FIELD OF THE INVENTION
[0001] The present invention relates to non-aqueous liquid detergent compositions comprising
a borate-releasing compound and a mannanase enzyme.
BACKGROUND OF THE INVENTION
[0002] Bleaching agents and in particular, perborate and percarbonate bleaching agents are
commonly used by the detergent industry. These peroxygen bleach system are well-known
in the art as detergent additives that provide available oxygen via a hydrogen peroxide
release mechanism.
[0003] Percarbonate is broadly used in detergent products due to its high performance and
its attractive cost. However, it has been surprisingly found that in the specific
context of non-aqueous liquid detergent formulation, percarbonate has a low chemical
stability and high sensitivity to free moisture, compared to perborate. Moreover,
it has been surprisingly found that if bleach activators are encompassed in such compositions,
they are more stable in presence of perborate than in presence of percarbonate.
[0004] However, it has been recognized in the art that the side product formed during the
release of hydrogen peroxide from perborate, i.e. meta borate derivatives, complex
with sugar polymers such as starch and lead to cleaning negative (EP-A-736 085). It
has been surprisingly found that perborate also interacts with food and cosmetics
containing mannose polymers such as guar gum, thereby rendering the food or cosmetic
stains even harder to remove.
[0005] Food and cosmetic stains/soils represent the majority of consumer relevant stains/soils
and often comprise food additives such as thickener / stabiliser agents. Indeed, hydrocolloids
gums and emulsifiers are commonly used food additives. The term "gum" denotes a group
of industrially useful polysaccharides (long chain polymer) or their derivatives that
hydrate in hot or cold water to from viscous solutions, dispersions or gels. Gums
are classified as natural and modified. Natural gums include seaweed extracts, plant
extrudates, gums from seed or root, and gums obtained by microbial fermentation. Modified
(semisynthetic) gums include cellulose and starch derivatives and certain synthetic
gums such as low methoxyl pectin, propylene glycol alginate, and carboxymethyl and
hydropropyl guar gum (Gums in
Encyclopedia Chemical Technology 4
th Ed. Vol. 12, pp842-862, J. Baird, Kelco division of Merck). See also Carbohydrate
Chemistry for Food Scientists (Eagan Press - 1997) by R. L. Whistler and J.N. BeMiller,
Chap 4, pp63-89 and Direct Food Additives in Fruit Processing by P. Laslo, Bioprinciples
and Applications, Vol1, Chapter II, pp313-325 (1996) Technomie publishing. Some of
these gums such as guar gum (E412), locust bean (E410) are widely used alone or in
combinations in many food applications (Gums in
ECT 4
th Ed., Vol. 12 pp842-862, J. Baird, Kelco division of Merck).
[0006] The guar gum used in these food and cosmetic stains is obtained from the seed endosperm
of the leguminous plant
Cyamopsis tetragonoloba. The guar gum (also called guaran) extracted from the dicotyledonous seed is composed
of a 1-4, b-D-mannopyranosyl unit backbone and is used as a thickening agent in dressing
and frozen products and cosmetics (H.-D. Belitz, Food Chemistry pp 243, English version
of the second edition, Springer-verlag, 1987, ISBN 0-387-15043-9 (US)) & (Carbohydrate
Chemistry for Food Scientists, R.L. Wilstler, eagan press, 1997, ISBN 0-913250-92-9)
& (Industrial Gum, second editions, R.L. Whistler pp 308, Academic Press, 1973, ISBN,
0-12-74-6252-x). The locust bean gum (also called carob bean gum or St Jon's bread)
is also used in the food industry and is extracted from the seed of an evergreen cultivated
in the Mediterranean area. The locust bean gum probably differs from the structure
of guar gum only in smaller number of D-galactosyl side chains and have the same 1-4,
b-D-mannopyranosyl backbone. In leguminous seeds, water-soluble galactomanann is the
main storage carbohydrate, comprising up to 20% of the total dry weight in some cases.
Galactomannan has a α-galactose linked to O-6 of mannose residues and it can also
be acetylated to various degree on O-2 and O-3 of the mannose residues.
[0007] It has now been surprisingly found that a borate-releasing compound and a mannanase
are compatible and highly efficient when encompassed in a non-aqueous laundry liquid
detergent, at a very specific ratio. Such non-aqueous laundry liquid detergent with
a balanced system of borate-releasing compound and mannanase, shows excellent chemical
stability upon storage, provides an excellent removal of difficult stains such as
food and cosmetic stains comprising mannans, in particular at low temperatures. These
compositions provide as well effective dingy cleaning and whiteness maintenance.
[0008] It has further been found that the non-aqueous liquid detergent compositions of the
present invention when further comprising a bleach catalyst and/or another detergent
enzyme, provide an even better stain/soil performance and in particular is especially
effective on such food and cosmetic stains/soil as well on colored stains/soils.
[0009] Indeed, colored stains / soils are often difficult to remove effectively from a soiled
item. Highly colored stains and soils i.e. derived from fruit and/or vegetables are
particularly challenging soils to remove. This stains and soils contain color-bodies
based on carotenoids compounds such as α-,β- and γ-carotene and lycopene and xanthophyls,
on porphyrins such as chlorophyll and on flavonoid pigments and dye components. This
latter group of natural flavonoid based dye components comprises the highly coloured
anthocyanins dyes and pigments based on pelargonidin, cyanidin, delphidin and their
methyl esters and the antoxanthins. These compounds are the origin of most of the
orange, red, violet and blue colors occurring in fruits and are abundant in all berries,
cherry, red and black currents, grapefruits, passion fruit, oranges, lemons, apples,
pears, pommegranate, red cabbage, red beets and also flowers. Derivatives of cyanidin
are present in up to 80% of the pigmented leaves, in up to 70% of fruits and in up
to 50% of flowers. Specific examples of such soils would include tea, coffee, spices
such as curry and paprika, orange, tomato, banana, tea, mango, broccoli, carrot, beetroot,
spinach soils and grass.
[0010] Ball pens' ink are also known to be highly difficult coloured stains to be removed.
[0011] Mannanases have been identified in several
Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., vol. 56, No. 11,
pp. 3505-3510 (1990) describes a β-mannanase derived from
Bacillus stearothermophilus in dimer form having a MW of 162 kDa and an optimum pH of 5.5-7.5. Mendoza et al.,
World J. Micobio. Boitech., vol. 10, no. 5, pp. 551-555 (1994) describes a β-mannanase
derived from
Bacillus subtilisis having a MW of 38 kDa, an optimum activity at pH 5.0 / 55°C and a pl of 4.8. J0304706
discloses a β-mannanase derived from
Bacillus sp. having a MW of 37+/- 3kDa measured by gel filtration, an optimum pH of 8-10 and a
pl of 5.3-5.4. J63056289 describes the production of an alkaline, thermostable β-mannase,
which hydrolyses β-1,4-D-mannopyranoside bonds of e.g. mannans and produces manno:oligo:saccharides.
J63036774 relates to a
Bacillus micro-organism FERM P-8856 which produces β-mannanase and β-mannosidase, at an alkaline
pH. A purified mannanase from
Bacillus amyloliquefaciens and its method of preparation useful in the bleaching of pulp and paper, is disclosed
in WO97/11164. WO91/18974 describes an hemicellulase such as a glucanase, xylanase
or mannanase, active at extreme pH and temperature and the production thereof. W094/25576
describes an enzyme exhibiting a mannanase activity derived from
Aspergillus aculeatus CBS 101.43, that might be used for various purposes for which degradation or modification
of plant or algae cell wall material is desired. W093/24622 discloses a mannanase
isolated from
Trichoderma reesie for bleaching lignocellulosic pulps.
[0012] Non-aqueous bleach- and enzyme-containing liquid laundry compositions are well known
in the art such as exemplified by : WO96/10073 which describes non-aqueous liquid
heavy duty liquid detergent composition in the form of a suspension of solids, comprising
nonionic surfactants, anionic surfactants, particles of peroxygen bleach, non-aqueous
low polarity solvent, particles of bleach activator and enzymes prills; EP 365 415
which discloses stable non-aqueous liquid detergent composition comprising suspended
particles on nonionic surfactants, builders, an amphiphilic carboxy-containing polymer,
a bleaching agent and enzymes; DE 37 29 565 which describes a liquid strongly foaming
detergent composition comprising a specific nonionic surfactant, a suspension of insoluble
inorganic builder and other components such as enzymes; DE 37 28 256 which describes
a non-aqueous liquid composition with bleach, comprising a liquid nonionic surfactant,
a agent preventing the gelling and controlling the viscosity, a precursor or an organic
peroxy compound and further optical brightener, enzymes and perfume; and DE 36 26
572 which discloses non-aqueous liquid detergent compositions with at least one nonionic
surfactant, a builder and acid-terminal nonionic surfactant as gelation and/or an
alkylene glycol monoalkyl ether as sedimentation inhibitor and further a bleach system,
an optical brightener, enzymes and a perfume.
[0013] However, none of the above cited prior art recognize the superior cleaning performance
i.e., superior stain removal, especially on mannans-containing cosmetic and food stains,
dingy cleaning and whiteness maintenance, while maintaining excellent chemical stability
upon storage, obtained with the combination of a borate-releasing compound and a mannanase,
at a specific ratio, in a non-aqueous liquid laundry detergent composition.
SUMMARY OF THE INVENTION
[0014] The present invention relates to a non-aqueous liquid detergent composition comprising
a borate-releasing compound and a mannanase enzyme, wherein the weight ratio of borate
(calculated as NaBO
3) to pure mannanase enzyme is comprised between 250:1 and 20,000:1; preferably between
1,000:1 and 10,000:1; more preferably between 2,000:1 and 7,000:1.
[0015] In a preferred embodiment, the present invention provides a non-aqueous liquid detergent
composition comprising a stable suspension of solid, substantially insoluble particulate
material dispersed throughout a non-aqueous, surfactant-containing liquid phase. Such
composition preferably comprises from 49% to 99.95% by weight of the composition of
a surfactant-containing, more preferably structured, non-aqueous liquid phase; a borate-releasing
compound and a mannanase enzyme; wherein the weight ratio of borate to pure mannanase
is comprised between 250:1 and 20,000:1; preferably between 1,000:1 and 10,000:1;
more preferably between 2,000:1 and 7,000:1.
[0016] The borate-releasing compound of the present invention is usually in the particulate
form. The compositions of the present invention preferably comprise from 1% to 50%,
more preferably from 30% to 44% by weight of the composition of insoluble particulate
material, including the borate-releasing compound of the present invention, which
ranges in size from 0.1 to 1500 microns. The particulate material is preferably substantially
insoluble in the liquid phase and other particulate material can be selected from
other bleaching agent, bleach activators, organic detergent builders, inorganic alkalinity
sources, colored speckles and combinations thereof.
[0017] Moreover, the structured, surfactant-containing liquid phase is preferably formed
by combining: i) from 1 % to 80% by weight of said liquid phase of one or more non-aqueous
organic diluents; and ii) from 20% to 99% by weight of said liquid phase of a surfactant
selected from anionic, nonionic and cationic surfactants and combinations thereof.
[0018] Preferably, the non-aqueous liquid detergent compositions of the present invention
will further comprise a bleach catalyst and/or other detergent enzymes.
DETAILED DESCRIPTION OF THE INVENTION
[0019] The present invention relates to a non-aqueous liquid detergent composition comprising
a borate-releasing compound and a mannanase enzyme, wherein the weight ratio of borate
(calculated as NaBO
3) to pure mannanase enzyme is comprised between 250:1 and 20,000:1; preferably between
1,000:1 and 10,000:1; more preferably between 2,000:1 and 7,000:1.
[0020] The detergent compositions of the present invention provide excellent cleaning performance
on food and cosmetic stains/soils whilst maintaining high chemical stability of the
detergent ingredients. These compositions provide as well effective dingy cleaning
and whiteness maintenance. Without wishing to be bound by theory, it is believed that
the gums and high molecule weight polysaccharide materials contained in the stains/soil
form a network of the polymeric filament type. The borate ions cross-link these polymeric
filaments together via the hydroxy groups present within these filaments, resulting
in a highly linked and viscous network. The mannanase enzyme is believed to hydrolyze
this polymeric network, thereby reducing its molecular weight and viscosity and hence
facilitating its removal. The ratio of the borate, coming from the dissolution of
the borate-releasing compound over the mannanase enzyme, is believed to be key as
the cross-linking effect of the borate-releasing compound needs to be properly balanced
with the enzymatic hydrolysis of the mannanase to achieve the optimum cleaning performance.
It has been found that such borate / mannanase ratio within the non-aqueous liquid
detergent compositions of the present invention, maximise the performance of both
ingredients and provide full bleaching performance as well as full enzymatic performance.
[0021] Preferably, the non-aqueous liquid detergent compositions of the present invention
will further comprise other enzymes to boost the cleaning performance of the compositions
of the present invention on food and cosmetic stains/soils. The non-aqueous liquid
detergent compositions of the present invention will preferably further comprise a
bleach catalyst to provide further cleaning performance on hydrophobic bleachable
colored stains/soils.
MANNANASE ENZYME
[0022] The first essential element of the non-aqueous liquid detergent compositions of the
present invention is a mannanase enzyme. Encompassed in the present invention are
the following three mannans-degrading enzymes : EC 3.2.1.25 : β-mannosidase, EC 3.2.1.78
: Endo-1,4-β-mannosidase, referred therein after as "mannanase" and EC 3.2.1.100 :
1,4-β-mannobiosidase (IUPAC Classification- Enzyme nomenclature, 1992 ISBN 0-12-227165-3
Academic Press).
