallo catalysts are described in co-pending European
Patent Application No. 92870181.2.
The Bleaching agen~
The detergent comrositions of the present invention can further include
bleaching agents such as hydrogen peroxide, PB1, PB4 and percar~G~ ~ate with a
particle size of 400-800 microns. These bleaching agent components can
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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 component for use herein can be any of the
bleaching agents useful for detergent compositions including oxygen bleaches
as well as others known in the art. The bleaching agent suitable for the presentinvention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used encori,passes
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~-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are disclosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446,
European Patent Application 0,133,354 and U.S. Patent 4,412,934. Highly
prefer,ed bleaching agents also include 6-nonylamino~-oxoperoxycaproic acid
as described in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used enco",passes the
halogen bleaching agents. Examples of hypohalite bleaching agents, for
example, include trichloro isocyanuric acid and the sodium and pot~ssi~
dichloroisocyanurates and N-chloro and N-bromo alkane sulphonamides. Such
materials are normally added at 0.5-10% by weight of the finished product,
preferably 1-5% by weight.
The hyd~oge" peroxide releasing agents can be used in combination with
bleach activatnrs such as tetraacetylethylenediamine (TAED),
nonanoyloxybenzene-sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,~91) or
pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6-
aminocaproic acid (NACA-OBS, described in W094128106), 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 disclosed in Co-pending European Patent Application No. 91870207.7.
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Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
detergent compositions according to the invention are described in our co-
pending applications USSN 08/136,626, PCT/US95/07823, W095/27772,
W095127773, W095/27774 and W095127775.
The hydrogen peroxide may also be present by adding an enzymatic
system (i.e. an enzyme and a substrate therefore) which is capable of generatinghydrogen 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 compositions, include cobalt-
containing catalysts such as Pentaamine acetate cobalt(lll) salts and
manganese-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 comprising 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 utili~ed 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 materials can be
deposited upon the substrate during the washing process. Upon irradiation with
light, in the prese"ce of oxygen, such as by hanging clothes out to dry in the
daylight, the sulfonated zinc phthalocyanine is activated and, cor,se.~uently, the
suLs~,dle is bleached. P,e~r,ecl zinc phthalocyanine and a photoactivated
bleaching ~rocess are described in U.S. Patent 4,033,718. Typically, detergent
co",positions will contain about 0.025% to about 1.25%, by weight, of sulfonatedzinc phthalocyanine.
Builder system
The con~posilions accorJir,y to the present invention may further comprise a
builder system. Any conventional builder system is suitable for use herein
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including aluminosilicate materials, silicates, polycarboxylates7 alkyl- or alkenyl-
succinic acid and fatty acids, materials such as ethylenediamine tetraacetate,
diethylene triamine pentamethyleneacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine tetramethylene
phosphonic acid and diethylene triamine pentamethylenephosphonic acid.
Phosphate builders can also be used herein.
Suitable builders can be an inorganic ion exchange material, commonly
an inorganic hydrated aluminosilicate material, more particularly a hydrated
synthetic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS~
(Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate
(Na2Si2~5)
Suitable polycarboxylates co"laining one carboxy group include lactic
acid, glycolic acid and ether derivatives thereof as disclQserl in Belgian Patent
Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy
groups include the water-soluble salts of succinic acid, malonic acid,
(ethylenedioxy) diacetic acid, maleic acid, diglycollic acid, tartaric acid, tartronic
acid and fumaric acid, as well as the ether carboxylates described in German
Offenlegenschrift 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and
the sulfinyl c~, l oxylates described in Belgian Patent No. 840,623.
Polyc~r6Oxylates containing three carboxy groups include, in particular, water-
soluble cilra~es, aconitrates and citracGnates as well as succinale derivatives
such as the ~. bo~(ymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates desc,ibed in Netherlands Application 7205873, and
the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
desc~ibeJ in British Patent No. 1,387,447.
Polycarboxylates containing four carboxy groups include oxydisll~,;nates
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 sulfosuccina~e
derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S.Patent No. 3,936,448, and the sulfonated pyrolysed citrates described in BritishPatent No. 1,082,179, while polycarboxylates containing phosphone substituents
are disclosed in British Patent No. 1,439,000.
