Note : Les descriptions sont présentées dans la langue officielle dans laquelle elles ont été soumises.
CA 02187518 1999-06-07
' 1
AMYLASE-CONTAINING GRANULAR
DETERGENT COMPOSITIONS
Technical Field
The present invention relates to granular .~.~etergent
compositions, exhibiting excellent soil removal
properties especially on particulate stains.
Background of the invention
Polymeric dispersing agents have been commonly used in
detergent compositions to assist in removal of
particulate soil from textiles. Typically used species
are homopolymers of acrylic acid, and copolymers .of
acrylic acids having an average molecular weight above
1,000, available from BASF under the trade mark Sokalan,
as well as polyethyleneglycols with a molecular weight
above 4,000. Among these, copolymers of acrylic and
malefic acids having an average MW in the range of 2, 000
to 100,000 are the most typically used.
On the other hand, other types of ingredients which are
quite useful to the detergent formulator, are dye
transfer inhibiting polymers. Said polymers are added
to detergent compositions in order to inhibit the
transfer from dyes of colored fabrics onto other fabrics
washed therewith. These polymers have the ability to
complex the fugitive dyes washed out of dyed fabrics
before the dyes have the opportunity to become attached
to other articles in the wash.
The presence of such dye transfer inhibition agents in
granular detergent compositions, however can lead to
certain negatives in particulate soil
removal/suspension, especially if dispersing agents of
the above type are not used.
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The present invention now permits the use of dye-
transfer inhibition agents in granular compositions,
without the need to use dispersing agents such as
described above.
The compositions of the invention exhibit excellent
particular soil removal properties, as well as an
optimal biodegradability profile.
It has surprisingly been found that the above results
can be met through the use of an amylase enzyme in
conjunction with dye transfer inhibition agents, while
keeping the level of conventional dispersing agents,
such as described above, to minimal or nil.
Summary of the Invention
The present invention provides a granular detergent
composition comprising, by weight, from 0.05% to 1.5s
amylase, from O.Olo to 2% polymeric dye transfer
inhibition agent, from Oo to 2% of a dispersing agent
comprising a homopolymer of acrylic acid or copolymer of
malefic acid and acrylic acid or salt thereof, with an
average molecular weight above 1,000, or a polyethylene
glycol with a molecular weight above 4,000, surfactant and
builder.
Detailed description of the Invention
Amylase
The composition herein comprise as an essential
ingredient an amylase enzyme.
Suitable amylases include, for example, -amylases
obtained from a special strain of B. licheniforms,
WO 95/29222 21 ~ 7 518 PCTlUS95/04708
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described in more detail in GB-1,296,839 (Novo).
Preferred commercially available amylases include for
~ example, Rapidase, sold by International Bio-Synthetics
Inc. and Termamyl, sold by Novo Nordisk A/S.
Other suitable amylases are fungal species such as
Fungamyl~ commercially available from Novo Nordisk A/S.
The amylase- should be used at levels of from 0.05 to
1.5~ by weight of the detergent composition. When a
bacterial-amylase such as Termamyl~ is used, the level
of amylase should be such as to provide an activity
typically in the range of 1 to -500_. KNU/100 g of
detergent composition (Kilo Novo Units). Examples are
so-called TermamylR 60T and TermamylR 120T (ex. Novo
Nordisk).
When a fungal amylase such as Fungamyl~ is used, the
level should be such as to provide an activity in the
range of from 1 to 5,000 FAU/IOOg of detergent
composition (Fungal Apha Amylase Unit).
The dye transfer inhibition agent
The detergent compositions according to the present
invention also comprise from O.OOlo to 10 0, preferably
from 0.01 to 2ti, more preferably from 0.02$ to 1n by
weight of a polymeric dye transfer inhibiting agent.
Especially suitable polymeric dye transfer inhibiting
agents are polyamine N-oxide polymers, copolymers of N-
vinylpyrrolidone and N-vinylimidazole,
~ polyvinylpyrrolidone polymers, polyvinyloxazolidones,
polyvinylimidazoles and cross-linked variants of these
~ polymers, and mixtures thereof.
a) Polyamine N-oxide Dolymers
WO 95129222 PCTIUS95104708
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4
The polyamine=N-axide polymers suitable for us_e contain
units having the-following stYUCture..formula
P
I
(I) Ax
I
R
wherein P is a poiymerisableunit, whereto the R-N-0
group can be attached to ory~herein -the R-N-0
group forms part of the polymerisable. unit or a -
combination of both.
A is NC, C0, ~, -O-,-S-, -N- ; x is 0 ~r 1;
R are aliphatic, ethoxylated aliphatics,
aromatic, heterocyclic or alicyclic groups or
any combination thereof whereto the nitrogen of
the N-0 group can be attached or wherein the
nitrogen of the N-0 group is part -of these : ,
groups.
