MXPA99001622A - Detergent compositions comprising antibody controlled amylolytic activity - Google Patents
Detergent compositions comprising antibody controlled amylolytic activityInfo
- Publication number
- MXPA99001622A MXPA99001622A MXPA/A/1999/001622A MX9901622A MXPA99001622A MX PA99001622 A MXPA99001622 A MX PA99001622A MX 9901622 A MX9901622 A MX 9901622A MX PA99001622 A MXPA99001622 A MX PA99001622A
- Authority
- MX
- Mexico
- Prior art keywords
- amylase
- detergent
- antibody
- alkyl
- detergent composition
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 188
- 239000003599 detergent Substances 0.000 title claims abstract description 122
- 230000003625 amylolytic effect Effects 0.000 title description 15
- 108010065511 Amylases Proteins 0.000 claims abstract description 59
- 102000013142 Amylases Human genes 0.000 claims abstract description 59
- 235000019418 amylase Nutrition 0.000 claims abstract description 55
- 239000004382 Amylase Substances 0.000 claims abstract description 47
- 239000004744 fabric Substances 0.000 claims abstract description 24
- 102000004190 Enzymes Human genes 0.000 claims description 70
- 108090000790 Enzymes Proteins 0.000 claims description 70
- 229940088598 enzyme Drugs 0.000 claims description 70
- -1 granular Substances 0.000 claims description 66
- 239000007844 bleaching agent Substances 0.000 claims description 40
- 229920000642 polymer Polymers 0.000 claims description 39
- 239000003795 chemical substances by application Substances 0.000 claims description 32
- 239000002736 nonionic surfactant Substances 0.000 claims description 20
- 239000007788 liquid Substances 0.000 claims description 19
- 239000000344 soap Substances 0.000 claims description 18
- 239000006260 foam Substances 0.000 claims description 14
- 235000008733 Citrus aurantifolia Nutrition 0.000 claims description 13
- 235000011941 Tilia x europaea Nutrition 0.000 claims description 13
- 239000004571 lime Substances 0.000 claims description 13
- 239000000654 additive Substances 0.000 claims description 12
- 230000009471 action Effects 0.000 claims description 11
- 239000002270 dispersing agent Substances 0.000 claims description 10
- 229940025131 amylases Drugs 0.000 claims description 9
- 239000003945 anionic surfactant Substances 0.000 claims description 8
- 230000000996 additive effect Effects 0.000 claims description 7
- 108090000637 alpha-Amylases Proteins 0.000 claims description 7
- 125000002091 cationic group Chemical group 0.000 claims description 6
- 239000000843 powder Substances 0.000 claims description 6
- 239000002689 soil Substances 0.000 claims description 6
- 230000001580 bacterial effect Effects 0.000 claims description 5
- 239000003093 cationic surfactant Substances 0.000 claims description 5
- 229910021647 smectite Inorganic materials 0.000 claims description 5
- 239000002888 zwitterionic surfactant Substances 0.000 claims description 5
- 125000000129 anionic group Chemical group 0.000 claims description 4
- 230000002538 fungal effect Effects 0.000 claims description 4
- 102100026367 Pancreatic alpha-amylase Human genes 0.000 claims 1
- 239000002280 amphoteric surfactant Substances 0.000 claims 1
- 238000004140 cleaning Methods 0.000 abstract description 18
- 125000000217 alkyl group Chemical group 0.000 description 46
- 239000004094 surface-active agent Substances 0.000 description 44
- 108091005804 Peptidases Proteins 0.000 description 34
- 102000035195 Peptidases Human genes 0.000 description 34
- 239000000463 material Substances 0.000 description 33
- 239000004365 Protease Substances 0.000 description 30
- 238000000034 method Methods 0.000 description 29
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical compound C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 27
- 108090001060 Lipase Proteins 0.000 description 26
- 102000004882 Lipase Human genes 0.000 description 26
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 26
- 239000004367 Lipase Substances 0.000 description 25
- 229920001577 copolymer Polymers 0.000 description 25
- 235000019421 lipase Nutrition 0.000 description 25
- 150000003839 salts Chemical class 0.000 description 25
- 125000004432 carbon atom Chemical group C* 0.000 description 24
- 235000019419 proteases Nutrition 0.000 description 24
- 239000002253 acid Substances 0.000 description 23
- 238000000576 coating method Methods 0.000 description 23
- HNPSIPDUKPIQMN-UHFFFAOYSA-N dioxosilane;oxo(oxoalumanyloxy)alumane Chemical compound O=[Si]=O.O=[Al]O[Al]=O HNPSIPDUKPIQMN-UHFFFAOYSA-N 0.000 description 23
- 229920000768 polyamine Polymers 0.000 description 22
- 229910021536 Zeolite Inorganic materials 0.000 description 20
- 239000011248 coating agent Substances 0.000 description 20
- 239000004615 ingredient Substances 0.000 description 20
- 238000005406 washing Methods 0.000 description 20
- 239000010457 zeolite Substances 0.000 description 20
- 239000000975 dye Substances 0.000 description 18
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 17
- 150000001875 compounds Chemical class 0.000 description 17
- 230000000694 effects Effects 0.000 description 17
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- 150000001204 N-oxides Chemical class 0.000 description 16
- 239000007859 condensation product Substances 0.000 description 16
- 108010059892 Cellulase Proteins 0.000 description 15
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 15
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 description 15
- 150000001412 amines Chemical class 0.000 description 15
- 229920005646 polycarboxylate Polymers 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 description 14
- 108010084185 Cellulases Proteins 0.000 description 14
- 102000005575 Cellulases Human genes 0.000 description 14
- KRKNYBCHXYNGOX-UHFFFAOYSA-N citric acid Chemical compound OC(=O)CC(O)(C(O)=O)CC(O)=O KRKNYBCHXYNGOX-UHFFFAOYSA-N 0.000 description 14
- 229920001296 polysiloxane Polymers 0.000 description 14
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- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 14
- 239000011734 sodium Substances 0.000 description 14
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 13
- PMZURENOXWZQFD-UHFFFAOYSA-L Sodium Sulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=O PMZURENOXWZQFD-UHFFFAOYSA-L 0.000 description 13
- 229940106157 cellulase Drugs 0.000 description 13
- 238000009472 formulation Methods 0.000 description 13
- 239000008187 granular material Substances 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910052708 sodium Inorganic materials 0.000 description 13
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 12
- 229920002134 Carboxymethyl cellulose Polymers 0.000 description 12
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 12
- 102000008394 Immunoglobulin Fragments Human genes 0.000 description 12
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- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 description 11
- 125000002768 hydroxyalkyl group Chemical group 0.000 description 11
- 238000004519 manufacturing process Methods 0.000 description 11
- 229910052760 oxygen Inorganic materials 0.000 description 11
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- BPQQTUXANYXVAA-UHFFFAOYSA-N Orthosilicate Chemical compound [O-][Si]([O-])([O-])[O-] BPQQTUXANYXVAA-UHFFFAOYSA-N 0.000 description 10
- 230000002209 hydrophobic effect Effects 0.000 description 10
- 239000001301 oxygen Substances 0.000 description 10
- 229910052938 sodium sulfate Inorganic materials 0.000 description 10
- 235000011152 sodium sulphate Nutrition 0.000 description 10
- FRPJTGXMTIIFIT-UHFFFAOYSA-N tetraacetylethylenediamine Chemical compound CC(=O)C(N)(C(C)=O)C(N)(C(C)=O)C(C)=O FRPJTGXMTIIFIT-UHFFFAOYSA-N 0.000 description 10
- 229920003171 Poly (ethylene oxide) Polymers 0.000 description 9
- 229920002472 Starch Polymers 0.000 description 9
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 9
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 9
- 229910052757 nitrogen Inorganic materials 0.000 description 9
- 229920000058 polyacrylate Polymers 0.000 description 9
- 229920001223 polyethylene glycol Polymers 0.000 description 9
- 235000019698 starch Nutrition 0.000 description 9
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 8
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerol Natural products OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 8
- 239000000427 antigen Substances 0.000 description 8
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 8
- 238000004061 bleaching Methods 0.000 description 8
- 125000000623 heterocyclic group Chemical group 0.000 description 8
- 230000002401 inhibitory effect Effects 0.000 description 8
- 235000019832 sodium triphosphate Nutrition 0.000 description 8
- 239000008107 starch Substances 0.000 description 8
- 239000000126 substance Substances 0.000 description 8
- 239000000758 substrate Substances 0.000 description 8
- 150000003512 tertiary amines Chemical class 0.000 description 8
- CPELXLSAUQHCOX-UHFFFAOYSA-M Bromide Chemical compound [Br-] CPELXLSAUQHCOX-UHFFFAOYSA-M 0.000 description 7
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- 125000003118 aryl group Chemical group 0.000 description 7
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- OSSNTDFYBPYIEC-UHFFFAOYSA-N 1-ethenylimidazole Chemical compound C=CN1C=CN=C1 OSSNTDFYBPYIEC-UHFFFAOYSA-N 0.000 description 6
- BMVXCPBXGZKUPN-UHFFFAOYSA-N 1-hexanamine Chemical compound CCCCCCN BMVXCPBXGZKUPN-UHFFFAOYSA-N 0.000 description 6
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- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical group [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 6
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- 125000001931 aliphatic group Chemical group 0.000 description 6
- 150000008051 alkyl sulfates Chemical class 0.000 description 6
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- 235000014113 dietary fatty acids Nutrition 0.000 description 6
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- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Natural products C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 6
- HWGNBUXHKFFFIH-UHFFFAOYSA-I pentasodium;[oxido(phosphonatooxy)phosphoryl] phosphate Chemical compound [Na+].[Na+].[Na+].[Na+].[Na+].[O-]P([O-])(=O)OP([O-])(=O)OP([O-])([O-])=O HWGNBUXHKFFFIH-UHFFFAOYSA-I 0.000 description 6
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- 239000000377 silicon dioxide Substances 0.000 description 6
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- QAEDZJGFFMLHHQ-UHFFFAOYSA-N trifluoroacetic anhydride Chemical compound FC(F)(F)C(=O)OC(=O)C(F)(F)F QAEDZJGFFMLHHQ-UHFFFAOYSA-N 0.000 description 6
- VTYYLEPIZMXCLO-UHFFFAOYSA-L Calcium carbonate Chemical compound [Ca+2].[O-]C([O-])=O VTYYLEPIZMXCLO-UHFFFAOYSA-L 0.000 description 5
- DBVJJBKOTRCVKF-UHFFFAOYSA-N Etidronic acid Chemical compound OP(=O)(O)C(O)(C)P(O)(O)=O DBVJJBKOTRCVKF-UHFFFAOYSA-N 0.000 description 5
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- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 5
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Abstract
The present invention relates to laundry detergent compositions comprising an amylase and an amylase-directed antibody in order to provide excellent cleaning performance and fabric care performance.
