MXPA99001624A - Detergent compositions comprising oxido-reductase antibody - Google Patents
Detergent compositions comprising oxido-reductase antibodyInfo
- Publication number
- MXPA99001624A MXPA99001624A MXPA/A/1999/001624A MX9901624A MXPA99001624A MX PA99001624 A MXPA99001624 A MX PA99001624A MX 9901624 A MX9901624 A MX 9901624A MX PA99001624 A MXPA99001624 A MX PA99001624A
- Authority
- MX
- Mexico
- Prior art keywords
- hydrogen peroxide
- detergent
- alkyl
- detergent composition
- antibody
- Prior art date
Links
- 239000000203 mixture Substances 0.000 title claims abstract description 203
- 239000003599 detergent Substances 0.000 title claims abstract description 115
- 108090001123 antibodies Proteins 0.000 title claims abstract description 81
- 102000004965 antibodies Human genes 0.000 title claims abstract description 81
- 102000004316 Oxidoreductases Human genes 0.000 title abstract description 10
- 108090000854 Oxidoreductases Proteins 0.000 title abstract description 10
- 239000007844 bleaching agent Substances 0.000 claims abstract description 47
- MHAJPDPJQMAIIY-UHFFFAOYSA-N hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 39
- 108010053835 EC 1.11.1.6 Proteins 0.000 claims abstract description 15
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- 125000004435 hydrogen atoms Chemical class [H]* 0.000 abstract 1
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- 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 9
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Abstract
The present invention relates to detergent compositions comprising a source of hydrogen peroxide, optionally a bleach activator and an antibody to control the hydrogen peroxyde bleach deactivation due to the presence of donor:hydrogen peroxide oxido-reductase enzyme, especially catalase enzyme.
Description
DETERGENT COMPOSITIONS COMPRISING OXIDE REDUCTASE ANTIBODY
FIELD OF THE INVENTION
The present invention relates to detergent compositions comprising an antibody for controlling deactivation of the bleach in the washing process, due to the presence of donor: hydrogen peroxide oxide reductase enzyme.
BACKGROUND OF THE INVENTION
An important part of the system that protects vertebrates against infections by bacteria and viruses is the humoral immune system. Specialized cells present in bone marrow, lymphoid tissues and blood, produce immunoglobulins (antibodies) that appear in response to the introduction of micro- or macromolecules foreign to the body, and that attach to the surface of the structure foreign to it, initiating its destruction . 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 and lipoteichoic acids.
The specific antibodies generated in this way can be combined with the antigen that produces their formation to form an antigen-antibody complex. The antibody molecules have binding sites that are very specific and complementary to the structural characteristics of the antigen that induces their formation. Several applications of such highly specific antigen-antibody recognition and binding have been discovered; such as the recognition agent, the binding agent or carrier agent in various domains such as analytical chemistry, therapeutic treatment and health and aesthetic 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 describes treatment compositions for topical application containing microcapsules comprising a beneficial agent in a targeted location, the microcapsules having an antibody or specific antibody fragment in the target location or a lectin. The document O92 / 04380 describes a newly formed human antibody or reshaped human antibody fragments having a specific character for the human polymorphic epithelial mucosa to be used in the treatment or diagnosis of cancer. The use of Epstein-Barr virus specific polypeptides for the production of
antibodies and the diagnosis and treatment of said disease are described in WO94 / 06470. Oral compositions comprising antibodies for the treatment of anticaries or periodontal diseases are described extensively in WO95 / 01155, 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 cosmetic hair compositions containing an antibody to the hair, or hair extract, obtained from the egg yolk or of poultry immunized with the hair or hair extract of 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. Compositions containing antagonists (tyrphostins or antibodies) against epidermal growth and transformation factors, suitable for use in the treatment of acne are described in document 095/24896. 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 the vaccine composition for dental caries in nasal drops that comprise an antigen
produced by the integration of a protein antigen, expressed in the chromosomal gel of a GS-5 strain of Streptococcus mutant. W094 / 25591 describes the production of antibodies or functionalized fragments thereof derived from a heavy chain of camelidae immunoglobulins. The use of antibodies in the general context of detergency has been suggested in Unilever Researchprijs "Molecule zoekt partner" 1992, where modified antibodies directed against specific strains are proposed to be used in the bleaching process. The detergent compositions today include a complex combination of active ingredients that meet certain specific needs: A surfactant system, enzymes that provide cleaning and fabric care benefits, bleaching agents, a builder system, foam suppressors , dirt suspending agents, soil release agents, optical brighteners, softening agents, dispersants, compounds for the inhibition of dye transfer, abrasives, bactericides and perfumes, and their overall performance has also been improved over time. However, there is still a need, by the consumer, for better removal of stains and / or dirt, maintenance of improved whiteness, softness and care of improved fabrics, and better disinfection with reduced detergent dosage.
Current detergent formulations generally include a bleaching system based on hydrogen peroxide or hydrogen peroxide together with a bleach activator, wherein the bleach activator is transformed into the active bleaching species (peroxy acid) by the action of the peroxide of hydrogen. One of the most common problems in the analysis of the bleaching performance of said detergents is the catalytic loss of bleaching activity due to the donor: hydrogen peroxide reductase enzyme, and especially catalase. The donor system: hydrogen peroxide reductase enzyme are enzymes produced by microorganisms developed on soils and stains present in fabrics, crockery and hard surfaces, and by the human body, and excreted in body fluids. The donor: hydrogen peroxide reductase enzyme are therefore found in body blemishes and / or dirt present in fabrics, crockery and hard surfaces. These enzymes catalyze the direct conversion of hydrogen peroxide into water, reducing the amount of hydrogen peroxide available in the wash solution for direct bleaching or for the perhydrolysis of the bleach activator in the active bleaching peracid. There is therefore a technical challenge to identify ways to block the catalytic activity of the donor: hydrogen peroxide reductase enzyme, and especially the
catalase enzyme, to avoid premature loss of the active bleaching agent in the washing solution. The above need has been covered by specific detergent compositions intended for laundry, dishwashing and hard surface cleaning, containing an antibody directed against the donor: hydrogen peroxide reductase enzyme, and especially catalase enzyme, during the process of cleaning. It has also surprisingly been found that antibodies directed specifically against the donor: hydrogen peroxide reductase enzyme, and especially towards catalase enzymes, block the catalytic activity of the enzyme and thus improve the yield under washing conditions of high content of dirtiness This finding also reduces the level of bleaching agents in the detergent, while providing an equal cleaning performance. In addition, the environmental profile of said detergent compositions is therefore improved.
BRIEF DESCRIPTION OF THE INVENTION
The present invention relates to detergent compositions comprising a source of hydrogen peroxide, optionally a bleach activator and an antibody to control the deactivation of the hydrogen peroxide bleach in the wash solution due to the presence of
donor: hydrogen peroxide reductase enzyme, and especially catalase enzyme.
DETAILED DESCRIPTION OF THE INVENTION
Antibody An essential element of the 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 promoted binding characteristics and are resistant to proteolytic hydrolysis. The antibody that can be monoclonal or polyclonal or an antibody fragment can be generated by techniques conventional in the art, for example by using recombinant DNA techniques that allow producing antibody variants with new properties: reduced immunogenicity, affinity driven, 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. The 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 a number of fusions, but for several 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. The preferred fruits for antibody fragments are through recombinant DNA technology, so that the fragment is expressed by a genetically transformed organism. Antibodies and antibody fragments produced by recombinant DNA technology need not be identical to the antibody fragment produced in vertebrates, yet have the same binding properties evaluated by their Km, Ki and Kcat. For example, they may include amino acid sequences and / or lycosylations that
They differ from those found in antibodies produced in other forms, especially sequences at the end of fragments. Analogously, antibody fragments produced by recombinant DNA technology can include extra amino acid sequences at their terminal ends that have no counterpart in the antibodies produced in another way. A related possibility is that the binding agent for use in this invention is a natural or synthetic polymer that resembles 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 immunization of mammals or birds with the corresponding antigens. Since mammals will be immunized, mice, rabbits, goats, sheep, horses, cows, etc. can be used. The antibody (immunoglobulin fraction) can be separated from the antiserum, milk or eggs according to the ordinary antibody purification method which includes the purification method, Polson extraction, filtration chromatography, gel, ion exchange chromatography , affinity chromatography and the like, the purification method that uses ammonium sulfate to produce the precipitates, dialyzing the precipitates against the physiological saline solution to obtain
the purified precipitates as the antibody. The plants are also capable of synthesizing and assembling all types of antibody molecules and allowing a large scale of antibody production as described in Tibtech. Dec 1995, Vol 13, pp 522-527; Plant Mol, Biol., 26, pp 1701-1710, 1994 and Biotechnol, proj, 1991, 7, pp. 455-461 and in the patent of E.U.A. 5,202,422. The 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 literature : Saiki et al. 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. Antibodies can be produced against any donor. -hydrogen peroxide reductase enzyme of class EC 1.11.1 which covers the oxidoreductase heme proteins, seleno cysteine oxidoreductases and flavoprotein oxidoreductases, and against cytochromes. The group of cytochromes includes all intracellular electron transfer hemoproteins, and includes cytochromes a, b, c, and d. In particular, antibodies against the haemoproteins belonging to the EC classification 1.11.1.6 which comprise catalases and pseudocatalases are produced, being a manganese protein containing Mn (III) in the resting state. The
Catalase, although derived from different organisms, presents a high degree of structural similarities, and the antibodies produced against a specific catalase have the ability to bind to any catalase of EC.1.11.1.6, providing cross-reactivity. Said antibodies will preferably be included in the detergent compositions of the present invention at a level of 10E-6% at 10E + 1% by weight of the total composition. More preferably, for monoclonal antibodies, the level of donor: antibody directed against hydrogen peroxide reductase will be from 3 × 10E-5% to 10E-3%, more preferably from 6 × 10E-5% to 7 × 10E-4% by weight of the total composition. More preferably for antibody fragments, the level of donor: antibody directed against hydrogen peroxide reductase oxide, will be from 10E-5% to 9xlOE-3%, more preferably from 3xlOE-5% to 4xlOE-4% by weight of the total composition. It has surprisingly been found that the immunoinhibition of the donor: hydrogen peroxide reductase enzyme, is especially observed in the process. Without wishing it to be limited by theory, it is thought that the immunoinhibition of the donor: hydrogen peroxide oxide reductase enzyme, is improved by the presence of fabrics. It is further thought that the adsorption of the donor: hydrogen peroxide reductase enzyme on the fabric, makes the enzyme more accessible for inhibition by the antibody.