[0023] Preferably, the detergent compositions of the present invention comprise a β-1,4-Mannosidase
(E.C. 3.2.1.78) referred to as "Mannanase". The term "mannanase" or "galactomannanase"
denotes a mannanase enzyme defined according to the art as officially being named
mannan endo-1,4-beta-mannosidase and having the alternative names beta-mannanase and
endo-1,4-mannanase and catalysing the reaction: random hydrolysis of 1,4-beta-D-mannosidic
linkages in mannans, galactomannans, glucomannans, and galactoglucomannans. In particular,
mannanases (EC 3.2.1.78) constitute a group of polysaccharases which degrade mannans
and denote enzymes which are capable of cleaving polyose chains contaning mannose
units, i.e. are capable of cleaving glycosidic bonds in mannans, glucomannans, galactomannans
and galactogluco-mannans. Mannans are polysaccharides having a backbone composed of
β-1,4- linked mannose; glucomannans are polysaccharides having a backbone or more
or less regularly alternating β-1,4 linked mannose and glucose; galactomannans and
galactoglucomannans are mannans and glucomannans with α-1,6 linked galactose sidebranches.
These compounds may be acetylated.
[0024] The degradation of galactomannans and galactoglucomannans is facilitated by full
or partial removal of the galactose sidebranches. Further the degradation of the acetylated
mannans, glucomannans, galactomannans and galactogluco-mannans is facilitated by full
or partial deacetylation. Acetyl groups can be removed by alkali or by mannan acetylesterases.
The oligomers which are released from the mannanases or by a combination of mannanases
and α-galactosidase and/or mannan acetyl esterases can be further degraded to release
free maltose by β-mannosidase and/or β-glucosidase.
[0025] Mannanases have been identified in several
Bacillus organisms. For example, Talbot et al., Appl. Environ. Microbiol., Vol.56, No. 11,
pp. 3505-3510 (1990) describes a beta-mannanase derived from
Bacillus stearothermophilus in dimer form having molecular weight of 162 kDa and an optimum pH of 5.5-7.5. Mendoza
et al., World J. Microbiol. Biotech., Vol. 10, No. 5, pp. 551-555 (1994) describes
a beta-mannanase derived from
Bacillus subtilis having a molecular weight of 38 kDa, an optimum activity at pH 5.0 and 55C and a
pl of 4.8. JP-03047076 discloses a beta-mannanase derived from
Bacillus sp., having a molecular wgt. of 373 kDa measured by gel filtration, an optimum pH
of 8-10 and a pl of 5.3-5.4. JP-63056289 describes the production of an alkaline,
thermostable beta-mannanase which hydrolyses beta-1,4-D-mannopyranoside bonds of e.g.
mannans and produces manno-oligosaccharides. JP-63036774 relates to the
Bacillus microorganism FERM P-8856 which produces beta-mannanase and beta-mannosidase at an
alkaline pH. JP-08051975 discloses alkaline beta-mannanases from alkalophilic
Bacillus sp. AM-001. A purified mannanase from
Bacillus amyloliquefaciens useful in the bleaching of pulp and paper and a method of preparation thereof is
disclosed in WO 97/11164. WO 91/18974 describes a hemicellulase such as a glucanase,
xylanase or mannanase active at an extreme pH and temperature. WO 94/25576 discloses
an enzyme from
Aspergillus aculeatus, CBS 101.43, exhibiting mannanase activity which may be useful for degradation or
modification of plant or algae cell wall material. WO 93/24622 discloses a mannanase
isolated from
Trichoderma reseei useful for bleaching lignocellulosic pulps. An hemicellulase capable of degrading
mannan-containing hemicellulose is described in WO91/18974 and a purified mannanase
from
Bacillus amyloliquefaciens is described in WO97/11164.
[0026] Preferably, the mannanase enzyme will be an alkaline mannanase as defined below,
more preferably, a mannanase originating from a bacterial source. Especially, the
compositions of the present invention will comprise an alkaline mannanase selected
from the mannanase from the strain
Bacillus agaradhaerens NICMB 40482; the mannanase from
Bacillus subtilis strain 168, gene yght; the mannanase from
Bacillus sp. 1633; the mannanase from
Bacillus sp. AAI12 and/or the mannanase from the strain
Bacillus halodurans. Most preferred mannanase for the inclusion in the detergent compositions of the present
invention is the mannanase enzyme originating from
Bacillus sp. 1633 as described in the co-pending Danish application No. PA 1998 01340.
[0027] The terms "alkaline mannanase enzyme" is meant to encompass an enzyme having an enzymatic
activity of at least 10%, preferably at least 25%, more preferably at least 40% of
its maximum activity at a given pH ranging from 7 to 12, preferably 7.5 to 10.5.
[0028] A first more preferred mannanase for use in the present invention is the alkaline
mannanase from
Bacillus agaradhaerens NICMB 40482 which is described in the co-pending U.S. patent application serial No.
09/111,256. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus agaradhaerens, NCIMB 40482; or
ii) a polypeptide comprising an amino acid sequence as shown in positions 32-343 of
SEQ ID NO:2 as shown in U.S. patent application serial No. 09/111,256; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 70% homologous
with said polypeptide, or is derived from said polypeptide by substitution, deletion
or addition of one or several amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
[0029] Also encompassed is the corresponding isolated polypeptide having mannanase activity
selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and
comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 97 to
nucleotide 1029 as shown in U.S. patent application serial No. 09/111,256;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that
is at least 70% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid
residue 32 to amino acid residue 343 as shown in U.S. patent application serial No.
09/111,256;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pSJ1678 comprising the polynucleotide molecule (the DNA sequence) encoding
said mannanase has been transformed into a strain of the
Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International
Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure
at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg
1b, D-38124 Braunschweig, Federal Republic of Germany, on 18 May 1998 under the deposition
number DSM 12180.
[0030] A second more preferred enzyme is the mannanase from the
Bacillus subtilis strain 168, which is described in the co-pending U.S. patent application serial No.
09/095,163. More specifically, this mannanase is:
i) is encoded by the coding part of the DNA sequence shown in SED ID No. 5 shown in
the U.S. patent application serial No. 09/095,163 or an analogue of said sequence;
and/or
ii) a polypeptide comprising an amino acid sequence as shown SEQ ID NO:6 shown in
the U.S. patent application serial No. 09/095,163; or
iii) an analogue of the polypeptide defined in ii) which is at least 70% homologous
with said polypeptide, or is derived from said polypeptide by substitution, deletion
or addition of one or several amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
[0031] Also encompassed in the corresponding isolated polypeptide having mannanase activity
selected from the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and
comprising a sequence of nucleotides as shown in SEQ ID NO:5 as shown in the U.S.
patent application serial No. 09/095,163
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that
is at least 70% identical to the amino acid sequence of SEQ ID NO: 6 as shown in the
U.S. patent application serial No. 09/095,163;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
[0032] A third more preferred mannanase is described in the co-pending Danish patent application
No. PA 1998 01340. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. 1633;
ii) a polypeptide comprising an amino acid sequence as shown in positions 33-340 of
SEQ ID NO:2 as shown in the Danish application No. PA 1998 01340; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous
with said polypeptide, is derived from said polypeptide by substitution, deletion
or addition of one or several amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule selected from
the group consisting of:
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and
comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 317
to nucleotide 1243 the Danish application No. PA 1998 01340;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that
is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid
residue 33 to amino acid residue 340 the Danish application No. PA 1998 01340;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM3 comprising the polynucleotide molecule (the DNA sequence) encoding
a mannanase of the present invention has been transformed into a strain of the
Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International
Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure
at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg
1b, D-38124 Braunschweig, Federal Republic of Germany, on 29 May 1998 under the deposition
number DSM 12197.
[0033] A fourth more preferred mannanase is described in the Danish co-pending patent application
No. PA 1998 01341. More specifically, this mannanase is:
i) a polypeptide produced by Bacillus sp. AAI 12;
ii) a polypeptide comprising an amino acid sequence as shown in positions 25-362 of
SEQ ID NO:2as shown in the Danish application No. PA 1998 01341; or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous
with said polypeptide, is derived from said polypeptide by substitution, deletion
or addition of one or several amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule selected from
the group consisting of
(a) polynucleotide molecules encoding a polypeptide having mannanase activity and
comprising a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 225
to nucleotide 1236 as shown in the Danish application No. PA 1998 01341;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that
is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid
residue 25 to amino acid residue 362 as shown in the Danish application No. PA 1998
01341;
(d) molecules complementary to (a), (b) or (c); and
(e) degenerate nucleotide sequences of (a), (b), (c) or (d).
[0034] The plasmid pBXM1 comprising the polynucleotide molecule (the DNA sequence) encoding
a mannanase of the present invention has been transformed into a strain of the
Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International
Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure
at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg
1b, D-38124 Braunschweig, Federal Republic of Germany, on 7 October 1998 under the
deposition number DSM 12433.
[0035] A fifth more preferred mannanase is described in Danish patent application PA 1998
01725. More specifically, this mannanase is :
i) a polypeptide produced by Bacillus halodurans,
ii) a polypeptide comprising an amino acid sequence as shown in positions 33-331 of
SEQ ID NO:2 as shown in the Danish patent application PA 1998 01725, or
iii) an analogue of the polypeptide defined in i) or ii) which is at least 65% homologous
with said polypeptide, is derived from said polypeptide by substitution, deletion
or addition of one or several amino acids, or is immunologically reactive with a polyclonal
antibody raised against said polypeptide in purified form.
Also encompassed is the corresponding isolated polynucleotide molecule selected from
the group consisting of:
a) polynucleotide molecules encoding a polypeptide having mannanase activity and comprising
a sequence of nucleotides as shown in SEQ ID NO: 1 from nucleotide 138 to nucleotide
1034 as shown in the in Danish patent application PA 1998 01725;
(b) species homologs of (a);
(c) polynucleotide molecules that encode a polypeptide having mannanase activity that
is at least 65% identical to the amino acid sequence of SEQ ID NO: 2 from amino acid
residue 33 to amino acid residue 331 as shown in the Danish patent application PA
1998 01725;
d) molecules complementary to (a), (b) or (c); and
e) degenerate nucleotide sequences of (a), (b), (c) or (d).
The plasmid pBXM5 comprising the polynucleotide molecule (the DNA sequence) encoding
a mannanase of the present invention has been transformed into a strain of the
Escherichia coli which was deposited by the inventors according to the Budapest Treaty on the International
Recognition of the Deposit of Microorganisms for the Purposes of Patent Procedure
at the Deutsche Sammlung von Mikroorganismen und Zellkulturen GmbH, Mascheroder Weg
1b, D-38124 Braunschweig, Federal Republic of Germany, on 9 October 1998 under the
deposition number DSM 12441.
[0036] The mannanases are generally included in the detergent compositions of the present
invention at a level of from 0.0001% to 0.2%, preferably from 0.0005% to 0.05%, more
preferably from 0.001% to 0.02% pure enzyme by weight of total composition.
BORATE-RELEASING COMPOUND
[0037] The second essential element of the compositions of the present invention is a borate-releasing
compound. The terms "borate-releasing compound" encompass any compound that releases
borate ions upon dilution in water. Suitable borate-releasing compound for the purpose
of the present invention are particles of alkali metal perborate materials; which
are frequently utilized in combination with a bleach activator.
[0038] Preferred for the purpose of the present invention is sodium perborate. The mono-
or tetra-hydrate form can be used, preferably the monohydrate form is used within
the present invention. Frequently inorganic peroxygen bleaches will be coated with
silicate, borate, sulfate or water-soluble surfactants.
[0039] The compositions of the present invention will preferably further comprise bleach
activators, which lead to the
in situ production in aqueous solution (i.e., during use of the compositions herein for fabric
laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Various
non-limiting examples of activators are disclosed in U.S. Patent 4,915,854, Issued
April 10, 1990 to Mao et al.; and U.S. Patent 4,412,934 Issued November 1, 1983 to
Chung et al. The nonanoyloxybenzene sulfonate (NOBS) and tetraacetyl ethylene diamine
(TAED) activators are typical. Mixtures thereof can also be used. See also the hereinbefore
referenced U.S. 4,634,551 for other typical bleaches and activators useful herein.
Other useful amido-derived bleach activators are those of the formulae:
R
1N(R
5)C(O)R
2C(O)L or R
1C(O)N(R
5)R
2C(O)L
wherein R
1 is an alkyl group containing from 6 to 12 carbon atoms, R
2 is an alkylene containing from 1 to 6 carbon atoms, R
5 is H or alkyl, aryl, or alkaryl containing from 1 to 10 carbon atoms, and L is any
suitable leaving group. A leaving group is any group that is displaced from the bleach
activator as a consequence of the nucleophilic attack on the bleach activator by the
perhydrolysis anion. A preferred leaving group is phenol sulfonate.
Preferred examples of bleach activators of the above formulae include (6-octanamido-caproyl)oxybenzenesulfonate,
(6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl)oxybenzenesulfonate
and mixtures thereof as described in the hereinbefore referenced U.S. Patent 4,634,551.
Such mixtures are characterized herein as (6-C
8-C
10 alkamidocaproyl)oxybenzenesulfonate.
