JP3095786B2 - Detergent composition containing a combination of α-amylases for odor removal - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention relates to detergent compositions comprising a combination of different α-amylases to achieve improved odor removal from articles in hard surface cleaning, dishwashing, and laundry applications. Things.

BACKGROUND OF THE INVENTION For many years, amylase enzymes have been used for a variety of different purposes, the most important of which are starch liquefaction, textile sizing, starch denaturation in the paper and pulp industry, and fermentation and baking. . A further application of an increasingly important amylase is the removal of starch, including dirt and contaminants when washing hard surfaces and dishes.

In fact, the amylase enzyme performs the removal of starchy food residues or starchy films from dishes, pans, glasses and hard surfaces, or provides cleaning performance against other soils commonly experienced in laundry applications, as well as starchy soils Has been evaluated for many years in dishwashing, hard surface cleaning and laundry compositions.

Novo Nordisk A / S, WO 94/02597, dated February 3, 1994, describes a cleaning composition mixed with a mutant amylase. At the same time Genencor WO 94/183
Issue 14 (August 18, 1994) and Novo Nordisk A
See / 95 WO 95/10603 (with 1920 days).

Other well-known amylases used in the cleaning compositions include both α- and β-amylases.
Alpha-amylases are well known and are described in U.S. Patent No. 5,003,257.
No .; EP 252,666; WO 91/00353; FR 2,676,456; EP
Nos. 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1,296,839 (Novo).

Commercially available α-amylase products are Novo Nordisk A / SD
"Termamyl ^R ", "Ban ^R " and "Fungamy" from enmark
l ^R ”.

Recently, a novel amylase was identified, and Novo Nordisk A / S
WO 95/26397, dated October 5, 1995,
Discloses α- amylase having a specific activity superior "Termamyl ^R".

A combination of a starch deblanch enzyme selected from pullulanase, isopululase and isoamylase with an α-amylase is disclosed in EP 368 341;
Nos. 40654 and 06172796 describe the enhancement of cleaning performance on starch, grease and protein containing soils during laundry and automatic dishwashing.

Various types of amylase sensitivity found on textiles, dishes, hard surfaces, etc. Odorous materials are incorporated during daily contamination, and incomplete and inefficient removal of such contamination can cause malodor formation. I understood.

It has now been found that the combined use of different α-amylases improves the elimination of offensive odors from various types of amylase-sensitive daily contamination. Particularly good malodor control against daily pollution such as body pollution is achieved when amylases are further used in combination with cellulases.

Accordingly, an object of the present invention is to provide an α-amylase-containing detergent composition that exhibits excellent odor control properties against amylase-sensitive daily contamination.

Another object of the present invention is to provide an α-amylase enzyme-containing detergent composition exhibiting excellent malodor control properties against body stains.

SUMMARY OF THE INVENTION The present invention is directed to a detergent composition comprising a combination of different α-amylases to achieve improved odor removal from articles in hard surface cleaning, dishwashing, and laundry applications.

DETAILED DESCRIPTION OF THE INVENTION α-Amylase enzymes An essential component of the detergent composition of the present invention is an α-amylase enzyme.

While not wishing to be bound by theory, the combination of several α-amylases provides a more effective solution activity than plain amylase, since different amylases exhibit different hydrolytic activities on various substrates, It is also believed to provide a broader hydrolysis pattern. Odor materials are trapped in these substrates and the rapid and efficient hydrolysis performed at several different decomposition points allows for more effective suspension and solubilization of the trapped odor material.

Preferred α-amylases include U.S. Pat.
No. 7; E No. 252,666; WO No. 91/00353; FR No. 2,676,456; EP
Nos. 285,123; EP 525,610; EP 368,341; and British Patent Specification No. 1,296,839 (Novo). Commercially available α-amylase products include Novo Nrdisk A /
Termamyl ^R , Ban ^R and Fung from S Denmark
amyl ^R ". Another preferred α-amylase is B. Subti
It is derived from llis or B. stearothermophilus.

Other α-amylases for use in the present invention may be derived from one or more Bacillus α-amylases, regardless of whether one, two or multiple strains of α-amylase are direct precursors. There is a commonality that it is derived using site-directed mutagenesis.

The α-amylases of the present invention include amylases having improved oxidative stability in detergents, especially improved oxidative stability. Generally, this stability-enhancing amylase is available from Novo Nordisk A / S or Genencor Interna
(a) Amylases described in WO 94/02597 by Novo Nordisk A / S, dated February 3, 1994: (i) one or more Met amino acid residues are Cys
And a mutant α-amylase substituted by any amino acid residue other than Met, (ii) the Bacillus α-amylase described in (i), (iii) one or more Met amino residues are Leu, T
hr, Ala, Gly, Ser, Ile, or Asp amino acid residue, preferably a mutant α-amylase when substituted with a Leu, Thr, Ala or Gly amino acid residue, (iv) B. lichenformis α-amylase Met at position 197
The variant α-amylase according to (i), or a similar parent such as B. amyloliquefaciens, B. Subtilis, or B. stearothermophilus, wherein the residue substitution is preferably performed by Ala or Thr, more preferably Thr. Homologous variants of amylase; (b) stability-enhancing amylase, including "Purfact Ox AM ^R ", as described in WO 94/18314 (dated August 18, 1994). Here, B. licheniformis NCIB 8
The oxidative stability improved amylase made by Genencor from 061 is noted. Met was identified as the most likely modified residue. Positions 8, 15, 197, 256, 3
Substitution of Met one at a time at 04, 366 and 438 results in specificity variants, among which M197L and M19
7L is of particular interest as the most stable mutant with M197T; therefore, the corresponding α-amylases include: (i) a mutant amylase that is the expression product of a mutant DNA sequence encoding an α-amylase; Mutant DN in case
The A sequence is derived from the precursor α-amylase by deletion or substitution of one or more amino acid residues selected from the group consisting of Met, Cys and Tyr amino acid residues in the precursor α-amylase; ii) The oxidizable amino acid residue to be deleted or substituted is Ba
+8, + in cillus licheniformis α-amylase
The mutant α-amylase according to (i) when it is Met in the precursor α-amylase corresponding to 15, +197, +256, +304, +366 or +438; (iii) the mutant according to (i) which is M197T α-amylase;

(C) Preferred in the present invention are amylase variants with additional modifications directly in the parent, which are commercially available from Novo Nordisk A / S. These amylase are described in WO 95/10603 (1995
(I) when one or more amino acids of the parent enzyme are replaced with different amino acids and / or one or more amino acids are deleted. And / or a variant of the parent amylase enzyme having improved washing and / or dishwashing performance relative to the parent enzyme when one or more amino acids are added to the parent α-amylase enzyme. However, this mutant is the parent B.li
Met at position 197 of cheniformis α-amylase is Ala
Or (ii) the C-terminal part of α-amylase from B. licheniformis and B. amyloliquefacies or B.stearotermophi
(i) the variant comprising the N-terminal part of α-amylase derived from lus, (iii) the Met amino acid residue at position 197 is preferably Leu,
A variant known as “Duramyl ^R ” according to (ii) when substituted with an amino acid residue of Thr, Ala, Gly, Ser, IIe or Asp; (d) WO 95/26397 (October 1995 Dated 05) contains other preferred amylase: 25 ° C to 55 ° C,
And at 10 from the pH range 8 "Termamyl ^R" a specific activity at least 25% higher than the specific activity (Phadebas ^R alpha-
Α-amylase (measured by an amylase activity test method). Such a method for testing Phadebas ^R α-amylase activity is described in WO 95/26397, pp. 9-10. These novel α-amylase variants demonstrate at least one of the following properties compared to the parent enzyme: 1) improved thermal stability, 2) oxidative stability and 3) reduced calcium ion dependence.

Examples of other desirable improvements or modifications of the properties (compared to the parent α-amylase) achieved by the variants of the invention are:
Increased stability and / or α-amylase activity at neutral or relatively high pH values, increased starch hydrolysis activity at relatively high temperatures, such that the pl-value of the α-amylase variant better matches the medium pH, etc. Increasing or decreasing the electric point (pl) is described in patent publication WO 96/23873 by Novo Nordisk.

(E) WO 95/35382 describes starch hydrolases having improved properties with respect to activity levels and a combination of thermal stability and high temperature activity levels. These improved properties make the α-amylase more adaptable to more acidic or alkaline conditions and allow a reduction in calcium concentration without a reduction in enzymatic activity: (i) the α-amylase is Bacillus licheniformis
Derived from α-amylase of Bacillus licheni
positions 104, 12 of the amino acid sequence of formis α-amylase
At least 70, including one or more amino acid changes at a position selected from the group consisting of 8, 187 and 188.
(Ii) at least one additional amino acid change selected from the group consisting of His at position 133 relative to Thr, and Thr at position 149 relative to IIe. Variants.

(F) Amylases described in WO 96/23874 by Novo Nordisk S / A, dated August 08, 1996, describing the parent "Termamyl" -like α-amylase variant. For this variant,
At least one amino acid residue of the parent α-amylase present in a fraction corresponding to amino acid fractions 44-57 of the amino acid sequence of SEQ.ID No. Has been replaced by one or more amino acid residues present in a fraction corresponding to amino acid fraction 66-84 of the amino acid sequence of SEQ ID NO: 10
Using the relevant part of the other "Fungam
One or more amino acid residues have been added using the corresponding portion of an "yl" -like α-amylase. Preferred is a Bacillus licheniformis α-amylase having at least 430 amino acid residues at the C-terminal part and the amino acid sequence found in SEQ.
An amino acid fraction corresponding to the 37N-terminal amino acid residue of amylase, and a parent hybrid α-containing an amino acid fraction corresponding to the 445C-terminal amino acid residue of Bacillus licheniformis α-amylase having the amino acid sequence found in SEQ.ID No. 2. Amylase.