.
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Alicyclic and heterocyclic polycarboxylates include cyclopentane-
cis,cis,cis-tetracarboxylates, cyclopentadienide pentacarboxylates, 2,3,4,5-
tetrahydro-furan - cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan -cis -
dicarboxylates, 2,2,5,5-tetrahydrofuran - tet~acarboxylates, 1,2,3,4,5,6-hexane -
hexacar-boxylates and and carboxymethyl derivatives of polyhydric alcohols
such as sorbitol, mannitol and xylitol. Aromatic poly-carboxylates include mellitic
acid, pyromellitic acid and the phthalic acid derivatives disclosed in British
Patent No. 1,425,343.
Of the above, the preferred polycarboxylates are hydroxyca,boxylates
containing up to three carboxy groups per molecule, more particularly citrates.
Pre~r,ed 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~), and a water-soluble carboxylate chelating agent such
as citric acid. Preferred builder systems for use in liquid detergent compositions
of the present invention are soaps and polycarboxylates.
A suitable chelant for inclusion in the detergent compositions in
accordance with the invention is ethylenediamine-N,N'-clisuccinic acid (EDDS) orthe alkali metal, alkaline earth metal, ammonium, or substituted a"""onium saltsthereof, or mixtures thereof. rrefelled EDDS compounds are the free acid form
and the sodium or magnesium salt thereof. Examples of such preferreJ sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The magnesium
salts are the most ,,,rel~r,~d for inclusion in compositions in accordance with the
invention.
r~fer, ecJ 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 materials such as alkali metal
carbonates, bicarbonates, silicates, and organic materials such as the organic
phospl,onates, amino polyalkylene phosphonates and amino polycarboxylates.
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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-1,596,756. Examples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such copolymers having a molecular weight of from 20,000 to 70,000, especially
about 40,000.
Detergency builder salts are normally included 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 optional ingredient is a suds suppressor, exemplified by silicones,
and silica-silicone mixtures. Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in finely divided forms
exemplified by silica aerogels and xerogels and hydrophobic silicas of various
types. These materials can be incorporated as particulates in which the suds
suppressor is advantageously releasably incorporated in a water-soluble or
water-dispersible, stlhst~nlially non-surface-active detergent impermeable
carrier. Alternatively the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of the other components.
A preferred silicone suds co-,~tolling agent is djSCIQSed in Bartollota et al.
U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-
emulsifying silicone suds suppressors, described in German Patent Application
DTOS 2 646 126 published April 28, 1977. An example of such a compound is
DC-544, commercially available from Dow Corning, which is a siloxane~lycol
copolymer. Fspeci~lly pre~r,ed suds controlling agent are the suds suppressor
system c~,n~)lising a mixture of silicone oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-butyl-octanol which are commercially 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 preferred silicone suds controlling agents are described in Co-
pending European Patent application N~92201649.8. Said compositions can
. ,
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preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the
compositiorl.
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-morpholino-4-anilino-s-triazin~-
ylamino-stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin~-
ylamino)stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri-
azin~ ylamino)stilbene-2-sulphonate, disodi~lrn 4,4' -bis-(2-anilino4-(N-methyl-N-2-hydroxyethylamino)-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-anilino~-(1-methyl-2-hydroxyethylamino)-s-triazin~- ylami-
no)stilbene-2,2'disulphonate, sodium 2(stilbyl~"-(naphtho-1',2':4,5)-1,2,3 -
triazole-2"-sulphonate and 4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred
brighteners are the specific brighteners of copending European Patent
- application No. 95201943.8.
Other useful polymeric materials are the polyethylene glycols, particularly
those of molecular weight 1000-10000, more particularly 2000 to 8000 and most
preferably about 4000. These are used at levels of from 0.20% to 5% more
preferably from 0.25% to 2.5~h 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.