Another class of useful bleach activators comprises the benzoxazin-type activators
disclosed by Hodge et al. in U.S. Patent 4,966, 723, Issued October 30, 1990, incorporated
herein by reference. A highly preferred activator of the benzoxazin-type is:
Still another class of useful bleach activators includes the acyl lactam activators,
especially acyl caprolactams and acyl valerolactams of the formulae:
wherein R
6 is H or an alkyl, aryl, alkoxyaryl, or alkaryl group containing from 1 to 12 carbon
atoms. Highly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam,
3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl
caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl
valerolactam, 3,5,5-trimethylhexanoyl valerolactam and mixtures thereof. See also
U.S. Patent 4,545,784, Issued to Sanderson, October 8, 1985, incorporated herein by
reference, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed
into sodium perborate.
[0040] In addition, it has been found that bleach activators, when agglomerated with certain
acids such as citric acid, are more chemically stable.
[0041] Also suitable for the purpose of the present invention are the water-soluble alkali
metal borates used as suitable alkalinity sources.
[0042] Borate-releasing compounds are used as all or part of the additional particulate
material, they will generally be comprised at a level of from 1% to 30% by weight
of the composition. More preferably, borate-releasing compounds will comprise from
1% to 20% by weight of the composition. Most preferably, borate-releasing compounds
will be present to the extent of from 5% to 20% by weight of the composition.
[0043] If utilized, bleach activators can comprise from 0.5% to 20%, more preferably from
3% to 10%, by weight of the composition. Frequently, activators are employed such
that the molar ratio of bleaching agent to activator ranges from 1:1 to 20:1, more
preferably from 1.5:1 to 10:1.
SURFACTANT-CONTAINING LIQUID PHASE
[0044] The non-aqueous liquid laundry detergent compositions of the present invention will
generally comprise a surfactant system wherein the surfactant can be selected from
nonionic and/or anionic and/or cationic and/or ampholytic and/or zwitterionic and/or
semi-polar surfactants. The surfactant-containing, non-aqueous liquid phase will generally
comprise from 49% to 99.95% by weight of the detergent compositions herein. More preferably,
this liquid phase is surfactant-structured and will comprise from 52% to 98.9% by
weight of the compositions. Most preferably, this non-aqueous liquid phase will comprise
from 55% to 70% by weight of the compositions herein. Such a surfactant-containing
liquid phase will frequently have a density of from 0.6 to 1.4 g/cc, more preferably
from 0.9 to 1.3 g/cc. The liquid phase of the detergent compositions herein is preferably
formed from one or more non-aqueous organic diluents into which is mixed a surfactant
structuring agent which is preferably a specific type of anionic surfactant-containing
powder. Insoluble particulate material is also preferably suspended in the surfactant-containing
liquid phase of the detergent compositions herein. Such additional particulate material
ranges in size from 0.1 to 1,500 microns. This additional particulate material can
include peroxygen bleaching agents, bleach activators, organic detergent builders
and inorganic alkalinity sources and combinations of these additional particulate
material types.
(A) Non-aqueous Organic Diluents
[0045] The major component of the liquid phase of the detergent compositions herein comprises
one or more non-aqueous organic diluents. The non-aqueous organic diluents used in
this invention may be either surface active, i.e., surfactant, liquids or non-aqueous,
non-surfactant liquids referred to herein as non-aqueous solvents. The term "solvent"
is used herein to connote the non-surfactant, non-aqueous liquid portion of the compositions
herein. While some of the essential and/or optional components of the compositions
herein may actually dissolve in the "solvent"-containing liquid phase, other components
will be present as particulate material dispersed within the "solvent"-containing
liquid phase. Thus the term "solvent" is not meant to require that the solvent material
be capable of actually dissolving all of the detergent composition components added
thereto.
[0046] The non-aqueous liquid diluent component will generally comprise from 50% to 100%,
more preferably from 50% to 80%, most preferably from 55% to 75%, of a structured,
surfactant-containing liquid phase. Preferably the liquid phase of the compositions
herein, i.e., the non-aqueous liquid diluent component, will comprise both non-aqueous
liquid surfactants and non-surfactant non-aqueous solvents.
i) Non-aqueous Surfactant Liquids
[0047] Suitable types of non-aqueous surfactant liquids which can be used to form the liquid
phase of the compositions herein include the alkoxylated alcohols, ethylene oxide
(EO)-propylene oxide (PO) block polymers, polyhydroxy fatty acid amides, alkylpolysaccharides,
and the like. Such normally liquid surfactants are those having an HLB ranging from
10 to 16. Most preferred of the surfactant liquids are the alcohol alkoxylate nonionic
surfactants.
[0048] Alcohol alkoxylates are materials which correspond to the general formula:
R
1(C
mH
2mO)
nOH
wherein R
1 is a C
8 - C
16 alkyl group, m is from 2 to 4, and n ranges from 2 to 12. Preferably R
1 is an alkyl group, which may be primary or secondary, that contains from 9 to 15
carbon atoms, more preferably from 10 to 14 carbon atoms. Preferably also the alkoxylated
fatty alcohols will be ethoxylated materials that contain from 2 to 12 ethylene oxide
moieties per molecule, more preferably from 3 to 10 ethylene oxide moieties per molecule.
[0049] The alkoxylated fatty alcohol materials useful in the liquid phase will frequently
have a hydrophilic-lipophilic balance (HLB) which ranges from 3 to 17. More preferably,
the HLB of this material will range from 6 to 15, most preferably from 8 to 15.
[0050] Examples of fatty alcohol alkoxylates useful in or as the non-aqueous liquid phase
of the compositions herein will include those which are made from alcohols of 12 to
15 carbon atoms and which contain 7 moles of ethylene oxide. Such materials have been
commercially marketed under the trade names Neodol 25-7 and Neodol 23-6.5 by Shell
Chemical Company. Other useful Neodols include Neodol 1-5, an ethoxylated fatty alcohol
averaging 11 carbon atoms in its alkyl chain with 5 moles of ethylene oxide; Neodol
23-9, an ethoxylated primary C
12 - C
13 alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C
9-C
11 primary alcohol having 10 moles of ethylene oxide. Alcohol ethoxylates of this type
have also been marketed by Shell Chemical Company under the Dobanol tradename. Dobanol
91-5 is an ethoxylated C
9-C
11 fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated
C
12-C
15 fatty alcohol with an average of 7 moles of ethylene oxide per mole of fatty alcohol.
[0051] Other examples of suitable ethoxylated alcohols include Tergitol 15-S-7 and Tergitol
15-S-9 both of which are linear secondary alcohol ethoxylates that have been commercially
marketed by Union Carbide Corporation. The former is a mixed ethoxylation product
of C
11 to C
15 linear secondary alkanol with 7 moles of ethylene oxide and the latter is a similar
product but with 9 moles of ethylene oxide being reacted.
[0052] Other types of alcohol ethoxylates useful in the present compositions are higher
molecular weight nonionics, such as Neodol 45-11, which are similar ethylene oxide
condensation products of higher fatty alcohols, with the higher fatty alcohol being
of 14-15 carbon atoms and the number of ethylene oxide groups per mole being 11. Such
products have also been commercially marketed by Shell Chemical Company.
[0053] If alcohol alkoxylate nonionic surfactant is utilized as part of the non-aqueous
liquid phase in the detergent compositions herein, it will preferably be present to
the extent of from 1% to 60% of the composition structured liquid phase. More preferably,
the alcohol alkoxylate component will comprise 5% to 40% of the structured liquid
phase. Most preferably, an alcohol alkoxylate component will comprise from 5% to 35%
of the detergent composition structured liquid phase. Utilization of alcohol alkoxylate
in these concentrations in the liquid phase corresponds to an alcohol alkoxylate concentration
in the total composition of from 1 % to 60% by weight, more preferably from 2% to
40% by weight, and most preferably from 5% to 25% by weight, of the composition.
[0054] Another type of non-aqueous surfactant liquid which may be utilized in this invention
are the ethylene oxide (EO) - propylene oxide (PO) block polymers. Materials of this
type are well known nonionic surfactants which have been marketed under the tradename
Pluronic. These materials are formed by adding blocks of ethylene oxide moieties to
the ends of polypropylene glycol chains to adjust the surface active properties of
the resulting block polymers. EO-PO block polymer nonionics of this type are described
in greater detail in Davidsohn and Milwidsky;
Synthetic Detergents, 7th Ed.; Longman Scientific and Technical (1987) at pp. 34-36 and pp. 189-191 and in U.S.
Patents 2,674,619 and 2,677,700. All of these publications are incorporated herein
by reference. These Pluronic type nonionic surfactants are also believed to function
as effective suspending agents for the particulate material which is dispersed in
the liquid phase of the detergent compositions herein.
[0055] Another possible type of non-aqueous surfactant liquid useful in the compositions
herein comprises polyhydroxy fatty acid amide surfactants. Materials of this type
of nonionic surfactant are those which conform to the formula:
wherein R is a C
9-17 alkyl or alkenyl, p is from 1 to 6, and Z is glycityl derived from a reduced sugar
or alkoxylated derivative thereof. Such materials include the C
12-C
18 N-methyl glucamides. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl
N-1-deoxyglucityl oleamide. Processes for making polyhydroxy fatty acid, amides are
know and can be found, for example, in Wilson, U.S. Patent 2,965,576 and Schwartz,
U.S. Patent 2,703,798, the disclosures of which are incorporated herein by reference.
The materials themselves and their preparation are also described in greater detail
in Honsa, U.S. Patent 5,174,937, Issued December 26, 1992, which patent is also incorporated
herein by reference.
[0056] The amount of total liquid surfactant in the preferred surfactant-structured, non-aqueous
liquid phase herein will be determined by the type and amounts of other composition
components and by the desired composition properties. Generally, the liquid surfactant
can comprise from 35% to 70% of the non-aqueous liquid phase of the compositions herein.
More preferably, the liquid surfactant will comprise from 50% to 65% of a non-aqueous
structured liquid phase. This corresponds to a non-aqueous liquid surfactant concentration
in the total composition of from 15% to 70% by weight, more preferably from 20% to
50% by weight, of the composition.
ii) Non-surfactant Non-aqueous Organic Solvents
[0057] The liquid phase of the detergent compositions herein may also comprise one or more
non-surfactant, non-aqueous organic solvents. Such non-surfactant non-aqueous liquids
are preferably those of low polarity. For purposes of this invention, "low-polarity"
liquids are those which have little, if any, tendency to dissolve one of the preferred
types of particulate material used in the compositions herein, i.e., the peroxygen
bleaching agents, sodium perborate or sodium percarbonate. Thus relatively polar solvents
such as ethanol are preferably not utilized. Suitable types of low-polarity solvents
useful in the non-aqueous liquid detergent compositions herein do include non-vicinal
C
4-C
8 alkylene glycols, alkylene glycol mono lower alkyl ethers, lower molecular weight
polyethylene glycols, lower molecular weight methyl esters and amides, and the like.
[0058] A preferred type of non-aqueous, low-polarity solvent for use herein comprises the
mono-, di-, tri-, or tetra- C
2-C
3 alkylene glycol mono C
2-C
6 alkyl ethers. The specific examples of such compounds include diethylene glycol monobutyl
ether, tetraethylene glycol monobutyl ether, dipropolyene glycol monoethyl ether,
and dipropylene glycol monobutyl ether. Diethylene glycol monobutyl ether, dipropylene
glycol monobutyl ether and butoxy-propoxy-propanol (BPP) are especially preferred.
Compounds of the type have been commercially marketed under the tradenames Dowanol,
Carbitol, and Cellosolve.
[0059] Another preferred type of non-aqueous, low-polarity solvent for use in the compositions
herein comprises the non-vicinal C
4-C
8 branched or straight chain alkylene glycols. Materials of this type include hexylene
glycol (4-methyl-2,4-pentanediol), 1,3-butylene glycol and 1,4-butylene glycol.
[0060] Another preferred type of non-aqueous, low-polarity organic solvent useful herein
comprises the lower molecular weight polyethylene glycols (PEGs). Such materials are
those having molecular weights of at least 150. PEGs of molecular weight ranging from
200 to 600 are most preferred.
[0061] Yet another preferred type of non-polar, non-aqueous solvent comprises lower molecular
weight methyl esters. Such materials are those of the general formula: R
1-C(O)-OCH
3 wherein R
1 ranges from 1 to 18. Examples of suitable lower molecular weight methyl esters include
methyl acetate, methyl propionate, methyl octanoate, and methyl dodecanoate.
[0062] The non-aqueous, generally low-polarity, non-surfactant organic solvent(s) employed
should, of course, be compatible and non-reactive with other composition components,
e.g., bleach and/or activators, used in the liquid detergent compositions herein.
Such a solvent component is preferably utilized in an amount of from 1% to 70% by
weight of the liquid phase. More preferably, a non-aqueous, low-polarity, non-surfactant
solvent will comprise from 10% to 60% by weight of a structured liquid phase, most
preferably from 20% to 50% by weight, of a structured liquid phase of the composition.
Utilization of non-surfactant solvent in these concentrations in the liquid phase
corresponds to a non-surfactant solvent concentration in the total composition of
from 1 % to 50% by weight, more preferably from 5% to 40% by weight, and most preferably
from 10% to 30% by weight, of the composition.
iii) Blends of Surfactant and Non-surfactant Solvents
[0063] In systems which employ both non-aqueous surfactant liquids and non-aqueous non-surfactant
solvents, the ratio of surfactant to non-surfaetant liquids, e.g., the ratio of alcohol
alkoxylate to low polarity solvent, within a structured, surfactant-containing liquid
phase can be used to vary the rheological properties of the detergent compositions
eventually formed. Generally, the weight ratio of surfactant liquid to non-surfactant
organic solvent will range 50:1 to 1:50. More preferably, this ratio will range from
3:1 to 1:3, most preferably from 2:1 to 1:2.