A preferred α-amylase combination is Bacillus l
icheniformis, B.amyloliquefacies, B.Subtilis or
A combination of a non-denatured α-amylase derived from B. stearotermophilus and an α-amylase described in the above (a)-(c) and / or WO 95/26397 and / or WO 95/35382. A more preferred combination is WO 95/106
No. 03, a combination of an α-amylase known as “Duramyl ^R ” and an α-amylase derived from Bacillus licheniformis known as “Termamyl ^R ”, or WO95 / 263
Amylase variants described in No. 97, preferably WO 96/23873
This is a combination with a variant showing improved thermal stability described in the above item. Another more preferred combination is an α-amylase from Bacillus liccheniformis known as `` Termamyl ^R '' and a variant of WO 95/26397 α-amylase, preferably having improved thermostability as described in WO 96/23873. Combination with the indicated α-amylase; “Purafact OX AM ^R ” (WO 94 /
18314) and / or a parent hybrid α-amylase described in WO 96/23874. The detergent composition of the present invention can include a combination of two or more α-amylases.

 Cellulase can be added to such a combination.

The enzyme is 0.0001% to 0.1% by weight of the total composition and total pure α-amylase, preferably 0.0002% to 0.06% by weight;
More preferably, it is uniformly mixed in an amount of 0.0003% to 0.05% by weight. The α-amylase is preferably present in the detergent composition in the range of 1: 3 to 3: 1, more preferably 1: 1, 3: 7 or
It is uniformly mixed in the range of 7: 3 ratio.

Cellulase enzymes Cellulase enzymes useful in the present invention include both bacterial and fungal cellulases. Their optimal pH is from 5
12, indicating an activity of 50 CEVU (cellulose viscosity unit) or more. Preferred cellulases are described in US Pat. No. 4,435,307 (B
arbesgoad et al.), Japanese Patent No. 61078384 and WO 96/02
No. 853, Humicola insolens, Trichoderm
Disclosed are mold cellulases that are each alive from a, Thielavia and Sporotrichum. EP 739 982 is a new Bacil
Disclosed are cellulases isolated from lus species. Preferred cellulases are GB-A-2.075.028; BG-A-2.095.27
No. 5, DE-OS-No. 2,247,832 and WO 95/26398.

Examples of useful cellulase components in the present invention: Commercially available cellulases complex under the tradename "Celluzyme ^R",
Or Humicola insolens, a cellobiohydrolase component immunoreactive with an antibody cultured against a high-purity “70 kD cellobiohydrolase (EC 3.2.1.91) derived from DSM 1800, or a homologue of“ 70 kD cellobiohydrolase that exhibits cellulase activity A cellobiohydrolase component that is a body or derivative, or
Humicola insolens, high purity from DSM 1800 “50kD showing endoglucanase component or cellulase activity immunoreactive with antibody cultured against 50kD endoglucanase” 50k
Endoglucanase component which is a homologue or derivative of D endoglucanase; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17244, or high purity "50 kD from Fusarium oxysporum, DSM 2672 (apparent molecular weight This amino acid composition corresponds to 45 kD having a 2n glycosylation site) an endoglucanase component that is immunoreactive with cultured antibodies against endoglucanase, or a homologue or derivative of a 50 kD endoglucanase that exhibits cellulase activity Ingredients; Preferred endoglucanase components have the amino acid sequence disclosed in PCT Patent Application No. WO 91/17244, or any of the cellulases disclosed in EP-A2-271004, wherein the cellulase has a non-degrading index of less than 500 An alkalophilic cellulase having an (NDI) and an optimum pH of less than 7; The specific activity at pH 8 or higher is 50% or more of the activity under optimal conditions when using carboxymethylcellulose as a substrate, or high-purity “43kD endoglucanase derived from Humicola insolens, DSM 1800. Endoglucanase component or cellulase activity that is immunoreactive with antibodies cultured in
Endoglucanase component which is a homologue or derivative of D endoglucanase; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/17243, or a highly pure “60 kD endoglucanase from Bacillus lautus, NCIMB 40250. Shows endoglucanase component or cellulase activity that is immunoreactive with antibodies cultured against
Endoglucanase component which is a homolog or derivative of 0 kD endoglucanase; a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application No. WO 91/10732.

Particularly preferred cellulases are those that have color care benefits. Examples of such cellulases are the cellulases described in European patent application WO 91202879.2 (dated November 6, 1991).

According to the invention, preferred cellulases are those described in Danish Patent Application No. 1159/90 and PCT Application WO 91/17243, which are Novo Nordisk A / s, Bagsvaer
d, well-known as "Carezyme ^(TM) " commercially available from Denmark. The cellulase preparation method described in these documents and "Carezyme ^(TM) ", which is not inconsistent with this description, consist essentially of a homogeneous endoglucanase component,
olens, immunoreactive with antibodies cultured against high purity ~ 43 kD cellulase from DSM 1800, or homologous to the ~ 43 kD endoglucanase described above. Another method for selecting cellulases suitable for use in the laundry detergent compositions according to the present invention is EP-A-495 258, more particularly EP-A-495 258.
A-350 098.

However, in the case of industrial production of cellulase preparations, it is preferred to employ techniques such as recombinant DNA technology, including microbial fermentation or the preparation of mutations involved in ensuring the overproduction of the desired enzyme activity. Such methods and techniques are known in the art and can be readily implemented by those skilled in the art.

Preferred cellulases used in the present invention are 50 kD endoglucanase and 43 kD endoglucanase.

Detergent component The detergent composition of the present invention also contains an additional detergent component. The precise nature of these additional components and amounts in the composition will depend on the physical form of the composition and the nature of the cleaning operation employed.

The form of the cleaning composition of the present invention is liquid, gel,
Bars, tablets, powders or granules. The particulate composition may be of the “compact” type, and the liquid composition may be “concentrated”
It may be a type.

The compositions of the present invention can be formulated as hard surface cleaners, manual and mechanical dishwashing compositions, manual and mechanical laundry detergent compositions, among which are the rinsing and / or cleaning of contaminated fabrics.
Alternatively, a composition suitable for pretreatment and a softening composition for addition at the time of rinsing are included.

When formulated as a manual dishwashing composition, the composition of the present invention comprises a surfactant, and a polymeric compound, a foam enhancer,
It preferably contains other detergent components selected from Group II metal ions, solvents, hydrotropes and additional enzymes.

When formulated as a composition suitable for laundry machine laundry, the detergent compositions of the present invention contain both surfactant and builder compounds, as well as organic polymeric (polymer) compounds, bleaches, additional enzymes, foam suppressants, dispersants, It preferably contains one or more additional detergent components selected from lime soap dispersants, soil suspending agents and anti-redeposition agents and corrosion inhibitors. Laundry compositions can also include softening agents as additional detergent components.

The composition of the present invention can also be used as a detergent additive product. Such additive products are intended to supplement or enhance the performance of conventional detergent compositions.

The density of the granular laundry detergent composition of the present invention may be, if necessary, 400 to 1200 liters, preferably 600 to 950 g /
Liters / composition (at 20 ° C).

"Compact" of the granular laundry detergent composition of the present invention
The morphology is directly reflected by the density and, in terms of composition, by the amount of salt of the inorganic filler (filler); the inorganic filler salt is a common component of a powdered detergent composition; It comprises from 17% to 35% by weight of the composition.

The filler in the compact detergent composition is 15% of the composition
%, Preferably not more than 10%, most preferably not more than 5% by weight.

The inorganic filler salts which are meant in the composition according to the invention are selected from alkali metal and alkaline earth metal sulfates and chlorides.

The liquid detergent composition of the present invention may be in a "concentrated" form, in which case the liquid detergent composition of the present invention contains a smaller amount of water than a conventional liquid detergent.

Typical water content in the concentrated liquid detergent composition is less than 40% of the detergent composition, more preferably less than 30%, most preferably
Less than 20% by weight.

Surfactant system The detergent composition of the present invention comprises a surfactant system, wherein the surfactant is a nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar. Can be selected from surfactants.

A typical amount of surfactant in the composition is 0.1% of the composition.
% To 60% by weight. A more preferred content is 1% to 35%, most preferably 1% to 20%, by weight of the detergent composition.

Preferably, the surfactant is formulated to be compatible with the enzyme components in the composition. In the case of a liquid or gel composition, the surfactant is preferably formulated to promote, or at least not to degrade, the stability of any enzyme in the composition.

Surfactant systems suitable for the present invention include nonionics and / or one or more of the anionic surfactants described in the present invention.