Soil release agents useful in compositions of the present invention are
conve,ltiGnally copolymers or terpolymers of terepl,tl)alic acid with ethylene
glycol and/or propylene glycol units in various arrangements. Examples of such
polymers are ~lisclQsed in the co,)"),o"ly assigned US Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272 033. A
particular prefer,ad polymer in accordance with EP-A-0 272 033 has the formula
(cH3(pEG)43)o~7s(poH)o 25~T-Po)2.8(T-pEG)o 4]T(
~t)0.25((PEG)43CH3)0.7~
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where PEG is -(OC2H4)O-,PO is (0C3H60) and T is (pcOC6H4C0).
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, "primarily", inthe 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 o~ ethylene
glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46% by weight of cJi",eli,yl
terepl,Ll,alic acid, about 16% by weight of propane -1.2 diol, about 10% by
weight ethylene glycol about 13% by weight of dimethyl sulfobenzoic acid and
about 15% by weight of sulfoisophthalic acid, and have a molecular weight of
about 3.000. The polyesters and their method of preparalion are described in
detail in EPA 311 342.
Is 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, ammonium sulfate, sodium sulphite or
polyethyleneimine at a levet above 0.1% by weight of total co"")osition, in the
formulas will provide improved through the wash stability of the detergent
enzymes. Compositions con~prising chlorine scavenger are described in the
European patent application 92870018.6 filed January 31, 1 992.
Alkoxylated polycarboxylates such as those prepared from polyacrylates
are useful herein to provide additional grease removal performance. Such
materials are described in WO 91/08281 and PCT 90101815 at p. 4 et seq.,
incorporated herein by reference. Chemically, these materials co",p, ise
polyacrylates having one ethoxy side~hain per every 7-8 acrylate units. The
side-chains are of the formula -(CH2CH20)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 molecnl~- weight can vary, but is
typically in the range of about 2000 to about 50,000. Such alkoxylated
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36
comprise a silicone/silica mixture in combination with fumed nonporous silica
such as AerosilR.
The suds suppressors described above are normally employed at levels
of from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1%
by weight.
Others
Other components used in detergent compositions may be employed,
such as soil-suspending agents, soil-release agents, optical brighteners,
abrasives, bactericides, tarnish inhibitors, coloring agents, andlor encapsulated
or non-enc~psul~ted perfumes.
Especially suitable encapsulating materials are water soluble c~psules
which consist of a matrix of polysaccharide and polyhydroxy compounds such as
described in GB 1,464,616.
Other suitable water soluble encapsulating materials comprise dextrins
derived from ungelatinized starch acid-esters of substituted dicarboxylic acids
such as described in US 3,455,838. These acid-ester dextrins are, preferably,
prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and
potato. Suitable examples of said enc~psul~ting materials include N-Lok
manufactured by National Starch. The N-Lok enc~psul~ting material consists of
a ",odiried maize starch and ~IUCOSe. The starch is modified by adding
monofunctional s~ Ihstih~ted groups such as octenyl succinic acid anhydride.
Antiredeposition and soil suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydtoxyethylcellulose, and homo- or co-polymeric polycarl,oxylic acids or their
salts. 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 methacrylic acid, the
maleic anhydride constituting at least 20 mole percent of the copolymer. These
materials are normally used at levels of from 0.5% to 10% by weight, more
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39
poiycarboxylates can comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
Soffenjng agents
Fabric softening agents can also be inco"~orated into laundry detergent
compositions in accordance with the present invention. These agents may be
inorganic or organic in type. Inorganic softening agents are exemplified by the
smectite clays disclosed in GB-A-1 400 898 and in USP 5,019,292. Organic
fabric softening agents include the water insoluble tertiary amines as disclosedin GB-A1 514 276 and EP-B0 011 340 and their combination 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 amides as disclosed in EP-B-0 242 919. Other useful
organic ingredients of fabric softening systems include high molecular weight
polyethylene oxide materials as disclosed in EP-A-0 299 575 and 0 313 146.
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 s~lei,i"g
agents such as the water-inscluhle tertiary amines or dilong chain amide
materials are incorporated at levels of from 0.5% to 5% by weight, normally from1% to 3% by weight whilst the high mol~cul~r weight polyethylene oxide
materials and the water soluble cationic materials are added at levels of from
0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are
normally added to the spray dried po,lion of the composition, although in some
instances it may be more convenient to add them as a dry mixed particu'~te, 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 radicals separated from each other by not more than two carbon atoms.
