Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING ANTIBODY
CONTROLLED AMYLOLYTIC ACTIVITY
FIELD of the INVENTION
The present invention relates to laundry detergent compositions
comprising an amylase and amylase-directed antibody in order to provide
excellent cleaning performance and fabric care performance.
BACKGROUND of the INVENTION
An important part of the system which protects vertebrates against
infections by bacteria and viruses is the humoral immune system. Specialised
cells present in bone mdr,uu~ Iymphoid tissues and blood, produce
immunoglobulins (antibody) which appear in response to the introduction of a
micro- or macromolecule foreign to that body and bind said body-foreign
structure initiating its destruction. Such a body-foreign molecule is called an
antigen. The antibody is directed against the antigenic determinant or hapten ofthe anti~e,- e.g. an amino acid sequence, parts of oligosaccharides,
pOi~dCCI ,arides, I".~polysaccharides, glycoproteins, lipoproteins, lipoteichoinic
aclds.
The specific anlil,od;es generated in this manner can combine with the
antigen which clicited their formation to form an antigen-antibody complex.
Antibody mo'ecules have binding sites that are very specific for and
comple,..enlary to the structural features of the antigen that induced their
for,.,a~iGn.
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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 do,llai.-s 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 treatment compositions for topical application contail ling
microc~rsules 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 fragments having specificity for human polymorphic epithelial mucin to
be used in the treatment or diagnosis of cancer. The use of Epstein-Barr virus
specific polypeplides for the production of antibodies and the diagnostic and
treatment of said dise~se is disclosed in W094/06470.
Oral compositions comprising antibodies as anti-caries or peri~dGntal
dise~ses tl~dllllent have been extensively desc~i6ed in WO95/01155,
WO95/00110, WO95/10612, EP 140 498, GB 2 151 923, GB 2 176 400, GB 2
167 299, DE 4324859, US 5 401 723 and EP 280 576.
EP 673 683 and EP 542 309 disclose hair cosmelic cGIllposiliGl)s
cGI)tainill9 an a.,li6O~ly to hair or hair extract, obtained from egg yolk or poultry
immunised with the hair or hair extract and a polymer emulsion to provide
reduced hair damage, softness, moistened feel and smoothness, said
composition being adsGrbed only onto a specified part of the hair.
Compositions containing antagonists (tyrphostins or antibodies) against
epidermal and tra"sr~r-"ing growth factors, suitable for use in l,eal",ent of acne
are described in W095/24896.
The use of antibodies in the overall detergency c~i ,lexl has been
suggested in Unilever Researchprijs "Molecule zoekt partner" 1992 wherein
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modified antibodies directed to specific stains are proposed to be used in
bleaching process.
The production of antibodies by hyperimmunisation of mammal such as a
cow with a vaccine derived from E. coli bacteria is described in EP 102 831. EP
400 569 discloses a method for preparing vaccine composition for dental caries
in nasal drops comprising an antigen produced by integrating a protein antigen-
expressing gene into the cl,ron,osomal gene of a streptococcus mutants GS-5
strain. WO94/25591 disclQses the production of antibodies or functionalised
fragments thereof derived from heavy chain immunoglobulins of camelidae.
Deteryen~ compositions include nowadays a complex combination of
active ingredients which fulfill certain specific needs: a surfactant system,
enzymes providing cleaning and fabric care benefits, bleaching agents, a buildersystem, suds suppressors, soil-suspending agents, soil-release agents, optical
brighteners, softening agents, dispersants, dye l~ansfer inhibition compounds,
abrasives, bactericides, perfumes, and their overall perfo".,ance has indeed
improved over the years.
In particular, current laundry detergent formulations generally include
detergent enzymes and more specifically amylases.
However, overexposure of the substrate to the amylolytic activity and/or
lldnsfer of the amylolytic activity to the post mainwash part of the washing cycl
such as rinse, spinning and/or drying steps can lead to unwanted effects.
"Resi~llal or transf~rr~u amylolytic activity will interfere negatively with the post
mainwash starch l~ealment of the washed fabrics. Starch can indeed be applied
e.g. during a rinse cycle or prior to ironing as a fabric care and/or ease of ironing
agent.
It has now been surprisingly found that the application of antibodies raised
~ against amylase enzyme prevents the occurrence of undesirable residual
amylolytic activity while maintaining optimal enzyme pe, ru"~,ance for stain
removal and cleaning. The amylolytic activity can be fully controlled during thecleaning process so that the negative effects can now be avoided.
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It is therefore an object of the present invention to provide an amylase-
containing- laundry detergent composition delivering excellent cleaning
performance such as stain and/or soil removal dingy cleaning while not
negatively interfering with any starch post mainwash treatment of the fabrics.
The above need has been met by specific laundry detergent compositions
comprising an amylase and an antibody directed to said amylolytic enzyme.
SUMMARY of the INVENTION
The present invention relates to laundry detergent compositions
comprising an amylase enzyme and an antibody raised against the amylolytic
enzyme in order to provide excellent cleaning performance and fabric care
perfo,~"ance.
DETAILED DESCRIPTION of the INVENTION
ANTIBODY
An essential ~le. "ent of the detergent compositions of the present
invention is an a"liL,o-ly.
The immunoglobulins are classified into 5 cl?sses r~spe~;ti-/ely: IgM IgG
IgA IgD and IgE. r,~ftr,ed types of immunoglobulins are IgG and IgA. Secretory
slgA which are found into human exc,t:ted body fluids such as milk saliva
,~:spiraloly and intealinal fluids are especially designed to survive in said
secretions they have enhanced binding characteristics and are resistant to
proteolytic hydrolysis.
Antihodies which may be monoclonal or polyclonal or an antibody
hay",ent may be generated by techniques conventional in the art for example
by using r~cor"binant DNA techniques allowing to produce antibodies variants
with new properties: reduced immunogenecity enhanced affinity altered size ...
Specific binding may also be used. Preferred for the purpose of the present
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invention is a monoclonal antibody, more preferred is a fragment thereof. These
fragments may be similarly generated by conventional techniques such as
enzymatic digestion by papain or pepsin, or using recombinant DNA techniques.
Antibody fragments may also be generdled by conventional recombinant DNA
techniques. Antihodies and antibodies' fragments may be humanised, such as
described in Meded. - Fac. Landbouwkd. Toegepast Biol. Wet. (Univ. Gent)
(1995), 60(4a, Forum forApplied Biotechnology, 1995, Part 1), 2057-63.
Heavy and light chains are indeed composed of constant and variable
domains. In the organisms producing immunoglobulins in their natural state the
constant domains are very important for a number of functions, but for many
applications in industrial processes and products their variable domains are
surficienl. Consequently many methods have been described to produce
antibody fragments.
Antibody fragments which are used may be a Fab, a ~v, a scFv or any
other r,agr"ent having similar binding properties. Preferred routes to anlil,od;es
frag"~enl:~ are through recombinant DNA technology, so that the fragment is
expressed by a genetically transformed organism.
Antibodies and antibody r dy",enl~ produced by ,~comb..)al1t DNA
techncl~y~ do not need to be identical to fragment of antibodies produced in
vertebrates, having nevertheless the same binding properties evaluated by their
Km, Ki and Kcat. For i~,~tance they may include sequences of amino acids and/or
glycosyl~lions which differ from those found in anlibodies produced in other
ways, es,)e~ lly sequences at the end of r,d~ "ents. Somewhat analogously,
antibody r,ag",ents produced through recombinant DNA technology may include
extra amino acid sequences at their termini which have no counterpart in
antibodies produced in other ways.
A related possibility is that a binding agent for use in this invention is a
natural or sy(lll,elic polymer which mimics the speciric binding activity of a natural
ai llil,ody's complementary region(s). Such a polymer is for exarn~le a
polypeptide or a polymer imprinting (Angew. Chem. Int. Ed. Engl. 1995, 34,
1812-1832).
,
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The usual method for the production of antibodies may be adopted in
immunising mammals or poultry with the corresponding antigens. As mammals to
be immunised, mice, rabbits, goats, sheep, horses, cows, etc. may be used. The
antibody (immunoglobulin fraction) may be separated from the antiserum, the
milk or the eggs according to the ordinary antibody purirlcalion method including
salting-out method, Polson exl,dction, gel-fill,dliG" chro,l,alography, ion-
exchange chrollldlo$~ldphy, afffinity chrolnalography and the like, the salting-out
method using ammonium sulfate to produce the precipitates, followed by
dialysing the precipitates against physi~logic~l saline to obtain the purified
precipitates as the antibody.
Plants are also capable of synthesising and assembling every kind of
anlibody molecule and allow a large scale of production of antibodies as
described in Tibtech. Dec 1995, Vol 13, pp ~22-527; Plant Mol. Biol., 26, pp
1701-1710, 1994 and Biotech"ol. proj. 1991, 7, pp 455461 and in US patent 5,
202,422. Antibodies can also be pro~luced into microoryal,i3."s such as F
coli or S. cerevisiae via biofermentation process as illusl,aled in the EP patent
667 394.
Techniques for the production of antibody 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 WO94/25591.
The drawbacks due to prcla.,ged activity of the enzyme can be avoided by
an effective control of the enzymatic activity trough the introduction of the
specifically cGr,t:s~,onding a,ltiL,oJy. Such antibodies can be either polyclonal -
directed to the whole enzyme structure - or monoclonal - dir~t~J to specific
epitopes of the enzyme activity controlling regions of the enzyme structure.
Antibodies raised against specific enzyme can effectively deactivate the enzyme
by the antibody-antigen binding in or very near the active site. The formation of
such col-lplex Ieads to the enzyme deactivation and could be exl iained by the
distollioll of the 3-di",ensional structure and/or steric hindrance at the subsl~dle
cleft. The deactivation of the enzyme can also be achieved by the precipitation of
the co,nplex antibody-antigen from the washing solution. Due to very high
specificity and efficiency of the antibody-antigen interaction, no other detergent
active is thereby affected.
