Note: Descriptions are shown in the official language in which they were submitted.
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DETERGENT COMPOSITIONS COMPRISING IMPROVED AMYLASE
FOR DINGY FABRIC CLEAN-UP
TECHNICAL FIELD
- The present invention relates to the use of a specific
amylase enzyme in laundry detergent compositions for
boosting fabric laundry performance, especially on dingy
stains and soils.
BACKGROUND OF THE INVENTION
For a number of years amylase enzymes have been used
for a variety of different purposes, the most important of
which are starch liquefaction, textile desizing, starch
modification in the paper and pulp industry, and for
brewing and baking. A further use of amylases which is
becoming increasingly important, is the removal of starch
containing soils and stains during the washing of fabrics,
hard surfaces and dishes.
.. .. . ...
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Indeed, amylase enzymes have long been recognised in
dishwashing, hard surface cleaning and laundry compositions
to provide the removal of starchy food residues or starchy
films from dishware, flatware, glasses and hard surfaces or
to provide cleaning performance on starchy soils as well as
other soils typically encountered in laundry applications.
WO/94/02597, Novo Nordisk A/S published February 03,
1994, describes cleaning compositions which incorporate
mutant amylases. See also W094/18314 Genencor, published
August 18, 1994; W096/05295, Genencor published February
22, 1996 and WO/95/10603, Novo Nordisk A/S, published April
20,1995.
Other amylases known for use in cleaning compositions
include both a- and ~-amylases. a-Amylases are known in
the art and include those disclosed in US Pat. no.
5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP
285,123; EP 525,610; EP 368,341; and British Patent
specification no. 1, 296,839 (Novo).
Examples of commercial a-amylases products are
Termamyl~ Ban~ Duramyl~ and Fungamyl~, all available from
Novo Nordisk A/S Denmark and Maxamyl~ available from Gist
Brocades and Purafact Ox Am~ from Genencor.
Recently new amylases have been identified and are
described in WO/95/26397, Novo Nordisk A/S, published
October 05, 1995, disclosing an a-amylase having a specific
activity at least 25~6 higher than the specific activity of
Termamyl~ at a temperature range of 25~C to 55~C and at a
pH value in the range of 8 to 10. Variants of these new
amylases demonstrating at least one of the following
properties relative to the parent enzymes : 1) improved
thermal stability, 2) oxidation stability and 3) reduced
calcium ion dependency properties. Examples of other
desirable improvements or modifications of properties
.
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W O 98/05748 PCT~US96/12612
(relative to the parent-a-amylase) which may be achieved
with a variant according to the present invention are :
increased stability and/or a-amylolytic activlty at neutral
to relatively high pH values, increased a-amylolytic
activity at relatively high temperature and increase or
decrease of the isoelectric point (pI) so as to better
match the pI value for a-amylase variant to the pH of the
medium, have been described in the co-pending application
by Novo Nordisk PCT/DK96/00056, and are hereinafter
referred as "specific amylase".
Therefore, while amylase is known to act on starchy
stains, there remains a substantial technical challenge in
formulating laundry components comprising specific amylase
in such a manner as to meet the consumer's need for
superior cleaning performance on starchy soils as well as
other soils typically encountered in laundry applications.
Moreover, such detergent compositions must provide an
excellent value and a safe, environmentally acceptable
product which leaves laundered fabrics, especially those
particularly prone to dingy soiling, in dingy-free and
undamaged condition. A need therefore exists for the
development of detergent compositions comprising specific
amylase enzymes designed to be especially effective at
dingy clean up.
It has been surprisingly found that specific amylase
enzymes provide unexpected superior dingy clean up,
whiteness maintenance and overall cleaning performance.
Such performance is illustrated but not limited to
excellent dingy soil removal present e.g. on pillow cases,
T-shirts and sock bottoms.
It is therefore an object of the present invention to
provide effective dingy stain removal and overall cleaning
benefits through laundry compositions containing specific
amylase.
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SUMMARY OF THE INVENTION
This invention relates to the use of a specific
amylase in a laundry detergent composition to provide
especially effective surface cleaning of textiles.
The present invention relates to the laundering of
fabrics to maintain or increase whiteness and provide dingy
clean up, by contacting fabrics in need of whiteness and/or
dingy clean up with an aqueous solution formed from a
detergent composition comprising a specific amylase at a
concentration and for a sufficient period such that the
dingy cleaning performance of said composition is
ncreased .
DETAILED DESCRIPTION OF THE INVENTION
Without limitation by theory, it is believed that
dingy soils and stains are the result of combinations of
various types of soils. For instance, fatty soils comprise
lipids, proteins and pigments that are deposited on fabrics
from contact with human or animal skin. The majority of
lipids are secreted from the sebaceous gland as sebum.
Proteins and pigments from skin fragments are liberated by
the breakdown of skin cells. It is believed that sebum is
the major soil present on laundry and its removal is
important because unremoved fat acts as a matrix to hold
particulate soils. It is further believed that compounds
present in the sebum oxidise to contribute to the yellowing
of the fabrics. Particulate soils comprise mostly airborne
soil and floor/ground dust and include topsoil and products
produced during the incomplete combustion of petroleum
products. "Dingy clean up" means the ability of a detergent
composition to remove such dingy soil built-up, over one or
more washes, resulting in a measurable improvement in
fabric appearance.
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Whiteness maintenance is the monitoring of the
whiteness of wash & wear fabrics over a number of washing
cycles. A good performing detergent has a good whiteness
maintenance profile, i.e. it ensures that the whiteness of
the washed fabrics is maintained at a high level during the
complete life cycle of washing & wearing.
Specific Amylase Enzymes
An essential component of the detergent compositions
of the present invention is a specific amylase enzyme. Such
specific amylase enzymes include those described in
W095/26397 and in co-pending application by Novo Nordisk
PCT/DK96/00056. These enzymes are incorporated into
detergent compositions at a level from 0.0001% to 0.1% pure
en~yme by weight of the total composition, preferably at a
level of from 0.00018% to 0.060~, more preferably from
0.00024% to 0.048% pure enzyme by weight of total weight
composition.
Specific amylase enzymes for use in the detergent
compositions of the present invention therefore include :
(a) a-amylases characterised by having a specific actlvity
at least 25% higher than the specific activity of Termamyl~
at a temperature range of 25~C to 55~C and at a pH value in
the range of 8 to 10, measured by the Phadebas~ a-amylase
activity assay. Such Phadebas~ a-amylase activity assay is
described at pages 9-10, W095/26397.
~b) a-amylases according (a) comprising the amino sequence
shown in SEQ ID No. 1 or an a-amylase being at least 80%
homologous with the amino acid sequence shown in SEQ ID
No.1.
(c) a-amylases according (a) comprising the amino sequence
shown in SEQ ID No. 2 or an a-amylase being at least 80%
homologous with the amino acid sequence shown in SEQ ID
No . 2 .
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(d) a-amylases according (a) comprising the following amino
sequence in the N-terminal : His-His-Asn-Gly-Thr-Asn-Gly-
Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-Asn-Asp (SEQ ID
No.3) or an a-amylase being at least 80% homologous with
the amino acid sequence shown (SEQ ID No.3) in the N-
terminal.
A polypeptide is considered to be X% homologous to the
parent amylase if a comparison of the respective amino
acid sequences, performed via algorithms, such as the one
described by Lipman and Pearson in Science 227, 1985, p.
1435, reveals an identity of X%
(e) a-amylases according (a-d) wherein the a-amylase is
obtainable from an alkalophilic Bacillus species; and in
particular, from any of the strains NCIB 12289, NCIB 12512,
NCIB 12513 and DSM 935.
In the context of the present invention, the term
"obtainable from" is intended not only to indicate an
amylase produced by a Bacillus strain but also an amylase
encoded by a DNA sequence isolated from such a Bacillus
strain and produced in an host organism transformed with
said DNA sequence.
(f)a-amylase showing positive immunological cross-
reactivity with antibodies raised against an a-amylase
having an amino acid sequence corresponding respectively to
SEQ ID No.1, ID No.2 or ID No.3.
(g) Variants of the following parent a-amylases which (i)
have one of the amino acid sequences shown in SEQ ID No.1,
ID No.2 or ID No.4 respectively, or (ii)displays at least
80% homology with one or more of said amino acid sequences,
and/or displays immunological cross-reactivity with an
antibody raised against an a-amylase having one of said
amino acid sequences, and/or is encoded by a DNA sequence
wich hybridizes with the same probe as a DNA sequence
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encoding an a-amylase having one of said amino acid
sequence; in which variants :
1. at least one amino acid residue of said parent a-amylase
has been deleted; and/or
2. at least one amino acid residue of said parent a-amylase
has been replaced by a different amino acid residue; and/or
3. at least one amino acid residue has been inserted
relative to said parent a-amylase;
said variant having an a-amylase activity and exhibiting at
least one of the following properties relative to said
parent a-amylase : increased thermostability, increased
stability towards oxidation, reduced Ca ion dependency,
increased stability and/or a-amylolytic activity at neutral
to relatively high pH values, increased a-amylolytic
activity at relatively high temperature and increase or
decrease of the isoelectric point (pI) so as to better
match the pI value for a-amylase variant to the pH of the
medium.
Said variants are described in the co-pending patent
application PCT/DK96/00056.
Detergent components
The detergent compositions of the invention may also
contain additional detergent components. The precise
nature of these additional components, and levels of
incorporation thereof will depend on the physical form of
the composition, and the nature of the cleaning operation
for which it is to be used.
The compositions of the invention may be formulated as
hand and machine laundry detergent compositions including
laundry additive compositions and compositions suitable for
use in the soaking and/or pretreatment of stained fabrics,
rinse added fabric softener compositions.
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When formulated as compositions suitable for use in a
laundry machine washing method, the compositions of the
invention preferably contain both a surfactant and a
builder compound and additionally one or more detergent
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. Such additive products are
intended to supplement or boost the performance of
conventional detergent compositions.