The N-0 group can be represented by the following
general structures : -
0 0
I I
(Rl)x -N- (R2)y =N- (Rl)x
I
(R3) z
wherein Rl, R2, and R3 are aliphatic groups, aromatic,
heteroeyclic or alicyclic groups or combinations
thereof, x or/and y or/and z is 0..or 1 and ,
wherein the nitrogen of the ,N-0 group can be
attached or -wherein the nitrogen of the N-0
group forms part of these-groups.
WO 95f29222 2-18 7 518 P~'~595/04708
The N-0 group can be part cf the polymerisable unit (P)
or --can be attached tn. the_.polymeric backbone or a
combination of both.
Suitable polyamine N-oxides wherein-the N-O group forms
part of the polymerisable unitcomprise 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-0
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 polyamineN-oxides comprises the
group-
of polyamine N-oxides wherein the nitrogen of the N-0
group is attached to the R-group.
Other suitable polyamine N-oxides are the polyamine
oxides whereto the N-O croup is attached to the
polymerisable unit.
Preferred class of these polyamine N-oxides are the
polyamine N-oxides having the general formula (I)
wherein R is an aromatic, heterocyclic or alicyclic
groups wherein the nitrogen of the N-0 functional group
is part of said R group.
Examples of these classes are polyamine oxides wherein R
is a heterocyclic compound such as pyrridine, pyrrole,
imidazole and derivatives thereof.
Another preferred class of polyamine N-oxides are the
polyamine oxides having the general formula (I) wherein
R are aromatic, heterocyclic or-alicyclic groups wherein
the nitrogen of the N-0 functiohal group is attached to
said R groups.
Examples of-these classes are polyamine oxides wherein R
groups can be aromatic such as phenyl.
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Any polymer backbone can be used as long as--the amine
oxide polymer --farmed is water-soluhie- and has .dye -
transfer. inhibiting properties. Examples of .- suitable . _.
polymeric backbones are polyvinyls, polyalkyleries,
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--1~1D0~000. 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-ox-ide is from 2:3 to 1:10000D0: --More-preferably
from 1:4 to 1:10000D0, most preferably from 1:7 to
1:1000D ~D~- The polymers of the- present- invention
actually encompass random or-block copolymers where- one
monomer type is an amine N-oxide and the other monomer
type is either an amine N-oxide or -not. The amine oxide -
unit of the polyamine N-oxides has a PKa < 10,
preferably PKa < 7, more preferred PKa < 6.
The polyamine oxides can -be 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 -SOD to 1000,000; -preferably from 1,000 to -
s0,000, more preferably from 2,000 to 30000, 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
WO 95129222 - ~ ~ ~ ~ 5 ~ ~ PCTlUS95I04708
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range from 5,000-1,000,000, preferably from 20,000-
200;000.
Highly preferred polymers for --use in detergent
compositions according to- the present invention
comprise a polymer selected -from-N-vinylimidazole N-
a
vinylpyrrolidone copolymers wherein said polymer has an
average molecular weight range from 5,000 to 50,000'niore
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 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
alsoutilize polyvinylpyrrolidone ("PVP" having an
. average molecular weight of from about 2,500 to-about
400,000, preferably from abo-ut 5,000 to about 200,000,
more preferably from about 5,000-to about 50,000, and
most preferably from- about 5,000 to about 15,000.
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Suitable polyvinylpyrrolidones are Commercially vailable
from ISP Corporation, New York, NY and Montreal, Canada -
under--the product names PVPK-15 (viscosity molecular
weight of 10;000), PVP IC-30 (average molecular weigh- of
40,000), PVP K-60 (averacje molecular weight of 160,000),
and PVP-K-90. (average molecular weight of 360,000).-PVP
K-15 is also available from ISP Corporation. Other
suitable polyvinylpyrrolidones which are commercially
available from BASF Cooperation include Sokalan HF 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 polyvinylpyrrolidone C" PVP" having an
average molecular weight of from
The detergent compositions of the present invention-may
also utilize -polyvinyloxazolidone as a polymeric --lye
transfer- inhibiting agent. Said polyvinyloxazolidones
have an average molecular weight of from about 2,500 to
about 400,000; preferably f-coin 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 polyvinylpyrro~.idone C"PVP" having an
average molecular weight of from
The detergent -compositions o~ the present inventionmay
also utilize --polyvinylimidazole as polymeric =dye _ '
transfer inhibiting a-gent. 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-
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5,000 to about -50,000,- and most preferably from about
5,000-to about 15,000.-
The polymeric dispersing agent
V
T_t is a particular feature of the present invention that
conventional polymeric dispersing- agents are not
essential to achieve good particulate soil- removal.