The 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 may include one or more oxygen bleaching agents and, depending on the bleaching agent chosen, one or more bleach activators. When present, oxygen bleach compounds will typically be present at levels of about 1% to about 25%. The bleaching agent component for use herein may be any of the bleaching agents useful for detergent compositions including oxygen bleaching as well as others known in the art. The bleaching agent suitable for the present invention can be an activated or non-activated bleaching agent. A category of oxygen bleaching agent that can be used encompasses percarboxylic acid bleaching agents and salts thereof. Suitable examples of this class of agents include in magnesium monoperoxyphthalate hexahydrate, the magnesium salt of meta-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydecanedioic acid. Such bleaching examples are set forth in U.S. Patent 4,483,781, the patent application of E.U.A. 740,446, European patent application 0,133,354 and US patent 4,412,934. The agents ofHighly preferred bleaching include 6-nonylamino-6-oxoperoxycaproic acid as described in the US patent. 4,634,551. Another category of bleaching agents that can be used encompasses halogen bleaching agents. Examples of hypohalogenite bleaching agents, for example, include isocyanuric acid and dichloroisocyanurates and sodium and potassium N-chloro- and N-bromo-alkan-sulfonamides. Such 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 the bleach activators such as tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), 3,5, -trimethylhexanoloxybenzenesulfonate (ISONOBS, described in EP 120,591) or pentaacetylglucose (PAG) or N-nonanoyl-6-aminocaproic acid phenoisulfonate-ether (NACA-OBS, described in WO94 / 28106), which are perhydrolyzed to form a peracid as the active bleaching species, producing an improved bleaching effect. Acylated citrate esters such as are disclosed in European Patent Application No. 91870207.7 are also suitable activators. Useful bleaching agents, including peroxyacids comprising bleach activators and peroxygen bleach compounds are described for use in detergent compositions according to the invention, in applications USSN 08 / 136,626, PCT / US95 / 07823, W095 / 27772,
W095 / 27773, W095 / 27774 and W096 / 27775. The hydrogen peroxide may also be present by adding an enzyme system (ie, an enzyme and therefore a substrate) which is capable of generating hydrogen peroxide at the beginning and where the washing and / or rinsing process is carried out. Such enzyme systems are disclosed in patent application EP 91202655.6 filed on October 9, 1991. Metal-containing catalysts for use in bleaching compositions include catalysts including cobalt such as cobalt (III) salts of pentamine-acetate and manganese-containing catalysts such as described in EPA 549 271; EPA 549 272; EPA 458 397; US 5,246,621; EPA 458 398; US 5,194,416 and US 5,114,644. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application No. 948702206.3. Bleaching agents other than oxygen bleaching agents and which can be used herein are also known in the art. One type of oxygen free bleaching agent of particular interest includes photoactivated bleaching agents such as zinc phthalocycins and / or sulfonated aluminum. These materials can be deposited on the substrate during the washing process. By irradiation with light, in the presence of oxygen, for example by hanging clothes outside to dry in daylight, activated zinc phthalocyanine is activated and, consequently,
the substrate is bleached. The preferred zinc phthalocyanine and a photoactivated bleaching process are described in the U.S.A. 4,033,718. Typically, the detergent compositions will contain from about 0.025% to about 1.25%, by weight, of the sulfonated zinc phthalocyanine.
Detergent Components The detergent compositions of the invention may also contain additional detergent components. The precise nature of said additional components, and levels of incorporation thereof depend on the physical form of the composition, and the nature of the cleaning operation for which they are to be used. The detergent compositions according to the invention can be liquids, pastes, gels, sticks, tablets, powder and granular forms. The granulated compositions can also be found in the "compact" form, the liquid compositions can also be found in a "concentrated" form. The compositions of the invention can, for example, be formulated as hand and machine laundry detergent compositions including laundry additive compositions and compositions suitable for use in the rinsing and / or pretreatment of soiled fabrics and in fabric softening compositions added during the rinse. Said compositions can provide benefits of
fabric cleaning, stain removal, maintenance of whiteness, softness, appearance of color and inhibition of dye transfer. When formulated as compositions suitable for use in a machine laundry method for laundry, the compositions of the invention preferably contain a surfactant and a builder compound and additionally one or more detergent components preferably selected from the polymeric compounds. organic, bleaching agents, additional enzymes, foam suppressors, dispersants, soap dispersants, dirt suspension and anti-rejection agents and corrosion inhibitors. The laundry compositions may also contain softening agents as additional detergent components. The compositions of the present invention can also be used as detergent additive products.
Said additive products are intended to supplement or increase the performance of conventional detergent compositions, and preferably comprise up to 50% by weight of antibodies of the total composition. If necessary, the density of the laundry detergent compositions herein ranges from 400 to 1,200 g / liter, preferably from 600 to 950 g / liter of the composition, measured at 20 ° C. The "compact" form of detergent compositions
for granular laundry of the present is best reflected by the density and, in terms of composition, by the amount of inorganic filler salt; the inorganic filler salts are conventional ingredients of 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%, more preferably not exceeding 5% by weight of the composition. The inorganic filler salts, as referred to in the present compositions, are selected from 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 can also be found in a "concentrated form", in which case, the liquid detergent compositions according to the present invention contain a lower amount of water, compared to conventional liquid detergents. Typically, the water content of the concentrated liquid detergent is preferably less than 40%, more preferably less than 30%, and most preferably less than 20% by weight of the detergent composition.
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 semi-polar. The surfactant is typically present at a level of 0.1% to 60% by weight. The levels of incorporation. More preferred 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 more 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 the 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,
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 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 M CO-630, marketed by GAF Corporation; and Triton ™ X-45, X-114, X-100 and X-102, all sold by Rohm & Haas Company. These surfactants are commonly known as alkylphenol alkoxylates (for example, 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 a group are preferred
alkyl containing from about 8 to about 20 carbon atoms, more preferably from about 10 to about 18 carbon atoms, with from about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles of ethylene oxide are present, and more 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 ^ 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 TM 45-9 (the linear condensation product of C14-C15 with 9 moles of ethylene oxide), Neodol TM 23-3 (the linear alcohol condensation product of Cj_2 ~ c13 with 3.0 moles of ethylene oxide ), Neodol 45-5 (the linear alcohol condensation product of C ^ -C] ^ with 7 moles of ethylene oxide), Neodol 45-5 (the linear alcohol condensation product of C ^ -C ^ with 5 moles of ethylene oxide), marketed by Shell Chemical Company, Kyro ™ EOB (the condensation product of C13-C15 alcohol with 9 moles of ethylene oxide), marketed by The Procter & Gamble Company, and Genapol LA 050 (the condensation product of Ci2 ~ c14 alcohol with 5 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, per example, a polyglycoside, a hydrophilic group containing from about 1.3 to about 10, preferably from about 1.3 to about 3, more preferably from about 1.3 to about 2.7 units of saccharide. Any reducing saccharide containing 5 or 6 carbon atoms can be used, for example, the glucose, galactose and galactosyl moieties can replace the glucosyl moieties (optionally the hydrophobic moiety is attached in the 2-, 3-, 4- positions). , etc., thus giving a glucose or galactose as opposed to a glucoside or galactoside). The intersaccharide bonds can be, for example, 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 (CnH2nO) t (glycosii; 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 from about 1.3 to about 3, more 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 solubility in
water 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 condensation product, which corresponds to condensation with up to about 40 moles of oxide of ethylene. Examples of compounds of this type include some Plurafac ™ LF404 and Pluroni • c ™ commercially available surfactants 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 Tetronic FM compounds, commercially available from BASF. Preferred to be used as the nonionic surfactant of the surfactant systems of the present invention are the condensates of polyethylene oxide 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 ^ alkylphenol ethoxylates having from 3 to 15 ethoxy groups and the Cg-C] 8 alcohol ethoxylates (preferably from average C ^ Q) 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
R '- C N Z, O
wherein R is H, or R is hydrocarbyl of C ^ -C ^, 2-p-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R is hydrocarbyl of C5-31 and Z is a polyhydroxyhydrocarbyl having a hydrocarbyl chain linear with at least 3 hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, Ri is methyl, R 2 is a straight C 1 -C 5 alkyl or straight Q 1 -C 8 alkyl or alkenyl chain, 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 the alkyl ether sulfonate surfactants which include linear esters of C8-C20 carboxylic acids (ie, fatty acids) which 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 sulphonate surfactants of the structural formula:
0 R- CH OR- SO3M
wherein R3 is a Cg-C20 hydrocarbyl / preferably an alkyl, or combination thereof, R is a hydrocarbyl of G ^ -Cg, preferably an alkyl or a combination thereof, and M is a cation forming a salt 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 tpetanolamine. Preferably, R ° is C 1 or C 6 alkyl and R is methyl, ethyl or isopropyl. It is especially preferred
^ 3 methylstersulfonates in which J is C 1 or C 6 alkyl *
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 hydrocarbyl of C? _o-C-24 / Preferably an alkyl or hydroxyalkyl having an alkyl component of C10 -C20 / m ^ s preferably an alkyl or hydroxyalkyl of C] _2-C] _3, and M is H or a cation, for example, an alkali metal cation (eg, sodium, potassium, lithium), or ammonium or substituted ammonium (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 similar). Typically, C12 ~ C16 alkyl chains are preferred for lower wash temperatures (eg, below about 50 ° C) and alkyl chains of - ^ Q - ± Q are preferred for higher wash temperatures (eg, about 50 ° C). Other anionic surfactants useful for detersive purposes may also be included in the detergent compositions of the present invention. These may include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono-, di- and triethanolamine salts) of soap, C8 ~ C22 primary or secondary alkanesulfonates > C8-C24 olefinsulfonates, sulfonated polycarboxylic acids prepared by the
sulfonation of the pyrolyzed product of alkaline earth metal citrates, for example, as described in the description of British Patent No. 1,082,179, C8-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, paraffin sulphonates, alkyl phosphates, isethionates, such as acyl isethionates, N-acyltaurates, alkylsuccinamates and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C] _2_ci8 monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated Cg-Cj_2 diesters), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglucoside sulfates (non-sulphonated non-ionic compounds are described below), branched primary alkyl sulphates and alkylpolyethoxy carboxylates such as those of the formula RO (CH2CH2? )]; - CH2COO-M +, wherein R is a C8-C22 alkyl k 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 said surfactants are
they generally also describe in the US patent. 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- I ~ Q ~ C24, preferably an alkyl or hydroxyalkyl of C ^ _2 ~ 20 'more preferably alkyl or hydroxyalkyl of Ci2 ~ CXg, - ^ is an ethoxy or propoxy unit, m is greater than zero, typically between about 0.5 and about 6, more preferably between about 0.5 and about 3, and M is H or a cation which may be, for example, a metal cation (eg, 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 trimethyl-ammonium cations, and quaternary ammonium cations such as cations of
tetramethylammonium and dimethylpiperidinium, and those derivatives of alkylamines such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Exemplary surfactants are polyethoxylated alkylsulfate (1.0) of C, j_2 ~ Cl8 (C12-C18E (1.0) M), polyethoxylated alkyl sulfate (2.25) of C ^ -C ^ (C1-C18E (2.25) M), polyethoxylated alkyl sulfate (3.0 ) of C ^ -Cxs (C1-C18E (3.0) M), and polyethoxylated alkyl sulfate (4.0) of C12-c18 (C12-C18E (4.0) M), wherein M is conveniently selected from sodium and potassium. The detergent compositions of the present invention may also contain cationic, ampholytic, zwitterionic and semipolar surfactants, as well as other nonionic and / or anionic surfactants than 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 (OR3) and] [R4 (OR3) 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 group that
consists of -CH2CH2-, -CH2CH (CH3) -, -CH2CH (CH2OH) -, -CH2CH2CH2-, and mixtures thereof; each R is selected from the group consisting of C1-C4 alkyl, C1-C4 hydroxyalkyl, benzyl ring structures formed by joining the two groups R4, -CH2CH0H-, -CHOHCOR6CHOHCH2OH, wherein R6 is any hexose or hexose polymer having a molecular weight less than about 1000, and hydrogen when and not 0; R5 is the same as R or is an alkyl chain wherein p [T] 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:
wherein R 1 is an alkyl of short chain length (Cg-C] _o) ° alkylamidoalkyl of 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;
whereby X "is a counterion, preferably a halide, for example, chloride, or methyl sulfate, R6 is C1-C4 and z is 1 or 2. Preferred quaternary ammonium surfactants are those defined in formula I with wherein R ^ is Cβ, C ^ or mixtures thereof, x = 0, R 3, R 4 = CH 3 and R 5 = CH 2 CH 20 H Highly preferred cationic surfactants are the water-soluble quaternary ammonium compounds useful in the present composition, which have the formula:
R1R2R3R4N + X "(i)
wherein R ^ is Cg-C ^ g alkyl, each of R2, R3 and R4 is independently C.sub.4 -C.sub.4 alkyl, hydroxyalkyl
Cl-C4 'benzyl and - (C2-H4o)? H, where 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 R] _ is C] _2 ~ C15 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 synthesis of alcohols 0X0. 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; decildimethylhydroxyethylammonium chloride or bromide; Ci2 ~ C15 dimethylhydroxyethylammonium chloride or bromide; cocodimethylhydroxyethylammonium chloride or bromide; myristyltrimethylammonium methylsulfate; lauryl dimethylbenzylammonium chloride or bromide; lauryldimethyl (ethenoxy) 4 ammonium chloride or bromide; esters of choline (compounds of formula (i) wherein
R] _ is CH2-CH2-0-C-alkyl of Cj_2-14 and R2R3R4 are methyl). 0
di-alkylimidazolines [compounds of formula (i)]. Other cationic surfactants useful herein are also described in the U.S.A. No. 4,228, 044, Cambre, issued October 14, 1980, and in the European Patent Application EP 000,224. When included, 1 when included in 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, for example, 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 they are 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 from about 10 to about 18 carbon atoms and 2 portions selected from the group consisting of alkyl groups and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; oxides of
water-soluble phosphines containing an alkyl portion of from 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:
O t R3 (OR4) xN (R5) 2
wherein RJ 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 about
2 to about 3 carbon atoms, or mixtures of the same; x is from 0 to about 3; and each R 5 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 can be linked to each other, for example, through an oxygen atom or
nitrogen to form a ring structure. These amine oxide surfactants include in particular C ó-C8 o alkyldimethylamine oxides and C C-C ^ alco alkoxyethyldihydroxyethylamine oxides. When included, the detergent compositions of the present invention typically comprise from about 0.2% to about 15%. %, preferably from 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 R ^ NHp, where R] _ is an alkyl chain of
R4 L (CH2) n 'X is -0 -, - C (0) NH- or -NH-, R4 is an alkyl chain of Cg-C] _2 / n is between 1 to 5, preferably 3. The chains alkyl of R ^ 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 c8-c10'-octyloxypropylamine oxypropylamine, 2-ethylethyloxypropylamine, laurylamido-propylamine and amidopropylamine.
Tertiary amines suitable for use herein include tertiary amines having the formula R-LR2R3, wherein Rj_ and R are alkyl chains of C ^ -Cg or
R5 I (CH2-CH-0)? H
R3 is an alkyl chain of
preferably Cg-C10, or R3 is R4X (CH2) n, wherein X is -0 -, - C (0) NH- or -NH-, R4 is a C4-C] _2, n is between 1 to 5, preferably 2-3. R5 is H or CQ_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 R 1 R 2 R 3 N wherein R 1 is an alkyl chain of Cg-C] _ 2, R 2 and R 3 are C 1 -C 3 alkyl, or
R5 (CH2-CH-0) xH
where R5 is H or CH3 and x = 1-2. Amidoamines of the formula are also preferred:
O R-L - C-NH- (CH2) n-N- (R2) 2
in. where R _ is C 6 -C 12 alkyl n is 2-4, preferably n is 3; R and R3 is C-j_-C4-
Most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, Cg-C ^ O oxypropylamine, N-coco-1-3-diaminopropane, cocoalkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) ) amine, coco-bis (hydroxyethyl) amine, propoxylated lauryl amine with 2 moles, propoxylated octylamine with 2 moles, laurylamidopropyldimethylamine, Cg-C amidopropyldimethylamine] Q and amidopropyldimethylamine of C] _Q • The most preferred amines for use in the compositions of the present 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 selected enzymes of cellulases, hemicellulases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenoloxidases, lipoxygenases, ligninases, pullulanases, tanases, pentosanas, malanases, β -glucanases, arabinosidases, hyaluronidase, chondroitinase, laccase or mixtures thereof. A preferred combination is a composition
detergent that has a cocktail of conventional applicable enzymes such as protease, amylase, lipase, cutinase and / or cellulase, in conjunction with one or more enzymes degrading the plant cell wall. 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 grisea 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. Other suitable cellulases are the EGIII cellulases of Trichoderma longibrachiatum described in WO 94/21801, Genencor, published on September 29, 1994. Particularly suitable cellulases are cellulases having
benefits of color care. Examples of these cellulases are the cellulases described in European Patent Application No. 9122879.2, filed on November 6, 1991 (Novo). Carezyme and Celluzyme (Novo Nordisk A / S) are especially useful. See also document W091 / 17243. Said cellulases 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, for example, 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. , Holland, and lipases, for example, from Pseudomonas gladioli. Lipases especially suitable are lipases such as Ml
Lipase® and Lipomax® (Gist-Brocades) and Lipolase® (Novo), which have been found to be most effective when used in combination with the compositions of the present invention. Also suitable are cutinases [EC 3.1.1.50], which can be considered as a special type of lipase, namely, lipases that do not require interfacial activation. Suitable cutinases are described in WO 94/14963 and WO / 94/14964. The addition of cutinases to detergent compositions has been described, for example, in WO-A-88/09367 (Genencor). 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 that are obtained from particular strains of B. subtilis and B. 1 i cheni formi s (subtilisins BPN and BPN '). A suitable protease is obtained from a strain of Bacillus, which has a maximum activity through the pH scale of 8-12, developed and sold as ESPERASER by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of said enzyme and analogous enzymes is described in GB 1,243,784 of Novo. Other suitable proteases include ALCALASER, DURAZYMR and SAVINASER from Novo and MAXATASER, MAXACALR, PROPERASER and MAXAPEMR (protein produced by Maxacal) from Gist-Brocades. The proteolytic enzymes also comprise modified bacterial serine proteases, such as those described in the application
European patent with serial No. 87303761.8, issued April 28, 1987 (particularly pages 17, 24 and 98), and which herein are called "Protease B", and in European patent application 199,404, Venegas , published October 29, 1986, which refers to the modified bacterial serine proteolytic enzyme which is called "Protease A" herein. Protease called in the present "Protease C" is suitable, which is a variant of a Bacillus alkaline serine protease in which lysine replaces arginine in position 27, tyrosine replaces valine in position 104, serine replaces aspargine at position 123, and alanine replaces trionine at position 274. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637, published May 16, 1991. Genetically modified variants, particularly of protease C, are also included herein. See also a high pH protease from Bacillus sp. , NCIMB 40338, described in WO 93/18140 A to Novo. Enzymatic detergents comprising protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. When desired, a protease having reduced adsorption and increased hydrolysis can be obtained as described in WO 95/07791 to Proter & Gamble. A recombinant trypsin-like protease for detergents, suitable herein, is described in WO 94/25583 to Novo. The preferred protease, referred to as "Protease D", is
a variant of a carbonyl hydrolase having an amino acid sequence but found in nature, which is derived from a carbonyl hydrolase precursor by replacing a different amino acid with a plurality of amino acid residues at a position on 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, +10, +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 subtilisin number of Bacillus amiloliquef aciens, as described in WO95 / 10591 and in the patent application C. Ghosh et al., "Bleaching Compositions Comprising Protease Enzymes" which has the US serial number 08 / 322,667, issued October 13, 1994. Also suitable for the present invention are the proteases described in patent applications EP 251 446 and WO 91/06637, 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. Amylases (ce and / or ß) can be included for the removal of carbohydrate-based stains. WO94 / 02597, Novo Nordisk A / S, published on February 3, 1994, describes cleaning compositions incorporating
mutant amylases. See also WO / 94/18314, Genencor, published on August 18, 1994 and WO / 95/10603, Novo TSIordisk A / S, published April 20, 1995. Other amylases for use in cleaning compositions include a- and β-amylases. A-amylases are known in the art and include those described in the U.S.A. No. 5,003,257; EP 252,666; WO / 91/00353; RF 2,676,456; EP 285,123; EP 525,610; EP 368,341; and in the description of British Patent No. 1,296,839 (Novo). Other suitable amylases are the improved stability β-amylases including Purafact Ox Am described in W094 / 18314, published August 18, 1994 and the amylase variants having further modification in the immediate parent, available from Novo Nordisk A / S and described in WO95 / 10603, published April 1995. Examples of p-products of commercial α-amylases are Purafact Ox Am from Genencor, and ppp -p Termamyl, Ban, Fungamyl and Duramyl, all available from Novo Nordisk A / S Denmark. W095 / 26397 describes other suitable amylases: α-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 a pH value in the scale from 8 to 10, measured by the Phadebas α-amylase activity test. Other amylolytic enzymes with improved properties with respect to the level of activity and the combination of thermostability and higher activity level are described in W095 / 35382. The enzymes mentioned above can be
any suitable origin, such as plant, animal, bacterial, fungal and yeast origin. Said enzymes are normally incorporated in the detergent composition at levels of 0.0001% to 2% active enzyme by weight of the detergent composition. They can be added as separate ingredients (pellets, granulates, stabilized liquids, etc., containing an enzyme), or as mixtures of two or more enzymes (for example, 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 are 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, 1985. Enzyme materials useful for liquid detergent formulations, and their incorporation into these formulations, are 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. Enzyme stabilization systems are also described, 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 for color care Technologies that provide a type of benefit for color care can also be included. Examples of these technologies are metallocatalysts for color maintenance. Metallocatalysts are also described in European Patent Application No. 92870181.2.
Detergency System and Speaker The compositions of the present invention may further comprise a builder system. Any conventional builder system is suitable for use herein including aluminosilicate materials, silicates, polycarboxilicates, alkylalkenyl succinic acid and fatty acids, materials such as ethylenediaminetetraacetate, diethylenetriaminpentamethylenacetate, metal ion sequestrants such as aminophosphonates,
particularly ethylenediaminetetramethylenephosphonic acid and diethylenetriaminpentamethylenephosphonic acid. Phosphate builders can also be used herein. Suitable builders may be an inorganic ion exchange material, commonly an inorganic hydrated aluminosilicate material, more particularly a hydrated synthetic zeolite such as zeolite A, X, B, HS or hydrated MAP. Another suitable inorganic builder material is layered silicate, for example SKS-6 (Hoechst). SK-6 is a crystalline statified silicate consisting of sodium silicate (Na2Si2? _5). Suitable polycarboxylates containing a carboxy group include lactic acid, glycolic acid and ether derivatives thereof as set forth in the Belgian patents Nos. 831,368, 821,369 and 821,370. Carboxylates containing two carboxy groups include the water-soluble salts of succinic acid, malonic acid, ethylenedioxydiacetic acid, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as other ether carboxylates described in German Patents 2,446,686, and 2,446,687 and the US patent No. 3,935,257, and the sulfonyl caboxylates described in Belgian Patent No. 3,935,257. The carboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates as well as succinate derivatives such as the carboxymethyloxysuccinates described in
British Patent No. 1,379,241, Lactoxysuccinates described in Dutch Application 7205873 and Oxypolycarboxylate materials such as 2-oxa-1,1,3-propane tricarboxylates described in British Patent No. 1,387,447. Polycarboxylates containing four carboxy groups include the oxydisuccinates described in British Patent No. 1,261,829,1,1,2,2-ethanetenetecorboxylates. 1, 1, 3, 3-propanotetraorboxylates and 1, 2, 1, 3-propanotetracarboxylatos. Polycarboxylates containing sulfo substituents including sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and in the US patent. No. 3,936,448, and the sulfonated pyrolysed sulfonates described in British Patent No. 1,082,179, while exposing the caboxylates containing phosphone substituents of British Patent No. 1,439,000. The alicyclic and heterocyclic polycarboxylates include cyclopentane-cis, cis, cis-tetracarbocylates, cyclo-pentadienidopentacarboxylates, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylates, 2,5-tetrahydro-furan-cis- dicarboxylates, 2, 2, 5, 5-tetrahydrofuran-tetracarboxylates, 1, 2, 3, 4, 5, 6-hexanohexacarboxylates and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include the melitic acid, pyromellitic acid and phthalic acid derivatives set forth in British Patent No. 1,425,343. Of the above, the preferred polycarboxylates
they are hydroxycarboxylates containing up to three carboxy groups per molecule, more 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 water soluble carboxylate chelating agent such as acid. citric. Preferred builders systems for use in liquid detergent compositions of the present invention are soaps and polycarboxylates. A suitable chelating agent for inclusion in the detergent compositions according to the invention is ethylenediamine-N, N 'disuccinic acid or salts of alkali metals, alkaline earth metals, ammonium or substituted ammonium thereof or mixtures thereof. The preferred EDDS compounds are the free acid form and the sodium or magnesium salt thereof. Examples of such preferred sodium salts of EDDS include Na EDDS and Na4EDDS. Examples of such preferred magnesium salts of EDDS include MgEDDS and Mg2EDDS. Magnesium salts are most preferred for inclusion in the compositions according to the invention. Preferred builder systems include a mixture of a water insoluble aluminosilicate builder such as zeolite A and a water soluble carboxylate chelating agent such as citric acid.
Other detergency builder materials that can be part of the builder system for use in granular compositions include inorganic materials such as carbonates, bicarbonates, silicates, and organic materials such as phosphonates, aminopoly-alkylene-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 one another by not more than two carbon atoms. The polymer of this type is exposed in GB-A-1, 596, 756. Examples of such salts are polyacrylates with MW of 2000-5000 and their copolymers with maleic anhydride, such as copolymers having a molecular weight of 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 usually 30% to 60% by weight.
Foam suppressor Another optional ingredient is a foam suppressant, exemplified by silicones and silica / silicone blends. The silicones can be represented generally by alkylated polysiloxane materials while the silicas are normally used in finely divided forms
exemplified by silica aerogels and xerogels and hydrophobic silicas of various types. These materials can be incorporated as particulate materials in which the foam suppressor is advantageously incorporated in a releasable manner in a water-soluble or water-dispersible detergent vehicle, substantially non-surfactant. 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 silicone foaming agent is disclosed, in Bartollota et al., U.S. Pat. 3 933 672. Other particularly useful foam suppressors are self-emulsifying silicone foam suppressors, described in the German patent application DTOS 2 646 126 published April 28, 1977. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. The especially preferred foaming agent is the foam suppressor system comprising a mixture of silicone oil and 2-alkylalkanols. The suitable 2-alkylalcanol is 2-butyloctanol which is commercially available under the factory name of Isofol 12 R. Such a foam suppressor system is described in European Patent Application No. 92870174.7, filed on November 10, 1992. describe the especially preferred silicone foam controlling agents, in European Patent Application No. 92201649.8. Such compositions may comprise
a silicone / silica mixture in combination with non-p porous fumed silica such as Aerosil. The foam suppressors described above are usually employed at levels from 0.001% to 2% by weight of the composition, preferably from 0.01% to 1% by weight.
Other components Other components used in the detergent compositions may be employed, such as soil suspending agents, soil release agents, optical brighteners, abrasives, bactericides, bleaching inhibitors, coloring agents and / or encapsulated or unencapsulated perfumes. Particularly suitable encapsulating materials are water-soluble capsules consisting of a matrix of polysaccharide and polyhydroxy compounds such as described in GB 1,464,616. Other suitable water-soluble encapsulating materials comprise dextrins derived from ungelatinized starch acid-esters of substituted dicarboxylic acids such as are described in US 3,455,838. These acid-ester dextrins are prepared, preferably, 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 polyfunctional substituted groups such as octenylsuccinic acid anhydride. Suitable antiredeposition and soil suspending agents herein include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymeric polycarboxylic acids or salts thereof. Polymers of this type include the polyacrylates and the maleic anhydride-acrylic acid copolymers previously mentioned as detergency builders, as well as copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, constituting maleic anhydride at least 20% by weight. mol of the copolymer.
These materials are normally used at levels of 0.5% to 10% by weight, more preferably from 0.75% to 8%, more preferably still from 1% to 6% by weight of the composition. Preferred optical brighteners are of anionic character, examples of which are 4,4'-bis- (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disodium disulfonate, , 4 '-bis- (2-mofolino-4-anilino-s-triazin-6-ylamino-stilbene-2, 2'-disodium disodium 4,4'-bis- (2,4-dianilino-s-triazin) -6-ylamino) stilbene-2, 2'-monosodium disulfonate, 4 ', 4"-bis- (2,4-dianilino-s-tri-azin-6-ylamino) stilbene-2-sulfonate disodium, 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-triazin-6-ylamino) -stilbene-2, 2 'disodium disulfonate, 2 (stilbyl-' '- (naphtho-1', 2 ': 4 , 5) sodium l-2,3-triazole-2"-sulfonate and 4,4'-bis (2-sulfostyril) biphenyl The highly preferred brighteners are the specific brighteners of European Patent Application No. 95201943.8. Other useful polymeric materials are polyethylene glycols, particularly those with a molecular weight of 1,000-10,000, more particularly 2,000 to 8,000, and most preferably about 4,000.They are used at levels of 0.20% to 5%, more preferably 0.25. % to 2.5% by weight These polymers and the abovementioned homo- or copolymeric polycarboxylate salts are valuable for improving the maintenance of whiteness, the deposition of ash on the fabric and the cleaning performance on clay, protein and oxidizable soils in the presence of transition metal impurities. The use of soils 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 distributions. Examples of such polymers are set forth in the U.S.A. Nos. 4116885 and 4711730, commonly assigned, and published European patent application No. 0 272 033. A particular preferred polymer in accordance with EP-A-0 272 033 has the formula
(CH3 (PEG) 43) 0.75 (POH) 0.25 [(T-PO) 2.8 (T-PEG) -0.43t (p ° - H) 0.25 ((PEG) 43CH-3) o.75
where PEG is - (OC2H4) 0-PO is (OC3HgO) and T is (pcOC6H CO). Also highly useful are polyesters polyesters such as random copolymers of dimethylterephthalate, dimethylsulfoisophthalate, ethylene glycol and 1,2-propanediol, the terminal groups consisting primarily of sulfonbenzoate and secondarily of ethylene glycol monoesters and / or propanediol. The objective is to obtain a polymer blocked at both ends by sulfobenzoate groups; "Primordially", in the present context most of said copolymers herein will be blocked at the ends by the sulfobenzoate groups. However, some copolymers will be less than completely blocked and therefore the end groups may consist of monoesters of ethylene glycol and / or popane-1,2-diol, of which they consist "secondarily" in such species. The polyesters selected herein contain about 46% by weight of dimethylterephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of methylsulfobenzoic acid and about 15% by weight of sulfoisophthalic acid, and has a molecular weight of about 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 from the tap water rapidly deactivates the enzymes comprised in the detergent compositions. Therefore, using chlorine scrubber such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine with a level greater than 0.1% by weight of the total composition, in the formulas, will provide improvement through the washing stability of the detergent enzymes. The compositions comprising chlorine scavenger are described in European patent application 92870018.6 filed on January 31, 1992. Alkoxylated polycarboxylates, such as those prepared from polyacrylate, are useful herein to provide additional yield in the elimination of fat. Such materials are described in WO 91/08281 and PCT 90/07815 on page 4 and the following, incorporated herein by reference. Chemically, these materials comprise polyacrylates that have a side chain of ethoxy for every 7 and 8 acrylate units. The side chains are of the formula - (CH2CH20) m (CH2) nCH3 where m is 2-3 and n is 6-12. The side chains are linked with esters to the polyacrylate "base structure" to provide a "comb" polymer type structure. The molecular weight may vary, but is typically in the range of about 2,000 to about 50,000. Such benzylated polycarboxylates can comprise from about
0. 05% to about 10%, by weight, of the compositions herein.
Fabric softening agents Fabric softening agents can be incorporated into laundry detergent compositions in accordance with the present invention. These agents may be of inorganic or organic type. Inorganic softening agents are exemplified with the smectite arecillas exposed in GB-A-1 400 898 and USP 5,019,292. Organic fabric softening agents include the water insoluble tertiary amines which are set forth in GBA-A1 514 276 and EP-BO 011 340 and their combination with quaternary ammonium momosales of 12_ 14 are set forth in EP-B-0 026 527 and EP-B-0 026 528 and dilarga chain amides are disclosed in EP-B-0 242 919. Other useful organic ingredients of fabric softener systems include high molecular weight polyethylene oxide materials as set forth in EP-A -0 299 575 and 0 313 146. The smectite clay levels are usually in the range of 2% to 20%, more preferably 5% to 15% by weight, the material being added as a dry mixed component to the rest of the formulation . Other organic fabric softening agents such as water-insoluble tertiary amines or dilarga chain amide materials are incorporated at levels of 0.5% to 5% by weight, usually 1% to 3% by weight while the oxide materials are added. from
high molecular weight polyethylene and water-soluble cationic materials at levels of 0.1% to 2%, usually from 0.15% to 1.15% 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 material in the form of particles or sprinkle them as molten liquid over the other solid components of the composition.
Dispersants The detergent composition of the present invention may also contain dispersants: 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 one another by no more than two carbon atoms. Polymers of this type are disclosed in GB-A-1,596, 756. Examples of such salts are polyacrylates with MW of 2000-5000 and copolymers with maleic anhydride, such copolymers having a molecular weight of 1,000 to 100,000. Especially, in the detergent compositions of the present invention, acrylate and methacrylate copolymers such as 480N having a molecular weight of 4000, at a level of 0.5 to 20% by weight of the composition can be added. The compositions of the invention may contain a peptizing compound of lime soap, having a potency
lime soap dispersant (LSDP), as hereinafter defined to be no more than 8 preferably no more than 7, more preferably no more than 6. The lime soap peptizer compound is preferably present at a level of 0% to 20% by weight. A numerical measure of the effectiveness of the lime soap peptizer is given by the lime soap dispersing power (LSDP) which is determined using the lime soap dispersant test, as described in an H.C. Borghetty and C.A. Bergman, J. Am. Oil. Chem. Soc., Volume 27, pages 88-90, (1950). This method of testing the dispersion of lime soap is used extensively by spatialists in this field of art who are referred to, for example, in the following articles of specialized journals: W.N. Linfield, Surfactant science Series, Volume 7, page 3: W.N. Linfield, Tenside surf. det., volume 27, pages 159-163, (1990); and M.K. Nagarajan, W.F. Masler, Cosmetics and Toiletries, volume 104, pages 71-73, (1989). The LSDP is the ratio of percent by weight of the dispersing agent to the sodium oleate required to disperse the lime soap deposits formed by 0.025 g of sodium oleate in 30 ml of water with equivalent hardness of 333 ppm of CaC 3 (Ca). : Mg = 3: 2). Surfactants having good lime soap peptising ability will include certain amine oxides, betaines, sulfobetaines, alkyl ethoxysulfate and ethoxylated alcohols.
Exemplary surfactants having an LSDP of not more than 8 for use in accordance with the present invention include C 16 -C 18 dimethylamine oxide C 12"C 18 alkyl ethoxy sulfates with an average degree of ethoxylation of 1 to 5, particularly ethoxysulfate surfactant of C12 ~ C15 with an ethoxylation degree of approximately 3 (LSDP = 4) and the ethoxylated alcohols of C14-C] _5 with an average degree of ethoxylation of either 12 (LSDP = 6) or 30, sold under the names of factory of Lutensol A012 and Lutensol A030 respectively, by BASF GmbH The polymeric lime soap peptizers suitable for use herein are described in the article by Nagarajan, WF Masier, which is found in Cosmetics and Toiletries, volume 104, pages 71-73, (1989). Hydrophobic bleaches such as 4- [N-octanoyl-6-aminohexanoyl] benzenesulfate, 4- [N-nonanoyl-6-aminohexanoyl] benzenesulfonate can also be used as lime soap peptizer compounds. , 4 - [N-decanoyl-6-aminohexa-noyl] benzenesulfonate, and mixtures thereof; and nonanoyloxy-benzenesulfonate together with hydrophilic / hydrophobic bleaching formulations.
Inhibition of dye transfer The detergent compositions of the present invention may include compounds to inhibit the transfer of dyes from one fabric to another, dyes
solubilized or suspended that are found during the operations for the washing of fabrics that involve 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%, more preferably from 0.05% to 1% by weight of polymeric transfer inhibiting agents. dyes Such polymeric dye transfer inhibiting agents are normally incorporated into the detergent compositions in order to inhibit the transfer of dyes from colored fabrics onto fabrics washed therewith. These polymers have the ability to form complexes or absorb the fugitive centers released in the washing of the dyed fabrics before the dyes have the opportunity to be fixed to other articles in the wash. Especially suitable dye transfer inhibiting polymeric agents 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 such polymers also enhances the performance of the enzymes according to the invention.
Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use contain units having the following structure formula:
(1) Ax R where P is a polymerizable unit, to which the group R-N-0 may be linked or where the group R-N-0 forms part of the polymerizable unit or a combination of both.
0 0 0 I! I I! 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 N-O group may be linked or in which the nitrogen of the N-O group is part of these groups. The N-O group can be represented by the following structures:
O O 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 combination thereof, xo / y Y or / and z is 0 or 1 and wherein the nitrogen of the NO group can be linked or where the nitrogen The group is NOT part of these groups. The N-O group can be part of the polymerizable unit (P) or it can be linked to the polymeric base structure or a combination of both. The N-O suitable polyamine oxides wherein the N-O group forms part of the polymerizable unit comprises N-oxide polyamines in which R is selected from aliphatic groups, aromatic, alicyclic or heterocyclic. A class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the NO forms part of the group R. The preferred polyamine N-oxides are those in which R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of said polyamine N-oxides comprises the group of polyamine N-oxides in which the nitrogen of the NO group is linked to the R group. Other suitable N-oxides of polyamine are the polyamine acids in which the NO group it is linked to the polymerizable unit. The preferred classes of these polyamine N-oxides are the polyamine N-oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups in which the nitrogen of the
functional group N-O is part of said group R. Examples of these classes are the polyamine oxides in which R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of N-polyamine oxides are the polyamine oxides having the general formula (I) wherein R are aromatic, heterocyclic or alicyclic groups in which the nitrogen of the functional group is NOT linked to said R groups. of these classes are the polyamine oxides in which the R groups can be aromatic such as phenyl. Any polymer base structure can be used as long as the formed amine oxide polymer is water soluble and has dye transfer inhibiting properties. Examples of polymeric base structures 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: 1,000,000. 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, in the ratio of the amine to the amine N-oxide is from 2: 3 to 1: 1,000,000, more preferably from 1: 4 to 1; 1,000,000, more preferably from 1: 7 to 1: 1,000,000. The
The polymers of the present invention actually include random or block copolymers in which one type of monomer is an amine N-oxide of another type of monomer or is an amine N-oxide or not. The amine oxide unit of the polyamine N-oxides has a PKa < 10, preferably PKa < 7, more 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 water solubility and the suspension potency in desired dyes. Typically, the average molecular weight is within the range of from 500 to 1,000,000, preferably from 1,000 to 50,000, more preferably from 2,000 to 30,000, more 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 a range of average molecular weights of 5000-1,000,000, preferably 5000-200,000. Highly preferred polymers for use in the detergent compositions according to the present invention comprise a polymer selected from copolymers of N-vinylimidazole and N-vinylpyrrolidone in which said polymer has a range of average molecular weights of from 5,000 to 50,000, more preferably from 8,000 to 30,000, more preferably even from 10,000 to 20,000. The range of average molecular weights was determined by light diffusion
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 a range of average molecular weights of from 5,000 to 50,000; more preferably from 8,000 to 30,000; more preferably from 10,000 to 20,000. The copolymers of N-vinylimidazole and N-vinylpyrrolidone characterized in that they have said range of average molecular weights provide excellent dye transfer inhibition properties while not adversely affecting the cleaning performance of the detergent compositions formulated therewith. The copolymer of N-vinylimidazole and N-vinylpyrrolidone of the present invention have a molar ratio of N-vinylimidazole to N-vinylpyrrolidone from 1 to 0.2, more preferably from 0.8 to 0.3, more preferably from 0.6 to 0.4.
c) Polyvinylpyrrolidone The detergent compositions of the present invention can also use polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 2,500 to about 400,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and more preferably still from about 5,000 to about 15,000. The
Suitable polyvinylpyrrolidones are commercially available from ISP Corporation, New York, NY and Montreal, Canada under the product names PVP K-15 (molecular weight with viscosity of 10,000), 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 obtainable from BASF Cooperation include Sokalan HP 165 and Sokalan HP 12; polyvinylpyrrolidones known to those skilled in the detergent field (see for example EP-A-262,897 and EP-A-256,696).
d) Polyvinyloxazolidone The detergent compositions of the present invention can also use polyvinyloxazolidone as the polymeric agent of the dye transfer division. Said polyvinyloxazolidones have an average molecular weight of from about 2,500 to about 40,000, preferably from about 5,000 to about 200,000, more preferably from about 5,000 to about 50,000 and more preferably still from about 5,000 to about 15,000.
e) Polyvinylimidazole The detergent compositions of the present invention can also use polyvinylimidazole as a polymeric agent for inhibiting dye transfer.
Said polyvinylimidazoles have an average of about 2,500 to about 400,000, preferably about 5,000 to 200,000, more preferably about 5,000 to about 50,000 and more preferably still about 5,000 to about 15,000.
f) Interlaced polymers Interlaced polymers are polymers whose base structure is interconnected to a certain degree; these links may be of a chemical or physical nature, possibly with an active group n in the base structure or on the branches; the entangled polymers have been described in Journal of Polymer Science, volume 22, pages 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. Such entangled polymers are described in 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 it can be added
a separate auxiliary rinsing composition. The process described herein comprises contacting the fabrics with a washing solution in the usual manner and exemplified herein. The method of the invention is conveniently carried out during the course of the cleaning process. The cleaning method is preferably carried out at 5 ° C and up to 95 ° C, especially between 10 ° C and 60 ° C. The pH of the treatment solution is preferably from 7 to 11. The following examples are intended to exemplify compositions of the present invention, but are not necessarily intended to limit or otherwise define the scope of the invention. In the detergent compositions, the level of enzymes is expressed in pure enzyme by weight of the total composition and the identifications of the abbreviated components have the following meanings: LAS: linear C ^ 2 sodium alkylbenzenesulfonate TAS: sodium tallow alkyl sulfate CXYAS : C1Y C1Y Alkylsulfate of sodium 25EY: A predominantly linear primary alcohol of C] _2-Ci5 condensed with an average of Y moles of ethylene oxide
CXYEZ A predominantly linear primary alcohol of C] _? - C2_? condensed with an average of Z moles of ethylene oxide XYEZS Alkylsulfate of C? -C; L? of condensed sodium with an average of Z moles of ethylene oxide per mole QAS R2. + (CH3) 2 (C2H4OH) with R2 = C12-C1 Linear solid sodium alkylcarboxylate soap derived from a mixture of 80/20 of tallow oils and of coconut TFAA Alkyl-N-methylglucamide of C ^ -C ^ g. TPKFA Fatty acids crowned with a complete cut of C ^ -C ^. DEQA Di- (tallowoxyethyl) dimethylammonium chloride. SDASA 1: 2 ratio of steryl dimethyl amine: triple-compressed stearic acid. Neodol 45-13 Linear primary alcohol of C ^ -C ^ ethoxylated, sold by Shell Chemical CO. Silicato amorphous sodium silicate (ratio Si02: Na20 = 2.0). NaSKS-6 Crystallized statified 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 an average molecular weight of 8,000, sold under the factory name PA30 by BASF GmbH. Zeolite A Hydrated sodium aluminosilicate of the formula Na1 (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 sodium perborate bleach monohydrate, empirical formula NaB? 2-H2? 2. PB4: Sodium perborate anhydrous tetrahydrate Percarbonate: Anhydrous sodium percarbonate bleach of the empirical formula 2Na2C03.3H2? 2. TAED: Tetraacetylethylenediamine. NOBS: Nonanoiloxybenzenesulfonate in the form of sodium salt. Photoactivated bleach: Sulfonated zinc phthalocyanine encapsulated in dextrin-soluble polymer. Antibody: Antibody directed against an enzyme according to the present invention. Protease: Proteolytic enzyme sold under the trade names Savinasa, Alcalasa, Durazim by Novo Nordisk A / S, Maxacal, Maxapem, Properasa sold by Gist-Brocades and the proteases described in patents WO91 / 06637 and / or WO95 / 10591 and / or EP 251 446.
Amylase Aminolytic enzyme sold with the p-name Ox Am, described in WO 94/18314, WO96 / 05295 sold by Genencor; Termamil, Fungamil p and Duramil, all obtainable from Novo Nordisk A / S and those described in W095 / 26397. Lipase Lipolytic enzyme sold under the factory name Lipolasa, Lipolasa Ultra by Novo Nordisk A / S. Cellulase Cellulite enzyme sold under the factory name Carezime, Celluzime and / or Endolasa by Novo Nordisk A / S.
CMC Sodium-carboxymethylcellulose. HEDP 1, 1-hydroxyethanediphosphonic acid DETPMP Diethylenetriaminpenta (methylene phosphoric acid), sold by Monsanto under the factory name Dequest 2060.
PVNO Poly (4-vinylpyridine) -N-oxide. PVPVI Poly (4-vinylpyridine) -N-oxide / copolymer of vinylimidazole and vinylpyrrolidone. Rinse aid 1 Disodium-4, 4 '-bis (2-sulfostyril) -biphenyl.
2 Disodium-4,4'-bis (4-anilino-6-morpholino-1,3,5-triazin-2-yl) stilbene-2: 2'-disulfonate brightener. Silicone antifoams 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. 12% silicone / silica granulated spupresor, 18% stearyl alcohol foam, 70% granular starch. SRP 1 esters blocked at the ends of sulfobenzoyl with base structure of oxyethyleneoxytephthaloyl. SRP 2 Short block polymer of poly (1, 2 -propikenteraphthalate) diethoxylate. Sulfate Anhydrous sodium sulfate. HMWPEO High molecular weight polyethylene oxide. PEG Polyethylene glycol. Encapsulated particle Fragrance-insoluble fragrance dispensing technology Zeolite 13x perfume and a binder agglomerator detrusor / glycerin is used.
EXAMPLE 1
One ml p-p of a 1 mg / ml emulsion of Savinase or Alcalase was injected into the muscle of the chicken breast. The proteolytic emulsion was prepared with a complete adjuvant of
Freunds (Freund and McDermott, 1942; Freund 1956), by intensively mixing an equal amount of Savmase or Alcalase solution (2 mg / ml) and complete Freunds adjuvant. The immunization schedule ended with injections using an incomplete Freunds adjuvant, and after a period of 4 weeks, the eggs were collected for a week. The extraction of the antibodies from the egg yolk was done in accordance with the Polson extraction method, as described in Immunological Investigation 19, 1990, pp 253-258. A catalase solution was prepared (50U at lOOU / ml) and incubated with 0.04 g of Polson extract for 30 minutes. An aliquot of 100 microliters of this incubated solution was added to a solution of hydrogen peroxide. Inactivation of catalase was measured according to the enzymatic catalase test of Sigma, EC 1.11.1.6. No decrease in the concentration of hydrogen peroxide was observed, demonstrating the complete inactivation of said enzyme.
EXAMPLE 2
The following laundry detergent compositions 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
QAS - 0.8 0.8 - 0.8 0.8
Zeolite A 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
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
Amylase 0.0009 0.0009 0.0009 0.0009 0.0009 0.0009
Protease 0.0026 0.0026 0.0026 0.0026 0.0026 0.0026
Antibody 10E-2 10E-4 1 10E-6 10E-5 10E-1
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
Bleach 15 15 15 15 15 15 photoactivated (ppm) Brightener! 0.09 0.09 0.09 0.09 0.09 0.09
EXAMPLE 2 (CONTINUED)
Perfume 0.3 0.3 0.3 0.3 0.3 0.3
Antifoams 0.5 0.5 0.5 0.5 0.5 0.5 silicone Various / minor ingredients for 100% Density in 850 850 850 850 850 850 g / liter
EXAMPLE 3
The following granular laundry detergent compositions having a bulk 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
C45 S - 2.24 3.89 C25AE3S - 0.76 1.18
C45E7 3.25 - 5.0
C25E3 - 5.5 - 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
EXAMPLE 3 (CONTINUED) Bicarbonate 2.0 2.0
Silicate 6.8 Sodium sulphate 39.8 - 14.3 PB4 5.0 12.7 2.5
TAED 0.5 3.1 0.25
DETPMP 0.25 0.2 0.2
HEDP - 0.3 0.3
Antibody 10E-2 10E-4 0.1 Protease 0.0026 0.0005 0.045
Lipasa 0.003 0.003 0.003
Cellulase 0.0006 0.0006 0.0006
Amylase 0.0009 0.0009 0.0009
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
Rinse aid 2 - 0.04 0.04
Perfume particles 0.3 0.3 0.3 Silicone antifoams 0.5 2.4 2.4
Minor / various components up to 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: I II III STPP blown powder 24.0-24.0 Zeolite A - 24.0 - C45 S 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
Application by sprinkling C45E7 2.5 2.5 2.0 C25E3 2.5 2.5 2.0 Silicone foam 0.3 0.3 0.3 Perfume 0.3 0.3 0.3
Dry additives
EXAMPLE 4 (CONTINUED)
Carbonate 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 A Ammiillaassaa 0 0..000022 0.003 0.001 Antibody 10E-3 10E-3 10E-2 sulfate sodium mixed 3.0 3.0 5.0 Dry rest (humidity e 100.0 100.0 100.0 various ingredients) Density (g / liter) 630 670 670
EXAMPLE 5
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 - -C25E5 / C45E7 _ 2.0 _ 0.5
EXAMPLE 5 (CONTINUED) 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 0.007 0.004 - 0.002
Lipasa 0.004 0.002 0.004 0.002
Cellulase 0.0015 0.0005 - - Antibody 10E-2 10E-1 1 1
Bleach 70 ppm 45 ppm - 10 ppm photoactivated (ppm) Brightener 1 0.2 0.2 0.08 0.2
PBl 6.0 2.0 1.0 1.0
NOBS 2.0 1.0 0.5 0.5
Rest (humidity 100 100 100 100 different ingredients)
EXAMPLE 6
The following detergent formulations were prepared in accordance with the present invention:
I II III IV Blown powder Zeolite A 30,, 0 22.0 6.0 6.7 Na SKS-6 - - - 3.3 Polycarboxylate - - - 7.1
Sodium sulphate 19. .0 5.0 7.0 - MA / AA 3. .0 3.0 6.0 - LAS 14., 0 12.0 22.0 21.5 C45 S 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 - Carbonate 8. .0 16.0 20.0 10.0 DETPMP _ 0.4 0.4 - Application by sprinkling C45E7 1.0 1.0 1.0 3.2
Dry Additives PVPVI / PVNO 0.5 0.5 - Antibody 10E-1 10E-2 10E-2 10E-3 Protease 0.052 0.01 0.01 0.01
EXAMPLE 6 (CONTINUED)
Lipasa 0. .009 0.009 0.009 0.009
Amylase 0.001 0.001 0.001 0.001
Cellulase 0. .0002 0.0002 0.0002 0.0002 NOBS - 6.1 4.5 3.2 PBl 1.0 5.0 6.0 3.9
Sodium sulphate - 6.0 - for the rest Rest (humidity e 100 100 100 100 various ingredients)
EXAMPLE 7
The following high density and bleach-containing detergent formulations were prepared in accordance with the present invention: I 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
EXAMPLE 7 (CONTINUED)
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
Application by spray Perfume 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 _ _
Dry additives Citrate 5.0 - 2.0 Bicarbonate - 3.0 - Carbonate 8.0 15.0 10.0 TAED 6.0 2t0 5.0 PBl 14.0 7.0 10.0
Polyethylene oxide with - - 0.2 MW of 5, 000, 000 Bentonite clay - - 10.0 Antibody 10E-4 10E-2 10E-3 Protease 0.01 0.01 0.01 Lipase 0.009 0.009 0.009 Amylase 0.005 0.005 0.005 Cellulase 0.002 0.002 0.002
EXAMPLE 7 (CONTINUED)
Silicone antifoams 5.0 5.0 5.0 Dry additives Sodium sulphate 0.0 3.0 0.0 Other (moisture and miscellaneous ingredients) 100.0 100.0 100.0 Density (g / l) 850 850 850
EXAMPLE 8
The following high density detergent formulations were prepared in accordance with 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 Spray application C25E5 5.0 5.0 Perfume 0.5 0.5
EXAMPLE 8 (CONTINUED) 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 10E-4 10E-5 Protease 0.014 0.014 Lipase 0.009 0.009 Cellulase 0.001 0.001 Amylase 0.005 0.005
Silicone antifoams 5.0 5.0 Brightener 1 0.2 0.2 Brightener 2 0.2 - Rest (moisture and ingredients 100 100 different) Density (g / liter) 850 850
EXAMPLE 9
The following granular detergent formulations were prepared in accordance with the present invention:
I II III IV V
LAS 21.0 25.0 18.0 18.0 - Coco- (AS de 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 1.0
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 10E-1 10E-1 10E-1 10E-3 10E-2 Protease 0.007 0.007 0.007 0.007 0.007 0.007
Amylase _ 0.004 0.004 _ 0.004
EXAMPLE 9 (CONTINUED)
Lipasa 0.003 0.003 0.003 Cellulase - 0.001 0.001 .001 .001
NOBS 0.5 0.5 0.5 1.2 1.0
PBl 0.6 0.6 0.6 2.4 1.2
Diethylenetriamine- - - - 0.7 1.0 pentaacetic acid Diethylenetriamine- - - 0.6 - - pentamethylphosphonic acid Mg - - 0.8 - - Photoactivated bleach 45 50 ppm 15 45 ppm 42 ppm ppm ppm
Polisher 1 0.05 - 0.04 0.04 0.04
Polisher 2 0.1 0.3 0.05 0.13 0.13
Water and minor ingredients up to 100%
EXAMPLE 10
The following non-aqueous liquid detergent formulation was prepared, in accordance with the invention:
Liquid base Sodium alkyl ether sulfate salt (EO = 3) of C12_15 19.0 CFAA 7.9 C24E5 16.5
EXAMPLE 10 (CONTINUED)
N-butoxy propoxy propanol 8.6
Salt of polymethoxylated hexamethylene diamine quaternized with methyl 2.0
Perfume 0.75
PEG 200 5.4
Acetyl triathyl citrate 10.2
Solids Sodium salt of palm kernel fatty acid 5.9
Citrate 2.0 Carbonate 8.0
Percarbonate 10.0
HEDP 1.8
Brightener 0.13
Silicone oil DB-100 0.47 Antibody 10E-2
Enzymes and minor components Up to 100%
EXAMPLE 11
Granular fabric cleaning compositions were prepared which provide "wash-softening" capability, according to the present invention:
I II 45AS - 10.0 LAS 7.6 68AS 1.3 45E7 4.0 25E3 - 5.0 Coconut-alkyl- 1.4 1.0 dimethylhydroxyethylammonium 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 PBl 15.0 Percarbonate - 15.0 TAED 5.0 5.0 Smectite clay 10.0 10.0 HMWPEO - 0.1 Antibody 10E-5 10E-5 Protease 0.02 0.01
EXAMPLE 11 (CONTINUED)
Lipase 0.02 0.01 Amylase 0.03 0.005 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 12
The following compact, high density dishwashing detergent compositions (0.96 Kg / 1) were prepared in accordance with the present invention:
I II III IV V VI
STPP - - 49.0 38.0 - - Citrate 33.0 17.5 - - 54.0 25.4
Carbonate - 17.5 - 20.0 14.0 25.4
Silicate 33.0 14.8 20.4 14.8 14.8 - Metasilicate - 2.5 2.5 - - - PBl 1.9 9.7 7.8 14.3 7.8 - PB4 8.6 _ _ _ _ -
EXAMPLE 12 (CONTINUED)
Percarbonate - - - - - 6.7
Agent tensioac1.5 2.0 1.5 1.5 1.5 2.6 non-ionic agent TAED 4.8 2.4 2.4 - 2.4 4.0
HEDP 0.8 1.0 0.5 - - - DETPMP 0.6 0.6 - - - - PAAC - - - 0.2 - - BzP - - - 4.4 - - Paraffin 0.5 0.5 0.5 0.5 0.5 0.2
Antibody 10E-3 10E-3 10E-2 10E-6 10E-2 10E-1
Protease 0.075 0.05 0.10 0.10 0.08 0.01
Lipase - 0.001 - 0.005 - - Amylase 0.01 0.005 0.015 0.015 0.01 0.0025
BTA 0.3 0.3 0.3 0.3 0.3 - Nitrate of - 0.3 - - - - bismuth PA30 4.0 - - - - - Terpolymer - - - 4.0 - - 480N - 6.0 2.8 - - - Sulphate 7.1 20.8 8.4 - 0.5 1.0 pH (solution 10.8 11.0 10.9 10.8 10.9 9.6 to 1%)
EXAMPLE 13
The following granular dishwashing detergent compositions were prepared, examples I to IV, with a density of 1.02 kg / 1, according to the present invention:
I II III IV V VI
STPP 30.0 30.0 30.0 27.9 34.5 26.7
Carbonate 30.5 30.5 30.5 23.0 30.5 2.80
Silicate 7.4 7.4 7.4 12.0 8.0 20.3
PBl 4.4 4.4 4.4 - 4.4 - NaDCC - - - 2.0 - 1.5
Agent tensioac0.75 0.75 0.75 1.9 1.2 0.5 non-ionic acid TAED 1.0 1.0 - '- 1.0 - PAAC - - 0.004 - - - BzP - 1.4 - - - - Paraffin 0.25 0.25 0.25 - - - Antibody 10E-3 10E-4 10E- 1 1 10E-1 1
Protease 0.05 0.05 0.05 - 0.1 - Lipase 0.005 0.005 0.001 0.01 0.002 0.002
Amylase 0.003 0.001 0.01 0.02 0.01 0.015
BTA 0.15 - 0.15 - - - Sulfate 23.9 23.9 23.9 31.4 17.4 -pH (solution 10.8 10.8 10.8 10.7 10.7 12, .3
al?%:
EXAMPLE 14
The following detergent composition tablets of 25 g in weight, according to the present invention, were prepared by compressing a granular dishwashing detergent composition at a pressure of 13 KN / cm using a regular rotary press of 12 heads:
II III
STPP 48.8 47.5
Citrate 26.4 Carbonate - 5.0 - Silicate 26.4 14.8 25.0
Antibody 10E-2 10E-3 10E-1
Protease 0.03 0.075 0.01
Lipasa 0.005 0.005 0.005
Amylase 0.01 0.005 0.001 PBl 1.6 7.8 - PB4 6.9 - 11.4
Surfactant 1.2 2.0 1.1 non-ionic TAED 4.3 2.4 0.8 HEDP 0.7 DETPMP 0.65
EXAMPLE 14 (CONTINUED)
Paraffin 0.4 0.5 - BTA 0.2 0.3 - PA30 3.2 - - Sulfate 25.0 14.7 3.2 pH (1% solution 10.6 10.6 11.0
EXAMPLE 15
The following liquid dishwashing compositions were prepared according to the present invention:
I II III C17ES 28.5 27.4 19.2
Amine oxide 2.6 5.0 2.0
Glucosamide of C12 - - 6.0
Betaine 0.9 xylene sulfonate 2.0 4.0 Neodol C11E9 - - 5.0
Fatty acid polyhydroxyamide - Diethylene pentaacetate sodium (40%) - - 0.03
TAED - Sucrose -
EXAMPLE 15 (CONTINUED)
Ethanol 4.0 5.5 5.5
Alkyl Diphenyl Oxide Disulfonate Calcium Formate 0.06 0.1 Sodium Chloride 1.0 Magnesium Chloride 3.3 0.7 Calcium Chloride 0.4 Sodium Sulfate 0.08 Magnesium Hydroxide Sodium Hydroxide 200 ppm 0.16 0.006 Antibody 10E-3 10E- 2 10E-1
Protease 0.017 0.005 .0035
Perfume 0.18 0.09 0.09
Water and minor components Up to 100%
EXAMPLE 16
The following liquid compositions were prepared for cleaning hard surfaces in accordance with the present invention:
Hydrogen peroxide 7.0 AS 1.7 DobanolR 91-10 1.6 DobanolR 23-3 1.1 LutensolR TO 3 1.5 2 -But octanol 0.5 Antibody 10E-3 DETPMP 0.18 Water and minor components Up to 100% H2S04 up to pH 4 Up to 100%
EXAMPLE 17
Detergent additives were prepared, in accordance with the present invention:
I II III LAS - - 5 STPP 30 30 Zeolite A - - 35 PBl 20 20 15 TAED 10 10 8 Protease - - 0.3 Amylase 0.1 - 0.06 Antibody 10E + 1 10E + 1 10E0
Claims (10)
1. - A detergent composition comprising a source of hydrogen peroxide, characterized in that said detergent composition further comprises a donor: antibody directed against hydrogen peroxide reductase oxide.
2. - The detergent composition according to claim 1, further characterized in that said donor: antibody directed against hydrogen peroxide reductase oxide, is contained at a level of 10E-6% at 10E + 1% by weight of the total composition .
3. - The detergent composition according to claim 1, further characterized in that said donor: hydrogen peroxide reductase oxide, is a catalase enzyme.
4. The detergent composition according to claim 1, further characterized in that it comprises a bleach activator.
5. - The detergent composition according to claim 1, further characterized in that it comprises one or more components selected from anionic, nonionic, cationic, amphoteric and switterionic surfactants, detergency builder component, foam suppressants, suspending and anti-redeposition agents from dirt, smectite clays, and the like.
6. The detergent composition according to claim 1, further characterized in that the composition is a granular detergent composition containing not more than 15% by weight inorganic filler salt.
7. The detergent composition according to claim 1, further characterized in that the composition is a heavy duty liquid composition.
8. The detergent composition according to claim 1, further characterized in that it comprises other enzymes that provide cleaning performance and / or fabric care benefits.
9. A detergent additive comprising a source of hydrogen peroxide, characterized in that said detergent additive further comprises a donor: antibody directed against hydrogen peroxide reductase oxide. 10.- The use of a donor: antibody directed against hydrogen peroxide reductase in a detergent composition to control the deactivation of the bleach due to the presence of the donor: hydrogen peroxide reductase enzyme.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
PCPCT/US1997/011545 | 1997-08-13 |
Publications (1)
Publication Number | Publication Date |
---|---|
MXPA99001624A true MXPA99001624A (en) | 1999-06-01 |
Family
ID=
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