U.S. patent application number 11/803056 was filed with the patent office on 2007-11-15 for aqueous liquid cleaning compositions and their use.
This patent application is currently assigned to Conopco Inc, d/b/a UNILEVER, Conopco Inc, d/b/a UNILEVER. Invention is credited to Olaf Cornelis P Beers, Lillimarlene Faucia Brouwn, Ian Charles Callaghan, Maartje Ouwendijk-Vrijenhoek, Derdiyok Sonmezer, Simon Marinus Veerman.
Application Number | 20070265182 11/803056 |
Document ID | / |
Family ID | 37153530 |
Filed Date | 2007-11-15 |
United States Patent
Application |
20070265182 |
Kind Code |
A1 |
Beers; Olaf Cornelis P ; et
al. |
November 15, 2007 |
Aqueous liquid cleaning compositions and their use
Abstract
An isotropic aqueous liquid detergent composition comprising: a
succinate dimer surfactant selected from alkyl and alkenyl
succinate dimers in which two succinic acid moieties or derivatives
thereof are joined by a (poly)alkyleneoxy bridge and each
carboxylic acid group is independently in the free acid form, salt
form or is esterified or is a corresponding amide group; and
mixtures thereof; one or more other surfactants; and water.
Inventors: |
Beers; Olaf Cornelis P;
(Vlaardingen, NL) ; Brouwn; Lillimarlene Faucia;
(Vlaardingen, NL) ; Callaghan; Ian Charles;
(Riding Mill, GB) ; Ouwendijk-Vrijenhoek; Maartje;
(Vlaardingen, NL) ; Sonmezer; Derdiyok;
(Vlaardingen, NL) ; Veerman; Simon Marinus;
(Vlaardingen, NL) |
Correspondence
Address: |
UNILEVER INTELLECTUAL PROPERTY GROUP
700 SYLVAN AVENUE,, BLDG C2 SOUTH
ENGLEWOOD CLIFFS
NJ
07632-3100
US
|
Assignee: |
Conopco Inc, d/b/a UNILEVER
|
Family ID: |
37153530 |
Appl. No.: |
11/803056 |
Filed: |
May 11, 2007 |
Current U.S.
Class: |
510/267 ;
510/314 |
Current CPC
Class: |
C11D 1/02 20130101; C11D
1/08 20130101 |
Class at
Publication: |
510/267 ;
510/314 |
International
Class: |
C23G 1/06 20060101
C23G001/06 |
Foreign Application Data
Date |
Code |
Application Number |
May 12, 2006 |
EP |
EP06076052 |
Claims
1. An isotropic aqueous liquid detergent composition comprising: a
succinate dimer surfactant consisting of at least one compound of
formula (I): ##STR00007## wherein in formula (I), each of R.sup.1
and R.sup.2 is independently selected from alkyl and alkenyl groups
having from 8 to 18, preferably from 12 to 18, most preferably 18
carbon atoms; each of R.sup.3 and R.sup.4 is independently selected
from hydrogen, groups M where M is a metal counter-cation,
preferably an alkali metal such as sodium, C.sub.1-C.sub.6,
preferably C.sub.1-C.sub.4 alkyl groups and groups of formula
--NR.sup.6R.sup.7 where R.sup.6 and R.sup.7 are independently
selected from hydrogen and C.sub.1-C.sub.6, preferably
C.sub.1-C.sub.4 alkyl groups; and R.sup.5 is selected from
poly(alkyleneoxy) groups, preferably groups of formula
--(C.sub.nH.sub.2n+1O).sub.m--C.sub.nH.sub.2n+1-- where m is from 0
to 12, preferably from 6 to 10, more preferably from 8 to 10, most
preferably 10 wherein in each C.sub.nH.sub.2n+1 moiety n is
independently from 2 to 4, more preferably 2 and preferably also,
each n is the same; one or more other surfactants; and water.
2. A composition according to claim 1, wherein R.sup.1 and R.sup.2
are independently selected from groups of formula
CH.sub.3--(CH.sub.2).sub.p--CH.dbd.CH--CH.sub.2-- where p is
preferably from 4 to 14, more preferably from 8 to 14 and most
preferably is 14.
3. A composition according to claim 1, comprising from 0.1% to 5%,
more preferably from 0.2% to 3%, most preferably from 0.5% to 2% by
weight of the disuccinate dimer surfactant.
4. A composition according to claim 1, comprising from 5% to 60%,
more preferably from 10% to 50%, most preferably from 12% to 45% by
weight of the one or more other surfactants.
5. A composition according to claim 1, comprising from 30% to 90%,
more preferably from 40% to 85%, most preferably from 50% to 80% by
weight of the water.
6. A composition according to claim 1, further comprising soap.
7. A composition according to claim 1, further comprising an
atmospheric oxygen bleach catalyst.
8. A method of preparing an isotropic liquid detergent composition,
the method comprising admixture of a succinate dimer surfactant
according to claim 1, one or more other surfactants, water and
optionally, one or more other ingredients.
9. Use of a succinate dimer surfactant according to claim 1, as a
stabiliser for an isotropic liquid detergent composition comprising
water and one or more other surfactants.
Description
FIELD OF INVENTION
[0001] The present invention relates to aqueous liquid cleaning
compositions. It also relates to methods of using such compositions
for the cleaning of fabrics.
BACKGROUND OF INVENTION
[0002] Aqueous liquid detergent compositions can generally be
considered to fall into one of two categories, namely isotropic or
structured. Structured compositions usually contain lamellar phases
formed of surfactant and water, which cause them to be relatively
viscous, shear thinning and often, to have solid suspending
properties. Isotropic compositions, on the other hand, usually have
a viscosity similar to that of water and are substantially
Newtonian. In addition, consumers generally prefer isotropic
compositions to be substantially transparent, or at least,
translucent.
[0003] Lack of clarity in such aqueous liquid detergent
compositions can be the result of a number of factors. One such
factor is the formation of micellar or more ordered phases. Another
cause of loss of clarity is potentially due to instability of one
or more ingredients. Such instability can be due to the presence of
highly reactive species, such as bleach catalysts, for example, of
the type used to catalyse bleaching by atmospheric oxygen. It can
also be due to species which degrade too readily. Reactive species
can attack and degrade organic molecules within the formulation. An
example of an ingredient of the kind which degrades very easily is
enzymes.
[0004] In isotropic aqueous liquid detergent compositions, it is
common to include one or more hydrotropes such as ethanol, sodium
xylene sulphonate (SXS) or sodium cumene sulfonate (SCS), as well
as polypropylene glycol (PPG). These materials have the function of
inhibiting the formation of ordered phases and so promote the
clarity of the liquid. However, they are relatively costly and do
not really contribute to the leaning performance of the
product.
[0005] It is also common to use organic bases to neutralise fatty
acids, in order to result in the formation of a more soluble soap.
Such basis are typically, monoethanolamine or triethanolamine.
Using these organic bases as the cation in a soap and/or adding an
organic base when a soap is present, can stabilise the formulation
at low temperatures. However, these materials have the potential
disadvantage of inducing colour instability at higher
temperatures.
[0006] Thus, the use of hydrotropes has a cost penalty in
formulation of the product. The use of organic bases as stabilisers
for soap can promote instability at high temperatures.
[0007] There is therefore a need to find an alternative form of
stabiliser which does not carry such a cost penalty and/or does not
have disadvantages to the same degree as conventional stabilisers.
To help avoid the cost penalty disadvantage, it would be helpful to
utilise a stabiliser which has another useful function in the
formulation. For example, if such an alternative stabiliser were a
surfactant, it would contribute to the cleaning performance of the
product.
[0008] We have now found that succinate dimer, optionally including
derivatives thereof, surfactants may fulfil this role of detergent
(surfactant) active and stabiliser.
[0009] In liquid detergent compositions, alkyl and alkenyl
disuccinates have been mentioned as possible detergency builders,
as disclosed in US-A-25/0124,528. Alkyl and alkenyl succinates have
been disclosed as builders for liquid detergents, according to U.S.
Pat. No. 5,945,394. Long chain (di)-alk(en)yl succinates have been
disclosed as useful surfactant ingredients in aqueous liquid
detergent compositions in many prior documents such as GB-A-2 232
420, GB-A-2 120 272, EP-A-476 212, EP-A-241 073, EP-A-212 713,
EP-A-200 263, EP-A-233 306 and EP-A-028 850. These materials have
also been disclosed as possible ingredients for fabric conditioner
compositions, as disclosed in WO-A-99/27056.
[0010] Alkyl succinates and unsubstituted tartrate succinate
builders have been described as such in EP-A-342 177.
SUMMARY OF INVENTION
[0011] A first aspect of the invention provides an isotropic
aqueous liquid detergent composition comprising:
[0012] a succinate dimer surfactant as specified in claim 1; one or
more other surfactants; and water.