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The amylase-directed antibodies are preferably included into the detergent
compositions of the present invention at a level of from 10E-6% to 10E+1% by
weight of total composition. In some instances, antibodies raised against a
specific amylase have the capability of binding other amylases of high structural
similarity, providing cross-reactivity. Typically, a m~lecul~r ratio of amylase-directed antibody to amylase will be of 100:1 or lower, preferably of 50:1 or lower.
For monoclonal antibodies or fragments thereof, the molecular ratio of amylase-
directed antibody to amylase will be generally of 50:1 or lower, preferably of 20:1
or lower.
The antibodies raised against the amylase are released in the wash
solution after a lag-period allowing the amylase to deliver excellent pe,rur",ance
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
forrn of the antibody-containing release agent is adapted to the physical form of
the co"~spo"d;. ,~ detergent or additive.
For granular and powder detergent and cleaning products, the a"~ odies
and release agents can be contained in a granulate. Said antibody granulate can
suitably contain various granulation aids, binders, fillers, plaslic;~ers, 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, polyvinylpyl ,olidGne, PVA, PEG, salts (e.g. sodiu
sulfate, calcium sulfate), titanium dioxide, talc, clays (kaolin or bentonite)and
nonionic sulra~;t;~nt~. Other ",at~r;als of relevance for incorporation in the
granulate are described in EP 304 331.
The release agent may be, for example, a cG~lillg. Said coating protects
said granulates in the wash environment for a certain period of time. The cGdling
will normally be applied to said granulates in an amount in the range of 1% to
50% by weight (calculated on the basis of the weight of the uncoated, dry
granulate), pref~:rably in the range of 5 % to 40 % by weight. The amount of
coating to be applied to said granulates will depend to a considerable extent onthe nature and composition of the desired coating, and to the kind of p,ote~,tion
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said coating should offer to said granulates. For example, the thickness of saidcoating or a multi-layered coating applied onto any of the above granulates may
determine the period in which the content of said granulates is released. A
possible multi-layered coating may be a coating in which, for example, a fast
releasc 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
the use thereof. Thus, for example, when a preparation of the invention is to beintroduced into a washing liquor co"tai"ing a washing detergent (normally
comprising, e.g. one or more types of surfactants), the coali"g should be one
which ensures the l~,lea3e of the cor)tents of said granulates from the release
agent when it is introduced into the washing medium.
Preferred release coating are coalil-gs which are sul~sla,llia'ly insDluble in
water. Rele~se coatings which are appropriate in washing media may suitably
comprise substances selected from the following: cellulose and celhll~se
derivatives, PVA, PVP, tallow; hydrogenated tallow; partially hydrolyzed tallow;fatty acids and fatiy alcohols of natural and sy"tl,~lic origin; long-chain fatty acid
mono-, di- and l~iester~ of glycerol (e.g. glycerol monostearate); ethoxylated fatty
alcohols; l~texes; hydrocarbons of melting point in the range of 50-80~C; and
waxes. Melt-codling agents are a preferred class of fast or slow release coatingagents which can be used without dilution with water. Reference may be made to
Controlled Rele~se Systems: Fab,icatiGn Technology, Vol. 1, CRC Press, 1988,
for further i"~or",dlion on slow release coating.
CGdtings may suitably further co"~,urise substances such as clays (e.g. kaolin),titanium dioxide, piglllel)ls, salts (such as calcium carbonate) and the like. The
person skilled in the art will be aware of further codling co"sliluents of relevance
in the present invention.
In liquid detergent compositions, the antibody can be incorporated as a
dispersion of particles containing in addition to the antibody, a release agent. The
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antibody can be present in a liquid or solid form. Suitable particles consist of a
porous hydrophobic material (e.g. silica with an average pore diameter of 500
Angstrom or higher) containing into the pores a solution of antibodies and a
surfactant as described in EP 583 512 of Surutzidis A. et al.
The release agent might be a coating which protects said particles in the wash
cycle for a certain period of time. The coating is preferably a hydrophobic coating
material such as a hydrophibic liquid polymer. Said polymer can be an organo
polysiloxane oil, alternatively a high olecula weight hydrocarbon or water
insoluble but water perr"eable polymeric material such as
carboxymethylcellulose, PVA, PVP. The polymer properties are selected to
achieve a suitable release profile of the antibody in the wash solution.
THE AMYLASE ENZYME
- The amylolytic enzymes are inco,l.oraled in the detergent compositions of
the present invention at a level of from 0.0001% to 2%, preferably from
0.00018% to 0.1%, more preferably from 0.00024% to 0.048% pure enzyme by
weight of the composition.
The amylolytic enzyme can be of various origin, e.g. produced by
mammals, plants, microorganisms. Origin can further be mesophilic or
extremophilic (psychrophilic, psyc~,rollophic, thermophilic, barophilic, alkalophilic,
acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes may
be used. Also inclu~ed by deli"ition, are mutants of native enzymes. Mutants canbe o~tai~)ed e.g. by protein and/or genetic engineering, chemical and/or physical
",odificaliG"s of native enzymes. CGIIIIIIOI1 practice as well is the expression of
the enzyme via host organisms in which the genetic material responsible for the
production of he enzyme has been cloned.
Amylases (a and/or ~) can be included for removal of carbohydrate-based
stains. W094/02597, Novo Nordisk A/S published February 03, 1994, describes
cleaning co"~positions which incorporate mutant amylases. See also
WO95/10603, Novo Nordisk A/S, published April 20, 1995. Other amylases
known for use in cleaning cor,~positions include both a- and ,B-amylases. a-
Amylases are known in the art and include those ~isclosed in US Pat. no.
~, ., ..... --.. . .. ..
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WO ~ o22 PCTIUS97/11543
5,003,257; EP 252,666; WO191/00353; FR 2,676,456; EP 285,123; EP 525,6~0;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Other suitable
amylases are stability-enhanced amylases described in WO94118314, published
August 18, 1994 and W096105295, Genencor, published February 22, 1996 and
amylase variants having additional modification in the immediate parent available
from Novo Nordisk A/S, disclosed in WO 95110603, published April 95. Also
suitable are amylases described in EP 277 216, W095126397 and W096/23873
(all by Novo Nordisk).
Examples of cG"~r,lercial a-amylases products are Purafect Ox Am~) from
Genencor and Termamyl@), Ban(~) ,Fungamyl@) and Duramyl~, all available from
Novo Nordisk A/S Denmark. W095/26397 describes other suitable amylases: a-
amylases characterised by having a specific activity at least 25% higher than the
specific activity of Termamyl(~) at a temperature range of 25~C to 55~C and at apH value in the range of 8 to 10, measured by the PhAdPb~S(Z~ a-amylase activityassay. Suitable are variants of the above enzymes, described in W096123873
(Novo Nordisk). Other amylolytic enzymes with improved properties with respect
to the activity level and the combination of thermostability and a higher activity
level are des~,iL ed in W095/35382.
Deteraent components
The detergent cG"",ositions of the invention may also contain additional
det~:ryel)t CGIllpGlle:nt:;. The precise nature of these additional components, and
levels of i, ICGI ~Gration thereof will depend on the physical form ef the
cGIllpositiori, and the nature of the cleaning operation for which it is to be used.
The det~ryent cGmpositio"s accor~Jing to the invention can be liquid,
paste, gels, bars, tablets, powder or granular forms. Granular CGmpOSitionS can
also be in "compact" form, the liquid col"positions can also be in a
"concenl,dted" form.
The cG",positions of the invention may be formulated as hand and
machine laundr,v detergent c~",positions including laundry additive compositionsand cG~positions suitable for use in the soaking and/or pretreatment of stained
fabrics, rinse added fabric softener compositions. Such compositions can provide
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11
fabric cleaning, stain removal, whiteness maintenance, softening, color
appearance and dye transfer 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 additionaliy one or more detergent
components preferably selected from organic polymeric compounds, bleaching
agents, additional enzymes, suds suppressors, dispersants, lime-soap
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 an amylase-directed antibody and will be added to a
conventional detergent amylase-containing composition. The detergent additive
can also comprise both the amylase and amylase-directed antibody. Such
additive products are intended to supplement or boost the perfor"lance of
conventional detergent corrpositions and preferably comprise up to 50%
antibodies by weight of total composition.
If nceded the density of the laundry detergent co",positions herein ranges
from 400 to 1200 g/litre, preferably 600 to 950 g/litre of composition measured at
20~C.
The "co",pact" form of the compositions herein is best reflected by density and,in terms of co,nposiliG", by the amount of inorganic filler salt; inorganic filler salts
are conventional ingredients of detergent compositions in powder form; in
convel,lional detergent compositions, the filler salts are present in su6s~d,llial
amounts, typically 17-35% by weight of the total composition.
In the co",pact compositions, the filler salt is present in amounts not
exceeding 15% of the total composition, preferably not e~ceeding 10%, most
preferably not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the present cornpositions are
selected from the alkali and alkaline-earth-metal salts of sulphates and chlorides.
A prefer,ed filler salt is sodium sulphate.
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Liquid detergent compositions according to the present invention can also
be in a "concentrated form", in such case, the liquid detergent compositions
according the present invention will contain a lower amount of water, compared
to conventional liquid detergents.
Typically the water content of the concer,l,dted liquid detergent is
preferably less than 40%, more preferably less than 30%, most preferably less
than 20% by weight of the detergent composition.
SL~ Pqt 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 and/or 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 su, rac~an~ is prefer~bly formulated to be compatible with enzyme
components present in the composition. In liquid or gel cGmposilions the
surfactant is most preferably formulated such that it prol"otes, or at least does
not degrade, the stability of any enzyme in these col"positions.
Preferred surfactant systems to be used according to the present invention
comprise as a surfactant one or more of the nGni~niC and/or anionic slJIfdctd~)~s
described herein.
Polyethylene, polypropylene, and polybutylene oxide condensates of alkyl
phenols are suit~hle for use as the nonionic surfactant of the surfactant systems
of the present invention, with the polyethylene oxide COI ,del~sates being
prer~r,e~. These compounds include the condensdtiGI~ products of alkyl phenols
having an alkyl group containing from about 6 to about 14 carbon atoms,
preferably from about 8 to about 14 carbon atoms, in either a straight-chain or
branched-chain configuration with the alkylene oxide. In a preferred embodiment,
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W O ~7022 13
the ethylene oxide is present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of ethylene oxide per
mole of alkyl phenol. Commercially available nonionic surfactants of this type
include IgepalTM C0-630, marketed by the GAF Corporation; and TritonTM X-
45, X-114, X-100 and X-102, all marketed by the Rohm & Haas Company. These
surfactants are coi.)n,only referred to as alkylphenol alkoxylates (e.g., alkyl
phenol ethoxylates).
