JP2001509537A - Alkaline detergent composition containing specific cellulase - Google Patents

Abstract

  (57) [Summary] The present invention comprises a fungal cellulase having an optimal pH of 4 to 10 and having no cellulose binding domain and having a 1% solution pH of 7.5 to 10 to provide excellent cleaning and whiteness performance effects. Which relates to a granular bleach-containing laundry detergent composition.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

【Technical field】

The present invention includes a specific cellulase, having a 1% solution pH of 7.5 to 10,
The present invention relates to a granular bleach-containing laundry detergent composition.

[0002]

BACKGROUND OF THE INVENTION

Detergent compositions now contain active ingredients that meet certain needs: surfactant systems, enzymes that exert cleaning and fabric care benefits, bleaches, builder systems,
Contains a complex combination of foam inhibitors, soil suspending agents, soil release agents, optical brighteners, softeners, dispersants, dye transfer inhibiting compounds, abrasives, bactericides, and fragrances. Dynamic performance has actually improved over the years. In particular, current detergent formulations usually contain detergent enzymes, more specifically cellulase.

[0003] The activity of cellulases is such that cellulosic fibers or substrates are hydrolyzed by cellulases depending on the specific function of the cellulases, including endo- or exo-cellulases and the respective hemicellulases. The cellulosic structure is depolymerized or cleaved into smaller, and thus more soluble or dispersible, fractions. This activity, especially on fabrics, presents generally improved feel characteristics to cleaning, regenerating, softening, and fabric construction.

[0004] The efficacy of cellulolytic enzymes, ie, cellulases, as textile cleaning and loosening agents for fabrics has at times been recognized; WO 89 /.
09259, GB-A-2,075,028, GB-A-2,095,275 and GB-A-2,094,826 disclose detergent compositions with cellulase for improved cleaning performance. GB-A-1,368,599 discloses the use of cellulase to reduce the texture of cotton-containing fabrics; US Pat. No. 4,435,307 discloses AC as a roughness-reducing detergent additive;
Disclosed is the use of cellulolytic enzymes from Humicola insolens, designated XI, and fractions thereof.

[0005] EP-A-0269168 is formulated in a mild alkaline pH range,
Demonstrate combined fabric cleaning, fabric softening and fabric care performance,
The best detergent composition containing cellulase is disclosed.

[0006] Particular cellulases suitable for the present invention are described in WO 91/17244,
There, single component enzymes selected for high specific activity are described, and enzymes capable of degrading cellulose or hemicellulose are disclosed.

[0007] The first cellulase component has a persistent type of activity to remove particulate soil, and the second cellulase component has a multi-domain with at least one non-catalytic domain linked to the catalytic domain. Also suitable are the cellulolytic enzymes in WO 95/02675, which describe detergent compositions containing two cellulase components capable of brightening the color, at least one of the cellulase components being a single component. The enzyme detergent composition described above provides both sufficient color clarification and particulate stain removal, and does not damage or partially degrade the cellulose-containing fabric even after a limited number of washing cycles. Suitable cellulases are described in Genencor's WO9 published September 29, 1994.
EGIII cellulase derived from Trichoderma longibrachiatum described in 4/21801.

[0008] Current granular bleach-containing laundry detergent compositions have a 1% solution pH of about 10.5, and provide the best bleach performance via optimal perhydrolysis obtained at that pH. are doing. It is known that the cleaning performance of such a bleach-containing laundry detergent composition deteriorates with a decrease in pH. Nevertheless, a lower pH is required to obtain sufficient enzyme performance with the cellulase-containing detergent. Accordingly, it is an object of the present invention to formulate a granular bleach-containing laundry detergent composition that combines the cleaning effect of a bleach with the enzyme cleaning performance of cellulase in order to exert excellent cleaning and whiteness performance effects. is there.

It has been surprisingly found that a laundry detergent composition containing a specific cellulase and having a 1% solution pH of 7.5 to 10 exerts the best cleaning and whitening performance effects.

[0010] In fact, it is believed that the above-mentioned best pH enhances the performance of a particular cellulase without drastically reducing the bleach cleaning and whiteness performance effects. A slight decrease in cleaning performance due to a slight decrease in perhydrolysis rate
This is compensated for by improved enzyme performance at low pH and reduced darkening of bleach sensitive stains.

[0011]

[Summary of the Invention]

The present invention relates to a granular bleach-containing laundry detergent composition containing a specific cellulase and having a 1% solution pH of 7.5 to 10 to exert excellent cleaning and whitening performance effects.