[0013] A second aspect of the present invention provides a method
of preparation of an isotropic aqueous liquid detergent
composition, the method comprising admixture of water, one or more
other surfactants and a succinate dimer surfactant of the
invention.
[0014] A third aspect of the present invention provides use of a
succinate dimer surfactant according to the present invention as a
stabiliser in an isotropic aqueous liquid detergent composition,
the composition also comprising one or more other surfactants and
water.
DETAILED DESCRIPTION OF THE INVENTION
[0015] The Succinate Dimer Surfactant
[0016] The succinate dimer surfactant present in the composition of
the invention comprises or consists of at least one compound of
formula (I):
##STR00001##
wherein in formula (I), each of R.sup.1 and R.sup.2 is
independently selected from alkyl and alkenyl groups having from 8
to 18, preferably from 12 to 18, most preferably 18 carbon atoms;
each of R.sup.3 and R.sup.4 is independently selected from
hydrogen, groups M where M is a metal counter-cation, preferably an
alkali metal such as sodium, C.sub.1-C.sub.6, preferably
C.sub.1-C.sub.4 alkyl groups and groups of formula
--NR.sup.6R.sup.7 where R.sup.6 and R.sup.7 are independently
selected from hydrogen and C.sub.1-C.sub.6, preferably
C.sub.1-C.sub.4 alkyl groups; and
[0017] R.sup.5 is selected from poly(alkyleneoxy) groups,
preferably groups of formula
--(C.sub.nH.sub.2n+1O).sub.m--C.sub.nH.sub.2n+1-- where m is from 0
to 12,
[0018] preferably from 6 to 10, more preferably from 8 to 10, most
preferably 10 wherein in each C.sub.nH.sub.2n+1 moiety n is
independently from 2 to 4, more preferably 2 and preferably also,
each n is the same.
[0019] In some preferred embodiments, R.sup.1 and R.sup.2 are
independently selected from groups of formula
CH.sub.3--(CH.sub.2).sub.p--CH.dbd.CH--CH.sub.2-- where p is
preferably from 4 to 14, more preferably from 8 to 14 and most
preferably is 14.
[0020] In some preferred embodiments, R.sup.1 and R.sup.2 are the
same as each other and R.sup.3 and R.sup.4 are the same as each
other, most preferably both hydrogen or both --O.sup.-M.sup.+.
[0021] Preferably also, the composition of the invention comprises
from 0.1% to 5%, more preferably from 0.2% to 3%, most preferably
from 0.5% to 2% by weight of the succinate dimer surfactant.
However, there is no specific limitation on level and it could
constitute, for example, from 0.001% to 15% or 0.005% to 10% by
weight of the composition.
[0022] Compounds of formula (I) can be readily prepared by the
following generic procedure using well known textbook chemistry.
Alkenyl-succinic anhydride precursors are commercially available
(e.g. ex Aldrich) or can be prepared via the "ene reaction" by
reaction of an alkene with maleic anhydride (J. March, Advanced
Organic Chemistry pg 711, 3.sup.rd Edn. 1984 and references cited).
If required, the double bond in the alkenylgroup can be
hydrogenated using catalytic hydrogenation (J. March, Advanced
Organic Chemistry pg 691, 3rd ed. 1984 and references cited). The
alkenyl-succinic anhydrides are converted to the mono-ester/diester
mix via ring-opening of the anhydride by reaction with one or both
alcohol endgroups of a polyethyleneglyccol of choice (J. March,
Advanced Organic Chemistry pg 347, 3.sup.rd. Edn. 1984 and
references cited). The ratio of mono/diester can be influenced by
varying the molar ratio of anhydride to polyethyleneglycol.
Reaction of 2 equivalents of anhydride with one equivalent of
polyethyleneglycol would give the most economic ratio of
non-reacted started materials with the products mono-ester and
di-ester. The reaction can be done without solvent and can be
followed by infrared spectroscopy by monitoring the disappearance
of the anhydride carbonyl stretch vibration absorption at 1860
cm.sup.-1 and formation of ester carbonyl stretch vibration
absorption 1733 cm.sup.-1.
The Water
[0023] The compositions according to the present invention
preferably also comprise from 30% to 90%, more preferably from 40%
to 85%, most preferably from 50% to 80% by weight of the water.
Other Surfactant
[0024] The compositions of the present invention comprise one or
more surfactants other than the succinate dimer. Based on the
weight of the total composition such other surfactant(s) preferably
are from 5 to 60%, more preferably from 10 to 50% by weight of one
or more other surfactants preferably selected from anionic,
nonionic, cationic, zwitterionic active detergent material or
mixtures thereof.
[0025] Non-limiting examples of such other surfactants useful
herein typically at levels from about 10% to about 70%, by weight,
include the conventional C10-C18 e.g. C10 to C13 alkylbenzene
sulphonates ("LAS"), the C10-C18 secondary (2,3) alkyl sulphates of
the formula CH3(CH2).sub.x(CHOS03-M+)CH3 and
CH3(CH2).sub.y(CHOS03-M+)CH2CH3 where x and (y+1) are integers of
at least about 7, preferably at least about 9, and M is a
water-solubilising cation, especially sodium, unsaturated sulphates
such as oleyl sulphate, C10-C18 alkyl alkoxy carboxylates
(especially the EO 1-7 ethoxycarboxylates), the C10-C18 glycerol
ethers, the C10-C18alkyl polyglycosides and their corresponding
sulphated polyglycosides, and C12-C18 alpha-sulphonated fatty acid
esters. If desired, the conventional nonionic and amphoteric
surfactants such as the C12-C18 alkyl ethoxylates ("AE") including
the so-called narrow peaked alkyl ethoxylates and C6-C12 alkyl
phenol alkoxylates (especially ethoxylates and mixed
ethoxy/propoxy), C12-C18 betaines and sulphobetaines ("sultaines"),
C10-C18 amine oxides, and the like, can also be included in the
overall compositions. The C10-C18 N-alkyl polyhydroxy fatty acid
amides can also be used. Typical examples include the C12-C18
N-methylglucamides. See WO 9,206,154. Other sugar-derived
surfactants include the N-alkoxy polyhydroxy fatty acid amides,
such as C10-C18 N-(3-methoxypropyl)glucamide. C10-C20 conventional
soaps may also be used. If high sudsing is desired, the
branched-chain C10-C16 soaps may be used.
[0026] Mixtures of anionic and nonionic surfactants are especially
useful. Other conventional useful surfactants are listed in
standard texts.
[0027] Other anionic surfactants useful for detersive purposes can
also be included in the isotropic compositions hereof. These can
include salts (including, for example, sodium potassium, ammonium,
and substituted ammonium salts such a mono-, di- and
triethanolamine salts) of soap, C9-C20 linear
alkylbenzenesulphonates, C8-C22 primary or secondary
alkanesulphonates, C8-C24 olefinsulphonates, sulphonated
polycarboxylic acids, alkyl glycerol sulphonates, fatty acyl
glycerol sulphonates, fatty oleyl glycerol sulphates, alkyl phenol
ethylene oxide ether sulphates, paraffin sulphonates, alkyl
phosphates, isothionates such as the acyl isothionates, N-acyl
taurates, fatty acid amides of methyl tauride, alkyl succinamates
and sulphosuccinates, monoesters of sulphosuccinate (especially
saturated and unsaturated C12-C18 monoesters) diesters of
sulphosuccinate (especially saturated and unsaturated C6-C14
diesters), N-acyl sarcosinates, sulphates of alkylpolysaccharides
such as the sulphates of alkylpolyglucoside, branched primary alkyl
sulphates, alkyl polyethoxy carboxylates such as those of the
formula RO(CH2CH20).sub.kCH2COO-M+ wherein R is a C8-C22 alkyl, k
is an integer from 0 to 10, and M is a soluble salt-forming cation,
and fatty acids esterified with isethionic acid and neutralised
with sodium hydroxide. Further examples are given in Surface Active
Agents and Detergents (Vol. I and II by Schwartz, Perry and
Berch).
[0028] The isotropic compositions of the present invention
preferably comprise at least about 5%, preferably at least 10%,
more preferably at least 12% and less than 70%, more preferably
less than 60% by weight, of an anionic surfactant.
[0029] Alkyl sulphate surfactants, either primary or secondary, are
a type of anionic surfactant of importance for use herein. Alkyl
sulphates have the general formula ROS03M wherein R preferably is a
C10-C24 hydrocarbyl, preferably an alkyl straight or branched chain
or hydroxyalkyl having a C10-C20 alkyl component, more preferably a
C12-C18 alkyl or hydroxyalkyl, and M is hydrogen or a water soluble
cation, e.g., an alkali metal cation (e.g., sodium potassium,
lithium), substituted or unsubstituted ammonium cations such as
methyl-, dimethyl-, and trimethyl ammonium and quaternary ammonium
cations, e.g., tetramethyl-ammonium and dimethyl piperdinium, and
cations derived from alkanolamines such as ethanolamine,
diethanolamine, triethanolamine, and mixtures thereof, and the
like.