Alkyl phenol polyethylene, polypropyne,
And polybutylene condensates are suitable for use as nonionic surfactants in the surfactant system of the present invention, with polyethylene oxide condensates being preferred. These compounds include condensates of alkylphenols containing from about 6 to about 14, preferably from about 8 to 14, carbon atoms and having either linear or branched alkyl groups and alkylene oxides. In a preferred embodiment, the amount of ethylene oxide is from about 2 to about 25 moles, more preferably from about 3 to about 15 moles of ethylene oxide per mole of alkylphenol.
Commercially available nonionic surfactants in this form include GAP Corporation
“Igepal ^™ CO-630” from Rohm & Hass, Inc. and “Triton ^™ , X-45, X-114, X-100 and X-10 from Rohm & Hass.
2 ”is included. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

Condensates of about 1 to about 25 moles of ethylene oxide with primary and secondary aliphatic alcohols are suitable as the nonionic surfactant of the present invention. The alkyl chain of the aliphatic alcohol can be straight or branched, either primary or secondary, and generally contains from about 8 to about 22 carbon atoms. Preferred are condensation products of an alcohol having an alkyl group of from about 8 to about 20, more preferably from about 10 to about 18, carbon atoms with about 2 to 10 moles of ethylene oxide per mole of alcohol. About 2 to 7 moles, most preferably about 2 to about 5 moles, of ethylene oxide are included in the condensate per mole of alcohol. Examples of commercially available nonionic surfactants of this type include "Terg
itol ^TM 15-s-9 "(C _11-15 condensation product of linear alcohol with 9 moles ethylene oxide)," Tergitol ^TM 24-L-6
NMW "(C _12-14 primary alcohol and ethylene oxide 6
Condensate with narrow molecular weight distribution with moles (both Union Caib
ide Corporation product); “Neodol ^™ 45-9” (C
_11-15 linear alcohol and condensate of 9 moles of ethylene oxide), “Neodol ^™ 23-3” (condensate of C _12-13 linear alcohol and 3.0 moles of ethylene oxide), “Neodol ^™ 45
-7 "(C _14-15 condensation product of linear alcohol with 7 mol ethylene oxide)," Neodol ^TM 45-5 "(C _14-15 condensation product of linear alcohol with 5 moles of ethylene oxide, (all Shell Chemical Kyro ^™ EOB ”(C _13-15)
Condensate of alcohol and 9 mol of ethylene oxide) (Th
e Procter & Gamble Company products); and "Genapol
LA 030 or 050 "(condensate of C _12-14 alcohol with 3 or 5 moles of ethylene oxide) (Hoechst). The preferred range of HLB for these products is 8-
1, most preferably 8-10 Useful as nonionic surfactants in the surfactant systems of the present invention are described in U.S. Pat. No. 4,655,647 (Lienado, 1986).
Alkyl polysaccharides disclosed on December 21, 2000). It has from about 6 to about 30 carbon atoms, preferably about
For example, a polyglycoside having a lipophilic group containing from 10 to about 16 wherein the hydrophilic group is from about 1.3 to about 10, preferably 1.3
From about 3, and most preferably from about 1.3 to about 2.7 saccharide units. Any reducing saccharide containing 5 or 6 carbon atoms can be used, such as glucose, galactose and galactosyl moieties at the glucosyl moiety (optionally the lipophilic group is bonded at the 2-, 3-, 4-etc. To give glucose or galactose as opposed to galactoside). This internal saccharide linkage may be, for example, between one position of the additional saccharide unit and the 2-, 3-, 4-, and / or 6-position on said saccharide unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x wherein} R ² is alkyl, alkylphenol, hisoroxyalkyl, and mixtures thereof. Wherein the alkyl group is from about 10 to about 18 carbon atoms,
Preferably comprises about 12 to about 14; n is 2 or 3, preferably 2; t is 0 to about 1, preferably 0; and x is about 1.3 to about 10, preferably about 1.3 to about 3, most preferably Is 1.3
This glycosyl is preferably derived from glucose. In preparing these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with a glucose or glucose source to form a glucoside (attached at one position). An additional glycosyl unit may then be attached between the 1-position and the aforementioned glycosyl unit 2-, 3-, 4- and / or 6-position, preferably mostly at the 2-position.

Condensation products of ethylene oxide with lipophilic groups formed by the condensation of propylene oxide and propylene glycol are also useful as additional nonionic surfactant systems of the present invention. The lipophilic portion of these compounds has a molecular weight of about 1500 to about 1800, and is preferably water soluble. The addition of polyoxyethylene moieties to this lipophilic moiety tends to increase the overall water solubility of the molecule, and the liquid properties of the product are such that the polyethylene oxide content is about 50% by weight, based on the weight of the condensation product. Which corresponds to a condensation of up to about 20 mol of ethylene oxide. Examples of compounds of this type include commercially available "Pluronic ^™ " surfactants (BASF
) Are included.

Suitable for use as a nonionic surfactant in the nonionic surfactant system of the present invention include condensates of the product from the reaction of propylene oxide with ethylenediamine and ethylene oxide. The lipophilic site 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. The lipophilic moiety condenses with ethylene oxide to the extent that the condensation product contains from about 40% to about 80% by weight polyoxyethylene and has a molecular weight of from about 5,000 to about 11,000. Examples of this type of nonionic surfactant include BA as a “Tetronic ^™ ” compound.
Certain types commercially available from SF are included.

Suitable for use as the nonionic surfactant in the surfactant system of the present invention are polyethylene oxide condensates of akylfenol, from about 1 to about 25 moles of primary and secondary aliphatic alcohols and ethylene oxide. Condensates, alkyl polysaccharides, and mixtures thereof. Most preferably, 3 to 15 ethoxy groups.
C _8-14 alkylphenol ethoxylates, C _8-18 ethoxy groups 2 to 10 (preferably having an average C ₁₀₎ alcohol ethoxylate, and mixtures thereof.

Particularly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants having the formula: Wherein R ₁ is H, or R ¹ is C _1-4 hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, R ² is C _5-31 hydroxycarbyl, and Z is a chain Or a polyhydroxyhydrocarbyl having a linear hydrocarbyl group having at least three hydroxyl groups directly bonded to the compound or an alkoxylated derivative thereof.] Preferably, R ¹ is methyl, R ² is linear C _11-15 alkyl or C _16- An alkenyl such as ₁₈ alkyl or coconut alkyl and a mixture thereof, and z is derived from a reducing sugar such as glucose, fructose, lactose in a reductive amino reaction.

Preferred anionic surfactants used are linear alkyl benzene sulfonates, alkyl ester sulfonates including linear esters of C _8-20 carboxylic acids (ie, aliphatic), and sulfonation is described in The Journal of t
he American oil Chemists Society ", 52 (1975), 323
Performed with gaseous SO ₃ according to page −329. Preferred starting materials include natural fatty substances derived from tallow, palm oil and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry purposes, include alkyl ester sulfonate surfactants of the formula: Wherein R ³ is C _18-20 hydrocarbyl, preferably alkyl or combinations thereof, R ⁴ is C _1-6 is hydrocarbyl, preferably alkyl or combinations thereof, and M is an alkyl ester sulfonate and water soluble Preferred salt-forming cations include metals such as sodium, potassium, and lithium, and substituted or unsubstituted cations such as monoethanolamine, diethanolamine, and triethanolamine. Preferably, R ³ is C _10-16 alkyl, and R ⁴ is methyl, ethyl or isopropyl. Particularly preferably, R ³ is C
It is a methyl ester sulfonate in the case of _10-16 alkyl.

Other preferred anionic surfactants include linear benzene sulfonate, alkyl sulfate surfactants, wherein the surfactant is a water-soluble salt or acid of the formula ROSO ₃ M, wherein: R is C _10-24 hydrocarbyl, preferably C
_10-20 alkyl components, more preferably alkyl or hydroxyalkyl having _12-18 alkyl or hydroxyalkyl, and M is H or ammonium or substituted ammonium (eg, tetramethylammonium and dimethylpiperdinium cations and ethylamine, diethylamine, triethylamine And quaternary ammonium cations derived from alkylamines such as mixed groups thereof. Typically, alkyl chains preferably have low temperature cleaning of C _12-16 (For example, about 50 ° C. or less), C _16-18 alkyl chains are hot wash (e.g., about 50 ° C. or higher) is preferred.

Other anionic surfactants useful for cleaning purposes can also be included in the detergent compositions of the present invention. These include the soaps (e.g., sodium, potassium, ammonium, and mono-, - di - include sulfonate and substituted ammonium salts such as triethanolamine) salts, C _8-22 second secondary alkanesulfonate Primary (sic), C _8-24 olefin sulfonic acid salts, such as sulfonated polycarboxylic acids prepared by the sulfonation of the pyrolysis products of alkaline earth metal citrates described in GB 1,082,179; C _8-24 alkyl polyglycol ether sulfate (including up to 10 moles of ethylene oxide); alkyl glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate alkyl phenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl Phosphates, isethionates such as acyl isethionates, - acyl Taurates, alkyl succinamates cinnamate and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C _12-18 monoester) and diesters of sulfosuccinates (especially saturated and unsaturated C
Alkyl polysaccharide sulfates such as _6-12 diesters), acyl sarcosinates, alkyl polyglucoside sulfates (nonionic non-sulfated compounds in this case are described below), branched primary alkyl sulfates, and formula RO (CH ₂ CH _{2
^{O) k -CH 2 COO - M}} + [ wherein, R C _8-22 alkyl, k is 1
And M is an integer of from 10 to 10, and M is a soluble salt-forming cation].
Rosin, hydrogenated rosin, resin acids present in or derived from tall oil and hydrogenated resin acids are also suitable.

A further example is “Surface Active Agents and Detergen
ts "[Volumes I and II (Schwartz, Perry and Berch)]
There is a description inside. Many of such surfactants have US
No. 9,678, dated December 30, 1975 (Laubhlin et al.), Column 23, line 58 to column 29, line 23 (incorporated herein by reference).

Particularly preferred anionic surfactants include alkyl alkoxylated sulfate surfactants, which have the formula
RO (A) _m SO ₃ M are water soluble salts or acids wherein R is a C _10-24 alkyl moiety, preferably C _12-20 alkyl or hydroxyalkyl, more preferably C _12-28 alkyl or Unsubstituted C with hydroxyalkyl
_10-24 alkyl or hydroxyalkyl;
Is an ethoxy or propoxy unit, m is greater than 0,
Typically from about 0.5 to about 6, most preferably from about 0.5 to about 3, where M is H, or a cation, which may be a metal cation (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium Is a cation. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are also candidates. Specific examples of substituted ammonium cations include quaternary ammonium cations such as methyl-, dimethyl-, trimethylammonium cations and tetramethylammonium and dimethylpiperdinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine, and mixtures thereof. Amine derived cations are included. Examples of surfactants include C _12-18 alkyl polyethoxylate (1.0) sulfate [C
_12-18 E (1.0) M], C _12-18 alkyl polyethoxylate (2.25) sulfate [C
_12-18 E (2.2) M], C _12-18 alkyl polyethoxylate (3.0) sulfate [C
_12-18 E (3.0) M] and C _12-18 alkyl polyethoxylate (4.0) sulfate [C
_12-18 E (4.0) M], wherein M is selected from sodium and potassium.