[0012]

DETAILED DESCRIPTION OF THE INVENTION Certain Cellulases The essential element of the present invention comprises from 0.0001 to 2% by weight of the total composition, more preferably from 0.
. Certain cellulases commonly contained in laundry detergent compositions of the present invention at pure enzyme levels of 0005-0.05%, most preferably 0.001-0.01%.

Particular cellulases suitable for the present invention are fungal strains, preferably the following organisms: Humico
It can be obtained from la insolens or Trichoderma longibrachiatum, reseei or viride. Certain cellulases are characterized by having a cellulose binding domain (CBD) with an optimal pH of 4-10. The term CBD is meant to indicate an amino acid sequence that allows cellulase to effectively bind to a cellulose substrate. It has been surprisingly found that a granular bleach-containing laundry detergent composition comprising a specific cellulase and having a 1% solution pH of 7.5 to 10 exhibits the best cleaning and whitening performance effects.

Examples of cellulase components that can be used in the present invention are: Highly purified from Humicola insolens DSM1800-immunoreactive with antibodies to 50 kD endoglucanase or exhibiting cellulase activity-5
An endoglucanase component that is a homolog or derivative of a 0 kD endoglucanase (preferred endoglucanase component is PCT Patent Application WO 91/1724).
No. 4); Fusarium oxysporum DSM26
Highly purified ~ 50 kD (apparent molecular weight, amino acid composition corresponding to 45 kD with a 2n glycosylation site) derived from E.72 ~ 50 kD endoglucanase homologue which is immunoreactive with antibodies to endoglucanases or which exhibits cellulase activity Or a derivative endoglucanase component (a preferred endoglucanase component has the amino acid sequence disclosed in PCT Patent Application WO 91/17244). With an estimated molecular weight of about 50 kDa, an isoelectric point of about 5.5,
Even more preferred is a cellulase derived from Humicola insolens DSM1800 containing 15 amino acids.

Endoglucanases are microorganisms known to be capable of producing cellulolytic enzymes, such as Humicola, Bacillus, Trichederma, Fusarium, Myceliophtora, Ph
anerochaete, Schizophyllum, Penicillium, Aspergillus and Geotricum
Or isolated and purified from the species The derived components may be the same or different components. Preferably, the components are homogeneous. However, heterologous components that are immunoreactive with antibodies to highly purified cellulase components having the desired properties and are derived from specific microorganisms are also preferred.

As described in WO 95/02675, other suitable endoglucanase components have the amino acid sequences disclosed in FIGS. 14A-E of SEQ ID NO: 2 or WO 91/17244 attached thereto. Or an amino acid sequence that is at least 60%, preferably at least 70%, more preferably at least 75%, more preferably at least 80%, more preferably at least 85%, especially at least 90%, homologous to the sequence It is a variant of the endoglucanase possessed.

The endoglucanase described above is immunoreactive with antibodies to highly purified 〜50 kD (apparent molecular weight, amino acid composition corresponding to 45 kD with a 2n glycosylation site) endoglucanase from Fusarium oxysporum DSM2672, or An endoglucanase component that is a homolog or derivative of a 〜50 kD endoglucanase exhibiting cellulase activity may be used. Preferred endoglucanase components have the amino acid sequence disclosed in FIG. 13 of WO 95/02675 or SEQ ID NO: 3 of WO 91/17244, or have at least 60%, preferably at least 70%, the above sequence. And more preferably 7
5%, more preferably at least 80%, more preferably 85%, especially at least 9%
A variant of the endoglucanase having an amino acid sequence that is 0% homologous.

The above-described endoglucanase component may be any of the SEQ ID NOs described in WO 95/02675.
A plasmid containing a DNA sequence corresponding to the amino acid sequence of ID NO: 3,
After transformation with Taka promoter and AMG terminator, Aspe
Produced by rgillus oryzae. This endoglucanase is uniformly purified using cationic chromatography and has a pI> 9. Calculated pI
Is based on amino acid composition using PHKa values from Adv. Protein Chem. 17, p. 69-165 (1962), C. Tanford. The molar extinction coefficient was calculated to be 58180.

Another suitable cellulase is Genencor's W, published September 29, 1994.
EGIII from Trichoderma longibrachiatum described in O94 / 21801
It is. More preferred cellulases for the laundry detergent compositions of the present invention are 22-27.
Estimated molecular weight of kDa, isoelectric point of 7.2-8.0 and optimal pH of 5.5-6.0
And a cellulase derived from Trichoderma sp.