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Polymers of this type are disclosed in GB-A-1,596,756. Examples of such salts
are polyacrylates of MW 2000-5000 and their copolymers with maleic anhydride,
such copolymers having a molecular weight of from 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 compositions 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, pre~erably 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 numerical 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. Bor!yl,elly and C.A.
Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, (1950). This lime
soap dispersion test method is widely used by practitioners in this art field being
referred to, for example, 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 cleposils
formed by 0.025g of sodium oleate in 30ml of water of 333ppm CaCo3
(Ca:Mg=3:2) equivalent ha,dl,ess.
S~"ractar,ts having good lime soap peptiser cap~l~ility 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 ~i,nelhyl 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
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41
ethoxylation of either 12 (LSDP=6) or 30, sold under the tradenames Lutensol
A012 and Lutensol A030 respectively, by BASF GmbH.
Polymeric lime soap peptisers suitable for use herein are described in the
article by M.K. Nagarajan, W.F. Masler, to be found in Cosmetics and Toiletries,volume 104, pages 71-73, (1989).
Hydrophobic bleaches such as 4-[N-octanoyl~-aminohexanoyl]ben~ene
sulfonate, 4-[N-nonanoyl~-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl~-
aminohexanoyl]benzene sulfonate and mixtures thereof; and nonanoyloxy
benzene sulfonate together with hydrophilic / hydrophobic bleach formulations
can also be used as lime soap peptisers compounds.
Dye transfer inhibition
The detergent compositions of the present invention can also include
compounds for inhibiting dye transfer 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
comprise from 0.001% to 10 %, preferably from 0.01% to 2%, more preferably
from 0.0~% to 1% by weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transrer inhibiting agents are normally incorporated into detergent
co",l-ositions 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,
polyvinylpyrrolidone polymers, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
Addition of such polymers also enhances the performance of the enzymes
acco,di"g the invention.
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42
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use contain units having the
following structure formula:
p
I
(I) Ax
I
R
wherein P is a polymerisable 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
combination of both.
O 00
Il 11 11
- AisNC, CO,C,-O-,-S-,-N-;xisOor1;
R are aliphatic, ethoxylated aliphatics, aromatic, heterocyclic or
alicyclic groups or any combination 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:
O O
(R1 )x -N- (R2)y =N- (R1 )x
I
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aro,natic, heterocyclic or alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and
wherein the nil,oyel- of the N-O group can be attached or wherein the
ni~o~en of the N-O group forms part of these groups.
The N-O group can be part of the polymerisable unit (P) or can be
attached to the polymeric backbone or a combination of both.
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Suitable polyamine N-oxides wherein the N-O group forms part of the
polymerisable unit comprise polyamine N-oxides wherein R is selected 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 comprises 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 attached to the polymerisable unit.
Praferled 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 nitrogen of the N-0 functional group is part of said R group.
Examples of these classes are polyamine oxides wherein R is a heterocyclic
compound such as pyrridine, pyrrole, imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the polyamine oxides having
the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groupswherein the nitrogen of the N-0 functional group is attached to said R groups.
Examples of these r~sses are polyamine oxides wherein R groups can be
aromatic such as phenyl.
Any polymer bachLone can be used as long as the amine oxide polymer
formed is water-soluble and has dye transfer inhibiling 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 present in the polyamine oxide polymer can be varied by
ap~.rop, iale copolymerization or by appropriate degree of N-oxidation.
Preferably, the ratio of amine to amine N-oxide is from 2:3 to 1:1000000. More
preferably from 1:4 to 1:1000000, most preferably from 1:7 to 1:1000000. The
polymers of the present invention actually e~ ,cG.,.pass random or block
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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 obtained in almost any degree of polymerisation.
The degree of polymerisation 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
1000000; preferably from 1 000 to 50000 more prererably from 2 000 to
30 000 most pre~erably from 3 000 to 20 000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole
The N-vinyli~"ida~ole N-vinylpyrrolidone polymers used in the present
invention have an average molecular weight range from 5000-1 000000
preferably from 5 000-200 000.