[0030] Typically, alkyl chains of C12-C16 are preferred for lower
wash temperatures (e.g., below about 50.degree. C. and C16-C18
alkyl chains are preferred for higher wash temperatures (e.g.,
about 50.degree. C.). Alkyl alkoxylated sulphate surfactants are
another category of preferred anionic surfactant. These
surfactants; are water soluble salts or acids typically of the
formula RO(A)mSO3M wherein R is an unsubstituted C10-C24 alkyl or
hydroxyalkyl group having a C10-C24 alkyl component, preferably a
C12-C20 alkyl or hydroxyalkyl, more preferably C12-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, and M is hydrogen or a water soluble
cation which can be, for example, a metal cation (e.g., sodium,
potassium, lithium, calcium, magnesium, etc.), ammonium or
substituted-ammonium cation. Alkyl ethoxylated sulphates as well as
alkyl propoxylated sulphates 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, e.g., monoethanolamine, diethanolamine, and
triethanolamine, and mixtures thereof. Exemplary surfactants are
C12-C18 alkyl polyethoxylate (1.0) sulphate, C12-C18 alkyl
polyethoxylate (2.25) sulphate, C12-C18 alkyl polyethoxylate (3.0)
sulphate, and C12-C18 alkyl polyethoxylate (4.0) sulphate wherein M
is conveniently selected from sodium and potassium.
[0031] The compositions of the present invention preferably
comprise at least about 5%, preferably at least 10%, more
preferably at least 12% and less than 70%, more preferably less
than 60% by weight, of a nonionic surfactant.
[0032] Preferred nonionic surfactants such as C12-C18 alkyl
ethoxylates ("AE") including the so-called narrow peaked alkyl
ethoxylates and C6-C12 alkyl phenol alkoxylates (especially
ethoxylates and mixed ethoxy/propoxy), block alkylene oxide
condensate of C6 to C12 alkyl phenols, alkylene oxide condensates
of C8-C22 alkanols and ethylene oxide/propylene oxide block
polymers (Pluronic.TM.-BASF Corp.), C8-C22 fatty acid methyl ester
ethoxylates, as well as semi polar nonionics (e.g., amine oxides
and phosphine oxides) can be used in the present isotropic
compositions. An extensive disclosure of these types of surfactants
is found in U.S. Pat. No. 3,929,678.
[0033] Alkylpolysaccharides such as disclosed in U.S. Pat. No.
4,565,647 are also preferred nonionic surfactants in the isotropic
compositions of the invention.
[0034] Further preferred nonionic surfactants are the polyhydroxy
fatty acid amides.
[0035] A particularly desirable surfactant of this type for use in
the isotropic compositions herein is alkyl-N-methyl glucamide.
Other sugar-derived surfactants include the N-alkoxy polyhydroxy
fatty acid amides, such as C10-C18 N-(3-methoxypropyl)glucamide.
The N-propyl through N-hexyl C12-C18 glucamides can be used for low
sudsing. C10-C20 conventional soaps may also be used. If high
sudsing is desired, the branched-chain C10-C16 soaps may be
used.
[0036] Another preferred anionic surfactant is a salt of fatty
acids. Examples of fatty acids suitable for use of the present
invention include pure or hardened fatty acids derived from
palmitoleic, safflower, sunflower, soybean, oleic, linoleic,
linolenic, ricinoleic, rapeseed oil or mixtures thereof. Mixtures
of saturated and unsaturated fatty acids can also be used
herein.
[0037] It will be recognised that the fatty acid will be present in
the liquid detergent isotropic composition primarily in the form of
a soap. Suitable cations include, sodium, potassium, ammonium,
monoethanol ammonium diethanol ammonium, triethanol ammonium,
tetraalkyl ammonium, e.g., tetra methyl ammonium up to tetradecyl
ammonium etc. cations.
[0038] The amount of fatty acid will vary depending on the
particular characteristics desired in the final detergent isotropic
composition. Preferably 0 to 30%, more preferably 1-20 most
preferably 5-15% fatty acid is present in the inventive isotropic
composition.
Hydrotropes
[0039] Liquid detergent compositions according to the invention may
be substantially free from or may contain low levels of hydrotrope
such as low molecular weight primary or secondary alcohols
exemplified by methanol, ethanol, propanol, and isopropanol are
suitable. Monohydric alcohols are preferred for solubilising
surfactant. The compositions may for example contain from up to
15%, more especially from 0.2% to 8%, typically 0.5% to 8% by
weight of hydrotrope material.
Clarity
[0040] The clarity of the isotropic compositions according to the
present invention does not preclude the isotropic composition being
coloured, e.g. by addition of a dye, provided that it does not
detract substantially from clarity. Moreover, an opacifier could be
included to reduce clarity if required to appeal to the consumer.
In that case the definition of clarity applied to the isotropic
composition according to any aspect of the invention will apply to
the base (equivalent) isotropic composition without the
opacifier.
Other Ingredients
[0041] Compositions according to the present invention preferably
also contain one or more other ingredients such as enzymes, enzyme
stabilisers, bleaches (including bleach systems and components
thereof).
Enzymes
[0042] "Detersive enzyme", as used herein, means any enzyme having
a cleaning, stain removing or otherwise beneficial effect in a
laundry application. Enzymes are included in the present detergent
compositions for a variety of purposes, including removal of
protein-based, saccharide-based, or triglyceride-based stains, for
the prevention of refugee dye transfer, and for fabric restoration.
Suitable enzymes include proteases, amylases, lipases, cellulases,
peroxidases, and mixtures thereof of any suitable origin, such as
vegetable, animal, bacterial, fungal and yeast origin. Preferred
selections are influenced by factors such as pH-activity and/or
stability optima, thermostability, and stability to active
detergents, builders and the like. In this respect bacterial or
fungal enzymes are preferred, such as bacterial amylases and
proteases, and fungal cellulases.
[0043] Enzymes are normally incorporated into detergent or
detergent additive compositions at levels sufficient to provide a
"cleaning-effective amount". The term "cleaning effective amount"
refers to any amount capable of producing a cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness
improving effect on substrates such as fabrics. In practical terms
for current commercial preparations, typical amounts are up to
about 5 mg by weight, more typically 0.001 mg to 3 mg, of active
enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.0001% to 10%,
preferably from 0.001% to 5%, more preferably 0.005%-1% by weight
of a commercial enzyme preparation.
Proteolytic Enzymes
[0044] Compositions according to the present invention may comprise
one or more proteolytic enzymes.
[0045] Endopeptidases (proteolytic enzymes or proteases) of various
qualities and origins and having activity in various pH ranges of
from 4-12 are available and can be used in the instant invention.
Examples of suitable proteolytic enzymes are the subtilisins, which
can be obtained from particular strains of B. subtilis, B. lentus,
B. amyloliquefaciens and B. licheniformis, such as the commercially
available subtilisins Savinase.TM., Alcalase.TM., Relase.TM.,
Kannase.TM. and Everlase.TM. as supplied by Novo Industri A/S,
Copenhagen, Denmark or Purafec.TM., PurafectOxP.TM. and
Properase.TM. as supplied by Genencor International. Chemically or
genetically modified variants of these enzymes are included such as
described in WO-A-99/02632 pages 12 to 16 and in WO-A-99/20727 and
also variants with reduced allergenicity as described in
WO-A-99/00489 and WO-A-99/49056.
[0046] It should be understood that the protease is present in the
liquid detergent composition in a dissolved or dispersed form,
i.e., the protease is not encapsulated to prevent the protease from
the liquid composition. Instead the protease in more or less in
direct contact with the liquid composition.
[0047] Suitable examples of proteases are the subtilisins which are
obtained from particular strains of B. subtilis and B.
licheniformis. One suitable protease is obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12,
developed and sold as ESPERASE.TM. by Novo Industries A/S of
Denmark, hereinafter "Novo". The preparation of this enzyme and
analogous enzymes is described in GB 1,243,784 to Novo. Other
suitable proteases include ALCALASE.TM. and SAVINASE.TM. from Novo
and MAXATASE.TM. from International Bio-Synthetics, Inc., The
Netherlands; as well as Protease A as disclosed in EP 130,756 A,
and Protease B as disclosed in EP 303,761 A and EP 130,756 A. See
also a high pH protease from Bacillus sp. NCIMB 40338 described in
WO 9318140 A to Novo. Enzymatic detergents comprising protease, one
or more other enzymes, and a reversible protease inhibitor are
described in WO 9203529 A. Other preferred proteases include those
of WO 9510591 A. When desired, a protease having decreased
adsorption and increased hydrolysis is available as described in WO
9507791. A recombinant trypsin-like protease for detergents
suitable herein is described in WO 9425583.