If needed the density of the granular laundry
detergent compositions herein ranges from 400 to 1200
g/litre, preferably 600 to 950 g/litre of composition
measured at 20~C.
The "compact" form of the granular laundry detergent
compositions herein is best reflected by density and, in
terms of composition, by the amount of inorganic filler
salt; inorganic filler salts are conventional ingredients
of detergent compositions in powder form; in conventional
detergent compositions, the filler salts are present in
substantial amounts, typically 17-35% by weight of the
total composition.
In the compact compositions, the filler salt is
present in amounts not exceeding 15% of the total
composition, preferably not exceeding 10%, most preferably
not exceeding 5% by weight of the composition.
The inorganic filler salts, such as meant in the
present compositions are selected from the alkali and
alkaline-earth-metal salts of sulphates and chlorides.
A preferred 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 concentrated liquid
detergent is preferably less than 40%, more preferably less
than 30%, most preferably less than 20% by weight of the
detergent composition.
Surfactant system
The detergent compositions according to the present
invention can additionally comprise a surfactant system
wherein the surfactant can be selected from anionic and/or
nonionic 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 accordance
with the present invention.
Preferred systems to be used according to the present
invention comprise as a surfactant one or more of the
nonionic and/or anionic surfactants described herein.
Polyethylene, polypropylene, and polybytylene oxide
condensates of alkyl phenols are suitable for use as the
nonionic surfactant of the surfactant systems of the
present invention, with the polyethylene oxide condensates
being preferred. These compounds include the condensation
products of alkyl phenols having an alkyl group 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
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oxide. In a preferred embodiment, the ethylene oxide is
present in an amount equal to from about 2 to about 25
moles, more preferably from about 3 to about 15 moles, of
ethylene oxide per mole of alkyl phenol. 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 commonly
referred to as alkylphenol alkoxylates (e.g., alkyl phenol
ethoxylates).
The condensation products of primary and secondary
aliphatic alcohols with from about 1 to about 25 moles of
ethylene oxide are suitable for use as the nonionic
surfactant of the nonionic surfactant systems of the
present invention. The alkyl chain of the aliphatic alcohol
can either be straight or branched, primary or secondary,
and generally contains from about 8 to about 22 carbon
atoms. Preferred are the condensation products of alcohols
having an alkyl group containing from about 8 to about 20
carbon atoms, more preferably from about lO to about 18
carbon atoms, with from about 2 to about 10 moles of
ethylene ox'de 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 commercially
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 distribytion), both marketed by Union Carbide
Corporation; NeodolTM 45-9 (the condensation product of
Cl4-C1s linear alcohol with 9 moles of ethylene oxide),
NeodolTM 23-3 (the condensation product of C12-C13 linear
alcohol with 3.0 moles of ethylene oxide), NeodolTM 45-7
(the condensation product of C14-C1s linear alcohol with 7
moles of ethylene oxide), NeodolTM 45-5 (the condensation
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product of C14-C1s linear alcohol with 5 moles of ethylene
oxide) marketed by Shell Chemical Company, KyroTM EOB (the
condensation product of C13-C1s alcohol with 9 moles
ethylene oxide), marketed by The Procter & Gamble Company,
and Genapol LA 030 or 050 (the condensation product of C12-
C14 alcohol with 3 or 5 moles of ethylene oxide) marketed
by Hoechst. Preferred range of HLB in these products is
from 8-11 and most preferred from 8-10.
Also useful as the nonionic surfactant of the
surfactant systems of the present invention are the
alkylpolysaccharides disclosed in U.S. Patent 4,565,647,
Llenado, issued January 21, 1986, having a hydrophobic
group containing from about 6 to about 30 carbon atoms,
preferably from about 10 to about 16 carbon atoms and a
polysaccharide, e.g. a polyglycoside, hydrophilic group
containing from about 1.3 to about 10, preferably from
about 1.3 to about 3, most preferably from about 1.3 to
about 2.7 saccharide units. Any reducing saccharide
containing 5 or 6 carbon atoms can be used, e.g., glucose,
galactose and galactosyl moieties 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 preferred alkylpolyglycosides have the formula
R2o(cnH2no)t~g~-ycosyl)x
wherein R2 is selected from the group consisting of alkyl,
alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures
thereof in which the alkyl groups contain from about 10 to
about 18, preferably from about 12 to about 14, carbon
atoms; n is 2 or 3, preferably 2; t is from 0 to about 10,
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12
preferably 0; and x is from about 1.3 to about 10,
preferably from about 1.3 to about 3, most preferably from
about 1.3 to about 2.7. The glycosyl is preferably derived
from glucose. To prepare these compounds, the alcohol or
alkylpolyethoxy alcohol is formed first and then reacted
with glucose, or a source of glucose, to form the glucoside
(attachment at the 1-position). The additional glycosyl
units can then be attached between their 1-position and the
preceding glycosyl units 2-, 3-, 4- and/or 6-position,
preferably predominately the 2-position.
The condensation products of ethylene oxide with a
hydrophobic base formed by the condensation of propylene
oxide with propylene glycol are also suitable for use as
the additional 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
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 PluronicTM surfactants, marketed by BASF.
Also suitable for use as the nonionic surfactant of
the nonionic surfactant system of the present invention,
are the condensation products of ethylene oxide with the
product resulting from the reaction of propylene oxide and
ethylenediamine. The hydrophobic moiety of these products
consists of the reaction product of ethylenediamine and
excess propylene oxide, and generally has a molecular
weight of from about 2500 to about 3000. This hydrophobic
moiety is condensed with ethylene oxide to the extent that
r
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13
the condensation product contains from about 40% to about
80~ by weight of polyoxyethylene and has a molecular weight
of from about 5,000 to about 11,000. Examples of this type
- of nonionic surfactant include certain of the commercially
available TetronicTM compounds, marketed by BASF.
Preferred for use as the nonionic surfactant of the
surfactant systems of the present invention are
polyethylene oxide condensates of alkyl phenols,
condensation products of primary and secondary aliphatic
alcohols with from about 1 to about 25 moles of ethylene
oxide, alkylpolysaccharides, and mixtures thereof. Most
preferred are Cg-Cl4 alkyl phenol ethoxylates having from 3
to 15 ethoxy groups and Cg-C1g alcohol ethoxylates
(preferably C1o avg.) having from 2 to 10 ethoxy groups,
and mixtures thereof.
Highly preferred nonionic surfactants are polyhydroxy
fatty acid amide surfactants of the formula.
R2 - C - N - Z,
Il
O Rl
wherein R1 is H, or R1 is C1_4 hydrocarbyl, 2-hydroxy
ethyl, 2-hydroxy propyl or a mixture thereof, R2 is Cs_31
hydrocarbyl, and Z is a polyhydroxyhydrocarbyl having a
linear hydrocarbyl chain with at least 3 hydroxyls directly
connected to the chain, or an alkoxylated derivative
thereof. Preferably, R1 is methyl, R2 is a straight C1l_1s
alkyl or C16_1g 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.
When included in such detergent compositions, the
nonionic surfactant systems of the present invention act to
~ .
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14
improve the greasy/oily stain removal properties of such
detergent compositions across a broad range of cleaning
conditions.
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 S03
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 sulfonate
surfactants of the structural formula :
o
l l
R3 - CH - C - oR4
I
S03M
wherein R3 is a Cg-C20 hydrocarbyl, preferably an alkyl, or
combination thereof, R4 is a C1-C6 hydrocarbyl, preferably
an alkyl, or combination thereof, and M is a cation which
forms a water soluble salt with the alkyl ester sulfonate.
Suitable salt-forming cations include metals such as
sodium, potassium, and lithium, and substituted or
unsubstituted ammonium cations, such as monoethanolamine,
diethanolamine, and triethanolamine. Preferably, R3 is
C1o-C16 alkyl, and R4 is methyl, ethyl or isopropyl.
Especially preferred are the methyl ester sulfonates
wherein R3 is C1o-C16 alkyl.
Other suitable anionic surfactants include the alkyl
sulfate surfactants which are water soluble salts or acids
of the formula ROS03M wherein R preferably is a C1o-C24
hydrocarbyl, preferably an alkyl or hydroxyalkyl having a
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C1o-C20 alkyl component, more preferably a C12-C18 alkyl or
hydroxyalkyl, and M is H or a cation, e.g., an alkali metal
cation ~e.g. sodium, potassium, lithium), or ammonium or
substituted ammonium (e.g. methyl-, dimethyl-, and
trimethyl ammonium cations and quaternary ammonium cations
such as tetramethyl-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_1g alkyl
chains are preferred for higher wash temperatures (e.g.
above about 50~C).
Other anionic surfactants useful for detersive
purposes can also be included in the detergent compositions
of the present invention. These can include salts
(including, for example, sodium, potassium, ammonium, and
substituted ammonium salts such as mono-, di- and
triethanolamine salts) of soap, Cg-C22 primary of secondary
alkanesulfonates, Cg-C24 olefinsulfonates, sulfonated
polycarboxylic acids prepared by sulfonation of the
pyrolyzed product of alkaline earth metal citrates, e.g.,
as described in British patent specification No. 1,082,179,
Cg-C24 alkylpolyglycolethersulfates (containing up to 10
moles of ethylene oxide); alkyl glycerol sulfonates, fatty
acyl glycerol sulfonates, fatty oleyl glycerol sulfates,
alkyl phenol ethylene oxide ether sulfates, paraffin
sulfonates, alkyl phosphates, isethionates such as the acyl
isethionates, N-acyl taurates, alkyl succinamates and
sulfosuccinates, monoesters of sulfosuccinates (especially
saturated and unsaturated C12-C1g monoesters) and diesters
of sulfosuccinates (especially saturated and unsaturated
C6-C12 diesters), acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates,
, . .