Highly preferred polymers for use in detergent compositions accordi"g to
the present invention comprise 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
preferably from 10 000 to 20 000.
The average molec~ r weight range was deter~ined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113"Modern
M~thods of Polymer Characterization".
Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers have an
average moleclJIar weight range from 5 000 to S0 000; more preferably from
8 000 to 30 000; most preferably from 10 000 to 20 000.
The N-vinylimidazole N-vinylpyrrolidone copolymers characterized by
having said average molecu~a weight range provide excellent dye lranster
inhibiting pr~,pe,lies while not adversely affecting the cleaning pe,rorl"ance of
detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has
a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2 more
~referdbly from 0.8 to 0.3 most preferably from 0.6 to 0.4 .
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c) Polyvinylpyrrolidone
The detergent compositions of the present invention may also utilize
polyvinylpyrrolidone ("PVP") having 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
51~~~ to about 15,000. Suitable polyvinylpyrrolidones are coi"ll,ercially vailable
from ISP Corporation, New York, NY and ~lor,l~eal, 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~0 (average molecular weight of 160,000),
and PVP K-90 (average molecular weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF CooperaliGn
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~olidone:
The detergent compositions of the present invention may also utilize
polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about 2,500 to
about 400,000, prefsr~bly from about 5,000 to about 200,000, more pre~erably
from about 5,000 to about 50,000, and most preferably from about 5,000 to about
1 5,000.
e) Polyvinylimidazole:
The ~Jeter~e~)t co",positions of the present invention may also utilize
polyvinylimidazole as polymeric dye transfer inhibiting agent. Said
polyvinylimidazoles have an average from about 2,500 to about 400,000,
l~referably from about 5~000 to about 200,000, more preferal)ly from about 5,000to about 50,000, and most preferably from about 5,000 to about 15,000.
.
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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
described 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-dimensional rigid structure, which can entrap dyes in the pores
formed by the three-dimensional structure. In another embodiment, the cross-
linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-pending patent
application 94870213.9
Method of washinq
The compositions of the invention may be used in essentially any washing
or cleaning methods, including soaking methods, pretreatment methods and
methods with rinsing steps for which a separate rinse aid composition may be
added.
The process described herein comprises contacting fabrics with a
laundering solution in the usual manner and exemplified 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 5~C to95~C, espesi~"y between 10~C and 60~C. The pH of the treatment solution is
preferably from 7 to 11.
The following 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 detergent compositions, the enzymes levels are expressed by pure
enzyme by weight of the total composition and unless otherwise specified, the
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detergent ingredients are expressed by weight of the total compositions. The
abbreviated component identifications therein have the following meanings:
LAS : Sodium linear C12 alkyl benzene 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
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.
TFM : 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 Chemical CO.
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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 ~m and 900~1m.
Bicarbo"ate : Anhydrous sodium bicarbonate with a particle size
between 400 ~m and 1 200~m.
STPP : Anhydrous sodium tripolyphosphate
MA/M : Copolymer of 1:4 maleic/acrylic acid average
molecular weight about 80 000
Polyacrylate : Polyacrylate homopolymer with an average molecular
weight of 8 000 sold under the tradename PA30 by
BASF GmbH
Zeolite A : Hydrated Sodium Aluminosili~te of formula
Na12(A1~2Si~2)12. 27H20 having a primary particle
size in the range from 0.1 to 10 micrometers
Citrate : Tri-sodium citrate dihydrate of activity 86 4% with a
particle size distribution between 425 ~m and 850 llm.
Citric : Anhydrous citric acid
PB1 : Anhydrous sodium perborate monohydrate bleach
e,llpi,ical formula NaBO2.H2O2
PB4 : Anhydrous sodium perborate tetrahydrate
PercarL,o"ate : Anhydrous sodium percarbonate bleach of empirical
formula 2Na2CO3.3H2O2
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TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
Photoactivated : Sulfonated zinc phtlocyanine encapsulated in dextrin
Bleach soluble polymer.