Description
DETERGENT COMPOSITION THAT INCLUDES AMYROLYTIC ACTIVITY CONTROLLED BY ANTIBODY
FIELD OF THE INVENTION f The present invention relates to laundry detergent compositions comprising an amylase and an antibody directed against amylase to provide excellent cleansing action and fabric care action. BACKGROUND OF THE INVENTION
An important part of the system that protects vertebrates against infections by bacteria and viruses is the humoral immune system. The specialized cells present in the bone marrow, lymphoid tissues and blood, produce immunoglobulins (antibodies) that appear in response to the introduction of a micro or macromolecule foreign to that body and bind to this strange structure for the body initiating or destroying it . This molecule foreign to the body is called antigen. The antibody is directed against the antigenic determinant or hapten of the antigen, for example an amino acid sequence, parts of oligosaccharides, polysaccharides, lipopolysaccharides, glycoproteins, lipoproteins,. 5 lipoteichoic acids. The specific antibodies generated in this manner can be combined with the antigen that caused their formation to form an antigen-antibody complex. The antibody molecules have binding sites that are very specific and complementary to the structural features of the antigen that
*? He induced his training. Several applications of such highly specific antigen-antibody recognition and binding have been found; such as recognition agent, binding agent or carrier agent in various domains such as analytical chemistry, therapeutic treatment and health and beauty care. EP 479 600, EP 453 097 and EP 450 800 relate to the use of antibodies or fragments thereof to deliver the active ingredients to a target site. EP 481 701 discloses treatment compositions for topical application containing microcapsules comprising a beneficial agent at a target site, the microcapsules having an antibody or antibody fragment specific for the target site or a lectin. 0 WO92 / 04380 describes a reconfigured human antibody or reconfigured human antibody fragments having a specific character for human polymorphic epithelial mucin, for use in the treatment or diagnosis of cancer. The use of the specific polypeptides of the Epstein-Barr virus for the production of antibodies and the diagnosis and treatment of said disease are described in document O94 / 06470. Oral compositions comprising antibodies as anti-caries treatment or periodontal diseases are described extensively in documents O95 / 01155,
^ B O95 / 00110, O95 / 10612, EP 140 498, GB 140 498, GB 2 151 923, GB 2 176 400, GB 2 167 299, DE 4324859, US 5 401 723 and EP 280 576. EP 673 683 and EP 542 309 describe hair cosmetic compositions containing an antibody to the hair, or hair extract, obtained from the egg yolk or from the poultry immunized with the hair or hair extract and a polymer emulsion, to provide reduced damage to the hair, softness, moisture sensation and softness; said composition is absorbed only in a specific part of the hair. Antagonist-containing compositions (tyrphostins or antibodies) against epidermal growth and transformation factors, suitable for use in the treatment of acne, are described in document 095/24896. The use of antibodies in the context of detergency has been suggested in general in Unilever Researchprijs "Molecule zoekt parther" 1992, where it is proposed to use modified antibodies directed to specific spots in the bleaching process. The production of antibodies by hyperimmunization of mammals, such as a cow, with a vaccine derived from the E. coli bacterium is described in EP 102 831. EP 400 569 describes a method for preparing a vaccine composition for dental caries in nasal drops, comprising an antigen produced <§ by the integration of a gene that expresses an antigen protein, into the chromosomal gel of a mutant GS-5 strain of Streptococcus. Document 094/25591 describes the production of antibodies or functionalized fragments thereof derived from an immunoglobulin heavy chain of 0 camelidae. Currently, the detergent compositions include a complex combination of active ingredients that meet certain specific needs: a surfactant system, detergent enzymes, bleaching agents, a builder system, foam suppressants, soil suspending agents, removers. of dirt, optical brighteners, softening agents, dispersants, dye transfer inhibition compound, abrasives, bactericides, perfumes and its overall performance has been improved over the years. In particular, current laundry detergent formulations generally include detergent enzymes, and more specifically amylases. However, the overexposure of the substrate to the amylolytic activity and / or the transfer of the amylolytic activity to the final part of the main wash of the washing cycle, such as the steps of rinsing, rotating and / or drying, can lead to effects inconveniences. The "residual or transferred" amylolytic activity will have a negative intervention with the subsequent treatment of washing starch
'• Main S of the washed fabrics. Actually, the starch is applied for example during a rinse cycle or before ironing as a fabric care agent and / or to facilitate ironing. Now it has surprisingly been found that the
The application of antibodies developed against the amylase enzyme prevents the occurrence of inconvenient residual amylolytic activity, while maintaining optimal action of the enzyme for dirt removal and cleaning. Activity
? amylolytic can be completely controlled during the
cleaning procedure in such a way that negative effects can be avoided. Therefore, an object of the present invention is to provide an amylase-containing laundry detergent composition, which produces excellent cleaning action such
as removal of stains and / or dirt, cleaning the dirt while at the same time not intervening negatively with any subsequent starch treatment of the main wash of the fabrics. This need has been satisfied through
specific laundry detergent compositions comprising an amylase and an antibody directed against said amylolytic enzyme.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to laundry detergent compositions comprising an amylase enzyme and an antibody developed against the amylolytic enzyme to provide excellent cleansing action and fabric care action. 10 DETAILED DESCRIPTION OF THE INVENTION
Antibody g An essential element of detergent compositions
of the present invention is an antibody. Immunoglobulins are classified into 5 classes, respectively: IgA, IgD and IgE. Preferred types of immunoglobulin are IgG and IgA. The secretory slgA that has been discovered in the secreted fluids of the human body such as milk, saliva, respiratory and intestinal fluids, which are specially designed to survive in said secretions, have binding characteristics boosted and are resistant to proteolytic hydrolysis . The antibody that can be monoclonal or polyclonal or
An antibody fragment can be generated by conventional techniques, for example by using recombinant DNA techniques that allow the production of antibody variants with new properties: reduced immunogenicity, increased affinity, altered size, etc. You can also use the specific link. The monoclonal antibody is preferred for the purpose of the present invention, much preferred is a fragment thereof. Such fragments can be generated similarly by conventional techniques such as enzymatic digestion by papain or pepsin, using recombinant DNA techniques. Antibody fragments can also be generated by conventional recombinant DNA techniques. Antibodies and antibody fragments can be humanized, as described in Meded.-Fac. Landbouwkd. Toegepast Biol. Wet. (Univ. Gent) (1995), 60 (4a, Forum for Applied Biotechnology, 1995, Part 1), 2057-63. Heavy and light chains are in fact composed of constant and variable domains. The organisms that produce immunoglobulin in their natural state, the constant domains are very important for several functions, but for many applications in industrial processes and products, their variable domains are sufficient. Consequently, many methods have been described to produce antibody fragments. The antibody fragments that are used can be a Fab, an Fv, a scFv or any other fragment that has similar link properties. Preferred routes for antibody fragments are through recombinant DNA technology, so that the fragment is expressed by means of a genetically transformed organism. Antibodies and antibody fragments produced by recombinant DNA technology need not be identical to the antibody fragment produced in the
• Vertebrates, however, have the same binding properties evaluated by their Km, Ki and Kcat, for example they may include amino acid sequences and / or glycosylations that differ from those found in antibodies produced in other forms, especially sequences at the end Likewise, antibody fragments produced by recombinant DNA technology may include extra amino acid sequences at their terminal ends that have no counterpart in the antibodies produced in another way.5 A related possibility is that a binding agent for use in this invention it is a natural or synthetic polymer that mimics the specific binding activity of a region complementary to the natural antibody, said polymer is for example a polypeptide or a polymer fingerprint (Angew.Chem. Int. Ed. Engl. , 1995, 34, 1812-1832) .The usual method for the production of antibody can be adopted in the immunizes of mammals or birds with the corresponding antigens. Since mammals are going to be immunized, mice, rabbits, goats, sheep, 5 horses, cows, etc. can be used. The antibody (immunoglobulin fraction) can be separated from the antiserum, milk or eggs in accordance with the ordinary antibody purification method including the purification method, Polson extraction, gel filtration chromatography, ion exchange chromatography , chromatography of < § affinity and the like, the purification method using ammonium sulfate to produce the precipitates, dialyzing the precipitates against the physiological saline solution to obtain the purified precipitates as the antibody. Plants are also able to synthesize and assemble all types of antibody molecules and allow a large scale of antibody production as described in
Tibtech Dec. 1995, Vol 13, p. 522-527; Plant Mol, Biol., 26, p. 1701-1710, 1994 and Biotechnol, proj, 1991, 7, pp 455-461 and in the patent of E.U.A. 5,202,422. Antibodies can also be produced in microorganisms such as E. coli or S. cerevisiae by the biofermentation process, as illustrated in the patent EP 667 394. The techniques for the production of antibody fragment are well known in the art. Literature: Saiki et al. 0 Science 230 1350-54 (1985); Orlani and other PNAS USA 86 3833-7 (1989); WO89 / 09825; EP 368 684; WO 91/08482 and W094 / 25591. The drawbacks due to the prolonged activity of the enzyme can be avoided by an effective control of the enzymatic activity through the introduction of the corresponding antibody specifically. Said antibodies can be polyclonal -directed to the whole structure of the enzyme- or monoclonal- directed to the specific epitopes of the control regions of the enzyme activity of the structure of the enzyme. Antibodies raised against the specific enzyme can effectively deactivate the enzyme by the antibody-antigen binding at, or very close to, the active site. The formation of said complex leads to the deactivation of the enzyme and can be explained by the distortion of the three-dimensional structure and / or steric hindrance in the slit of the substrate. The deactivation of the enzyme can also be achieved by precipitation of the antibody-antigen complex from the wash solution. Due to the very high specificity and efficiency of the antibody-antigen interaction, no other detergent active is affected in this way. Antibodies directed against amylase are preferably included in the detergent compositions of the present invention at a level of 10E-6% at 10E + 1% by weight of the total composition. In some cases, the antibodies developed against a specific amylase have the ability to bind to other amylases of high structural similarity, giving cross-reactivity. Typically, a molecular ratio of antibody directed against amylase to amylase will be 100: 1 or less, preferably 50: 1 or less. For monoclonal antibodies or fragments thereof, the molecular ratio of antibody directed against amylase to amylase will generally be 50: 1 or less, preferably 20: 1 or less.
The antibodies developed against the amylase are released into the wash solution after a period of delay allowing the amylase to produce excellent cleaning action benefits that are achieved at the end of the washing procedure. Therefore, antibodies are preferably incorporated in a release agent to control their time and rate of release in the wash solution. The physical form of the release agent containing antibodies is adapted to the physical form of the corresponding detergent or additive. For the granulated and powdered detergent and cleaning products, the antibodies and release agents may be contained in a granulate. Said antibody granulate may suitably contain various granulation aids, binders, fillers, plasticizers, lubricants, cores and the like. Examples thereof include cellulose (i.e. cellulose fibers or in microcrystalline form), cellulose derivative (CMS, MC, HPC, HPMC), gelatin, starch, dextrins, sugars, polyvinylpyrrolidone,
PVA, PEG, salts (ie, sodium sulfate, calcium sulfate), titanium dioxide, talc, clays (caolin or pentonite) and nonionic surfactants. Other materials of relevance for incorporation into the granulate are described in EP 304 331. The release agent can be, for example, a coating. Said coating protects said granules in the washing environment for a certain period. The coating is normally applied to said granulates in an amount in the range of 1% to 50% by weight (calculated on the weight basis basis of the uncoated, dry granules), preferably in the range of 5% to 40% by weight. weight. The amount of coating to be applied to said granulates depends to a large extent on the nature of the desired coating composition, and on the kind of protection that said coating must offer to said granules. For example, the thickness of said coating or a multilayer coating applied in any of the above granulates can determine the period in which the content of said granulates is released. A possible multiple layer coating can be a coating in which, for example, a quick release coating is applied in a slow release coating. Likewise, cogranulates containing in the outer layer the detergent enzyme and a rapid release agent can be formed and in the inner core, the antibody and a slow release agent. Suitable release coatings are the coatings that give rise to the release of the contents of the granulates containing antibodies under the conditions prevailing during the use thereof. Thus, for example, when a preparation of the invention is to be introduced into a washing liquor containing a washing detergent (typically comprising, for example, one or more types of surfactants), the coating should be such that ensure the release of the contents of said granules from the release agent when it is introduced into the washing medium. The preferred release coating are coatings that are substantially insoluble in water. The release coatings which are suitable in the washing means may suitably comprise substances selected from the following: cellulose and cellulose derivatives, PVA, PVP, tallow; hydrogenated tallow; partially hydrolyzed tallow; fatty acids and fatty alcohols of natural and synthetic origin; long chain fatty acid mono-di- and glycerol triesters (ie, glycerol monostearate); ethoxylated fatty alcohols; latexes; hydrocarbon melting point in the 50-80 ° C scale; and waxes. Fusion coating agents are a preferred class of fast or slow release coating agents that can be used without dilution with water. Reference can be made to Controlled Reléase Systems: Fabrication Technology, Vol. I, CRC Press, 1988, for more information on slow release coating. The coatings may also suitably comprise substances such as clays (eg, kaolin), titanium dioxide, pigments, salts (such as calcium carbonate) and the like. The person skilled in the art is aware of other coating constituents of importance in the present invention. In liquid detergent compositions, the antibody can be incorporated as a particle dispersion containing, in addition to the antibody, a release agent. The antibody can be present in a liquid or solid form. Suitable particles consist of a porous hydrophobic material, ie, silica with an average pore diameter of 500 Angstroms or greater) containing the pores an antibody solution and a surfactant as described in EP 583 512 of Surutzidis. A and others.
The release agent can be a coating that protects said particles in the wash cycle for a certain period. The coating is preferably a hydrophobic coating material such as the liquid hydrophobic polymer. Said polymer may be an organo polysiloxane oil, alternatively a hydrocarbon of high molecular weight or water insoluble but with polymeric or water permeable material such as carboxymethylcellulose, PVA, PVP. The polymer properties are selected to achieve a proper release profile of the antibody in the wash solution.
The enzyme amylase The amylolytic enzymes are incorporated in the detergent compositions of the present invention at a level of from 0.0001% to 2%, preferably from 0.00018% to 0.1%, preferably from 0.00024% to 0.48% pure enzyme by weight of the composition. The amylolytic enzyme can be of different origin, for example produced by mammals, plants, microorganisms. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. Mutants of natural enzymes are also included by definition. Mutants can be obtained, for example, by genetic engineering and / or protein, chemical and / or physical modifications of natural enzymes. Also the common practice is the expression of the enzyme by host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Amylase (alpha and beta) can be included for carbohydrate-based stain removal. WO94 / 02597, Novo Nordisk A / S published on February 3, 1994, describes cleaning compositions that incorporate mutant amylases. See also WO95 / 10603, Novo Nordisk A / S, published April 20, 1995. Other amylases known to be used in cleaning compositions include both alpha and beta amylases. Alpha-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP252,666; WO / 91/00353; FR2,676, 456; EP285,123; EP525,610; EP368,341; and British Patent Specification No. 1,296,939 (Novo). Other suitable amylases are amylases of improved stability described in W094 / 18314, published August 18, 1994 and WO96 / 05295, Genencor, published on February 22, 1996 and amylase variants having additional modification in the immediate original available from Novo. Nordisk A / S, described in WO95 / 10603, published in April 1995. Also suitable are the amylases described in EP277 216, W095 / 26397 and W096 / 32873 (all from Novo Nordisk). Examples of commercial alpha-amylases products are Purafect Ox AmR from Gnencor and Termamyl®, BanR, Fungamyl® and Duramyl, all available from Novo Nordisk A / S Denmark. W095 / 26397 describes other suitable amylases: alpha-amylases characterized 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 scale from 8 to 10, measured by means of the Phadebas alpha-amylase activity test. The variants of the above enzymes, described in W096 / 23873 (Novo Nordisk), are suitable. Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher level of activity are described in W095 / 35382.