Accordingly, such conventional polymers as homopolymers-
of acrylic acid and copolymers of acrylic and malefic
acids and salts thereof, with an average molecular
weight above 1,000, as well as polyethylene glycols with
an average molecular weight above 4,000, can be
dispensed of, or their- levels minimized in the
compositions of the present invention.
Preferred among those are copolymers of acrylic and -
maleic acid, normally in the form of their water-soluble
salts. The average molecular weight of such copolymers
in the acid-fDrm ranges from about 2,000 to 100,000,
more preferably from about 5,000 to about80,000, most
preferably from about 7,000 to-70,000. The ratio of
acrylate to maleate segments in such copolymers will
generally range from about -30:1 to about l:i, more
preferably from about 10:1 to 2:1. Water-soluble salts
of such acrylic acid/maleic acid-copolymers can include,
for example, the alkali--metal, ammonium and substituted
ammonium salts. Soluble-acrylateJmaleate copolymers of
this type are known materials which are described in
European Patent Application No. 66915.
The level of the polymeric dispersants above should be
kept below 2~ by weight of the total detergent
composition, and is preferably close to zero.
Alternative dispersing agents can be used optionally, as
described hereinafter.
WO 95/29222 PCTIITS95104708
2187518
The crranular detergent compositions herein. are
_... ..
preferably laundry detergent compositions and contain a
surfactant '°and a detergent builder as essential -
ingredients. Suitable surfactants .and builders = are _
described in detail--hereinafter: -
Alkyl Sulfate Surfactant
Alkyl sulfate surfactants hereofare-water soluble salts ,
or acids of .theformula ROS03M wherein R preferably is a
C10-CZq-hydrocarbyl, preferably an alkyl or hydroxyalkyl
having a Clp-C2p-alkyl component, more preferably a C12-
C18 alkyl or hydroxyalkyl,- and M is H or a cation, e.g.,
an alkali metal canon --(e. g., sodium, potassium,
lithium), or ammonium or substituted ammonium (e. g.,
methyl-, dimethyl-, and trimethyl ammonium catians_.and
quaternary ammonium cations, such as tetramethyl-
ammonium and dimethyl piperdinium canons and
quarternary ammonium- cations derived from alkylamines
such as ethylamine, -diethyiamine, triethylamine, and
mixtures thereof, and - the like). Typically, alkyl
chains of C12-16 are preferred :.for. lower, -wash
temperatures ie.g., below about 50°C). and C16-18 alkyl
chains are preferred for higher wash temperatures--(e_g.,
above about 50°C).
Alkyl Alkoxylated Sulfate Surfactant ., .,
Alkyl alkoxylated sulfate surfactants hereof.,are water -
soluble salts or-acids of.the formula,RO(A)mS03M wherein
R is an unsubstituted C10-C2q alkyl or hydroxyalkyl
group having a -Clp-CZq -alkyl component,- preferably a-
C12-C2p alkyl or hydroxyalkyl, more preferably C12-C18
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,
WO 95129222 21 ~ ~ 5 i 8 PCT/US95/04705
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and M is H or a cationwhich 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 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 C12-
C18 alkyl polyethoxylate (I.0) sulfate, C12-ClgE(1.0)M),
C12-Clg alkyl polyethoxylate (2.25) sulfate, C12-
ClgE(2.25)M), C12-Clg alkyl polyethoxylate (3.0) sulfate
C12-ClgE(3.0), and C12-Clg alkyl -polyethoxylate (4.0)
sulfate C12-C18E(4.0)M), 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. These can
include salts (including, for example, sodium,
potassium, ammonium, and substituted ammonium salts such
as mono-, di- and triethanolamine salts) of soap, Cg-C20
linear alkylbenzenesulphonates, Cg-C22 primary or
secondary alkanesulphonates, Cg-C2q olefinsulphonates,
sulphonated - polycarboxylic acids prepared by
sulphonation- of the pyrolyzed product of alkaline earth
metal citrates, e.g., as described in British patent
specif3ca~ion No. - 1,082,179, Cg-C2a
alkylpolyglycolethersulfates (containing up to 10 moles
of ehtylene oxide); alkyl ester sulfonates such as 014-
16 methyl ester sulfonatest acyl glycerol sulfonates,
fatty oleyl glycerol sulfates,- alkyl phenol ethylene
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oxide ether sulfates, paraffin sulfonates, alkyl
phosphates, isethionates such as the acyl isethionates,
N-acyl taurates, alkyl succinamates and sulfosuccinates,
monoesters of sulfosuccinate (especially saturated and
unsaturated C12-Clg monoesters) diesters of
sulfosuccinate (especially saturated and unsaturated C6-
Clg diesters), acyl sarcosinates, sulfates of
alkylpolysaccharides such as the sulfates of
alkylpolyglucoside (the nonionic nonsulfated compounds
being described below), branched primary alkyl sulfates,
alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH20)kCH2C00-M+ wherein R is a C8-C22
alkyl, k is an integer from 0 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 given in "Surface Active Agents and Detergents"
(Vol. I and II by Schwartz, Perry and Herch). 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.