Protease : Proteolytic enzyme sold under the tradename
Savinase, Alc~l~se, Durazym by Novo Nordisk AIS,
Maxacal, Maxapem sold by Gist-Brocades and
proteases described in patents WO91/06637 andlor
WO95/10591 and/or EP 251 446.
Amylase : Amylolytic enzyme sold under the tradename Purafact
Ox AmR ~Jesc, iL,ed in WO 94/18314, W096/05295
sold by Genencor; Termamyl~, Fungamyl~) and
Duramyl~), all available from Novo Nordisk A/S and
those described in WO95126397.
Lipase : Lipolytic enzyme sold under the tradename Lipolase,
Lipolase Ultra by Novo Nordisk A/S
Cellulase : Cellulytic enzyme sold under the tradename
Carezyme, Celluzyme and/or Endol~se by Novo
Nordisk A/S.
Antibody : Rabbit anti-Carezyme antibody available from Novo
Nordisk A/S at a dilution 1: 1000
Batch #: Ra17-11195 (anti-Carezyme PPC 3404).
CMC : Sodiumcarboxymethyl cellulose.
HEDP : 1,1 -hydroxyetharie diphosphonic acid.
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~iO
DETPMP Diethylene triamine penta (methylene phosphonic
acid), marketed by Monsanto 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.
Brightener 1 : Disodium4,4'-bis(2-sulphostyryl)biphenyl.
Brightener 2 : Disodium 4,4'-bis(4-anilino~-morpholino-1.3.5-triazin-
2-yl) stilbene-2:2'-disulfonate.
Silicone antifoam : Polydimethylsiloxane 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 ~pped esters with oxyethylene oxy
and terephtaloyl backbone.
SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short
block polymer.
Sulphate : Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethy~ene oxide
PEG : Polyethyleneglycol.
Encapsulated : Insoluble fragrance delivery technology utilising
perfume particles zeolite 1 3x, perfume and a dextrose/glycerin
agglomerating binder.
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Example 1:
Antibodies' production
Chickens were injected in the breast muscle with 1 ml of a 1 mg/ml Carezyme~)
emulsion. The Carezyme emulsion was prepared with a Freunds completed
adjuvants (Freund and McDermott, 1942; Freund 1956) by intensively mixing an
equal amount of the Carezyme solution (2 mg/ml) Freunds complete 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)~lracRol~ of the antibodies from the eg~s yolks was done
accor~Jing to the Polson extraction method as described in Immunological
Investi~tion 19, 1990, pp 253-258.
Carezyme enzymatic inactivation
A Carezyme stock solution was prepared in a Tris Buffer (5x10-2M Tris, 25 mM
NaCI, pH=8) and three Tris buffers (O.OSM KH2P04) were prepared at a pH of
resr~ctively to 7, 8 and 9.5. The Carezyme solution was diluted in the Tris buffer
to a final concel,l(ation of 0.6 CEVU/ml.
The carezyme preparalio,l was ina~ ted with the antibody solution (0.18 mg/ml)
during 60 minutes at 30~C, 40~C and 50~C.
The resict~ Carezyme activity was measured according to the Illethod
desaibed by Novo Nordisk publication AF253. Within 5 minutes, the enzymatic
activity of Carezymo was completely blocked as shown in the table below.
Residual Carezyme(E9 activity
(in % after 5 minutes)
pH (Tris buffer) T=30~C T=40~C T=50~C
7 2 3 3
8 2 6 3
9.5 3 6 4
.. . . . .. . _
. . .
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Example 2
The Carezyme(~)-directed antibodies were prepared according to the method
described in example 1. The Carezyme enzymatic deactivation was measured
into commercially available detergent soMtions comprising Ariel liquid (0.8% in
city water, pH 8.5) and Ariel Color Futur (0.8% in city water, pH 9.5).
In example A, the same procedure as illustrated in example 1 was followed
wherein the ina Ih~tion solution was added to the detergent solution.
In example B, the detergent sohltion already contained Carezyme at an initial
level of 0.6 CEVUlml and the antibody was subsequently thereto added.