Detergent components The detergent compositions of the invention may also contain additional detergent components. The precise nature of these additional components and the levels of incorporation thereof will depend on the physical form of the composition, and the nature of the cleaning operation in which they will be used. The detergent compositions according to the invention can be in liquid, paste, gel, stick, tablet, powder or granular form. The granular compositions can also be in "compact" form, the liquid compositions may also be in a "concentrated" form. The compositions of the invention can be formulated for example as detergent compositions for automatic and manual washing, including additive laundry compositions and compositions suitable for use in soaking and / or pretreatment of dyed fabrics, such as fabric softener compositions added in the rinse. Said compositions can provide the fabrics: cleaning, stain removal, maintenance of whiteness, softness, appearance of color and inhibition of dye transfer. When formulated as suitable compositions for use in an automatic laundry method, the compositions of the invention preferably contain both a surfactant and a builder and additionally one or more detergent components preferably selected from organic polymeric compounds, bleaching agents. , additional enzymes, suds suppressors, dispersants, lime soap dispersants, suspending and antiredeposition agents for dirt and corrosion inhibitors. The laundry compositions may also contain softening agents as additional detergent components. The compositions of the invention can also be used as detergent additive products comprising an antibody directed against amylase, and will be added to a conventional detergent composition containing amylase. The detergent additive can also comprise both the amylase and the antibody directed against amylase. Said additive products are intended to complement or enhance the performance of conventional detergent compositions and preferably comprise up to 50% antibodies by weight of the total composition. If necessary, the density of the laundry detergent compositions herein ranges from 400 to 1200 g / liter, preferably 600 to 950 g / liter of the composition, measured at 20 ° C. The "compact" form of the compositions herein is best reflected by density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of the detergent compositions in powder form; in conventional detergent compositions, the filler salts are present in substantial amounts, typically 17-35% by weight of the total composition. In compact compositions, the filler salt is present in amounts not exceeding 15% of the total composition, preferably not exceeding 10%, and very = 5 preferably does not exceed 5% by weight of the composition. The inorganic filler salts, as understood in the present compositions, are selected from the alkali metal and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate. The liquid detergent compositions according to the present invention may also be in a "concentrated form", in which case, the liquid detergent compositions according to the present invention will contain a lower amount of water, as compared to liquid detergents. conventional Typically, the water content of the concentrated liquid detergent is preferably less than 40%, most preferably less than 30%, and preferably less than 20% by weight of the detergent composition. 0 Surfactant system The detergent compositions according to the present invention comprise a surfactant system in which the surfactant can be selected from nonionic and / or anionic and / or cationic and / or ampholytic and / or zwitterionic surfactants and / or semipolar
The surfactant is typically present at a level of 0.1% to 60% by weight. Very preferred levels of incorporation are 1% to 35% by weight, preferably 1% to 30% by weight of the detergent compositions according to the invention. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, the surfactant is most preferably formulated in a manner that promotes, or at least does not degrade, the stability of any enzyme in these compositions. Preferred surfactant systems for use in accordance with the present invention comprise as one surfactant one or more of the nonionic and / or anionic surfactants described herein. The polyethylene oxide, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant systems of the present invention, with the polyethylene oxide condensates being preferred. These compounds include the condensation products of alkylphenols having an alkyl group containing from about 6 to about 14 carbon atoms, preferably from about 8 to about 14 carbon atoms, either in a straight chain or branched chain configuration with the alkylene oxide. In a preferred embodiment, the ethylene oxide is present in an amount equal to about 2 to about 25 moles, preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include
Igepal TM CO-630, marketed by GAF Corporation; and TritonTiMli X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (e.g., alkylphenol ethoxylates). The condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide are suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention. The alkyl chain of the aliphatic alcohol may be either straight or branched, primary or secondary, and generally contains from about 8 to about 22 carbon atoms. The condensation products of alcohols having an alkyl group containing from about 8 to about 20 carbon atoms, most preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide are preferred. mol of alcohol. About 2 to about 7 moles of ethylene oxide are present, and most preferably 2 to 5 moles of ethylene oxide per mole of alcohol in said condensation products. Examples of commercially available nonionic surfactants of this type include Tergitol 15-S-9 (the linear alcohol condensation product of C? _-C-_ 5 with 9 moles of ethylene oxide,), Tergitol ™ 24 - L-6 NMW (the primary alcohol condensation product of C ^ -C ^ with 6 moles of ethylene oxide with a limited molecular weight distribution), both marketed by Union Carbide Corporation; Neodol ™ 45-9 (the linear alcohol condensation product of C1-C15 with 9.0 moles of ethylene oxide), Neodol 23-3 (the linear alcohol condensation product of < ^ 2 ~ (^ 1.3 with 3.0 moles of ethylene oxide), Neodol TM 45-5 (the linear condensation product of C14-C15 with 7 moles of ethylene oxide), Neodol 45-5 (the linear alcohol condensation product of 5] _4 ' -C] _5 with 5 moles of ethylene oxide), marketed by
Shell Chemical Company, Kyro TM EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & amp;; Gamble Company, and Genapol LA 050 (the condensation product of alcohol of C] _2_c14 with 5.0 moles of ethylene oxide), marketed by Hoechst. The preferred scale of HLB in these products is 8-11, and most preferred is 8-10. Also useful as the nonionic surfactant of the surfactant systems of the present invention are the alkylpolysaccharides described in the U.S.A. No. 4,565,647, Filling, issued January 21, 1986, having a hydrophobic group containing from about 6 to about 30 carbon atoms, preferably from about 10 to about 16 carbon atoms, and a polysaccharide, v.gr ., a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, e.g. , portions of glucose, galactose and galactosyl can replace the glucosyl moieties (optionally the hydrophobic group is attached at the 2-, 3-, 4-, etc. positions, thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide linkages can be, eg, between position one of the additional saccharide units and positions 2-, 3-, 4- and / or 6- of the preceding saccharide units. Preferred alkyl polyglycosides have the formula
R ^ O (CnH2n0) t (glycosyl) x
wherein R is selected from the group consisting of alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof, wherein the alkyl groups contain from about 10 to about 18, preferably from about 12 to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 to about 10, preferably 0; and x is from about 1.3 to about 10, preferably about 1.3 to about 3, most preferably from about 1.3 to about 2.7. The glycosyl is preferably derived from glucose. To prepare these compounds, the alkylpolyethoxylated alcohol or alcohol is first formed, and then reacted with glucose or a glucose source to form the glucoside (linkage at position 1). The additional glycosyl units can then be linked between their position 1 and the preceding glycosyl units in the 2-, 3-, 4- and / or 6- position, preferably predominantly in the 2-position. The condensation products of ethylene oxide with a hydrophobic base, formed by the condensation of propylene oxide with propylene glycol, are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds will preferably have a molecular weight of from about 1500 to about 1800, and will exhibit insolubility in water. The addition of polyoxethylene portions to this hydrophobic portion tends to increase the water solubility of the molecule in general, and the liquid character of the product is retained to the point where the polyoxethylene content is about 50% of the total weight of the product. condensation product, which corresponds to condensation with up to about 40 moles of ethylene oxide.
Examples of compounds of this type include some Plurafac ™ LF404 and Pluronic ™ surfactants commercially available from BASF. Also suitable for use as the nonionic surfactant of the nonionic surfactant system of the present invention, are the condensation products of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylenediamine. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, and generally has a molecular weight of about 2500 to about 3000. This hydrophobic portion is condensed with ethylene oxide to the extent that the product of condensation contains about 40% to about 80% by weight of polyoxyethylene and has a molecular weight of about 5000 to about 11,000. Examples of this type of nonionic surfactant include some of the Tetromc ™ compounds, commercially available from BASF. Preferred to be used as the nonionic surfactant of the surfactant systems of the present invention are the polyethylene oxide condensates of alkylphenols, the condensation products of primary and secondary aliphatic alcohols with from about 1 to about 25 moles of ethylene oxide. , alkylpolysaccharides and mixtures thereof. Preferred are Cg-C-4 alkylphenol ethoxylates having from 3 to 15 ethoxy groups and the Cg-C g alcohol ethoxylates (preferably from average C o) having from 2 to 10 ethoxy groups, and mixtures thereof. The highly preferred nonionic surfactants are the polyhydroxy fatty acid amide surfactants of the formula
R2 - C - N - Z, II I, O Rx
wherein R 1 is H, or R 1 is C 1 -C 4 hydrocarbyl, 2-hydroxyethyl p, 2-hydroxypropyl or a mixture thereof, R 5 is hydrocarbyl and Z is a polyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R 1 is methyl, R is an alkyl chain of C-C 5 or alkyl or alkenyl of straight C g C, such as cocoalkyl or mixtures thereof, and Z is derived from a reducing sugar such as glucose, fructose, maltose and lactose , in a reductive amination reaction. Suitable anionic surfactants that are used are alkyl ether sulfonate surfactants that include linear esters of C-C2o carboxylic acids (ie, fatty acids) that are sulfonated with gaseous SO3 according to "The Journal of the American Oil Chemists Society" , 52 (1975), p. 323-329. Suitable starting materials would include natural fatty substances such as those derived from tallow, palm oil, etc. The preferred alkyl ether sulphonate surfactant, especially for laundry applications, comprises alkyl ether sulfonate surfactants of the structural formula:
0 R- CH - C OR ^ S03M
3 wherein RJ is a Cg-C2o hydrocarbyl-preferably an alkyl, or combination thereof, R is a C1-C5 hydrocarbyl, preferably an alkyl or a combination thereof, and M is a salt-forming cation soluble in water with the alkyl ether sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and substituted or unsubstituted ammonium cations such as monoethanolamine, diethanolamine and -3-4 tpetanolamm. Preferably, R is CiQ-Cig alkyl and R is methyl, ethyl or isopropyl. Methyl ester sulfonates in which R3 is C1-C15 alkyl are especially preferred. Other suitable anionic surfactants include the alkyl sulfate surfactants which are salts or water soluble acids of the formula ROSO3M, wherein R is preferably a C10-C24 hydrocarbyl, preferably an alkyl or hydroxyalkyl having an alkyl component of
C10-C20- most preferably an alkyl or hydroxyalkyl of c12"c18 'and M is H or a cation, e.g., an alkali metal cation (e.g., sodium, potassium, lithium), or ammonium or ammonium substituted (e.g., methyl-, dimethyl-, and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine and mixtures thereof , and the like). Typically, the Ci2-Ci6 alkyl chains are preferred for lower wash temperatures (e.g., below about 50 ° C) and the C? g_? alkyl chains are preferred for further washing temperatures. high (eg, about 50 ° C.) Other anionic surfactants useful for detersive purposes may also be included in the detergent compositions of the present invention, which may include salts (including, for example, sodium, potassium salts, ammonium and d substituted ammonium such as mono-, di- and triethanolamine salts) of soap, primary or secondary alkanesulfonates of C-C22-C-C24-olefinsulfonates, sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolyzed product of alkaline earth metal citrates, v .gr., as described in the description of British Patent No. 1,082,179, Cg-C24 alkyl polyglycol ether sulphates (containing up to 10 moles of ethylene oxide); alkyl glycerol sulfonates, fatty alkyl glycerol sulfonates, alkyl phenol ethers sulfates of ethylene oxide, paraffinsulfonates, alkyl phosphates, isethionates, such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C 2 -C 8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Ci2 diesters), acyl sarcosinates, alkylpolyacharide sulfates such as the alkyl polyglycoside sulphates (non-sulphonated nonionic compounds are described below), branched primary alkyl sulphates and alkyl polyethoxy carboxylates such as those of the formula RO ( CH2CH2O) ^ -CL ^ COO-M +, wherein R is a C-C22-alkyl is an integer from 1 to 10, and M is a soluble salt-forming cation. Resin acids and hydrogenated resin acids are also suitable, such as rosin, hydrogenated rosin and rosin acids, as well as hydrogenated rosin acids present in, or derived from, tallow tree oil. Additional examples are described in "Surface Active Agents and Detergents" (Vol. I and II by Schwartz, Perry and Berch). A variety of such surfactants are generally also described in the U.S.A. No. 3,929,678, issued December 30, 1975 to Laughlin et al., In Column 23, line 58 to Column 29, line 23 (incorporated herein by reference). When included herein, the laundry detergent compositions of the present invention typically comprise from about 1% to about 40%, preferably from about 3% to about 20% by weight of said anionic surfactants. Highly preferred anionic surfactants include alkoxylated alkylsulphate surfactants which are water soluble salts or acids of the formula RO (A) mS03M, wherein R is an unsubstituted C10-C24 alkyl or hydroxyalkyl group having an alkyl component of C Q-c24- preferably a C12-C20 alkyl or hydroxyalkyl, most preferably C2-C6 alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, most preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.) or an ammonium cation or of substituted ammonium. The ethoxylated alkyl sulphates, as well as the propoxylated alkyl sulphates, are also contemplated herein. Specific examples of substituted ammonium cations include methyl-, dimethyl-, and trimethylammonium cations, and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and those derived from alkylamines such as ethylamine, diethylamine, triethylamine, mixtures of the same and similar. Exemplary surfactants are polyethoxylated alkyl sulfate (1.0) of C - ^ - C-Lg (C12-C18E (1.0) M), polyethoxylated alkyl sulfate (2.25) of C? 2-C? 8 (Ci2-C? 8'E (2.25) ) M), polyethoxylated alkyl sulfate (3.0) of Ci2-C? G (C? 2-C? GE (3.0) M), and polyethoxylated alkyl sulfate (4.0) of C2-C8 (C? 2-C? 8E ( 4.0) M), in which M is conveniently selected from sodium and potassium. The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic and semi-polar surfactants, as well as other nonionic and / or anionic surfactants different from those already described herein. Suitable cationic detersive surfactants for use in the detergent compositions of the present invention are those having a long chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants such as alkyltrimethylammonium halides and surfactants having the formula:
[R2 (0R3) and] [R4 (0R3) and] 2R5N + X- p wherein R is an alkyl or alkylbenzyl group having from about 8 to about 18 carbon atoms in the alkyl chain, each R3 is selected from a group consisting of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH20H) -, CH2CH2CH2-, and mixtures thereof; each R 4 is selected from the group consisting of C -C alkyl, C 1 -C 4 hydroxyalkyl, benzyl ring structures formed by joining the two groups R 4, -CH 2 CH 0 H-, -CH 0 H 0 0 R 6 CH 0 HCH 20 H, wherein R 6 is any hexose or polymer of hexose having a molecular weight less than about 1000, and hydrogen when and not 0; R5 is the same as R4 or is an alkyl chain in which the total number of carbon atoms of R plus R is not greater than about 18; each y is from 0 to approximately 10 and the sum of the values of y is from 0 to approximately 15; and X is any compatible anion. The quaternary ammonium surfactants suitable for the present invention have the formula:
Formula I
wherein R 1 is an alkyl of short chain length (Cg-C g) or alkylamidoalkyl of formula (II):
Ce-Cu. M18 or Formula II
wherein y is 2-4, preferably 3, whereby R2 is H or a C1-C3 alkyl; whereby x is 0-4, preferably 0-2, very preferably 0; whereby R3, R4 and R5 are the same or different and may be a short chain alkyl (C1-C3) or alkoxylated alkyl of formula III;
Formula lll
whereby X ~ is a counterion, preferably a halide, e.g., chloride, or methylisulfate. R6 is C -C4 and z is 1 or 2. Preferred quaternary ammonium surfactants are those defined in formula I with which R1 is Cg, Cio ° mixtures thereof, x = 0, R3, R4 = CH3 and R5 = CH2CH2OH Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition, having the formula:
RlR2R3R4N + X (i)
wherein Ri is C -Cig alkyl, each of R2, R3 and R4 is independently C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl and - (C2H4o)? H, wherein x has a value of 2. to 5 and x is an anion. No more than one of R2, R3 or R4 must be benzyl. The preferred length of the alkyl chain for Ri is C 12 -C 15, particularly when the alkyl group is a mixture of chain lengths derived from palm or coconut seed fat, ie synthetically derived by olefin formation or 0X0 alcohol synthesis . Preferred groups for R2, R3 and R4 are methyl and hydroxyethyl groups, and the anion X can be selected from halide, methosulfate, acetate and phosphate ions. Examples of quaternary ammonium compounds of the formula (i) suitable for use herein are: cocotrimethylammonium chloride or bromide; cocomethyldihydroxyethylammonium chloride or bromide; decyltriethylammonium chloride, decylmethylhydroxyethylammonium chloride or bromide; dimethylhydroxyethylammonium chloride or bromide of C 2- C15; cocodimethylhydroxyethylammonium chloride or bromide; myristyltrimethylammonium methylisulfate; lauryl dimethylbenzylammonium chloride or bromide; lauryldimethyl (ethenoxy) 4 ammonium chloride or bromide; Choline esters (compounds of formula (i) in which Ri is CH2-CH2-0-C-C2-14 alkyl and R2R3R4 are methyl). Or di-alkylimidazolines [compounds of formula (i)]. Other cationic surfactants useful herein are also described in the U.S.A. Do not.