The condeosdlion products of primary and secondary a';pl)dtic 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 alcohols having an alkyl group
contai.)ing from about 8 to about 20 carbon atoms, more preferably from about
10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene
oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide and most
preferably from 2 to 5 moles of ethylene oxide per mole of alcohol are present in
said condensation products. Examples of c~mn~eroially available nonionic
surfactants of this type include TergitolTM 15-S-9 (the condensation product of
C11-C1s linear alcohol with 9 moles ethylene oxide), TergitolTM 24-L-6 NMW
(the condensation product of C12-C14 primary alcohol with 6 moles ethylene
oxide with a narrow molecular weight distribution), both marketed by Union
Carbide Corporation; NeodolTM 45-9 (the condensation product of C14-C1s
linear alcohol with 9 moles of ethylene oxide), NeodolTM 23-3 (the condensation
product of Cj2-C13 linear alcohol with 3.0 moles of ethylene oxide), NeodolTM
45-7 (the condei,salion product of C14-C1s linear alcohol with 7 moies of
ethylene oxide), NeodolTM 45-5 (the condensation product of C14-C1s linear
alcohol with 5 moles of ethylene oxide) marketed by Shell Chemical Company,
KyroTM EOB (the condensdlion product of C1 3-C1 s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA
030 or 050 (the condel)sation product of C12-C14 alcohol with 3 or 5 moles of
ethylene oxide) marketed by Hoechst. Preferred range of HLB in these products
is from 8-11 and most preferred from 8-10.
.. .
.. . . . ..
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14
Also useful as the nonionic surfactant of the surfactant systems of the present
invention are the alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic group 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 containing5 or 6 carbon atoms can be used, e.g., glucose, galactose and galactosyl
",oieties can be substituted for the glucosyl moieties (optionally the hydrophobic
group is attached at the 2-, 3-, 4-, etc. positions thus giving a glucose or
galactose as opposed to a glucoside or galactoside). The intersaccharide bonds
can be, e.g., between the one position of the additional saccharide units and the
2-, 3-, 4-, and/or 6- positions on the preceding saccharide units.
The p~fer~ed alkylpolyglycosides have the forrnula
R20(CnH2nO)t(91YC~sYl)x
wherein R2 is 5~: lected 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, pr~rerably 2; t is from 0 to about 10, preferably 0; and x is from
about 1.3 to about 10, preferdbly 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 co""~ounds, the alcohol or alkylpolyethoxy alcohol is formed firstand then It:a~,~d with glucose, or a source of glucose, to form the glucoside
(attacl"Y~ant 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, pr~:ferdbly predominately the 2-position.
The condensaliGn products of ethylene oxide with a hydrophobic base formed
by the condeosdlion of propylene oxide with propylene glycol are also suitable for
use as the acJditiol)al nonionic surfactant systems of the present invention. The
hydrophobic portion of these compounds will preferably have a molecular weight
of from about 1500 to about 1800 and will exhibit water insolubility. The addition
of polyoxyethylene moieties to this hydrophobic portion tends to increase the
water solubility of the molecule as a whole, and the liquid character of the
CA 02263427 1999-02-11
WO 98/07822 PCI/US97/11543
product is retained up to the point where the polyoxyethylene content is about
50% of the total weight of the condensation product, which corresponds to
condensation with up to about 40 moles of ethylene oxide. Examples of
compounds of this type include certain of the commercially-available PlurafacTM
LF404 and PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic su,ractant of the nonionic surfactant
system of the presenl invention, are the condensation products of ethylene oxidewith the product resulting from the reaction of propylene oxide and
ethylenecliarni"e. The hydrophobic moiety of these products consists of the
reaction product of ethylenediamine and excess propylene oxide, and generally
has a ,nole~u'~r weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that the condensation
product cGnt~ins 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 co,nmercially available
TetronicTM compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the surfactant systems of the
present invention are polyethylene oxide condensates of alkyl phenols,
conde"saliol, products of primary and secondary aliphatic alcohols with from
about 1 to about 25 moles of ethylene oxide, alkylpolysaccharides, and mixtures
thereof. Most prefer,~d are Cg-C14 alkyl phenol ethoxylates having from 3 to 15
ethoxy groups and Cg-C1g alcohol ethoxylates (preferabiy C10 avg.) having from
2 to 10 ethoxy groups, and mixtures thereof.
Highly pr~f~ d nonionic SUI ractdllls are polyhydroxy fatty acid amide
surfactants of the formula.
R2 C-N-Z
Il I
o R1
wherein R1 is H, or R i j5 C1~ hydrocarl,yl, 2-hydroxy ethyl, 2-hydroxy propyl or
a mixture ll,erc:of, R2 is Cs 31 hydrocarbyl, and Z is a polyhydroxyhydrocarbyl
having a linear hydrocarbyl chain with at least 3 hydroxyls directly connected to
CA 02263427 l999-02-ll
WO ~ ,7D22 rCTtUS97/11543
16
the chain, or an alkoxylated derivative thereof. Preferably, R1 is methyl, R2 is a
straight C~ 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, lactose, in a reductive amination reaction.
Suitable anionic surfactants to be used are linear alkyl benzene sulfonate,
alkyl ester sulfonate surfactants including linear esters of Cg-C20 carboxylic
acids (i.e., fatty acids) which are sulfonated with gaseous SO3 according to "The
Journal of the American Oil Chemists Society", 52 (1975), pp. 323-329. Suitable
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 sulrollate surfactants of the structural formula:
o
Il
R3 - CH - C - oR4
I
SO3M
wherein R3 is a Cg-C20 hydrocarLyl, preferably an alkyl, or co,.,binalion 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 sl,lrondle. Suitable
salt-forming calions include metals such as sodium, potassium, and lithium, and
substituted or unsubstit-lted a-"n,ol-ium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is C10-C16 alkyl, and R4 is
methyl, ethyl or jSG~IO~YI. Especially preferred are the methyl ester sulfonateswherein R3 is C10-C~6 alkyl.
Other suitable anionic su,tactd"l~ include the alkyl sulfate surfactants which
are water soluble salts or acids of the formula ROSO3M wherein R preferably is
a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having a C10-C20
alkyl component, more pl~ferdbly a C12-C1g alkyl or hydroxyalkyl, and M is H or
a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), or
ammonium or s~ ~bstituted ammonium (e.g. methyl-, dimethyl-, and ll imethyl
ammonium cdLions and quaternary ammonium cations such as tetramethyl-
CA 02263427 1999-02-11
W O ~ 22 PCT~US97/115~3
17
ammonium and dimethyl piperdinium cations and quaternary 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 preferred for higher wash temperatures (e.g. above about 50~C).
Other anionic surfactants useful for detersive purposes can also be included in
the detergent compositions of the present invention. These can include salts
(including, for example, sodium, pot~ssium, ammonium, and sl ~hstituted
ammonium salts such as mono-, di- and triethanolamine salts) of soap, Cg-C22
primary of seco"da~ alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the pyrolyzed product of alkaline
earth metal eitrates, e.g., as described in British patent specir,cdlion No.
1,082,179, Cg-C24 alkylpolyglycolethersulfates (containing up to 10 moles of
ethylene oxide); alkyl glycerol sulfonates, fatty acyl glycerol sulfonales, fatty oleyl
glycerol s!~lf~tes, alkyl phenol ethylene oxide ether sulfates, paraffin sulf~"ates,
alkyl phosphates, isethionates such as the acyl isethionates, N-acyl taurates,
alkyl succina",ales and sulfosuccinates, monoesters of sulfosucc;nates
(especially saturated and unsaturated C12-C1g monoesters) and diesters of
sulfosuccinates (especially saturated and unsaturated C6-C12 diester:~), acyl
sarcosinates, sulfates of alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nGniouic nonsulfated compounds being described below),
branched primary alkyl sulf~tes, and alkyl polyethoxy carboxylates such as thoseof the formula RO(CH2CH2O)k-CH2COO-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 andhydro~e"ated resin acids are also suitable, such as rosin, hydrogenated rosin,
and resin acids and hydlo~ellated resin acids present in or derived from tall oil.
Further examples are described in "Surface Active-Agents and Detergents"
(Vol. l and ll by Schwartz, Perry and Berch). A variety of such surfactants are
also generally disclcs~ in U.S. Patent 3,929,678, issued December 30, 1975 to
Laughlin, et al. at Column 23, line 58 through Column 29, line 23 (herein
incorporated by reference).
When included therein, the laundry detergent co,npositions of the present
invention typically co"lprise from about 1% to about 40%, preferably from about
3% to about 20% by weight of such anionic sul rdc~anls.
CA 02263427 1999-02-11
WO 9X~D22 PCT~US97111543
18
Highly preferred anionic surfactants include alkyl alkoxylated sulfate
surfactants hereof are water soluble salts or acids of the formula RO(A)mSO3M
wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having a C10-
C24 alkyl component, preferably a C12-C20 alkyl or hydroxyalkyl, more
preferably C12-C1g alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is
greater than zero, typically between about 0.5 and about 6, more preferably
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""ag"esium,
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, l,i,l,ell,yl-ammoniumcations and quaternary ammonium cations such as tel,d",ell,yl-ain"~onium and
dimethyl piper~i"ium cations and those derived from alkylamines such as
ethylamine, diethylamine, triethylamine, mixtures thereof, and the like. Exemplary
surfactants are C12-C1g alkyl polyethoxylate (1.0) sulfate (C12-C1gE(1.0)M),
C12-C1g alkyl polyethoxylate (2.25) sulfate (C12-C1gE(2.25)M), C12-C1g alkyl
polyethoxylate (3.0) sulfate (C12-C1gE(3.0)M), and C12-C1g alkyl polyethoxylate
(4.0) sulfate (C12-C1gE(4.0)M), wherein M is conveniently selected from sodium
and potassium.