In the context of the present invention, the term “homolog” refers to (eg pre-soaked in 5 × SSC, 20% formamide, 5 × Denhardt's solution, 50 mM sodium phosphate, pH 6.8 and denatured sonicator About 40 ° C. in a solution of 50 μg of bovine thymus DNA
Under one specific condition for about 1 hour, followed by 18 hours at about 40 ° C. in a similar solution supplemented with 100 μM ATP) for the endoglucanase enzyme having this amino acid sequence. It is meant to indicate a polypeptide encoded by DNA that hybridizes to a probe similar to DNA. The term refers to the addition of one or more amino acid residues at one or both of the C- and N-termini of the native sequence, substitution of one or more amino acid residues at one or more sites in the native sequence, one of the native amino acid sequences Or a derivative of said sequence obtained by deletion of one or more amino acid residues at one or more sites at both ends or at one or more sites in the native sequence, or insertion of one or more amino acid residues at one or more sites in the native sequence. It is the meaning including.

However, for the industrial production of the present cellulase preparations, the recombinant DN involved in the regulation of the fermentation or mutation of the microorganism to ensure that the desired enzymatic activity is overproduced.
It is preferred to use the A technique or other techniques. Such methods and techniques are known in the art and can be readily performed by those skilled in the art.

[0022] The enzymes described above may be of any suitable origin, such as of plant, animal, bacterial, fungal and yeast origin. The origin may also be mesophilic or extremophilic (cryophilic, eutrophic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. At present, it is customary to modify wild-type enzymes by protein / genetic engineering techniques to maximize performance efficacy with the cleaning compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the common components of such compositions. On the other hand, the optimal pH for enzyme variants
Variants may be designed such that bleed or chelant stability, catalytic activity, etc., are tailored to a particular cleaning application.

In particular, attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of surfactant compatibility. The isoelectric point of such enzymes may be modified by substitution of some charged amino acids, for example, increasing the isoelectric point helps to improve compatibility with anionic surfactants. Enzyme stability can be further enhanced, for example, by forming additional salt bridges and reinforcing calcium binding sites to increase the stability of the chelants.

The bleach bleach contained in the bleach-containing laundry detergent of the present invention, for example, hydrogen peroxide, PB1, PB4, and a percarbonate having a particle size of 400-800 microns. These bleach components can include one or more oxygen bleaches and, depending on the bleach selected, one or more bleach activators. When present, the oxygen bleaching compound is typically present at a level of about 1 to about 25%.

[0025] The bleach component used in the present invention can be any bleach useful in cleaning compositions, including oxygen bleaches and others known in the art. Bleaches suitable for the present invention are activated or deactivated bleaches. One category of oxygen bleaches that can be used includes polycarboxylic acid bleaches and salts thereof. Suitable examples of this class of agents include magnesium monoperoxyphthalate hexahydrate, the magnesium salt of m-chloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxidedecanedioic 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. 4,412,934. Have been. Highly preferred bleaches include US Pat. No. 4,634,551.
There are also 6-nonylamino-6-oxoperoxycaproic acids as described in US Pat.

Another category of bleaches that can be used is halogen bleaches. Examples of hypohalous acid bleaches include, for example, trichloroisocyanuric acid, sodium and potassium dichloroisocyanurates, N-chloro and N-bromoalkanesulfonamides. Such substances are usually added at 0.5 to 10% by weight, preferably 1 to 5% by weight of the final product.

The hydrogen peroxide releasing agent is tetraacetylethylenediamine (TAE), which is perhydrolized to form peracid as an active bleaching species and exerts an improved bleaching effect.
D), nonanoyloxybenzenesulfonate (NOBS, US Pat. No. 4,412,9)
34), 3,5-trimethylhexanoloxybenzenesulfonate (
ISONOBS, EP120,591), pentaacetylglucose (P
AG) or a phenolsulfonate ester of N-nonanoyl-6-aminocaproic acid (NACA-OBS, described in WO 94/28106). Co-pending European Patent Application 91870207.
No. 7, acylated citrate esters, and Procter &
Gamble as disclosed in co-pending US patent application Ser. Nos. 60 / 022,786 (filed July 30, 1996) and 60 / 028,122 (filed October 15, 1996). Asymmetric acyclic imido bleach activators of the following formula are also suitable activators:

Embedded image In the above formula, R ₁ is a C ₇ -C ₁₃ linear or branched saturated or unsaturated alkyl group, R ₂ is a C ₁ -C ₈ linear or branched saturated or unsaturated alkyl group, and R ₃ is C ₁ -C ₄ straight or branched chain saturated or unsaturated alkyl group.