[0048] Useful proteases are also described in PCT publications: WO
95/30010, WO 95/30011, WO 95/29979.
[0049] Preferred proteolytic enzymes are also modified bacterial
serine proteases, such as those described in EP-A-251446
(particularly pages 17, 24 and 98), and which is called herein
"Protease B", and in EP-A-199404, which refers to a modified
bacterial serine proteolytic enzyme which is called "Protease A"
herein, Protease A as disclosed in EP-A-130756.
[0050] The preferred liquid laundry detergent compositions
according to the present invention comprise at least 0.001% by
weight, of a protease enzyme. However, an effective amount of
protease enzyme is sufficient for use in the liquid laundry
detergent compositions described herein. The term "an effective
amount" refers to any amount capable of producing a cleaning, stain
removal, soil removal, whitening, deodorizing, or freshness
improving effect on substrates such as fabrics. In practical terms
for current commercial preparations, typical amounts are up to
about 5 mg by weight, more typically 0.001 mg to 3 mg, of active
enzyme per gram of the detergent composition. Stated otherwise, the
compositions herein will typically comprise from 0.001% to 5%,
preferably 0.01%-1% by weight of a commercial enzyme preparation.
Typically, the proteolytic enzyme content is up to 0.2%, preferably
from 4.times.10.sup.-5% to 0.06% by weight of the composition of
pure enzyme.
Other Enzymes
[0051] Optionally the compositions of the invention may
additionally or alternatively contain one or more other enzymes.
For example, they may contain 10-20,000 LU per gram of the
detergent composition of a lipolytic enzyme selected from the group
consisting of Lipolase, Lipolase ultra, LipoPrime, Lipomax,
Liposam, and lipase from Rhizomucor miehei (e.g. as described in
EP-A-238 023 (Novo Nordisk).
[0052] The enzymatic detergent compositions of the invention
further comprise 10-20,000 LU per gram, and preferably 50-2,000 LU
per gram of the detergent composition, of an lipolytic enzyme. In
this specification LU or lipase units are defined as they are in
EP-A-258 068 (Novo Nordisk).
[0053] A further method of assessing the enzymatic activity is by
measuring the reflectance at 460 nm according to standard
techniques.
[0054] Suitable other enzymes for use in the compositions of the
invention can be found in the enzyme classes of the esterases and
lipases, (EC 3.1.1.*, wherein the asterisk denotes any number).
[0055] A characteristic feature of lipases is that they exhibit
interfacial activation. This means that the enzyme activity is much
higher on a substrate which has formed interfaces or micelles, than
on fully dissolved substrate. Interface activation is reflected in
a sudden increase in lipolytic activity when the substrate
concentration is raised above the critical micel concentration
(CMC) of the substrate, and interfaces are formed. Experimentally
this phenomenon can be observed as a discontinuity in the graph of
enzyme activity versus substrate concentration. Contrary to
lipases, however, cutinases do not exhibit any substantial
interfacial activation.
[0056] Suitable lipase enzymes for detergent usage include those
produced by microorganisms of the Pseudomonas group, such as
Pseudomonas stutzeri ATCC 19.154, as disclosed in GB 1,372,034. See
also lipases in Japanese Patent Application 53,20487. This lipase
is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," or "Amano-P." Other suitable
commercial lipases include Amano-CES, lipases ex Chromobacter
viscosum, e.g. Chromobacter viscosum var. lipolyticum NRRLB 3673
from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases
from U.S. Biochemical Corp., U.S.A. and Disoynth Co., The
Netherlands, and lipases ex Pseudomonas gladioli. LIPOLASE.TM.
enzyme derived from Humicola lanygiriosa and commercially available
from Novo, see also EP 341,947, is a preferred lipase for use
herein. Lipase and amylase variants stabilized against peroxidase
enzymes are described in WO 9414951 A to Novo. See also WO 9205249.
Cutinase enzymes suitable for use herein are described in WO
8809367 A to Genencor.
[0057] Because of this characteristic feature, i.e. the absence of
interfacial activation, we define for the purpose of this patent
application Cutinases as lipolytic enzymes which exhibit
substantially no interfacial activation. Cutinases therefor differ
from classical lipases in that they do not possess a helical lid
covering the catalytic binding site. Cutinases belong to a
different subclass of enzymes (EC 3.1.1.50) and are regarded to be
outside the scope of the present invention.
[0058] Of main interest for the present invention are fungal
lipases, such as those from Humicola lanuginosa and Rhizomucor
miehei. Particularly suitable for the present invention is the
lipase from Humicola lanuginosa strain DSM 4109, which is described
in EP-A-305 216 (Novo Nordisk), and which is commercially available
as Lipolase.TM.. Also suitable ar variants of this enzyme, such as
described in WO-A-92/05249, WO-A-94/25577, WO-A-95/22615,
WO-A-97/04079, WO-A-97/07202, WO-A-99/42566, WO-A-00/60063.
Especially preferred is the variant D96L which is commercially
available from Novozymes as Lipolase ultra, and the variant which
is sold by Novozymes under the trade name LipoPrime.
[0059] The lipolytic enzyme of the present invention can usefully
be added to the detergent composition in any suitable form, i.e.
the form of a granular composition, a slurry of the enzyme, or with
carrier material (e.g. as in EP-A-258 068 and the Savinase.TM. and
Lipolase.TM. products of Novozymes). A good way of adding the
enzyme to a liquid detergent product is in the form of a slurry
containing 0.5 to 50% by weight of the enzyme in a ethoxylated
alcohol nonionic surfactant, such as described in EP-A-450 702
(Unilever).
[0060] The enzyme to be used in the detergent compositions
according to the invention can be produced by cloning the gene for
the enzyme into a suitable production organism, such as Bacilli, or
Pseudomonaceae, yeasts, such as Saccharomyces, Kluyveromyces,
Hansenula or Pichia, or fungi like Aspergillus. The preferred
production organism is Aspergillus with especial preference for
Aspergillus oryzae.
[0061] Other optional suitable enzymes which may be included alone
or in combination with any other enzyme may, for example, be
oxidoreductases, transferases, hydrolases, lyases, isomerases and
ligases. Suitable members of these enzyme classes are described in
Enzyme nomenclature 1992: recommendations of the Nomenclature
Committee of the International Union of Biochemistry and Molecular
Biology on the nomenclature and classification of enzymes, 1992,
ISBN 0-12-227165-3, Academic Press. The most recent information on
the nomenclature of enzymes is available on the Internet through
the ExPASy WWW server (http://www.expasy.ch/).
[0062] Examples of the hydrolases are carboxylic ester hydrolase,
thiolester hydrolase, phosphoric monoester hydrolase, and
phosphoric diester hydrolase which act on the ester bond;
glycosidase which acts on O-glycosyl compounds; glycosylase
hydrolysing N-glycosyl compounds; thioether hydrolase which acts on
the ether bond; and exopeptidases and endopeptidases which act on
the peptide bond. Preferable among them are carboxylic ester
hydrolase, glycosidase and exo- and endopeptidases. Specific
examples of suitable hydrolases include (1) exopeptidases such as
aminopeptidase and carboxypeptidase A and B and endopeptidases such
as pepsin, pepsin B, chymosin, trypsin, chymotrypsin, elastase,
enteropeptidase, cathepsin B, papain, chymopapain, ficain,
thrombin, plasmin, renin, subtilisin, aspergillopepsin,
collagenase, clostripain, kallikrein, gastricsin, cathepsin D,
bromelain, chymotrypsin C, urokinase, cucumisin, oryzin, proteinase
K, thermomycolin, thermitase, lactocepin, thermolysin,
bacillolysin. Preferred among them is subtilisin;
[0063] (2) glycosidases such as .alpha.-amylase, .beta.-amylase,
glucoamylase, isoamylase, cellulase, endo-1,3(4)-.beta.-glucanase
(.beta.-glucanase), xylanase, dextranase, polygalacturonase
(pectinase), lysozyme, invertase, hyaluronidase, pullulanase,
neopullulanase, chitinase, arabinosidase, exocellobiohydrolase,
hexosaminidase, mycodextranase, endo-1,4-.beta.-mannanase
(hemicellulase), xyloglucanase, endo-.beta.-galactosidase
(keratanase), mannanase and other saccharide gum degrading enzymes
as described in WO-A-99/09127. Preferred among them are
.alpha.-amylase and cellulase; (3) carboxylic ester hydrolase
including carboxylesterase, lipase, phospholipase, pectinesterase,
cholesterol esterase, chlorophyllase, tannase and wax-ester
hydrolase.