The detergent c~mpositions of the present invention may also contain caliGnic,
ampholytic, zwitleriGIlic, and semi-polar surfactants, as well as the nonionic
and/or anionic s~" racta,)ts other than those already described herein.
Cationic detersive surfactants suitable for use in the detergeul compositions ofthe present invention are those having one long-chain hydrocarbyl group.
Examples of such calionic surfactants include the ammonium surfactants such as
alkyll,i",ell"~ldr"",onium halogenides, and those SUI fdCtanl~; having the formula:
[R2(oR3)y][R4(0R3)yj2R5N+x-
wherein R2 is an alkyl or alkyl benzyl group having from about 8 to about 18
carbon atoms in the alkyl chain, each R3 is selected from the group consisting of
-CH2CH2-, -CH2CH(CH3)-, -CH2CH(CH2OH)-, -CH2CH2CH2-, and mixtures
thereof; each R4 is selected from the group consisting of C1-C4 alkyl, C1-C4
hydroxyalkyl, benzyl ring structures formed by joining the two R4 groups, -
CH2CHOH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or hexose
CA 02263427 1999-02-ll
W O ~ 7~22 PCT~US97/11543
19
polymer having a molecular 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.
Quaternary ammonium surfactant suitable for the present invention has
the formula (I):
~o~ "'R~
Formula I
whereby R1 is a short chaifi'ersyll, alkyl (C6-C10) or alkylamidoalkyl of the
formula (Il):
o
Formula ll
y is 2-4, preferably 3.
whereby R2 is H or a C1-C3 alkyl,
whereby x is 04, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and can be either a shortchain alkyl (C1-C3) or alkoxylated alkyl of the formula lll,
whereby X~ is a counterion, preferably a halide, e.g. chloride or methylsulfate.
R6
~~~z
Formula lll
R6 is C1-C4 and z is 1 or2.
Preferred quat ammonium surfactants are those as defined in formula I
whereby
R1 is Cg, C10 or mixtures thereof, x=o,
.
CA 02263427 1999-02-ll
W O ~*~ 22 PCTrUS97/115~3
R3 R4 = CH3 and Rs = CH2CH2OH.
Highly preferred cationic surfactants are the water-soluble quaternary
ammonium compounds useful in the present composition having the formula:
R1R2R3R4N+X- (i)
wherein R1 is Cg-C16 alkyl each of R2 R3 and R4 is independently C1-C4
alkyl C1-C4 hydroxy alkyl benzyl and -(C2H40)XH where x has a value from 2
to 5 and X is an anion. Not more than one of R2 R3 or R4 should be benzyl.
The preferred alkyl chain length for R1 is C12-C1s particularly where the alkyl
group is a mixture of chain lengths derived from coconut or palm kernel fat or is
derived synthetically by olefin build up or OXO alcohols synthesis. Prer~r,ed
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 a"""onium compounds of formulae (i) for use
herein are:
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl a---",onium chloride or bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl am-"onium chloride or bromide;
C12 15 dimethyl hydroxyethyl ammonium chloride or bromide;
coconut di."ell,yl hydroxyethyl a"""o"ium cl ,loride or bromide;
myristyl trimethyl ar~monium methyl sulphate;
lauryl dimethyl benzyl alnmonium chloride or bromide;
lauryl di~ tllyl (elll~noxy)4 a~r""Gnium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-~-C-C12 14 alkyl and R2R3R4 are methyl).
Il
o
di-alkyl imidazolines [compounds of formula (i)].
Other cationic surfactants useful herein are also clescriL,ad in U.S. Patent
4 228 044 Cambre issued October 14 1980 and in European Patent
Application EP 000 224.
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W O 98/07822 PCT~US97/11543
21
When included 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 surfàctants.
Ampholytic surfactants are also suitable for use in the detergent compositions
of the present invention. These surfactants can be broadly described as aliphatic
derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic
secondary and tertiary amines in which the aliphatic radical can be straight- orbranched-chain. One of the aliphatic substituents contains at least about 8
carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one
contains an anionic water-solubilizing group, e.g. carl.oxy, sulfonate, sulfate. See
U.S. Patent No. 3,929,678 to Laughlin et al., issued Decer"ber 30, 1975 at
column 19, lines 18-35, for examples of ampholytic SUI ~dCtal IIS.
When included therein, the detergent composilio"s of the present invention
typically comprise from 0.2% to about 15%, preferably from about 1% to about
10% by weight of such a,n~holytic surfactants.
ZwitltriG,lic surfactants are also suitable for use in detergent compositions.
These sl"ractdllt~ can be broadly described as derivatives of secol-ddry and
tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or
derivatiYes of quaternary a"""onium, quaternary phosphonium or tertiary
sulfonium co"lpounds. See U.S. Patent No. 3,929,678 to Laughlin et al., issued
Dece,nber 30, 1975 at column 19, line 38 through column 22, line 48, for
examples of zwitl~:rionic su, racta"~s.
When included ll,ere;n, the deteryent compositions of the present invention
typically c~"",rise from 0.2% to about 15%, preferably from about 1% to about
10% by weight of such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category of nonionic s~"ractants
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 hydroxyaikyl groups containing from about 1 to
about 3 carbon atoms; water-soluble phosphine oxides containing one alkyl
moiety of from about 10 to about 18 carbon atoms and 2 moieties selected from
...
CA 02263427 1999-02-ll
W O ~ 7&22 PCTrUS97/11543 22
the group consisting of alkyl groups and hydroxyalkyl groups containing from
about 1 to about 3 carbon atoms; and water-soluble sulfoxides containing one
alkyl moiety of from about 10 to about 18 carbon atoms and a moiety selected
from the group consisting of alkyl and hydroxyalkyl moieties of from about 1 to
about 3 carbon atoms.
Semi-polar nonionic detergent surfactants include the amine oxide surfactants
having the formula
o
R3(oR4)xN(R5)2
wherein R3 is an alkyl, hydroxyalkyl, or alkyl phenyl group or mixtures thereof
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 co"taini"g 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 slJIr~dllt~ in particular include C10-C1g alkyl di,.,etl,yl
amine oxides and Cg-C12 alkoxy ethyl dihydroxy ethyl amine oxides.
When included U,erei", the detergent con,positions of the pr~sen~ invention
typically comprise from 0.2% to about 15%, pl~ferdbly from about 1% to about
10% by weight of such semi-polar nonionic surfactants.
The detergent cGn,position of the pr~se"l invention may further
comprise a cosurfactant sele~,ted from the group of primary or tertiary amines.
Suitable primary a,n;l,es for use herein include amines according to the formula
R1NH2 wherein R1 is a C6-C12 preferably C6-C10 alkyl chain or R4X(CH2)n, X
is -O-,-C(O)NH- or-NH- R4 is a C6-C12 alkyl chain n is beh,veen 1 to 5,
preferably 3. R1 alkyl chains may be straight or branched and may be
interrupted with up to 12, preferably less than 5 ethylene oxide moieties.
rl~:fer,ed amines according to the formula herein above are n-alkyl amines.
Suitable a"~ines for use herein may be selecte~ from 1-hexylamine, 1-
CA 02263427 1999-02-ll
W O 981'~lo~2 PCT~US97/11543
23
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 theformula R1 R2R3N wherein R1 and R2 are C1-Cg alkylchains or
- (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,
pr~ferably 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 "~ieties.
Preferred tertiary amines are R1R2R3N where R1 is a C6-C12 alkyl chain,
R2 and R3 are C1-C3 alkyl or
R5
--( CH2--CE~--~ )~cH
where R5 is H or CH3 and x = 1-2.
Also preferred are the amidoamines of the formula:
o
Rl--C--NH--( CH2 )--N--( R2 )2
wherein R1 is C6-C12 alkyl; n is 2~,
p~eferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include 1-octylamine, 1-
hexylamine, 1-decylamine, 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
CA 02263427 1999-02-ll
W O ~ 7022 PCTAUS97/11543
24
amidopropyldimethylamine, C8-10 amidopropyldimethylamine and C10
amidopropyldimethylamine.
The most preferred amines for use in the compositions herein are 1-hexylamine,
1-octylamine, 1-decylamine, 1-dodecylamine. Especially desirable are n-
dodecyldimethylamine and bishydroxyethylcoconutalkylamine and oleylamine 7
times ethoxylated, lauryl amido propylamine and cocoamido propylamine.
Conventional detergent enzymes
The detergent compositions can further comprise one or more enzymes
which provide detergent performance and/or fabric care benefits.
Said enzymes include enzymes selecterl from hemicellulases, peroxiclAses,
protoascs, gluco-amylases, xylanases, lip~ses, phospholip~ses, esterases,
cutinases, pectinases, keratanases, reduct~ses, oxidases, phenoloxidAses,
- lipoxygenases, ligninases, pullulanases, tannases, pentosanases, malanases, ~-
glucanases, arabinosid~ses, hyaluronidase, chond~ilinase, l~cc~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.
The cellulases usable in the present invention include both bacterial or
fungal cellulase. Preferably, they will have a pH optimum of between 5 and 9.5.
Suitable cellulases are disclosed in U.S. Patent 4,435,307, Barbesgoard et al,
which discloses fungal cellulase produced from Humicola insolens. Suitable
cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275 and DE-OS-
2.247.832.
Examples of such cellulases are cellul~ses produced by a strain of
Humicola insolens (Humicola grisea var. thermoidea), particularly the Humicola
strain DSM 1800.
Other suitable cellulases are cellulases originated from Humicola insolens having
a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415
amino acids and a -43kD endoglucanase derived from Hu~r,icola insolens, DSM
CA 02263427 l999-02-ll
W 09~ 7~22 PCTrUS97/11543
1800, exhibiting cellulAse activity; a preferred endoglucanase component has theamino acid sequence disclosed in PCT Patent Application No. WO 91/17243.
~ Especially suitabie cellulases are the cellulases having color care benefits. Other
suitable cellulases are the EGIII cellulases from Trichoderma longibrachiatum
described in WO94/21801, Genencor, published Se,~ter"ber 29, 1994. Examples
of such cellulases are cellulases described in European patent application No.