4,228, 044, Cambre, issued October 14, 1980, and in the European Patent Application EP 000,224. When included, the detergent compositions of the present invention typically comprise from 0.2% to about 25%, preferably from about 1% to about 8% by weight of said cationic surfactants. The ampholytic surfactants are also suitable for use in the detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or as aliphatic derivatives of heterocyclic secondary or tertiary amines in which the aliphatic radical can be a straight or branched chain. One of the aliphatic substituents contains at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one contains an anionic water solubilization group, e.g., carboxy, sulfate, sulfonate . See the patent of E.U.A. No. 3,929,678 to Laughlin et al., Issued December 30, 1975, column 19, lines 18-35, for examples of ampholytic surfactants. When included, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10%, by weight of said ampholytic surfactants. Zwitterionic surfactants are also suitable for use in detergent compositions. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. See the patent of E.U.A. No. 3,929,678 to Laughlin et al., Issued December 30, 1975, in column 19 line 38, to column 22 line 48, for examples of zwitterionic surfactants. When included, the detergent compositions of the present invention typically comprise from 0.2% to about 15%, preferably from about 1% to about 10% by weight of said zwitterionic surfactants. Semi-polar nonionic surfactants are a special category of nonionic surfactants that include water-soluble amine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and groups hydroxyalkyl containing from about 1 to about 3 carbon atoms; water-soluble phosphine oxides containing an alkyl portion of about 10 to about 18 carbon atoms and two portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; and water soluble sulfoxides containing an alkyl portion of about 10 to about 18 carbon atoms, and a portion selected from the group consisting of alkyl and hydroxyalkyl portions of about 1 to about 3 carbon atoms. Semi-polar nonionic surfactants include the amine oxide surfactants having the formula:
OR R3 (0R) xN (R5) 2
wherein R is an alkyl, hydroxyalkyl or alkylphenyl group, or mixtures thereof, containing from about 8 to about 22 carbon atoms; R is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms, or mixtures thereof; x is from 0 to about 3; and each R is an alkyl or hydroxyalkyl group containing from about 1 to about 3 carbon atoms, or a polyethylene oxide group containing from about 1 to about 3 ethylene oxide groups. The R groups may be attached to each other, eg, through an oxygen or nitrogen atom to form a ring structure. These amine oxide surfactants include in particular Cig-Ci alkyldimethylamine oxides and C 2 -C 2 alkoxyethyldihydroxyethylamine oxides. When included, the detergent compositions of the present invention typically comprise from about 0.2% to about 15%, preferably about 1% to about 10% by weight of said semi-polar nonionic surfactants. The detergent composition of the present invention may further preferably comprise a co-surfactant selected from the group of primary or tertiary amines. Primary amines suitable for use herein include amines according to the formula R1NH2, where Ri is an alkyl chain of C-Cig, preferably Cg-CiQ, or RX (CH2) n, X is -0-, - C (0) NH- or -NH-, R4 is an alkyl chain of Cg-Ci2 / n is between 1 to 5, preferably 3. The alkyl chains of Ri can be straight or branched and can be interrupted with up to 12, preferably less than 5 portions of ethylene oxide. Preferred amines according to the above formula are the n-alkylamines. Amines suitable for use herein may be selected from 1-hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines include C-CιO oxypropylamine, octyloxypropylamine, 2-ethylexyl-oxypropylamine, laurylamido-propylamine and amidopropylamine. Tertiary amines suitable for use herein include tertiary amines having the formula R R 2 R 3 N, wherein R and R are C 1 -C alkyl chains or
i5 (CH2-CH-0) xH R3 is an alkyl chain of Cg-C2, preferably Cg-CiQ, or R3 is R4X (CH2) n, where X is -0 -, - C (0) NH- or -NH-, < R4 is a C4-C12, n is between 1 to 5, preferably 2-3. R5 is H or C1-C2 alkyl and x is between 1 to 6. R3 and R4 can be linear or branched; the alkyl chains of R3 can be interrupted with up to 12, preferably less than 5, portions of ethylene oxide. Preferred tertiary amines are R1R2R3N where
R1 is an alkyl chain of C -C2, R2 and 3 are C?
C3, or
(CH2-? CH-0)? H
where R5 is H or CH3 and x = 1-2. Amidoamines of the formula are also preferred:
O p R1 - C-NH- (CH2) n-N- (R2) 2
wherein Ri is C -C 2 alkyl; n is 2-4, preferably n is 3; R2 and R3 is C1-C4. Highly preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C-CιO oxypropylamine, N-coco-1-3-diaminopropane, cocoalkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine , coco-bis (hydroxyethyl) amine, lauryl amine propoxylated with 2 moles, propoxylated octylamine with 2 moles, laurylamidopropyldimethylamine, amidopropyldimethylamine of C-C and amidopropyldimethylamine of C Q. The most preferred amines for use in the compositions herein are 1-hexylamine , 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly suitable are n-dodecyldimethylamine and bishydroxyethylcocoalkylamine and 7-fold ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.
Conventional detergent enzymes The detergent compositions may also contain one or more enzymes that provide cleansing action and / or fabric care benefits. Said enzymes include the selected enzymes of hemicellulases, peroxidases, glucoamylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, ß-glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures from the same. A preferred combination is a detergent composition having a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase, in conjunction with one or more plant cell wall degrading enzymes. Cellulases useful in the present invention include both bacterial and fungal cellulase.
Preferably, they will have an optimum pH of between 5 and 9.5. Suitable cellulases are described in the US patent. No. 4,435,307, Bargesgoard et al., Which describe a fungal cellulase produced from Humicola insolens. Suitable cellulases are also described in GB-A-2,075,028, * GB-A-2,095,275 and DE-OS-2,247,832. Examples of these cellulases are those produced by a strain of Humicola insolens (Humicola grísea var. Thermoidea), particularly the DSM 1800 strain of Humicola. Other suitable cellulases are the cellulases originated from Humicola insolens which have a molecular weight of approximately 50 KDa, an isoelectric point of 5.5 and contain 415 amino acids; and a -43 kD endoglucanase derived from Humicola insolens DSM 1800, which exhibits cellulase activity; a preferred component of endoglucanase has the amino acid sequence described in PCT patent application No. WO 91/17243. Particularly suitable cellulases are cellulases that have color care benefits. Other suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum described in WO 94/21801, Genencor, published on September 29, 1994. Examples of these cellulases are the cellulases described in European Patent Application No. 9122879.2, filed on 6 November 1991 (Novo). The peroxidase enzymes are used in combination with oxygen sources, e.g., percarbonate, perborate, persulfate, hydrogen peroxide, etc. They are used for "solution bleaching", that is, to avoid the transfer of dyes or pigments removed from the substrates during the washing operations, to other substrates in the washing solution. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, and haloperoxidase such as chloro- and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in the PCT International Application WO89 / 099813, and in European Patent Application No. 91202882.6, filed on November 6, 1991. Other suitable oxidases are the laccase enzyme, which uses oxygen or hydrogen peroxide as the primary substrate. Said cellulases and / or peroxidases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Suitable lipase enzymes for detergent use include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, such as those described in British Patent 1,372,034. Suitable lipases include those that show a positive immunological cross-reaction with the lipase antibody, 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, Chromobacter viscosum lipases, e.g., Chromobacter viscosum var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata Japan; Chromobacter viscosum lipases from U.S. Biochemical Corp. E.U.A. and Disoynth Co., The Netherlands, and lipases ex Pseudomonas gladioli. Lipases especially suitable are lipases such as Ml Lipase and Lipomax
(Gist-Brocades) and Lipolase and Lipolase Ultra (Novo), which have been found very effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50] that can be considered as a special type of lipase, namely lipases that do not require interfacial activation. The addition of cutinases to detergent compositions has been described in, e.g., WO-A-88/09367 (Genencor). The lipases and / or cutinases are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Suitable proteases are subtilisins, which are obtained from particular strains of B. subtilis and B. licheniformis (subtilisin BPN and BPNp). A suitable protease is obtained from a strain of Bacillus, which has maximum activity across the pH range of 8 to 12, developed and sold as ESPERASER from Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 by Novo. Other suitable proteases include ALCLASER, DURAZYMR and SAVINASER from Novo and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (engineered protein from Gist-Brocades.) Proteolytic enzymes also encompass modified bacterial serine proteases such as those described in the European patent application. Serial No. 87 303761.8, filed on April 28, 1987 (in particular pages 17, 24 and 98), and which is dominated here "Protease B" and in European patent application 199,404, Venegas, published on 29 October 1986, which refers to a modified bacterial serine proteolytic enzyme, referred to herein as "protease A." What is referred to herein as "protease C", which is a variant of an alkaline serine protease from Bacillus, is more preferred. which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces asparagine in position 123, and alanine replaces threonine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published on May 16, 1991. Also included are genetically modified variants, particularly C protease. See also protease of high pH of Bacillus sp. NCIMB 40338, described in Wo 93/18140 A for Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A for Novo. When desired, a protease having decreased absorption and increased hydrolysis is available, as described in WO 95/07791 for Procter & amp;; Gamble. A recombinant trypsin-like protease for detergents suitable herein is described in WO 94/25583 for Novo. In more detail, the 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 carbonyl hydrolase precursor by substituting a different amino acid from a plurality of amino acid residues in a position in said carbonyl hydrolase equivalent at 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 numeration of the subtilisin of Bacillus amyloliquefaciens, as described in WO95 / 10591 and in the patent application of C. Ghosh, et al., "Bleachin Compositions Protease Enzymes Protease ", which has a US serial number No. 08 / 322,677, filed October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and Wo / 91/106637 and the BLAPR protease, described in WO91 / 02792. The protease enzyme can be incorporated in the compositions according to the invention at a level of 0.0001% to 2% active enzyme by weight of the composition. The enzymes mentioned can be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast. The origin can also be mesophilic or extremophilic (psychrophilic, psychrotrophic, thermophilic, barophilic, alkalophilic, acidophilic, halophilic, etc.). Purified or non-purified forms of these enzymes can be used. Mutants of natural enzymes are also included by definition. Mutants can be obtained, for example, by genetic engineering and / or protein, chemical and / or physical modifications of natural enzymes. Also the common practice is the expression of the enzyme by host organisms in which the genetic material responsible for the production of the enzyme has been cloned. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. Enzymes can be added as separate individual ingredients (pills, granules, stabilized liquids, etc., containing an enzyme) or as mixtures of two or more enzymes (eg cogranulates). Other suitable detergent ingredients that may be added are enzyme oxidation scavengers which are described in European Copending Patent Application No. 92870018.6, filed January 31, 1992. Examples of these enzyme oxidation scavengers are the ethoxylated tetraethylene polyamines. A variety of enzyme materials and means for their incorporation into synthetic detergent compositions is also disclosed in WO 9307263 A and WO 9307260 A for Genencor International, WO 8908694 A for Novo, and US Pat.