As shown in the table below, the Carezyme enzymatic activity in a detergenl
sol~tion has been completely blocked by the additio-, of a Carezyme-directed
- antibody in both instances.
Residual Car~ ."eactivity
(in % after 5 minutes)
Mix;nq sequence Ariel liquid solution Ariel Color Solution
A 3 7
B 4 3
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Example 3
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 18.1 18.1 18.1 18.1 18.1 18.1
Carbonate 13.0 13.0 13.0 27.0 27.0 27.0
Silicate 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
H E D P 0.3 0.3 0.3 0.3 0.3 0.3
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009
Cellulase 0.0006 0.0006 0.008 0.03 0.005 0.05
Antibody 0.25 5 10E-1 1 10E-2 0.5
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
Photoa~;~i./ated 15 15 15 15 15 15
bleach (ppm)
Brightener 1 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone anlir~din 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
. .
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54
Example 4
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/citricacid (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 0.02 0.1
Protease 0.0026 0.0005 0.045
Lipase 0.003 0.003 0.003
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 bleach 15 ppm 27 ppm 27 ppm
(ppm)
Brightener 1 0.08 0.19 0.19
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Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.3
particles
Silicone antifoam 0.5 2.4 2.4
Minors/misc to 100%
ExamPie S
The following detergent formulations, according to the present invention were
prepared, where I is a phosphorus-containing detergent composition, ll is a
zeolite-containing detergent composition and lll is a compact detergent
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
Silicate 7.0 3.0 3.0
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
C45E7 2.5 2.5 2.0
C25E3 2.5 2.5 2.0
Silicone ar,lirod.,~ 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 0
TAED 3.0 3.0 1.0
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Photoactivated bleach 0.02 0.02 0.02
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.002 0.003 0.001
Cellulase 0.05 0.005 0 0005
Antibody 1 1 OE-1 1 OE-1
Dry mixed sodiumsulfate 3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
Example 6
The following nil bleach-containing detergent formulations of particular use in the
washing of colored clothing, according to the present invention were prepared:
Blown Powder
Zeolite A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DETPMP 0.4 0.5
CMC 0.4 0.4
MA/AA 4.0 4.0
~gglomerates
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
MAIAA - - 2.0
Carbonate 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
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Dry additives
MA/AA - - 3 ~
NaSKS-6 - - 12.0
Citrate 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
Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase 0.006 0.006 0.006
Antibody 1 0.05 0.01
Silicone anliroar" 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 9.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Misce"-neous)
Density (g/litre) 700 700 700
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Example 7
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
Bicarbonate - 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 0.026 0.026
Amylase 0.007 0.004 - 0.002
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0005 0.05 0.005
Antibody 0.003 0.001 1 0.01
Photoactivated 70ppm 45ppm - 1 Oppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0
NOBS 2.0 1.0
Balance (Moisture 100 100 100 100
and Miscell~neous)
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Example 8
The following detergent 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/M 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
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0 3.2
Dry additives
PVPVIIPVNO 0.5 0.5 0.5
Antibody 0.005 0.005 0.005 0.005
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0.0002 0.001 0.0002 0.001
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
Miscellaneous)
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Example 9
The following high density and bleach-containing detergent formulations,
according to the present invention were prepared:
11 11
Blown Powder
Zeolite A 15.0 15.0 15.0
Sodium sulfate 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 0.4 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
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Antibody 0.1 0.1 0.1
Protease 0.01 0.01 0.01
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Lipase 0.009 0.009 0.009
Amylase 0.005 0.005 0.005
Cellulase 0.002 0.0006 0.002
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
. ~ . .....