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and alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH20)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 and hydrogenated resin acids
are also suitable, such as rosin, hydrogenated rosin, and
resin acids and hydrogenated resin acids present in or
derived from tall oil.
Further examples are described in "Surface Active Agents
and Detergents" (Vol. I and II by Schwartz, Perry and
Berch). A variety of such surfactants are also generally
disclosed in U.S. Patent 3,929,678, issued December 30,
1975 to Laughlin, et al. at Column 23, line 58 through
Column 29, line 23 (herein incorporated by reference).
Highly preferred anionic surfactants include alkyl
alkoxylated sulfate surfactants hereof are water soluble
salts or acids of the formula RO(A)mS03M wherein R is an
unsubstituted Clo-C24 alkyl or hydroxyalkyl group having a
Clo-C24 alkyl component, preferably a C12-C20 alkyl or
hydroxyalkyl, more preferably C12-Cl8 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, magnesium, etc.),
ammonium or substituted-ammonium cation. Alkyl ethoxylated
sulfates as well as alkyl propoxylated sulfates are
contemplated herein. Specific examples of substituted
ammonium cations include methyl-, dimethyl, trimethyl-
ammonium cations and quaternary ammonium cations such as
tetramethyl-ammonium and dimethyl piperdinium cations and
those derived from alkylamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are C12-C18 alkyl
polyethoxylate (1.0) sulfate (C12-ClgE(l.O)M)~ C12-C18
alkyl polyethoxylate (2.25) sulfate (C12-ClgE(2.25)M), C12-
Clg alkyl polyethoxylate (3.0) sulfate (C12-ClgE(3.0)M),
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17
and C12-C1g alkyl polyethoxylate (4.0) sulfate (C12-
C18E(4. O)M), wherein M is conveniently selected from sodium
and potassium.
Cationic detersive surfactants suitable for use in the
laundry detergent compositions of the present invention are
those having one long-chain hydrocarbyl group. Examples of
such cationic surfactants include the ammonium surfactants
such as alkyltrimethylammonium halogenides, and those
surfactants having the formula :
[R2(oR3)y][R4(OR3)y]2R5N+X~
wherein R2 is an alkyl or alkyl benzyl group having from
about 8 to about 18 carbon atoms in the alkyl chain, each
R3 is selected from the group consisting of -CH2CH2-, -
CH2CH(CH3)-, -CH2CH(CH20H)-, -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
polymer having a molecular weight less than about 1000, and
hydrogen when y is not O; 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 O to
about 10 and the sum of the y values is from O to about 15;
and X is any compatible anion.
Highly preferred cationic surfactants are the water-
soluble quaternary ammonium compounds useful in the
present composition having the formula :
RlR2R3R4N+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.
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18
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 byild up or OXO alcohols
synthesis.
Preferred groups for R2R3 and R4 are methyl and
hydroxyethyl groups and the anion X may be selected from
halide, methosulphate, acetate and phosphate ions.
Examples of suitable quaternary ammonium compounds of
formulae (i) for use herein are :
coconut trimethyl ammonium chloride or bromide;
coconut methyl dihydroxyethyl ammonium chloride or
bromide;
decyl triethyl ammonium chloride;
decyl dimethyl hydroxyethyl ammonium chloride or bromide;
C12_1s dimethyl hydroxyethyl ammonium chloride or
bromide;
coconut dimethyl hydroxyethyl ammonium chloride or
bromidei
myristyl trimethyl ammonium methyl sulphate;
lauryl dimethyl benzyl ammonium chloride or bromide;
lauryl dimethyl (ethenoxy)4 ammonium chloride or bromide;
choline esters (compounds of formula (i) wherein R1 is
CH2-CH2-O-C-C12_14 alkyl and R2R3R4 are methyl).
l l
o
di-alkyl imidazolines [compounds of formula ~
Other cationic surfactants useful herein are also
described in U.S. Patent 4,228,044, Cambre, issued October
14, 1980 and in European Patent Application EP 000,224.
Quaternary ammonium surfactants suitable for the present
invention have the formula (I):
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19
~RI 3 R4 X-
Formula I
whereby Rl is a short chainlength alkyl (C6-C10) or
alkylamidoalkyl of the formula (II) :
C6-C~ ~N~
Formula II
y is 2-4, preferably 3.
whereby R2 is H or a Cl-C3 alkyl,
whereby x is 0-4, preferably 0-2, most preferably 0,
whereby R3, R4 and R5 are either the same or different and
can be either a short chain alkyl (Cl-C3) or alkoxylated
alkyl of the formula III,
whereby X~ is a counterion, preferably a halide, e.g.
chloride or methylsulfate.
~~~z
Formula III
R6 is Cl-C4 and z is 1 or 2.
Preferred quat ammonium surfactants are those as
defined in formula I whereby
Rl is Cg, Clo or mixtures thereof, x=o,
R3, R4 = CH3 and Rs = CH2CH2OH.
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 surfactants.
.
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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- or
branched-chain. One of the aliphatic substituents contains
at least about 8 carbon atoms, typically from about 8 to
about 18 carbon atoms, and at least one contains an anionic
water-solubilizing group, e.g. carboxy, sulfonate, sulfate.
See U.S. Patent No. 3,929,678 to Laughlin et al., issued
December 30, 1975 at column 19, lines 18-35, for examples
of ampholytic surfactants.
When included therein, the detergent compositions of
the present invention typically comprise from 0. 2% to about
15%, preferably from about 1% to about 10% by weight of
such ampholytic surfactants.
Zwitterionic surfactants are also suitable for use in
detergent compositions. These surfactants can be broadly
described as derivatives of secondary and tertiary amines,
derivatives of heterocyclic secondary and tertiary amines,
or derivatives of quaternary ammonium, quaternary
phosphonium or tertiary sulfonium compounds. See U.S.
Patent No. 3, 929,678 to Laughlin et al., issued December
30, 1975 at column 19, line 38 through column 22, line 48,
for examples of zwitterionic surfactants.
When included therein, the detergent compositions of
the present invention typically comprise from 0. 2% to about
15%, preferably from about 1% to about 10% by weight of
such zwitterionic surfactants.
Semi-polar nonionic surfactants are a special category
of nonionic surfactants which include water-soluble amine
oxides containing one alkyl moiety of from about 10 to
about 18 carbon atoms and 2 moieties selected from the
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21
group consisting of alkyl groups and hydroxyalkyl 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 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 therof containing from about 8 to about 22
carbon atoms; R~ is an alkylene or hydroxyalkylene group
containing from about 2 to about 3 carbon atoms or mixtures
thereof; x is from 0 to about 3; and each R5 is an alkyl or
hydroxyalkyl group containing from about 1 to about 3
carbon atoms or a polyethylene oxide group containing from
about 1 to about 3 ethylene oxide groups. The R5 groups can
be attached to each other, e.g., through an oxygen or
nitrogen atom, to form a ring structure.
These amine oxide surfactants in particular include
C1o-C1g alkyl dimethyl amine oxides and Cg-C12 alkoxy ethyl
dihydroxy ethyl amine oxides.
When included therein, the detergent compositions of
the present invention typically comprise from 0.2% to about
15%, preferably from about 1% to about 10% by weight of
such semi-polar nonionic surfactants.
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22
The detergent composition of the present invention may
preferably further comprise a cosurfactant selected from
the group of primary or tertiary amines.
Suitable primary amines for use herein include amines
according to the formula R1NH2 wherein R1 is a C6-C12,
preferably C6-C1o alkyl chain or R4X~CH2)n, X is -O-,-
C(O)NH- or -NH-, R4 is a C6-C12 alkyl chain n is between 1
to 5, preferably 3. R1 alkyl chains may be straight or
branched and may be interrupted with up to 12, preferably
less than 5 ethylene oxide moieties.
Preferred amines according to the formula herein above are
n-alkyl amines. Suitable amines for use herein may be
selected from 1-hexylamine, 1-octylamine, 1-decylamine and
laurylamine. Other preferred primary amines include C8-C10
oxypropylamine, octyloxypropylamine, 2-ethylhexyl-
oxypropylamine, lauryl amido propylamine and amido
propylamine.
Suitable tertiary amines for use herein include
tertiary amines having the formula R1R2R3N wherein R1 and
R2 are C1-Cg alkylchains or
R5
- (CH2-CH - O)XH
R3 is either a C6-C12, preferably C6-C1o alkyl chain, or R3
is R4X(CH2)n, whereby X is -O-, -C(O)NH- or -NH-,Rg is a
C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-
C2 alkyl and x is between 1 to 6 .
R3 and Rg may be linear or branched ; R3 alkyl chains may
be interrupted with up to 12, preferably less than 5,
ethylene oxide moieties.
Preferred tertiary amines are R1R2R3N where R1 is a
C6-C12 alkyl chain, R2 and R3 are C1-C3 alkyl or
R5
- (CH2-CH - O)XH
where R5 is H or CH3 and x = 1-2.
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Also preferred are the amidoamines of the formula:
R1 -C-NH -(CH2)-N-(R2)2
wherein R1 is C6-C12 alkyl; n is 2-4,
preferably n is 3; R2 and R3 is C1-C4
Most preferred amines of the present invention include
~-octylamine, 1-hexylamine,1-decylamine, 1-dodecylamine,C8-
lOoxypropylamine, N coco 1-3diaminopropane, coconut-
alkyldimethylamine,lauryldimethylamine,lauryl bis(hydroxy-
ethyl)amine, coco bis(hydroxyehtyl)amine, lauryl amine 2
moles propoxylated, octyl amine 2 moles propoxylated,
lauryl 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.
Other detergent enzymes
The detergent compositions can in addition to specific
amylase enzymes further comprise one or more enzymes which
provide cleaning performance and/or fabric care benefits.
Preferred enzymes are proteases.