In the detergent composition of the present invention, cationic, amphoteric, amphoteric, and semipolar surfactants, and nonionics other than the above,
And / or may also contain anionic surfactants.

Detergent cationic surfactants suitable for use in the detergent compositions of the present invention are those having hydrocarbyl groups on one long chain. Examples of such cationic surfactants include alkyl trimethyl ammonium halides,
And the following ^{formula: [R 2 (OR 3)} y] [R 4 (OR 3) y] 2 R 5 N + X - alkyl having [wherein, R ² is about carbon atoms to about 8 in the alkyl chain 18 Or an alkylbenzyl group, and each R ³
_{-CH 2 CH 2, -CH 2 CH} (CH 3) is _{-, - CH 2 CH (CH} 2 OH) -, -CH 2 CH 2 CH 2 - is selected from and mixtures groups thereof; R ⁴ is
C _1-4 alkyl, C _1-4 hydroxyalkyl, these two R ⁴
Benzyl ring structures group formed by combining, -CH ₂ CHOH-CHO
HCOR ⁶ CHOHCH ₂ OH, where R ⁶ is a hexose or hexose polymer having a molecular weight of less than about 1000, and hydrogen if y is not zero; R ⁵ is the same as R ⁴ , or R ² If the total number of carbon atoms plus R ⁵ is about 18 or less R ⁴ represents an alkyl chain; each y is from 0 to about 10,
The sum of the y values is from 0 to about 15; and x is any of the compatible anions].

A quaternary ammonium surfactant suitable for the present invention is represented by formula (I): 中 In the formula, R ¹ is the following formula (II); [Y represents 2-4, preferably 3] short-chain alkyl (C _6-10 ) or alkylamidoalkyl, R ² is H or C _1-3 alkyl, x is 0-4,
Preferably 0-2, most preferably 0, R ³ , R ⁴ ,
R ⁵ is either the same or different, and either short-chain alkyl (C _1-3 ) or alkoxylated alkyl of formula (II), and X ⁻ is a counter ion, preferably a halide such as a chloride such as chloride Substance or methyl sulfate. Wherein R ⁶ is C _1-4 and z is 1 or 2. Preferred quaternary ammonium surfactants are the surfactants defined by formula (I) wherein R ₁ is C _{8- 10} or a mixture thereof, x = 0, R ₃ , R ₄ = CH ₃ and R ₅ = CH ₂ CH ₂ OH].

Particularly preferred cationic surfactants of the formula, in the present invention compositions which are useful water-soluble quaternary ammonium _{compounds: R 1 R 2 R 3 R} 4 N + X - (i) [ wherein, R ₁ represents C _8-16 alkyl, each of R ₂ R ₃ R ₄ is C _1-4
Alkyl, C _1-4 hydroxyalkyl, benzyl, and — (C ₂ H ₄ O) _x H (x is 2 to 5), and X is an anion, and at most one of R ₂ R ₃ or R ₄ is benzyl The preferred alkyl chain length for R ₁ is C _12-15 , wherein the alkyl group is a mixed chain length derived from coconut or palm kernel fat, or synthesized synthetically by an olefin build-up reaction or oxo synthesis. Be guided. R ₂ R ₃
And preferred groups for R ₄ are methyl and hydroxyethyl groups, and the anion x is selected from halide, methosulphate, acetate and phosphate ions.

Examples of preferred quaternary ammonium compounds of formula (i) for use in the present invention are: coconut trimethylammonium chloride or bromide; coconut methyldihydroxyethylammonium chloride or bromide; decyl triethylammonium chloride; decyl dimethyl hydroxyethyl ammonium chloride or bromide; C _12-15 dimethyl hydroxyethyl ammonium chloride or bromide; coconut dimethyl hydroxyethyl ammonium chloride or bromide; myristyl trimethyl ammonium methyl sulphate lauryl dimethyl benzyl ammonium chloride or bromide; lauryl dimethyl _{(ethoxy) 4} ammonium chloride or bromide; co Down (choline) ester [compound of the formula (i) (R ₁
Is Alkyl and R ₂ R ₃ R ₄ are methyl], dialkyl imidazoline [compound of formula (i)] Another cationic surfactant useful in the present invention is Camb
re is also described in US Patent No. 4,228,044 (dated October 14, 1980) and European Patent Application No. 000,224.

When such cationic surfactants are included in the compositions of the present invention, the amount is from 0.2% to about 25%, preferably from about 1% to about 8%, by weight of the composition.

Amphoteric surfactants are also suitable for use in the present invention.
These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or of heterocyclic secondary or tertiary amines in which the aliphatic radica is linear or branched. It can also be described as an aliphatic derivative. One of the aliphatic substituents contains at least about 8, and typically about 8 to about 18, carbon atoms, and at least one contains an anionic water solubilizing group, for example, carboxy, sulfonate, sulfate, and the like. . Amphoteric surfactants are described in US Pat. No. 3,929,678 to Laughlin et al., Dated December 30, 1975.
See col., Lines 18-35.

The amount in the composition when including such an amphoteric surfactant is:
From 0.2% to about 15%, preferably from about 1% to about 10%, by weight of the composition.

Zwitterionic surfactants are also suitable for use in the present invention. These surfactants are broadly defined as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or quaternary ammonium derivatives, quaternary phosphoniums or tertiary amines. Described as sulfonium compounds. For examples of zwitterionic surfactants, see US Pat. No. 3,929,678 to Laughlon et al., Dated December 30, 1975.
Column 19, line 38 to column 22, line 48. The amount in the composition containing such a zwitterionic surfactant is from 0.2% to 15% by weight, preferably from about 1% to about 10% by weight.

Semipolar nonionic surfactants are aqueous amine oxides containing one alkyl moiety from about 10 to about 18 carbon atoms, and
A category of nonionic surfactants containing two moieties selected from the group consisting of alkyl and hydroxyalkyl groups containing from about 1 to about 3 carbon atoms; from about 10 to about 18 carbon atoms
One alkyl moiety comprising from about 1 to about 3 carbon atoms
A water-soluble phosphine oxide containing two moieties selected from an alkyl group and a hydroxyalkyl group, including: one alkyli moiety having about 10 to about 18 carbon atoms and an alkyl and hydroxy alkyl moiety having about 1 to 3 carbon atoms. Water-soluble sulfoxides containing selected sites.

Semi-polar nonionic detergent surfactants include amine oxides having the formula: Wherein R ³ is an alkyl, hydroxyalkyl, or alkylphenol group containing from about 8 to about 22 carbon atoms or a mixture thereof; R ⁴ is an alkylene or hydroxyalkylene group containing from about 2 to about 3 carbon atoms or Wherein x is 0 to about 3; and each R ⁵ is an alkyl or hydroxyalkyl group containing about 1 to about 3 carbon atoms or a polyethylene oxide group containing about 1 to about 3 ethylene oxide groups. The R ⁵ groups may be linked together, for example via an oxygen or nitrogen atom, to form a ring structure.] These amine oxide surfactants are C _10-18 alkyldimethylamine oxide and C _8-12 alkoxyethyldihydroxyethylamine oxide Is included.

The amount of such semi-polar nonionic surfactant in the composition is:
0.2% to about 15% by weight of the composition, preferably about 15 to about 1%
0% by weight.

The detergent composition of the present invention may further comprise a co-surfactant selected from the group of primary or tertiary amines.

Primary amines suitable for use in the present invention include those of the formula R ₁ NH ₂
Wherein R ₁ is a C _6-12 , preferably a C _6-10 alkyl chain or
R ₄ X (CH ₂ ) _n , where X is —O—, —C (O) NH— or —NH
-, R ₄ is C _6-12 alkyl, n is 1 to 5, preferably 3
Are included. The R ₁ alkyl chain is straight or branched and has up to 12 ethylene oxide moieties,
Preferably, it may be interrupted by less than 5.

A preferred amine represented by the above formula is n-alkylamine. Amines suitable for use in the present invention are 1
-Hexylamine, 1-octylamine, 1-decylamine and laurylamine. Other preferred primary amines are _C8-10 oxypropylamine, octyloxypropylamine, 2-ethylhexyloxypropylamine, larylaminopropylamine and amidopropylamine.

Tertiary amines suitable for use in the present invention include those of the formula R ₁ R ₂ R ₃
N wherein R ₁ and R ₂ are a C _1-8 alkyl chain or R ₃ is a C _6-12 preferably C _6-10 alkyl chain, or R ₃ is R ₄ X
(CH ₂ ) _n (x is -O-, -C (O) NH-, or -NH
R ₄ is C _4-12 , n is 1 to 5, preferably 2 to 3), R ₅ is H or C _1-2 alkyl, and x is 1
To 6] are included.

Preferred tertiary amines have the formula R ₁ R ₂ R ₃ N wherein R ₁ is C
_6-12 alkyl chain, R ³ and R ₃ are C _1-3 alkyl or R ₅ is represented by H or CH _3, an x = 1-2].

Also preferred amines are of the formula: Wherein R ₁ is a C _6-12 alkyl group; n is 2-4, preferably
3; R ₂ and R ₃ are amidoamines represented by C _1-4 ].