Useful bleaching agents, including bleach activators and peroxygen bleaching compounds, and peroxy acids, for use in detergent compositions according to the present invention, are described in our co-pending application USSN 08 / 136,626. , PCT / US95 /
07823, WO95 / 27772, WO95 / 27773, WO95 / 277
74 and WO 95/27775.

[0029] Hydrogen peroxide may also be present at the beginning or during the washing and / or rinsing process by adding an enzyme system capable of generating hydrogen peroxide (ie, the enzyme and its substrate). Such an enzyme system is described in EP-A-
It is disclosed in patent application 91202655.6.

The metal-containing catalyst used in the bleach composition includes a cobalt-containing catalyst such as a pentaamine cobalt (III) acetate salt, and a manganese-containing catalyst such as EPA 549271.
EPA 549272, EPA 458 397, US 5,246,621, EPA 4
58398, US 5,194,416 and US 5,114,611. A bleaching composition comprising a peroxy compound, a manganese-containing bleach catalyst and a chelating agent is described in patent application 94870206.3. Transition metal complexes of macropolycyclic hard ligands are preferred metal-containing catalysts for the purposes of the present invention and are described in Procter & Gamble co-pending patent applications USSN 60/040629, 60/039915, 60, filed March 7, 1997. / 040222,
60/040156, 60/040115, 60/038714 and 60/0
39920.

Bleaches other than oxygen bleaches are known in the art and may be used in the present invention. One type of non-oxygen bleach that is of particular interest is a light activated bleach such as a sulfonated zinc and / or aluminum phthalocyanine. These substances can adhere to the substrate during the cleaning process. Like hanging clothes in the sun and drying
Upon irradiation with light in the presence of oxygen, the sulfonated zinc phthalocyanine is activated, thereby bleaching the substrate. A preferred zinc phthalocyanine and light activated bleaching process is described in U.S. Pat. No. 4,033,718. Typically, the detergent compositions contain from about 0.025 to about 1.25% by weight of the sulfonated zinc phthalocyanine.

PH Range of 7.5-10 The granular bleach-containing laundry detergent composition of the present invention has a 1% solution pH of 7.5-10. The 1% solution pH is measured as follows: 10 g of the product are added to 200 ml of warm deionized water and dissolved by magnetic stirring. Dilute the solution to 1 L,
The pH is measured for a portion of 50 ml. The 1% solution pH range is obtained by a buffer system that ensures that the pH of the composition is buffered to a 1% solution pH value of 7.5-10. The solid granular bleach-containing laundry detergent composition preferably comprises a pH buffering component in an amount of 1 to 40%, more preferably 1.5 to 35%, most preferably 2 to 30% by weight of the total composition. contains. pH buffering components include builders in the form of alkali salts and acids, as described below.

[0033] Suitable pH-buffering components for use in the present invention include carbonate, bicarbonate, citric acid, citrate, polycarbonate, sesquicarbonate, silicate, polysilicate, borate, metaborate, phosphate, stannate.
, Aluminate alkali metal salts and mixtures thereof. Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates or their acid forms, homo- or copolymeric polycarboxylic acids or their salts (the polycarboxylic acids are at least two polycarboxylic acids separated from each other by no more than two carbon atoms). Having a carboxyl group), carbonate, bicarbonate, borate, phosphate,
There are silicates and mixtures of any of the above.

[0034] Carboxylate or polycarboxylate builders include monomers or oligomers as a type, but monomeric polycarboxylates are usually preferred for cost and performance reasons.

Suitable carboxylates having one carboxy group include water-soluble salts of lactic acid, glycolic acid and their ether derivatives. Polycarboxylates having two carboxy groups include water-soluble salts of succinic, malonic, (ethylenedioxy) diacetate, maleic, diglycolic, tartaric, tartronic and fumaric acids, and ether carboxylates and There is sulfinyl carboxylate. Polycarboxylates having three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, and British Patent 1,379,2.
Carboxymethyloxysuccinate described in U.S. Pat. No. 41, British Patent No. 1
No. 3,389,732, succinate derivatives such as aminosuccinate described in Dutch Application No. 7205873, and British Patent No. 1,387,447. There are oxypolycarboxylate materials such as 2-oxa-1,1,3-propanetricarboxylate that have been used.