Said enzymes include enzymes selected from cellulases,
hemicellulases, peroxidases, proteases, gluco-amylases,
other amylases, xylanases, lipases, esterases, cutinases,
pectinases, reductases, oxidases, phenoloxidases,
lipoxygenases, ligninases, pullulanases, tannases,
pentosanases, malanases, ~-glucanases, arabinosidases
chondroitinase, laccase or mixtures thereof.
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A preferred comblnation is a cleaning composition
having a 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 cellulases 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.
Especially suitable cellulases are the cellulases having
color care benefits. 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'l, i.e.
to prevent transfer of dyes or pigments removed from
substrates during wash operations to other substrates in
the wash solution. Peroxidase enzymes are known in the art,
and include, for example, horseradish peroxidase,
ligninase, and haloperoxidase such as chloro- and bromo-
peroxidase.
Peroxidase-containing detergent compositions are
disclosed, for example, in PCT International Application WO
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89/099813 and in European Patent application EP No.
91202882.6, filed on November 6, 1991.
Said cellulases and/or peroxidases are normally
incorporated in the detergent composition at levels from
0.0001% to 2% of active enzyme by weight of the detergent
composition.
Preferred commercially available protease enzymes
include those sold under the tradenames Alcalase, Savinase,
Primase, Durazym, and Esperase by Novo Nordisk A/S
(Denmark), those sold under the tradename Maxatase,
Maxacal, Maxapem and Properase by Gist-Brocades, those sold
by Genencor International, and those sold under the
tradename Opticlean and Optimase by Solvay Enzymes. Also
proteases described in our co-pending application USSN
08/136,797 can be included in the detergent composition of
the invention. Protease 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.
Other preferred enzymes that can be included in the
detergent compositions of the present invention include
lipases. Suitable lipase enzymes for detergent usage
include those produced by microorganisms of the Pseudomonas
group, such as Pseudomonas stutzeri ATCC 19.154, as
disclosed in British Patent 1,372,034. Suitable lipases
include those which show a positive immunological cross-
reaction with the antibody of the lipase, produced by the
microorganism Pseudomonas fluorescent IAM 1057. This lipase
is available from Amano Pharmaceutical Co. Ltd., Nagoya,
Japan, under the trade name Lipase P "Amano," hereinafter
referred to as "Amano-P". Especially suitable lipases are
lipases such as M1 LipaseR and LipomaxR (Gist-Brocades) and
LipolaseR and Lipolase UltraR~Novo) which have found to be
very effective when used in combination with the
compositions of the present invention.
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26
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. Suitable
cutinases are described in WO 94/14963 and WO 94/14964.
Addition of cutinases to detergent compositions have been
described in e.g. WO-A-88/09367 (Genencor).
The lipases and/or cutinases are normally incorporated
in the detergent composition at levels from 0.0001% to 2~6
of active enzyme by weight of the detergent composition.
Other amylases (~ and/or ~) can be included for
removal of carbohydrate-based stains. Suitable amylases are
TermamylR~ (Novo Nordisk), FungamylR and BANR (Novo
Nordisk).
The above-mentioned enzymes may be of any suitable
origin, such as vegetable, animal, bacterial, fungal and
yeast origin.
Said enzymes are normally incorporated in the
detergent composition at levels from 0.0001~ to 2% of
active enzyme by weight of the detergent composition.
Other suitable detergent ingredients that can be added
are enzyme oxidation scavengers which are described in the
copending European patent application 92870018.6 filed on
January 31, 1992. Examples of such enzyme oxidation
scavengers are ethoxylated tetraethylene polyamines.
Color care benefits
Technologies which provide a type of color care benefit
can also be included. Examples of these technologies are
metallo catalysts for color maintenance. Such metallo
catalysts are described in the European patent EP 0 596 184
and in the copending European Patent Application No.
94870206.3.
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27
Bl ea chi ng agent
Bleach systems that can be included in the detergent
compositions of the present invention include bleaching
agents such as PB1, PB4 and percarbonate with a particle
size of 400-800 microns. These bleaching agent components
can include one or more oxygen bleaching agents and,
depending upon the bleaching agent chosen, one or more
bleach activators. When present oxygen bleaching compounds
will typically be present at levels of from about 1% to
about 25~. In general, bleaching compounds are optional
components in non-liquid formulations, e.g. granular
detergents.
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 encompasses percarboxylic acid bleaching agents and
salts thereof. Suitable examples of this class of agents
include magnesium monoperoxyphthalate hexahydrate, the
magnesium salt of meta-chloro perbenzoic acid, 4-
nonylamino-4-oxoperoxybytyric acid and
diperoxydodecanedioic acid. Such bleaching agents are
disclosed in U.S. Patent 4,483,781, U.S. Patent Application
740,446, European Patent Application 0,133,354 and U.S.
Patent 4,412,934. Highly preferred bleaching agents also
include 6-nonylamino-6-oxoperoxycaproic acid as described
in U.S. Patent 4,634,551.
Another category of bleaching agents that can be used
encompasses the halogen bleaching agents. Examples of
hypohalite bleaching agents, for example, include trichloro
isocyanuric acid and the sodium and potassium
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dichloroisocyanurates and N-chloro and N-bromo alkane
sulphonamides. Such materials are normally added at 0.5-10%
by weight of the finished product, preferably 1-5% by
weight.
The hydrogen peroxide releasing agents can be used in
combination with bleach activators such as
tetraacetylethylenediamine (TAED), nonanoyloxybenzene-
sulfonate (NOBS, described in US 4,412,934), 3,5,-
trimethylhexanoloxybenzenesulfonate ( ISONOBS, described in
EP lZ0,591) or pentaacetylglucose (PAG), which are
perhydrolyzed to form a peracid as the active bleaching
species, leading to improved bleaching effect. Also
suitable activators are acylated citrate esters such as
disclosed in Copending European Patent Application No.
91870207.7.
Useful bleaching agents, including peroxyacids and
bleaching systems comprising bleach activators and
peroxygen bleaching compounds for use in detergent
compositions according to the invention are described in
our co-pending applications USSN 08/136,626,
PCT/US95/07823, W095/27772, 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 substrate therefore)
which is capable of generating hydrogen peroxide at the
beginning or during the washing and/or rinsing process.
Such enzymatic systems are disclosed in EP Patent
Application 91202655.6 filed October 9, 1991.
Bleaching agents other than oxygen bleaching agents
are also known in the art and can be utilized herein. One
type of non-oxygen bleaching agent of particular interest
includes photoactivated bleaching agents such as the
sulfonated zinc and/or aluminum phthalocyanines. These
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29
materials can be deposited upon the substrate during the
washing process. Upon irradiation with light, in the
presence of oxygen, such as by hanging clothes out to dry
in the daylight, the sulfonated zinc phthalocyanine is
activated and, consequently, the substrate is bleached.
Preferred zinc phthalocyanine and a photoactivated
bleaching process are described in U.S. Patent 4,033,718.
Typically, detergent compositions will contain about 0.025%
to about 1.25%, by welght, of sulfonated zinc
phthalocyanine.
Builder system
The compositions according to the present invention
may further comprise a builder system.
Any conventional builder system is suitable for use
herein including aluminosilicate materials, silicates,
polycarboxylates and fatty acids, materials such as
ethylenediamine tetraacetate, diethylene triamine
pentamethyleneacetate, metal ion sequestrants such as
aminopolyphosphonates, particularly ethylenediamine
tetramethylene phosphonic acid and diethylene triamine
pentamethylenephosphonic acid. Though less preferred for
obvious environmental reasons, phosphate builders can also
be used herein.
Suitable builders can be an inorganic ion exchange
material, commonly an inorganic hydrated aluminosilicate
material, more particularly a hydrated synthetic zeolite
such as hydrated zeolite A, X, B, HS or MAP.
Another suitable inorganic builder material is layered
silicate, e.g. SKS-6 (Hoechst). SKS-6 is a crystalline
layered silicate consisting of sodium silicate (Na2Si2Os).
Suitable polycarboxylates containing one carboxy group
include lactic acid, glycolic acid and ether derivatives
thereof as disclosed in Belgian Patent Nos. 831,368,
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821,369 and 821,370. Polycarboxylates containing two
carboxy groups include the water-soluble salts of succinic
acid, malonic acid, (ethylenedioxy) diacetic acid, maleic
acid, diglycollic acid, tartaric acid, tartronic acid and
fumaric acid, as well as the ether carboxylates described
in German Offenlegenschrift 2,446,686, and 2,446,687 and
U.S. Patent No. 3,935,257 and the sulfinyl 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
carboxymethyloxysuccinates described in British Patent No.
1,379,241, lactoxysuccinates 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.
Polycarboxylates containing four carboxy groups
include oxydisuccinates disclosed in British Patent No.
1,261,829, 1,1,2,2-ethane tetracarboxylates, 1,1,3,3-
propane tetracarboxylates and 1,1,2,3-propane
tetracarboxylates. Polycarboxylates containing sulfo
substituents include the sulfosuccinate derivatives
disclosed in British Patent Nos. 1,398,421 and 1,398,422
and in U.S. Patent No. 3,936,448, and the sulfonated
pyrolysed citrates described in British Patent No.
l,082,179, while polycarboxylates containing phosphone
substituents are disclosed in British Patent No. 1,439,000.
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-
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31
carboxylates include mellitic acid, pyromellitic acid and
the phthalic acid derivatives disclosed in British Patent
No. 1, 425,343.
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy groups
per molecule, more particularly citrates.
Preferred builder systems for use in the present
compositions include a mixture of a water-insoluble
aluminosilicate builder such as zeolite A or of a layered
silicate (SKS-6), and a water-soluble carboxylate chelating
agent such as citric acid.