Most preferred amines in the present invention include 1-oculamine, 1-hexylamine, 1-dodecylamine, C
_8-10 oxypropylamine, N-coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, laurylamine (2-mollopoxylated), octyl amine (2 moles propoxylated), lauryl amidopropyl dimethylamine, C _8-10 amidopropyl di Mel amine and C ₁₀ amidopropyl dimethylamine, and the like.

The most preferred amine for use in the composition of the present invention is 1
-Hexylamine, 1-octylamine, 1-decylamine and 1-dodecylamine. Particularly preferred are n-dodecyldimethylamine and bishydroxyethyl coconut alkylamine and oleylamine (7-fold ethoxylated), laurylamidopropylamine and cocoamidopropylamine.

Optional Detergent Ingredients Other Detergent Enzymes The detergent composition further comprises, in addition to the combination of the α-amylase enzyme and simultaneously the cellulase, one or more enzymes that provide cleaning performance and / or fabric care benefits. .

The enzymes include hemicellulase, peroxidase,
Proteases, glucoamylases, other amylases,
Xylanase, lipase, esterase, cutinase,
An enzyme selected from pectinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase, chondroitinase, lactase or a mixture thereof is included.

A preferred combination is a cleaning composition suitably mixed with well-known applicable enzymes such as protease, amylase, lipase, cutinase and / or cellular in combination with one or more plant cell wall degrading enzymes.

The peroxidase enzyme is used in combination with an oxygen source such as per (per) carbonate, perborate, persulfate, hydrogen peroxide and the like. They are used for "solution bleaching", which prevents dyes or pigments removed from the substrate during washing from transferring to other substrates in the washing solution. Peroxidase enzymes are well known in the art and include, for example, horseradish peroxyligninase, and halooxidases such as chloro- and bromo-peroxidase.

Peroxidase-containing detergent compositions are described in PCT International Application WO
No. 89/099813 and European Patent Application EP 91202882.6 (199
(November 6, 2001).

The amount of the peroxidase in the detergent composition is 0.0001% or 2% by weight of the detergent composition.

Preferred commercially available protease enzymes include Novo Nordisk
A / S (Denmark) brand name "Alcalase, Savinase, P
rimase, Durazyme, and Esperase ", which are trade names" Maxatase, Maxaca "from Gist-Brocades.
l, Maxpem, and Properase "and Genenc
or from International or Solvay E
Opticlean and Optimase from nzymes
Is included. Similarly, EP-A 251 446 and WO 9
Nos. 1/06637, 94/10591 and U.S. Pat.
The protease described in Japanese Patent Application Laid-Open Publication No. H11-216, can also be included in the detergent composition of the present invention. The amount of protease enzyme in the composition is from 0.0001% to 2% active enzyme by weight of the composition.

The addition of a protease in combination with the α-amylase of the present invention enhances the removal of odors from soiled articles.

Another preferred enzyme that can be included in the detergent compositions of the present invention is lipase. Lipase enzymes suitable for detergents include Pseud, as disclosed in GB 1,372,034.
omonas stutzeri ATCC 19.154 and the like, which are produced by microorganisms of the Pseudomonas group. Suitable lipases include enzymes produced by the microorganism Pseudomonasfluorescent IAM 1057 and exhibiting a positive immune interaction with lipase antibodies. This lipase is Amano Ph
"Lipase P" A from armaceutical Co. Ltd., Nagoya, Japan
mano "", and hereinafter referred to as "Amano-P". Particularly preferred lipases include M1 Lipase ^R and Lipomax ^R (Gist-Brocades) and Lipolase ^R and Lipolase Ultra ^R (Novo), which have been found to be extremely effective when used in combination with the compositions of the present invention.

The addition of lipase in combination with the α-amylase of the present invention enhances the effect of removing odors from soiled articles.

Also suitable are cutinases [EC3.1.1.50], which are considered to be special lipases as so-called lipases that do not require surface activation. Preferred cutinases are described in WO 94/14963 and WO 94/14963.
It is described in No. 64. The addition of cutinase to detergent compositions is described in WO-A-88 / 09367 (Genencor).

Typical amounts of the lipases and cutinases used are 0.0001% or 2% by weight of the composition.

The enzymes are from any suitable source, such as plants, animals, bacteria, molds and yeasts. The amount of the enzyme in the detergent composition is usually at least 0.0001% to 2% by weight of the composition of active enzyme. These are separate components (pills,
Particles) or as co-particles of one or more enzymes.

Another preferred detergent component that can be added is an enzyme oxidized scavenger, which is described in EP 92870018.6 (January 31, 1992).
Date). Enzymatic oxidation scavengers are ethoxylated tetraethylene polyamines.

Color protection effects Techniques that provide one type of color protection effect can also be included. Examples of these techniques are metallocatalysts for color maintenance. Such metallocatalysts are described in EP 0 596 184 and EP 94870206.3.

Bleach Bleach systems that may be included in the detergent compositions of the present invention include bleaching agents such as PB1, PB4 and per (per) carbonate having a particle size of 400-800 microns. These bleaching components can include one or more enzyme bleaches and, depending on the type of bleach selected, one or more bleach activators. When an enzyme bleach is included, the amount is from about 1% to about 25% by weight of the composition.

The bleach component used in the present invention can be any bleach useful for detergent compositions, including enzyme bleaches as well as other well-known bleaches.

One category of enzymatic bleaches that can be used includes bleaches of percarboxylic acids and their salts. This type of bleach includes magnesium monoperoxyphthalate hexahydrate, magnesium salts of metachlorobenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid, and diperoxidedecandioic acid. Such bleaches are disclosed in U.S. Patent No. 4,483,781, U.S. Patent Application No. 740,446, European Patent Application No. 0.133,354, and U.S. Patent No. 4,412,935. Particularly preferred bleaching agents are U.S. Pat.
No. 4,551, 6-nonylamine-6-oxoperoxycaproic acid.

Another category of bleaches that can be used are the halogen bleaches. Examples of hypohalite bleaches include, for example, trichloroisocyanuric acid and sodium and potassium dichloroisocyanuric acid, N-chloro and N-chloroisocyanuric acid.
Bromoalkanesulfonamides are included. The amount of such materials is 0.5% to 10%, preferably 1% to 5% by weight of the final composition.

Hydrogen peroxide releasing agents include tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in U.S. Pat. No. 4,412,923), and 3,5-trimethylhexanoloxybenzenesulfonate (ISONOB).
S, EP No. 120,591), phenol sulfonate of N-nonanoyl-6-aminocaproic acid (NACA-
OBS, described in WO 94/28106) or in combination with a bleaching active additive such as pentaacetylglucose, which forms peracid as an active bleaching species upon perhydrolysis and exhibits an improved bleaching effect.

Useful bleaching agents including per (peroxy) acids and bleaching agents for use in the detergent compositions of the present invention and bleaching systems comprising peroxygen-based bleaching compounds are described in USSN No.
08 / 136,626, PCT / US95 / 07823, WO 95/27772, WO
Nos. 95/27773, WO 95/27774 and WO 95/27775.

Hydrogen peroxide may be included at the beginning or during the washing and / or rinsing step by adding an enzyme system capable of releasing hydrogen peroxide (ie, enzymes and their substrates). Such an enzyme system is described in EP-A-9120.
2655.6, dated October 9, 1991.

Bleaching agents other than oxygen bleaching agents are well known and can be used in the present invention. One type of oxygen-based bleach that is of particular interest includes photoactivated bleaches such as zinc sulfonated and / or aluminum phthalocyanine. These materials can be deposited on the substrate during the washing process. When light is irradiated in the presence of oxygen, such as drying clothes outdoors during the day, the sulfonated zinc phthalane is activated and the substrate is bleached. Preferred zinc phthalocyanines and bleaching methods are described in U.S. Pat. No. 4,033,718. Typically, the amount of phosphonated zinc phthalocyanine in the detergent composition is about 0.02
5% to about 1.25% by weight.

Builder system The composition of the present invention further comprises a builder system.

Materials such as aluminosilicate materials, silicates, polycarboxylic acids and fatty acids, ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, etc., sequestering of aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid Any of the well known builder systems, including agents, can be used in the present invention. Phosphate builders such as sodium tripolyphosphate can also be used in the present invention.

Preferred builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, more specifically hydrated
There are hydrated synthetic zeolites such as Zeolite A, X, B, HS or MAP. Another preferred inorganic builder material is a layered silicate, such as SKS-6 (Hoech). SKS-6 is a crystalline layered silicate made of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable carboxylate salts containing one carboxy group include:
Butyric acid, glycolic acid and its ether derivatives are included (disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370). Polycarboxylates containing two carboxy groups include water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid; 2,446,686, 2,446,687 and US Pat. No. 3,935,257, and the sulfinyl carboxylate described in Belgian Patent 840,623.

Polycarboxylates containing three carboxy groups include, in particular, water-soluble citrates, aconitates and citraconic acid salts and succinate derivatives such as carboxymethyloxysuccinate described in GB 1,379,241.
Oxypolycarboxylate materials such as lactoxysuccinate described in Dutch Patent Application No. 7205873 and 2-oxa-1,1,3-propanetricarboxylate described in British Patent No. 1,387,447 are included.

Polycarboxylates containing four carboxy groups include oxydisuccinates disclosed in British Patent 1,261,829,
1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-pronetetracarboxylate are included. Polycarboxylates containing a sulfo substituent include the sulfosuccinic acid derivatives disclosed in British Patent Nos. 1,398,421 and 1,398,422 and U.S. Pat.No.3,936,448, and sulfonated pyrolytic citrates described in Acid salts are included.