(B) Surfactant Structurant
[0064] The non-aqueous liquid phase of the detergent compositions of this invention is prepared
by combining with the non-aqueous organic liquid diluents hereinbefore described a
surfactant which is generally, but not necessarily, selected to add structure to the
non-aqueous liquid phase of the detergent compositions herein. Structuring surfactants
can be of the anionic, nonionic, cationic, and/or amphoteric types. Organo-modified
clays and/or polymers can also be used to structure the non-aqueous detergent compositions
of this invention
[0065] Preferred structuring surfactants are the anionic surfactants such as the alkyl sulfates,
the alkyl polyalkxylate sulfates and the linear alkyl benzene sulfonates. Another
common type of anionic surfactant material which may be optionally added to the detergent
compositions herein as structurant comprises carboxylate-type anionics. Carboxylate-type
anionics include the C
10-C
18 alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C
10-C
18 sarcosinates, especially oleoyl sarcosinate. Yet another common type of anionic surfactant
material which may be employed as a structurant comprises other sulfonated anionic
surfactants such as the C
8-C
18 paraffin sulfonates and the C
8-C
18 olefin sulfonates. Structuring anionic surfactants will generally comprise from 1%
to 30% by weight of the compositions herein.
[0066] As indicated, one preferred type of structuring anionic surfactant comprises primary
or secondary alkyl sulfate anionic surfactants. Such surfactants are those produced
by the sulfation of higher C
8-C
20 fatty alcohols.
[0067] Conventional primary alkyl sulfate surfactants have the general formula
ROSO
3-M
+
wherein R is typically a linear C
8 - C
20 hydrocarbyl group, which may be straight chain or branched chain, and M is a water-solubilizing
cation. Preferably R is a C
10-14 alkyl, and M is alkali metal. Most preferably R is C
12 and M is sodium.
[0068] Conventional secondary alkyl sulfates may also be utilized as a structuring anionic
surfactant for the liquid phase of the compositions herein. Conventional secondary
alkyl sulfate surfactants are those materials which have the sulfate moiety distributed
randomly along the hydrocarbyl "backbone" of the molecule. Such materials may be depicted
by the structure:
CH
3(CH
2)
n(CHOSO
3-M
+) (CH
2)
mCH
3
wherein m and n are integers of 2 or greater and the sum of m + n is typically 9 to
15, and M is a water-solubilizing cation.
[0069] If utilized, alkyl sulfates will generally comprise from 1% to 30% by weight of the
composition, more preferably from 5% to 25% by weight of the composition. Non-aqueous
liquid detergent compositions containing alkyl sulfates, peroxygen bleaching agents,
and bleach activators are described in greater detail in Kong-Chan et al.; WO 96/10073;
published April 4, 1996, which application is incorporated herein by reference.
[0070] Another preferred type of anionic surfactant material which may be optionally added
to the non-aqueous cleaning compositions herein as a structurant comprises the alkyl
polyalkoxylate sulfates. Alkyl polyalkoxylate sulfates are also known as alkoxylated
alkyl sulfates or alkyl ether sulfates. Such materials are those which correspond
to the formula
R
2-O-(C
mH
2mO)
n-SO
3M
wherein R
2 is a C
10-C
22 alkyl group, m is from 2 to 4, n is from 1 to 15, and M is a salt-forming cation.
Preferably, R
2 is a C
12-C
18 alkyl, m is 2, n is from 1 to 10, and M is sodium, potassium, ammonium, alkylammonium
or alkanolammonium. Most preferably, R
2 is a C
12-C
16, m is 2, n is from 1 to 6, and M is sodium. Ammonium, alkylammonium and alkanolammonium
counterions are preferably avoided when used in the compositions herein because of
incompatibility with peroxygen bleaching agents.
[0071] If utilized, alkyl polyalkoxylate sulfates can also generally comprise from 1% to
30% by weight of the composition, more preferably from 5% to 25% by weight of the
composition. Non-aqueous liquid detergent compositions containing alkyl polyalkoxylate
sulfates, in combination with polyhydroxy fatty acid amides, are described in greater
detail in Boutique et al; PCT Application No. PCT/US96/04223, which application is
incorporated herein by reference.
[0072] The most preferred type of anionic surfactant for use as a structurant in the compositions
herein comprises the linear alkyl benzene sulfonate (LAS) surfactants. In particular,
such LAS surfactants can be formulated into a specific type of anionic surfactant-containing
powder which is especially useful for incorporation into the non-aqueous liquid detergent
compositions of the present invention. Such a powder comprises two distinct phases.
One of these phases is insoluble in the non-aqueous organic liquid diluents used in
the compositions herein; the other phase is soluble in the non-aqueous organic liquids.
It is the insoluble phase of this preferred anionic surfactant-containing powder which
can be dispersed in the non-aqueous liquid phase of the preferred compositions herein
and which forms a network of aggregated small particles that allows the final product
to stably suspend other additional solid particulate materials in the composition.
[0073] Such a preferred anionic surfactant-containing powder is formed by co-drying an aqueous
slurry which essentially contains a) one of more alkali metal salts of C
10-16 linear alkyl benzene sulfonic acids; and b) one or more non-surfactant diluent salts.
Such a slurry is dried to a solid material, generally in powder form, which comprises
both the soluble and insoluble phases.
[0074] The linear alkyl benzene sulfonate (LAS) materials used to form the preferred anionic
surfactant-containing powder are well known materials. Such surfactants and their
preparation are described for example in U.S. Patents 2,220,099 and 2,477,383, incorporated
herein by reference. Especially preferred are the sodium and potassium linear straight
chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl
group is from 11 to 14. Sodium C
11-14, e.g., C
12, LAS is especially preferred. The alkyl benzene surfactant anionic surfactants are
generally used in the powder-forming slurry in an amount from 20 to 70% by weight
of the slurry, more preferably from 20% to 60% by weight of the slurry.
[0075] The powder-forming slurry also contains a non-surfactant, organic or inorganic salt
component that is co-dried with the LAS to form the two-phase anionic surfactant-containing
powder. Such salts can be any of the known sodium, potassium or magnesium halides,
sulfates, citrates, carbonates, sulfates, borates, succinates, sulfo-succinates and
the like. Sodium sulfate, which is generally a bi-product of LAS production, is the
preferred non-surfactant diluent salt for use herein. Salts which function as hydrotropes
such as sodium sulfo-succinate may also usefully be included. The non-surfactant salts
are generally used in the aqueous slurry, along with the LAS, in amounts ranging from
1 to 50% by weight of the slurry, more preferably from 5% to 40% by weight of the
slurry. Salts that act as hydrotropes can preferably comprise up to 3% by weight of
the slurry.
[0076] The aqueous slurry containing the LAS and diluent salt components hereinbefore described
can be dried to form the anionic surfactant-containing powder preferably added to
the non-aqueous diluents in order to prepare a structured liquid phase within the
compositions herein. Any conventional drying technique, e.g., spray drying, drum drying,
etc., or combination of drying techniques, may be employed. Drying should take place
until the residual water content of the solid material which forms is within the range
of from 0.5% to 4% by weight, more preferably from 1% to 3% by weight.
[0077] The anionic surfactant-containing powder produced by the drying operation constitutes
two distinct phases, one of which is soluble in the inorganic liquid diluents used
herein and one of which is insoluble in the diluents. The insoluble phase in the anionic
surfactant-containing powder generally comprises from 10% to 45% by weight of the
powder, more preferably from 15% to 35% by weight of a powder.
[0078] The anionic surfactant-containing powder that results after drying can comprise from
45% to 94%, more preferably from 60% to 94%, by weight of the powder of alkyl benzene
sulfonic acid salts. Such concentrations are generally sufficient to provide from
0.5% to 60%, more preferably from 15% to 60%, by weight of the total detergent composition
that is eventually prepared, of the alkyl benzene sulfonic acid salts. The anionic
surfactant-containing powder itself can comprise from 0.45% to 45% by weight of the
total composition that is eventually prepared. After drying, the anionic surfactant-containing
powder will also generally contain from 2% to 50%, more preferably from 2% to 25%
by weight of the powder of the non-surfactant salts.
[0079] After it is dried to the requisite extent, the combined LAS/salt material can be
converted to flakes or powder form by any known suitable milling or comminution process.
Generally at the time such material is combined with the non-aqueous organic solvents
to form the structured liquid phase of the compositions herein, the particle size
of this powder will range from 0.1 to 2000 microns, more preferably from 0.1 to 1000
microns.
[0080] A structured, surfactant-containing liquid phase of the preferred detergent compositions
herein can be prepared by combining the non-aqueous organic diluents hereinbefore
described with the anionic surfactant-containing powder as hereinbefore described.
Such combination results in the formation of a structured surfactant-containing liquid
phase. Conditions for making this combination of preferred structured liquid phase
components are described more fully hereinafter in the "Composition Preparation and
Use" section. As previously noted, the formation of a structured, surfactant-containing
liquid phase permits the stable suspension of colored speckles and additional functional
particulate solid materials within the preferred detergent compositions of this invention.
[0081] Additional suitable surfactants for use in the present invention included nonionic
surfactants, specifically, polyhydroxy fatty acid amides of the formula:
wherein R is a C
9-17 alkyl or alkenyl, R
1 is a methyl group and Z is glycityl derived from a reduced sugar or alkoxylated derivative
thereof. Examples are N-methyl N-1-deoxyglucityl cocoamide and N-methyl N-1-deoxyglucityl
oleamide. Processes for making polyhydroxy fatty acid amides are known and can be
found in Wilson, U.S. Patent 2,965,576 and Schwartz, U.S. Patent 2,703,798, the disclosures
of which are incorporated herein by reference.
[0082] Other suitable surfactants for use in the detergent compositions described herein
are amine based surfactants of the general formula:
wherein R
1 is a C
6-C
12 alkyl group; n is from 2 to 4, X is a bridging group which is selected from NH, CONH,
COO, or O or X can be absent; and R
3 and R
4 are individually selected from H, C
1-C
4 alkyl, or (CH
2-CH
2-O(R
5)) wherein R
5 is H or methyl. Especially preferred amines based surfactants include the following:
R
1-(CH
2)
2-NH
2
R
1-O-(CH
2)
3-NH
2
R
1-C(O)-NH-(CH
2)
3-N(CH
3)
2
CH
2-CH(OH)-R
5
wherein R
1 is a C
6-C
12 alkyl group and R
5 is H or CH
3. Particularly preferred amines for use in the surfactants defined above include those
selected from the group consisting of octyl amine, hexyl amine, decyl amine, dodecyl
amine, C
8-C
12 bis(hydroxyethyl)amine, C
8-C
12 bis(hydroxyisopropyl)amine, C
8-C
12 amido-propyl dimethyl amine, or mixtures thereof.
[0083] In a highly preferred embodiment, the amine based surfactant is described by the
formula:
R
1-C(O)-NH-(CH
2)
3-N(CH
3)
2
wherein R
1 is C
8-C
12 alkyl.
Ethoxylated quaternized amine clay material
[0084] It is envisioned that the non-aqueous liquid detergent compositions of the present
invention will be used, that is, transported and stored, at temperatures in the range
of from 4°C to 35°C. It is especially important that these detergent compositions
remain pourable within this temperature range. The non-aqueous, liquid, heavy-duty
detergent compositions of the present invention will preferably comprise from 0.1%
to 10%, preferably 0.5% to 5%, and most preferably 0.5% to 3%, by weight of the detergent
composition, an ethoxylated quaternized amine clay material.
[0085] Preferred ethoxylated quaternized amine clay materials are selected from the group
consisting of compounds having the general formula:
wherein each x is independently less than 16, preferably from 6 to 13, more preferably
from 6 to 8, or wherein each x is independently greater than 35. Materials suitable
for use in the present invention, such as those defined above, can be purchased from
the BASF Corporation in Germany, and the Witco Chemical Company.
[0086] It has been determined that the degree of ethoxylation is important to the viscosity
of the final detergent compositions described herein. Specifically, for the general
structure:
when x is less than 13 the ethoxylated quaternized amine clay materials can be added
to the present non-aqueous, liquid heavy duty detergent compositions as liquids without
causing undesired thickening at low temperatures. Likewise, when the degree of ethoxylation
for the same structure is greater than 35, that is when x is greater than 35, these
higher ethoxalated materials can be added to non-aqueous formulations as stable solid
without melting at high temperatures and without causing low temperature product thickening.
[0087] Additionally preferred ethoxylated quaternized amine clay materials for use in the
present invention are those having the general formula:
wherein x is from 10 to 14, y is from 12 to 16, and from 16% to 24% of the nitrogens
are quaternized. Materials of this general structure are often referred to as a "PEI"
because they are polyethylenimine based materials. Preferred PEI compounds for use
in the present invention have an average molecular weight of from 400 to 800, more
preferably the molecular weight is 600. Example III, below, details one method of
producing these materials and other synthesis methods will be apparent to those skilled
in the art.
[0088] Not only do these materials help stabilize the viscosity profile of the liquid detergent
compositions described herein, but they provide clay cleaning benefits as well. The
particulate-containing non-aqueous liquid detergent compositions herein will be relatively
viscous and phase stable under conditions of commercial marketing and use of such
compositions. Frequently the viscosity of the compositions herein will range from
300 to 4,500 cps, more preferably from 500 to 3,000 cps.
[0089] The viscosity of the detergent compositions described herein can be measured by any
of a number of tests known to those skilled in the art. For purposes of this invention,
viscosity can be measured with a Carrimed CSL2 Rheometer at a shear rate of 20 s
-1. Additionally, the melting point can be used to characterize the ethoxylated quaternized
amine clay materials of the present invention. A useful standardized test method for
measuring the melting point of the amine clay materials of this invention follows
ASTM method E 794-95. Specifically, samples are analyzed in duplicate on a TA Instruments
2920 Differential Scanning Calorimeter in hermetic pans with an atmosphere of UHP
Nitrogen at a flow rate of 50 mL/min. The samples are cooled down to -40°C and held
there for 5 minutes, then the temperature is ramped up to 100°C at a scan rate of
10°C/min. This method can be run with an indium calibration check sample.
SOLID PARTICULATE MATERIALS
[0090] The non-aqueous detergent compositions herein also preferably comprise from 1 % to
50% by weight, more preferably from 30% to 44% by weight, of additional solid phase
particulate material which is dispersed and suspended within the liquid phase, including
the borate-releasing compound of the present invention.
[0091] Generally such particulate material will range in size from 0.1 to 1500 microns,
more preferably from 0.1 to 900 microns. Most preferably, such material will range
in size from 5 to 200 microns.
[0092] The additional particulate material utilized herein can comprise one or more types
of detergent composition components which in particulate form are substantially insoluble
in the non-aqueous liquid phase of the composition. The types of particulate materials
which can be utilized are described in detail as follows:
(A) Other Peroxygen Bleaching Agent With Optional Bleach Activators
[0093] The non-aqueous liquid detergent compositions of the present invention can comprise
in addition to the borate-releasing compound, another bleaching agent. The most preferred
type of particulate material useful in the detergent compositions herein comprises
particles of a peroxygen bleaching agent. Such peroxygen bleaching agents may be organic
or inorganic in nature. Inorganic peroxygen bleaching agents are frequently utilized
in combination with a bleach activator as described above.
[0094] Useful organic peroxygen bleaching agents include percarboxylic acid bleaching agents
and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate
hexahydrate, the magnesium salt of metachloro perbenzoic acid, 4-nonylamino-4-oxoperoxybutyric
acid and diperoxydodecanedioic acid. Such bleaching agents are disclosed in U.S. Patent
4,483,781, Hartman, Issued November 20, 1984; European Patent Application EP-A-133,354,
Banks et al., Published February 20, 1985; and U.S. Patent 4,412,934, Chung et al.,
Issued November 1, 1983. Highly preferred bleaching agents also include 6-nonylamino-6-oxoperoxycaproic
acid (NAPAA) as described in U.S. Patent 4,634,551, Issued January 6, 1987 to Burns
et el.
[0095] Inorganic peroxygen bleaching agents may also be used in particulate form in the
detergent compositions herein. Inorganic bleaching agents are in fact preferred. Such
inorganic peroxygen compounds include alkali metal percarbonate materials. Suitable
inorganic bleaching agents can also include sodium or potassium carbonate peroxyhydrate
and equivalent "percarbonate" bleaches, sodium pyrophosphate peroxyhydrate, urea peroxyhydrate,
and sodium peroxide. Persulfate bleach (e.g., OXONE, manufactured commercially by
DuPont) can also be used. Frequently inorganic peroxygen bleaches will be coated with
silicate, borate, sulfate or water-soluble surfactants. For example, coated percarbonate
particles are available from various commercial sources such as FMC, Solvay Interox,
Tokai Denka and Degussa.
[0096] As described above, inorganic peroxygen bleaching agents are preferably combined
with bleach activators, which lead to the
in situ production in aqueous solution (i.e., during use of the compositions herein for fabric
laundering/bleaching) of the peroxy acid corresponding to the bleach activator. Suitable
bleach activators are described above.
[0097] If other peroxygen bleaching agents are used as all or part of the additional particulate
material, they will generally comprise from 1% to 30% by weight of the composition.
More preferably, other peroxygen bleaching agent will comprise from 1% to 20% by weight
of the composition. Most preferably, other peroxygen bleaching agent will be present
to the extent of from 5% to 20% by weight of the composition. If utilized, bleach
activators can comprise from 0.5% to 20%, more preferably from 3% to 10%, by weight
of the composition. Frequently, activators are employed such that the molar ratio
of bleaching agent to activator ranges from 1:1 to 20:1, more preferably from 1.5:1
to 10:1.
(B) Organic Builder Material
[0098] Another possible type of additional particulate material which can be suspended in
the non-aqueous liquid detergent compositions herein comprises an organic detergent
builder material which serves to counteract the effects of calcium, or other ion,
water hardness encountered during laundering/bleaching use of the compositions herein.
Examples of such materials include the alkali metal, citrates, succinates, malonates,
fatty acids, carboxymethyl succinates, carboxylates, polycarboxylates and polyacetyl
carboxylates. Specific examples include sodium, potassium and lithium salts of oxydisuccinic
acid, mellitic acid, benzene polycarboxylic acids and citric acid. Other examples
of organic phosphonate type sequestering agents such as those which have been sold
by Monsanto under the Dequest tradename and alkanehydroxy phosphonates. Citrate salts
are highly preferred.
[0099] Other suitable organic builders include the higher molecular weight polymers and
copolymers known to have builder properties. For example, such materials include appropriate
polyacrylic acid, polymaleic acid, and polyacrylic/polymaleic acid copolymers and
their salts, such as those sold by BASF under the Sokalan trademark which have molecular
weight ranging from 5,000 to 100,000.
[0100] Another suitable type of organic builder comprises the water-soluble salts of higher
fatty acids, i.e., "soaps". These include alkali metal soaps such as the sodium, potassium,
ammonium, and alkylolammonium salts of higher fatty acids containing from 8 to 24
carbon atoms, and preferably from 12 to 18 carbon atoms. Soaps can be made by direct
saponification of fats and oils or by the neutralization of free fatty acids. Particularly
useful are the sodium and potassium salts of the mixtures of fatty acids derived from
coconut oil and tallow, i.e., sodium or potassium tallow and coconut soap.
[0101] If utilized as all or part of the additional particulate material, insoluble organic
detergent builders can generally comprise from 2% to 20% by weight of the compositions
herein. More preferably, such builder material can comprise from 4% to 10% by weight
of the composition.
(C) Inorganic Alkalinity Sources
[0102] Another possible type of additional particulate material which can be suspended in
the non-aqueous liquid detergent compositions herein can comprise a material which
serves to render aqueous washing solutions formed from such compositions generally
alkaline in nature. Such materials may or may not also act as detergent builders,
i.e., as materials which counteract the adverse effect of water hardness on detergency
performance.
[0103] In addition to borates, examples of suitable alkalinity sources include water-soluble
alkali metal carbonates, bicarbonates, silicates and metasilicates. Although not preferred
for ecological reasons, water-soluble phosphate salts may also be utilized as alkalinity
sources. These include alkali metal pyrophosphates, orthophosphates, polyphosphates
and phosphonates. Of all of these alkalinity sources, alkali metal carbonates such
as sodium carbonate are the most preferred.
[0104] The alkalinity source, if in the form of a hydratable salt, may also serve as a desiccant
in the non-aqueous liquid detergent compositions herein. The presence of an alkalinity
source which is also a desiccant may provide benefits in terms of chemically stabilizing
those composition components such as the peroxygen bleaching agent which may be susceptible
to deactivation by water.
[0105] If utilized as all or part of the additional particulate material component, the
alkalinity source will generally comprise from 1% to 25% by weight of the compositions
herein. More preferably, the alkalinity source can comprise from 2% to 15% by weight
of the composition. Such materials, while water-soluble, will generally be insoluble
in the non-aqueous detergent compositions herein. Thus such materials will generally
be dispersed in the non-aqueous liquid phase in the form of discrete particles.
(D) Colored Speckles
[0106] The non-aqueous liquid detergent compositions herein also essentially contain from
0.05% to 2%, more preferably 0.1% to 1%, of the composition of colored speckles. Such
colored speckles themselves are combinations of a conventional dye or pigment material
with a certain kind of carrier material that imparts specific characteristics to the
speckles. For purposes of this invention, "colored" speckles are those which have
a color that is visibly distinct from the color of the liquid detergent composition
in which they are dispersed.
[0107] The colorant materials which can be used to form the colored speckles can comprise
any of the conventional dyes and pigments known and approved for use in detergent
products for use in the home. Such materials can include, for example, Ultramarine
Blue dye, Acid 80 Blue dye, Red HP Liquitint, Blue Liquitint and the like.
[0108] Dye or pigment material can be combined with a specific type of carrier material
to form the colored speckles for use in the detergent compositions herein. The carrier
material is selected to impart to the speckles certain specific density and solubility
characteristics. Materials which have been found to be suitable as carriers for the
colored speckles include polyacrylates; polysaccharides such as starches, celluloses,
gums and derivatives thereof; and polyethylene glycols. Especially preferred carrier
material comprises polyethylene glycol having a molecular weight from 4,000 to 20,000,
more preferably from 4,000 to 10,000.
[0109] The colored speckles can be produced by dispersing the dye or pigment material within
the carrier material. This can be done, for example, by a) melting the carrier and
dispersing the dye or pigment therein under mixing, b) mixing the dye/pigment powder
and carrier powder together, or c) by dissolving the dye/pigment and the carrier in
aqueous solution. The colorant/carrier mixture can then be formed into particles by
flaking, spray drying, prilling, extruding or other conventional techniques. Generally
the colored speckles will contain from 0.1 % to 5% by weight of the speckles of the
colorant (dye or pigment) material.
[0110] The colored speckles produced in this manner will generally range in size from 400
to 1,500 microns, more preferably from 400 to 1,200 microns. Speckles made from the
carrier materials specified will have a density less than 1.4 g/cc, preferably from
1.0 to 1.4 g/cc. Such speckles will also be substantially insoluble in the non-aqueous
liquid phase of the liquid detergent compositions herein. Thus, the colored speckles
can be stably suspended in the non-aqueous matrix of the liquid detergent compositions
of this invention without dissolving therein. Such speckles, however, rapidly dissolve
in the aqueous wash liquors prepared from the liquid detergent compositions herein.
OTHER OPTIONAL COMPOSITION COMPONENTS
[0111] In addition to the composition liquid and solid phase components as hereinbefore
described, the detergent compositions herein can, and preferably will, contain various
other optional components. Such optional components may be in either liquid or solid
form. The optional components may either dissolve in the liquid phase or may be dispersed
within the liquid phase in the form of fine particles or droplets. Some of the other
materials which may optionally be utilized in the compositions herein are described
in greater detail as follows:
(a) Optional Inorganic Detergent Builders
[0112] The detergent compositions herein may also optionally contain one or more types of
inorganic detergent builders beyond those listed hereinbefore that also function as
alkalinity sources. Such optional inorganic builders can include, for example, aluminosilicates
such as zeolites. Aluminosilicate zeolites, and their use as detergent builders are
more fully discussed in Corkill et al., U.S. Patent No. 4,605,509; Issued August 12,
1986, the disclosure of which is incorporated herein by reference. Also crystalline
layered silicates, such as those discussed in this '509 U.S. patent, are also suitable
for use in the detergent compositions herein. If utilized, optional inorganic detergent
builders can comprise from 2% to 15% by weight of the compositions herein.
(b) Optional Enzymes
[0113] The detergent compositions herein will preferably comprise one or more types of detergent
enzymes other than the mannanase. More preferably, the detergent compositions of the
present invention will comprise another detergent enzyme selected from a cellulase,
a protease and/or an amylase. It has been surprisingly found that the compositions
of the present invention further comprising another detergent enzyme, provide superior
food and cosmetic stains/soils removal.
[0114] Said enzymes include enzymes selected from cellulases, hemicellulases, peroxidases,
proteases, gluco-amylases, amylases, lipases, cutinases, pectinases, xylanases, reductases,
oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tannases, pentosanases,
β-glucanases, arabinosidases or mixtures thereof.
[0115] The enzyme may be incorporated into the non-aqueous liquid detergent compositions
herein in the form of suspensions, "marumes" or "prills". Another suitable type of
enzyme comprises those in the form of slurries of enzymes in nonionic surfactants,
e.g., the enzymes marketed by Novo Nordisk under the tradename "SL" or the microencapsulated
enzymes marketed by Novo Nordisk under the tradename "LDP."
[0116] Enzymes added to the compositions herein in the form of conventional enzyme prills
are especially preferred for use herein. Such prills will generally range in size
from 100 to 1,000 microns, more preferably from 200 to 800 microns and will be suspended
throughout the non-aqueous liquid phase of the composition. Prills in the compositions
of the present invention have been found, in comparison with other enzyme forms, to
exhibit especially desirable enzyme stability in terms of retention of enzymatic activity
over time. Thus, compositions which utilize enzyme prills need not contain conventional
enzyme stabilizing such as most frequently used when enzymes are incorporated into
aqueous liquid detergents.
[0117] The other detergent enzymes are generally incorporated in the detergent compositions
of the present invention a level of from 0.0001% to 0.2%, preferably from 0.001% to
0.05%, more preferably '-om 0.005% to 0.1% pure enzyme by weight of the composition.
[0118] Cellulases : The cellulases usable in the present invention include both bacterial or fungal
cellulases. Preferably, they will have a pH optimum of between 5 and 12 and a specific
activity above 50 CEVU/mg (Cellulose Viscosity Unit). Suitable cellulases are disclosed
in U.S. Patent 4,435,307, Barbesgoard et al, J61078384 and W096/02653 which discloses
fungal cellulase produced respectively from Humicola insolens, Trichoderma, Thielavia
and Sporotrichum. EP 739 982 describes cellulases isolated from novel Bacillus species.
Suitable cellulases are also disclosed in GB-A-2.075.028; GB-A-2.095.275; DE-OS-2.247.832
and W095/26398.
[0119] Examples of such cellulases are cellulases produced by a strain of Humicola insolens
(Humicola grisea var. thermoidea), particularly the Humicola strain DSM 1800.
[0120] Other suitable cellulases are cellulases originated from Humicola insolens having
a molecular weight of about 50KDa, an isoelectric point of 5.5 and containing 415
amino acids; and a
∼43kD endoglucanase derived from Humicola insolens, DSM 1800, exhibiting cellulase
activity; a preferred endoglucanase component has the amino acid sequence disclosed
in PCT Patent Application No. WO 91/17243. Also suitable cellulases are the EGIII
cellulases from Trichoderma longibrachiatum described in W094/21801, Genencor, published
September 29, 1994. Especially suitable cellulases are the cellulases having color
care benefits. Examples of such cellulases are cellulases described in European patent
application No. 91202879.2, filed November 6, 1991 (Novo). Carezyme and Celluzyme
(Novo Nordisk A/S) are especially useful. See also WO91/17244 and WO91/21801. Other
suitable cellulases for fabric care and/or cleaning properties are described in WO96/34092,
WO96/17994 and WO95/24471.
[0121] Proteases : Suitable proteases are the subtilisins which are obtained from particular strains
of
B. subtilis and
B. licheniformis (subtilisin BPN and BPN'). One suitable protease is obtained from a strain of
Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE®
by Novo Industries A/S of Denmark, hereinafter "Novo". The preparation of this enzyme
and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases
include ALCALASE®, DURAZYM® and SAVINASE® from Novo and MAXATASE®, MAXACAL®, PROPERASE®
and MAXAPEM® (protein engineered Maxacal) from Gist-Brocades. Also suitable for the
present invention are proteases described in patent applications EP 251 446 and WO
91/06637, protease BLAP® described in WO91/02792 and their variants described in WO
95/23221. See also a high pH protease from Bacillus sp. NCIMB 40338 described in WO
93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes,
and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired,
a protease having decreased adsorption and increased hydrolysis is available as described
in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergents
suitable herein is described in WO 94/25583 to Novo. Other suitable proteases are
described in EP 516 200 by Unilever.
[0122] Proteolytic enzymes also encompass modified bacterial serine proteases, such as those
described in European Patent Application Serial Number 87 303761.8, filed April 28,
1987 (particularly pages 17, 24 and 98), and which is called herein "Protease B",
and in European Patent Application 199,404, Venegas, published October 29, 1986, which
refers to a modified bacterial serine protealytic enzyme which is called "Protease
A" herein. Suitable is what is called herein "Protease C", which is a variant of an
alkaline serine protease from
Bacillus in which lysine replaced arginine at position 27, tyrosine replaced valine at position
104, serine replaced asparagine at position 123, and alanine replaced threonine at
position 274. Protease C is described in WO 91/06637. Genetically modified variants,
particularly of Protease C, are also included herein.
[0123] A preferred protease referred to as "Protease D" is a carbonyl hydrolase variant
having an amino acid sequence not found in nature, which is derived from a precursor
carbonyl hydrolase by substituting a different amino acid for a plurality of amino
acid residues at a position in said carbonyl hydrolase equivalent to position +76,
preferably also in combination with one or more amino acid residue positions equivalent
to those selected from the group consisting of +99, +101, +103, +104, +107, +123,
+27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216,
+217, +218, +222, +260, +265, and/or +274 according to the numbering of
Bacillus amyloliquefaciens subtilisin, as described in WO95/10591 and WO95/10592. The "protease D" variants
have preferably the amino acid substitution set 76/103/104, more preferably the substitution
set N76D/S103A/V1041. Also suitable is a carbonyl hydrolase variant of the protease
described in WO95/10591, having an amino acid sequence derived by replacement of a
plurality of amino acid residues replaced in the precursor enzyme corresponding to
position +210 in combination with one or more of the following residues : +33, +62,
+67, +76, +100, +101, +103, +104, +107, +128, +129, +130, +132, +135, +156, +158,
+164, +166, +167, +170, +209, +215, +217, +218, and +222, where the numbered position
corresponds to naturally-occurring subtilisin from
Bacillus amyloliquefaciens or to equivalent amino acid residues in other carbonyl hydrolases or subtilisins,
such as
Bacillus lentus subtilisin (co-pending patent application published under W098/55634).
[0124] More preferred proteases are multiply-substituted protease variants. These protease
variants comprise a substitution of an amino acid residue with another naturally occuring
amino acid residue at an amino acid residue position corresponding to position 103
of
Bacillus amyloliquefaciens subtilisin in combination with a substitution of an amino acid residue positions
corresponding to positions 1, 3, 4, 8, 9, 10, 12, 13, 16, 17, 18, 19, 20, 21, 22,
24, 27, 33, 37, 38, 42, 43, 48, 55, 57, 58, 61, 62, 68, 72, 75, 76, 77, 78, 79, 86,
87, 89, 97, 98, 99, 101, 102, 104, 106, 107, 109, 111, 114, 116, 117, 119, 121, 123,
126, 128, 130, 131, 133, 134, 137, 140, 141, 142, 146, 147, 158, 159, 160, 166, 167,
170, 173, 174, 177, 181, 182, 183, 184, 185, 188, 192, 194, 198, 203, 204, 205, 206,
209, 210, 211, 212, 213, 214, 215, 216, 217, 218, 222, 224, 227, 228, 230, 232, 236,
237, 238, 240, 242, 243, 244, 245, 246, 247, 248, 249, 251, 252, 253, 254, 255, 256,
257, 258, 259, 260, 261, 262, 263, 265, 268, 269, 270, 271, 272, 274 and 275 of
Bacillus amyloliquefaciens subtilisin; wherein when said protease variant includes a substitution of amino acid
residues at positions corresponding to positions 103 and 76, there is also a substitution
of an amino acid residue at one or more amino acid residue positions other than amino
acid residue positions corresponding to positions 27, 99, 101, 104, 107, 109, 123,
128, 166, 204, 206, 210, 216, 217, 218, 222, 260, 265 or 274 of
Bacillus amyloliquefaciens subtilisin and/or multiply-substituted protease variants comprising a substitution
of an amino acid residue with another naturally occuring amino acid residue at one
or more amino acid residue positions corresponding to positions 62, 212, 230, 232,
252 and 257 of
Bacillus amyloliquefaciens subtilisin as described in PCT application Nos. PCT/US98/22588, PCT/US98/22482 and
PCT/US98/22486 all filed on October 23, 1998 from The Procter & Gamble Company. Preferred
multiply substituted protease variants have te amino acid substitution set 101/103/104/159/232/236/245/248/252,
more preferably 101 G/103A/104I/159D/232V/236H/245R/248D/252K according to the numbering
of
Bacillus amyloliquiefaciens subtilisin.
[0125] Amylases : Amylases (α and/or β) can be included for removal of carbohydrate-based stains.
W094/02597, Novo Nordisk A/S published February 03, 1994, describes cleaning compositions
which incorporate mutant amylases. See also WO95/10603, Novo Nordisk A/S, published
April 20, 1995. Other amylases known for use in cleaning compositions include both
α- and β-amylases. α-Amylases are known in the art and include those disclosed in
US Pat. no. 5,003,257; EP 252,666; WO/91/00353; FR 2,676,456; EP 285,123; EP 525,610;
EP 368,341; and British Patent specification no. 1,296,839 (Novo). Examples of commercial
α-amylases products are Purafect Ox Am® from Genencor and Termamyl®, Ban® ,Fungamyl®
and Duramyl®, all available from Novo Nordisk A/S Denmark. W095/26397 describes other
suitable amylases : α-amylases characterised by having a specific activity at least
25% higher than the specific activity of Termamyl® at a temperature range of 25°C
to 55°C and at a pH value in the range of 8 to 10, measured by the Phadebas® α-amylase
activity assay.
[0126] Suitable are variants of the above enzymes, described in W096/23873 (Novo Nordisk).
Preferred variants are those demonstrating improved thermal stability, wherein at
least one amino acid residue equivalent to F180, R181, G182, T183, G184, or K185 has
been deleted from the parent α-amylase. Preferably said variants having improved thermal
stability comprise the amino acid deletions R181* + G182*, or T183* + G184*.
[0127] Other amylolytic enzymes with improved properties with respect to the activity level
and the combination of thermostability and a higher activity level are described in
W095/35382.
[0128] Other suitable amylases are stability-enhanced amylases described in WO94/18314,
published August 18, 1994 and W096/05295, Genencor, published February 22, 1996 and
amylase variants having additional modification in the immediate parent available
from Novo Nordisk A/S, disclosed in WO 95/10603, published April 95. Also suitable
are amylases described in EP 277 216, W095/26397 and W096/23873 (all by Novo Nordisk).
Cleaning compositions which incorporate mutant amylases are described in W094/02597,
Novo Nordisk A/S published February 03, 1994. See also WO95/10603, Novo Nordisk A/S,
published April 20, 1995.
[0129] Bleaching enzymes : Peroxidase enzymes are used in combination with oxygen sources, e.g. percarbonate,
perborate, persulfate, hydrogen peroxide, etc and with a phenolic substrate as bleach
enhancing molecule. They are used for "solution bleaching", i.e. to prevent transfer
of dyes or pigments removed from substrates during wash operations to other substrates
in the wash solution. Peroxidase enzymes are known in the art, and include, for example,
horseradish peroxidase, ligninase and haloperoxidase such as chloro- and bromo-peroxidase.
Peroxidase-containing detergent compositions are disclosed, for example, in PCT International
Application WO 89/099813, WO89/09813 and in European Patent application EP No. 91202882.6,
filed on November 6, 1991 and EP No. 96870013.8, filed February 20, 1996. Also suitable
is the laccase enzyme.
[0130] Enhancers are generally comprised at a level of from 0.1% to 5% by weight of total
composition. Preferred enhancers are substitued phenthiazine and phenoxasine 10-Phenothiazinepropionicacid
(PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid
(POP) and 10-methylphenoxazine (described in WO 94/12621) and substitued syringates
(C3-C5 substitued alkyl syringates) and phenols. Sodium percarbonate or perborate
are preferred sources of hydrogen peroxide.
[0131] Said peroxidases are normally incorporated in the compositions herein at levels from
0.0001% to 2% of pure enzyme by weight of the composition. Enzymatic system may be
used as bleaching agents : The hydrogen peroxide may also be present by adding an
enzymatic system (i.e. an enzyme and a substrate therefore) which is capable of generating
hydrogen peroxide at the beginning or during the washing and/or rinsing process. Such
enzymatic systems are disclosed in EP Patent Application 91202655.6 filed October
9, 1991.
[0132] Lipases : Other enzymes that can be included in the compositions of the present invention
include lipases. Suitable lipase enzymes for detergent usage include those produced
by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154,
as disclosed in British Patent 1,372,034. Suitable lipases include those which show
a positive immunological cross-reaction with the antibody of the lipase, produced
by the microorganism
Pseudomonas fluorescent IAM 1057. This lipase is available from Amano Pharmaceutical Co. Ltd., Nagoya, Japan,
under the trade name Lipase P "Amano," hereinafter referred to as "Amano-P". 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. Especially suitable lipases are lipases such as M1 Lipase
R and Lipomax
R (Gist-Brocades) and Lipolase
R and Lipolase Ultra
R(Novo) which have found to be very effective when used in combination with the compositions
of the present invention. Also suitables are the lipolytic enzymes described in EP
258 068, WO 92/05249 and WO 95/22615 by Novo Nordisk and in WO 94/03578, WO 95/35381
and WO 96/00292 by Unilever.
Also suitable are cutinases [EC 3.1.1.50] which can be considered as a special kind
of lipase, namely lipases which do not require interfacial activation. Addition of
cutinases to detergent compositions have been described in e.g. WO-A-88/09367 (Genencor);
WO 90/09446 (Plant Genetic System) and WO 94/14963 and WO 94/14964 (Unilever).
[0133] The above-mentioned enzymes may be of any suitable origin, such as vegetable, animal,
bacterial, fungal and yeast origin. Origin can further be mesophilic or extremophilic
(psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic,
halophilic, etc.). Purified or non-purified forms of these enzymes may be used. Also
included by definition, are mutants of native enzymes. Mutants can be obtained e.g.
by protein and/or genetic engineering, chemical and/or physical modifications of native
enzymes. Common practice as well is the expression of the enzyme via host organisms
in which the genetic material responsible for the production of the enzyme has been
cloned.
[0134] Other suitable detergent ingredients that can be added are enzyme oxidation scavengers
which are described in Copending European Patent application 92870018.6 filed on January
31, 1992. Examples of such enzyme oxidation scavengers are ethoxylated tetraethylene
polyamines.
[0135] 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. 3,553,139, January 5, 1971 to McCarty et al. Enzymes
are further disclosed in U.S. 4,101,457, Place et al, July 18, 1978, and in U.S. 4,507,219,
Hughes, March 26, 1985. Enzyme materials useful for liquid detergent formulations,
and their incorporation into such formulations, are disclosed in U.S. 4,261,868, Hora
et al, April 14, 1981. Enzymes for use in detergents can be stabilised by various
techniques. Enzyme stabilisation techniques are disclosed and exemplified in U.S.
3,600,319, August 17, 1971, Gedge et al, EP 199,405 and EP 200,586, October 29, 1986,
Venegas. Enzyme stabilisation systems are also described, for example, in U.S. 3,519,570.
A useful Bacillus, sp. AC13 giving proteases, xylanases and cellulases, is described
in WO 9401532 A to Novo.
(c) Optional Chelating Agents
[0136] The detergent compositions herein may also optionally contain a chelating agent which
serves to chelate metal ions, e.g., iron and/or manganese, within the non-aqueous
detergent compositions herein. Such chelating agents thus serve to form complexes
with metal impurities in the composition which would otherwise tend to deactivate
composition components such as the peroxygen bleaching agent. Useful chelating agents
can include amino carboxylates, phosphonates, amino phosphonates, polyfunctionally-substituted
aromatic chelating agents and mixtures thereof.
[0137] Amino carboxylates useful as optional chelating agents include ethylenediaminetetraacetates,
N-hydroxyethyl-ethylenediaminetriacetates, nitrilotriacetates, ethylene-diamine tetrapropionates,
triethylenetetraaminehexacetates, diethylenetriaminepentaacetates, ethylenediaminedisuccinates
and ethanol diglycines. The alkali metal salts of these materials are preferred.
[0138] Amino phosphonates are also suitable for use as chelating agents in the compositions
of this invention when at least low levels of total phosphorus are permitted in detergent
compositions, and include ethylenediaminetetrakis (methylene-phosphonates) as DEQUEST.
Preferably, these amino phosphonates do not contain alkyl or alkenyl groups with more
than 6 carbon atoms.
[0139] Preferred chelating agents include hydroxy-ethyldiphosphonic acid (HEDP), diethylene
triamine penta acetic acid (DTPA), ethylenediamine disuccinic acid (EDDS) and dipicolinic
acid (DPA) and salts thereof. The chelating agent may, of course, also act as a detergent
builder during use of the compositions herein for fabric laundering/bleaching. The
chelating agent, if employed, can comprise from 0.05% to 4% by weight of the compositions
herein. More preferably, the chelating agent will comprise from 0.2% to 2% by weight
of the detergent compositions herein.
(d) Optional Thickening. Viscosity Control and/or Dispersing Agents
[0140] The detergent compositions herein may also optionally contain a polymeric material
which serves to enhance the ability of the composition to maintain its solid particulate
components in suspension. Such materials may thus act as thickeners, viscosity control
agents and/or dispersing agents. Such materials are frequently polymeric polycarboxylates
but can include other polymeric materials such as polyvinylpyrrolidone (PVP) or polyamide
resins.
[0141] Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing
suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric
acids that can be polymerized to form suitable polymeric polycarboxylates include
acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic
acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence in the
polymeric polycarboxylates herein of monomeric segments, containing no carboxylate
radicals such as vinylmethyl ether, styrene, ethylene, etc. is suitable provided that
such segments do not constitute more than 40% by weight of the polymer.
[0142] Particularly suitable polymeric polycarboxylates can be derived from acrylic acid.
Such acrylic acid-based polymers which are useful herein are the water-soluble salts
of polymerized acrylic acid. The average molecular weight of such polymers in the
acid form preferably ranges from 2,000 to 100,000, more preferably from 2,000 to 10,000,
even more preferably from 4,000 to 7,000, and most preferably from 4,000 to 5,000.
Water-soluble salts of such acrylic acid polymers can include, for example, the alkali
metal, salts. Soluble polymers of this type are known materials. Use of polyacrylates
of this type in detergent compositions has been disclosed, for example, Diehl, U.S.
Patent 3,308,067, issued March 7, 1967. Such materials may also perform a builder
function.
[0143] If utilized, the optional thickening, viscosity control and/or dispersing agents
should be present in the compositions herein to the extent of from 0.1% to 4% by weight.
More preferably, such materials can comprise from 0.5% to 2% by weight of the detergents
compositions herein.
(e) Optional Clay Soil Removal/Anti-redeposition Agents
[0144] The compositions of the present invention can also optionally contain water-soluble
ethoxylated amines having clay soil removal and anti-redeposition properties. If used,
soil materials can contain from 0.01% to 5% by weight of the compositions herein.
[0145] The most preferred soil release and anti-redeposition agent is ethoxylated tetraethylenepentamine.
Exemplary ethoxylated amines are further described in U.S. Patent 4,597,898, VanderMeer,
issued July 1, 1986. Another group of preferred clay soil removal-anti-redeposition
agents are the cationic compounds disclosed in European Patent Application 111,965,
Oh and Gosselink, published June 27, 1984. Other clay soil removal/anti-redeposition
agents which can be used include the ethoxylated amine polymers disclosed in European
Patent Application 111,984, Gosselink, published June 27, 1984; the zwitterionic polymers
disclosed in European Patent Application 112,592, Gosselink, published July 4, 1984;
and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22,
1985. Other clay soil removal and/or anti-redeposition agents known in the art can
also be utilized in the compositions herein. Another type of preferred anti-redeposition
agent includes the carboxy methyl cellulose (CMC) materials. These materials are well
known in the art.
(f) Optional Liquid Bleach Activators
[0146] The detergent compositions herein may also optionally contain bleach activators which
are liquid in form at room temperature and which can be added as liquids to the non-aqueous
liquid phase of the detergent compositions herein. One such liquid bleach activator
is acetyl triethyl citrate (ATC). Other examples include glycerol triacetate and nonanoyl
valerolactam. Liquid bleach activators can be dissolved in the non-aqueous liquid
phase of the compositions herein.
(g) Optional Bleach Catalysts
[0147] Preferably, the detergent compositions of the present invention will further comprise
a bleach catalyst. It has been surprisingly found that such compositions comprising
further a bleach catalyst are highly efficient on the removal of bleachable hydrophobic
stains soils.
[0148] The bleaching compounds can be catalyzed by means of a manganese compound. Such compounds
are well known in the art and include, for example, the manganese-based catalysts
disclosed in U.S. Pat. 5,246,621, U.S. Pat. 5,244,594; U.S. Pat. 5,194,416; U.S. Pat.
5,114,606; and European Pat. App. Pub. Nos. 549,271 A1, 549,272A1, 544,440A2, and
544,490A1; Preferred examples of these catalysts include Mn
IV2(u-O)
3(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(PF
6)
2, Mn
III2(u-O)
1(u-OAc)
2(1,4,7-trimethyl-1;4,7-triazacyclononane)
2(ClO
4)
2, Mn
IV4(u-O)
6(1,4,7-triazacyclononane)
4(ClO
4)
4, Mn
IIIMn
IV4(u-O)
1 (u-OAC)
2-(1,4,7-trimethyl-1,4,7-triazacyclononane)
2(ClO
4)
3, Mn
IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH
3)
3(PF
6), and mixtures thereof.
[0149] More preferred for use therein are the transition -metal bleach catalysts being complexes
of a transition metal and a cross bridged macropolycyclic ligands such as described
in Procter & Gamble patent applications WO 98/39405, WO 98/39406 and WO 98/39098.
Most preferred is the Mn Complex Bleach Catalyst of the formula [Mn(Bcyclam)Cl
2] illustrated as:
"Bcyclam" (5,12-dimethyl-1,5,8,12-tetraaza-bicyclo[6.6.2]hexadecane). Such transition
-metal bleach catalyst can be prepared according to Procter & Gamble patent application
W098/39335 or according to J.Amer.Chem.Soc., (1990), 112, 8604. Bcyclam (1.00 g.,
3.93 mmol) is dissolved in dry CH
3CN (35 mL, distilled from CaH
2). The solution is evacuated at 15 mm until the CH
3CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This
degassing procedure is repeated 4 times. Mn(pyridine)
2Cl
2 (1.12 g., 3.93 mmol), synthesized according to the literature procedure of J. Inorg.
Nucl. Chem., (1974), 36, 1535, is added under Ar and the mixture is stirred overnight
at room temperature. The reaction solution is filtered with a 0.2µ filter. The filtrate
is evaporated. 1.35 g. of product is collected, 90% yield. Another method of preparation
generally used is to process the Mn bleach catalyst into solid particulates according
to the following steps. First, the Mn bleach catalyst is dissolved in an aqueous solution
of starch (30% starch; 3-5% Mn bleach catalyst). Next, the solution is spray dried
to form a powder (particle size up to 50 microns). Next, the powder is mixed with
molten PEG (PEG 4000) to form a slurry (20% slurry of starch in PEG). Last, the slurry
is processed through a prilling tower resulting in the final solid particulate.
[0150] Other metal-based bleach catalysts include those disclosed in U.S. Pat. 4,430,243
and U.S. Pat. 5,114,611. The use of manganese with various complex ligands to enhance
bleaching is also reported in the following United States Patents: 4,728,455; 5,284,944;
5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.
[0151] As a practical matter, and not by way of limitation, the compositions and processes
herein can be adjusted to provide on the order of at least one part per ten million
of the active bleach catalyst species in the aqueous washing liquor, and will preferably
provide from 0.1 ppm to 700 ppm, more preferably from 1 ppm to 500 ppm, of the catalyst
species in the laundry liquor.
[0152] Cobalt bleach catalysts useful herein are known, and are described, for example,
in M. L. Tobe, "Base Hydrolysis of Transition-Metal Complexes",
Adv. Inorg. Bioinorg. Mech., (1983), 2, pages 1-94. The most preferred cobalt catalyst useful herein are cobalt
pentaamine acetate salts having the formula [Co(NH
3)
5OAc] T
y, wherein "OAc" represents an acetate moiety and "T
y" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH
3)
5OAc]Cl
2; as well as [Co(NH
3)
5OAc](OAc)
2; [Co(NH
3)
5OAc](PF
6)
2; [Co(NH
3)
5OAc](SO
4); [Co(NH
3)
5OAc](BF
4)
2; and [Co(NH
3)
5OAc](NO
3)
2 (herein "PAC").
[0153] These cobalt catalysts are readily prepared by known procedures, such as taught for
example in the Tobe article and the references cited therein, in U.S. Patent 4,810,410,
to Diakun et al, issued March 7,1989,
J. Chem. Ed. (1989),
66 (12), 1043-45; The Synthesis and Characterization of Inorganic Compounds, W.L. Jolly
(Prentice-Hall; 1970), pp. 461-3;
Inorg. Chem., 18, 1497-1502 (1979);
Inorg. Chem.,
21, 2881-2885 (1982);
Inorg. Chem.,
18, 2023-2025 (1979); Inorg. Synthesis, 173-176 (1960); and
Journal of Physical Chemistry,
56, 22-25 (1952).
[0154] As a practical matter, and not by way of limitation, the compositions and cleaning
processes herein can be adjusted to provide on the order of at least one part per
hundred million of the active bleach catalyst species in the aqueous washing medium,
and will preferably provide from 0.01 ppm to 25 ppm, more preferably from 0.05 ppm
to 10 ppm, and most preferably from 0.1 ppm to 5 ppm, of the bleach catalyst species
in the wash liquor. In order to obtain such levels in the wash liquor of an automatic
washing process, typical compositions herein will comprise from 0.0005% to 0.2%, more
preferably from 0.004% to 0.08%, of bleach catalyst, especially manganese or cobalt
catalysts, by weight of the cleaning compositions.
(h) Optional Brighteners, Suds Suppressors, Dyes and/or Perfumes
[0155] The detergent compositions herein may also optionally contain conventional brighteners,
suds suppressors, bleach catalysts, dyes and/or perfume materials. Such brighteners,
suds suppressors, silicone oils, bleach catalysts, dyes and perfumes must, of course,
be compatible and non-reactive with the other composition components in a non-aqueous
environment. If present, brighteners suds suppressors, dyes and/or perfumes will typically
comprise from 0.0001% to 2% by weight of the compositions herein. Suitable bleach
catalysts include the manganese based complexes disclosed in US 5,246,621, US 5,244,594,
US 5,114,606 and US 5,114,611.
(i) Structure Elasticizing Agents
[0156] The non-aqueous liquid detergent compositions herein can also contain from 0.1% to
5%, preferably from 0.1% to 2% by weight of a finely divided, solid particulate material
which can include silica, e.g., fumed silica, titanium dioxide, insoluble carbonates,
finely divided carbon or combinations of these materials. Fine particulate material
of this type functions as a structure elasticizing agent in the products of this invention.
Such material has an average particle size ranging from 7 to 40 nanometers, more preferably
from 7 to 15 nanometers. Such material also has a specific surface area which ranges
from 40 to 400m
2/g.
[0157] The finely divided elasticizing agent material can improve the shipping stability
of the non-aqueous liquid detergent products herein by increasing the elasticity of
the surfactant-structured liquid phase without increasing product viscosity. This
permits such products to withstand high frequency vibration which may be encountered
during shipping without undergoing undersirable structure breakdown which could lead
to sedimentation in the product.
[0158] In the case of titanium dioxide, the use of this material also imparts whiteness
to the suspension of particulate material within the detergent compositions herein.
This effect improves the overall appearance of the product.
COMPOSITION FORM
[0159] As indicated, the non-aqueous liquid detergent compositions herein are preferably
in the form of bleaching agent and/or other materials in particulate form as a solid
phase suspended in and dispersed throughout a surfactant-containing, more preferably
structured non-aqueous liquid phase.
[0160] The particulate-containing liquid detergent compositions of this invention are substantially
non-aqueous (or anhydrous) in character. While very small amounts of water may be
incorporated into such compositions as an impurity in the essential or optional components,
the amount of water should in no event exceed 5% by weight of the compositions herein.
More preferably, water content of the non-aqueous detergent compositions herein will
comprise less than 1% by weight.
COMPOSITION PREPARATION AND USE
[0161] The non-aqueous liquid detergent compositions herein can be prepared by first forming
the surfactant-containing, preferably structured non-aqueous liquid phase and by thereafter
adding to this structured phase the additional particulate components in any convenient
order and by mixing, e.g., agitating, the resulting component combination to form
the phase stable compositions herein. In a typical process for preparing such compositions,
essential and certain preferred optional components will be combined in a particular
order and under certain conditions.
[0162] In a first step of a preferred preparation process, the anionic surfactant-containing
powder used to form the structured, surfactant-containing liquid phase is prepared.
This pre-preparation step involves the formation of an aqueous slurry containing from
30% to 60% of one or more alkali metal salts of linear C
10-16 alkyl benzene sulfonic acid and from 2% to 30% of one or more diluent non-surfactant
salts. In a subsequent step, this slurry is dried to the extent necessary to form
a solid material containing less than 4% by weight of residual water.
[0163] After preparation of this solid anionic surfactant-containing material, this material
can be combined with one or more of the non-aqueous organic diluents to form a structured,
surfactant-containing liquid phase of the detergent compositions herein. This is done
by reducing the anionic surfactant-containing material formed in the previously described
pre-preparation step to powdered form and by combining such powdered material with
an agitated liquid medium comprising one or more of the non-aqueous organic diluents,
either surfactant or non-surfactant or both, as hereinbefore described. This combination
is carried out under agitation conditions which are sufficient to form a thoroughly
mixed dispersion of particles of the insoluble fraction of the co-dried LAS/salt material
throughout a non-aqueous organic liquid diluent.
[0164] In a subsequent processing step, the non-aqueous liquid dispersion so prepared can
then be subjected to milling or high shear agitation under conditions which are sufficient
to provide a structured, surfactant-containing liquid phase of the detergent compositions
herein. Such milling or high shear agitation conditions will generally include maintenance
of a temperature between 10°C and 90°C, preferably between 20°C and 60°C; and a processing
time that is sufficient to form a network of aggregated small particles of the insoluble
fraction of the anionic surfactant-containing powdered material. Suitable equipment
for this purpose includes: stirred ball mills, co-ball mills (Fryma), colloid mills,
high pressure homogenizers, high shear mixers, and the like. The colloid mill and
high shear mixers are preferred for their high throughput and low capital and maintenance
costs. The small particles produced in such equipment will generally range in size
from 0.4 to 2 microns. Milling and high shear agitation of the liquid/solids combination
will generally provide an increase in the yield value of the structured liquid phase
to within the range of from 1 Pa to 8 Pa, more preferably from 1 Pa to 4 Pa.
[0165] After formation of the dispersion of LAS/salt co-dried material in the non-aqueous
liquid, either before or after such dispersion is milled or agitated to increase its
yield value, the additional particulate material to be used in the detergent compositions
herein can be added. Such components which can be added under high shear agitation
include a silica or titanium dioxide elasticizing agent; particles of substantially
all of an organic builder, e.g., citrate and/or fatty acid, and/or an alkalinity source,
e.g., sodium carbonate, can be added while continuing to maintain this admixture of
composition components under shear agitation. Agitation of the mixture is continued,
and if necessary, can be increased at this point to form a uniform dispersion of insoluble
solid phase particulates within the liquid phase.
[0166] After some or all of the foregoing solid materials have been added to this agitated
mixture, the particles and the highly preferred peroxygen bleaching agent can be added
to the composition, again while the mixture is maintained under shear agitation. By
adding the peroxygen bleaching agent material last, or after all or most of the other
components, and especially after alkalinity source particles, have been added, desirable
stability benefits for the peroxygen bleach can be realized. If enzyme prills are
incorporated, they are preferably added to the non-aqueous liquid matrix last.
[0167] As a final process step, after addition of all of the particulate material, agitation
of the mixture is continued for a period of time sufficient to form compositions having
the requisite viscosity, yield value and phase stability characteristics. Frequently
this will involve agitation for a period of from 1 to 30 minutes.
[0168] In adding solid components to non-aqueous liquids in accordance with the foregoing
procedure, it is advantageous to maintain the free, unbound moisture content of these
solid materials below certain limits. Free moisture in such solid materials is frequently
present at levels of 0.8% or greater. By reducing free moisture content, e.g., by
fluid bed drying, of solid particulate materials to a free moisture level of 1.0%
or lower prior to their incorporation into the detergent composition matrix, significant
stability advantages for the resulting composition can be realized.
[0169] The compositions of this invention, prepared as hereinbefore described, can be used
to form aqueous washing solutions for use in the laundering and bleaching of fabrics.
Generally, an effective amount of such compositions is added to water, preferably
in a conventional fabric laundering automatic washing machine, to form such aqueous
laundering/bleaching solutions. The aqueous washing/bleaching solution so formed is
then contacted, preferably under agitation, with the fabrics to be laundered and bleached
therewith.
[0170] An effective amount of the liquid detergent compositions herein added to water to
form aqueous laundering/bleaching solutions can comprise amounts sufficient to form
from 500 to 7,000 ppm of composition in aqueous solution. More preferably, from 800
to 3,000 ppm of the detergent compositions herein will be provided in aqueous washing/bleaching
solution.
[0171] The following examples illustrate the preparation and performance advantages of the
non-aqueous liquid detergent compositions of the present invention. Such examples,
however, are not necessarily meant to limit or otherwise define the scope of the invention
herein. In the detergent compositions, unless otherwise specified, the detergent ingredients
are expressed by weight active of the total compositions.
Example 1
[0172] The following non-aqueous liquid detergent compositions were prepared in accordance
with the present invention :
|
I |
II |
III |
Linear Alkyl Benzene Sulphonate Na Salt |
16.0 |
16.0 |
16.0 |
C12-13 E05 alcohol ethoxylate |
21.5 |
21.5 |
19.0 |
Butoxy Propoxy Propanol |
18.5 |
- |
16.0 |
Hexylene Glycol |
- |
18.5 |
5.0 |
Sodium citrate dihydrate |
6.8 |
6.8 |
3.8 |
[4-[N-nonanoyl-6-aminohexanoyloxy] benzene sulfonate] Na salt |
6.0 |
6.0 |
6.0 |
Methyl sulfate salt of methyl quaternized polyethoxylated hexamethylene diamine |
1.3 |
1.3 |
1.3 |
Ethylenediamine disuccinic acid Na salt |
1.2 |
1.2 |
1.2 |
Maleic-acrylic copolymer (Sokalan CP5® sold by BASF) |
- |
- |
3.0 |
Sodium Carbonate |
10.0 |
10.0 |
10.0 |
Protease Prills** (40mg active enzyme/g) |
0.4 |
0.4 |
0.4 |
Amylase Prills (Duramyl® 60CT, sold by |
0.8 |
0.8 |
0.8 |
Novo Nordisk A/S) |
|
|
|
Cellulase Prills (Carezyme 5T®, sold by |
0.03 |
0.03 |
0.03 |
Novo Nordisk A/S) |
|
|
|
Mannanase Prills*** (10mg active |
0.2 |
0.2 |
0.2 |
enzyme/g) |
|
|
|
Sodium Perborate monohydrate |
12.0 |
12.0 |
12.0 |
Silicone 3565 sold by Dow Corning |
0.75 |
0.75 |
1.1 |
Perfume |
1.7 |
1.7 |
1.7 |
Titanium Dioxide |
0.5 |
0.5 |
0.5 |
Bleach Catalyst* |
- |
0.03 |
0.03 |
Brightener **** |
0.2 |
0.2 |
0.2 |
Sodium hydrogenated C16-18 fatty soap |
1 |
1 |
0.5 |
Colored Speckles (PEG8000 and dye) Miscellaneous up to 100% |
0.4 |
0.4 |
0.4 |
* Bleach catalyst = Dichloro -5,12-Dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane
Manganese (II). |
** Protease variant with the substitution set N76D/S103A/V104l as described in WO95/10591
and sold by Genencor. |
*** Mannanase enzyme originating from Bacillus sp. l633 as described in the co-pending Danish application No. PA 1998 01340 and sold
by Novo Nordisk A/S. |
**** Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl) stilbene-2:2'-disulfonate. |
[0173] These compositions are chemically stable anhydrous liquid laundry detergent compositions
which provide excellent stain and soil removal performance when used in normal fabric
laundering operations.
Example 2
[0174] A non-aqueous liquid detergent composition of the present invention can be prepared
as follows :
1) Part of the Butoxy-propoxy-propanol (BPP), a C23EO(5) ethoxylated alcohol nonionic surfactant (Neodol 23/50), a methyl sulfate salt
of methyl quaternized polyethoxylated hexamethylene diamine and a mixture of LAS/BPP/Ethylenediamine
disuccinic acid Na salt (EDDS) are mixed for a short time (15 minutes) using a blade
impeller in a mix tank into a single phase.
2) Solid ingredients are prepared for addition to the composition. Such solid ingredients
include : Sodium carbonate (particle size 100 microns), Sodium citrate dihydrate,
Maleic-acrylic copolymer, Brightener, Titanium dioxide particles (5 microns), Amylase,
Mannanase and Cellulase enzyme prills (400-800 microns, specific density below 1.7
g/mL), Silicone suds suppressor, [4-[N-nonanoyl-6-aminohexanoyloxy] benzene sulfonate]
Na salt.
These solid materials, which are all millable, are added to the mix tank and mixed
with the liquid base until smooth. This takes approximately 1 hour after addition
of the last solid.
3) The batch is pumped once through a colloid mill, which is a simple rotor-stator
configuration in which a high-speed rotor spins inside a stator which creates a zone
of high shear. This wet grinding reduces particle size of all of the solids. This
leads to an increase in yield value (i.e. structure). The batch is then recharged
to the mix tank after cooling.
4) Other solid materials could be added after these first processing steps. These
include the following : Sodium perborate (40 microns), Protease enzyme prills (400-800
microns, specific density below 1.7 g/mL), Bleach Catalyst, Speckles, Sodium hydrogenated
C16-18 fatty soap.
These non-millable solid materials are then added to the mix tank followed by liquid
ingredients (perfume). The batch is then mixed for 30 minutes.
5) The resulting composition has the formula set forth in Table I.
EXAMPLE 3
[0175] The following non-aqueous liquid detergent compositions were prepared in accordance
with the present invention :
|
I |
II |
III |
IV |
Linear Alkyl Benzene Sulfonate Na Salt |
16.0 |
16.0 |
16.0 |
16.0 |
C12-13 E05 alcohol ethoxylate |
21.5 |
21.5 |
21.5 |
21.5 |
Butoxy Propoxy Propanol |
18.5 |
18.5 |
18.5 |
18.5 |
Sodium citrate dihydrate |
3.8 |
3.8 |
3.8 |
3.8 |
[4-[N-nonanoyl-6-aminohexanoyloxy] benzene sulfonate] Na salt |
6.0 |
6.0 |
6.0 |
6.0 |
Methyl sulfate salt of methyl quaternized polyethoxylated hexamethylene diamine |
1.3 |
1.3 |
1.3 |
1.3 |
Ethylenediamine disuccinic acid Na salt |
1.2 |
1.2 |
1.2 |
1.2 |
Maleic-acrylic copolymer (Sokalan CP5® sold by BASF) |
3.0 |
3.0 |
3.0 |
3.0 |
Sodium Carbonate |
16.0 |
10.0 |
6.7 |
3.2 |
Protease Prills** (40mg active enzyme/g) |
0.4 |
0.4 |
0.4 |
0.4 |
Amylase Prills (Duramyl 60CT) |
0.8 |
0.8 |
0.8 |
0.8 |
Cellulase Prills (Carezyme 5T) |
0.03 |
0.03 |
0.03 |
0.03 |
Mannanase Prills*** (10mg active enzyme/g) |
0.05 |
0.2 |
0.5 |
1.0 |
Sodium Perborate monohydrate |
6.0 |
12.0 |
15.0 |
18.0 |
Silicone 3565 sold by Dow Corning |
1.1 |
1.1 |
1.1 |
1.1 |
Perfume |
1.7 |
1.7 |
1.7 |
1.7 |
Titanium Dioxide |
0.5 |
0.5 |
0.5 |
0.5 |
Brightener**** |
0.2 |
0.2 |
0.2 |
0.2 |
Sodium hydrogenated C16-18 fatty soap |
0.5 |
0.5 |
0.5 |
0.5 |
Colored Speckles (PEG8000 and dye) Miscellaneous up to 100% |
0.4 |
0.4 |
0.4 |
0.4 |
** Protease variant with the substitution set N76D/S103A/V104l as described in W095/10591
and sold By Genencor. |
*** Mannanase enzyme originating from Bacillus sp. l633 as described in the co-pending Danish application No. PA 1998 01340 and sold
by Novo Nordisk A/S. |
**** Disodium 4,4'-bis(4-anilino-6-morpholino-1.3.5-triazin-2-yl) stilbene-2:2'-disulfonate. |
[0176] These compositions are chemically stable anhydrous liquid laundry detergent compositions
which provide excellent stain and soil removal performance when used in normal fabric
laundering operations.