A suitable chelant for inclusion in the detergent
compositions in accordance with the invention is
ethylenediamine-N,N'-disuccinic acid (EDDS) or the alkali
metal, alkaline earth metal, ammonium, or substituted
ammonium salts thereof, or mixtures thereof. Preferred EDDS
compounds are the free acid form and the sodium or
magnesium salt thereof. Examples of such preferred sodium
salts of EDDS include Na2EDDS and Na4EDDS. Examples of such
preferred magnesium salts of EDDS include MgEDDS and
Mg2EDDS. The magnesium salts are the most preferred for
inclusion in compositions in accordance with the invention.
Preferred builder systems include a mixture of a
water-insoluble aluminosilicate builder such as zeolite A,
and a watersoluble carboxylate chelating agent such as
citric acid.
Other builder materials that can form part of the builder
system for use in granular compositions include inorganic
materials such as alkali metal carbonates, bicarbonates,
silicates, and organic materials such as the organic
phosphonates, amino polyalkylene phosphonates and amino
polycarboxylates.
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32
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 10% to 80% by weight of the composition
preferably from 20% to 70'~ and most usually from 30% to 60%
by weight.
Suds suppressor
Another optional ingredient is a suds suppressor,
exemplified by silicones, and silica-silicone mixtures.
Silicones can be generally represented by alkylated
polysiloxane materials while silica is normally used in
finely divided forms exemplified by silica aerogels and
xerogels and hydrophobic silicas of various types. These
materials can be incorporated as particulates in which the
suds suppressor is advantageously releasably incorporated
in a water-soluble or water-dispersible, substantially non-
surface-active detergent impermeable carrier. Alternatively
the suds suppressor can be dissolved or dispersed in a
liquid carrier and applied by spraying on to one or more of
the other components.
A preferred silicone suds 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 suppressors, described in German
Patent Application DTOS 2 646 126 published April 28, 1977.
An example of such a compound is DC-54~, commercially
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33
available from Dow Corning, which is a siloxane-glycol
copolymer. Especially preferred suds controlling agent are
the suds suppressor system comprising a mixture of silicone
oils and 2-alkyl-alcanols. Suitable 2-alkyl-alkanols are 2-
bytyl-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 Copending European Patent application
N~92201649.8. Said compositions can comprise a
silicone/silica mixture in combination with fumed nonporous
silica such as AerosilR.
The suds suppressors described above are normally
employed at levels of from 0.001% to 2% by weight of the
composition, preferably from 0.01% to 1% by weight.
Others
Other components used in detergent compositions may be
employed, such as soil-suspending agents, soil-release
agents, optical brighteners, abrasives, bactericides,
tarnish inhibitors, coloring agents, and/or encapsulated or
non-encapsulated perfumes.
Especially suitable encapsulating materials are water
soluble capsules which consist of a matrix of
polysaccharide and polyhydroxy compounds such as described
in GB 1,464,616.
Other suitable water soluble encapsulating materials
comprise dextrins derived from ungelatinized starch acid-
esters of substituted dicarboxylic acids such as described
in US 3,455,838. These acid-ester dextrins are,preferably,
prepared from such starches as waxy maize, waxy sorghum,
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34
sago, tapioca and potato. Suitable examples of said
encapsulating 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 monofunctional substituted groups such
as octenyl succinic acid anhydride.
Antiredeposition 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 materials are normally used at levels of from 0.5~ to
10% by weight, more preferably from 0.75% to 8%, most
preferably from 1% to 6% by weight of the composition.
Preferred optical brighteners are anionic in
character, examples of which are disodium 4,4'-bis-(2-
diethanolamino-4-anilino -s- triazin-6-ylamino)stilbene-
2:2' disulphonate, disodium 4, - 4'-bis-(2-morpholino-4-
anilino-s-triazin-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-sodium 4,4' -bis-(4-phenyl-2,1,3-triazol-
2-yl)-stilbene-2,2' disulphonate, di-so-dium 4,4'bis(2-
anilino-4-~1-methyl-2-hydroxyethylamino)-s-triazin-6-
ylami-no)stilbene-2,2'disulphonate, sodium 2(stilbyl-4''-
(naphtho-1',2':4,5)-1,2,3 - triazole-2''-sulphonate and
4,4'-bis(2-sulphostyryl)biphenyl. Highly preferred
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brighteners are the specific brighteners of copending
European Patent application No. 95201943.8.
Other useful polymeric materials are the polyethylene
glycols, particularly those of molecular weight 1000-10000,
more particularly 2000 to 8000 and most preferably about
4000. These are used at levels of from 0.20~ to 5% more
preferably from 0.25~ to 2.5% by weight. These polymers and
the previously mentioned homo- or co-polymeric
polycarboxylate salts are valuable for improving whiteness
maintenance, fabric ash deposition, and cleaning
performance on clay, proteinaceous and oxidizable soils in
the presence of transition metal impurities.
Soil release agents useful in compositions of the
present invention are conventionally copolymers or
terpolymers of terephthalic acid with ethylene glycol
and/or propylene glycol units in various arrangements.
Examples of such polymers are disclosed in the commonly
assigned US Patent Nos. 4116885 and 4711730 and European
Published Patent Application No. 0 272 033. A particular
preferred polymer in accordance with EP-A-0 272 033 has the
formula
(CH3(pEG)43)o.7s(poH)o.2s[T-po)2.8(T-pEG)o 4]T(PO-
H)o.2s((pEG)43cH3)o.75
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, ethylene glycol and 1-2 propane diol,
the end groups consisting primarily of sulphobenzoate and
secondarily of mono esters of ethylene glycol and/or
propane-diol. The target is to obtain a polymer capped at
both end by sulphobenzoate groups, "primarily", in the
present context most of said copolymers herein will be end-
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36
capped by sulphobenzoate groups. However, some copolymers
will be less than fully capped, and therefore their end
groups may consist of monoester of ethylene glycol and/or
propane 1-2 diol, thereof consist "secondarily" of such
species.
The selected polyesters herein contain about 4 6% by
weight of dimethyl terephthalic acid, about 16% by weight
of propane -1.2 diol, about 10% by weight ethylene glycol
about 13% by weight of dimethyl sulfobenzoic acid and about
15% by weight of sulfoisophthalic acid, and have a
molecular weight of about 3.000. The polyesters and their
method of preparation are described in detail in EPA 311
342.
Is is well known in the art that free chlorine in tap
water rapidly deactivates the enzymes comprised in
detergent compositions. Therefore, using chlorine scavenger
such as perborate, ammonium sulfate, sodium sulphite or
polyethyleneimine at a level above 0.1% by weight of total
composition, in the formulas will provide improved through
the wash stability of the specific amylase enzymes.
Compositions comprising chlorine scavenger are described in
the European patent application 92870018.6 filed January
31, 1992.
Sof t ening agen t s
Fabric softening 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 disclosed in GB-A-1 400 898 and in USP
5,019,292. Organic fabric softening agents include the
water insoluble tertiary amines as disclosed in GB-A1 514
276 and EP-B0 011 340 and their combination with mono C12-
C14 quaternary ammonium salts are disclosed in EP-B-0 026
. .
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37
527 and EP-B-0 026 528 and di-long-chain amides as
disclosedin 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 softening
agents such as the water-insoluble tertiary amines or
dilong chain amide materials are incorporated at levels of
from 0.5% to 5% by weight, normally from l9o 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.
Dye transfer inhibition
The detergent composition of the present invention can
also include compounds for inhibiting dye transfer from one
fabric to another of solubilized and suspended dyes
encountered during fabric laundering operations involving
colored fabrics.
Polymeric dye transfer inhibiting agents
The detergent compositions according to the present
invention also comprise from 0.001% to 10 %, preferably
from 0.01% to 2~, more preferably from 0.05% to 1% by
weight of polymeric dye transfer inhibiting agents. Said
polymeric dye transfer inhibiting agents are normally
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38
incorporated into detergent compositions in order to
inhibit the transfer of dyes from colored fabrics onto
fabrics washed therewith. These polymers have the ability
to complex or adsorb the fugitive dyes washed out of dyed
fabrics before the dyes have the opportunity to become
attached to other articles in the wash.
Especially suitable polymeric dye transfer inhibiting
agents are polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone
polymers, polyvinyloxazolidones and polyvinylimidazoles or
mixtures thereof.
Addition of such polymers also enhances the performance of
the enzymes according the invention.
a) Polyamine N-oxide polymers
The polyamine N-oxide polymers suitable for use
contain units having the following structure formula :
p
I
(I) AX
I
R
wherein P is a polymerisable unit, whereto the R-N-O group
can be attached to or wherein the R-N-O group forms
part of the polymerisable unit or a combination of
both.
O O O
Il 11 11
A is NC, CO, C, -O-,-S-, -N- ; x is O or 1;
R are aliphatic, ethoxylated aliphatics, aromatic,
heterocyclic or alicyclic groups or any
combination thereof whereto the nitrogen of the N-O
group can be attached or wherein the nitrogen of
the N-O group is part of these groups.
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39
The N-O group can be represented by the following
general structures :
O O
(Rl~x -N- (R2)y =N- (Rl)x
I
(R3)z
wherein R1, R2, and R3 are aliphatic groups, aromatic,
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 attached or
wherein the nitrogen of the N-O group forms part of
these groups.
The N-O group can be part of the polymerisable unit
(P) or can be attached to the polymeric backbone or a
combination of both.
Suitable polyamine N-oxides wherein the N-O group forms
part of the polymerisable unit comprise polyamine N-oxides
wherein R is selected from aliphatic, aromatic, alicyclic
or heterocyclic groups.
One class of said polyamine N-oxides comprises the group of
polyamine N-oxides wherein the nitrogen of the N-O group
forms part of the R-group. Preferred polyamine N-oxides
are those wherein R is a heterocyclic group such as
pyrridine, pyrrole, imidazole, pyrrolidine, piperidine,
quinoline, acridine and derivatives thereof.