No. 3,553,139, January 5, 1971 for McCarty et al. Enzymes are also described in U.S. Pat. No. 4,101,457, Place et al., July 18, 1978, and in the US Patent. No. 4,507,219, Hughes, March 26, J5 1985. Useful enzyme materials for liquid detergent formulations, and their incorporation into these formulations, is described in US Pat. No. 4,261,868, Hora et al., April 14, 1981. Enzymes for use in detergents can be stabilized by means of various techniques. Enzyme stabilization techniques are described and are exemplified in U.S. Pat. No. 3,600,319, of August 17, 1971, Gedge et al., EP 199,405 and EP 200,586, of October 29, 1986, for Venegas. Also described are enzyme stabilization systems for example in the U.S. Patent. No. 3,519,570. A Bacillus, sp. AC13 useful for giving proteases, xylanases and cellulases in WO 9401532 A for Novo.
Benefits of color care 0 Technologies that provide a type of color care benefit can also be included. Examples of these technologies are metallocatalysts for color maintenance. These metallocatalysts are described in the copending European Patent Application No. 92870181.2.
Bleaching agent The detergent compositions of the present invention may further include bleaching agents such
* as hydrogen peroxide, PBl, PB4 and percarbonate with a particle size of 400-800 microns. These bleaching agent components can include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When present, the oxygen bleach compounds will typically be present at levels of about 1% to about 25%. The bleach agent component for use herein may be any of the bleaching agents useful for detergent compositions, including oxygen bleach, as well as others known in the art. The bleaching agent suitable for the present invention may be an activated or non-activated bleaching agent. A category of oxygen bleaching agent that can be used encompasses the percarboxylic acid or bleaching agents and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Said bleaching agents are described in the patent of E.U.A. No. 4,483,781, patent application of E.U.A. No. 740,446, European patent application No.
0,133,354 and patent of E.U.A. No. 4,412,934. Highly preferred bleaching agents also include 6- nonylamino-6-oxoperoxycaproic acid as described in the patent E.U.A. No. 4,634,551. Another category of ß-bleaching agents that can be used encompasses halogen bleaching agents. Examples of hypohalogenite bleaching agents, for example, include trichloroisocyanuric acid and the sodium and potassium dichloroisocyanurates and N-chloro and N-bromoalkanesulfonamides. Said materials are usually added to 0.5-10% by weight of the finished product, preferably 1-5% by weight. The hydrogen peroxide releasing agents can be used in combination with bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzene sulfonate (NOBS, described in US Patent 4,412,934), 3,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenolsulfonate ester (NACA-OBS, described in WO94 / 28106), which are perhydrolyzed to form a peracid
as the active bleaching species, leading to an improved bleaching effect. Also suitable activators are acylated citrate esters such as those described in co-pending European patent application No. 91870207.7. Useful whitening agents, including
Peroxyacids and bleaching systems comprising bleach activators and peroxygen bleach compounds useful in the detergent compositions according to the invention are described in the co-pending applications of applicant USSN 08 / 136,626, PCT / US95 / 07823, W095 / 27772, W095 / 27773, W095 / 27774 and W095 / 27775. Hydrogen peroxide may also be present by adding an enzyme system (i.e., an enzyme and a substrate therefor) that is capable of generating hydrogen peroxide at the beginning or during the washing and / or rinsing process. Said enzymatic systems are described in European patent application 91202655.6, filed on October 9, 1991. Metal-containing catalysts for use in bleaching compositions include cobalt-containing catalysts such as cobalt (III) pentaamineacetate salts and catalysts containing manganese such as those described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application No. 94870206.3 Other bleaching agents other than oxygen bleaching agents are also known in the art, and can be use in the present. A type of bleaching agent that is not oxygen of particular interest includes photoactivated bleaching agents such as sulfonated zinc and / or aluminum phthalocyanines. These materials can be deposited on the substrate during the washing process. After irradiating with light in the presence of oxygen,
* for example by hanging clothes to dry in daylight, sulfonated zinc phthalocyanine is activated and, as a result, the substrate is bleached. The preferred zinc phthalocyanine and a photoactivated bleaching process are described in the U.S.A. No. 4,033,718. Typically, the detergent compositions will contain from about 0.025% to about 0.25% by weight of sulfonated zinc phthalocyanine.
Metering System of Detergency The compositions according to the present invention may further comprise a detergency builder system. Any conventional builder system is suitable for use herein, including aluminosilicate materials, silicates, polycarboxylates, alkyl- or alkenylsuccinic acids and fatty acids, materials such as ethylenediamine tetraacetate, diethylenetriamine pentamethylene-acetate or, metal ion sequestrants such as aminopolyphosphonates, particularly ethylenediaminetetra-methylene phosphonic acid and diethylenetriaminepentamethylene phosphonic acid. Phosphate builders can also be used in the present invention. Suitable builders can be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, most particularly a synthetic hydrated zeolite such as hydrated zeolite A, X, B, HS or MAP. "Other inorganic detergent builder material
Suitable is the stratified silicate, e.g., SKS-6 (Hoechst).
SKS-6 is a crystalline layered silicate consisting of sodium silicate (Na2Si2? 5). Suitable polycarboxylates contain a carboxyl group and include lactic acid, glycolic acid and ether derivatives thereof, such as those described in the patents
Belgian Nos. 831,368, 821,369 and 821,370. Polycarboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ether carboxylates described in the German patent 2,446,686 and
2,446,687 and in the US patent. No. 3,935,257, and the sulfinylcarboxylates described in Belgian Patent No. 840,623.
Polycarboxylates containing three carboxyl groups 0 include, in particular, the water-soluble citrates, aconitrates and citraconates, as well as the succinate derivatives such as the carboxymethyloxysuccinates described in British Patent No. 1,379,241, the lactoxysuccinates described in the Dutch application 7205873 , and oxypolycarboxylate materials such as 2-oxa-l, l-3-propane tricarboxylates described in British Patent No. 1,387,447.
Polycarboxylates containing four carboxyl groups include the oxydisuccinates described in the patent
British No. 1,261,829, 1, 1, 2, 2-ethano-tetracarboxylates, 1, 1, 3, 3 -propane-tetracarboxylates and 1, 1, 2, 3-propane tetracarboxylates. Polycarboxylates containing sulfo substituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and
1,398,422, and in the patent of E.U.A. No. 3,936,448, as well as the sulfonated pyrolysed citrates described in British Patent No. 1,082,179, while polycarboxylates containing phosphone substituents are described in the patent.
British No. 1,439,000. The alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarboxylates, cyclopentadienidapentacarboxylates, 2, 3, 4, 5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydrofuran-cis-dicarboxylates, 2.2, 5, 5-tetrahydrofuran-tetracarboxylates, 1, 2, 3, 4, 5, 6-hexane-hexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melific acid, pyromellitic acid and the phthalic acid derivatives described in British Patent No. 1,425,343. Of the above, preferred polycarboxylates are hydroxycarboxylates containing up to three carboxyl groups per molecule, most particularly citrates. Preferred builder systems for use in the present compositions include a mixture of a water-insoluble aluminosilicate builder such as zeolite A, or a layered silicate (SKS-6) * and a soluble carboxylate chelating agent. water such as citric acid. The preferred detergency builders for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates. A suitable chelator for inclusion in the present compositions according to the invention, is ethylenediamine-NN '-disuccinic acid (EDDS), or the salts of alkali metal, alkaline earth metal, ammonium or substituted ammonium, or mixtures thereof . The preferred EDDS compounds are the free acid form and its sodium or magnesium salts. Examples of said preferred sodium salts of EDDS include a2EDDS and Na4EDDS. Examples of said preferred magnesium salts of EDDS include MgEDDS and Mg2 EDDS. Magnesium salts are more preferred for inclusion in the compositions according to the invention. Preferred builder systems include a mixture of a water insoluble aluminosilicate improver such as Zeolite A, and a water soluble carboxylate chelating agent such as citric acid. Other detergency builder materials that can form part of the builder system for use in granular compositions include inorganic materials such as carbonates, bicarbonates and alkali metal silicates, and organic materials such as phosphonates, aminopolyalkylene phosphonates and aminopolycarboxylates. Other suitable water-soluble organic salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from each other by not more than two carbon atoms. Polymers of this type are described in GB-A-1, 596, 756. Examples of such salts are the polyacrylates of PM 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from 20,000 to 70,000, especially about 40,000. Builder salts are usually included in amounts of 5% to 80% by weight of the composition, preferably 10% to 70%, and most commonly 30% to 60% by weight.
Foam suppressor Another optional ingredient is a foam suppressor, exemplified by silicones and silica-silicone blends. Silicones can be represented in general as alkylated polysiloxane materials, while silica is used in finely divided forms exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particles in which the suds suppressor is conveniently incorporated in a releasable manner in a vehicle that is impermeable to detergent, substantially non-surfactant, dispersible in water. Alternatively, the foam suppressant can be dissolved or dispersed in a liquid vehicle and applied by spraying on one or more of the other components. A preferred foam controller silicone agent is described in the U.S. Patent. 3 933 672 of Bartollota et al. Other particularly preferred suds suppressors are self-emulsifying silicone foam suppressors, described in the German Patent Application DTOS 2 646 126, published on April 28, 1977. An example of such compounds is DC-544, commercially available from Dow Corning, which is a copolymer of siloxane and glycol. An especially preferred foam controlling agent is the foam suppressor system comprising a mixture of silicone oils and 2-alkyl alkanols. A suitable 2-alkyl-alkanol is 2-butyl-octanol, which is commercially available under the brand name Isofol 12 R. This foam suppressor system is described in co-pending European Patent Application No. 92870174.7, filed on November 10, 1992. Especially preferred silicone foam controlling agents are described in co-pending European Patent Application No. 92201649.8. Said compositions may comprise a silica / silica mixture in combination with fumed non-porous silica, such as Aerosil. The foam suppressors described above are normally employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
Others Other components used in detergent compositions, such as soil suspending agents, soil removal agents, optical brighteners, abrasives, bactericides, tarnish inhibitors, coloring agents and / or encapsulated or unencapsulated perfumes may be employed. Particularly suitable encapsulating materials are water-soluble capsules consisting of a polysaccharide matrix and polyhydroxy compounds such as those described in GB 1,464,616. Other suitable water-soluble encapsulating materials comprise dextrins derived from acid esters of non-gelatinized starch of substituted dicarboxylic acids such as those described in the U.S. Patent. 3,455,838. These acid ester dextrins are preferably prepared from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. Suitable examples of such encapsulating materials include N-Lok, manufactured by National Starch. The N-Lok encapsulating material consists of a modified corn starch and glucose. The starch is modified by adding monofunctional substituted groups such as octenylsuccinic acid anhydride. Suitable suspension and anti-redeposition agents for the present include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or co-polymeric polycarboxylic acids or their salts. Polymers of this type include the polyacrylates and copolymers of maleic anhydride and acrylic acid mentioned above as detergency builders, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, the maleic anhydride constituting at least 20 mole percent of the copolymer . These materials are normally used at levels of 0.5% to 10% by weight, preferably 0.75% to 8%, most preferably 1% to 6% by weight of the composition. Preferred optical brighteners are anionic in nature, examples of which are 4,4'-bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2: 2'-disodium disulfonate, 4,4'-bis- (2 -morpholino-4-anilino-s-triazin-6-ylamino-stilbene-2: 2'-disodium disulfonate, 4,4'-bis- (2, 4-dianilino-s-triazin-6-ylamino) stilbene 2: 2'-disodium disulfonate, 4 ', 4"-bis- (2,4-dianilino-s-triazin-6-ylamino) stilben-2-sulfonate monosodium, 4,4'-bis- (2 -anilino-4- (N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) stilbene-2,2'-disodium disulfonate, 4,4'-bis- (4-phenyl-2, 1,3-triazol-2-yl) stilbene-2, 2'-disodium disulfonate, 4,4 '-bis- (2-anilino-4- (l-methyl-2-hydroxyethylamino) -s-triazine-6 -ylamino) stilbene-2, 2'-disodium disulfonate, 2- (stilbe-4"- (naphtho-1 ', 2': 4, 5) -1, 2,3-triazole-2" -sulfonate of sodium and 4,4'-bis (2-sulphotrisyl) biphenyl The highly preferred brighteners are the specific brighteners of co-pending European Patent Application No. 95201943.8. Other useful polymeric materials are polyethylene glycols, particularly those of molecular weight of 1000-10000, more particularly 2000 to 8000, and most preferably about 4000. These are used at levels of 0.20% to 5%, preferably from 0.25% to 2.5% in weigh. These polymers and the homo- or co-polymeric polycarboxylate salts mentioned above are valuable for improving the maintenance of whiteness, deposition of cloth ash, and cleaning action on clay, proteinaceous and oxidizable soils, in the presence of metal impurities. of Transition. The soil removal agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid with ethylene glycol and / or propylene glycol units in various arrangements. Examples of such polymers are described in the U.S. Patents. commonly assigned Nos. 4116885 and 4711730 and published European Patent Application No. 0 272 033. A particular preferred polymer according to EP-A-0 272 033, has the formula:
(CH3 (PEG) 43) 0.75 (POH) or .25 [T-PO) 2.8 (T-PEG) 0.4] T (PO-H) 0.25"((PEG) 43CH3) o.75 where PEG is - ( OC2H4) 0-, PO is (OC3HgO) and T is (pcOCgH4CO) Modified polyethers are also very useful as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, the end groups consist mainly of of sulfobenzoate and secondarily of monoesters of ethylene glycol and / or propanediol The objective is to obtain a polymer blocked at both ends by sulfobenzoate groups, "mainly", in the present context means that most of said copolymers will be blocked at their ends by groups However, some copolymers will be little more than completely blocked, and therefore, their end groups may consist of monoester of ethylene glycol and / or 1,2-propanediol, so they consist "secondarily" of said species. selected polyesters of l present contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of 1,2-propanediol, about 10% by weight of ethylene glycol, about 13% by weight of dimethyl sulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and they have
- a molecular weight of approximately 3,000. The polyesters and their method of preparation are described in detail in EPA 311 342. It is well known in the art that free chlorine in the tap water rapidly deactivates the enzymes comprised in the detergent compositions. Therefore, using a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine at a level above 0.1% by weight of the total composition, in the formulas will provide improved stability through the washing of the amylases enzymes. Compositions comprising a chlorine scavenger are described in European Patent Application No. 29870018.6, filed on January 31, 1992. Alkoxylated polycarboxylates such as those prepared from polyacrylates, are useful herein to provide for a stirring action. of additional fat. These materials are described in WO 91/08281 and PCT 90/01815 on pages 4 et seq., Incorporated herein by reference. Chemically, these materials comprise polyacrylates having an ethoxy side chain for every 7-8 acrylate units. The side chains are of the formula (CH2CH2?) M (CH2) nCH3 'where m is 2-3 and n is 6-12. The side chains are linked by ester linkage to the polyacrylate backbone to give a "comb" type polymer structure. The molecular weight may vary, but typically ranges from about 2000 to about 50,000. These alkoxylated polycarboxylates can comprise from about 0.05% to about 10% by weight of the compositions herein.
Softening agents Fabric softening agents may also be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be of inorganic or organic type. The inorganic softening agents are exemplified by the smectite clays described in GB-A-1 400 898 and in USP 5,019,292. Organic fabric softening agents include the water-soluble tertiary amines as described in GB-A1 514 276 and EP-BO 011 340, and their combination with quaternary monoammonium salts of 12 ~ c14 are described in EP-B-0 026 527 and EP-B-0 026 528 and di-long chain amides, as described in EP-B-0 242 919. Other useful organic ingredients of fabric softener systems include high molecular weight polyethylene oxide materials as is described in EP-A-0 299 575 and 0 313 146. Smectite clay levels are usually in the range of 2% to 20%, preferably 5% to 15% by weight, adding the material as a mixed component dry to the rest of the formulation. Organic fabric softening agents such as water-insoluble tertiary amines or long-chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually 1% to 3% by weight, while the materials of High molecular weight polyethylene oxide and water soluble cationic materials are added at levels from 0.1% to 2%, usually from 0.15% to 1.5% by weight.
These materials are usually added to the spray-dried portion of the composition, although in some cases it may be more convenient to add them as dry mixed particles, or sprinkle them as molten liquid over other solid components of the composition.
Dispersants The detergent composition of the present invention may also contain dispersants. Suitable organic water-soluble salts are homo- or copolymeric acids or their salts, in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by not more than two carbon atoms. Polymers of that type are described in GB-A-1, 596, 756. Examples of such salts are polysaccharides of MW 2000-5000 and their copolymers with maleic anhydride, said copolymers have a molecular weight of from
1, 000 to 100, 000. Especially, the acrylate-methacrylate copolymer such as 480N having a molecular weight of 4000, at a level of 0.5-20% by weight in the composition, can be added in the detergent compositions of the present invention. The compositions of the invention may contain a lime soap peptide compound preferably having a lime soap dispersion power.
(LSDP), as defined hereinafter, of no more than 8, preferably no more than 7, most preferably no more than 6. The lime soap peptidizer compound is preferably present at a level of 0% to 20% by weight. weight. A numerical measurement of the effectiveness of a lime soap peptide is given by the lime soap dispersion power (LSDP), which is determined using the lime soap dispersant test as described in an article by H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., Volume 27, p. 88-90, (1950). This lime soap dispersion test method is widely used by practitioners in this technique referred to, for example, in the following articles; W.N. Linfield, Surfactant Science Series, Volume 7, p. 3, W.N. Linfield, Tenside surf. det. , volume 27, pgs. 159-163, (1990); and M.N. Linfield, Tenside surf. det., volume 27, pgs. 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, p. 71-73, (1989). The LSDP is the ratio of the percentage by weight of dispersing agent to sodium oleate required to disperse the lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with an equivalent hardness of 333 ppm of CaCo3 (Ca: Mg = 3.2). Surfactants having an adequate lime soap peptide capacity will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols. Exemplary surfactants having an LSDP of not more than 8 to be used in accordance with the present invention include dimethylamine oxide of C? G-C? , C 2 -C 2 alkylcyl sulfates with an average degree of ethoxylation of 1-5, particularly in C 2 -C 5 alkylcytoisulfate surfactant with an ethoxylation degree of approximately 3 (LSDP = 4) and ethoxylated C 14 alcohols -C15 with an average degree of ethoxylation of 12 (LSDP = 6) or 30, sold under the trade names Lutensol A012 and Litensol A030 respectively, by BASF GmbH. Suitable polymeric lime soap peptides for use herein are described in an article by M.K. Nagarajan, W.F. Masler, which is in Cosmetics and Toiletries, volume 104, pgs. 71-73, (1989). Lime soap peptidizers can also be used as hydrophobic whiteners such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate, 4- [N-decanoyl-6-] aminohexanoyl] -benzenesulfonate and mixtures thereof; and nonanoyloxybenzenesulfonate together with hydrophilic / hydrophobic bleach formulations.
Inhibition of dye transfer The detergent compositions of the present invention may also include compounds to inhibit the transfer, from one fabric to another, of the solubilized and suspended dyes encountered during washing operations including colored fabrics.
Polymeric Dye Transfer Inhibitory Agents The detergent compositions according to the present invention also comprise from 0.001% to 10%, preferably from 0.01% to 2%, most preferably from 0.05% to 1% by weight of polymeric transfer inhibiting agents. Colorant. Said polymeric dye transfer inhibiting agents are normally incorporated in the detergent compositions to inhibit the transfer of dyes from the colored fabrics onto other fabrics washed therewith. These polymers have the ability to form complexes with, or adsorb to, the fugitive dyes that come out of the colored fabrics, before the dyes have the opportunity to become attached to other articles in the wash. Polymeric dye transfer inhibiting agents which are especially suitable are polymers of polyamine N-oxide, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polymers of polyvinylpyrrolidone, polyvinyloxazolidones and polyvinylimidazoles or mixtures thereof. The addition of said polymers also improves the performance of the enzymes according to the invention.
a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use contain units having the following structural formula:
P I (I) Ax [R
wherein P is a polymerizable unit, to which the group R-N-0 may be attached, or wherein the group R-N-0 forms part of the polymerizable unit, or a combination of both.
0 0 P if A is NC, CO, C, -0-, -S-, -N-; x is 0 or 1;
R are aliphatic, aliphatic ethoxylated, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the group N-0 may be attached, or where the nitrogen of the group N-O is part of these groups. The N-O group can be represented by the following general structures:
O 0 i i (Rl) x - N- (R2) y = N- (Rl) x (R3) z
wherein R 1, R 2 and R 3 are aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof, xy / oyo / yz is 0 or 1, and wherein the nitrogen of the NO group may be attached, or wherein the nitrogen of the group is NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be attached to the polymeric backbone, or a combination of both. Suitable polyamine N-oxides, wherein the N-O group forms part of the polymerizable unit, comprise polyamine N-oxides wherein R is selected from aliphatic, aromatic, alicyclic or heterocyclic groups. One class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the NO group is part of the R group. The preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine , pyrrole, imidazole, pyrrolidine, piperazine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides wherein the nitrogen of the NO group is attached to the group R. Other suitable N-oxides of polyamine are the polyamine oxides to which the group is attached NO to the polymerizable unit. A preferred class of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the functional group is NOT part of said group R Examples of these classes are polyamine oxides wherein R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides are the polyamine oxides having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group wherein the nitrogen of the functional group is NOT attached to said R groups. these classes are the polyamine oxides wherein the R groups can be aromatic such as phenyl. Any polymer skeleton can be used, provided that the amine oxide polymer formed is soluble in water and has dye transfer inhibiting properties. Examples of suitable polymeric backbones are polyvinyls, polyalkylenes, polyesters, polyethers, polyamides, polyimides, polyacrylates and mixtures thereof. The amine N-oxide polymers of the present invention typically have a ratio of amine to amine N-oxide from 10: 1 to 1: 1000000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by appropriate copolymerization or by an appropriate degree of N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1000000. Most preferably from 1: 4 to 1: 000000, most preferably still from 1: 7 to 1: 1000000. The polymers of the present invention actually encompass random or block copolymers wherein one type of monomer is an amine N-oxide and the other type of monomer is either an amine N-oxide or not.
The amine oxide unit of the polyamine N-oxides have a pKa < 10, preferably pKa < 7, most preferably pKa < 6. Polyamine oxides can be obtained in almost any degree of polymerization. The degree of polymerization is not critical, as long as the material has the desired water solubility and the desired dye suspension power. Typically, the average molecular weight is within the range of 500 to 1,000,000; preferably from 1,000 to 50,000, most preferably from 2,000 to 30,000, most preferably even from 3,000 to 20,000.
b) Copolymers of N-vinylpyrrolidone and N-vinylimidazole The polymers of N-vinylimidazole and N-vinylpyrrolidone used in the present invention have an average molecular weight scale of 5,000 to 1,000,000, preferably 20,000 to 200,000. Highly preferred polymers for use in detergent compositions according to the present invention comprise a polymer selected from N-vinylimidazole-N-vinylpyrrolidone copolymers, wherein said polymer has an average molecular weight scale of from 5,000 to 50,000, most preferably from 8,000 to 30,000, most preferably even 10,000 to 20,000. The average molecular weight scale was determined by light scattering, as described by Barth H. G. and Mays J. W., Chemical Analysis Vol 113, "Modern Methods of Polymer Characterization". The highly preferred N-vinylimidazole and N-vinylpyrrolidone copolymers have an average molecular weight scale of from 5,000 to 50,000, preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000. The copolymers of N-vinylimidazole and N-vinylpyrrolidone characterized by having said average molecular weight scale, provide excellent dye transfer inhibiting properties, while not adversely affecting the cleaning performance of the detergent compositions formulated therewith. The N-vinylimidazole-N-vinylpyrrolidone copolymer of the present invention has a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, most preferably from 0.8 to 0.3, most preferably from 0.6 to 0.4.
c) Polyvinylpyrrolidone The detergent compositions of the present invention may also use polyvinylpyrrolidone ("PVP"), which has an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, preferably from about 5,000 to about 50,000. , and most preferably from about 5,000 to about 15,000. Suitable polyvinyl pyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the trademarks PVP K-15 (molecular weight of 10,000 with viscosity), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000), and PVP K-90 (average molecular weight of 360,000). Other suitable polyvinyl pyrrolidones which are commercially available from BASF Corporation, include Sokalan HP 165 and Sokalan HP 12; the polyvinylpyrrolidones are known to those skilled in the detergent field (see, for example, EP-A-262,897 and EP-A256, 696).
d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as a polymeric dye transfer inhibiting agent. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
e) Polyvinylimidazole The detergent compositions of the present invention can also use polyvinylimidazole as a polymeric dye transfer inhibiting agent. Said polyvinylimidazoles have an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, preferably from about 5,000 to about 50,000, and most preferably from about 5,000 to about 15,000.
f) Interlaced polymers Interlaced polymers are polymers whose skeleton is interconnected to a certain degree; these links can be of a chemical or physical nature, possibly with active groups in the skeleton or on branches; crosslinked polymers have been described in the Journal of Polymer Science, vol. 22 p. 1035-1039. In one embodiment, the entangled polymers are made in such a way that they form a rigid three-dimensional structure, which can trap dyes in the pores formed by the three-dimensional structure. In another embodiment, the entangled polymers trap the dyes by swelling. Crosslinked polymers are described in co-pending patent application 94870213.9.