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Example 10
The following high density detergent formulations, according to the present
invention were prepared:
ll
Ag~lomerate
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 50
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
P~r~r~onate 20.0 20.0
SRP 1 0.3 0.3
Antibody 0. 1
Protease 0.014 0.014
Lipase 0.009 0.009
Cell~ se 0.001 0.0006
Arnylase 0.005 0.005
Silicone ~ Itiroa~ 5.0 5.0
Bri$~h~e"er 1 0.2 0.2
Brightener 2 0.2
Balance (Moisture and 100 100
Miscellaneous)
Density (g/litre) 850 850
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Example 1 1
The following granular detergent formulations, according 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 di,netl,yl 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
MA/M - - 0 9 0 9
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
Antibody 1 0.01 0.005 0.01 0.0001
Protease 0.007 0.007 0.007 0.007 0.007
Amylase - 0.004 0.004 0.004 0.004
Lipase 0.003 0.003 0.003
Cellulase 0.001 0.001 0.001 0.001 0.001
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~rated bleach 45 50 ppm 15 45 ppm 42 ppm
ppm ppm
Bri~htener 1 0.05 - 0.04 0.04 0.0
Briyhle. .er 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to 100%
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Example 12
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 4.0
C25E7 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
acids
Citric 2.0 3.0 1.0 1.~ 1.0 1.0 1.0 1.0
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 - - 9.0 9.0
Amine
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
SRP 2 0.3 - 0.3 0.1 - - 0.2 0.1
PVNO - - - - - - - 0.10
Antibody 0.01 0.005 0.1 0.02 1 0.05 0.01 0.000
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Protease. 005 . 005 . 004 . 003 0. 08 . 005 . 003 . 006
Lipase - .002 - .001 - - 003 003
Amylase .002 .002 .005 .004 .002 .008 .005 .005
Cellulase .005 .002 .005 0.000 .002 .005 0.000 0.000
4 3
Boric acid 0.1 0.2 - 2.0 1.0 1.5 Z.5 2.5
Na formate - - 1.0
Ca chloride - 0.015 - 0.01
Bentonite clay - - - - 4.0 4.0
Suspending clay - - - - 0.6 0.3
SD3
Balance Moisture and Miscellaneous: Up to 100%
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66
Example 13
Granular fabric cleaning compositions which provide "softening through the
wash" capability were prepared in accord with the present invention:
ll
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~ - 11.0
Zeolite A 15.0 15.0
MA/M 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 0.01 0.5
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0 03 0.005
Cellul~se 0.001 0.05
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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ExamPIe 14
The following rinse added fabric softener composition was prepared in
accord with the present invention:
Softener active 20.0
Antibody 0.003
Amylase o.oo1
Cellulase 0.001
HCL ~~
A"liroa,n agent 0.01
Blue dye 25ppm
CaCI2 0.20
Perfume o.go
Water / minors Up to 100%
ExamPle 15
The following fabric softener composition was prepared in accord with the
present invention:
DEQA 2.6 19.0
SDASA - - 70.0
Stearic acid of IV=0 0.3
Neodol 45-13 - - 13.0
Hydrochloride acid 0.02 0.02
Ethanol - - 1.0
PEG - 0.6
Antibody 0.1 1 0.0003
Cellul~se 0.05 0.003 0.001
Perfume 1.0 1.0 0.75
Di~erai!yl Succinate - - 0.38
Silicone anliro~,n 0.01 0.01
Electrolyte - 600ppm
Dye 1 OOppm 50ppm 0.01
Water and minors 100% 100%
-
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Example 16
Syndet bar fabric cleaning compositions were prepared in accord with the
present invention:
11 111 lV
C26 AS 20.0 20.0 20.0 20.0
CFAA 5.0 5.0 5.0 50
LAS (C1 1-13) 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 7.0 7.0 7.0 7.0
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
Coconutmonethanolamide 5.0 5.0 5.0 5.0
Antibody 0.01 0.05 0.07 0.1
Cellulase 0.001 0.02 0.03 0.05
Amylase 0.01 0.02 0.01 0.01
Protease 0.3 0.5 0.05
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MsSO4 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filler~: balance to 100%
~Can be selected from convenient materials such as CaC03, talc, clay (Kaolinite,Sroectile), silicates, and the like.
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Example 17
Detergent additives were prepared in accord with the present invention:
ll lll
LAS - - 5
STPP 30 30
Zeolite A 35
PB1 20 20 15
TAED 10 10 8
Prutease - - 0.3
ce~ se o. 1 - o~ 1
Antibody 1 OE I 1 1 OE~1 1 OEO