Alicyclic and heterocyclic polycarboxylates include cyclopentane cis, cis, cis tetracarboxylate, cyclopentadienepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetra Carboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,2,5,5-tetrahydrofuran-tetracarboxylate, 1,2.3,4,5,6-
Hexane-hexacarboxylate, and sorivitol,
There are carboxymethyl derivatives of polyhydric alcohols such as mannitol and xylitol. Aromatic polycarboxylic acids include the merit acids, pyromellitic acids and phthalic acid derivatives described in GB 1,425,343.

Preferred polycarboxylates among the above are hydroxycarboxylates containing up to three carboxyl groups per mole, more specifically citric acid.

Preferred builder systems suitable for use in the present invention include mixtures of water-insoluble aluminosilicate builders such as Zeolite A, Zeolite MAP or layered silicates (SKS-
6) and a water-soluble carboxylate chelating agent such as citric acid.

A preferred chelating agent for inclusion in the detergent composition of the present invention is ethylenediamine N, N, -disuccinic acid (EDDS) or an alkali metal, alkaline earth metal, ammonium, or substituted ammonium salt thereof, or a mixture thereof. . Preferred EDDS compounds are the free acid form and the sodium or magnesium salt. Such preferred sodium salts of EDDS include Na ₂ EDDS and Na ₄ EDDS. Among the preferred magnesium salts of EDDS are MgED
DS and Mg ₂ EDDS are included. The magnesium salt is most preferred for inclusion in the composition of the present invention.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder, such as Zeolite A, Zeolite MAP, and a water-soluble carboxylic acid chelating agent, such as citric acid.

Other builder materials that may form part of the builder system used in the particulate composition include alkali metal carbonates, bicarbonates,
Inorganic materials such as silicates and organic materials such as aminopolyalkylenephosphonates and aminopolycarboxylates are included.

Other preferred water-soluble organic salts are homo- or copolymeric polyacids whose polycarboxylic acid contains at least two carboxyl groups separated from each other by up to two carbon atoms or salts thereof.

A polymer of this type is disclosed in British Patent Application No. 1,596,756. Examples of such salts include those having a molecular weight of 20,0
2000 to 2000, especially about 40,000 copolymers
-5000 polyacrylates and their copolymers with maleic anhydride.

The usual amount of builder salts for detergents is from 10% of the composition
80% by weight. Preferably it is 20% to 70% by weight, most preferably 30% to 60% by weight.

Other optional ingredients are foam inhibitors, exemplified by silicones and silica-silicone mixtures. Silicones are generally represented by an alkylated polysiloxane material,
Silica, on the other hand, is usually used in finely divided form, exemplified by silica airgel and xerogel and various types of lipophilic silica. These materials can be homogeneously mixed as particles, in which case the foam control agent is preferably water-soluble or water-dispersible and homogeneously mixed so that it can be released into a substantially non-surfactant, detergent-impermeable carrier. . Alternatively, the foam control agent may be dissolved or dispersed in the liquid carrier, or may be applied by spraying on one or more other components.

Preferred silicone foam control agents are described in U.S. Pat.
There is a disclosure in Japanese Patent Publication No. Another particularly useful foam control agent is German Patent Application No. DTOS 2646 126 (March 28, 1977).
It is a self-emulsifying silicone foam inhibitor described in the above. Examples of such compounds are siloxanes commercially available from Dow Corning.
Glycol copolymer “C-544”. A particularly preferred foam control agent is a foam control system comprising a mixture of silicone oil and a 2-alkyl alkanol. Preferred 2
-Alkyl akanol is 2-butyl octanol, which is marketed under the trade name "Isofol 12R". Such a bubble suppression system is disclosed in European Patent N9 2870174.7
(With November 10, 1992).

Particularly preferred silicone foam control agents are described in European Patent Application No. N92201649.8. The above composition is "Aer
It may contain OSIL ^R "silicone / silica mixture in combination with non-porous Hiyumudoshirika such.

The amount of the foam inhibitor used is 0.001% to 2% by weight of the composition, preferably 0.01% to 1% by weight.

Others Other components used in detergent compositions such as soil suspending agents, soil removers, optical brighteners, abrasives, bactericides, anti-fog agents, colorants and / or encapsulated or unencapsulated fragrances are also included. Can be adopted.

A particularly preferred encapsulating material is a water-soluble capsule consisting of a matrix of a polysaccharide and a polyhydroxy compound as described in GB 1,464,616.

Other preferred water-soluble encapsulation materials are described in U.S. Pat.
No. 3,455,838, which includes dextrins derived from ungelled starch-esters of substituted dicarboxylic acids. These acid-ester dextrins are prepared from starches such as waxy corn, waxy sorghum, sago, tapioca and potato. Preferred encapsulation materials include Nationai Sta
Includes “N-Lok” manufactured by rch. The N-Lok encapsulation material consists of modified corn starch and glucose. This starch is modified by the addition of a monofunctional substituent such as octeylsuccinic anhydride.

Antiredeposition agents and soil suspending agents suitable for the present invention include cellulose derivatives such as methylcellulose, carbosimercellulose and hydroxyethylcellulose, as well as ho- or copolymeric polycarboxylic acids or salts thereof. Polymers of this type include the polyacrylates and maleic anhydride-acrylic acid copolymers described above as builders, and copolymers of ethylene, methyl vinyl ether or methacrylic acid with maleic anhydride, in which case Maleic anhydride accounts for at least 20 mole percent of the copolymer. Usually, these materials comprise from 0.5% to 10% by weight of the composition, more preferably
0.75% to 8% by weight, most preferably 1% to 6% by weight
Used in quantity.

Preferred optical brighteners are anionic and are disodium 4,4'-bis (2-diethanolamino-4-
Anilino-s-triazin-6-ylamino) stilbene-2: 2'disulfonate, disodium 4,4'-bis-
(2-morpholino-4-anilino-s-triazine-6
-Ylamino) stilbene-2: 2'disulfonate, disodium 4,4'-bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2: 2'disulfonate, monosodium 4 , 4'-Bis- (2,4-dianilino-s-triazin-6-ylamino) stilbene-2
-Disulfonate, disodium 4,4'-bis- (2-anilino-4 (N-
Methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino) stibene-2,2'-disulfonate, disodium 4,4'-bis- (4-phenyl-2,1,3- Triazol-2-yl) stilbene-2,2-disulfonate, disodium 4,4'-bis- (2-anilino-4 (1-
Methyl-2-hydroxyethylamino) -s-triazin-6-ylamino) stiben-2,2'-disulfonate, sodium 2 (stilbill-4 "(naphtho) -1 ',
Examples thereof include 2 ': 4,5) -1,2,3-triazole-2 "-sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Particularly preferred brighteners are disclosed in European Patent Application No. 9520194
No. 3.8.

Other useful polymeric materials are, in particular, molecular weights of 1000-1000.
0, more preferably 2000-8000, most preferably about 4000 polyethylene glycol. These amounts may range from 0.20% to 5% by weight of the composition, more preferably from 0.25% to 2.%.
5% by weight. These polymers and the above homo- or copolymeric polycarboxylates are valuable materials for maintaining whiteness, depositing textile ash, and improving the cleaning performance of clayey, protein and oxidative soils in the presence of transition metal impurities. It is.

Soil release agents for use in the compositions of the present invention include well-known copolymers or terpolymers of ethylene glycol and / or propylene glycol units of various arrangements with terephthalic acid. Examples of such polymers are described in U.S. Pat.
No. 16885, No. 4711730 and European Published Patent Application No. 0272
No. 033 discloses this. A particularly preferred polymer of EP-A-0272033 has the following formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [T-PO) _2.8 − (T-PEG) _0.4 ] TPOH) _0.25 (PEG) ₄₃ CH ₃ ) _{0.75 wherein} PEG represents — (OC ₂ H ₄ ) O—, PO represents (OC ₃ H ₆ O), and T represents (pcOC ₆ H ₄ CO).

Also useful are modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1-2 propanediol, the terminal groups of which are primarily comprised of sulfobenzoates; It is composed of secondary ethylene glycol and / or propanediol monomonoester. The goal is to obtain a polymer which is "essentially" capped at both ends with sulfobenzoate, in which context the majority of the copolymers are end-capped with sulfobenzoate groups. However, some of the copolymers do not reach full capping and their end groups are therefore terminated by the "secondary" components of such species, ethylene glycol and / or propane-1,2-diol mono- It may be composed of an ester.

The polyester selected here is about 46% by weight of dimethyl terephthalic acid, about 16% by weight of propane-1,2-diol, about 10% by weight of ethylene glycol, about 13% by weight of dimethyl sulfobenzoic acid, and about 15% by weight of sulfoisophthalic acid. %
And the molecular weight is about 3,000. Details of this polyester and its preparation are described in EPA 311342.

It is well known that free chlorine in tap water rapidly destroys the enzymatic activity of detergent compositions. Therefore, use chlorine scavengers such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine,
When used in an amount of about 0.1% of the total composition in this formulation, the stability of the α-amylase enzyme is improved throughout the wash period. Compositions containing chlorine scavengers are described in European Patent Application No. 92870018.6 (January 31, 1992).

Softeners Fabric softeners (softeners) may also be uniformly mixed into the laundry detergent composition of the present invention. These softeners are of the inorganic or organic type. Examples of inorganic softeners are GB-A-first
No. 400 898 and the sm disclosed in U.S. Pat.No. 5,019,292.
An example is ectite clay. GB-A for organic fabric softener
No. 614 276 and EP-B 0 011 340 disclose the water-soluble tertiary amines and their combination with mono-C _12-14 quaternary ammonium salts as EP-B-0 026 527,
No. 026528, and EP-B-0242.
No. 019 discloses long chain diamides. Other useful organic components in the fabric softening system include high molecular weight polyethylene oxide materials and are described in EP-A 0 299 6575 and EP 0 313 146.