Washing Method The compositions of the invention can be used essentially in any washing or cleaning method, including soaking methods, pretreatment methods and methods with rinsing steps for which a separate rinse aid composition can be added. The process described herein comprises contacting fabrics with a washing solution, in the usual manner and exemplified below. The process of the invention is conveniently carried out in the course of the cleaning process. The cleaning method is preferably carried out from 5 ° C to 95 ° C.
° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 11. The following examples exemplify the compositions of the present invention, but do not necessarily limit or otherwise defend the scope of the invention. In detergent compositions, the enzyme levels are expressed in pure enzyme by weight of the total composition, and unless otherwise specified, the detergent ingredients are expressed by weight of the total composition. The identifications of abbreviated components have the following meanings.
LAS: C12 linear sodium alkylbenzenesulfonate TAS: Sodium tallow alkyl sulfate CXYAS: 1X ^ C sodium alkylsulphate ?? 25EY: A predominantly linear primary alcohol of C12-C15 condensed with an average of Y moles of ethylene oxide CXYEZ A predominantly linear primary alcohol of C? -C? condensed with an average of Z moles of ethylene oxide XYEZS Sodium alkylsulfate of C -C? condensed with an average of Z moles of ethylene oxide per mole QAS R2N + (CH3) 2 (C2H40H) with R2 = C12-C1 Linear sodium alkylcarboxylate soap derived from an 80/20 mixture of tallow and coconut oils TFAA Alquil -N-methylglucamide from Cig-Ci. TPKFA C12-C complete cut crowned fatty acids 4. DEQA Di- (tallowoxyethyl) dimethylammonium chloride. SDASA Ratio of 1: 2 stearyldimethyl amine: triple-compressed stearic acid. Neodol 45-13 Ethoxylated C14-C15 linear primary alcohol, sold by Shell Chemical CO. Silicato amorphous sodium silicate (Si? 2 ratio: Na20 = 2.0).
NaSKS-6 Crystalline layered silicate of the formula delta-Na2SÍ2? 5. Carbonate Anhydrous sodium carbonate with a particle size between 200μm and 900μm. Bicarbonate Anhydrous sodium bicarbonate with a particle size between 400μm and 1200μm. STPP Anhydrous sodium tripolyphosphate. MA / AA Copolymer of maleic / acrylic acid at 1: 4, an average molecular weight of approximately 80,000. Polyacrylate Polyacrylate homopolymer with average molecular weight of 8,000, sold under the trade name PA30 by BASF GmbH. Zeolite A Hydrated sodium aluminosilicate of the formula Nai2 (A102SiO2) 12.27H20 having a primary particle size in the range of 0.1 to 10 microns. Citrate trisodium citrate dihydrate with activity of 86.4%, with a particle size distribution between 425 μm and 850 μm. Citrus anhydrous citric acid.
PBl: Anhydrous perborate sodium monohydrate bleach, empirical formula NaB? 2-H2? 2- PB4: Sodium perborate anhydrous tetrahydrate Percarbonate: Anhydrous sodium percarbonate bleach of the empirical formula 2Na2C? 3.3H2? 2. TAED: Tetraacetylethylenediamine. NOBS: Nonanoiloxybenzenesulfonate in the form of sodium salt. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin soluble polymer. Antibody: Anti-Termamyl ERT 860418 (500/150 μl) and anti-BAN PPY 1747 (200 μl), available from Novo Nordisk A / S. Amylase: Amylolytic enzyme sold under the -p brand Purafact Ox Am, described in WO 94/18314, and WO96 / 05295, sold by Genencor; Termamil R, BanR, -p and Duramil, all available from Novo Nordisk A / S and those described in W095 / 26397. Protease: Proteolytic enzyme sold under the trademarks Savinase, Alcalase, Durazym of Novo Nordisk A / S, Maxacal, Maxapem, sold by Gist-Brocades and the proteases described in patents WO91 / 06637 and / or WO95 / 10591 and / or EP 251 446. Lipase: Lipolytic enzyme sold under the Lipolase brand, Lipolase Ultra by Novo Nordisk A / S. Cellulase: Cellulite enzyme sold under the trademark Carezyme, Celluzyme and / or Endolase by Novo Nordisk A / S. CMC: Sodium carboxymethylcellulose. HEDP: 1, 1-hydroxyethanediphosphonic acid
DETPMP: Diethylenetriaminpenta (methylene phosphonic acid), sold by Monsanto under the brand name Dequest 2060. PVNO: N-oxide of poly (4-vinylpyridine).
PVPVI: Poly (4-vinylpyridine) N-oxide / vinylimidazole copolymer and vinylpyrrolidone. Polisher 1: 4,4 '.- bis (2-sulphotrisyl) biphenyl sodium. Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) stilben-2: 2'-disodium disulphonate. Silicone antifoam: Polydimethylsiloxane foam controller with siloxane-oxyalkylene copolymer as a dispersing agent with a ratio of said foam controller to said dispersing agent from 10: 1 to 100: 1. Spupresor granul ar 12% silicone / silica, 18% stearic alcohol foam, 70% starch in granular form. SRP 1 Esters blocked at the ends of sulfobenzoyl with skeleton of oxyethyleneoxy and teraphthaloyl. SRP 2 Short block polymer of poly (1, 2-propyleneteraphthalate) diethoxylate. Sulfate Anhydrous sodium sulfate. HMWPEO High molecular weight polyethylene oxide. PEG Polyethylene glycol. Encapsulated particle Fragrance-insoluble fragrance dispensing technology using Zeolite 13x, perfume and a dextrose / glycerin agglomerating binder.
EXAMPLE 1
Production of antibodies Chickens were injected into the breast muscle with 1 ml of a 1 mg / ml Termamyl or Ban emulsion. The amylolytic emulsion was prepared with adjuvants completed from
Freund (Freund and McDermott, 1942; Freund 1956) by mixing an equal amount of the TermanylT solution? Y
Ban (2mg / ml) and Freund's complete adjuvant. The immunization schedule was completed with injections using an incomplete Freund's adjuvant and after a period of 4 weeks, the eggs were harvested for one week. The extraction of the antibodies from the egg yolks was done according to the Polson extraction method, as described in Immunological Investigation 19, 1990, p. 253-258.
Enzymatic inactivation of amylase A supply solution of Termamyl R or BanR was prepared in a Tris buffer (Tris 5x10"2M, NaCl 25 mM, pH = 8) at a concentration of 0.005% of active enzyme.A buffer of phosphate (KH2PO4 0.05M) , pH 6.8) contained the antibody (0.28 mg / ml) Interaction between the amylolytic enzyme (final concentration of 0.004%) and the antibody, was carried out in commercially available detergent solutions comprising liquid Ariel (0.8% in tap water, pH 8.5) and Ariel Color Futur (0.8% in tap water, pH 9.5) for 15 minutes at 40 ° C. The amylolytic residual activity was measured, and in the course of 5 minutes, the enzymatic activity of the amylase »5 It was blocked rightly.
EXAMPLE 2
The following laundry detergent compositions or detergents according to the invention were prepared:
I II III IV V VI
LAS 8.0 8.0 8.0 8.0 8.0 8.0 C25E3 3.4 3.4 3.4 3.4 3.4 3.4 5 QAS - 0.8 0.8 - 0.8 0.8 Zeolite A 18.1 18.1 18.1 18.1 18.1 18.1 18.1 Carbonate 13.0 13.0 13.0 27.0 27.0 27.0 Silicate 1.4 1.4 1.4 3.0 3.0 3.0 Sulfate 26.1 26.1 26.1 26.1 26.1 26.1 0 PB4 9.0 9.0 9.0 9.0 9.0 9.0 TAED 1.5 1.5 1.5 1.5 1.5 1.5 DETPMP 0.25 0.25 0.25 0.25 0.25 0.25 HEDP 0.3 0.3 0.3 0.3 0.3 0.3 Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026 5 Amylase 0.002 0.05 0.0009 0.0003 0.0009 0.01 Antibody 0.01 0.5 0.005 0.0001 0.05 0.09 EXAMPLE 2 (CONTINUED)
MA / AA 0.3 0.3 0.3 0.3 0.3 0.3 CMC 0.2 0.2 0.2 0.2 0.2 0.2 Brightener 15 15 15 15 15 15 photoactivated (ppm) Brightener 0.09 0.09 0.09 0.09 0.09 0.09
Perfume 0.3 0.3 0.3 0.3 0.3 0.3 Antifoaming 0.5 0.5 0.5 0.5 0.5 0.5 silicone Miscellaneous / secondary ingredients for 100% Density in 850 850 850 850 850 850 g / liter
EXAMPLE 3
The following granular laundry detergent compositions with overall density of 750 g / liter were prepared according to the invention:
I II III
LAS 5.25 5.61 4.76 TAS 1.25 1.86 1.57 C45AS - 2.24 3.89
C25AE3S - 0.76 1.18
C45E7 3.25 _ - 5.0
C25E3 - 5.5 EXAMPLE 3 (CONTINUED)
QAS 0.8 2.0 2.0
STPP 19.7 - -Zeolite A - 19.5 19.5
NaSKS-6 / citric acid (79:21) - 10.6 10.6
Carbonate 6.1 21.4 21.4
Bicarbonate - 2.0 2.0
Silicate 6.8 - Sodium sulfate 39.8 - 14.3
PB4 5.0 12.7 - TAED 0.5 3.1 - DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3 Antibody 0.0009 0.005 0.09
Protease 0.0026 0.0085 0.045
Lipasa 0.003 0.003 0.003
Cellulase 0.00064 0.00064 0.00064
Amylase 0.0002 0.0008 0.005 MA / AA 0.8 1.6 1.6
CMC 0.2 0.4 0.4
Photoactivated bleach (ppm) 15 27 27
Polisher 1 0.08 0.19 0.19
Polisher 2 - 0.04 0.04 Encapsulated perfume particles 00..33 0.3 0.3
Silicone antifoam 0.5 2.4 2.4
Secondary ingredients / miscellaneous for 100- EXAMPLE 4
The following detergent formulations were prepared, in accordance with the present invention, wherein I is a phosphorus-containing detergent composition, II is a detergent composition containing zeolite and III is a compact detergent composition:
II III Blown powder STPP 24.0 - 24.0 Zeolite A - 24.0 - C45AS 9.0 6.0 13.0 MA / AA 2.0 4.0 2.0 LAS 6.0 8.0 11.0 TAS 2.0 - - Silicate 7.0 3.0 3.0 CMC 1.0 1.0 0.5 Brightener 2 0.2 0.2 0.2 Soap 1.0 1.0 1.0 DETPMP 0.4 0.4 0.2 Spray C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicon defoamer 0.3 0.3 0.3 Perfume 0.3 0.3 0.3 EXAMPLE 4 (CONTINUED)
dry carbides 6.0 13.0 15.0 PB4 18.0 18.0 10.0 PBl 4.0 4.0 0 TAED 3.0 3.0 1.0
Photoactivated bleach 0.02 0.02 0.02 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.002 0.0004 0.01 Antibody 0.007 0.005 0.1
Sodium sulphate mixed 3.0 3.0 5.0 Dry rest (humidity e 100.0 100.0 100.0 miscellaneous ingredients) Density (g / liter) 630 670 670
EXAMPLE 5
The following detergent formulations that do not contain bleach, of particular use in washing color laundry, were prepared according to the present invention:
I II III blown Zeolite A 15.0 15.0 Sodium sulphate 0.0 5.0 LAS 3.0 3.0 DETPMP 0.4 0.5 CMC 0.4 0.4 MA / AA 4.0 4.0 Agglomerate C45AS - 11.0 LAS 6.0 5.0 TAS 3.0 2.0 S Siilliiccaattoo 4 4..00 4.0 Zeolite A 10.0 15.0 13.0 CMC - 0.5 MA / AA - 2.0 Carbonate 9.0 7.0 7.0 Spray Perfume 0.3 0.3 0.5 EXAMPLE 5 (CONTINUED)
C45E7 4.0 4.0 4.0 C25E3 2.0 2.0 2.0 dry values MA / AA - - 3.0 NaSKS-6 - - 12.0 Citrate 10.0 - 8.0 Bicarbonate 7.0 3.0 5.0 Carbonate 8.0 5.0 7.0 PVPVI / PVNO 0.5 0.5 0.5 Protease 0.026 0.016 0.047 Lipase 0.009 0.009 0.009 Amylase 0.01 0.005 0.0003 Cellulase 0.004 0.004 0.004 Antibody 0.1 0.05 0.001
Silicone antifoam 5.0 5.0 5.0 dry ingredients Sodium sulfate 0.0 9.0 0.0
Remainder (humidity e 100.0 100.0 100.0 miscellaneous ingredients) Density (g / liter) 700 700 700
EXAMPLE 6
The following detergent formulations were prepared, in accordance with the present invention:
I II III IV
LAS 20.0 14.0 24.0 22.0 QAS 0.7 1.0 - 0.7 TFAA - 1.0 - - 10 C25E5 / C45E7 - 2.0 - 0.5 C45E3S - 2.5 - - STPP 30.0 18.0 30.0 22.0 Silicate 9.0 5.0 10.0 8.0 Carbonate 13.0 7.5 - 5.0
Bicarbonate - 7.5 - - DETPMP 0.7 1.0 - - SRP 1 0.3 0.2 - 0.1 MA / AA 2.0 1.5 2.0 1.0 CMC 0.8 0.4 0.4 0.2
Protease 0 .008 0.01 0.026 0.026 Amylase 0 .004 0.0003 0.002 0.007 Lipase 0 .004 0.002 0.004 0.002 Cellulase 0. 0004 0.0001 - - Antibody 0 .01 0.005 0.01 0.08 5 Whitener 70 45 - 10 ppm photoactivated (ppm) EXAMPLE 6 ( CONTINUATION)
Rinse aid 1 0.2 0.2 0.08 0.2
PBl 6.0 2.0 NOBS 2.0 1.0 Rest (humidity e 100 100 100 100 miscellaneous ingredients)
EXAMPLE 7
The following detergent formulations were prepared, in accordance with the present invention:
II III IV Blown powder Zeolite A 30.0 22.0 6.0 6.7 Na SKS-6 - - - 3.3 Polycarboxylate - - - 7.1
Sodium Sulfate 19.0 5.0 7.0 - MA / AA 3.0 3.0 6.0 - LAS 14.0 12.0 22.0 21.5 C45AS 8.0 7.0 7.0 5.5
Surfactant _ _ _ 1.0 Cationic Silicate - 1.0 5.0 11.4 Soap - - 2.0 - Brightener 1 0.2 0.2 0.2 _ EXAMPLE 7 (CONTINUED)
Carbonate 8.0 16.0 20.0 10.0 DETPMP - 0.4 0.4 - Spray C45E7 1.0 1.0 1.0 3.2
Dry Additives PVPVI / PVNO 0.5 0.5 0.5 - Antibody 0.1 0.005 0.001 0.1 Protease 0.052 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.009 0.09 0.12
Sodium Sulfate - 6.0 - for the rest
Rest (humidity e 100 100 100 100 miscellaneous ingredients)
EXAMPLE 8
The following high density and bleach-containing detergent formulations were prepared according to the present invention:
II III
Blown powder Zeolite A 15.0 15.0 15.0 Sodium sulphate 0.0 5.0 0.0 LAS 3.0 3.0 3.0 QAS - 1.5 1.5 DETPMP 0.4 0.4 0.4 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0
Agglomerates LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 Silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Carbonate 8.0 8.0 4.0
Spray Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 - _ EXAMPLE 8 (CONTINUED) Dry Additives Citrate 5.0 - 2.0
* Bicarbonate - 3.0 - * 5 Carbonate 8.0 15.0 10.0 TAED 6.0 2.0 5.0 PBl 14.0 7.0 10.0 Polyethylene oxide with - - 0.2 MW of 5,000,000 10 Clay bentonite - - 10.0 Antibody 0.07 0.03 0.00 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.02 0.005 0.000
Celulasa 0.004 0.004 0.004
Silicone antifoam 5.0 5.0 5.0 Dry additives Sodium sulfate 0.0 3.0 0.0
Remainder (humidity and ingredients 20 (miscellaneous) 100.0 100.0 100.0
Density (g / liter) 850 850 850
EXAMPLE 9
The following high density detergent formulations were prepared according to the present invention:
II Agglomerate C45AS 11.0 14.0 Zeolite A 15.0 6.0 Carbonate 4.0 8.0 MA / AA 4.0 2.0 CMC 0.5 0.5 DETPMP 0.4 0.4 Aspersion C25E5 5.0 5.0 Perfume 0.5 0.5 Dry additives HEDP 0.5 0.3 SKS 6 13.0 10.0 Citrate 3.0 1.0 TAED 5.0 7.0 Percarbonate 20.0 20.0 SRP 1 0.3 0.3 Antibody 0.5 0.03 Protease 0.014 0.014 EXAMPLE 9 (CONTINUED)
Lipase 0.009 0.009 Cellulase 0.001 0.001 Amylase 0.05 0.005 Silicone antifoam 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Rest (moisture and ingredients 100 100 miscellaneous) Density (g / liter) 850 850
EXAMPLE 10
The following granular detergent formulations were prepared according to the present invention:
I II III IV V
LAS 21.0 25.0 18.0 18.0 - Coco-AS of C12-14 - - - - 21.9
AE3S - - 1.5 1.5 2.3
Decildimethylhydroxyethyl- - 0.4 0.7 0.7 0.8
NH4 + C1 Surfactant 1.2 - 0.9 0.5 -non-ionic Coco- (Fatty alcohol of _ _ _ 1.0 EXAMPLE 10 (CONTINUED)
C12-14) STPP 44.0 25.0 22.5 22.5 22.5 Zeolite A 7.0 10.0 - - 8.0 MA / AA - - 0.9 0.9 - SRP1 0.3 0.15 0.2 0.1 0.2
CMC 0.3 2.0 0.75 0.4 1.0
Carbonate 17.5 29.3 5.0 13.0 15.0 Silicate 2.0 - 7.6 7.9 - Antibody 0.005 0.05 0 .006 0.5 1.0
Protease 0.005 0.04 0 .007 0.09 0.15
Amylase .0008 0.004 0 .001 0.04 0.1
Lipase 0.003 0.003 0 .003 - -Celulasa - 0.001 0 .001 .001 .001
NOBS - - - 1.2 1.0
PBl - - - 2.4 1.2
Diethylenetriamine- _ _ 0.7 acid 1.0 pentaacetic acid Diethylenetriamine-0.6 pentamethylphosphonic acid Mg sulphate 0.8 Photoactivated bleach 45 50 15 45 ppm (ppm) Brightener 1 0.05 0.04 0.04 0.04
Polisher 2 0.1 0.3 0.05 0.13 0.13
Water and secondary ingredients up to 100% EXAMPLE 11
The following liquid detergent formulations were prepared, in accordance with the present invention: • I II III IV V VI VII VIII
LAS 10.0 13.0 9.0 - 25.0 - - - C25AS 4.0 1.0 2.0 10.0 - 13.0 18.0 15.0 C25E3S 1.0 - - 3.0 - 2.0 2.0 4.0 0 C25E7 6.0 8.0 13.0 2.5 - - 4.0 4.0 TFAA - - 4.5 - 6.0 8.0 8.0 QAS - - - 3.0 1.0 - - TPKFA 2.0 - 13.0 2.0 - 15.0 7.0 7.0 Fatty acids - - 5.0 - - 4.0 4.0 5 Rapeseed oil Citric acid 2.0 3.0 1.0 1.5 1.0 1.0 1.0 1.0 Acid 12.0 10.0 - - 15.0 - - - dodecetyltetra- decenylsuccinic acid 0 oleic 4.0 2.0 1.0 - 1.0 - - - Ethanol 4.0 4.0 7.0 7.0 7.0 2.0 3.0 2.0 1.2 -Propanodiol 4.0 4.0 2.0 7.0 6.0 8.0 10.0 13.0 Monoethanolamine - - 5.0 - - 9.0 9.0 Triethanolamine - 8 - - - - - 5 NaOH ( pH) 8.0 8.0 7.6 7.7 8.0 7.5 8.0 8.2 Tetraethylene 0.5 _ 0.5 0.2 - _ 0.4 0.3 EXAMPLE 11 (CONTINUED)
Ethoxylated pentamine DETPMP 1.0 1.0 0.5 1.0 2.0 1.2 1 1..00 - SRP-2 0.3 0.3 0.1 - 0 0..22 0.1
PVNO - - • - - - - 0.10
Antibody 0.09 .0005 .005 0.5 .005 0.5 0. .0088 .005
Protease .005 .005 .004 .003 0.08 .005. .000033. .006
Lipasa - .002 .0002 -. .000033. .003
Amylase .02 .0002 .0008 .004 .002 .05. .000055. .0004
Cellulase - - .0001 -. .00000044. .0004
Boric acid 0.1 0.2 2.0 1.0 1.5 2 2..55 2.5
Na Formate - 1.0 - - - Chloride of Ca - 0.015 0.01 - - Clay of - - - 4.0 4.0 Bentonite Clay in - - - 0.6 0.3 SD3 Other (moisture and miscellaneous ingredients): up to 100%
EXAMPLE 12
Granular fabric cleaning compositions were prepared that provide "wash softening" capability,
• ti5 according to the present invention:
I II 45AS - 10.0 LAS 7.6 10 68AS 1.3 45E7 4.0 25E3 - 5.0 Coconut-alkyl- 1.4 1.0 * dimethylhydroxyethylammonium 15 Citrate 5.0 3.0 Na-SKS-6 - 11.0 Zeolite A 15.0 15.0 MA / AA 4.0 4.0 DETPMP 0.4 0.4 20 PBl 15.0 Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO - 0.1 25 Antibody 0.1 0.002 Protease 0.02 0.006 EXAMPLE 12 (CONTINUED)
Lipase 0.02 0.01 Amylase 0.03 0.0005 Cellulase 0.001 - Silicate 3.0 5.0 Carbonate 10.0 10.0 Granular foam suppressor 1.0 4.0 CMC 0.2 0.1 Water / secondary ingredients up to 100%
EXAMPLE 13
The following fabric softening composition was prepared to be added in the rinse, according to the present invention:
Active softener 20.0 Antibody 0.009 Amylase 0.001 Cellulase 0.001 HCL 0.03 Antifoaming agent 0.01 Blue coloring 25 ppm CaCl2 0.20 Perfume 0.90 Water / secondary ingredients up to 100% EXAMPLE 14
The following fabric softening composition was prepared, according to the present invention: ^ 5 I II III
DEQA 2.60 19.00 - SDASA - 70.0 Stearic acid with IV = 0 0.30 - - 10 Neodol 45-13 - 13.00 Hydrochloric acid 0.02 0.02 - Ethanol - 1.00 PEG 0.60 - Antibody 0.06 0.0004 0.05 15 Amylase 0.01 0.0005 0.008 Protease 0.008 - Cellulase 0.001 0.001 - Perfume 1.00 1.00 0.75 Digeranyl succinate - 0.38 20 Silicone antifoam 0.01 0.01 - Electrolyte 600ppm - Colorant lOOppm 50ppm 0.01 Water and secondary ingredients 100% 100% _ EXAMPLE 15
Syndet bar compositions for fabric cleaning were prepared, according to the present invention:
I II III IV C26 AS 20.00 20.00 20.00 20.00
CFAA 5.0 5.0 5.0 5.0
LAS (Cll-13) 10.0 10.0 10.0 10.0
Sodium carbonate 25.0 25.0 25.0 25.0
Sodium pyrophosphate 7.0 7.0 7.0 7.0
STPP 7.0 7.0 7.0 7.0
Zeolite A 5.0 5.0 5.0 5.0
CMC 0.2 0.2 0.2 0.2
Polyacrylate (PM 1400) 0.2 0.2 0.2 0.2
Coconut Monetanolamide 5.0 5.0 5.0 5.0
Antibody 0.062 0.032 0.091 0.0009
Amylase 0.01 0.001 0.002 0.0003
Protease 0.08 0.01 0.005 0.001
Rinse aid, perfume 0.2 0.2 0.2 0.2
CaS04 1.0 1.0 1.0 1.0
MgS04 1.0 1.0 1.0 1.0
Water 4.0 4.0 4.0 4.0
Filling *: rest for 100i
Suitable materials may be selected, such as CaCO3, talc, clay (kaolinite, smectite), silicates and the like.
EXAMPLE 16 ß The following detergent additives were prepared according to the present invention.
II III 0 LAS 5 STPP 30 30 Zeolite A - 35 - PBl 20 15 20 TAED 10 8 10 5 Protease - 0. 3 - Amylase 0. 4 0. 2 - Antibody 5 2 5
Claims (11)
1. A detergent composition comprising an amylase and an antibody directed against amylase.
2. A detergent composition according to claim 1, characterized in that said antibody directed against amylase is comprised of a level of 10E-6% at 10E + 1% by weight of the total composition.
3. A detergent composition according to claim 1, characterized in that the amylase is selected from alfa-amylases [EC 3.2.1.1.].
4. A detergent composition according to claim 3, characterized in that said amylase is of fungal or bacterial origin.
5. A detergent composition according to claim 1, characterized in that the amylase is comprised at a level of 0.0001% to 2%, preferably 0.00018% to 0.1%, preferably 0.00024% to 0.048% pure enzyme by weight of the total composition.
6. A detergent composition according to claim 1, characterized in that said antibody directed against amylase is incorporated in a release agent.
7. A detergent composition according to claim 1, further characterized in that it comprises one or more components selected from anionic, nonionic, cationic, amphoteric and zwitterionic surfactants, c "detergency builder, bleach system, supressor of 5 foam, dirt remover polymer, lime soap dispersant, soil suspending and anti-redeposition agents, smectite clays and the like
8. A detergent composition according to claim 1, characterized in that it is in the form of a 10 liquid, granular, powder, gel, paste or bar.
9. A detergent additive comprising an antibody directed against amylase.
10. A detergent additive according to claim 9, further characterized in that it comprises an amylase.
11. The use of an antibody directed against amylase in a laundry detergent composition to provide fabric care action.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| PCPCT/US1996/013367 | 1996-08-16 | ||
| PCPCT/US1997/014288 | 1997-08-13 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| MXPA99001622A true MXPA99001622A (en) | 1999-06-01 |
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