91202879.2, filed November 6, 1991 (Novo).
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
sub:jl,ates during wash operaliG"s to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include, for example, horseradish
peroxidase, ligninase, and haloperoxid~se such as chloro- and bromo-
peroxiclAse.
PeroxidAse-containing detergent compositions are disclosed, for example,
in PCT Inter"dlional Application WO 89/099813 and in Eulopca. l Patent
application EP No. 91202882.6, filed on November6, 1991.
Other suitable oxidases is the lAccAse enzyme, using oxygen or hydrogen
peroxide as primary sL-bsl,ate.
Said cellulases and/or peroxidAses are normally incorporated in the
detergent co""~osition at levels from 0.0001 % to 2% of active enzyme by weight
of the detergent composition.
Other pref~"t:cl enzymes that can be inclucled in the detergent
COIIl,uOSitiGl~s of the present invention include lipAses. Suitable lipase enzymes
for deter~ent usage include those produced by microorganisms of the
PseudG",onas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed
in British Patent 1,372,034. Suitable lipAses include those which show a positive
immL",c' l~ic~l cross-reaction with the antibody of the lipase, produced by the
microor~anisl" Pseudomonas fluorescent IAM 1057. This lipase is available from
Amano PharmAceutic~l Co. Ltd., Nagoya, Japan, under the trade name Lipase P
"Amano," hereinafter referred to as "Amano-P". Other suitable commercial
ses include Amano-CES, lipases ex Chromobacter viscosl~tn, e.g.
Chromobacter viscosum var. Iipolyticum NRRLB 3673 from Toyo Jozo Co.,
CA 02263427 1999-02-ll
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26
Tagata, Japan; Chromobacter viscosum lipases from U.S. Biochen, ~l Corp.,
U.S.A. and Disoynth Co., The Netherlands, and lip~ses 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 con,~ination with the co"")ositions of the
present 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 cutinases to ~letergent composilions have been described in e.g. WO-A-
88/09367 (Genencor).
The lir~ses and/or cutinases are normally incorporated in the deteryent
composition at levels from 0.0001% to 2% of active enzyme by weight of the
detergent composition.
Suitable proteases are the subtilisins which are obtained from particular
strains of B. subtilis and B. Iichenfforrnis (subtilisin BPN and BPN'). One suitable
protease is obtained from a strain of Bacillus, having maximum activity
throughout the pH range of 8-12, developed and sold as ESPERASE~E9 by Novo
Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme
and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable
- proteases include ALCALASE~), DURAZYM~ and SAVINASE~) from Novo and
MAXATASE~). MAXACAL~, PROPERASE~g) and MAXAPEM~ (protein
engineered M~YaCal) from Gist-Broc~des. P"~teolytic enzymes also encompass
modified bacterial serine ~.r~teases, such as those desc,ibed in European PatentAPP!jCaljGII Serial Number 87 303761.8, filed April 28, 1987 (particularly pages17, 24 and 98), and which is called herein "P,~,tease B", and in Eu,opean PatentApplica(ion 199,404, Venegas, published October 29, 1986, which refers to a
modified bacterial serine protealytic enzyme which is called "r~otease A" herein.
More preferred is what is called herein "Protease C", which is a variant of an
alkaline serine p~otease from Bacillus in which Iysine replaced arginine at
position 27, tyrosine repl-ced 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. Gel)elically .nociir,ed 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 co"",rising protease, one or
CA 02263427 l999-02-ll
W O 981~~7~22 PCTrUS97/11543
2~
more other enzymes, and a reversible protease inhibitor are described in WO
92/03529 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 recombinant 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 position in said carbonyl hydrolase
e~uivalent 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, +101, ~103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156,
+166, +195, ~197, +204, +206, +210, +216, +217, +218, +222, +260, +265,
and/or +274 according to the numbering of Bacillus amyloliquefaciens subtilisin,as described in WO95/10591 and in the patent a~plicalion 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 arlplic~lions EP 251 446 and WO91/06637 and
protease BLAP~) described in WO91/02792. rlotease enzyme may be
incorporated into the compositions in accordance with the invention at a level of
from 0.0001% to 2% active enzyme by weight of the composition.
The above-mer,lionecl enzymes may be of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Origin can further be
",esGphilic or exl,~"~ophilic (psychrophilic, psychrotrophic, thermophilic,
barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms
of these enzymes may be used. Also included by definition, are mutants of nativeenzymes. Mutants can be obtained e.g. by protein and/or genetic eng;.,ee,ii 9,
chemical and/or physical modiricalions of native enzymes. Common practice as
well is the expressiG~I 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 compositiGn at levels from
0.0001% to 2% of active enzyme by weight of the detergent co""~osition. The
enzymes can be added as separate single ingredients (prills, granulates,
stabilized liquids, etc., co-,taiuil-g one enzyme) or as mixtures of two or moreenzymes (e.g., cogranulates).
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28
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 "~ateri&ls and means for their incorporation into
synthetic detergent cGr,.positions is also disclosed in WO 9307263 A and WO
9307260 A to Genencor International, WO 8908694 A to Novo, and U.S.
3,5~3,139, January 5, 1971 to McCarty et al. Enzymes are further disclosed in
U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219, Hughes,
March 26, 1985. Enzyme materials useful for liquid detergent formulations, and
their incorporation into such formulations, are disclosed 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 ~I;sclosed 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 beneflts
Techr,ologies which provide a type of color care benefit can also be
incl~ ~ded. Exa",ples of these technologies are metallo catalysts for color
maintenance. Such metallo catalysts are described in co-~.en-Ji,)g European
Patent Application No. 92870181.2.
The Bleaching agent
The detergent co,nro~itions of the present invention can further include
bleaching agents such as hydrogen peroxide, PB1, PB4 and percar6Onate with a
, a,licle size of 400-800 microns. These bleaching agent components can
include one or more oxygen bleaching agents and, depending upon the
bleaching agent chose", one or more bleach activators. When present oxygen
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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 present
invention can be an activated or non-activated bleaching agent.
One category of oxygen bleaching agent that can be used er,cGr,~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-nonylamino4-
oxoperoxybutyric acid and diperoxydodecanedioic acid. Such bleaching agents
are di.sGlosed in U.S. Patent 4,483,781, U.S. Patent Application 740,446,
European Patent Applicdliol- 0,133,354 and U.S, Patent 4,412,934. Highly
- preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic acid
as descriL,ed in U.S. Patent 4,634,551.
Another categoly of bleaching agents that can be used encompasses the
halogen bleaching agents. Examples of hypohalite bleachi. ,g agents, for
example, include trichloro isocyanuric acid and the sodium and potassillm
dichloruisG~;yanurates 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 hydrogen peroxide releasi"g agents can be used in combination with
bleach activators such as tel,dacetylethylenediamine (TAED),
nonar,oyloxyl,e,,~ene-sulru,,ale (NOBS, described in US 4,412,934), 3,5,-
l,i",elhyll,exanoloxybel,~e"esulfonate (ISONOBS, described in EP 120,591) or
pentaacetylglucose (PAG)or Phenolsulfonate ester of N-nonanoyl-6-
aminocaproic acid (NACA-OBS, described in WO94/28106), which are
perhydrolyzed to form a peracid as the active bleaching species, leading to
improved bleaching effect. Also suitable activators are acylated citrate esters
such as dirclosed in Co-pending European Patent Application No. 91870207.7.
Useful bleaching agents, including peroxyacids and bleaching systems
comprising bleach activators and peroxygen bleaching compounds for use in
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detergent compositions according to the invention are described in our co-
pending applications USSN 08/136,626, PCT/US95/07823, W095/27772,
W095/27773, W095/27774 and W095/27775.
The hydrogen peroxide may also be present by adding an enzymatic
system (i.e. an enzyme and a suLalldte therefore) which is capable of generatinghydrogen peroxide at the beyin~ ly or during the washing and/or rinsing process.Such enzymatic systems are disclosed in EP Patent Application 91202655.6 filed
October9, 1991.
Metal-contai,lii)g catalysts for use in bleach co"~ ositions, 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. Bleachi.lg co"".osition comprising a peroxy compound, a
mang3nese-col,laining bleach catalyst and a chelating agent is descril~ed in thepatent applic~tion No 94870206.3.
Bleaching agents other than oxygen bleaching agents are also known in
the art and can be utilized herein. One type of non-oxygen bleaching agent of
particular interest includes photoacti~ated bleaching agents such as the
sulronated zinc and/or aluminum phthalocyanines. These ",alerials can be
deposited upon the suL:jl,dte during the washing process. Upon i"adialion with
light, in the presence of oxygen, such as by hanging clull,es out to dry in the
daylight, the sulrol,dt~J zinc phthalocyanine is activated and, co"sequently, the
substrate is bleached. P,ef~r"2d zinc phthalocyanine and a photo~ctivated
bleaching process are desc,iLecl in U.S. Patent 4,033,718. Typically, detergent
col"posiliol)s will contain about 0.025% to about 1.25%, by weight, of sulfonated
zinc phthalocyanine.
Buflder s~sh."
The compositions according to the present invention may further comprise a
builder system. Any conventional builder system is suitable for use herein
including alumifiosilic~te ",alerials, silicates, polycarboxylates, alkyl- or alkenyl-
succinic acid and fatty acids""aterials such as ethylenediamine tel,dacetate,
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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 aluminosilic-ate ",dterial, more particularly a hydrated
sy"lhelic zeolite such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered silicate, e.g. SKS-6
(Hoechst). SKS-6 is a crystalline layered silicate consisting of sodium silicate
(Na2Si2~5)
Suitable polycarboxylates containing one carboxy group include lactic
acid, glycolic acid and ether derivatives thereof as disclQsed in Belgian PatentNos. 831,368, 821,369 and 821,370. Polycarboxylates contai,ling 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
Offenlege"sch,ilrl 2,446,686, and 2,446,687 and U.S. Patent No. 3,935,257 and
the sulfinyl carboxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxy groups include, in particular, water-
soluble citrates, aconitrates and citraconates as well as succinate derivatives
such as the carboxymethyloxysuccinales descril.ed in British Patent No.