[0064] Examples of transferases and ligases are glutathione
S-transferase and acid-thiol ligase as described in WO-A-98/59028
and xyloglycan endotransglycosylase as described in
WO-A-98/38288.
[0065] Examples of lyases are hyaluronate lyase, pectate lyase,
chondroitinase, pectin lyase, alginase II. Especially preferred is
pectolyase, which is a mixture of pectinase and pectin lyase.
[0066] Examples of the oxidoreductases are oxidases such as glucose
oxidase, methanol oxidase, bilirubin oxidase, catechol oxidase,
laccase, peroxidases such as ligninase and those described in
WO-A-97/31090, monooxygenase, dioxygenase such as lipoxygenase and
other oxygenases as described in WO-A-99/02632, WO-A-99/02638,
WO-A-99/02639 and the cytochrome based enzymatic bleaching systems
described in WO-A-99/02641.
[0067] Peroxidase enzymes may be used in combination with oxygen
sources, e.g., percarbonate, perborate, hydrogen peroxide, etc.,
for "solution bleaching" or prevention of transfer of dyes or
pigments removed from substrates during the wash to other
substrates present in the wash solution. Known peroxidases include
horseradish peroxidase, ligninase, and haloperoxidases such as
chloro- or bromo-peroxidase.
[0068] Peroxidase-containing detergent compositions are disclosed
in WO 89099813 A, Oct. 19, 1989 to Novo and WO 8909813 A to
Novo.
[0069] A range of enzyme materials and means for their
incorporation into synthetic detergent compositions is also
disclosed in WO 9307263 A and WO 9307260 A to Genencor
International, WO 8908694 A to Novo, and U.S. Pat. No. 3,553,139,
Jan. 5, 1971 to McCarty et al.
[0070] A process for enhancing the efficacy of the bleaching action
of oxidoreductases is by targeting them to stains by using
antibodies or antibody fragments as described in WO-A-98/56885.
Antibodies can also be added to control enzyme activity as
described in WO-A-98/06812.
[0071] A preferred combination is a detergent composition
comprising of a mixture of the protease of the invention and
conventional detergent enzymes such as lipose, amylase and/or
cellulase together with one or more plant cell wall degrading
enzymes.
[0072] Suitable amylases include those of bacterial or fungal
origin. Chemically or genetically modified variants of these
enzymes are included as described in WO-A-99/02632 pages 18,19.
Commercial cellulase are sold under the tradename Purastar.TM.,
Purastar OxAm.TM. (formerly Purafact Ox Am.TM.) by Genencor;
Termamyl.TM., Fungamyl.TM., Duramyl.TM., Natalase.TM., all
available from Novozymes.
[0073] Amylases suitable herein include, for example, alfa-amylases
sescribed in GB 1,296,839 to Novo; RAPIDASE.TM., International
Bio-Synthetics, Inc. and TERMAMYL.TM., Novo. FUNGAMYL.TM. from Novo
is especially useful.
[0074] See, for example, references disclosed in WO 9402597.
Stability-enhanced amylases can be obtained from Novo or from
Genencor International. One class of highly preferred amylases
herein have the commonality of being derived using site-directed
mutagenesis from one or more of the Baccillus amylases, especialy
the Bacillus cc-amylases, regardless of whether one, two or
multiple amylase strains are the immediate precursors.
[0075] Oxidative stability-enhanced amylases vs. the
above-identified reference amylase are preferred for use,
especially in bleaching, more preferably oxygen bleaching, as
distinct from chlorine bleaching, detergent compositions herein.
Such preferred amylases include (a) an amylase according to WO
9402597, known as TERMAMYL.TM.,
[0076] Particularly preferred amylases herein include amylase
variants having additional modification in the immediate parent as
described in WO 9510603 A and are available from the assignee,
Novo, as DURAMYL.TM.. Other particularly preferred oxidative
stability enhanced amylase include those described in WO 9418314 to
Genencor International and WO 9402597 to Novo Or WO 9509909 A to
Novo.
[0077] Suitable cellulases include those of bacterial or fungal
origin. Chemically or genetically modified variants of these
enzymes are included as described in WO-A-99/02632 page 17.
Particularly useful cellulases are the endoglucanases such as the
EGIII from Trichoderma longibrachiatum as described in
WO-A-94/21801 and the E5 from Thermomonospora fusca as described in
WO-A-97/20025. Endoglucanases may consist of a catalytic domain and
a cellulose binding domain or a catalytic domain only. Preferred
cellulolytic enzymes are sold under the tradename Carezyme.TM.,
Celluzyme.TM. and Endolase.TM. by Novo Nordisk A/S; Puradax.TM. is
sold by Genencor and KAC.TM. is sold by Kao corporation, Japan.
[0078] Cellulases usable herein include both bacterial and fungal
types, preferably having a pH optimum between 5 and 9.5. U.S. Pat.
No. 4,435,307 discloses suitable fungal cellulases from Humicola
insolens or Humicola strain DSM1800 or a cellulase 212-producing
fungus belonging to the genus Aeromonas, and cellulase extracted
from the hepatopancreas of a marine mollusk, Dolabella Auricula
Solander. Suitable cellulases are also disclosed in GB-A-2.075.028;
GB-A-2.095.275 and DE-OS-2.247.832. CAREZYME.TM. (Novo) is
especially useful. See also WO 9117243.
[0079] Detergent enzymes are usually incorporated in an amount of
0.00001% to 2%, and more preferably 0.001% to 0.5%, and even more
preferably 0.005% to 0.2% in terms of pure enzyme protein by weight
of the composition. Detergent enzymes are commonly employed in the
form of granules made of crude enzyme alone or in combination with
other components in the detergent composition. Granules of crude
enzyme are used in such an amount that the pure enzyme is 0.001 to
50 weight percent in the granules. The granules are used in an
amount of 0.002 to 20 and preferably 0.1 to 3 weight percent.
Granular forms of detergent enzymes are known as Enzoguard.TM.
granules, prills, marumes or T-granules. Granules can be formulated
so as to contain an enzyme protecting agent (e.g. oxidation
scavengers) and/or a dissolution retardant material. Other suitable
forms of enzymes are liquid forms such as the "L" type liquids from
Novo Nordisk, slurries of enzymes in nonionic surfactants such as
the "SL" type sold by Novo Nordisk and microencapsulated enzymes
marketed by Novo Nordisk under the tradename "LDP" and "CC".
[0080] The enzymes can be added as separate single ingredients
(prills, granulates, stabilised liquids, etc. containing one
enzyme) or as mixtures of two or more enzymes (e.g. cogranulates).
Enzymes in liquid detergents can be stabilised by various
techniques as for example disclosed in U.S. Pat. No. 4,261,868 and
U.S. Pat. No. 4,318,818.
[0081] The detergent compositions of the present invention may
additionally comprise one or more biologically active peptides such
as swollenin proteins, expansins, bacteriocins and peptides capable
of binding to stains.
Enzyme Stabilisers
[0082] Compositions according to the present invention which
contain one or more enzymes also preferably contain at least one
enzyme stabiliser. Such enzyme stabilisers may be selected from
boron-containing protease enzyme stabilisers, non-boron protease
enzyme stabilisers and mixtures thereof.
Boron-Containing Enzyme Stabilisers
[0083] Typical boron-based stabilisers include boron-based
reversible stabilisers which comprise a boron compound and another
substance capable of complexing with the boron compound to
stabilise the enzyme in the composition but which complexes
dissociate in the wash liquor to render the enzyme active.
[0084] Suitable boron compounds include sodium metaborate or sodium
tetraborate (borax).
[0085] Typical substances which form a reversible complex with the
boron compound including polyols such as glycerol, propylene
glycol, and sorbitol. However, these are not enzyme stabilisers in
the absence of the boron compound.
[0086] Typical inorganic boron sources are derivatives of boric
acid including boric oxide, polyborates, orthoborates and
metaborates or mixtures thereof. Preferred compounds are the alkali
salts of the boric acid derivatives, such as sodium borate and
borax. Typical organic boron stabilisers are aromatic borate esters
and boronic acid derivatives, such as alkyl, aryl and peptide
boronic acids. Boronic acids are well-known as reversible
inhibitors for subtilisine type of proteases.
[0087] Another boron-based stabilising system which may be used is
the combination of boric acid or a boron compound capable of
forming boric acid in the composition and a source of calcium ions,
such as disclosed in EP-A-0 199 405.
Non-Boron Enzyme Stabilisers
[0088] Non-boron enzyme stabilisers include water soluble calcium
compounds such as calcium chloride and/or formate and water soluble
short chain carboxylic acids, as well as sources of chlorine
scavenge ions such as ammonium sulphates, bisulphites,
thiosulphites, thiosulphate and thiols.