Another class of said polyamine N-oxides comprises the
group of polyamine N-oxides wherein the nitrogen of the N-O
group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine
oxides whereto the N-O group is attached to the
polymerisable unit.
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Preferred class of these polyamine N-oxides are the
polyamine N-oxides having the general formula (I) wherein R
is an aromatic, heterocyclic or alicyclic groups wherein
the nitrogen of the N-O functional group is part of said R
group.
Examples of these classes are polyamine oxides wherein R is
a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the
polyamine oxides having the general formula ~I) wherein R
are aromatic, heterocyclic or alicyclic groups wherein the
nitrogen of the N-O functional group is attached to said R
groups.
Examples of these classes are polyamine oxides wherein
R groups can be aromatic such as phenyl.
Any polymer backbone can be used as long as the amine
oxide polymer formed is water-soluble and has dye transfer
inhibiting properties. Examples of suitable polymeric
backbones are polyvinyls, polyalkylenes, polyesters,
polyethers, polyamide, polyimides, polyacrylates and
mixtures thereof.
The amine N-oxide polymers of the present invention
typically have a ratio of amine to the amine N-oxide of
10:1 to 1:1000000. However the amount of amine oxide groups
present in the polyamine oxide polymer can be varied by
appropriate copolymerization or by appropriate degree of N-
oxidation. Preferably, the ratio of amine to amine N-oxide
is from 2:3 to 1:1000000. More preferably from 1:4 to
1:1000000, most preferably from 1:7 to 1:1000000. The
polymers of the present invention actually encompass random
or block copolymers where one monomer type is an amine N-
oxide and the other monomer type is either an amine N-oxide
or not. The amine oxide unit of the polyamine N-oxides has
a PKa < 10, preferably PKa ~ 7, more preferred PKa < 6.
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~1
The polyamine oxides can be obtained in almost any degree
of polymerisation. The degree of polymerisation is not
critical provided the material has the desired water-
solubility and dye-suspending power.
Typically, the average molecular weight is within the
range of 500 to 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-vinylimidazole
The N-vinylimidazole N-vinylpyrrolidone polymers used
in the present invention have an average molecular weight
range from 5,000-1,000,000, preferably from 5,000-200,000.
Highly preferred polymers for use in detergent
compositions according to the present invention comprise a
polymer selected from N-vinylimidazole N-vinylpyrrolidone
copolymers wherein said polymer has an average molecular
weight range from 5,000 to 50,000 more preferably from
8,000 to 30,000, most preferably from 10,000 to 20,000.
The average 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 preferred 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-vinylimidazole 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
present invention has a molar ratio of N-vinylimidazole to
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~2
N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8
to 0.3, most preferably from 0.6 to 0.4 .
c) Polyvinylpyrrolidone
The 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 commercially vailable from ISP
Corporation, New York, NY and Montreal, Canada under the
product names PVP K-15 (viscosity molecular weight of
10,000), PVP K-30 ~average molecular weight of 40,000), PVP
K-60 (average molecular weight of 160,000), and PVP K-90
(average molecular 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 detergent compositions of the present invention
may also utilize polyvinyloxazolidone as a polymeric dye
transfer inhibiting agent. Said polyvinyloxazolidones have
an average molecular weight of from about 2,500 to about
400,000, 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.
e) Polyvinylimidazole :
The detergent compositions of the present invention
may also utilize polyvinylimidazole as polymeric dye
T ~
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43
transfer inhibiting agent. Said polyvinylimidazoles 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.
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 with active groups n
the backbone or on branches; cross-linked polymers have
been described in the Journal of Polymer Science, volume
22, pages 1035-1039.
In one embodiment, the cross-linked polymers are made
in such a way that they form a three-dimensional rigid
structure, which can entrap dyes in the pores formed by the
three-dimensional structure. In another embodiment, the
cross-linked polymers entrap the dyes by swelling.
Such cross-linked polymers are described in the co-
pending patent application 94870213.9
Method of washing
The cleaning compositions according to the invention
can be liquid, paste, gels, bars, tablets, powder or
granular forms. Granular compositions can also be in
"compact " form, the liquid compositions can also be in a
"concentrated" form.
The compositions of the invention may be used in
essentially any washing or cleaning methods, including
soaking methods, pretreatment methods and methods with
.
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44
rinsing steps for which a separate rinse aid composition
may be added.
The process described herein comprises contacting
fabrics with a laundering solution in the usual manner and
exemplified hereunder.
The process of the invention is conveniently carried
out in the course of the cleaning process. The method of
cleaning is preferably carried out at 5 ~C to 95 ~C,
especially between 10~C and 60~C. However, specific amylase
enzymes within the specified enzymatic concentration, have
demonstrated superior starch cleaning even for wash cycles
occuring at very low temperatures ~between 10~C and 25~C).
The pH of the treatment solution is preferably from 7 to
11 .
The following examples are meant to exemplify
compositions of the present invention, but are not
necessarily meant to limit or otherwise define the scope of
the invention.
In the detergent compositions, the enzymes levels are
expressed by pure enzyme by weight of the total composition
and unless otherwise specified, the detergent ingredients
are expressed by weight of the total compositions. The
abbreviated component identifications therein have the
following meanings:
LAS : Sodium linear C12 alkyl benzene
sulphonate
TAS : Sodium tallow alkyl sulphate
CXYAS : Sodium C1x - C1y alkyl sulfate
---T -~
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25EY : A C12_C1s predominantly linear primary
alcohol condensed with an average of Y
moles of ethylene oxide
CXYEZ : A Clx - C1y predominantly linear primary
alcohol condensed with an average of Z
moles of ethylene oxide
XYEZS : C1x ~ C1y sodium alkyl sulfate condensed
with an average of Z moles of ethylene
oxide per mole
QAS : R2.N+(CH3)2(C2H4OH~ with R2 = C12-C14
Soap : Sodium linear alkyl carboxylate derived
from a 80/20 mixture of tallow and
coconut oils.
Nonionic : C13-C1s mixed ethoxylated/propoxylated
fatty alcohol with an average degree of
ethoxylation of 3.8 and an average
degree of propoxylation of 4.5 sold
under the tradename Plurafac LF404 by
BASF Gmbh.
CFAA : C12-C14 alkyl N-methyl glucamide
TFA~ : C16-C1g alkyl N-methyl glucamide.
TPKFA : C12-C14 topped whole cut fatty acids.
DEQA : Di-(tallow-oxy-ethyl) dimethyl ammonium
chloride.
DTDMAMS : Ditallow dimethyl ammonium
methylsulfate.
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SDASA : 1:2 ratio of stearyldimethyl
amine:triple-pressed stearic acid.
Neodol 45-13 : C14-C15 linear primary alcohol
ethoxylate, sold by Shell Chemical CO.
Silicate : Amorphous Sodium Silicate (SiO2:Na2O
ratio = 2.0)
NaSKS-6 : Crystalline layered silicate of formula
a-Na2Si205 .
Carbonate : Anhydrous sodium carbonate with a
particle size between 200 ~m and 900~m.
Bicarbonate : Anhydrous sodium bicarbonate with a
particle size between 400 ~lm and 1200~m.
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
molecular weight of 8,000 sold under the
tradename PA30 by BAS~ GmbH
Zeolite A : Hydrated Sodium Aluminosilicate of
formula Na12(AlO2SiO2)12. 27H20 having a
primary particle size in the range from
0.1 to 10 micrometers
Citrate : Tri-sodium citrate dihydrate of activity
86,4% with a particle size distribution
between 425 ~m and 850 ~m.
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47
Citric : Anhydrous citric acid
PB1 : Anhydrous sodium perborate monohydrate
bleach, empirical formula NaBO2.H2O2
PB4 : Anhydrous sodium perborate tetrahydrate
~ercarbonate : Anhydrous sodium percarbonate bleach of
empirical formula 2Na2CO3.3H2O2
TAED : Tetraacetyl ethylene diamine.
NOBS : Nonanoyloxybenzene sulfonate in the form
of the sodium salt.
~hotoactivated : Sulfonated zinc phtlocyanine
Bleach encapsulated in dextrin soluble polymer.
Protease : Proteolytic enzyme sold under the
tradename Savinase, Alcalase, Durazym by
Novo Nordisk A/S, Maxacal, Maxapem sold
by Gist-Brocades and proteases described
in patents WO91/06637 and/or WO95/10591
and/or EP 251 446.
Amylase : Specific amylase according to the
present invention.
Lipase : Lipolytic enzyme sold under the
tradename Lipolase, Lipolase Ultra by
Novo Nordisk A/S
Cellulase : Cellulytic enzyme sold under the
tradename Carezyme, Celluzyme and/or
Endolase by Novo Nordisk A/S.
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48
CMC : Sodium carboxymethyl cellulose.
HEDP : 1,1-hydroxyethane diphosphonic acid.
DETPM~ 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 : Polydimethylsiloxane foam controller
antifoam with siloxane-oxyalkylene copolymer as
dispersing agent with a ratio of said
foam controller to said dispersing agent
of 10:1 to 100:1.
Granular Suds : 12% Silicone/silica, 18% stearyl
Suppressor alcohol,70% starch in 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.
.
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49
Sulphate : Anhydrous sodium sulphate.
HMWPEO : High molecular weight polyethylene oxide
PEG : Polyethylene glycol.
Encapsulated : Insoluble fragrance delivery technology
perfume utilising zeolite 13x, perfume and a
particles dextrose/glycerin agglomerating binder.