The amount of semetite clay (clay) is usually 2% to 20% by weight, preferably 5% to 15% by weight, and is added as a dry mix component to the rest of the formulation. The amount of organic fabric softener, such as water-insoluble tertiary amine or di-long chain amide material, is 0.5% to 5% by weight, usually 1% to 3% by weight,
The amount of high molecular weight polyethylene oxide material and water-soluble cationic material should be 0.1% to 2% by weight of the agent, usually 0.15%
1.5% by weight. It is more convenient to add these materials to the spray-dried portion of the composition, in some cases as dry mix particles, or spoon as a melt onto the other solid components of the composition.

Dye Transfer Inhibitor The detergent composition of the present invention may also contain a compound for preventing the transfer of soluble and suspendable dyes between the fabrics, which involves colored fabrics experienced during washing.

Polymeric dye transfer inhibitor in the detergent composition of the present invention
0.0015 to 10% by weight, preferably 0.01% to 2% by weight,
More preferably, it is contained at 0.05% to 1% by weight. Such polymeric dye transfer inhibitors are uniformly mixed into the detergent composition for the purpose of preventing the transfer of the dye from the colored fabric onto the fabric being washed. These polymers are capable of complexing or absorbing suspect dyes washed out of the colored fabric prior to the opportunity for the dye to adhere to other fabrics during washing.

Particularly preferred high molecular weight dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone, polyvinyloxazolidone and polynylimidazole or mixtures thereof. Addition of such a polymer enhances the performance of the enzyme of the present invention.

a) Polyamine N-oxide polymers Suitable polyamine N-oxide polymers for use have the following structural formula: [Wherein, P is a polymerizable unit, and the R—N—O group can be bonded to or constitute a part of the P unit, or a combination of both. x represents 0 or 1; R represents an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic group or a combination thereof, and the nitrogen of the N-O- group is bonded to these groups or Can form a part].

This NO group has the following general structural formula: Wherein R ₂ , R ₂ and R ₃ are aliphatic, aromatic, heterocyclic or alicyclic groups or a combination thereof, x or /
And y or / and z are 0 or 1, and NO
The nitrogen of the group can be attached to or form part of these groups].

The N-O group can form part of the polymerizable unit (P) or be attached to the polymer backbone, or both.

Suitable polyamine N-oxides when the N-O groups form part of a polymerizable unit include those polyamines N-oxides wherein R is selected from aliphatic, aromatic, cycloaliphatic or heterocyclic groups. I do. One example of such a polyamine N-oxide includes the group of polyamine N-oxides where the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are those where R is pyridine, pyrrole, pyrrolidine, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of polyamine N-oxides includes the polyamine N-oxides where the nitrogen of the NO group is attached to the R group.

Other preferred polyamine N-oxides are those where the N-O group is attached to a polymerizable unit. A preferred type of these polyamine N-oxides is a polyamine N-oxide represented by the general formula (I),
R in this case is an aromatic, heterocyclic or alicyclic group, and the nitrogen of the NO functional group forms part of the R group.

Examples of these types are polyamine oxides where R is pyridine, pyrrole, imidazole and derivatives thereof. Other preferred polyamine N-oxide types are
A polyamine oxide having the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the NO functional group is bonded to the R group.

Examples of these types are polyamine oxides where the R group is an aromatic group such as phenyl.

The amine oxide polymer formed is water-soluble,
Any polymer main chain can be used as long as it has dye transfer inhibiting properties. Examples of suitable polymer backbones include polyvinyl, polyalkylene, polyester, polyether,
Polyamides, polyimides, polyacrylates and mixtures thereof.

The amine N-oxide polymers of the present invention have an amine: amine N-oxide ratio of 10: 1 to 100,000. However, the amount of amine oxide present in the polyamine oxide polymer depends on the degree of copolymerization or the degree of N-oxidation. Preferred amine: amine N-oxide ratios are from 2: 3
1: 100000, more preferably 1: 4 or 1: 100000, etc.
Most preferably it is from 1: 7 to 1: 1000000. The polymers of the present invention actually include random or block copolymers where one monomer type is an amine oxide and the other monomer type is not an amine N-oxide or an amine N-oxide. The PKa of the amine oxide unit of the polyamine N-oxide is <10, preferably PKa <7, and more preferably the PKa is <6.

The degree of polymerization of the polyamine oxide is obtained in almost all degrees. The degree of polymerization is not critical as long as the material has the desired water dissolving and dye suspending properties.

Typical average molecular weight is 500 to 1,000,000, preferably 1,00
It ranges from 0 to 50,000, more preferably 2,000 to 30,000, most preferably 3,000 to 20,000.

b) Copolymer of N-vinylpyrrolidone and N-vinylimidazole The copolymer suitable for the present invention has an average molecular weight of 5,000 to 1,0.
It is a copolymer of N-vinylimidazole and N-vinylpyrrolidone in the range of 00,000, preferably 5,000-200,000.

Particularly preferred polymers for use in the detergent composition of the present invention are selected from N-vinylimidazole / N-vinylpyrrolidone copolymers, wherein the average molecular weight of the polymer is 5,000.
It is in the range from 0 to 50,000, more preferably from 8,000 to 30,000, most preferably from 10,000 to 20,000.

Average molecular weights are from Barth HG and Mays JW Chemical
Analysis Vol 113, “Modern Methods of Polymer Chara
cterization ".

Particularly preferred N-vinylimidazole / N-vinylpyrrolidone copolymers have an average molecular weight of 5,000 to 50,000, more preferably 8,000 to 30,000; most preferably 10,000 to
20,000.

The N-vinylimidazole / N-vinylpyrrolidone copolymer characterized by the above average molecular weight range exhibits excellent dye transfer inhibition properties, but does not adversely affect the cleaning performance of a detergent composition formulated using the same. .

The N-vinylimidazole / N-vinylpyrrolidone copolymer of the present invention has an N-vinylimidazole: N-vinylpyrrolidone ratio of 1 to 0.2, more preferably 0.8 or 0.3, and most preferably 0.6 to 0.4.

c) Polyvinylpyrrolidone The detergent composition of the present invention has an average molecular weight of 2,500 to 400,000.
0, preferably from 5,000 to about 2000,000, more preferably from about 5,000 to about 50,000, most preferably from 5,000 to about 15.0.
Polyvinyl pyrrolidone ("PVP") of 00 can also be used. Preferably, polyvinylpyrrolidone is trade name PVPK-15 (viscosity average molecular weight 10,000), PVP K-30 (average molecular weight 40,00
0), PVPK-60 (average molecular weight 160,000), and PVP K
ISP Corpora under the trade name of −90 (average molecular weight 360,000)
commercially available from Action, New York, NY and Montreal, Canada. PVPK-15 is also available from ISP Corporation. BASF
Other suitable polyvinylpyrrolidones commercially available from Corporation include polyvinylpyrrolidone "Sokalan HP 165" and "Sokalan HP 12" well known to those skilled in the art (e.g., EP-A-262,897 and 256,696). No.).

d) Polyvinyl oxazolidone: The detergent composition of the present invention can utilize polyvinyl oxazolidone as a polymeric dye transfer inhibitor. The average molecular weight of the polyvinyl oxazolidone is 2,500 to 400,000.
Preferably from about 5,000 to about 200,000, more preferably about 5,
000 to about 50,000, most preferably about 5,000 to about 15,000
It is.

e) Polyvinyl imidazole: The detergent composition of the present invention can utilize polyvinyl imidazole as a polymeric dye transfer inhibitor. The average molecular weight of the polyvinyl imidazole is about 400,000, preferably about 5,000 to about 200,000, more preferably about 5,000 to about 5
0,000, most preferably from about 5,000 to about 15,000.

f) Crosslinked polymers: polymers in which the backbone is linked to some extent are crosslinked polymers: these bonds are of a chemical or physical nature due to active groups on the backbone or branches; About Polymer Science, Vol 22, page 1
035-1039.

In embodiments, the cross-linked polymer is made in a manner that forms a three-dimensional rigid structure that is capable of entrapping the dye in pores formed by the three-dimensional structure. In another embodiment, the crosslinked polymer confines the dye by swelling.

Such crosslinked polymers are described in co-pending application Ser. No. 94870213.9.

Laundry Methods The compositions of the present invention can be used in virtually any laundering or cleaning method, including maceration (soaking), pre-treatment, and methods involving a rinsing step to which a separate rinsing accelerating composition can be added.

The method according to the invention comprises the step of contacting the fabric with the cleaning solution in the usual manner, as exemplified below.

The process of the present invention is conveniently performed during the cleaning process. This cleaning method is 5 ° C to 95 ° C,
It is particularly preferred to carry out at a temperature of from 10 ° C to 60 ° C. However, certain amylase enzymes in a specific enzyme concentration range have extremely low
(25 ° C. to 25 ° C.). The pH of the treatment solution is preferably 7 to 11.

A preferred machine dishwashing method involves treating a soiled article with an aqueous solution of a machine dishwashing or rinsing composition. The usual effective amount of the machine dishwashing composition means 8-60 g of the product dissolved or dispersed in a 3-10 liter washing volume.

In manual dishwashing, an effective amount of the dishwashing composition,
Typically contact with 0.5-20 g (per 25 dishes to be processed). Preferred manual dishwashing methods also include applying a concentrated solution to the dish surface or maceration with a large amount of detergent dilute solution.

The composition of the present invention can also be formulated as a hard surface cleaner composition.

The following examples illustrate exemplary embodiments of the present invention and are not meant to limit or change the scope of the invention.

In detergent compositions, the amount of enzyme is expressed as pure enzyme based on the weight of the total composition, and the abbreviations of the components have the following meanings: LAS: sodium C ₁₂ linear alkyl benzene sulfonate TAS: sodium tallow oil (tallow) Alkyl sulfate XYAS: Sodium C _1x -C _1y alkyl sulfate SAS: C _12-14 Sodium secondary (2,3) alkyl sulfate AES: Alkyl ethoxy carboxylic acid surface activity of formula C ₁₂ ethoxy (2) carboxylate Agent SS:: secondary soap surfactant of the formula 2-butyloctanoic acid 25EY: condensed with average Y mole of ethylene oxide
C _12-15 linear main primary alcohol 45EY: engaged ethylene oxide average Y moles condensed
C _14-15 linear main primary alcohol XYEZS: moles per average of ethylene oxide Z moles condensed with C _1X-1Y sodium Le kills sulfate Nonionic: an average degree of ethoxylation of 3 to 7 and the average degree of propoxylation 4.5 C _{12- 14} Mixed ethoxylated and / or propoxylated fatty alcohol CFAA: C _12-14 alkyl N-methylglucamide TFAA: C _16-18 alkyl N-methylglucamide Silicate: amorphous sodium silicate (SiO ₂ : Na ₂ ratio =
2.0) NaSKS-6: crystalline layered silicate of the formula δ-Na ₂ Si ₂ O ₅ carbonate: anhydrous sodium carbonate metasilicate: sodium metasilicate (SiO ₂ : Na ₂ O ratio =
2.0) Phosphate or STPP:: Sodium tripolyphosphate MA / AA: 1: 4 maleic acid / acrylic acid copolymer with average molecular weight 80,000 PA30 Polyacrylic acid with average molecular weight 8,000 Terpolymer: acrylic acid: maleic acid: ethyl acrylic Terpolymer having an average molecular weight of 7,000 containing acid monomer units 60:20:20 480N: 3: 7 acrylic / methacrylic acid random copolymer having an average molecular weight of about 3,500 Polyacrylate: an average commercially available from BASF GmbH under the trade name "PA30" polyacrylate homopolymers Zeolite molecular weight 8,000 a: formula _{Na 12 (AlO 2 SiO 2)} 12 · 27H 2 O hydrated aluminum except helium (primary particle size ranging from 1 to 10 micrometer) citrate: trisodium citrate・ 2H ₂ O Citric: Citric acid Per (per) boric acid: Empirical formula NaBO ₂・ H ₂ O ₂ anhydrous sodium perborate ・ 1H ₂ O PB4: Anhydrous sodium perborate percarbonate: Formula 2Na ₂ CO ₃・ 3H ₂ O ₂ anhydrous sodium percarbonate bleach TAED: Tetraacetylethylenediamine Paraffin: Paraffin oil commercially available under the trade name “Winog 70” from Wintershall Pectinase: Trade name “Pectinex from Novo Nordisk A / s
Peptolytic enzyme xylanase, commercially available as "AR": Tradename "Pulpzyme" from Novo Nordisk A / s
HB "or" SP 43 "or" Lyxasan "(Gist
-Brocades) or "Optipulp" or "Xylanase"
Xylanolytic enzyme protease commercially available as (Solvay) from Novo Nordisk A / s under the trade name "Savians
e "," Alcalase "and" Durazyme "and G
Pro available from ist-Brocade as "Maxapem" and "Maxacal" and further described in patent applications WO 91/06637 and / or 95/10591 and / or EP 251 446.
teolytic enzyme lipase: Trade name "Lipolas" from Novo Nordisk A / s
e "and" Lipolase Ultra "Chi to commercial Lipolytic enzyme peroxidase: peroxidase enzyme cellulase I, II: endoglucanases 50 kd, endoglucanase 43kD amylase I, II: B. licheniformis derived from α- amylase" Termamyl ^R "," Duramyl ^R "and an α-amylase CMC: sodium carboxymercellulose HEDP: 1,1-hydrogen described in WO 95/10603, WO 96/23873 and WO 96/23874. Cietanediphosphonic acid DETPMP: diethylenetriaminepentane (methylenephosphonic acid) commercially available from Monsanto under the trade name "Dequest 2060" PAAC: pentaamine acetate cobalt (II
I) Salt BzP: Benzoyl peroxide PVP: Polyvinylpyrrolidone polymer EDDS: Ethylenediamine-N, N'-disuccinic acid, [SS] isomeric nato granular bubbles Inhibitor: 12% silicone / silica, 18% stearyl alcohol, 70% starch ( Granular) SCS: Cumene sulfonate sodium sulfate: Anhydrous sodium sulfate HMWPEO: High molecular weight polyethylene oiside PGMS: Polyglycerol monostearate of trade name "Radiasurf 248" TAE25: Tallow alcohol ethoxylate (25) BTA: Benzotriazole bismuth nitrate : Bismuth nitrate salt NaDCC: Sodium dichloroisocyanurate KOH: 100% active solution of potassium hydroxide pH: pH measured with 1% solution in distilled water (20 ° C) Example 1 The granular fabric cleaning composition of the present invention is as follows: Prepared as: Example 2 A particulate fabric cleaning composition of the present invention was prepared as follows: Example 3 A particulate fabric cleaning composition of the present invention, particularly useful for washing colored fabrics, was prepared as follows: Example 4 A particulate fabric cleaning composition of the present invention was prepared as follows: Example 5 A compact particulate cleaning composition of the present invention was prepared as follows: Example 6 A compact particulate cleaning composition of the present invention providing "softening through washing" performance was prepared as follows: Example 7 A liquid fabric cleaning composition of the present invention was prepared as follows: Example 8 A liquid fabric cleaning composition of the present invention was prepared as follows: Example 9 A liquid fabric cleaning composition of the present invention was prepared as follows: Example 10 A heavy liquid textile chestnut composition suitable for pretreatment of contaminated textiles and use in a mechanical laundry process was prepared as follows: Example 11 A heavy liquid textile cleaning composition was prepared as follows: Example 12 The following rinse additive fabric softener was prepared according to the present invention (parts by weight): softener (activity) 24.5 PGMS 2.0 TAE25 1.5 Amylase I 0.0005 Amylase II 0.0005 Cellulase I 0.001 Cellulase II-HCL 0.02 Foam inhibitor 0.019 Blue Dye 80 ppm CaCl ₂ 0.35 Fragrance 0.90 Example 13 A Syndet bar fabric cleaning composition was prepared according to the present invention: Example 14 The following compact high density (0.96 Kg / l) dishwashing detergent composition was prepared according to the present invention: Example 15 The following granular dishwashing detergent composition (Examples I to IV, bulk density
1.02 Kg / l) was prepared according to the invention: Granular dishwashing detergent composition is compressed using an embodiment 16 standard 12 head rotary press (13 kN / cm ² pressure), was prepared in accordance with the present invention the following detergent composition tablets weighing 25 g: Example 17 The following liquid dishwashing detergent composition according to the invention (from I to II) having a density of 1.40 Kg / l was prepared I II STPP 33.30 20.00 carbonate 2.70 2.00 silicate-4.40 NaDCC 1.10 1.15 nonion 2.50 1.00 paraffin 2.20- Protease 0.03 0.02 Amylase I 0.0025 0.0018 Amylase II 0.00025 0.0007 Cellulase I 0.04 0.01 Cellulase II-0.005 480N 0.50 4.00 KOH-6.00 Sulfate 1.60-pH (1% solution) 9.10 10.00 Example 18 The following liquid hard surface cleaning composition Prepared according to the invention: Example 19 The following spray composition for hard surface cleaning and domestic mildew removal was prepared according to the present invention: I amylase I 0.005 amylase I 0.005 cellulase I-cellulase II 0.01 protease 0.01 sodium octyl sulfate 2.00 sodium hydroxide 4.00 0.80 Silicate (Na) 0.04 Fragrance 0.35 Water / Others (up to 100%)

──────────────────────────────────────────────────続 き Continuation of the front page (56) References JP-A-6-299196 (JP, A) JP-A-63-102694 (JP, A) JP-A-9-501840 (JP, A) US Patent 4,933,279 (US) , A) (58) Fields investigated (Int. Cl. ⁷ , DB name) C11D 3/386 CA (STN) CAOLD (STN) REGISTRY (STN) WPIDS (STN)

Claims (12)

(57) [Claims] 1. A detergent composition comprising at least two kinds of α-amylases. 2. The detergent composition according to claim 1, wherein the total amount of the at least two α-amylases is 0.0001% to 0.1% by weight based on the total composition. 3. The method according to claim 2, wherein the α-amylase is (B) Bacillus.
α-amylase from licheniformis and (b) B. liche
niformis α-amylase C-terminal and B.amyl
α derived from oliquefaciens or B. stearothermophilus
The N-terminus of the amylase, in this case the M at position 197
The detergent composition according to claim 1, which comprises an α-amylase mutant in which et amino acid residue is substituted. 4. The detergent composition according to claim 1, further comprising a cellulase. 5. The detergent composition according to claim 4, wherein the cellulase is 50 kD endoglucanase or 43D endoglucanase. 6. One or more components selected from anions, cations, amphoteric and amphoteric surfactants, builders, bleaching systems, foam inhibitors, soil suspending and anti-redeposition agents, smectite clays and others. Further comprising:
The detergent composition according to any one of claims 5 to 10. 7. The detergent composition according to claim 1, further comprising another enzyme providing a cleaning performance and / or a fabric protection effect. 8. The detergent composition according to claim 7, wherein said other enzyme is a protease. 9. The method according to claim 7, wherein said other enzyme is lipase.
Or a detergent composition according to item 8. 10. A detergent additive comprising at least two α-amylases. 11. A detergent composition comprising the detergent additive according to claim 10. 12. A method for removing malodor from an article, comprising: providing an article; providing a detergent composition comprising at least two types of α-amylase; and bringing the article into contact with the detergent composition. The method.