CZ312997A3 - Detergent and process of wetting clothes - Google Patents

Abstract

Soaking compositions are disclosed which comprise a bleach, a builder; an anionic surfactant, a proteolytic enzyme; and a stability enhanced amylase enzyme . A process of soaking fabrics is also disclosed, wherein said fabrics are immersed in a soaking liquor comprising water and an effective amount of the composition above.

Description

Technical field

The present invention relates to a detergent composition and a method of soaking fabrics. More particularly, the present invention relates to a detergent composition comprising an oxygen bleach, a builder, a proteolytic enzyme, and an amylase enzyme with enhanced stability. Furthermore, the present invention relates to a method of soaking substances in a soaking liquid according to which the substance is immersed in a wicking liquid containing a detergent composition.

BACKGROUND OF THE INVENTION

Methods of soaking fabrics are described in the art. When soaking, the substances are contacted with the soaking liquid for an extended period of time ranging from several hours to overnight. This washing method has the advantage of maximizing the contact time between the substances and the key active ingredients of the soaking liquid. It also has the advantage of reducing or eliminating the need for typical washing procedures, which include the need for mechanical agitation, or improving the efficiency of subsequent typical washing.

These soaking processes are typically effective for removing stubborn stains, such as blood and food stains, which contain a mixture of protein substances as well as starch. It is therefore desirable that the soaking compositions comprise both a protease and amylase. However, in such dipping compositions, amylases are exposed to proteolytic action when the dipping composition dissolves to form a dipping liquid. This is a particularly acute soaking problem where the contact time of the components in general, and the amylase and protease in particular, is usually considerably longer than typical washing procedures. It is therefore an object of the present composition to provide soaking compositions comprising amylase and protease and in which the amylase resists proteolytic action for a significant period of time.

· · · · · · · · · · · · · · · · · · Toto · · · · · · · · · · · · · · · · · · · · · · · · · · To ·

Another requirement for soaking compositions is that they should contain an oxygen bleaching agent, preferably a large amount of such bleaching agent. Indeed, it has been found that oxygen bleaching agents have suitable conditions for bleaching efficacy in soaking, where the contact time between the active ingredients of the compositions and the soiled substances is maximized. The presence of a bleaching agent is also detrimental to the stability of the enzymes during soaking. In fact, bleaching agents, especially in large quantities, denature the quaternary structure of the enzymes, thus exposing the amylase to an even more aggressive proteolytic effect.

Another requirement for soaking compositions is that they should contain significant amounts of builders. In fact, the presence of building components is necessary to effectively control the water hardness. The builders are even more necessary in soaking, where the contact time between the substances and the washing solution is longer compared to normal washing and hence the hardness has to be regulated for a much longer time. Thus, in order to overcome the particularities of the soaking process, the soaking means must contain large amounts of building components. However, the presence of large amounts of builders is also detrimental to the action of enzymes. Indeed, these builders tend to bind all of the calcium present in the soaking solution, inter alia, while some calcium is needed to provide the appropriate enzyme activity.

Finally, a further requirement for soaking compositions is that they should contain significant amounts of anionic surfactant. The preferred class of anionic surfactants is, for reasons of cost and performance, an alkylbenzene sulfonate, especially a linear alkylbenzene sulfonate. However, some anionic surfactants, especially linear alkylbenzene sulfonates (LAS), appear to be detrimental to enzyme stability.

It is therefore an object of the present invention to provide a soaking composition suitable for soaking comprising amylase in combination with a protease, a bleaching system, a large amount of builder, and an anionic surfactant, preferably. · ♦ ·· ····· <? With LAS, the amylase remains active for a long time, consistent with the soaking properties.

SUMMARY OF THE INVENTION

In one embodiment, the present invention relates to compositions comprising:

- oxygen bleach,

from 5 to 50 wt. components from the total weight of the product,

from 0.5 to 20 wt. anionic surfactant, preferably linear alkylbenzene sulfonates, of the total weight of the composition,

proteolytic enzyme, and

- an amylase enzyme with increased stability, this stability increase being considered relative to the original / unmated form of the amylase enzyme.

In another embodiment, the present invention comprises a method of soaking fabrics, wherein the substances are immersed in a soaking liquid comprising water and an effective amount of the above composition.

The present invention includes a composition and method for soaking fabrics. This composition, hereinafter referred to as the soaking means, is used for soaking.

In a first embodiment, the present invention relates to a composition comprising a bleaching agent, a builder, an anionic surfactant, a proteolytic enzyme, and an amylolytic enzyme.