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Example 1
The following laundry detergent compositions were
prepared in accord with the invention:
I II III IV V VI
L~S 8.0 8.0 8.0 8.0 8.0 8.0
C25E3 3.4 3.4 3.4 3.4 3 4 3.4
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 18.1 18.118.118.1 18.1 18.1
Carbonate 13.0 13.013.0 27.0 27.0 27.0
Silicate 1.4 1.4 1.4 3.0 3.0 3.0
Sulfate 26.1 26.126.1 26.1 26.1 26.1
PB4 9.0 9.0 9.0 9.0 9.0 g.o
TAED 1.5 1.5. 1.5 1.5 1.5 1.5
DETPMP 0.25 0.250.25 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 0.0009 0.0003 0.0009 0.05 0.002 0.01
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
Photoactivated 15 15 15 15 15 15
bleach (ppm)
Brightener 10.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Silicone 0.5 0.5 0.5 0.5 0.5 0.5
antifoam
Misc/minors to 100%
Density in 850 850 850 850 850 850
g/litre
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51
Example 2
The following granular laundry detergent compositions
of bulk density 750 g/litre were prepared in accord with
the invention:
I II III
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 - 10.6 10.6
acid (79:21)
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
Protease 0.0026 0.0085 0.045
Lipase 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006
Amylase 0.0008 0.005 0.0002
MA/AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated 15 ppm 27 ppm 27 ppm
bleach (ppm)
Brightener 1 0.08 0.19 0.19
Brightener 2 - 0.04 0.04
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Encapsulated 0.3 0.3 0.3
perfume particles
Silicone antifoam 0. 5 2.4 2.4
Minors/misc to
1 0 0%
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53
Example 3
The following detergent formulations, according to the
present invention were prepared, where I is a phosphorus-
containing detergent composition, II is a zeolite-
- containing detergent composition and III is a compact
detergent composition:
I II III
Blown Powder
STPP 24.0 - 24.0
Zeolite A - 24.0
C45AS 9.0 6.0 13.0
MA/AA 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
Photoactivated 0.02 0.02 0.02
bleach
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.002 0.0004 0.01
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54
Dry mixed sodium 3.0 3.0 5.0
sulfate
Balance (Moisture &100.0 100.0 100.0
Miscellaneous)
Density tg/litre) 630 670 670
r
CA 022617~4 1999-01-28
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Example 4
The following nil bleach-containing detergent
formulations of particular use in the washing of colored
clothing, according to the present invention were prepared:
I II III
Blown Powder
Zeollte A 15.0 15.0
Sodium sulfate 0.0 5.0
LAS 3.0 3.0
DETPMP 0.9 0.5
CMC 0.4 0.4
MA/AA 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/AA - - 2.0
Carbonate 9.0 7.0 7.0
Spray On
Perfume 0.3 0.3 0.5
C45E7 4.0 4.0 4 0
C25E3 2.0 2.0 2.0
Dry additives
MA/AA - - 3.0
NaSKS-6 - - 12.0
Citrate 10.0 - 8.0
Bicarbonate 7.0 3.0 5.0
Carbonate 8.0 5.0 7.0
PVPVI/PVNO 0.5 0.5 0.5
Protease 0.026 0.016 0.047
Lipase 0.009 0.009 0.009
Amylase 0.005 0.0003 0.01
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56
Cellulase 0.004 0.004 0.004
Silicone antifoam 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
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57
Example 5
The following detergent formulations, according to the
present invention were prepared:
I II III IV
LAS 20.0 14.0 24.0 22.0
QAS 0.7 1.0 - 0.7
TFAA - 1.0 - -
C25E5/C95E7 - 2.0 - 0.5
C45E3S - 2.5
STPP 30.0 18.0 30.0 22.0
Silicate 9.0 5.0 10.0 8.0
Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5
DETPMP 0.7 1.0
SRP 1 0.3 0.2 - 0.1
MA/AA 2.0 1.5 2.0 1.0
CMC 0.8 0.4 0.4 0.2
Protease 0.008 0.01 0.025 0.026
Amylase 0.007 0.004 0.0003 0.002
Lipase 0.004 0.002 0.004 0.002
Cellulase 0.00035 0.0001
Photoactivated7Oppm 45ppm - lOppm
bleach (ppm)
Brightener 1 0.2 0.2 0.08 0.2
PB1 6.0 2.0
NOBS 2.0 1.0
Balance 100 100 100 100
(Moisture and
Miscellaneous)
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58
Example 6
The following detergent formulations, according to the
present invention were prepared:
I II III IV
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/AA 3.0 3.0 6.0
LAS 14.0 12.0 22.0 21.5
C45AS 8.0 7.0 7.0 5.5
Cationic - - - 1.0
Silicate - 1.0 5.0 11.4
Soap - - 2.0
Brightener 1 0.2 0.2 0.2
Carbonate 8.0 16.0 20.0 10.0
DETPMP - 0.4 0.4
Spray On
C45E7 1.0 1.0 1.0 3.2
Dry additives
PVPVI/PVNO 0.5 0.5 0.5
Protease 0.052 0.01 0.01 0.01
Lipase 0.009 0.009 0.009 0.009
Amylase 0.0008 0.0015 0.02 0.0004
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 100 100 100
and Miscellaneous)
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59
Example 7
The following high density and bleach-containing
detergent formulations, according to the present invention
were prepared:
I II III
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/AA 4.0 2.0 2.0
Agglomerates
LAS 5.0 5.0 5.0
TAS 2.0 2.0 1.0
Silicate 3.0 3.0 4.0
Zeolite A 8.0 8.0 8.0
Carbonate 8.0 8.0 4.0
Spray On
Perfume 0.3 0.3 0.3
C45E7 2.0 2.0 2.0
C25E3 2.0 - -
Dry additives
Citrate 5.0 - 2.0
Bicarbonate - 3.0
Carbonate 8.0 15.0 10.0
TAED 6.0 2.0 5.0
PB1 14.0 7.0 10.0
Polyethylene oxide of MW - - 0.2
5,000,000
Bentonite clay - - 10.0
Protease 0.01 0.01 0.01
Lipase 0.009 0.009 0.009
Amylase 0.005 0.003 0.02
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Cellulase 0.002 0.002 0.002
Silicone antifoam 5.0 5.0 5.0
Dry additives
Sodium sulfate 0.0 3.0 0.0
Balance (Moisture and 100.0 100.0 100.0
Miscellaneous)
Density (g/litre) 850 850 850
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61
Example 8
The following high density detergent formulations,
according to the present invention were prepared:
I II
Agglomerate
C45AS 11.0 19.0
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 0.9
Spray On
C25E5 5.0 5 0
Perfume 0.5 0.5
Dry Adds
HEDP 0.5 0.3
SKS 6 13.0 10.0
Citrate 3.0 1.0
TAED 5.0 7.0
Percarbonate 20.0 20.0
SRP 1 0.3 0.3
Protease 0.015 0.015
Lipase 0.009 0.009
Cellulase 0.002 0.002
Amylase 0.005 0.005
Silicone antifoam 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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62
Example 9
The following granular detergent formulations,
according to the present invention were prepared:
I II III IV 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 - 0.4 0.7 0.7 0. 8
hydroxyethyl NH4+Cl
Nonionic 1. 2 - 0.9 0.5
Coco C12-14 Fatty - - - - 1.0
Alcohol
STPP 44.0 25.0 22.5 22.5 22.5
Zeolite A 7.0 10.0 - - ~.0
MA/AA - - o.g o.g
SRPl 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
Protease 0.007 0.007 0.0070.007 0.007
Amylase 0. 008 0.004 0.0030.004 0.04
Lipase 0.003 0.003 0.003
Cellulase - 0.001 0.0010.001 0.001
NOBS - - - 1. 2 1.0
PB1 - - - 2.4 1.2
Diethylene triamine - - - 0.7 1.0
penta acetic acid
Diethylene triamine - - 0.6
penta methyl
phosphonic acid
Mg Sulfate - - 0.8
Photoactivated bleach 45 50 15 45 42
ppm ppm 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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63
Example 10
The following liquid detergent formulations, according
to the present invention were prepared:
- I II III IV V VI VII VIII
LAS 10.013.0 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
TFAA - - - 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 - - _ 5 0 _ _ 4 0 4 0
fatty aclds
Citric 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0
Dodecenyl/ 12.010.0 - - 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 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.-
Propanediol
Mono Ethanol - - - 5.0 - - 9.C 9.0
Amine
Tri Ethanol - - 8
Amine
NaOH tpH) 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
tetra-
ethylene
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
Protease .016.016 .013 .008.048 .016 0.01 .019
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64
Lipase - .002 - .001 - - ~003 ~003
Amylase .002 .002.0005 .04 .0008.0008 .005 .005
Cellulase - - - .001 - - .002 .001
Boric acid 0.1 0.2 - 2.0 1.0 1.5 2.5 2.5
Na formate - - 1.0
Ca chloride - 0.01 - 0.01
Bentonite - - - - 4.0 4 C
clay
Suspending - - - - 0.6 0.3
clay SD3
Balance 100 100 100 100 100 100 100 100
Moisture and
Miscellaneou
s
CA 022617~4 1999-01-28
W O 98/05748 PCT~US96112612
Example 11
Granular fabric cleaning compositions which provide
"softening through the wash" capability were prepared in
accord with the present invention :
I II
45AS - 10.0
LAS 7.6
68AS 1.3
45E7 4.0
25E3 - 5.0
Coco-alkyl-dimethyl hydroxy- 1.4 1.0
ethyl ammonium chloride
Citrate 5.0 3.0
Na-SKS-6 - 11.0
Zeolite A 15.0 15.0
MA/AA 4.0 4.0
DETPMP 0.4 0.4
PB1 15.0
Percarbonate - 15.0
TAED 5.0 5.0
Smectite clay 10.0 10.0
HMWPEO - O.1
Protease 0.02 0.01
Lipase 0.02 0.01
Amylase 0.03 0.005
Cellulase 0.001
Silicate 3.0 5.0
Carbonate 10.0 10.0
Granular suds suppressor 1.0 4.0
CMC 0.2 0.1
Water/minors Up to 100%
CA 0226l754 l999-0l-28
WO 9810~748 PCT~US96/12612 66
Example 12
The following rinse added fabric softener composition
was prepared in accord with the present invention :
Softener active 20.0
Amylase 0.001
Cellulase 0.001
HCL 0.03
Antifoam agent 0.01
Blue dye 25ppm
CaCl2 0.20
Perfume 0.90
Water / minors Up to 100~
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67
Example 13
The following fabric softener composition was prepared
in accord with the present invention :
I II III
DEQA 2.60 19.00
DTDMAMS
SDASA - - 70.0
o
Stearic acid of IV=0 0.30 - -
Neodol 45-13 - - 13.0
o
Hydrochloride acid 0.02 0.02
Ethanol - - 1.00
PEG - 0.60
Amylase 0.0010.0005 0.01
Perfume 1.00 1.00 0.75
Digeranyl Succinate - - 0.38
Silicone antifoam 0.01 0.01
Electrolyte - 600ppm
Dye lOOppm 50ppm 0.01
Water and minors 100% 100%
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68
Example 14
Syndet bar fabric cleaning compositions were prepared
in accord with the present invention :
I II III IV
C26 AS 20.00 20.00 20.00 20.00
CFAA 5.0 5 0 5 o 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
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
Amylase 0.01 0.02 0.01 0.01
Protease 0.3 - 0.5 0.05
Brightener, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
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.