[0036] Polycarboxylates having four carboxy groups are described in GB 1,26
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propane disclosed in 1,829 There are tetracarboxylates. Polycarboxylates having sulfo substituents include those described in GB 1,398,421,
There are the sulfosuccinate derivatives disclosed in 398,422 and US Pat. No. 3,936,448, and the sulfonated pyrolytic citrates described in British Patent 1,439,000.

Preferred for the purposes of the present invention are mixtures of the monomeric or oligomeric polycarboxylates with the parent acid or salts thereof, such as citric acid or citrate / citric acid, and / or carbonate builders, such as carbonic acid and sesquicarbonic acid Alkaline earth carbonates and alkali metals, including sodium, and mixtures with ultrafine calcium carbonate as disclosed in German Patent Application No. 2,321,001 published November 15, 1973. is there.

Suitable acids for lowering the pH of bleach-containing laundry detergents are: citric, succinic, tartaric, oxalic, glutamic, succinamic, pivalic, glutaconic, hexanoic, muconic, Pentanoic acid, aspartic acid, adipic acid, mucinic acid, gluconic acid, galacturonic acid, glucuronic acid, fumaric acid, oxoadipic acid, valeric acid, orotic acid, luronic acid, glutaric acid, butyric acid, glyoxylic acid, oxamide Acid, glycolic acid, propidic acid, parabanic acid, tetronic acid, 2-butyric acid, maleamic acid, malic acid, acrylic acid,
Diglycolic, crotonic, malonic, lactic, propionic, maleic, lactic and glyceric acids. Preferred acids are citric, succinic, oxalic, muconic, aspartic, luuronic, glutaric, malic, diglycolic, malonic and maleic acids.

Other acids suitable for the present invention are diethylenetriaminepentamethylphosphonic acid (DETPMP), (EDDS), 1,1-hydroxyethanediphosphonic acid (H
EDP), methyl ester sulfonic acid (HMES), linear alkylbenzene sulfonic acid (HLAS), and copolymer of acrylic and maleic acid (MA / AA)
It is.

Detergent Component The granular bleach-containing laundry detergent composition of the present invention may also contain additional detergent components. The exact nature of these additional components, and their level of incorporation, will depend on the physical form of the composition and the nature of the cleaning operation in which it is used. The granular bleach-containing laundry detergent composition according to the present invention includes pastes, gels, bars,
Available in tablet, spray, foam, powder or granule form. Granular compositions may be in "compact" form.

The compositions of the present invention include, for example, hand and machine laundry detergent compositions, such as laundry additive compositions, compositions suitable for soaking and / or pretreating soiled fabrics, rinse-added fabric softener compositions. Is prescribed as

The composition of the present invention preferably comprises both a surfactant and a builder compound,
Preferably, one or more detergent components selected from an organic polymer compound, a bleach, an additional enzyme, a foam inhibitor, a dispersant, a lime soap dispersant, a stain suspending and anti-redeposition agent, and a corrosion inhibitor. It also contains. Laundry compositions can also contain softening agents as additional detergent components.

Such alkaline granular bleach-containing laundry detergent compositions, when formulated as laundry detergent compositions, provide fabric cleaning, stain removal, whiteness maintenance, flexibility, color appearance and color transfer inhibition. It can demonstrate the nature.

The compositions of the present invention can also be used as detergent additive products. Such additive products are to reinforce or enhance the performance of conventional detergent compositions. If necessary, the density of the laundry detergent composition is 4% for the composition measured at 20 ° C.
It is 00 to 1200 g / L, preferably 600 to 950 g / L.

The “compact” form of the composition is best reflected in terms of density and composition in terms of the amount of inorganic filler salt; inorganic filler salt is a conventional component of detergent compositions in powder form; In some detergent compositions, the filler salt is present in a substantial amount, typically 17-35% by weight of the total composition. In a compact composition, the filler salt does not exceed 15% by weight of the total composition;
Preferably it is present in an amount not exceeding 10%, most preferably not exceeding 5% of the composition.

The inorganic filler salts as meant in the present composition are selected from the alkali and alkaline earth metal salts of sulfates and chlorides. A preferred filler salt is sodium sulfate.