As a first essential component, the compositions of the invention comprise an oxygen bleaching agent. Suitable bleaching agents in the composition may come from a variety of sources, such as hydrogen peroxide or any addition compounds of hydrogen peroxide, organic peracids or mixtures thereof. By hydrogen peroxide addition compounds is meant those compounds which are formed by the addition of hydrogen peroxide to a second chemical compound, which may be, for example, an inorganic salt, urea or organic carboxylate, so as to obtain an addition compound. Examples of hydrogen peroxide addition compounds include inorganic hydrogen peroxide hydrates, hydrogen peroxide compounds with organic carboxylates and urea, and compounds in which hydrogen peroxide is in the form of clathrates.

Examples of inorganic persolates include perborates, percarbonates and per silicates. Inorganic compounds are normally alkali metal salts. Preferred inorganic compounds for use herein are alkali metal percarbonate and perborate or mixtures thereof. A preferred alkali metal percarbonate is sodium percarbonate.

Other oxygen bleaching agents include persulfates, especially potassium persulfate K ₂ S ₂ 0 ₈ and sodium persulfate Na ₂ S ₂ 0 ₈ .

The soaking compositions of the present invention may comprise from 1 to 60, preferably from 2 to 40, and more preferably from 15 to 40 wt. a source of hydrogen peroxide by weight of the composition.

As a second essential component, the compositions according to the invention comprise the builder component or mixtures thereof in an amount of from 5 to 50, preferably from 10 to 40, most preferably from 15 to 30% by weight. of the total weight of the composition. Suitable builders for use herein include both inorganic and organic builders.

Inorganic or phosphorus-containing detergent builders include, but are not limited to, alkali metal polyphosphates (e.g., triphosphates, pyrophosphates, and glassy polymeric metaphosphates), ammonium and alkanolammonium salts, phosphonates, phytic acid, silicates, carbonates, and bicarbonates sulphates and aluminosilicates. Non-phosphate components are required in some areas. Surprisingly, the compositions according to the invention function in the same manner as the flour. Well in the presence of so-called weak builders (as compared to phosphates) such as citrates, or in so-called under-built situations that may occur for zeolite or layered silicate builders.

Examples of silicate builders are alkali metal silicates, especially those having a SiO ₂ :: Na ₂ O ratio of from 1.6: 1 to 3.2: 1, and layered silicates such as the sodium layered silicates described in U.S. Patent 4,664 839 HPRiecke, issued May 12, 1987. NaSKS-6 is a trademark of crystalline layered silicate sold by Hoechst (usually abbreviated as SKS-6 "). Unlike the zeolite components NaSKS-6, the silicate component does not contain aluminum. NaSKS-6 has delta-Na ₂ SiO ₅ morphological form of layered silicate. It can be produced by methods such as those described in A-3 417 649 and A-3 742 043. SKS-6 is a highly preferred layered silicate for use herein, but other layered silicates such as are silicates of the formula NaMSi _x O _{2 + 1} .y H ₂ O in which M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0 Various other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 such as alpha, beta and gamma forms. As mentioned above, the most preferred for use herein is delta-Na ₂ SiO ₅ (NaSKS-6 form). Other silicates may also be useful, such as magnesium silicate, which may serve as an aid in shaping granular compositions, as a stabilizer for oxygen bleaching agents, and as a component for suds control systems.

Examples of carbonate builders are alkali metal and alkaline earth carbonates as described in German Patent Application No. 2,321,001, published November 15, 1973.

Aluminosilicate components are useful in the present invention. Aluminosilicate builders are very important in the most commonly marketed high performance granular detergent compositions. They may also be an important builder in liquid detergent compositions. The aluminosilicate components include compounds of formula

M _z [(zA 102 ₂ ) _y ] .x H ₂ O, wherein z and z are at least 6, the molar ratio of z is in the range of 1.0 to 0.5 and x is from 15 to 264.

Useful aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring or synthetically derived aluminosilicates. A method for producing aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669 to Krummel et al., Issued October 12, 1976. Preferred synthetic crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite. X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the general formula

Na ₁₂ [(A10 ₂ ) _12. (SiO ₂ ) ₁₂ ] .x H ₂ O, where x is a number from 20 to 30, especially 27. This material is known as Zeolite A. Dehydrated zeolites can also be used here ( x is from 0 to 10). The aluminosilicate preferably has a particle size (diameter) of from 0.1 to 10 μια.