[0089] Mixtures of one or more boron- and or non-boron enzyme
stabilisers may also be based.
[0090] The total amount of enzyme stabiliser or stabiliser system
is typically from 0.001% to 10%, preferably from 0.005% to 7.5%,
especially from 0.01% to 5% by weight of the total composition.
Many non-boron stabilisers are protein inhibitors from various
sources and modified peptides (such as peptide aldehydes and
peptide trifluoromethyl ketones). Suitable examples of these and
other non-boron stabilisers include the following:--
[0091] WO-A-00/01826 discloses stabilized variants of Streptomycin
subtilisin inhibitor (protein inhibitor+variants).
[0092] WO-A-98/13459 discloses liquid detergents containing
proteolytic enzyme, peptide aldehydes and calcium ions.
[0093] EP-A-0 583 534 discloses liquid detergents containing a
peptide aldehyde.
[0094] EP-A-0 583 535 describes liquid detergents containing a
peptide trifluoromethylketone.
[0095] WO-A-97/00392 describes enzymatic compositions with improved
storage stability of the enzymes contained therein are obtained by
including an enzyme stabiliser, preferably by way of a particular
process concerns the use of lignosulphonates.
[0096] WO-A-00/01831 describes a fusion between a subtilisin and
streptomyces inhibiors variants).
[0097] Another suitable class of non-boron enzyme stabiliser
comprises the reversible protease inhibitors of peptide or protein
type, e.g. as disclosed in WO92/03529.
[0098] Further, our unpublished European Patent Application No.
00202092.3 discloses other suitable non-boron enzyme stabilisers
comprising at least one saccharide selected from disaccharides,
trisaccharides and derivatives of either as well as mixtures of
these disaccharides, trisaccharides and derivatives.
[0099] Yet others are disclosed in WO-A-98/13458, WO-A-98/13460,
WO-A-98/13461, U.S. Pat. No. 5,178,789, WO92/03529, WO-A-93/20175
and U.S. Pat. No. 5,156,773.
[0100] Further non-boron compounds which may be incorporated as
compounds which are capable of stabilising proteases in liquids are
organic substances which form complexes with a transition metal,
the complex being capable of catalysing bleaching of a substrate by
atmospheric oxygen. Such compounds may be used as the free ligand
and/or in complex with a transition metal, e.g. as disclosed in
WO-A-00/12677. One specific ligand of this kind is
N,N-bis(pyridin-2-yl-methyl)-1,1-bis(pyridin-2-yl)-1-aminoethane.
Yet other suitable non-boron protease stabilisers are
polyoxometalates such as disclosed in CA-A-2 183 814, EP-A-1 141
210 and WO-A-98/20101.
Bleaches
[0101] Optionally, any composition according to the invention may
contain a bleach or bleach system. Preferred are catalysts for
bleaching by atmospheric oxygen.
[0102] Alternatively, oxygen bleaches and oxygen bleach systems may
be employed, for example in the form of an inorganic persalt
preferably with an activator, or as a peroxy acid compound.
[0103] In the case of the inorganic persalt bleaches, the activator
makes the bleaching more effective at lower temperatures, i.e. in
the range from ambient temperature to about 60.degree. C., so that
such bleach systems are commonly known as low-temperature bleach
systems and are well known in the art. The inorganic persalt such
as sodium perborate, both the monohydrate and the tetrahydrate,
acts as release active oxygen n solution, and activator is usually
an organic compound havine one or more reactive acyl residues,
which cause the formation of peracids, the latter providing for
more effective bleaching action at lower temperatures than the
peroxy-bleach compound alone. The ratio by weight of the peroxy
bleach compound to the activator is from about 15:1 to about 2:1,
preferably from about 10:1 to about 3.5:1. Whilst the amount of the
bleach system, i.e. peroxy bleach compounds and activator may be
varied between about 5% and about 35% by weight of the total
liquid, it is preferred to use from about 6% to about 30% of the
ingredients forming the bleach system. Thus, the preferred level of
the peroxy bleach compound in the composition is between 5.5% and
about 27% by weight, while the preferred level of the activator is
between about 0.5% and about 40%, most preferably between about 1%
and about 5% by weight.
[0104] Typical examples of the suitable peroxybleach compounds are
alkalimetal perborates, both tetrahdyrates and monohydrates, alkali
metal, percarbonates, alkylhydroperoxides such as cumene
hydroperoxide and t-butyl hydroperoxide, persilicates and
perphosphates, of which sodium perborate is preferred. Activators
for peroxybleach compounds have been amply described in the
literature, including in British patent specifications 836988,
855735, 907356, 907358, 907950, 1003310 and 1246339, U.S. Pat. Nos.
3,332,882 and 4,128,494, Canadian patent specification 844481 and
South African patent specification 68/6344.
[0105] The exact mode of action of such activators is not known,
but it is believed that peracids are formed by reaction of the
activators with the inorganic peroxy compound, which peracids then
liberate active-oxygen by decomposition.
[0106] They are generally compounds which contain N-acyl or O-acyl
residues in the molecule and which exert their activating action on
the peroxy compounds on contact with these in the washing
liquor.
[0107] Typical examples of activators within these groups are
polyacylated alkylene diamines, such
N,N,N.sup.1N,.sup.1-tetraacetylethylene diamine (TAED) and
N,N,N.sup.1,N.sup.1-tetraacetylmethylene diamine (TAMD); acylated
glycolurils, such as tetraacetylgylcoluril (TAGU);
triacetylcyanurate and sodium sulphophenyl ethyl carbonic acid
ester.
[0108] A particularly preferred activator is
N,N,N.sup.1,N.sup.1-tetraacetylethylene diamine (TAED). The
activator may be incorporated as fine particles or even in granular
form, such as described in the applicants' UK patent specification
GB 2 053 998 A. Specifically, it is preferred to have an activator
of an average particle size of less than 150 micrometers, which
gives significant improvement in bleach efficiency. The
sedimentation losses, when using an activator with an average
particle size of less than 150 .mu.m, are substantially decreased.
Even better bleach performance is obtained if the average particle
size of the activator is less than 100 .mu.m. However, too small a
particle size can give increased decomposition and handling
problems prior to processing. However, these particle sizes have to
be reconciled with the requirements for dispersion in the solvent
(it will be recalled that the aforementioned first product from
requires particles which are as small as possible within practical
limits). Liquid activators may also be used, e.g. as hereinafter
described.
[0109] The organic peroxyacid compound bleaches (which in some
cases can also act as structurants/deflocculants) are preferably
those which are solid at room temperature and most preferably
should have a melting point of at least 50.degree. C. Most
commonly, they are the organic peroxyacids and water-soluble salts
thereof having the general formula
##STR00002##
wherein R is an alkylene or substituted alkylene group containing 1
to 20 carbon atoms or an arylene group containing from 6 to 8
carbon atoms, and Y is hydrogen halogen, alkyl, aryl or any group
which provides an anionic moiety in aqueous solution. Such Y groups
can include, for example:
##STR00003##
wherein M is H or a water-soluble, salt-forming cation.
[0110] The organic peroxyacids and salts thereof usable in the
present invention can contain either one, two or more peroxy groups
and can be either aliphatic or aromatic. When the organic
peroxyacid is aliphitic, the unsubstituted acid may have the
general formula:
##STR00004##
wherein Y can be H, --CH.sub.3, --CH.sub.2Cl,
##STR00005##
[0111] And n can be an integer from 60 to 20. Peroxydodecanoic
acids, peroxytetradecanoic acids and peroxyhexadecanoic acids are
the most preferred compounds of this type, particularly
1,12-diperoxydodecandioic acid (sometimes known as DPDA),
1,14-diperoxytetradecandioic acid and 1,16diperoxyhexadecandioic
acid. Examples of other preferred compounds of this type are
diperoxyazelaic acid, diperoxyadipic and diperoxysebacic acid.
[0112] When the organic peroxyacid is aromatic, a unsubstituted
acid may have the general formula:
##STR00006##
wherein Y is, for example hydrogen, halogen, alkyl or a group as
defined for formulae (IV) above.
[0113] The percarboxy and Y groupings can be in any relative
position around the aromatic ring. The ring and/or Y group (if
alkyl) can contain any non-interfering substitutents such as
halogen or sulphonate groups. Examples of suitable aromatic
peroxyacids and saltes thereof include monoperoxyphthalic acid,
diperoxyterephthalic acid, 4-chlorodiperoxy-phthalic acid,
diperoxyisophthalic acid, peroxy benzoic acids and ring-substituted
peroxy benzoic acids, such as peroxy-alpha-naphthoic acid. A
preferred aromatic peroxyacid is diperoxyisophthalic acid.