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69
SEQUENCE DESCRIPTION: SEQ ID No. 1
His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp Tyr
Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ala
Asn Leu Lys Ser Lys Gly lle Thr Ala Val Trp lle Pro Pro Ala Trp
Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr
Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly
Thr Arg Asn Gln Leu Gln Ala Ala Val Thr Ser Leu Lys Asn Asn Gly
lle Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp
100 105 110
Gly Thr Glu lle Val Asn Ala Val Glu Val Asn Arg Ser Asn Arg Asn
115 120 125
Gln Glu Thr Ser Gly Glu Tyr Ala lle Glu Ala Trp Thr Lys Phe Asp
130 135 140
Phe Pro Gly Arg Gly Asn Asn His Ser Ser Phe Lys Trp Arg Trp Tyr
145 150 155 160
His Phe Asp Gly Thr Asp Trp Asp Gln Ser Arg Gln Leu Gln Asn Lys
165 170 175
lle Tyr Lys Phe Arg Gly Thr Gly Lys Ala Trp Asp Trp Glu Val Asp
180 185 190
Thr Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met
195 200 205
Asp His Pro Glu Val lle His Glu Leu Arg Asn Trp Gly Val Trp Tyr
210 215 220
Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg lle Asp Ala Val Lys His
225 230 235 240
lle Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Thr
245 250 255
Thr Gly Lys Pro Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu
260 265 270
CA 022617~4 1999-01-28
W 098/05748 PCT~US96/12612
Gly Ala lle Glu Asn Tyr Leu Asn Lys Thr Ser Trp Asn His Ser Val
275 280 285
Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly
290 295 300
Gly Tyr Tyr Asp Met Arg Asn lle Leu Asn Gly Ser Val Val Gln Lys
305 310 315 320
His Pro Thr His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro
325 330 335
Gly Glu Ala Leu Glu Ser Phe Val Gln Gln Trp Phe Lys Pro Leu Ala
340 345 350
Tyr Ala Leu Val leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr
355 360 365
Gly Asp Tyr Tyr Gly lle Pro Thr His Gly Val Pro Ala Met Lys Ser
370 375 380
Lys lle Asp Pro leu Leu Gln Ala Arg Gln Thr Phe Ala Tyr Gly Thr
385 390 395 400
Gln His Asp Tyr Phe Asp His His Asp lle lle Gly Trp Thr Arg Glu
405 410 415
Gly Asn Ser Ser His Pro Asn Ser Gly Leu Ala Thr lle Met Ser Asp
420 425 430
Gly Pro Gly Gly Asn Lys Trp Met Tyr Val Gly Lys Asn Lys Ala Gly
435 440 445
Gln Val Trp Arg Asp lle Thr Gly Asn Arg Thr Gly Thr Val Thr lle
450 455 460
Asn Ala Asp Gly Trp Gly Asn Phe Ser Val Asn Gly Gly Ser Val Ser
465 470 475 480
Val Trp Val Lys Gln
485
CA 0226l7~4 l999-0l-28
W 098105748 PCT~US96/12612 71
SEQUENCE DESCRIPTION: SEQ ID No. 2
His His Asn Gly Thr Asn Gly Thr Met Met Gln Tyr Phe Glu Trp His
Leu Pro Asn Asp Gly Asn His Trp Asn Arg Leu Arg Asp Asp Ala Ser
Asn Leu Arg Asn Arg Gly lle Thr Ala lle Trp lle Pro Pro Ala Trp
Lys Gly Thr Ser Gln Asn Asp Val Gly Tyr Gly Ala Tyr Asp Leu Tyr
Asp Leu Gly Glu Phe Asn Gln Lys Gly Thr Val Arg Thr Lys Tyr Gly
Thr Arg Ser Gln Leu Glu Ser Ala lle His Ala Leu Lys Asn Asn Gly
Val Gln Val Tyr Gly Asp Val Val Met Asn His Lys Gly Gly Ala Asp
100 105 110
Ala Thr Glu Asn Val Leu Ala Val Glu Val Asn Pro Asn Asn Arg Asn
115 120 125
Gln Glu lle Ser Gly Asp Tyr Thr lle Glu Ala Trp Thr Lys Phe Asp
130 135 140
Phe Pro Gly Arg Gly Asn Thr Tyr Ser Asp Phe Lys Trp Arg Trp Tyr
145 150 155
His Phe Asp Gly Val Asp Trp Asp Gln Ser Arg Gln Phe Gln Asn Arg
160 165 170 175
lle Tyr Lys Phe Arg Gly Asp Gly Lys Ala Trl Asp Trp Glu Val Asp
180 185 190
Ser Glu Asn Gly Asn Tyr Asp Tyr Leu Met Tyr Ala Asp Val Asp Met
195 200 205
Asp His Pro Glu Val Val Asn Glu Leu Arg Arg Trp Gly Glu Trp Tyr
210 215 220
Thr Asn Thr Leu Asn Leu Asp Gly Phe Arg lle Asp Ala Val Lys His
225 230 235
lle Lys Tyr Ser Phe Thr Arg Asp Trp Leu Thr His Val Arg Asn Ala
240 245 250 255
Thr Gly Lys Glu Met Phe Ala Val Ala Glu Phe Trp Lys Asn Asp Leu
260 265 270
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72
Gly Ala Leu Glu Asn Tyr Leu Asn Lys Thr Asn Trp Asn His Ser Val
275 280 285
Phe Asp Val Pro Leu His Tyr Asn Leu Tyr Asn Ala Ser Asn Ser Gly
290 295 300
Gly Asn Tyr Asp Met Ala Lys Leu Leu Asn Gly Thr Val Val Gln Lys
305 310 315
His Pro Met His Ala Val Thr Phe Val Asp Asn His Asp Ser Gln Pro
320 325 330 335
Gly Glu Ser Leu Glu Ser Phe Val Gln Glu Trp Phe Lys Pro Leu Ala
340 345 350
Tyr Ala Leu lle Leu Thr Arg Glu Gln Gly Tyr Pro Ser Val Phe Tyr
355 360 365
Gly Asp Tyr Tyr Gly lle Pro Thr His Ser Val Pro Ala Met Lys Ala
370 375 380
Lys lle Asp Pro lle Leu Glu Ala Arg Gln Asn Phe Ala Tyr Gly Thr
385 390 395
Gln His Asp Tyr Phe Asp His His Asn lle lle Gly Trp Thr Arg Glu
400 405 410 415
Gly Asn Thr Thr His Pro Asn Ser Gly Leu Ala Thr lle Met Ser Asp
420 425 430
Gly Pro Gly Gly Glu Lys Trp Met Tyr Val Gly Gln Asn Lys Ala Gly
435 440 445
Gln Val Trp His Asp lle Thr Gly Asn Lys Pro Gly Thr Val Thr lle
450 455 460
Asn Ala Asp Gly Trp Ala Asn Phe Ser Val Asn Gly Gly Ser Val Ser
465 470 475
lle Trp Val Lys Arg
480
CA 02261754 1999-01-28
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7 3
SEQUENCE DESCRIPTION: SEQ ID No. 3
His-His-Asn-Gly-Thr-Asn-Gly-Thr-Met-Met-Gln-Tyr-Phe-Glu-Trp-Tyr-Leu-Pro-
Asn-Asp
CA 022617~4 1999-01-28
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74
SEQUENCE DESCRIPTION: SEQ 1~ No. 4
AAPFNGTMMQ YFEWYLPDDG TLWTKVANEA NNLSSLGITA LWLPPAYKGT
SRSDVGYGVY DLYDLGEFNQ KGAVRTKYGT KAQYLQAIQA
AHAAGMQVYA
DVVFDHKGGA DGTEWVDAVE VNPSDRNQEI SGTYQIQAWT KFDFPGRGNT
YSSFKWRWYH FDGVDWDESR KLSRIYKFRG IGKAWDWEVD
TENGNYDYLM
YADLDMDHPE VVTELKSWGK WYVNTTNIDG FRLDAVKHIK FSFFPDWLSD
VRSQTGKPLF TVGEYWSYDI NKLHNYIMKT NGTMSLFDAP LHNKFYTASK
SGGTFDMRTL MTNTLMKDQP TLAVTFVDNH DTEPGQALQS
WVDPWFKPLA
YAFILTRQEG YPCVFYGDYY GIPQYNIPSL KSKIDPLLIA RRDYAYGTQH
DYLDHSDIIG WTREGVTEKP GSGLAALITD GPGGSKWMYV
GKQHAGKVFY
DLTGNRSDTV TINSDGWGEF KVNGGSVSVW VPRKTTVSTI AWSITTRPWT
DEFVRWTEPR LVAWP