Organic components suitable for the purposes of the present invention include, but are not limited to, a variety of polycarboxylate compounds. The term polycarboxylate as used herein means compounds with multiple carboxylate groups, preferably at least three carboxylates. The polycarboxylate builder can generally be added to the composition in acid form, but can also be added in the form of a neutralized salt. When used in salt form, alkali metal salts such as sodium, potassium and lithium salts or alkanolammonium salts are preferred.

Polycarboxylate builders include various categories of useful materials. One important category of polycarboxylate components includes ether polycarboxylates, including oxy disuccinates, as described in U.S. Patent 3,128,287 Berg, issued April 7, 1964, and U.S. Patent 3,635,830 Lamberti. et al., issued Jan. 18, 1972. See also TMS / TDS builders in U.S. Patent 4,663,071 to Bush et al. Suitable polycarboxylates also include cyclic compounds, especially alicyclic compounds such as those described in U.S. Patents 3,923,679, 3,835,163, 4,120,874, and U.S. Pat.

102 903.

Other useful builders include ether hydroxypolycarboxylates such as 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, various salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid with an alkali metal and ammonia, and substituted ammonium salts of these acids as well as polycarboxylates such as melitic acid, succinic acid, oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid, and soluble salts thereof.

Other polycarboxylate builders for use herein include those of Formula I

R ¹ - [-Y _P - (-CH ₂ -CR ³ -) -] - - R ²

I (I), CO ₂ M wherein Y is a comonomer or comonomer mixture, R ¹ and R ² are bleaching and alkali-stable polymer end groups, R ³ is hydrogen, OH or C 1 -C 4 alkyl, M is a hydrogen atom, an alkali metal, an alkaline earth metal, ammonium or substituted ammonium, p is a number from 0 to 2 and n is at least a number 10, or mixtures thereof.

Preferred polymers for use herein fall into two categories. The first category belongs to a group of copolymer polymers that are formed from an unsaturated polycarboxylic acid such as maleic, citraconic, itaconic, mesaconic acid.

4 • 4

And its salts as the first monomer and an unsaturated monocarboxylic acid such as acrylic acid or α-alkyl (C 1 -C 4) acrylic acid as the second monomer. Referring to the above formula (I), the polymers belonging to the first group are those wherein p is not 0 and Y is a group selected from the above acids. Preferred polymers of this group are those of formula (I) above wherein Y is maleic acid. Preferably also R ³ and M represent hydrogen atoms and n is a number such that the polymers have a molecular weight of from 1000 to 400 000th

A second category of preferred polymers for use in the present invention is the group of polymers in which, given the above general formula I, p is 0 and R ³ is hydrogen or C 1 -C 4 alkyl. In a preferred embodiment, n is such that the polymers have a molecular weight of from 1000 to 400,000. In a highly preferred embodiment, R ³ and M are hydrogen.

Among the alkali-stable polymer end groups R ¹ and R ² in the above general formula I include alkyl groups, oxyalkyl groups and alkyl carboxylic acid groups and salts and esters thereof.

In the above, the degree of polymerization n can be determined from the weight average molecular weight of the polymer by dividing the second value by the average molecular weight of the monomer. For a maleic / acrylic acid copolymer with a weight average molecular weight of 15,000 containing 30 mole% units derived from maleic acid is n 182 (i.e., 15,500 / (116.0.3 + 72.0.7)).

Temperature controlled columns at 40 ° C are used against polymer standards of sodium polystyrene sulfonate, available from Polymer Laboratories Ltd., Shropshire, England, polymer standards are 0.15M sodium dihydrogen phosphate and 0.02M tetramethylammonium hydroxide at pH 7.0 in water / acetonitrile. (80/20).

Of all the above, the highly preferred polymers for use herein are those of the first category wherein n is an average of from 100 to 800, preferably from 120 to 400.

Citrate components, such as citric acid and its soluble salts (especially sodium salt), are polycarboxylate components particularly important for their availability from renewable sources and their biodegradability. Citrates can also be used in combination with zeolite and / or layered silicate builders. Oxydisuccinates are particularly useful in these compositions and combinations thereof.

Also suitable in the detergent compositions of the present invention are 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the like, which are described in U.S. Patent 4,566,984, Bush, issued Jan. 28, 1986. acids include alkyl and alkenyl (C 5 -C 20) succinic acids and salts thereof. A particularly preferred compound of this type is dodecenylsuccinic acid. Specific examples of succinate components include: lauryl succinate, myristyl succinate, palmityl succinate, 20-dodecenyl succinate (preferred), 2-pentadecenyl succinate and the like. Lauryl succinates, which are preferred components of this group, are described in European Patent Application 86200690.5 / 0 200 263, published November 5, 1986.

Other suitable polycarboxylates are described in U.S. Patent 4,144,226 to Crutchfield et al., Issued March 13, 1979, and U.S. Patent 3,308,067 to Diehl, issued March 7, 1967. See also U.S. Patent No. 3,723,322 to Diehl.

Fatty acids, such as C 12 -C 18 monocarboxylic acids, may also be included in the compositions alone or in combination with the aforementioned builders, especially citrate and / or succinate builders, to provide additional activity.

·· ····

In situations where phosphorus-based components can be used, and especially in the handwash bar type composition, various alkali metal phosphates such as the well-known sodium triphosphates, sodium pyrophosphate and sodium ortho-phosphate can be used. Phosphonate components such as ethane-1-hydroxy-1,1-diphosphonate and other known phosphonates can also be used (see, for example, U.S. Patents 3,159,581, 3,213,030, 3,422,021, 3,400,148 and 3,422,137).

As a third essential component, the compositions of the invention comprise anionic surfactant or mixtures thereof in an amount of from 0.5 to 20, preferably from 3 to 15, and most preferably from 5 to 10% by weight. of the total weight of the composition.

Suitable anionic surfactants for use in the present invention include water-soluble salts or acids of the formula RSO ₃ M, wherein R is preferably a C 10 -C 24 hydrocarbon group, preferably an C 10 -C 24 alkyl or hydroxyalkyl group. And C represents a hydrogen atom or a cation, e.g. an alkali metal cation (e.g., sodium, potassium, lithium) or an ammonium or substituted ammonium cation (e.g., methyl-, C,-C, alky); dimethyl and trimethylammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines (such as ethylamine, diethylamine, triethylamine and mixtures thereof and the like). For lower wash temperatures, alkyl chains of 12 to 16 carbon atoms (e.g. below 50 ° C) are preferred, for higher wash temperatures, alkyl chains of 16 to 18 carbon atoms are preferred.

Other suitable anionic surfactants for use herein include water soluble salts or acids of the general formula R0 (A) _m S0 ₃ M wherein R is an unsubstituted alkyl or hydroxyalkyl group having 10 to 24 carbon atoms having an alkyl component of from 10 to 24 carbon atoms, preferably an alkyl or hydroxyalkyl group having 12 to 20 carbon atoms, more preferably an alkyl or hydroxyalkyl group having 12 to 18 carbon atoms, A is an ethoxy or propoxy unit, m is a number greater than zero , typically between 0.5 and 6, more preferably between 0.5 and 3, and M represents a hydrogen atom or a cation, which may be, for example, a metal cation (e.g., sodium, potassium, lithium, calcium, magnesium, etc.), an ammonium cation or substituted ammonium cation. Also included are alkyl ethoxylated sulfates and alkyl propoxylated sulfates. Specific examples of substituted ammonium cations include methyl, dimethyl, trimethyl ammonium and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium, and alkanolamine-derived cations such as ethylamine, diethylamine, triethylamine, mixtures thereof and the like. Examples of surfactants are alkyl (12 to 18 carbon atoms) polyethoxy (1,0) sulfate, denoted C ₁₂ -C ₁₈ E (1,0) M, alkyl (12 to 18 carbon atoms) polyethoxy (2,25 ) sulfate, C ₁₂ -C ₁₈ E (2,25) M, alkyl (C ₁₂ -C ₁₈ ) polyethoxy (3,0) sulfate, C ₁₂ -C ₁₈ E (3,0) M, and alkyl (s) 12 to 18 carbon atoms) poly ethoxy (4,0) sulfate, C ₁₂ -C ₁₈ E (4,0) M, wherein M is suitably selected from sodium and potassium.