Preferred surfactants for use in the compositions herein
are the alkyl sulfates, alkyl alkoxylated sulfates, and
mixtures thereof.
The laundry detergent compositions of the present
invention typically comprise from about 1 ~ to about 40
, preferably from about 3 g to about 20 ~ by weight of
such anionic surfactants.
Nonionic Surfactants
The present laundry detergent compositions preferably
also comprise a nonionic surfactant.
W095f29222 -= PCTlU595104708
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While any nonionic surfactant may be normally employed
in the present invention, two families of nonionics have
been found 'to be particularly useful. These are nonionic
surfactants based on alkoxylated (especially
ethoxylated) alcohols, and those nonionic 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 the condensation of allcylene 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 -etfiylene oxide per mole of
alkyl phenol.
Preferred nonionics are -the water-soluble condensation
products of aliphatic alcohols containing from 8 to 22
WO 95/29222 PCTIUS95104708
14
carbon atoms, in either straight chain or branched
configuration,- with an average of up to 25 moles of
ethylene oxide per more o~ alcohol. Particularly
,.
preferred -ara the...~o~densation products -of alcohols
having an alkyl group containing from about 9 to 15
carbon atoms with from about- 2 to 10 , moles of 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 component:
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 glucamine -
with C12=C20 fatty acirimethyl ester.
Methods of manufacturing polyhydroxy fatty acid amides_
have been described in WO 92 6073, published on 16th _
April, 1992:--This application describes the preparation
of polyhydroxy fatty acid amides in the presence of
solvents. In- a highly preferred embodiment 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-thepresent-invention, such as
WO 95129222 2 i 8 7 518 PCTlUS95/04708
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those coiaprising N-methyl glucamide and C12-C14 alcohols
with an average of -3 e'thoxylatagroups per molecule.
Nonionic surfactant systems, and granular detergents
made from such systems have been described in WO 92
6160, published on 16th April, 1992. This application
describes (example 15) a granular -detergent composition
prepared by fine dispersion mixing in an Eirich RV02
mixer which comprises N-methyl glucamide (10's), 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
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,
preferabl-y 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.
positians thus giving a glucose or galactose as opposed
W0 95129222 PCTlUS95f04~08
i
I6-
to a qlucoside or. galactoside). The .intersaccharide -
bonds can be, e.g., between the one position of-the , _
additional saccharide units-. and- ,the 2,-, 3-~ i 4-, and/or
6- positions on the precedingsaccharide units.
The preferred alkylpolyglycosides have.the formuh ,.
R20(CnH2n0)t(qlYcosyl)X -
wherein RZ is selec=ted -from the group consisting of .
alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl,
and mixtures-thereaf in whidh the alkyl groups contain
from about 10 to about 18, preferably from about 12 to
about 14, carbon atoms; n is 2 ar 3, preferably 2; t is -
from 0 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 qlycosyl units can then
be attached between their -I-position-and the preceding
glycosyl units -2-, 3-, -4- and/or- 6-position, preferably -
predominantely the 2-position.
Other Surfactants
The laundry detergent compositions of the present-
invention may also contain cationic, ampholytic,
zwitterionic, 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 i~ the
laundry detergent compositions of the present invention
are those having one long-chain hydrocarbyl group.
Examples of such cationic surfactants include,. the
CA 02187518 1999-06-07
17
ammonium surfactants such as alkyldimethylammonium
halogenides, and those surfactants having the formula .
[R2 (OR3) y) (R4 (OR3) y] 2RSN+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,
-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; RS is the same as R4
or is an alkyl chain wherein the total number of carbon
atoms of R2 plus R5 is not more than about 18; each y is
from 0 to about 10 and the sum of the y values is from 0
to about 15; and X is any compatible anion.
Other cationic surfactants useful herein are also
described in US Patent 4,228,044, Cambre, issued October
14, 1980.
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-solubilizing group e.g.
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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 laundry detergent
compositions of the present invention typically comprise
form 0 ~ to about 15 b, preferably from about 1 b to
about 10 $ by weight of such ampholytic surfactants.