1,379,241, lactoxysucc"~Ptes described in Netherlands Application 7205873, and
the oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates
described in British Patent No. 1,387,447.
PolycarLoxylates contai"iny four carboxy groups include oxydislJcc;,)ales
disclQsed in British Patent No. 1,261,829, 1 ,1 ,2,2-ethane tet, acarboxylates,
1,1 ,3,3-propa"e tetracarboxylates and 1,1 ,2,3-propane tet, acarboxylates.
Polycarboxylates containing sulfo substituents include the sulfosuccinate
derivatives discl~sed in British Patent Nos. 1,398,421 and 1,398,422 and in U.S.Patent No. 3,936,448, and the sulrollated pyrolysed cit,dles described in British
Patent No. 1,082,179, while polycarboxylates containing phosphone substit-lents
are disclQserl 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 - tetracarboxylates, 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 prefijned polycarboxylates are hydroxycarboxylates
containing up to three carboxy groups per molecule, more particularly citldtes.
Preferled builder systems for use in the present compositions include a
mixture of a water-insoluble aluminosilicate builder such as zeolite A or of a
layered silicate (SKS-6), and a water-soluble carboxylate chelating agent such as
citric acid. 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 ethyl~nedia,),i"e-N,N'-disuccinic acid (EDDS) or
the alkali metal, alkaline earth metal, a"""onium, or substituted a"""Gnium salts
thereof, or mixtures thereof. P~ef~r,~d EDDS compounds are the free acid form
and the sodium or magnesium salt thereof. Examples of such pre~r,ed sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such preferred
magnesium salts of EDDS include MgEDDS and Mg2EDDS. The ",ag"esium
salts are the most preferred for inclusion in co~"positions in accordance with the
invention.
Preferred builder systems include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A, and a watersol ~bl~ carboxylate
cl)elaling agent such as citric acid.
Other builder materials that can form part of the builder system for use in
granular cGIllpositions include inorganic ",alerials such as alkali metal
carbonates, bicarbona~es, silicates, and organic materials such as the organi
phosphonates, amino polyalkylene phosphonates and amino polycarboxylates.
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33
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 cor"posilion 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 r,~a~erials while silica is normally used in finely divided forms
exemplified by silica aerogels and xerogels and hydrophobic silicas of various
types. These ",dlerials can be incor~,orated as particul~tes in which the suds
suppressor is advant~geously rele~s~hly incorporated in a water-soluble or
water-dispersible sub:j~a- ,lially 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 p,efer,ed silicone suds controlling agent is disclosed in Bartollota et al.
U.S. Patent 3 933 672. Other particularly useful suds suppressors are the self-
emulsifying silicone suds suppressor~ described in German Patent Application
DTOS 2 646 126 published April 28 1977. An example of such a compound is
DC-544 co"""ercially available from Dow Corning which is a siloxane-glycol
copolymer. Especially prefer,ed suds controlling agent are the suds suppressor
system comprising 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 are described in Copending 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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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, ccloring agents, and/or enc~ps!~ated
or non-encaps~ ted perfumes.
Especially suitable enc~psul~ting materials are water sohJb!e capsules
- which consist of a matrix of polysaccharid~ and polyhydroxy coi"pounds such as
described in GB 1,464,616.
Other suitable water soluble encaps~ ting ",aterials comprise dextrins
derived from ungelali"i ed starch acid-esters of substituted dicarboxylic acids
such as described in US 3,455,838. These acid-ester dextrins are, pr~rably,
prepared from such starches as waxy maize, waxy sorghum, sago, tapioca and
potato. SuiPhle examples of said enc~psu!~ting materials include N-Lok
manufactured by National Starch. The N-Lok encapsulating material consists of a
modified maize starch and glucose. The starch is modified by adding
monofu.,ctional s~ ~hstihlted groups such as octenyl succinic acid anhydride.
Anli,e~leposit~on and soil suspension agents suitable herein include
cellulose derivatives such as methylcellulose, carboxymethylcellulose and
hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic 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
",alerials are nG,-"ally used at levels of from 0.5% to 10% by weight, more
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preferably from 0.75% to 8%, most preferably from 1% to 6% by weight of the
composition.
Preferred optical brighteners are anionic in character, examples of which
are disodium 4,4'-bis-(2-diethanolamino4-anilino -s- triazin-6-ylamino)stilbene-2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-anilino-s-triazin-6-ylamino-
stilbene-2:2' - disulphonate, disodium 4,4' - bis-(2,4-dianilino-s-triazin-6-
ylamino)stilbene-2:2' - disulphonate, monosodium 4',4" -bis-(2,4-dianilino-s-tri-
azin-6 ylamino)stilbene-2-sulphonate, disodium 4,4' -bis-(2-anilino-4-(N-methyl-N-
2-hydroxyethylamino)-s-triazin-6-ylamino)stilbene-2,2' - disulphonate, di-sodium4,4' -bis-(4-phenyl-2, 1 ,3-triazol-2-yl)-stilbene-2,2' disulphonate, di-so-dium4,4'bis(2-anilino4-(1-methyl-2-hydroxyethylamino)-s-triazin-6- ylami-no)stilbene-
2,2'disulphonate, sodium 2(stilbyl4"-(naphtho-1',2':4,5)-1,2,3 - triazole-2"-
sulphonate and 4,4'-bis(2-sulphostylyl)biphenyl. Highly preferred brighteners are
the specific brighleners of copending European Patent application No.
95201 943.8.
Other useful polymeric malelials are the polyethylene glycols, particularly
those of mlcl~cul~r 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% by weight. These polymers and the previously
",enliGned homo- or co-polymeric polycarboxylate salts are valuable for
improving whiteness maintenance, fabric ash deposition, and cleaning
pe,ror",a"ce on clay, proteinaceous and oxidizable soils in the presence of
transition metal impurities.
Soil release agents useful in compositions of the ~resel,l invention are
conventionally copolymers or terpolymers of terephthalic acid with ethylene
glycol and/or propylene glycol units in various arrangements. Examples of such
polymers are disclosed in the con)l))only assigned US Patent Nos. 4116885 and
4711730 and European Published Patent Application No. 0 272 033. A particular
preferred polymer in accor~ance with EP-A-0 272 033 has the formula
(cH3(pEG)43)o.75(poH)o.25[T-po)2.8(T-pEG)o 4]T(
H)0.25((PEG)43CH3)0.75
.. , . . . . . , -- . .
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where PEG is-(OC2H4)O-,PO is (OC3H6O) and T is (pcOC6H4CO).
Also very useful are modified polyesters as random copolymers of
dimethyl terephthalate, dimethyl sulfoisophthalate, ethylen~e 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 contex~ most of said copolymers herein will be end-capped by
sulphobe"~oate groups. However, some copolymers will be less than fully
capped, and therefore their end groups may consist of monoester of ethylene
glycol and/or propane 1-2 diol, thereof consist "secondarily" of such species.
The selected polyesters herein contain about 46% by weight of dimethyl
terephthalic acid, about 16% by weight of propane -1.2 diol, about 10% by weightethylene glycol about 13% by weight of di,llethyl 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 preparation are described in detail inEPA 311 342.
Is is well known in the art that free chlorine in tap water rapidly deactivates
the enzymes comprised in detergent composiliGns. Therefore, using chlorine
scavenger such as pe,Lordte, ammonium sulfate, sodium sulphite or
polyethyleneimine at a level above 0.1% by weight of total co",position, in the
formulas will provide improved through the wash stability of the detergent
enzymes. Compositions comprising chlorine scavenger are described in the
European patent application 92870018.6 filed January 31, 1992.
Alkoxylated polycarboxylates such as those prepared from polyacrylates
are useful herein to provide additional grease removal performance. Such
materials are described in WO 91/08281 and PCT 90/01815 at p. 4 et seq.,
incorporated herein by reference. Chemically, these ",aterials comprise
polyacrylates having one ethoxy side-chain per every 7-8 acrylate units. The
side-chains are of the formula -(CH2CH2O)m(CH2)nCH3 wherein m is 2-3 and n
is 6-12. The side-chains are ester-linked to the polyacrylate "backbone" to
provide a "comb" polymer type structure. The m~lec~ r weight can vary, but is
typically in the range of about 2000 to about ~0,000. Such alkoxylated
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polycarboxylates can comprise from about 0.05% to about 10%, by weight, of the
compositions herein.
Soffening agen*
Fabric son~ning agents can also be incorporated 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 disclQsed in GB-A-1 400 898 and in USP 5,019,292. Organic
fabric softening agents include the water insoluble tertiary amines as disclosed in
GB-A1 514 276 and EP-B0 011 340 and their 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 sorleni"g
agents such as the water-insoluble tertiary a",ines or dilong chain amide
materials are ir,co"~orated at levels of from 0.5% to 5% by weight, normally from
1% to 3% by weight whilst the high molecular weight polyethylene oxide
materials and the water soluble cationic materials are added at levels of from
0.1% to 2%, normally from 0.15% to 1.5% by weight. These materials are
normally added to the spray dried portion of the composition, although in some
instances it may be more convenient to add them as a dry mixed particulate, or
spray them as molten liquid on to other solid components of the composition.
Dispersan*
The deterye,ll cGm~osition of the present invention can also contail1
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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38
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, copoiymer 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 co",positions of the invention may contain a iime soap peptiser
compound, which has a lime soap dispersing power (LSDP), as defined
hereinafter of no more than 8, preferably 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 dete".,il,ed using the lime
soap dispersant test as described in an article by H.C. Borghetty and C.A.
Bergman, J. Am. Oil. Chem. Soc., volume 27, pages 88-90, t1950). This lime
soap dispersion test method is widely used by pra~;tilioners in this art field being
referred to, for ex~ ple, in the following review a,li-,les; W.N. Linfield, Surfactant
science Series, Volume 7, page 3; W.N. Linfield, Tenside surf. det., volume 27,
pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and
Toiletries, volume 104, pages 71-73, (1989). The LSDP is the % weight ratio of
dispersing agent to sodium oleate required to disperse the lime soap deposits
ru,l"e~l by 0.025g of sodium oleate in 30ml of water of 333ppm CaCo3
(Ca:Mg=3:2) equivalent hardness.