Other anionic surfactants may also be used herein for cleaning purposes. These include salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts, such as mono-, di-, and triethanolamine salts) of soaps, linear C 9 -C 20 linear alkylbenzene sulfonates, C 8 -C 22 primary or secondary alkane sulfonates, C 8 -C 24 olefin sulfonates, sulfonated polycarboxylic acids prepared by sulfonating a pyrolyzed alkaline earth citrate product, e.g. as described in British Patent No. 1,082,179, alkyl (C 8 -C 24) polyglycol ether sulfates (containing up to 10 moles of ethylene oxide) ), alkyl ester sulfonates such as C14-C16 methyl ester sulfonates, acylglycerol sulfonates, oleyl glycerol sulfates, alkylphenol ethylene oxide ether sulfates, paraffin sulfates, alkyl phosphates, isethionates such as acyl isethionate, N-acyltaurates, mono-succinate sulfates, alkyl succinamate sulfates 12 to 18 carbon atoms), sulfosuccinate diesters (especially saturated and unsaturated diesters of 6 to 14 carbon atoms), acyl sarcosinates, alkylpolysaccharide sulfates such as alkylpolyglycoside sulfates (nonionic unsulfated compounds described below), branched primary alkyl sulfates, alkylpolylate polyethoxylates such as compounds of formula RO (CH ₂ CH ₂ O) _to CH ₂ CO-M ⁺ , wherein R is an alkyl group of 8 to 22 carbon atoms, k is an integer from 0 to 10 and M is a soluble salt-forming cation. Also suitable are resin acids and hydrogenated resin acids such as rosin, hydrogenated rosin, and resin acids and hydrogenated resin acids present in or derived from tallow oil. Further examples are given in Surface Active Agents and Detergents (Parts I and II by Schwartz, Perry and Berch). These various surfactants are also generally described in U.S. Patent 3,929,678 to Lauglin et al., Issued December 30, 1975, at column 23, line 58, to column 29, line 23 (herein incorporated by reference).

Highly preferred surfactants for use in the compositions of the invention are alkylbenzene sulfonates, especially linear alkylbenzene sulfonates.

As a fourth essential element, the compositions of the invention comprise a protease or mixtures thereof. Protease enzymes are usually present in preferred embodiments of the invention in amounts sufficient to provide 0.005 to 0.2 Anson Units (AU) of activity per gram of composition. The proteolytic enzyme may be of animal, vegetable or preferably microorganism origin. More preferred is a serine proteolytic enzyme of bacterial origin. Purified or uncleaned forms of the enzyme may be used. Proteolytic enzymes produced by chemically or genetically modified mutants are included herein by definition, such as closely related structural enzyme variants. A particularly preferred proteolytic enzyme is a bacterial serine proteolytic enzyme derived from Bacillus, B. subtilis and / or B. odd niformis. Suitable commercial proteolytic enzymes include Alcalase ^(R> , Esperase ^(R) , Durazym ^(R) , Savinase ^<R> , Muxatase ^<R> , Maxacal ^(R) and Maxapam ^<R> 15 (protein assembled by Maxacal), commercially available also Purafect ^(R &apos; and subtilisin BPN and BPN &apos;). Preferred proteolytic enzymes also include modified serine proteases such as those described in European Patent Application No. 87303761.8, filed April 28, 1987 (particularly pages 17, 24 and 98) and which is referred to herein as Protesia B, and in European Patent Application 199,404 Venegase, published October 29, 1986, which refers to a modified bacterial serine proteolytic enzyme referred to herein as Protease A. More preferred is Protease C, which is a triple variant of alkaline serine protease. from Bacillus, in which tyrosine replaces valine at position 104, serine asparagine at position 123 and alanine threonine at position 274. Protease C is described in European patent 90915958.4, disclos See WO 91/06637, published May 16, 1991, which is incorporated herein by reference. Also included are genetically mutated variants, particularly Protease C.

Also suitable for use in the present invention is a protease called Protease D, which is a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence that is derived from a precursor carbonyl hydrolase by substituting different amino acids for multiple amino acid residues at a position of the carbonyl hydrolase that is + 76 position equivalent, in combination with one or more amino acid residue positions that are equivalent to positions selected from the group consisting of +99, +101, +103, +107 and +123 in Bacillus amyloliguefaciens subtilisin, as described in co-administered A. Baeck, CKGhoshe, PP Greycar, RRBott and LJ Wilson, entitled Protease-Containing Cleaning Compositions as US Patent Application No. 08/136 797 (P&G Time 5040) and Bleaching Compositions Comprising Protease Enzymes as US Patent Application No. 08/136 626, which are incorporated herein as a reference.

Some preferred proteolytic enzymes are selected from the group consisting of: 9 · φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ φ <<<

Pins consisting of the proteases Savinase ^(R) , Esperase ^(R) , Maxacal ^(R) , Purafect ^(R) , BPN ', Protease A and Protease B, and mixtures thereof. Preferred are bacterial serine protease enzymes derived from Bacillus subtilis and / or Bacillus licheniformis. Particularly preferred are Savinase ^(R) , Alcalase ^(R) , Protease A, and Protease B.

As a fifth essential element, the compositions of the invention comprise amylase. It is known to modify enzymes for improved stability, for example stability to oxidation. See, for example, J. Biological Chem. 260 (11). 6518 (June 1985).

Reference amylase herein refers to amylase outside the amylase components of the invention and with which the stability of any amylase of the invention can be measured.

Accordingly, the present invention allows the use of amylases with improved stability in detergent compositions, in particular improved oxidation stability. A suitable absolute stability reference point to which the amylases in the present invention are compared is to measure the stability improvement of Termamyl ^(R) in commercial use in 1993, available from Novo Nordisk A / S. This Termamyl ^(R) amylase is a reference amylase. Amylases within the spirit and scope of the present invention, which are amylases with improved stability, are characterized by having at least a measurable improvement in one or more of the following: oxidation stability, e.g., hydrogen peroxide / tetraacetylethylenediamine in a buffered solution at pH 9-10, thermal stability, e.g. at conventional wash temperatures, such as about 60 ° C, or stability to an alkaline environment, e.g. at pH from 8 to 11, all measured against the above reference amylase. Preferred amylases of the invention may represent a further improvement over selected reference amylases, which are illustrated by one or more precursor amylases, wherein the amylases of the invention are variants thereof. These precursor amylases may be a natural product or a genetic engineering product. Stability can be measured using any of the technical tests described in the art. See the references described in WO 94/02597 itself and in the documents cited therein, which are incorporated herein by reference.

Amylases with increased stability according to the invention can generally be obtained from Novo Nordisk A / S or from Genencor International.

Preferred amylases of the invention are most often derived from site-directed mutagenesis of one or more Bacillus amylases, particularly Bacillus alpha-amylases, regardless of whether the immediate precursors are one, two or more amylase strains.

As noted above, amylases with enhanced oxidation stability are preferred for use in the present invention. These amylases are illustrated without limitation by the following examples:

a) Amylase according to the above WO 94/02597, Novo Nordisk A / S, published February 3, 1994, as further illustrated by a mutant substitution using alanine or threonine (preferably threonine) methionine residue located at position 197 Bacillus licheniformis alpha-amylase, known as Termamyl ^(R) , or homologous position variations similar to parental amylase, such as Bacillus amyloliquefaciens, Bacillus subtilis or Bacillus stearothermophilus.

(b) Amylases with enhanced stability, as described by Genencor International in Oxidatively Resistant alpha-Amylases, presented by C. Mitchinson at the 207th National Meeting of the American Chemical Society on 13-17 March 1994. This work states that bleaching agents in automatic laundry detergent compositions, they inactivate alpha-amylases, but that Genencor has made amylases with improved oxidation stability from Bacillus Licheniformis NCIB8061. Methionine (Met) was identified as the most likely modified residue. Methionine was substituted all at once at positions 8, 15, 197, 256, 304, 366 and 438, resulting in specific mutants, of which the following were particularly important: · 4444 ··· · 49 ·· · 4444 4 4 4 · ··· ·

The variants M197L and M197T were the most stable expressing variants, the variant M197T. Stability was measured for Cascade (R) and Sunlight (R). These enzymes are commercially available from Genencor under the tradename Plurafact Oxam (R).

c) Particularly preferred according to the invention are amylase variants with further modifications in parental amylase available from Novo Nordisk A / S. These amylases do not yet have a trade name, but are amylases, which the supplier refers to as QL37 + M197T. These enzymes are commercially available under the tradename SP 703 from Novo Nordisk.

Any other stability-enhanced amylases may be used, for example, amylases derived by site-directed mutagenesis of known chimeric, hybrid, or simply mutated parent forms of available amylases.

The soaking compositions of the present invention may further comprise various other ingredients.

Optional but preferred components after use according to the invention are bleach activators. Examples of suitable compounds of this type are described in British Patent 1,586,769 and 2,143,231. Preferred examples of such compounds are tetraacetylethylenediamine (TAED), sodium 3,5,5-trimethylhexanoyloxybenzenesulfonate, diperdodecanoic acid, as described, for example, in U.S. Patent No. 4. 818,425, peradipic acid nonylamide as described, for example, in U.S. Patent 4,259,201, and nonanoyloxybenzenesulfonate (NOBS) and acetyltriethyl citrate (ATC), as described in European Patent Application 91870207.7. Particularly preferred are also N-acyl-caprolactams selected from the group consisting of substituted or unsubstituted benzoylcaprolactam, octanylcaprolactam, nonanoylcaprolactam, hexanoylcaprolactam, decanoylcaprolactam, pentanoylcaprolactam, propylcaprolactam, formylcaprolactam, formyl. The soaking compositions of the invention may comprise mixtures of such bleach activators.

· · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · · * ·· ··· 4

Preferred bleach activator compositions of the invention comprise nonanoyloxybenzene sulfonate (NOBS) together with a second bleach activator which has a low tendency to generate diacyl peroxide but which mainly provides peracid. Second bleach activators may include tetraacetylethylenediamine (TAED), acetyl triethyl citrate (ATC), acetyl caprolactam, benzoyl caprolactam and the like or mixtures thereof. These bleach activator mixtures are preferably used in embodiments of the present invention, wherein the soaking liquids are adjusted to have a pH below 50 ° C.

9.5. Indeed, bleach activator mixtures containing nonanoyloxybenzene sulfonate and second bleach activators have been found to enhance cleaning performance while at the same time showing good performance in diacyl peroxide-sensitive soils (e.g. beta-carotene) and peracid-sensitive soils (e.g. body soils).

The soaking compositions of the invention may comprise from 0 to 15, preferably from 1 to 10, more preferably from 3 to 7 wt. and from 0 to 15, preferably from 1 to 10, more preferably from 3 to 7% by weight of nonanoyloxybenzenesulfonate. a second bleach activator based on the total weight of the composition.

It may be desirable that the compositions further comprise chelating agents that help control the level of heavy metal ions in the soaking liquids to prevent rapid decomposition of the oxygen released by the available oxygen source. Suitable amine carboxylate chelating agents which may be used according to the invention include diethylenetriaminepentaacetic acid, ethylenediaminetetraacetates (EDTA), N-hydroxyethylethylenediamine triacetates, nitrile triacetates, ethylenediaminetetrapropionates, triethylenetetramine hexaacetates and the metal salts thereof, ethanediglycetes, and their ethanediglycates. Other suitable chelating agents include ethylenediamine-N, N'-disuccinic acids (EDDS) or their alkali metal, alkaline earth metal, ammonia or substituted ammonium salts thereof. Particularly preferred EDDS compounds are the free acid and the sodium salt, the magnesium salt and the magnesium salt.

9 Φ Φ Φφ • 999 · 999 999 99 «or its complex. Other suitable chelating agents may be organic phosphonates, including aminalkylene poly (alkylene phosphonate), alkali metal ethane-1-hydroxy-diphosphonates, nitrile trimethylene phosphonates, ethylenediaminetetramethylene phosphonates and ethylenetriaminepentamethylene phosphonates. The phosphonate compounds may be present either in acid form or in the form of their alkali metal salt. If present, preferred phosphonate compounds are in the form of their magnesium salts.

The soaking compositions of the present invention may contain 0 to 5, preferably 0 to 3, more preferably 0.05 to 2 wt. of the total weight of the compositions.

The soaking compositions of the present invention may further comprise other optional ingredients such as other non-anionic surfactants, fillers, optical brighteners, other enzymes, soil release agents, photoactivated bleaching agents such as zinc phthalocyanine sulfonate, dyes, transfer inhibitors dyes, pigments and perfumes. Said optional ingredients may be added in various amounts, as desired.

The compositions of the invention may be manufactured in solid, preferably granulated, or liquid form.

In a second embodiment, the present invention comprises a method of soaking fabrics. The term "wetting process" as used herein means that the substances are soaked in a soaking liquid containing water and a composition as described above for a time sufficient to purify the substances. The soaking process may be performed independently of other processes, such as a typical washing operation, or a first stage prior to a second typical washing stage. According to a preferred method of soaking, the substances are allowed to soak for a period of from 10 minutes to 24 hours, preferably from 30 minutes to 24 hours, most preferably from 4 hours to 24 hours after the substances have been immersed in said soaking liquid. remove it and rinse with water. Substances are then after soaking mo44 4 · ♦ 4 • 4 · ·· ···

4 4 · * · ······ 4 «·

4 ··· 4 ··· 444 Can be washed by normal washing procedure with or without rinsing between soaking and subsequent washing.

In the soaking process of the invention, the above soaking means is diluted with an appropriate amount of water to obtain a soaking liquid. Suitable dosages may be from 45 to 50 g of the soaking composition in 3.5 to 5 liters of water to 90 to 100 g of the soaking composition in 25 to 45 liters of water. A typical dose is 45 to 50 g in 3.5 to 5 L for a concentrated soaking solution (bucket per container). For washing in a washing machine, a dose of 90 to 100 g in 20 (Europe) to 45 (US) 1 water is used. The substances to be soaked are then immersed in the soaking solution for an appropriate period of time.

There are factors that can affect the overall performance of this method with the respective dirt / dirt. These factors include extended soaking time. The longer the soaking time, the better the results will be. The ideal soaking time is overnight soaking, ie 12 to 24 hours. Another factor is the initial warm or slightly warm temperature. A higher initial temperature of the dipping liquids ensures better performance.

DETAILED DESCRIPTION OF THE INVENTION

The following compositions are made by mixing said ingredients in the proportions indicated. The soaking liquids are prepared by diluting each time 45 g of said compositions with 3.5 to 5.0 L of water. Thereafter, 0.5 to 2 kg of substances are immersed in said soaking liquid for 10 minutes to 24 hours. Finally, the fabrics are removed from the soaking liquids, rinsed in water and washed by a conventional washing method, manually or in a washing machine, with conventional detergent compositions, with or without the use of a dipping liquid, and then allowed to dry. Thus, compositions 1 to 6 are produced (the amount of ingredients in the tables is given in% by weight).

• · · A * 9 • 9 • · · · · · • ···· · · • · · ··· ♦ <·· * 9 • · ··· ·· 20 May component 1 2 3 Plurafact Oxam (R) or SP 703 0.29 0.29 0.29 (@ 4% active protein) Protease B (@ 4% active protein) 0.26 0.52 0.52 sodium perborate monohydrate 29 29 29 sodium percarbonate 0 0 0 citric acid 11 11 11 Zeolite A 12 12 12 polyacrylate (Acusol 445ND) 10 10 10 sodium silicate (amorphous; 1,6r) 0.3 0.3 0.3 anionic reagent (LAS) 7 7 7 NOBS 10 10 5 TAED 0 0 5 DTPA 0.2 0.2 0.2 other inert and minor additives add to 100 ALIGN!

and··

component 4 5 6 Plurafact Oxam (R) or SP 703 0.26 0.26 0.26 (@ 4% active protein) Protease B (@ 4% active protein) 1.00 0.50 0.50 sodium perborate monohydrate 0 0 0 sodium percarbonate 31 31 31 citric acid 10 10 10 Zeolite A 0 0 0 polyacrylate (Acusol 445ND) 11 11 11 sodium silicate (amorphous; 1,6r) 0.4 0.4 0.4 anionic reagent (LAS) 4 4 4 NOBS 6 6 0 TAED 6 6 12 DTPA 0.2 0.2 0.2 other inert and minor additives add to 100 ALIGN!

·· ····

Claims (6)

PATENT CLAIMS A detergent composition comprising: - oxygen bleach, from 5 to 50 wt. components from the total weight of the product, from 0.5 to 20 wt. anionic surfactant of the total weight of the composition, proteolytic enzyme, and an amylase enzyme with increased stability, this stability increase being considered relative to the original / unmutated form of the amylase enzyme. 2. A detergent composition according to claim 1 wherein the anionic surfactant is a linear sodium alkyl benzene sulfonate. Detergent composition according to any one of the preceding claims 1 to 3, characterized in that it comprises from 3 to 15, preferably from 5 to 10% by weight. anionic surfactant. Detergent composition according to any one of the preceding claims 1 to 4, characterized in that the amylase anezoid with increased stability has an increased stability to oxidation. 5. A detergent composition according to claim 4 wherein the oxidation stability is enhanced by substituting a threonine for a methionine residue located at position 197 of Bacillus lichenformis or a variation in the homologous position similar to the original amylase. Detergent composition according to any one of the preceding claims 1 to 5, characterized in that it contains 10 to 40, preferably 15 to 30 wt. house • · ···· · ·· 8. 8. 9. 9. 10. 10. 11. 11. 12. 12. folders A detergent composition according to any one of the preceding claims, characterized in that it contains from 1 to 60% by weight, preferably from 15 to 40% by weight. an oxygen bleaching agent. A detergent composition according to any one of the preceding claims wherein the oxygen bleaching agent is an alkali metal perborate or percarbonate salt. A detergent composition according to any one of the preceding claims, further comprising a bleach activator. A detergent composition according to any one of claims 1 to 9, wherein the protease is Savinase ^(R) , Allacalase ^(R) and Protease A and Protease B. A method of soaking fabrics, characterized in that the substance is immersed in an absorbent liquid containing an effective amount of a composition according to any one of the preceding claims 1 to 10 for an effective period of time and then removed from the soaking solution. A method of soaking according to claim 11, wherein the soaking time is 10 minutes to 24 hours.