Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
~ wo g~l29224 ~ 1 8 8 4 0 ~ . ~ l/L ~ 1710
A~LASE-CONTAINING L~ CoMPoSITIoNS
Technical Field
The present invention relates to detergent
compositions containing specific amylases.
Background of the Invention
The use of amylases in detergent compositions is
well known in the art.
The practical use of amylases in detergents has
however been limited so far to bacterial amylases such
as Termamyl~, BAN~9 sold by Novo Nordisk, ~axamyl~ and ex
Gist-Brocades, Rapidase~-
On the other hand, certain fungal amylases arebeing sold ~ y Novo Nordisk under the trade name
Fungamyl~, fc_ use in the starch industry, brewing
industry, alcohol industry, and baking
In the starch industry, Fungamyl~ is used for
production of high maltose syrups, or high conversion
SyrUpS .
In the brewing industry, Fungamyl~ is added during
fermentation in order to increase fermentability of the
wort .
In the alcohol industry, Fungamyl~D may be used for
liquefaction of starch in a distillery mash.
In baking, Fungamyl~) is used for supplementation of
wheat flour low in alpha-amylase.
Fungamylæ is however not used nor suggested for
use, in detergent applications; furthermore, the trade
W0 95129224 2 18 8 4 3 3 r~ 1710
brochure from Novo Nordisk, indicates that alkaline pHs
have a detrimental effect on Fungamyl~ activity.
It has now been surprisingly found that FungamylQi~
can provide substantial cleaning benefits, espe~cially
in laundry context as ~egards whiteness maintenance and
cleaning of body soils, these benefits being seen as
well at A 1 kA l; nf~ pE~s .
It has ~lso been found that said Fungamyl~9 en7ymes
exhibit CMCase activity, contrary to the currently used
amylase described above. == = =
It is -Arrnr~i;n~l y the object of: the prese~t
invention to provide detergent compositions containing
an amylase enzyme which showing CMCase activity and/or
is an amylase showing a positive immunological cross
reaction with the antibody of the Fungamyl~D amylase, or
an amylase produced by a host organism in which the gene
encoding the Fungamyl~D has been cloned.
Summary of the Invention
A detergent composition comprising an ~ amylase
enzyme which shows CMCase activity and/or is an amylase
showing a positive immunological cross reaction with the
antibody of the Eungamyl~ amylase, or an amylase
produced by a host organism in which the gene encoding
the FungamylO has been cloned.
Detailed Description of the Invention _~
The Amylase
WO 95/29224 r~ t710
~ 21 884(~3
The compositions herein comprise as an essential
ingredient a specific amylase, which shows CMCase and/or
is an amylase showing a positive im~unological cross
reaction with the antibody of the Fungamyl~ amylase, or
an amylase produced by a host organism in which the gene
encoding the Fungamyl(~ has been cloned. Fungamyl~ is
described by Novo Nordisk trade brochure dated February
1993, as being a 1, 4- -D-glucan glucano-hydrolase,
obtainable from a selected stain of Asperillys oryzae.
The CMCase activity of the amylase herein is
defined and as follows:
An aqueous solution of CMC (1000 g/l) is `incubated at pH
10 . 5 adjusted with NCOH and 50C, in the presence of
amylase (0.05g of an amylase solution at 800 FAU/g) .
The amylase is considered to have CMCase activity if
after 1 minute incubation, at least 0.1, more preferably
O . 5, most preferable 1 ppm or more glucose is fQrmed as
detected by ion chrmoatography/pulsed amperometric
detection ( IC/PAD) .
In the tests run with Fungamyl~ 0.05g of 800FAU/l
amylase was added to lOOml of the CMC (1000 g/l)
solution .
A Dionex 4500 gradient ion chromatography system was
used with an AS7 colu~n. H20 / lOOmM NaOH / 500 mM Na
Acetate eluents were used.
The PAD settings used were
V T/sec
E1 + O . 05 480
E2 + O . 06 300
E3 - O. 61 240
Polarity of the system is positive. The response time
is 1 second.
WO 9S129224 r~ 'G 1710
21 88~a3
The amylases of the present inventiOn are
preferably fungal and an example thereof ~ is Fungamyl
itself_ ~
The Fungamyl~ amylase herein should be used in a
substantially pure form. By substantially pure form is
meant, that the specific fungal alpha amylase of the
invention should not be present in the form ~=of an
impurity included in another enzyme, separately added to
the present composition to provided a different
function .
Xowever, it is understood that the substantially
pure Fungamyl~B can be used in conjunction with other
en~ymes .
The level of the fungal amylase in the composition
of the invention should be such that an activity of from
1 to 5000 FAU/lOOg of compositions (Fungal alpha-Amylase
Unit), preferably 50 to 500.
One Fungal alpha-Amylase Unit (1 E~U) is the amount
of enzyme which breaks down- 5,26 g starch ~Merck, ~mylum
solubile Erg. B. 6, Batch 9947275) per hour at Novo
Nordisk' s standard method for determination of ~ alpha-
amylase based upon the following standard conditions:
Substrate soluble starch
Reaction time 7-20 min.
Temperature 37C
pH 4.7
Typically, a 800 FAU/g Fungamyl preparation will be
used at levels of from O .1 to O . 5~ by weight of the
detergent compositions herein.
.
-
Wo 95129224 Zr~~ 710
21 88~03
The present amylase can be used in liquid or
granular form, e.g. in the form of prills or marumes,
possibly admixed or cogranulated with another optional
enzyme as described hereinbelow.
The detergent compositions herein are preferably
laundry detergent compositions, either in granular or
liquid form, or can be laundry additives.
Automatic ~i qhr~rr~shin~ compositions are also
Pn( ~ ~csed.
Granular and liquid laundry detergent compositions
contain a surfactant and a laundry detergent builder as
essertial ingredients; the laundry addities herein will
preferably consist in addition to the enzyme, of a
bleaching agent; automatic dishwashing compositions
contain a builder as an essential ingredient. Suitable
surfactants and builders are described in detail
hereinafter:
Wo gsl29224 2 1 8 8 4 0 3 P~
Alkyl Sulfate Surfactant
Alkyl sulfate surfactants hereQf are hrater soluble
salts or acids Qf the ~ formula RDS03M wherein R
preferably is a C1o-C24 hydrocarbyl, preferably an alkyl
or hydroxyalkyl havinq a Clo-C20 alkyl ~ t, more
preferably a C12-C1g alkyl or hydroxyalkyl, and M is H
or a cation, e . g., an alkali metal cation (e . g ., sodium,
potassium, lithium), or ammonium or substituted ammonium
(e . g ., methyl-, dimethyl-~ and trlmethyl ammonium
cations and quaternary ammonium cations, such as
tetramethyl-ammonium and dimethyl piE~erdinium cations
and quarternary ammonium cations derived from
alkylamines such as ethylamine, diethylamine,
triethylamine, and mixtures thereof, and the like).
Typically, alkyl chains of C12-16 are preferred for
lower wash temperatures (e.g., below about 50C) and
C16-18 alkyl chains are preferred for higher wash
temperatures (e.g., above about 50C).
Alkyl Alkoxylated Sulfate Surfactant
Alkyl alkoxylated sulfate surfactants hereof are
water soluble salts or acids of the formula RO(A)mSO
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-C18 alkyl or hydroxyalkyl, A is an ethoxy
or propoxy unit, m is qreater than zero, typically
between about 0.5 and about 6, more preferably between
about 0.5 and about 5, 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-,
.
~ wogsl2s~24 21 ~8403 r~ 5 1710
trimethyl-ammonium and quaternary ammonium cationS, such
as tetramethyl-ammonium, dimethyl piperdinium and
cations derived from alkanolamines such as ethylamine,
diethylamine, triethylamine, mixtures thereof, and the
like. Exemplary surfactants are Cl2-C18 alkyl
polyethoxylate (1.0) sulfate, Ci2-C18E(1-)M)~ C12-C18
alkyl polyethoxylate (2.25) sulfate, C12-C18E (2.25)M),
C12-Cl8 alkyl polyethoxylate ~3.0) sulfate
C1gE(3.0), and C12-C1g alkyl pol~ethoxylate (4.0)
sulfate Cl2-ClgE(4.0)~), wherein M is conveniently
selected from sodium and potassium.
Other Anionic Surfactants
other anionic surfactants useful for detersive
purposes can also be included in the laundry detergent
compositions of the present invention with or without
the species described above. These can include salts
( including, for example, sodium, potassium, ammc~ium,
and substituted i -n;llm salts such as mono-, di- and
triethanolamine salts) of soap, Cg-C20 linear
alkylbenzenesulphonates, Cg-C22 primary or secondary
alkanesulphonates, Cg-C24 olefinsulphonates, sulphonated
polycarboxylic acids prepared by sulphonation of the
pyroIyzed product of ~lkiqlin~ earth metal citrates,
e . g ., as described in British patent specification No .
l, 082,179, Cg-C24 alkylpolyglycolethersulfates
(containing up to 10 moles of ehtylene oxide); alkyl
ester sulfonates such as C14_16 methyl ester sulfonates;
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 s--~;niq~tes
and sulfosuccinates, monoesters of sulfosuccinate
(especially saturated and unsaturated Cl2-Cl8
monoesters) diesters of sulfosuccirate (especially
saturated and unsaturated C6-C14 diesters), acyl
WO 95/29224 P~,l/l 1710
2 ~ 88403
:sarcosi~ates, sul~ates Or alkylpolysaccharides such as
the sulfates of alkylpolyglucoside ~the nonionic
nonsulfated - compounds being described below), branched
prir~ary alkyl sulfates, alkyl polyethoxy carboxylates
such as those of the ~ormula R0 ~CH2CH20~ kC~32COO-M
wherein R is a C~-C22 alkyl, k is an integer from 0 to
10, and M is a solllble salt-forming cation. ~esin
zcids and hydrogenated r2sin acids are also suit~ble,
such as rosin, hydrogenated rosin, and resin acids arld
hydrogenated resin acids present in or derived from tall
oil. Further examples are given in "Surface ~ctive
Agents and Detergents" (Vol. I and II by Schwartz, Perry
and Berch). A variety o~ sucl~ surfactants are al~o
generally disclosed in U.S. P~tent 3, 929, 678, issued
December 30, 1975 to T.~lqhl in, et al. at Column 23, line
58 through Column 29, line 23 ~herein incorporated by
ref erence ) .
Preferred surfactants for use in the compositio~s
herein are the alkyl sulfa~es, alkyl alkoxylated
sulfates, and mixtures thereo~.
When ~n~lu~ therein, the laundry detergent
co~positions of the present invention typically comprise
~rom about 1 ~ to about ~0 ~, preferably from about 3
to about 20 ~d by weight o~ such anionic surfactants.
Nonionic Surfactants
The present laundry detergent compositions
preferably also comprise a nonionic surfactant.
While any nonionic sur~actant may be `normally
employed in the present invention, two familles of
nonionics have been found to be particu~:arly useful.
These are nonionic surfactants ba~ed on alkoxylated
~especially ethoxylated) alcohols, and those nonionic
~ w~g5l2s2u 21 88403 r~ 1710
surfactants based on amidation products of fatty acid
esters and N-alkyl polyhydroxy amine. The amidation
products of the esters and the amines are generally
referred to herein as polyhydroxy fatty acid amides.
Particularly useful in the present invention are
mixtures comprising two or more nonionic surfactants
wherein at least one nonionic surfactant is selected
from each of the groups of alkoxylated alcohols and the
polyhydroxy fatty acid amides.
Suitable nonionic surfactants include compounds
produced by ~he condensation of alkylene oxide groups
(hydrophilic in nature) with an organic hydrophobic
compound, which may be aliphatic or alkyl aromatic in
nature. The length of the polyoxyalkylene group which
is condensed with any particular hydrophobic group can
be readily adjusted to yield a water-soluble compound
having the desired degree of balance between hydrophilic
and hydrophobic elements.
Particularly preferred for use in the present
invention are nonionic surfactants such as the
polyethylene oxide condensates of alkyl phenols, e.g.,
the condensation products of alkyl phenols having an
alkyl group containing from about 6 to 16 carbon atoms,
in either a straight chain or branched chain
configuration, with from about 4 to 25 moles of ethylene
oxide per mole of alkyl phenol.
Preferred nonionics are the water-soluble
condensation products of aliphatic alcohols containing
from 8 to 22 carbon atoms, in either straight chain or
branched configuration, with an average of up to 25
moles of ethylene oxide per more of alcohol.
Particularly preferred are the r~n~lPnqation products of
alcohols having an alkyl group containing from about 9
to 15 carbon atoms with from about 2 to 10 moles of
. ,, .... . .. .... ~
Wo 95/29224 2 ~ 8 8 ~ 0 3 r~~ G 1710 ~
ethylene oxide per mole of ~alcohol; and condensation
products of propylene glycol with ethylene oxide. Most
preferred are condensation products of alcohols having
an alkyl group containing from about 12 =to 15 carbon
atoms with an average of about 3 to 7 moles of ethylene
oxide per mole of alcohol, preferably 3 to 5.
The nonionic surfactant system herein can also
include a polyhydroxy fatty acid amide compQnent.
Polyhydroxy fatty acid amides may be produced by
reacting a fatty acid ester and an N-alkyl polyhydroxy
amine. The preferred amine for use in the present
invention is N- (R1) -CH2 ~CH20H) 4-CH2-OH and the preferred
ester is a C12-C20 fatty acid methyl ester.~ Most
preferred is the reaction product of N-methyl qlucamine
with C12-C20 fatty acid methyl ester.
Methods of manufacturing polyhydroxy fatty acid
amides have been described in WO 92 6073, puhlished on
16th April, 1992. This application describes the
preparation of polyhydroxy fatty acid amides in the
presence of solvents. In a highly preferred e~[bodiment
of the invention N-methyl glucamine is reacted` with a
C12-C20 methyl ester. It also says that the formulator
of granular detergent compositions may find it
convenient to run the amidation reaction in the presence
of solvents which comprise alkoxylated, especially
ethoxylated (EO 3-8) C12-C14 alcohols (page 15, lines
22-27). This directly yields nonionic surfactant systems
which are preferred in the present invention, such as
those comprising N-methyl glucamide and C12-C14 alcohols
with an average of 3 ethoxylate groups per molecule.
Nonionic surfactant systems, and granular
detergents made from such systems have been described in
Wo 92 6160, pllhl i cllerl on 16th April, 1992. This
~ W095129~4 2 1 88433 P l/ V0~710
11
appllcation describeS (example 15) a granular detergent
composition prepared by fine dispersion mixing in an
Eirich RV02 mixer which comprises N-methyl glucamide
~10%), nonionic surfactant ~10%).
Both of these patent applications describe nonionic
surfactant systems together with suitable manufacturing
processes for their synthesis, which have been found to
be suitable for use in the present invention.
The polyhydroxy fatty acid amide may be present in
compositions of the present invention at a level of from
0% to 50% by weight of the detergent component or
composition, preferably from 5~ to 40% by weight, even
more preferably from 10% to 30% by weight.
Also useful as the nonionic surfactant of the
surfactant systems of the present invention are the
alky~polysaccharides disclosed in U.S. Patent 4,565,647,
11en-do, issued Jariuary 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
.... .
W0 95/2922~ 8 8 4 0 3 P~ 5'C I710
12
R20 (CnH2nO) t (glycosyl ) 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 O 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 E~repare
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
pre~ mi n~ntely the 2-position.
Other Surfactants _ ~
The laundry detergent compositions of the present
invention may also contain cationic, ampholytic,
2witterionic, and semi-polar surfactants, as well as
nonionic surfactants other than those already described
herein, including the semi-polar nonionic amine oxides
described below.
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 s=uch cationic surfactants include
the am~onium surfactants such as alkyldi- or tri-
methylammonium - ,u,-ds, and those surfactants having
the formula:
[R2 (oR3) y] [R4 ~oR3) y]2R5N+X-
WO 9!il29224 P~ '04710
21 88403
13
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 _, -CH2 CH ( CH3 ) -, - CH2CX ( CH2OH ) -, - CH2 CH2CH2 -, and
mixtures thereof i 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,
-CH2COH-CHOHCOR6CHOHCH20H wherein R6 is any hexose or
hexose polymer having a molecular weight less than about
1000, and hydrogen when y is not 0; R5 is the same as R4
or is an alkyl chain wherein the total nu~ber Df carbon
atoms of R2 plus R5 is not more than about 18; each y is
from 0 to about 10 and the sum of the y values is from 0
to about 15; and X is any compatible anion.
Other cationic surfactants useful herein are also
described in US Patent 4,~28,044, Ca~bre, issued October
14, 1980, incorporated herein by reference.
When included therein, the laundry detergent
compositions of the present invention typically comprise
from 0 % to about 25 ~, preferably form about 3 ~ to
about 15 ~ by weight of such cationic surfactants.
Ampholytic surfactants are also suitable for use in
the laundry 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 8 carbon atoms,
typically from about 8 to about 18 carbon atoms, and at
least one contains an anionic water-solllhil;7;ng group
e.g. carboxy, sulfonate, sulfate. See U.s. Patent No.
3, 929, 678 to Laughlin et al., issued Dece~ber 30, 1975
W095/29224 21 88~03 r l,~ s~l7l0 ~
14
at column 19, lines 18-35 (herein incorporated by
reference) for~examples of ~mpholytic surfactants.
When included therein, the laundry detergent
compositions of th~ present invention typically comprise
form 0 % to about 15 %, preferably from- about 1 ~ to
about 10 % by weight of such ampholytic su-rfactants.
Zwitterionic surfactants are also suitable for use
in laundry detergent compositions. These surfactants
can be broadly described as derivatives of secondary and
tertiary amines, derivates of heterocyclic secondary and
tertiary amines, or derivatives of quaternary ammonium,
quarternary phosphonium or tertiary sulfonium compounds.
See U.S. Patent No. 3, 929, 678 to laughlin et al., issued
December 30, 1975 at columns l9, line 38 through column
22, line 48 (herein incorporated by reference) for
examples of zwitterionic surfactants.
When included therein, the laundry detergent
compositions of the present invention typically comprise
form 0 % 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 cf~nt~;n;r~ one alkyl moiety of from
about 10 to about 18 carbor~ atoms and 2 moieties
selected from the group consisting af alkyl groups and
hydrocyalkyl groups containing form about l to about 3
carbon atoms; water-soluble phosphine oxides ~~nnt;.;n;n~
one alkyl moiety of form about lO to about 18 carbon
atoms and 2 moieties selected form the group consisting
of alkyl groups and hydroxyalkyl groups rnl~t~in;n~ from
about 1 to about 3 carbon atoms.
Semi-polar nonior~ic detergent surfactants include
the amine oxide surfactants having the formula:
- '
WO 95/2922~1
2 1 88433 ~ 04711~
o
R3 ~oR4 ) xN (R5) 2
Builder _ ~
The laundry detergent compositions and automatic
dishwashing compositions herein contain a builder,
preferably non-phosphate detergent b~_lders, although
phosphate-containing species are not ~xcl ~lc ecl in the
content of the present invention. These can include,
but are not restricted to alkali metal carbonates,
bicarbonates, silicates, aluminosilicates, carboxylates
and mixtures of any of the foregoing. The builder
system is present in an amount of from 1% to 80~ by
weight of the composition, typically preferable from 20~
to 60% by weight in granular laundry detergent
compositions herein, and from 1~ to 30~ in liquid
laundry detergent compositions herein.
suitable silicates are those having an SiO2: Na2O
ratio in the range from 1.6 to 3.4, the so-called
amorphous silicates of SiO2 : Na2O ratios from 2 . 0 to
2 . 8 being preferred.
Within the silicate class, highly preferred
materials are crystalline layered sodium silicates of
general formula
NaMSixO2x + 1 y~20
wherein M is sodium or hydrogen, x is a number from l . 9
to 4 and y is a number from 0 to 20. Crystalline
layered sodium silicates of this type are disclosed in
EP-A-0164514 and methods for their preparation are
disclosed in DE-A-3417649 and DE-A-3742043. For the
WO 95/29224 - 2 1 8 & 4 0 3 1 ~l/U~ , 1710
16
purpos~s of the present invention, x in the general
formula above has a value of 2, 3 or 4 and is preferably
2. More preferably M is sodium and y is O and a
preferred example of this $ormula comprise ~the form of
Na25i20s. These materials are available from Hoechst AG
ERG as respectively NaSKS-5, NaSKS-7, NaSKS-ll and
NaSKS-6. The most preferred material is ~ -Na2Si205,
NaSKS-6. Crystalline layered silicates are incorporated
either as dry mixed solids, or as solid components of
agglomerates with other components.
Whilst a range of ~aluminosilicate ion exchange
materials can be used, preferred sodium aluminosilicate
zeolites have the unit cell formula
Naz [ (Al02) z (si2) y] xH20
wherein z and y are at least about 6, the molar ratio of
z to y is from about 1.0 to about 0.4 and z is from
about lO to about 264. Amorphous hydrated
aluminosilicate materials useful herein have the
empirical formula
Mz ( zAl02 ySiO2 )
wherein M is sodium, potassium, ammonium or substituted
ammonium, z is from aboùt 0.5 to about 2 and y is l,
said material having a magnesium ion exchange capacity
of at least about 50 milligram equlvalents of CaC03
hardness per gram of anhydrous al--m;noc;1 ;~te.
Hydrated sodium Zeolite A with a particle size Df from
about O . 01 to lO microns is preferred.
The aluminosilicate ion exchange builder materials
herein are in hydrated form and contain from about lO~
to about 28~ of water by weight if crystalline, and
potentially even higher amounts of water if amQrphous.
~ WO 95/29224 2 1 8 d 4 0 3 r~". ~i 1710
Highly preferred crystalline aluminosilicate ion
exchange materials contain from about 18~ to about 22~
water in their crystal matrix. The crystalline
aluminosilicate ion exchange materials are further
characteriz d by a particle size diameter of from about
0 . l micron to about lO microns . Amorphous materials are
often smaller, e.g., down to less than about O.Ol
micron. Preferred ion exchange materials have a
particle size diameter of from about 0 . 2 micron to about
4 microns. The term "particle size diameter" herein
represents the average particle size diameter by weight
of a given ion exchange material as determined by
conventional analytical techniques such as, for example,
microscopic determination u~i 1 i 7in~ a scanning electron
mi cros cope .
Aluminosilicate ion exchange materials useful in
the practice of this invention are commercially
available. The aluminosilicat~s useful in this
invention can be crystalline or amorphous in structure
and can be naturally occurring aluminosilicates or
synthetically derived. A method for producing
aluminosilicate ion exchange materials is discussed in
U.S. Pat. No. 3,985,669, Krummel et al., issued Oct. 12,
1976, incorporated herein by reference. Preferred
synthetic crystalline aluminosilicate ion exchange
materials useful herein are available under the
designations Zeolite A, Zeolite X, P and ~P, the latter
species being described in EPA 384 070. In an
especially preferred embodiment, the crystalline
aluminosilicate ion exchange material is a Zeolite A
having the formula
Nal2 [ (AlO2 ) 12 (SiO2 ) 12] XH2O
wo ss/29224 2 1 8 ~3 ~ 0 3 r~ 4710
18
wherein x is from about 20 -to about 30, especially about
27 and has a particle size gener~lly less than a~out 5
microns .
Suitable carboxylate builders containing one
carboxy group include lactic acid, glycollic acid and
ether deriva~ives thereof as disclosed in Belgian Patent
Nos. 83I, 368, 821, 369 and 821, 370 . Polycarboxylates
containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy)
diacetic acid, maleic acid, diglycollic acid, tartaric
acid, tartronic acid and fumaric acid, as well as the
ether carboxylates described in German Offenlegenschrift
2,446,686 ana 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, and the 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 US Patent No. 3, 936, 448, and the sulfonated
pyrolysed citrates described in British Patent No.
1,082,179, while polycarboxylates containing phosphone
.... , , _ _ _ .
~ WO95Q9224 21 8 8 4 03 P~ 47ln
19
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-
tetrahydrofuran - cis, cis, cis-tetracarboxylates, 2, 5-
tetrahydrofuran -cis- dicarboxylates, 2, 2, 5, 5, -
tetrahydrofuran - tetracarboxylates, 1, 2, 3, 4, 5, 6-hexane
hox~ rh~xylates and carbxoymethyl derivatives o~
polyhydric alcohols such as sorbitol, mannitol and
xylitol. Aromatic polycarboxylates include mellitic
acid, pyromellitic acid and the phtalic acid derivates
disclosed in British Patent No. 1, 425, 343.
Chelating Agents
The detergent compositions herein may also
optionally contain one or more iron and~or manganese
chelating agents. Such chelating agents can be selected
from the group consisting of amino carboxylates, amino
phosphonates, polyfunctionally-substituted aromatic
chelating agents and mixtures therein, all as
hereinafter defined. Without intending to be bound by
theory, it is believed that the benefit of these
materials is ~ ~e in part to their exceptional ability to
remo~re iron and manganese ions from washing solutions by
formation of soluble chelates.
Amino carboxylates useful as optional chelating
agents include ethylPn~ Tn; n~tetracetates/ N-
hydroxyethylethylene-diaminetriacetates,
nitrilotriacetates, ethylenediamine tetra-prionates,
triethylenetetraamine-hexacetates, diethylene-
triaminepentaacetates, and ethanoldiglycines, alkali
metal, ammonium, and substituted ammonium salts therein
and mixtures therein.
Wo95l29224 2 1 8 8~ 03 Y~ 710
Amino phosphonates are also suitable for ~se as
chelating agents in the compositions of the invention
when at least low levels of total phosphorous are
permitted in detergent = compositons, and include
ethyl~n ~ m i n etetrakis (methy1enepho sphonates ) as
DEQUEST. Preferred, these amino phosphonates do not
contain alkyl or alkenyl groups with more than about 6
carbon atoms.
Polyfunctionally-sUbstituted aromatic chelating
agents are also useful in the compositions herein. See
U.S. Patent 3,812,044, issued May 21, 1974, to Connor et
al. Preferred compounds of this type in acid form are
dihydroxydisulfobenzenes such as 1, 2-dihydroxy-3, 5-
disulfobenzene .
A pre~erred biodegradable chelator for use herein
is ethyele~ n;ne disuccir,ate ~"EDDS"), especially the
[S,S] isomer as described in U.S. Pate~t 4,704,233,
November 3, 1987, to Hartman and Perki~s.
If utili2ed, these chelating agents will generally
comprisç from about 0.1% to about 10% by weight of the
detergent compositions ~erein. More preferably, if
utilized, the chelating agents wilL comprise from about
0 .1% to about 3 . 0% by weight of such compositions .
Of the above, the preferred polycarboxylates are
hydroxycarboxylates containing up to three carboxy
groups per molecule, more particularly citrates.
The granular detergent compositions and automatic
dishwashing compositions herein have a p~I above 8.5,
preferably in the range of from 9 to ll.
-
w0 95l29224 2 ~ 8 4 0 3 r~ 5 _ ~71~
The present laundry granular compositiOnS arepreferably in a compact form, having a bulk density of
at least 650 g/l, preferably at least 750g/1, but can
also be in a conventional form, with densities in a
range of from 200 g/l to 700 g/l.
In another embodiment of the invention, are
provided Automatic Dishwashing Compositions:
Automatic dishwashing compositions typically contain, in
addition to the amylase of the invention a builder, such
as described above, a source of ~1 k~ 1 i n i ty, such as
silicate or carbonate, and a bleaching agent, preferably
percarbonate, those ingredients amounting to up to 70~
of the formulation. Optional ingredients include
polymers and other enzymes.
In still another embodiment of the invention, are
provided Laundry Additive Compositions : such
compositions preferably contain in addition to the
amylase of the invention, a bleaching agent at levels of
from 15 to 80~ by weight.
Optional Ingredients
Other ingredients which are known fQr use in
detergent compositions may also be used as optional
ingredients in the various embodiments of the present
invention, such as bleaching agents, bleach activators,
polymers, other enzymes, suds suppressing agents, fabric
softening agents, in particular fabric softening clay,
as well as dyes, fillers, optical brighteners, pH
adjusting agents, non builder ~lk~linity sources, enzyme
stability agents, hydrotopes, solvents, perfumes.
Bleaching agents
W095/29224 ~ 188403 r~l~.J ol7lo ~
22
The granular laundry detergent, automatic
dishwashing compositions or laundry additives herein may
contain a bleaching agent; this is a pre~erred
ingredient in automatic =dish and laundry additives
herein, and in granular laundry detergents herein,
although bleach-free granular detergent compositions are
also desirable, particular for the treatment of ~certain
fabrics requiring special carei therefore, such bleach-
free components are also encompassed by the present
invention .
The bleaching agent, if used, is either an
inorganic persalt such as perborate, persulfate,
percarbonate -or a preformaced organic peracid or
perimidic acid, such as N, N phtaloylaminoperoxy caproic
acid, 2-carboxy-phtaloylaminoperoxy caproic acid, N, N
phtaloylaminoperoxy valeric acid, Nonyl amide of peroxy
adipic acid, l, 12 diperoxydod~nf~ ic acid,
Peroxybenzoic acid and ring substituted~ peroxybenzoic
acid, Monoperoxyphtalic acid (magnesium salt,
hexhydrate), Diperoxybrassylic acid.
The preferred bleaching agent is percarbonate.
The bleach-containing laundry detergent of
automatic diswashing compositions hererein typically
contain from 1% to ~0%, preferably from 3~ to 30~ by
weight, most preferably from 5~ to 25~ by weight of
alkali metal percarbonate bleach, in the form of
particles having a mean size from 1 to 1500 micrometers,
preferably from 200 to 90D micrometers, most preferably
500 to 700 micrometers.
Laundry additives typically contain from 15~ to 80
of said percarbonate particles ~
The alkali metal percarbonate bleach is usually in
the form of the sodium salt. Sodium percarbonate is an
.
~ WO 95/29224 2 1 8 8 4 0 3 ~ 5 t l7l0
addition compound having a formula corresponding to
2Na2CO3 3H202 To er~ance storage stability the
percarbonate bleach can be coated with e . g. a further
mixed salt Qf an alkali metal sulphate and carbonate.
Such coatings together with coating processes have
previously been described in GB-1,466,799, granted to
Interox on 9th March 1977. The weight ratio of the
mixed salt coating material to percarbonate lies in the
range from 1:2000 to 1:4, more preferably from 1:99 to
1:9, and most preferably from 1:49 to 1:19. Preferably,
the mixed salt is of sodium sulphate and sodium
carbonate which has the general formula Na2SO4.n.Na2CO3
wherein n is from 0.1 to 3, preferably n is from 0.3 to
1.0 and most preferably n is from 0.2 to 0.5.
Other suitable coating materials are sodium
silicate, of SiO2:Na2 ratio from 1.6:1 to 2.8:1, and
magnesium silicate.
Commercially available carbonate/sulphate coated
percarbonate bleach may include a low level of a heavy
metal sequestrant such as EDTA, 1-hydroxyethylidene 1 ,1-
diphosphonic acid (HEDP) or an ;Imi n~ph~sphonate~ that is
incorporated during the manufacturing process.
Bleach activators
The present compositions, especially the granular
laundry detergent compositions and laundry additives
described above, preferably contain from 1% to 20~ by
weight of the composition, preferably from 2~ to 15~ by
weight, most preferably from 3% to 10% by weight of a
peroxyacid bleach activator, in addition to the
bleaching agent described above.
Peroxyacid bleach activators ~bleach precursors ) as
additional hl ~ h; ng components in ~ccordance with the
W095/29224 21 88403 ~ '0~710
24
invention can be selected from a wide range of class and
are preferably those containing one or more N-or O-acyl
groupS .
Suitable classes irLclude anhydrides, esters,
amides, and acylated derlvatives of imidazoles and
oximes, and e~amples of useful materials within these
classes are disclosed in GB-A-1586789. The most
preferred classes are esters such as are disclosed in
GB-A-836 988, 864, 798, 1 197 871 and 2 143 231 and
amides such as are disclosed in GB-A-855 735 and 1 246
338 .
Particularly preferred bleach activator compounds
as additional bleaching components in accordance with
the invention are the N-,N,N'N' tetra acetylated
compounds of the formula
o
CX3lC CCH3
/N--~ CEI2 )--N\
C~30 CCH3
o
where x can be O or an integer between 1 and 6.
Examples include tetra acetyl methylene diamine
(TAMD) in which x=1, tetra acetyl ethylene diamine
(TAED) in which x=2 and Tetraacetyl hexylene diamine
(TA~D) in which x=6. These and analogous compounds are
described in GB-A-907 356. The most preferred
peroxyacid bleach activator as an additional bleaching
component is TAED.
..
~ wo gsl29224 2 1 8 8 4 0 3 r~ r47ln
Another preferred class of peroxyacid bleach
compounds are the amide substituted compounds of the
following general formulae:
R1 - C - N-R2 - ~ - L or R1 - I - 8-R2 - IC - L
wherein R1 is an aryl or alkaryl group with from about l
to about 14 carbon atoms, R2 is an alkylene, arylene,
and alkarylene group containing from about l to about 14
carbon atoms, and R5 is H or an alkyl, aryl, or alkaryl
group containing 1 to 10 carbon atoms and L can be
essentially any leaving group. R1 preferably contains
from about 6 to 12 carbon atoms. R2 preferably contains
from about g to 8 carbon atoms. R1 may be straight
chain or branched alkyl, substituted aryl or alkylaryl
containing branching, substitution, or both and may be
sourced from either synthetic sources or natural sources
including for example, tallow fat. Analogous structural
variations are permissible for R2. The substitution can
include alkyl, aryl, halogen, nitrogen, sulphur and
other typical substituent groups or organic compounds.
R5 is preferably H or methyl. R1 and R5 should not
contain more than 18 carbon atoms total. Amide
substituted bleach activator compounds of this type are
described in EP-A-0170386.
Another class of bleach activators to use in
combination with percarbonate comprises C8, Cg, andJor
C1o (6-octanamidocaproyl) oxybenzenesulfonate, 2-phenyl-
(4H) 3,1 benzoxazin-4-one, benzoyllactam preferably
benzoylcaprolactam and nonanoyl lactam preferably
nonanoyl caprolactam.
Polymers
W095/29224 2 1 8 8 4 03 P~ 710
26
Polymers
Also useful are various organic polymers, some of
which also may ~unction as builders to improve
detergency. Tn~ pf~ among such polymers may be
mentioned sodium carboxy-lower alkyl celluloses, sodium
lower alkyl celluloses and sodium hydroxy-lower alkyl
celluloses, such as sodium carboxymethyl cellulose,
sodium methyl cellulose arld sQdium hydroxypropyl
cellulose, polyvinyl alcohols (which often ~ also include
some polyvinyl acetate~, polyacrylamides, polyacrylates
and various copolymers, such as those of maleic and
acrylic acids. ~Iolecular weights for such polymers vary
widely but most are within the range ~ of 2, 000 to
100, 000. Also useful are terpolymers of maleic/acrylic
acid and vinyl alcohol having a molecular weight ranging
from 3.000 to 70.000.
Polymeric polycarboxylate builders are set forth in
U.S. Pater~t 3, 308, 067, Dlehl, issued ~arch 7, 1967 .
Such materials include the water-soluble salts of homo-
and copolymers of aliphatic carboxylic acids such as
maleic acid, itaconic acid, mesaco~ic }Lcid, fumaric
acid, acor,itic acid, citraconic acid and
methylenemalonic acid.
Polyaspartate and polyglutamate dispersing agents
may be used, especially with zeolite builders.
Dispersing agents such as polyasparatate preferably have
a molecular weight of about 10, 000.
Other useful polymers include species known as soil
release polymers, such as described in EPA 185 ~27 and
EPA 311 3~2.
Still other polymers suitable i'or use herein
include dye transfer inhibition polymers such as
~ W095r29224 2 1 88403 r~l~Vv.~ 4710
27
polyvinylpyrrolidone, polyvinylpyrridine, N-oxide, N-
vinylpyrrolidone, N-imidazole, polyvinyloxozolidone or
polyvinylimidazole .
Other Enzymes
Enzymatic materials can be incorporated into the
detergent compositions herein. Suitable are proteases,
lipases, cellulases, peroxidases, amylases and mixtures
thereof .
A suitable lipase enzyme is manufactured and sold by
Novo Industries A/S (Denmark~ under the trade name
Lipolase and mentioned along with other suitable lipases
in EP-A-0258068 (Novo Nordisk) .
Suitable cellulases are described in e . g . Wo-
91/17243 and WO 91/17244 ~Novo Nordisk).
Preferred com~ercially available protease e~zymes
include those sold under the trade names Alcalase and
Savinase by Novo Industries A/S (Denmark) and Maxatase
by International Bio-Synthetics, Inc. (The Netherlands).
Other proteases include Protease A (see European
Patent Application 130 756, pllhl; checl January 9, 1985)
and Protease B (see European Patent Application Serial
No. 87303761.8, filed April 28, 1987, and European
Patent Application 11~ 756, Bott et al, published
January 9, 1985).
Peroxidase enzymes are used in combination with
oxygen sources, e.g. percarbonate, perborate,
persulfate, hydrogen peroxide, etc. They are used for
"solution bleaching", i.e. to prevent transfer of dyes
or pigments removed from substrates during wash
operations to other substrates in the wash solution.
Peroxidase enzymes are known in the art, and include,
_ _ _ _ _ _ _ _ _ _ . . .. . .. . .
w095/29~24 2 1 Y8~3 P~ /01710
for example, horseradish peroxidase, ligninase, and
haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase--~nt~nin~ detergent compositions are
disclosed, for example, in PCT International Application
WO 89/099813 and in WO 9l/05839. -
Preferred additional amylases include for examE~le,- amylases otbained from a special strain of B.
licheniforms, described in more detail in ~B-l, 296, 839
(Novo). Preferred commercially available amylases
include for example, RapidaseR, sold by International
Bio-Synthetics Inc. and so-called TermamylR 60T and
TermamylR 120T, sold by Novo Nordisk A/S.
~ WO95~29224 2 1 8 8 4 ~3 r~ 710
29
~O N
~I r ~ I I I N I I I I I O
N r N N
I I I I U'1 I r~ ~i I U~ O I O
~1 1 1 ~D I 1 ~1 1 0 1 1 1 1 1 0
N r~l N
~1 0 1 111 1 1 1~ I ri I ~I N I I O
O N r1
N
I I ~ I I ~ I ~1 1 ~I r~ o I o
r N N
r N I ~1 N I I ~1 ~r I O O
r U~ N
r I I r N I ~ N I I ~1 It~ O I O
~D I I r I N ~r N I I ~1 10 I N ~1
u7 1 I r N I ~O t~l I I I I I O O
~ I I 1'~) r1 1 Ul N ~I r ~ -
(~) I I rl N I ~ C I I N ~1 1 0 N
N I I ~ N I U) N I I N ~D O I O
N O
r ~ I o I ~r I I N I IS'1 0 1 0
; ra
n
~, ~ rD
o
0 0 rl ~
r~ Y Y ~ r ~ "~ ~ r 1
ra r1 ~ ~ ~
W0 95/29224 2 1 8 8 4 0 3 . ~ `C I710
o
o
o
N
N N
O O
N N
O O
N N
O O
~1 ~rl
O O
~N
N .-1
O O
N N
O O
O O
D
a)
o
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-.1 C
,~ L
~ WO95/29224 2~ 8403 r l, ,710
,_
N ~ , ~ N I O
~ NI I r ~ ~ u~ O
O I Irr~ I ~ ~ I I I I I I I I
O I Ir~l I I ~ ~D I I I I I I I
O
~1 1-- ~ ~ ~ O
O
O r~ r O
O r~ r~ O
O~1 O~ I I ~ O O I O
O ~ r'7 r~7
O O II ~ I _I ~1 1 I CO O O ~1
Nulrr~ 111 rr) rr) ~
O O OI ~1 ~ I ~ I O L~7 0 0 1 1 0
~ ~ r'1 O
O O II ~1 ~1 Ul CO I I Ir) O O I O
O I I~1 1 If~) _I ~ I ~ O O
r''1 C
o r U 1 r~
O ' ~ ' e
O r r
~ U -~
U ~ . r ~ 'U r ~n ~ C O ~ C o
wogsng~ 21 88~ ~3 r~ t710
32
O N
N
O
N
O
N
O
N
O
N
O
N
O
U~
O
11'~ N
O O
r~
O
O
N
O
' .
.
'
C~
... ..
WO 95/29224 P~-~U~ ~710
2 1 88403
.
L~1 N ~1
~ O N H Ll)
HI N O O ~1 1 Il-t N N H r~ o I o o o
n ~t
) u~ o ~ o
~I H r, ~ ~ I Lr) N H Cl N r) N U ) I O O O
1-- 0 ,~ U) ~ NH1 .--1 Ul ll-t _I I U 1 N ~1 1-- ~ H N ~ I O O O
Il) N
~I rt I I I ~1 I rt N ~1 ~I N N tn r~ I O O o
~n o ~--, H H
H N I I I H L17 H Ll~ H H N H H N O O O O
o r,.
~:r o u-t o rl
I II r~ ul ~ ~ ~ t~ N ~1 .--1 .-1 0 0 0 0
_ . .
0 ~
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,~ tO 0
.~ . , ~
1 ~, tD
._ D~ D . 0 , t
~ 1 0 ~ ~ L H
. . ~ ~ ~ C O Y O
~, ,~ ~ . ~ tD ~ O
L, U ~ t
Cl 0 ~~ ~ ~ L L ~ U L
I ~ H 0 0 .~ 1 -~ E3 0 - O tt
H~ ~ V C ~ C~ t_ t~ ~1 E
. .. . . . . . . . .. . . _ . ... .. , . ... .: . _ .
r~ 'l'710
W095/29224 21 88=$~3
o o o
,,
o o o
~1 ~I N
O O O
r) 11)
~1 ~1 ~1
O O O
O
O
U
~ O
(D O
O - o
O ,1
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.. . . . .
W09~/29224 35 1~ D~7l0
EXPERIMENTAI ~: v 1 L)hN ~
The composition of Example 2 above was compared for
cleaning of body soils and whiteness maintenance
J benefits, to the same composition without Fungamyl~D-
The materials tested where dingy and greasy items,
washed at 40C with two long cycles,; the washed items
were judged by panellists and results are given in panel
score units:
Comparative cleaning assessment was done by expert
judges using a scale of a 0 to 4 panel-score-units. In
this scale 0 is given for no difference and 4 is given
f or maximum di f f erence
ITEM Example 2 Example 2
(Benefit test~-~ ) (without
Fungamyl~)
Pillow (whiteness maintenance) + 0 . 9~ Ref
Shirt collor (body soil + 0.8~ Ref
cleaning)
Shirt cuff (body soil + l.l-t Ref
cleaning)
Tea towel (whiteness + 0 . 4 Ref
maintenance )
~ Stati~tically sig ificant at 95~ confidence.