Surfactant System The granular bleach-containing laundry detergent composition according to the present invention is characterized in that the surfactant is nonionic and / or anionic and / or cationic and / or amphoteric and / or
Or, it usually includes a surfactant system, which can be selected from bipolar and / or semi-polar surfactants.

[0048] Surfactants are typically present at a level of 0.1-60% by weight. A more preferred loading level is 1 to 35% by weight, most preferably 1 to 30% by weight, for the granular bleach-containing laundry detergent composition according to the invention. The surfactant is preferably formulated to be compatible with the enzyme components present in the composition. In liquid or gel compositions, surfactants are most preferably formulated to promote the stability of, or at least degrade, the enzyme in these compositions.

[0049] Preferred surfactant systems used according to the present invention include the ones described herein.
One or more nonionic and / or anionic surfactants are included as surfactants.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant system of the present invention, with polyethylene oxide condensates being preferred. These compounds include the condensation products of alkyl phenols with alkyl phenols having an alkyl group of from about 6 to about 14, preferably from about 8 to about 14, carbon atoms in a linear or branched configuration. In a preferred embodiment, the ethylene oxide is present in an amount corresponding to about 2 to about 25 moles, more preferably about 3 to about 15 moles of ethylene oxide per mole of alkylphenol. Commercially available nonionic surfactants of this type include GAF Cor
Igepal ^™ CO-630 from poration, all Rohm & Haas Compan
Triton ^™ X-45, X-114, X-100 and X-1 sold by y
02. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

[0051] The primary and secondary aliphatic alcohols are combined with about 1 to about 25 moles of ethylene oxide.
The condensation product is used as a nonionic surfactant in the nonionic surfactant system of the present invention.
Suitable for The alkyl chain of the aliphatic alcohol is linear or branched, primary or
It is secondary and usually has about 8 to about 22 carbon atoms. About 8 to about 20 carbon atoms
More preferably an alcohol having an alkyl group of about 10 to about 18 carbon atoms;
Condensation products with about 2 to about 10 moles of ethylene oxide per mole of alcohol are preferred.
Good. About 2 to about 7 moles of ethylene oxide per mole of alcohol, most preferably
Alternatively, 2 to 5 moles of ethylene oxide are present in the above condensation product. This Thailand
Examples of commercially available nonionic surfactants include Union Carbide Corporation
Sold by Tergitol^TM15-S-9 (C₁₁-C_FifteenStraight-chain alcohols and ethi
Condensation product with 9 mol of lenoxide), Tergitol^TM24-L-6NMW (C₁₂-C ₁₄ Condensation product of primary alcohol and 6 moles of ethylene oxide with narrow molecular weight distribution)
; Neodol sold by Shell Chemical Company^TM45-9 (C₁₄-C_Fifteenstraight
Condensation product of a chain alcohol and 9 moles of ethylene oxide), Neodol^TM23-3 (C ₁₂ -C₁₃Condensation product of linear alcohol and 3.0 moles of ethylene oxide), Neodol ^TM 45-7 (C₁₄-C_FifteenCondensation product of linear alcohol with 7 mol of ethylene oxide
), Neodol^TM45-5 (C₁₄-C_FifteenLinear alcohol and 5 moles of ethylene oxide
Kyro sold by The Procter & Gamble Company^TMEOB
(C₁₃-C_FifteenCondensation product of alcohol and 9 moles of ethylene oxide);
LA O3O or O5O (C₁₂-C₁₄With alcohol
Condensation products with 3 or 5 moles of ethylene oxide). In these products
The preferred range of HLB is 8-11, most preferably 8-10.

The nonionic surfactants of the surfactant system of the present invention include hydrophobic groups having about 6 to about 30 carbon atoms, preferably about 10 to about 16 carbon atoms, and about 1.3 to about 10 carbon atoms. ,
Llenado, published January 21, 1986, having a polysaccharide having preferably from about 1.3 to about 3, most preferably from about 1.3 to about 2.7 saccharide units, such as a polyglycoside hydrophilic group. Also useful are the alkyl polysaccharides disclosed in U.S. Patent No. 4,565,647. Reducing sugars having 5 or 6 carbon atoms can also be used, for example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moiety (optionally a hydrophobic group is attached to the 2, 3, 4 position, etc. to form a glucoside or Give glucose or galactose instead of galactoside). For example, an intersugar linkage may be present between one position of the additional saccharide unit and positions 2, 3, 4, and / or 6 of the preceding saccharide unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x wherein} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and (Alkyl groups have about 10 to about 18, preferably about 12 to about 14 carbon atoms); n is 2 or 3, preferably 2; t is 0 to about 10, preferably 0; x is about 1
. 3 to about 10, preferably about 1.3 to about 3, most preferably about 1.3 to about 2.7.
It is. Glycosyl is preferably derived from glucose. To make these compounds, an alcohol or alkyl polyethoxy alcohol is first formed and then reacted with glucose or a source of glucose to form glucoside (1).
Bond). Additional glycosyl units may also be linked between their 1-position and the preceding glycosyl unit at positions 2, 3, 4, and / or 6, preferably predominantly at position 2.