[0114] Another preferred class of peroxygen compounds which can be
incorporated to enhance dispensing/dispersibility in water are the
anyhdrous perborates described for that purpose in the applicants'
European patent specification EP-A-217 454. Alternatively or in
addition to, a transition metal catalyst may used with the peroxyl
species, see, for example WO-A-02/48301. A transition metal
catalyst may also be used in the absence of peroxyl species where
the bleaching is termed to be via atmospheric oxygen, see, for
example WO-A-00/52124 and WO-A-02/48301. The transition metal
catalysts disclosed in WO-A-00/52124 and WO-A-02/48301 are
generally both applicable to what is known in the art as "air mode"
and "peroxyl mode" bleaching. Another example of a suitable class
of transition metal catalysts is found in WO-A-02/48301 and
references found therein.
[0115] It is also preferred to include in the compositions, a
stabiliser for the bleach or bleach system, for example ethylene
diamine tetramethylene pholphonate and diethylene triamine
pentamethylene phosphonate or other appropriate organic phosphonate
or salt thereof, such as the Dequest range hereinbefore described.
These stabilisers can be used in acid or salt form which as the
calcium, magnesium, zinc or aluminium salt form. The stabiliser may
be present at a level of up to about 1% by weight, preferably
between about 0.1% and about 0.5% by weight.
[0116] Since many bleaches and bleach systems are unstable in
aqueous liquid detergents and/or other interact unfavourably will
other components in the composition, e.g. enzymes, they may for
example be protected, e.g. by encapsulation or by formulating a
structured liquid composition, whereby they are suspended in solid
form.
Other Optional Ingredients
[0117] The compositions herein can further comprise a variety of
optional ingredients. A wide variety of other ingredients useful in
detergent compositions can be included in the compositions herein,
including other active ingredients, carriers, hydrotropes,
processing aids, dyes or pigments, solvents for liquid
formulations, solid fillers for bar compositions, etc. If high
sudsing is desired, suds boosters such as the C10-C16 alkanolamides
can be incorporated into the compositions, typically at 1%-10%
levels. The C10-C14 monoethanol and diethanol amides illustrate a
typical class of such suds boosters. Use of such suds boosters with
high sudsing; adjunct surfactants such as the amine oxides,
betaines and sultaines noted above is also advantageous. If
desired, soluble magnesium salts such as MgCl.sub.2, MgSO.sub.4,
and the like, can be added at levels of, typically, 0.1%-2%, to
provide additional suds and to enhance grease removal
performance.
[0118] Various detersive ingredients employed in the present
compositions optionally can be further stabilized by absorbing said
ingredients onto a porous hydrophobic substrate, then coating said
substrate with a hydrophobic coating. Preferably, the detersive
ingredient is admixed with a surfactant before being absorbed into
the porous substrate. In use, the detersive ingredient is released
from the substrate into the aqueous washing liquor, where it
performs its intended detersive function.
[0119] By this means, ingredients such as the aforementioned,
bleaches, bleach activators, bleach catalysts, photoactivators,
dyes, fluorescers, fabric conditioners and hydrolyzable surfactants
can be "protected" for use in detergents, including liquid laundry
detergent compositions.
[0120] Liquid detergent compositions can contain water and other
solvents as carriers.
Chelating Agents
[0121] The detergent compositions herein may also optionally
contain one or more iron, copper and/or manganese chelating agents.
Such chelating agents can be selected from the group consisting of
amino carboxylates, amino phosphonates,
polyfanctionally-substituted aromatic chelating agents and mixtures
therein, all as hereinafter defined.
[0122] If utilized, these chelating agents will generally comprise
from about 0.1% to about 10% by weight of the detergent
compositions herein. More preferably, if utilized, the chelating
agents will comprise from about 0.1% to about 3.0% by eight of such
compositions.
Clay Soil Removal/Anti-Redeposition Agents
[0123] The compositions of the present invention can also
optionally contain water-soluble ethoxylated amines having clay
soil removal and antiredeposition properties.
[0124] Liquid detergent compositions typically contain about 0.0 1%
to about 5% of these agents.
[0125] One preferred soil release and anti-redeposition agent is
ethoxylated tetraethylenepentamine. Exemplary ethoxylated amines
are further described in U.S. Pat. No. 4,597,898,
[0126] Another type of preferred antiredeposition agent includes
the carboxy methyl cellulose (CMC) materials. These materials are
well known in the art.
Brightener
[0127] Any optical brighteners or other brightening or whitening
agents known in the art can be incorporated at levels typically
from about 0.05% to about 1.2%, by weight, into the detergent
compositions herein. Commercial optical brighteners which may be
useful in the present invention can be classified into subgroups,
which include, but are not necessarily limited to, derivatives of
stilbene, pyrazoline, cournarin, carboxylic acid, methinecyanines,
dibenzothiphene-5,5-dioxide, azoles, 5- and 6-membered-ring
heterocycles, and other miscellaneous agents. Examples of such
brighteners are disclosed in "The Production and Application of
Fluorescent Brightening Agents", M. Zahradnik, Published by John
Wiley & Sons, New York (1982).
Suds Suppressors
[0128] Compounds for reducing or suppressing the formation of suds
can be incorporated into the compositions of the present invention.
Suds suppression can be of particular importance in the so-called
"high concentration cleaning process" as described in U.S. Pat.
Nos. 4,489,455 and 4,489,574 and infront-loading European-style
washing machines.
[0129] A wide variety of materials may be used as suds suppressors,
and suds suppressors are well known to those skilled in the art.
See, for example, Kirk Othmer Encyclopedia of Chemical Technology,
Third Edition, Volume 7, pages 430-447 (John Wiley & Sons,
Inc., 1979). One category of suds suppressor of particular interest
encompasses monocarboxylic fatty acid and soluble salts therein.
See U.S. Pat. No. 2,954,347. The monocarboxylic fatty acids and
salts thereof used as suds suppressor typically have hydrocarbyl
chains of 10 to about 24 carbon atoms, preferably 12 to 18 carbon
atoms. Suitable salts include the alkali metal salts such as
sodium, potassium, and lithium salts, and ammonium and
alkanolammonium salts.
[0130] The detergent compositions herein may also contain
non-surfactant suds suppressors. These include, for example: high
molecular weight hydrocarbons such as paraffin, fatty acid esters
(e.g., fatty acid triglycerides), fatty acid esters of monovalent
alcohols, aliphatic C 1 8-C40 ketones (e.g., stearone), etc.
[0131] The preferred category of non-surfactant suds suppressors
comprises silicone suds suppressors. This category includes the use
of polyorganosiloxane oils, suchas polydimethylsiloxane,
dispersions or emulsions of polyorganosiloxane oils or resins, and
combinations of polyorganosiloxane with silica particles wherein
the polyorganosiloxane is chemisorbed or fused onto the silica.
Silicone suds suppressors are well known in the art and are, for
example, disclosed in U.S. Pat. No. 4,265,779.
[0132] For any detergent compositions to be used in automatic
laundry washing machines, suds should not form to the extent that
they overflow the washing machine.
[0133] Suds suppressors, when utilized, are preferably present in a
"suds suppressing amount".
[0134] By "suds suppressing amount" is meant that the formulator of
the composition can select an amount of this suds controlling agent
that will sufficiently control the suds to result in a low-sudsing
laundry detergent for use in automatic laundry washing
machines.
[0135] The compositions herein will generally comprise from 0.1% to
about 5% of suds suppressor.
Fabric Softeners
[0136] Various through-the-wash fabric softeners, especially the
impalpable smectite clays of U.S. Pat. No. 4,062,647 as well as
other softener clays known in the art, can optionally be used
typically at levels of from about 0.5% to about 10% by weight in
the present compositions to provide fabric softener benefits
concurrently with fabric cleaning. Clay softeners can be used in
combination with amine and cationic softeners as disclosed, for
example, in U.S. Pat. No. 4,375,416 and U.S. Pat. No. 4,291,071.
Also useable are the amphiphilic carboxy containing polymers as
disclosed in US-A-2005/0124528.
Dye Transfer Inhibiting Agents
[0137] The compositions of the present invention may also include
one or more materials effective for inhibiting the transfer of dyes
from one fabric to another during the cleaning process. Generally,
such dye transfer inhibiting agents include polyvinyl pyrrolidone
polymers, polyamine N-oxide polymers, copolymers of
N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine,
peroxidases, and mixtures thereof. If used, these agents typically
comprise from about 0.01% to about 10% by weight of the
composition, preferably from about 0.01% to about 5%, and more
preferably from about 0.05% to about 2%.
[0138] The invention will now be further illustrated by way of the
following non-limiting examples:
EXAMPLES
Example I
Method:
[0139] The additives A-D are post-dosed to liquids 1-4 and
incorporated by mixing. All prepared liquids are physical stable
and transparent at room temperature. A panel of experts examines
the physical stability and transparency after 4 weeks of storage at
0 and 5.degree. C. The observations are described in table 1-4 and
the panel used the following terms to describe their
observations.
[0140] Clear/no particles=transparent liquid without white
particles, no difference with liquids stored at room
temperature.
[0141] Clear/small particles=transparent liquid with white
particles formed during storage. Hazy/no particles=during storage
the liquid becomes not transparent but there are no particles
formed.
[0142] Hazy/white particles=during storage the liquid becomes not
transparent and there are white particles formed.
TABLE-US-00001 TABLE I The physical stability of liquid 1 with
different levels additives determined by a panel of experts after 4
weeks of storage at 0 and 5.degree. C. additive (see Physical
stability Physical stability Table 7) level (%) (0.degree. C.)
(5.degree. C.) None 0 hazy, small particles hazy, small particles A
0.5 hazy, small particles clear, small particles A 1 hazy, small
particles clear, small particles A 2 hazy, small particles hazy,
small particles B 0.5 hazy, small particles clear, small particles
B 1 hazy, small particles clear, small particles B 2 hazy, small
particles hazy, small particles C 0.5 clear, small particles clear,
no particles C 1 clear, no particles clear, no particles C 2 clear,
no particles clear, no particles D 0.5 hazy, small particles hazy,
small particles D 1 Hazy, no particles hazy, small particles D 2
Hazy, no particles clear, no particles
TABLE-US-00002 TABLE 2 The physical stability of liquid 2 with
different levels additives determined by a panel of experts after 4
weeks of storage at 0 and 5.degree. C. Physical stability Physical
stability additive level (%) (0.degree. C.) (5.degree. C.) None 0
Hazy, no particles clear, small particles A 0.5 Hazy, no particles
clear, small particles A 1 Hazy, small particles clear, small
particles A 2 Hazy, small particles clear, small particles B 0.5
Hazy, small particles clear, small particles B 1 Hazy, small
particles clear, small particles B 2 Hazy, small particles clear,
small particles C 0.5 clear, no particles clear, no particles C 1
clear, no particles clear, no particles C 2 clear, no particles
clear, no particles D 0.5 Hazy, small particles clear, small
particles D 1 Hazy, small particles clear, small particles D 2
Hazy, small particles clear, small particles
TABLE-US-00003 TABLE 3 The physical stability of liquid 3 with
different levels additives determined by a panel of experts after 4
weeks of storage at 0 and 5.degree. C. Physical stability Physical
stability Additive level (%) (0.degree. C.) (5.degree. C.) None 0
hazy, no particles hazy, small particles A 0.5 Clear, small
particles hazy, no particles A 1 Clear, small particles clear,
small particles A 2 Clear, small particles clear, small particles B
0.5 Clear, small particles clear, small particles B 1 Clear, small
particles clear, small particles B 2 Clear, small particles clear,
small particles C 0.5 Clear, no particles clear, no particles C 1
Clear, no particles clear, no particles C 2 Clear, no particles
clear, no particles D 0.5 Clear, small particles clear, small
particles D 1 Clear, small particles clear, small particles D 2
Clear, small particles hazy, small particles
TABLE-US-00004 TABLE 4 The physical stability of liquid 4 with
different levels additives determined by a panel of experts after 4
weeks of storage at 0 and 5.degree. C. Physical stability Physical
stability Additive level (%) (0.degree. C.) (5.degree. C.) None 0
Hazy, small particles hazy, small particles A 0.5 Hazy, small
particles clear, small particles A 1 Hazy, small particles clear,
small particles A 2 Hazy, small particles hazy, small particles B
0.5 Hazy, small particles hazy, small particles B 1 clear, small
particles hazy, small particles B 2 Hazy, small particles hazy,
small particles C 0.5 clear, no particles clear, no particles C 1
clear, no particles clear, no particles C 2 clear, no particles
clear, no particles D 0.5 Hazy, small particles hazy, small
particles D 1 Hazy, small particles hazy, small particles D 2
clear, small particles clear, small particles
Example 2
Method:
[0143] Additive C is post-dosed to liquid 5 and incorporated by
mixing. All prepared liquids are physical stable and transparent at
room temperature. A panel of experts examines the physical
stability and transparency after 8 weeks of storage at 0 and
5.degree. C.
[0144] The observations are described in table 5 and the panel used
the following terms to describe theft observations.
[0145] Clear/no particles=transparent liquid without white
particles, no difference with liquids stored at room
temperature.
[0146] Clear/small particles=transparent liquid with white
particles formed during storage. Hazy/no particles=during storage
the liquid becomes not transparent but there are no particles
formed.
[0147] Hazy/white particles=during storage the liquid becomes not
transparent and there are white particles formed.
TABLE-US-00005 TABLE 5 The physical stability of liquid 5 w/wo
addition of additive C determined by a panel of experts after 8
weeks of storage at 0 and 5.degree. C. level Physical stability
Physical stability Additive (%) (0.degree. C.) (5.degree. C.) None
0 hazy, small particles hazy, small particles C 1 clear, no
particles clear no particles
TABLE-US-00006 TABLE 6 composition liquids (as 100%) Liquid Liquid
Liquid Liquid 1 (%) 2 (%) 3 (%) 4 (%) Liquid 5 Monopropylene 1 1 1
1 0 glycol NaOH 1.49 1.17 1.64 1.53 1.45 Tinopal CBS-X 0.02 0.02
0.02 0.02 0.02 Citric acid 0.37 0 0.37 0 0.74 Dequest 2066 1 1 1 1
1 Nipacide BIT 20 LC 0.02 0.02 0.02 0.02 0.02 NeodoI25-7 E 7.18
7.17 8.18 8.16 7.66 Prifac 5908 1.70 1.70 1.70 1.70 1.69 LAS acid
7.18 7.18 8.18 8.16 7.66 SLES 3 EO 1.99 1.97 8.18 8.16 0 Relase 16
L ultra 0.38 0.38 0.38 0.38 0.38 Stainzyme 12 L 0.10 0.10 0.10 0.10
0.10 Perfume 0.4 0.4 0.4 0.4 0.4 pH 8.3 8.3 8.3 8.3 8.3 Liquid A
Liquid 6 Liquid B Liquid 7 (%) (%) (%) (%) Monopropylene 2 2 10 10
glycol NaOH 1.37 1.37 3.44 3.44 MEA 2.23 2.23 0 0 TEA 0 0 3.39 3.39
Tinopal CBS-X 0.02 0.02 0.02 0.02 NaCl 0.25 0.25 0 0 Citric acid 0
0 1.31 1.31 Dequest 2066 1 1 0 0 Proxel GXL 0.02 0.02 0 0 NeodoI
25-7 E 4.45 4.45 14 14 Prifac 5908 8.00 8.00 5 5 LAS acid 9.0 9.0
21 21 SLES 2 EO 0 0 7 7 LR400 0.2 0.2 0.25 0.25 PVPK15 0.1 0.1 0 0
Additive C 0 1.0 0 1 Water To 100 To 100 To 100 To 100 pH(.+-.0.1)
8.3 8.3 8.3 8.3 Stability 5.degree. C. over Hazy Clear Hazy Clear 1
week
Materials:
[0148] LAS acid .dbd.C10-C14 alkyl benzene sulphonic acid;
[0149] sLES 3 EO=sodium lauryl ether sulphate (with on average 3
oxide groups);
[0150] sLES 2 EO=sodium lauryl ether sulphate (with on average 2
oxide groups);
[0151] NI 7EO=C12-C13 fatty alcohol ethoxylated with an average of
7 ethylene oxide groups; MPG=monopropylene glycol;
[0152] Prifac 7908=palmkernel fatty acid;
[0153] Proxel GXL=trade name biocide Proxel GXL (20% active)
[0154] Dequest 2066=diethylenetriamino-penta-(methylenenephosphonic
acid) DETPMP
[0155] MEA=monoethanolamine
[0156] TEA=triethanolamine
[0157] Tinopal CBA-X=4,4-bis(2-disulfonic acid styryl) biphenyl PVP
K15=polyvinylpyrrolidone K15
[0158] NaOH=Sodium hydroxide
[0159] NaCl=Sodium chloride
[0160] Nipacide BIT 20 LC=trade name Nipacide BIT 20 LC 20%
active
[0161] Relase 16 L ultra=protease (relase 16 L ultra)
[0162] Stainzyme 12 L=amylase (stainzyme 12 L)
[0163] citric acid
[0164] perfume: commercial detergent perfume
TABLE-US-00007 TABLE 7 tested additives (referring to Formula (I)):
additive R.sup.1 and R.sup.2 M (av.) n (av.) A C.sub.12 alkenyl ca.
8 2 B C.sub.12 alkenyl ca. 12 2 C C.sub.18 alkenyl ca. 12 2 D
C.sub.8 alkenyl ca. 12 2
* * * * *
References