Su,ractdnls having good lime soap peptiser capability will include certain
amine oxides, betaines, sulfobetaines, alkyl ethoxysulfates and ethoxylated
alcohols.
Exemplary surfactants having a LSDP of no more than 8 for use in accord
with the present invention include C16-C1g dimethyl amine oxide, C12-C1g alkyl
ethoxysulfates with an average degree of ethoxylation of from 1-5, particularly
C12-C1s alkyl ethoxysulfate surfactant with a degree of ethoxylation of amount 3(LSDP=4), and the C14-C1s ethoxylated alcohols with an average degree of
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39
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-lN-octanoyl-6-aminohexanoyl]benzene
sulfonate, 4-[N-nonanoyl-6-aminohexanoyl]benzene sulfonate, 4-[N-decanoyl-6-
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 h ,sf~r inhibition
- The detergent compositions of the present invention can also include
co",pounds for inhibiting dye transfer from one fabric to another of solubilizedand suspended dyes encountered during fabric laundering operations involving
colored fabrics.
Polymeric dye b~.,sf~r inhibiffng agents
The detergent compositions according to the present invention also
comprise from 0.001% to 10 %, p~ferably from 0.01% to 2%, more preferably
from 0.05% to 1% by weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally incorporated into detergent
cor"positions in order to inhibit the transfer of dyes from colored fabrics ontofabrics 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 allicles in the wash.
Especially suitable polymeric dye transfer inhibiting agents are polyamine N-
oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimicla~ole,
polyvinylpy"olido"e polymers, polyvinylox~7olidones and polyvinylimidazoles or
mixtures Ihert:of.
Addition of such polymers also enhances the performance of the enzymes
accordillg the invention.
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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 poly",erisable unit, whereto the R-N-O group can be attached to
or wherein the R-N-O group forms part of the polymerisable unit or a
combination of both.
O O O
Il 11 11
AisNC, CO,C,-O-,-S-,-N-;xisOor1;
R are aliphatic, ethoxylated aliphatics, arol "~ic, 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 represe"ted 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",alic, heterocyclic or alicyclic
groups or combinations thereof, x or/and y or/and z is 0 or 1 and
wherein the nitrogen of the N-O group can be allached or wherein the
nitrogen of the N-O group forms part of these groups.
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41
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.
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 wl,er~il, 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 a~lached to the polymerisable unit.
Preferred class of these polyamine N-oxides are the polyamine N-oxides having
the general formula (I) wherein R is an aroi"alic, heterocyclic or alicyclic groups
wherein the r,it~ogen of the N-0 functiG"al group is part of said R group.
~xamples of these cl~ses 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 aro",dtic, heterocyclic or alicyclic groups
wherein the "it,ogen of the N-0 functional group is attached to said R groups.
Examples of these Cl;?SS9S are polyamine oxides wherein R groups can be
aromatic such as phenyl.
Any polymer bacl~LGne can be used as long as the amine oxide polyme
~.rn~ed is water-soluble and has dye transfer inhibiting properties. Examples ofsuitable polymeric b~ckhones 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
apprupriate copolymeri~alion 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
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42
from 1:4 to 1:1000000 most preferabiy from 1:7 to 1:1000000. The polymers of
the present invention actually encompass random or block copolymers where
one monomer type is an amine N-oxide and the other monomer type is either an
amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa
< 10 preferably PKa < 7 more preferred PKa c 6.
The polyamine oxides can be obtained in almost any degree of polymerisation.
The degree of polymerisation is not critical provided the mal~:rial has the desired
water-solubility and dye-suspending power.
Typically the average molQc~ r weight is within the range of 500 to 1000 000;
preferably from 1 000 to 50 000 more preferably from 2 000 to 30 000 most
preferably from 3 000 to 20 000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimid~-ole
The N-vinylimidazole N-vinylpyrrolidone polymers used in the present
invention have an average molecuiar weight range from 5 000-1 000 000
preferably from 5 000-200 000.
Highly preferred polymers for use in detergent compositions accGr~Jing to
the present invention comprise a polymer~ele~ted from N-vinylimidazole N-
vinylpyrrolidone copolymers wherein said polymer has an average mclQcl~br
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 molecular weight range was determined by light scattering as
described in Barth H.G. and Mays J.W. Chemical Analysis Vol 113"Modern
Methods of Polymer Characterization".
Highly prert:rl~:d N-vinylimidazole N-vinylpyrrolidone copolymers have 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 N-vinyli" ,ida~ole N-vinylpyrrolidone copolymers characterized by
having said average molecular weight range provide excellent dye transfer
inhibiting properties while not adversely affecting the cleaning performance of
detergent compositions formulated therewith.
The N-vinylimidazole N-vinylpyrrolidone copolymer of the ~.resent invention has a
molar ratio of N-vinylimi~ to N-vinylpyrrolidone from 1 to 0.2 more
preferably 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
5,000 to about 15,000. Suitable polyvinylpyrrolidones are co",ri,er~,ially available
from ISP Corporation, New York, NY and Montreal, Canada under the product
names PVP K-15 (viscosity molecular weight of 10,000), PVP K-30 (average
molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000),
and PVP K-90 (average ,ne'ecul?r weight of 360,000). Other suitable
polyvinylpyrrolidones which are commercially available from BASF Cooperation
include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to
persons skilled in the detergent field (see for example EP-A-262,897 and EP-A-
256,696).
d) Polyvinyloxazolidone:
The deter~ei-t compositions of the present invention may also utilize
polyvinylo)~ e' done as a polymeric dye transfer inhibiting agent. Said
polyvinyloxazolidones have an average molecular weight of from about 2,500 to
about 400,000, preferably from about 5,000 to about 200,000, more p,t:ferably
from about 5,000 to about 50,000, and most preferably from about 5,000 to about
1 5,000.
e) Polyvinylimidazole:
The deteryent compositions of the present invention may also utilize
polyvinylimi~ le as polymeric dye transfer inhibiting agent. Said
polyvinylimida~eles have an average about 2,500 to about 400,000, preferably
from about 5,000 to about 200,000, more preferably from about 5,000 to about
50,000, and most preferably from about 5,000 to about 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
- 9487021 3.9
-
Method of washing
The compositions of the invention may be used in essentially any washing
or cleaning methods, including soaking methods, plet,edl",ent methods and
Illetllods with rinsing steps for which a separate rinse aid composition may be
added.
The process described herein CGI I ,,urises contacting fabrics with a
laundering solution in the usual manner and exe",plified hereunder.
The process of the invention is conveniently carried out in the course of
the claani.)s~ process. The method of cleaning is preferably carried out at 5~C to
95~C, especia~y between 10~C and 60~C. The pH of the treatment solution is
prefer~4bly 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.
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In the detergent compositions, the enzymes levels are expressed by pure
enzyme by weight of the total composition and unless otherwise specified, the
detergent ingredients are expressed by weight of the toal 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
conde,lsed 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.
TFAA : C16-C1g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium chloride.
SDASA : 1:2 ratio of stearyldimethyl amine:triple-pressed stearic
acid.
.
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Neodol 45-13 : C14-C15 linear primary alcohol ethoxylate, sold by
Shell Chemical CO.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula ~-Na2Si2Os
Carbonate : Anhydrous sodium carbonate with a particle size
bctwccn 200 ~lm and 900~1m.
Bicarbonate : Anhydrous sodium bicarbonate with a particle size
between 400 ~lm and 1200~1m.
STPP : Anhydrous sodium tripolyphosphate
MA/AA : Copolymer of 1 :4 maleic/acrylic acid, average
molecular weight about 80,000
Polyacrylate : Polyacrylate homopolymer with an average m~l~cul~r
weight of 8,000 sold under the tradename PA30 by
BASF GmbH
Zeolite A : Hydrated Sodium Aluminosilicate 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 apa. licle size distribution between 425 ~lm and 850 llm.
Citric : Anhydrous citric acid
PB1 : Anhydroussodium perboratemonohydrate bleach,
empirical formula NaBO2 H2o2
PB4 : Anhydrous sodium perborate tetrahydrate
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Percarbonate : Anhydrous sodium percarbonate bleach of empirical
formula 2Na2CO3.3H2O2
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form of the
sodium salt.
Photoactivated : Sulfonated zinc phtlocyanine encapsulated in dextrin
Bleach soluble polymer.
Antibody : Anti-Termamyl ERT 860418 (500/150~1) and anti-BAN
PPY 1747 (200~1), available from Novo Nordisk A/S.
Amylase : Amylolytic enzyme sold under the tradename Purafact
Ox AmR described in WO 94/18314 and
W096/05295, sold by Genencor; Ter",al")~ ), Ban~
and Duramyl~l9, all available from Novo Nordisk AIS
and those described in W095/26397.
Protease : P,oleolytic enzyme sold under the tradename
Savinase, Alcalase, Durazym by Novo Nordisk A/S,
M~X~C~I, M?Yarem sold by Gist-Broc~des and
proteases described in patents WO91/06637 and/or
WO95/10591 and/or EP 251 446.
Lipase : Lipolytic enzyme sold under the lrdde"a,ne 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.
CMC : Sodiumcarboxymethyl cellulose.
HEDP : 1,1-hydroxyethane diphosphonic acid.
.
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PCT/USg7tl 1543
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48
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 : Disodium 4,4'-bis(2-sulphostyryl)biphenyl.
Brightener 2 : Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-
2-yl) stilbene-2:2'-disulfonate.
Silicone an~iroa", : 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% Siliconelsilica, 18% stearyl alcohol,70% starch in
Suppressor granular form
SRP 1 : Sulfobenzoyl end capped esters with oxyethylene oxy
and terephtaloyl backbone.
SRP 2 : Diethoxylated poly (1,2 propylene terephtalate) short
block polymer.
Sulphate : Anhydroussodiumsulphate.
HMWPEO : High molecul~r weight polyethylene oxide
PEG : Polyethylene glycol.
Encarsul~ted : Insoluble fragrance delivery technology utilising zeolite
perfume particles 13x, 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 Ter",a"lyl~
or Ban@ ) emulsion. The amylolytic emulsion was prepared with a Freunds
completed adjuvants (Freund and McDermott, 1942; Freund 1956) by mixing
intensively an equal amount of the Termamyl~) or Ban~g) solution (2mg/ml) and
the Freunds complete adjuvant.
The immunisation scheme was completed with injections using a Freunds
unco,llplete adjuvant and after a 4 weeks period, the eggs were collected duringone week. The extraction of the antibodies from the eggs yolks was done
according to the Polson extraction method as described in Immunological
Investig~tion 19, 1990, pp 253-258.
Amylase enzymafic inactivation:
- A Ter"la""~l~) or Ban~g) stock solution was prepared in a Tris Buffer (5x10-2M
Tris, 25 mM NaCI, pH=8) at a concent,alion of 0.0~% active enzyme. A
Phosphate Buffer (0.05M KH2PO4, pH 6.8)contained the antibody (0.18 mg/ml).
The interaction amylolytic enzyme (Final concentration 0.004%) / antibody was
achieved in co",mercially available detergent solutions comprising Ariel liquid
(0.8% in city water, pH 8.5) and Ariel Color Futur(0.8% in city water, pH 9.5)
during 15 minutes at 40~C.
The amylolytic residual activity was measured and within 5 minutes the
enzymatic activity of the amylase was successfully blocked.
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Exam~le 2
The following laundry detergent compositions were prepared in accord with the
invention:
11 111 lV V Vl
LAS 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3.4 3.4
Q A S - 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
Silic~te 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.1 26.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 9.0
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.25 0.25 0.25 0.25 0.25
HEDP 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 0.002 0.05 0.0009 0.0003 0.0009 0.01
Antibody 0.01 0.5 0.005 0.0001 0.05 0.09
MA/AA 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
rh otoactivated 15 15 15 15 15 15
bleach (ppm)
B,iyl~tel~er 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 a"liroa,ll 0.5 0.5 0.5 0.5 0.5 0.5
Misc/minors to 100%
Density in g/litre 850 850 850 850 850 850
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Example 3
The following granular laundry detergent compositions of bulk density 750 g/litre
were prepared in accord with the invention:
ll lll
LAS 5.25 5.61 4.76
TAS 1.25 1.86 1.57
C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 5 5
QAS 0.8 2.0 2.0
STPP 19.7
Zeolite A - 19.5 19.5
NaSKS-6/citric acid (79:21) - 10.6 10.6
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8
Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7
TAED 0.5 3.1
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Antibody o.ooog 0.005 o.og
Amylase 0.0002 0.0008 0.005
Pl~tease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
Cellul~se 0.00064 0.00064 0.00064
MA/M 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach 15 ppr~ 27 ppm 27 ppm
(ppm)
Bl ightel~er 1 0.08 0.19 0.19
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52
Brightener 2 - 0.04 0.04
Encapsulated perfume 0.3 0.3 0.3
particles
Siliconeantifoam 0.5 2.4 2.4
Minors/misc to 100%
Example 4
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:
ll lll
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 antifoam 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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53
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 0.0004 0.01
Antibody 0.007 0.005 0.1
Drymixed sodium sulfate 3.0 3.0 5.0
Balance (Moisture & 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 630 670 670
ExamPle 5
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/M 4.0 4.0
Agglomerates
C45AS - - 11.0
LAS 6.0 5.0
TAS 3.0 2.0
Silicate 4.0 4.0
Zeolite A 10.0 15.0 13.0
CMC - . 0.5
MA/M - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4.0
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54
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - 3 o
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
Cellulase 0.004 0.004 0.004
Amylase 0.01 0.005 0.0003
Antibody 0.1 0.05 0.001
Silicone ar,lirod", 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
Miscellaneous)
Density (g/litre) 700 700 700
Exa,l"~le 6
The following detergent formulations, accorcli"g 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
TFAA - 1.0
C25E5/C45E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
.Si'ic~te 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7 5
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W 098/07822 PCTrUS97/11543
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
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.0004 0.0001
Amylase 0.004 0.0003 0.002 0.007
Antibody 0.01 0.005 0.01 0.08
Photoactivated 70ppm 45ppm - 1 Oppm
bleach (ppm)
Brightener 10.2 0.2 0.08 0.2
P B1 6.0 2.0 - -
N O B S 2.0 1.0
Balance (Moisture 100 100 100 100
and Miscellaneous)
ExamPle 7
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
B,iyhlener 1 0.2 0.2 0.2
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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
PVPVI/PVNO 0.5 0.5 0.5
Antibody 0.1 0.005 0.001 0.1
Amylase 0.02 0.0008 0.0004 0.02
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Cellulase 0.0002 0.0002 0.0002 0.0002
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)
ExamPle 8
The following high density and bleach-containing detergent formulations,
according to the present invention were prepared:
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
Agglor"erates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
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57
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 0.07 0.03 0.009
Amylase 0.02 0.005 0.0005
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0 009
Cellulase 0.004 0.004 0.004
Silicone antiroa", 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 9
The following high density detergent formulations, according to the present
invention were prepared:
ll
Agglomerate
C45AS 11.0 14.0
Zeolite A 15.0 6.0
Carbonate 4.0 8.0
MA/AA 4.0 2.0
CMC 0.5 0.5
DETPMP 0.4 0.4
Spray On
C25E5 5.0 5.0
Perfume 0.5 05
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Antibody 0.5 0.03
Amylase 0.05 0.005
Protease 0.014 0.014
Lipase 0.009 0 009
Ce'hllase 0.001 0.001
Silicone a"liroa,n 5.0 5.0
Brightener 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 10
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 dimethyl hydroxyethyl - 0.4 0.7 0.7 0.8
NH4+CI
Nonionic 1.2 - 0.9 0.5
Coco C12-14 Fatty Alcohol - - - - 1.0
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - 8.0
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 0.005 0.05 0.006 0.5 1.0
Amylase .0008 0.004 0.001 0.04 0.1
Protease 0.005 0.04 0.007 0.09 0.15
Lipase 0.003 0 003 0 003
Cellulase - 0.001 0.001 .001 .001
NOBS - - - 1.2 1.0
PB1 - - - 2.4 1.2
Diethylene triamine penta - - - 0.7 1.0
acetic acid
Diethylene t,ia",ine penta - - 0.6
methyl phosphonic acid
Mg Sulfate - - 0.8
Photoactivated bleach 45 50 ppm 15 45 ppm 42
ppm ppm ppm
Brightener 1 0.05 - 0.04 0.04 0.04
Brightener 2 0.1 0.3 0.05 0.13 0.13
Water and Minors up to 100%
,
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Example 11
The following liquid detergent formulations, according to the present invention
were prepared:
11 111 lV V Vl Vll Vlll
L~S 10.0 1 3.0 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 1.5 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
tell dell ,ylene
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 0.09 .0005 .005 0.5 .005 0.5 0.08 .005
Amylase 0.02 0.000 0.000 0.04 0.002 0.05 .005 0.000
2 8 4
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Protease.005 .005 .004 .003 0.08 .005 .003 .006
Lipase - .002 - .0002 - - .003 .003
Cellulase - - - 0.000 - 0.000 0.000
4 4
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0
Ca chloride - 0.015 - 0.01
Bento"ite clay - - - - 4.0 4.0
Suspending clay - - - - 0.6 0.3
SD3
Balance Moisture and Miscellaneous: Up tp 100%
Example 12
Granular fabric cleaning cor"positions which provide "sorleniny 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-.li. "t:tl "rl hydroxy- 1.4 1 .0
ethyl a.,..l,onium chloride
Citrate 5.0 3.0
Na-SKS-6 - 11.0
Zeolite A 15.0 15.0
MA/M 4.0
DETPMP 0 4 0 4
PB1 1 5.0
Percarbonate - 15.0
TAED 5.0 5.0
S,nectite clay 10.0 10.0
HMWPEO - 0.1
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Antibody 0.1 0.002
Amylase 0.03 0.0005
Protease 0.02 0.006
Lipase 0.02 0.01
Cellulase 0.001
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
Example 13
The following rinse added fabric softener composition was prepared in
accord with the present invention:
Softener active 20.0
Antibody 0.009
Amylase 0.001
Cell~ se 0.001
HCL 0 03
Ar,liroa", agent 0.01
Blue dye 25ppm
CaCI2 0.20
Perfume 0.90
Water / minors Up to 100%
Example 14
The following fabric softener composition was pre~.c.r~d in accord with the
present invention:
l~
DEQA 2.60 19.00
SDASA - - 70.0
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Stearic acid of IV=0 0.30 - -
Neodol 45-13 - - 13.0
Hydrochloride acid0.02 0.02
Ethanol - - 1.0
PEG - 0.60
Antibody 0.06 0.0004 0.05
Amylase 0.01 0.0005 0.008
Protease - 0.008
Cellulase 0.001 0.001
Perfume 1.00 1.00 0.75
Digeranyl Succinate - - 0.38
Silicone al-li~arll0.01 0.01
Electrolyte - 600ppm
Dye 100ppm 50ppm 0.01
Water and minors 100% 100%
Exa~ le 15
Syndet bar fabric cleaning compositions were prepared in accord with the
present invention:
11 111 lV
C26 AS 20.00 20.00 20.00 20.00
CFM 5.0 5.0 5.0 5.0
LAS (C11-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
STPP . 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
Coconut monethanolamide 5.0 5.0 5.0 5.0
Antibody 0.06 0.03 0.09 0.0009
Amylase 0.01 0.001 0.002 0.0003
Protease 0.08 0.01 0.005 0.001
Brightener, perfume 0.2 0.2 0.2 0.2
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CaS04 1.0 1.0 1.0 1.0
MgSO4 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,Smectite), silicates, and the like.
Example 16
Detergent additives were prepared in accord with the present invention:
ll lll
LAS - 5
- STPP 30 - 30
Zeolite A - 35
PB1 20 15 20
TAED 10 8 10
Protease - 0 3
Amylase 0.4 0.2
Anti~ody 5 2 5