The condensation products of ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol are also suitable for use as the additional nonionic surfactant system of the present invention. The hydrophobic portion of these compounds is preferably about 1500
It has a molecular weight of ~ 1800 and is water-insoluble. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the overall water solubility of the molecule, and the liquidity of the product is such that the polyoxyethylene content is up to about 50% of the total weight of the condensation product. Again, this corresponds to condensation with up to about 40 moles of ethylene oxide. Examples of compounds of this type include certain commercially available Plurafac ^™ LF sold by BASF
There are 404 and Pluronic ^™ surfactants.

As the nonionic surfactant of the nonionic surfactant system of the present invention, a product obtained from the reaction of propylene oxide with ethylenediamine and a condensation product of ethylene oxide are also suitable for use. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide, usually from about 2500 to about 300
It has a molecular weight of 0. The hydrophobic moiety is condensed with ethylene oxide to an extent that the condensation product contains about 40 to about 80% by weight polyoxyethylene and has a molecular weight of about 5000 to about 11,000. Examples of nonionic surfactants of this type include certain commercial Tetronic ^™ compounds sold by BASF.

The nonionic surfactants of the surfactant system of the present invention include polyethylene oxide condensates of alkylphenols, primary and secondary aliphatic alcohols and about 1 to about 25.
Condensation products with moles of ethylene oxide, alkyl polysaccharides, and mixtures thereof are preferred for use. _C 8 -C ₁₄ alkyl phenol ethoxylates having from 3 to 15 ethoxy groups, _C 8 -C ₁₈ alcohol ethoxylates having from 2 to 10 ethoxy groups (preferably C ₁₀ average), and mixtures thereof are most preferred.

Highly preferred nonionic surfactants are polyhydroxyfatty acid amide surfactants of the formula: R ² —CNZＺ∥OR ^{1 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 hydrocarbyl, Z is directly coupled to the chain with linear hydrocarbyl chain A polyhydroxyhydrocarbyl having at least three hydroxyl groups, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl, R ² is a linear C _11-15 alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or a mixture thereof, and Z is glucose, It is derived from reducing sugars such as fructose, maltose and lactose.

Suitable anionic surfactants used are described in “The Journal of the American O.
il Chemists Society ", 52 (1975 ), C 8 -C 20 carboxylic acids which are sulfonated with gaseous SO ₃ according Pp.323-329 (i.e., fatty acids), including straight-chain esters of, linear alkylbenzene sulfonates, alkyl It is an ester sulfonate surfactant.
Suitable starting materials include natural fatty substances such as those derived from tallow, palm oil and the like.

Preferred alkyl ester sulfonate surfactants, especially for laundry applications, include:
And alkyl ester sulfonate surfactants of the structural ^{formula: R 3 -CH-CO-OR} 4 | SO 3 M above wherein ^{R 3} is _C 8 -C ₂₀ hydrocarbyl, preferably an alkyl, or combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is a cation that forms a water-soluble salt with the alkyl ester sulfonate. Suitable salt-forming cations include metals such as sodium, potassium and lithium, substituted or unsubstituted ammonium cations, for example, monoethanolamine, diethanolamine and triethanolamine. Preferably, R ³ is C ₁₀ -C ₁₆ alkyl and R ⁴ is methyl, ethyl or isopropyl. Methyl ester sulfonates wherein R ³ is C ₁₀ -C ₁₆ alkyl are particularly preferred.

Other suitable anionic surfactants include alkyl sulfate surfactants, which are water-soluble salts or acids of the formula ROSO ₃ M, wherein R is preferably C ₁₀ -C ₂₄ hydrocarbyl, preferably alkyl or hydroxyalkyl having a C ₁₀ -C ₂₀ alkyl moiety, more preferably C ