Non-aqueous liquid detergent compositions comprising a borate-releasing compound and a mannanase

Abstract

 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 to pure mannanase enzyme is comprised between 250:1 and 20,000:1 for excellent chemical stability upon storage and excellent cleaning performance on food and cosmetic stains.

Description

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 NaBO₃) 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 NaBO₃) 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:

        R¹N(R⁵)C(O)R²C(O)L   or   R¹C(O)N(R⁵)R²C(O)L

wherein R¹ is an alkyl group containing from 6 to 12 carbon atoms, R² is an alkylene containing from 1 to 6 carbon atoms, R⁵ 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-C₈-C₁₀ 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 R⁶ 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:

        R¹(C_mH_2mO)_nOH

wherein R¹ is a C₈ - C₁₆ alkyl group, m is from 2 to 4, and n ranges from 2 to 12. Preferably R¹ 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 C₁₂ - C₁₃ alcohol having 9 moles of ethylene oxide and Neodol 91-10, an ethoxylated C₉-C₁₁ 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 C₉-C₁₁ fatty alcohol with an average of 5 moles ethylene oxide and Dobanol 25-7 is an ethoxylated C₁₂-C₁₅ 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 C₁₁ to C₁₅ 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 C₁₂-C₁₈ 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 C₄-C₈ 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- C₂-C₃ alkylene glycol mono C₂-C₆ 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 C₄-C₈ 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: R¹-C(O)-OCH₃ wherein R¹ 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 C₁₀-C₁₈ alkyl alkoxy carboxylates (especially the EO 1 to 5 ethoxycarboxylates) and the C₁₀-C₁₈ 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 C₈-C₁₈ paraffin sulfonates and the C₈-C₁₈ 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 C₈-C₂₀ fatty alcohols.

[0067] Conventional primary alkyl sulfate surfactants have the general formula

        ROSO₃^-M⁺

wherein R is typically a linear C₈ - C₂₀ 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 C₁₂ 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:

        CH₃(CH₂)_n(CHOSO₃^-M⁺) (CH₂)_mCH₃

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

        R²-O-(C_mH_2mO)_n-SO₃M

wherein R² is a C₁₀-C₂₂ alkyl group, m is from 2 to 4, n is from 1 to 15, and M is a salt-forming cation. Preferably, R² is a C₁₂-C₁₈ alkyl, m is 2, n is from 1 to 10, and M is sodium, potassium, ammonium, alkylammonium or alkanolammonium. Most preferably, R² is a C₁₂-C₁₆, 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., C₁₂, 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, R₁ 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 R₁ is a C₆-C₁₂ 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 R₃ and R₄ are individually selected from H, C₁-C₄ alkyl, or (CH₂-CH₂-O(R₅)) wherein R₅ is H or methyl. Especially preferred amines based surfactants include the following:

        R₁-(CH₂)₂-NH₂



        R₁-O-(CH₂)₃-NH₂



        R₁-C(O)-NH-(CH₂)₃-N(CH₃)₂



        CH₂-CH(OH)-R₅



wherein R₁ is a C₆-C₁₂ alkyl group and R₅ is H or CH₃. 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, C₈-C₁₂ bis(hydroxyethyl)amine, C₈-C₁₂ bis(hydroxyisopropyl)amine, C₈-C₁₂ amido-propyl dimethyl amine, or mixtures thereof.

[0083] In a highly preferred embodiment, the amine based surfactant is described by the formula:

        R₁-C(O)-NH-(CH₂)₃-N(CH₃)₂

wherein R₁ is C₈-C₁₂ 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(PF₆)₂, Mn^III₂(u-O)₁(u-OAc)₂(1,4,7-trimethyl-1;4,7-triazacyclononane)₂(ClO₄)₂, Mn^IV₄(u-O)₆(1,4,7-triazacyclononane)₄(ClO₄)₄, Mn^IIIMn^IV₄(u-O)₁ (u-OAC)_2-(1,4,7-trimethyl-1,4,7-triazacyclononane)₂(ClO₄)₃, Mn^IV(1,4,7-trimethyl-1,4,7-triazacyclononane)- (OCH₃)₃(PF₆), 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)Cl₂] 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 CH₃CN (35 mL, distilled from CaH₂). The solution is evacuated at 15 mm until the CH₃CN begins to boil. The flask is then brought to atmospheric pressure with Ar. This degassing procedure is repeated 4 times. Mn(pyridine)₂Cl₂ (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(NH₃)₅OAc] T_y, wherein "OAc" represents an acetate moiety and "T_y" is an anion, and especially cobalt pentaamine acetate chloride, [Co(NH₃)₅OAc]Cl₂; as well as [Co(NH₃)₅OAc](OAc)₂; [Co(NH₃)₅OAc](PF₆)₂; [Co(NH₃)₅OAc](SO₄); [Co(NH₃)₅OAc](BF₄)₂; and [Co(NH₃)₅OAc](NO₃)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 400m²/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.

Claims

1. A non-aqueous liquid detergent composition comprising a borate-releasing compound and a mannanase enzyme at a weight ratio of borate to pure mannanase enzyme 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.

2. A non-aqueous liquid detergent composition according to claim 1 wherein the mannanase is comprised 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.

3. A non-aqueous liquid detergent composition according to claims 1-2 wherein the borate-releasing compound is comprised at a level of from 1% to 30%, preferably from 1% to 20%, more preferably from 5% to 20% by weight of the total composition.

4. A non-aqueous liquid detergent composition according to claims 1-3 which is in the form of a suspension of solid, substantially insoluble particulate material dispersed throughout a surfactant-containing non-aqueous liquid phase.

5. A non-aqueous liquid detergent composition according to claim 4 wherein said surfactant-containing non-aqueous liquid phase is comprised at a level of from 49% to 99.95% by weight of the total composition.

6. A non-aqueous liquid detergent composition according to claims 4-5 wherein said surfactant-containing non-aqueous liquid phase has a density of from 0.6 to 1.4 g/cc.

7. A non-aqueous liquid detergent composition according to claims 4-6 wherein surfactant-containing liquid phase is 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.

8. A non-aqueous liquid detergent composition according to claims 4-7 wherein said substantially insoluble particulate material is comprised at a level of from 1% to 50%, preferably from 30% to 44% by weight of the detergent composition and which ranges in size from 0.1 to 1500 microns.

9. A non-aqueous liquid detergent compositions according to claims 4-8 wherein said particulate material is selected from other peroxygen bleaching agents, bleach activators, organic detergent builders, inorganic alkalinity sources, colored speckles and combinations thereof.

10. A non-aqueous liquid detergent composition according to any of the preceding claims wherein said borate-releasing bleaching agent is selected from perborate monohydrate, perborate tetrahydrate and/or mixtures thereof, preferably perborate monohydrate .

11. A non-aqueous liquid detergent composition according to any of the preceding claims further comprising a bleach catalyst, preferably a complex of a transition metal and a cross bridged macropolycyclic ligands, more preferably Dichloro -5,12-Dimethyl-1,5,8,12-tetraazabicyclo [6.6.2] hexadecane Manganese (II).

12. A non-aqueous liquid detergent composition according to any of the preceding claims further comprising another detergent enzyme, preferably selected from protease, cellulase, amylase and/or mixtures thereof.