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 19, line 38 through column
22, line 48 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~l o 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
to about 18 carbon atoms and 2 moieties selected from
the group consisting of alkyl groups and hydrocyalkyl
groups containing form about 1 to about 3 carbon atoms;
water-soluble phosphine oxides containing one alkyl
moiety of form about 10 to about 18 carbon atoms and 2
moieties selected form the group consisting of alkyl
groups and hydroxyalkyl groups containing from about 1
to about 3 carbon atoms.
WO 95f29222 -
PCTlUS95I04708
19
Semi-polar nonionic dete-rgent surfactants include the
amine oxide surfactants having the formula
0
I
R3(OR4)xN(RS)2
Builder
The laundry detergent compositions herein contain a
builder, preferably non-phosphate detergent builders,
although phosphate-containing species are not excluded
in the content of the presentinvention. 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 25o to
80~ by weight of the composition, more preferably fr-om
30~ to 60~ by weight.
Suitable silicates are those having an Si02 : Na20 ratio
in the range from 1.6 to 3.4, the so-called amorphous
silicates of Si02 : Na20 ratios from 2.0 to 2.8 being
preferred. -
Within the silicate class, highly-preferred materials
are crystalline layered sodium silicates of general
formula
NaMSix02x + 1~YH20
wherein M is sodium or hydrogen, x is a number from 1.9
to 4 and y is a number from 0 to -20. Crystalline
layered -sodium silicates of this type are disclosed in
W O 95/29222 .P PCT/US95104708
~~;~ I 5~ ~
EP-A-0164514 and methods for .theix preparation are
disclosed in DE-A-3417649 and DE-A-3742043: _ Forthe .
purposes -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 0 and a
preferred example of this formula comprise the form of
Na2Si205. These.materials, are available from Hoechst-.AG -
FRG as respectively NaSKS=5, NaSKS-7, NaSKS-11 and
NaSKS-6. The most preferred -material is -Na25i205,
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[(A102)zO Si02)y1-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 10 to about 264. Amorphous hydrated-
aluminosilicate -materials useful. herein - have the
empirical formula -
Mz(zA102-y5i02)
wherein M is sodium, potassium, ammonium or substituted-
ammonium, z is from about 0.5 to, .:about 2 and y is l,
saidmaterial having a magnesium ion exchange capacity
of at -least about 50 milligram equivalents of CaC03 ;
hardness per gram of anhydrous aluminosilicate._ _,
Hydrated sodium Zeolite A W th a particle size of- from
about 0.01 to LO_ microns is preferred. ,
The aluminosilicate ion exchange builder--materials
herein are in hydrated form and contain from about 10
CA 02187518 1999-06-07
21
to about 28' of water by weight if crystalline, and
potentially even higher amounts of water if amorphous.
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
characterized by a particle size diameter of from about
0.1 micron to about 10 microns. Amorphous materials are
often smaller, e.g., down to less than about 0.01
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 utilizing a scanning electron
microscope.
Aluminosilicate ion exchange materials useful in the
practice of this invention are commercially available.
The aluminosilicates 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.
Preferred synthetic crystalline aluminosilicate ion
exchange materials useful herein are available under the
designations Zeolite A, Zeolite X, P and MAP, 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[(A102)12(Si02)121~xH20
CA 02187518 1999-06-07
22
wherein x is from about 20 to about 30, especially about
27 and has a particle size generally less than about 5
microns.
Suitable carboxylate builders containing one carboxy
group include lactic acid, glycoll.ic acid and ether
derivatives thereof as disclosed in Belgian Patent Nos.
831,368, 821,369 and 821,370. Polycarboxylates
containing two carboxy groups include the water-soluble
salts of succinic acid, malonic acid, (ethylenedioxy)
diacetic acid, malefic acid, ~~diglycolic 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
Canadian Patent No. 973,771, 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
substitue~nts 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
CA 02187518 1999-06-07
23
substituents are disclosed in British Patent No.
1, 439, 000.
A'_icyclic 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
hexacarboxylates and carbxoymethyl derivatives of
polyhydric alcohols such as sorbitol, mannitol and
xylitol. Aromatic polycarboxylates 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.
pH and density
The granular detergent compositions herein typically
have a .pH above 8.5, preferably in the range of from 9
to 11.
The present laundry granular compositions are preferably
in a compact form, having a bulk density of at least 650
g/1, preferably at least 750g/1, but can also be in a
conventional form, with densities in a range of from 200
g/1 to 700 g/1.
Chelating Agents
The detergent compositions herein may also optionally
contain one or more iron and/or manganese chelating
WO 95!29222 PCTIUS95104708
24
agents. Such chelating agents can be. selected fromthe
group consisting- of amino carboxylates, amino
phosphonates, polyfunctionally-substituted arqmatic -
chelating agents and mixtures .-therein, all as
hereinafter defined. L~ithout intending to be bound by
theory, it is- believed that the ,b-enefit of these
materials is-due ~.n-part to their exceptional ability to
remove iron and manganese ions from washing solutions by
formation of soluble ekielatesl ___
Amino carboxylates useful as optional chelating agents
include --ethylenediaminetetracetates, -- N-
hydroxyethylethylenediaminetriacetates,
nitrilotriacetates, ethylenediamine ~etraprionates,
triethylenetetraamine-hexacetates, -
diethylenetriaminepentaacetates, and ethanoldiglycines,
alkali metal, ammonium, and substituted ammonium salts
therein and mixtures therein.
Amino phosphonates are also suitable foz use- as
chelating agents in the compositions of the invention
when at least low levels of total- phosphorous are
permitted- -in detergent compositons, and include -
ethylenediaminetetrakis (methylenephosphonates) 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 compasitions .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-
disulfobehzene. - - -
A preferred biodegradable chelator for use herein is
ethyelediamine disuccinate ("EDDS"), especially the
W0 95129222 218 7 518 PCTlUS95/04708
[S, S] isomer as -described in U_5_ Patent 4,704,233,
November 3, -1987, to Hartman and Perkins.
If utilized, these chelating agents will generally
comprise from about O.lo to about l0a -by wei-ght of the
detergent compositions herein- More preferably, if
utilized, the chelating agents will comprise ,from about
O.lo to about 3:0$-by weight of such compositions.
Of the above, the preferred =polycarboxylates are
hydroxycarboxylates -containing up to three carboxy
groups per molecule, more--particularly citrates.
The granular detergent compositions and --automatic
dishwashing compositions herein have a pH above 8.5,
preferably in the range of from 9 to 11.
The present laundry granular compositions are preferably
in a compact form, having a-bulk density of at least 650
g/1, preferably at least 750g/1, but can also be in a
conventional form, with densities in a range of from 200
g/1 to 700 g/1:
In another -embodiment -of the invention, are provided
Automatic Dishwashing Compositions
Automatic dishwashing compositions typically contain, in
addition to the amylase of the invention, a builder,
such as described above, a source of alkalinity, such as
silicate or--carbonate, and a bleaching agent, preferably
percarbonate; those ingredients amounting to up to 70$
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
W0 95129222 PC1'IUS95104~08
amylase--o ~ the invention, a bleaching agent at levels of
from 15 to 80_~ by weight-. -
Other Inslredients
Other ingredients which are known for use in detergent
compositions may also be used as optional ingredients in
the various embodiments of the prasentinvention, such
as bleaching agents, bleach activators, polymers,
biodegradable dispersing agents, 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- alkalinity sources,- enzyme- stability agents,
hydrotopes, solvents, perfumes.
Alternative dispersing agents
Such agents may be used in the present composition, as
levels rahgihg from 1 to 6$- =Among such dispersants can
be mentioned polyvinylalcohols with a molecular weight
up to 70,000, polyethyleneglycols with a molecular
weight below 4,000, preferable I.to 3;000, or
terpolymers of maleic/acrylic acid and vinyl alcohol
having a molecular weight ranging-from,-3,000 to 70,OD0, -
with the percentage of vinyl alcohol being from 5 to
60$. _ _
Polyaspartate and polyglutamate dispersing agents may
also be used; especially in conjunction with zeolite
builders. Dispersing agents such as polyasparatate -
preferably have a mo-lecular weight of about 10,000. -
Polysuccinimide and acrylic-acrolein and mixtures
thereof may also be used in this respect.
J
Other enzymes
CA 02187518 1999-06-07
27
Enzymatic materials other than the specific amylases
herein can be incorporated into the detergent
compositions herein. Suitable are proteases, lipases,
cellulases, peroxidases, other amylases and mixtures
thereof .
A suitable lipase enzyme is manufactured and sold by
Novo Industries A/S (Denmark) under the trade mark
Lipolase and mentioned along with other suitable lipases
in EP-A-0258068 (Novo Nordisk).
Bleaching agents
In the embodiment of the present invention, the granular
laundry detergent compositions herein contain a
bleaching agent; however bleach-free granular detergent
compositions are also desirable, particular for the
treatment of certain fabrics requiring special care;
therefore, such bleach-free detergent compositions 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, 1,12 diperoxydodecanedoic 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 herein typically
contain from 1$ to 40$, preferably from 3a to 30~ by
weight, most preferably from 5$ to 25o by weight of
alkali metal percarbonate bleach, in the form of
CA 02187518 1999-06-07
28
particles having a mean size from 250 to 900
micrometers, preferably 500 to 700 micrometers.
The alkali metal percarbonate bleach is usually in the
form of the sodium salt. Sodium percarbonate is an
addition compound having a formula corresponding to
2Na2C03 3H202. To enhance storage stability the
percarbonate bleach can be coated with e.g. a further
mixed salt of 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 Na2S04.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
Si02:Na20 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 aminophosphonate. that is
incorporated during the manufacturing process.
Preferred heavy metal sequestrants for incorporation as
described herein above include the organic phosphonates
and amino alkylene poly(alkylene phosphonates) such as
the alkali metal ethane 1-hydroxy diphosphonates, the
nitrilo trimethylene phosphonates, the ethylene diamine
tetra methylene phosphonates and the diethylene triamine
penta methylene phosphonates.
W095I29222 - - PCT/US95/04708
29
Bleach activators
The bleach containing detergent-compositions, according
to the above-described embodiment, preferably contain
from to to 2~o by weight of the composition, preferably
from 2~ to 15o by weight, most preferably from 3b to l00
by weight of a peroxyacid bleach activator, in addition
to the hleaching agent described above.
Peroxyacid bleach activators (bleach precursors) as
additional bleaching components in accordance with the
invention can be selected from a wide range of class and
are preferably those containing one or more N-or 0-acyl
groups.
Suitable classes include anhydrides, esters, amides, and
acylated derivatives of -"imidazoles and oximes, and
examples 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, 1 147 871 and 2 I43 231 and amides such as are
disclosed ih 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
WO 95/29222 PCT/US95104708
0
I I
CH3C'
-N-( CH2
CH3 i/ 3
O
where x can be 0 or.an integer between 1 and 6.
Examples include tetra acetyl methylene diamine (TAMD)
in which x=I, tetra acetyl ethylene diamine (TAED)in
which x=2 and Tetraacetyl hexylene diamine (TAHD) 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.
Another-preferred class of. peroxyacid bleach compounds
are the amide substituted compounds-of the folldiaing
general formulae
R1 _ ~ _ NSg2 _ ~ _ L or R1 - RS- ~-R2 _ ,~ - L
'i~0
wherein R1 is an aryl or alkaryl group with from about 1
to about 14 carbon atoms, RZ is an alkylene, arylene,
and alkarylene group containing from about 1 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 I2 carbon atoms. RZ preferably contains
from-ahbut 4 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.:
includihg for example, tallow fat. Analogous structural
variations are permissible for Rz. The substitution can
WO 95!29222 PCTlUS95I0470S
31
including for example, tallowfat. analogous structural
variations are permissible for.R2. The substitution can
include alkyl, aryl, halogen, nitrogen, sulphur and
other typical substituent groups or organic compounds.
RS is preferably H or methyl. Rl and RS should not
contain more than I8 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 Cg, Cg, and/or C10 (6-
octanamidocaproyl) oxybenzenesulfonate, 2-phenyl-(4H)3,1
benzoxazin-4-one, benzoyllactam preferably
benzoylcaprolactam and nonanoyl lactam preferably
nonanoyl caprolactam.
Polymers
Also useful are certain organic-polymers other than the
dye transfer exhibiting or dispersants described
hereinabove. Among such polymers may be mentioned
sodium carboxy-lower alkyl celluloses and sodium
hydroxy-lower alkyl celluloses, such as sodium
carboxymethyl cellulose,- sodium methyl cellulose and
sodium hydroxypropyl cellulose.- Molecular weights for
such polymers vary widely but most are within the range
of 2,000 to 100,000.
Other useful polymers include-species known as soil
release polymers, such as described in EPA 185 427 and
EPA 311 3-42_
WO 95129222 PCTIUS95104708
32
EXAMPLE 1
The following formulae were prepared
C~OSrTZON Example Example
8 1 2
$ BY WEIGHT
Linear Alkyl Benzene
Sulfonate -
Talloc~-Alkyl Sulfate 2 2 2
C25 alkyl ethoxysulfate 0.2 0.2 0.2
C45 alcool 7 times 4.0 0.4 0.4
ethoxylated
Tallow alcohol ethoxylate 1.0 1.0 1.0
11 times ethoxylated
Zeolite 20 20 20
Trisodium citrate 5 5 5
Carbonate 16 16 16
Silicate 3 3 3
Carboxymethylcellulose 0.3 0.3 0.3
Soil release polymer 0.3 0.3 0.3
Protease (Savinase) 0.3 0.3 0.3
Cellulase (1000 cevu) 0.3 0.3 0.3
Lipase (Lipolase) 0.3 0.3 0.3
(100 KLU)
Perborate Tetrahydrate 12 12 12
TAED* 5 5 5
.
PVNO** 1 1 1
Amylase 1 1
(Termamyl 60KNPU
~S'O 95129222 218 7 51 ~ P~~S95I04708
33
erpolymer*** I 4
nors ~ up to 1
* Tetraacetylethylene diamine
' ** Polyvinyl N-oxide
*** malefic anhydride/acrylic
acid/vinylalcoholterpolymer. (10-30$ vinylalcohol).
The compositions of Example 1 and Example 2 showed
significantly better clay soil removal properties than
the composition A.
Results are as follows (expressed in Panel Score Units)
Clay on different
stain clays
removalbased from
geographical (clays
origins 1
= to
4)
Com osition Exam1e Exam le 2
A 1
Clay 1 ref + 7* + 1*
1. 2.
Clay 2 ref + 1* + 9*
1. 1.
Clay 3 ref + 3* + 4*
1. 1.
Clay 4 ref + 0* + 2*
0. 1.
* Significant difference at 95$ confidence
Comparative cleaning assessment was done by expert
judges using a scale of D to 4 panel-score-units (PSU).
In this scale 0 is given for no difference and 4 is
given for maximum difference.
Conditions : 40°C, Sotax, City water 12°H.
Stir rate 150 rpm, 30 minutes, cold
rinse
clay stains painted onto flat cotton.
W 0 95129222 ~ PCTlUS95104708
34
EXAMPLE 3
Additional detergent composi a ons according to the
invention were prepared.:
Granular Laundxq
Detergents
F..samples 3 4 5 6 7 8 9 10
Linear Alkyl Sulpho- 7 0 0 0 0 0 0 0
nate
Tallow Alkyl Sul- 3 0 0 0 0 0 0 0
hate
Alk 1 Sulphate 0 9 6 9 12 12 9 6
Alkyl Ethoxylate - 0.2 2 1 2 2 3 3 3
Sulphate
Alkyl xri-methyl 0 0 2 0 0 0 0 0
Ammonium Chloride
Alkyl Ethoxylate 4 5 10 6 4 7 8 12
Alkyl-N-Methyl 0 2 3 3 1 3.5 3.5 3.5
Glucosamide
Perborate 22 0 0 0 0 0 0 0
Percarbonate 0 22 19 22 24 0 0 0
N,N,N,N-Tetra acetyl 5 6 5 5 5 0 0 0
ethylene diamine
Diethylene tri-amine 0.4 0.5 0 0 0 0 0 0
penta(methylene
phosphonic acid)
S,S-Ethylene-di- 0 0 0.5 0.5 0.5 0 0 0
succinic acid
Fungamyl 1600 FAU 0 0.125 0.2 0.2 0 0 0.3 0.3
Lipolase 165 KLU 0.3 0.2 0.2 0.2 0.2 0.2 0.2 0.2
Cellulase 1000-cevu 0.1 0.2 0.3 0.3 0.3 0.2 0.2 0.2
Endoglucanase SOOD 0 0.1 0.1 0.1 0.1 0.1 0.1 0.1 .
s-
cevu
WO 95129222 PCT/US95/04708
Granular Laundry
Detergents
F~camples 3 4 5 6 7 8 9 10
Protease(Savinase)0.4 0.5 0.7 0.7 0.5 0.7 0.7 0.7
13KNPU
Termamyl 60 KNU 0.6 0.3 0 0.2 0.5 0.8 0.2 0.2
Alcalase 3 AU 0 0 0 0 0 1 1 1
Alumino Silicate 21 13 15 15 18 19 21 23
(zeolite A)
Layered Silicate 0 12 11 11 9 9 11 7
Sodium Citrate 6 5 4 4 3 11 9 8
Sodium Carbonate 16 8 7 7 7 lI 11 9
Sodium Silicate 3 0 0 0 D 4 6 8
Sulphate 4 0.6 D.6 0.6 0.6 0 0 0
Malefic & Acrylic 0 1.5 1 0 0 1 0 0
Acid Sodium Salt
copolymer MW ...
Carboxymethyl,cel-3 0.3 0.3 0.3 0.3 0.3 0.3 0.3
lulose Sodium Salt
Soil Release 0.3 0.3 0.2 0.2 0.2 U.2 0.2 0.2
Pol er
Polyvinylpyridone 0 0.5 1 0 0 0.5 0 0
Polyvinyl-N-Oxide 0.3 0 0.5 0.2 0.2 0.4 0.3
(PVNO)
PVPVI 0 0.0 D 0 0.2 0.5 0.1
5
Polyethylene 0 0 0 0 2 1 0 2
Glycol
MW 1000-3000
Terpolymer 0 0 3 4 0 3 0 0
Polyaspartate . 0 0 0 0 0 4 2
Minors
up
to
110
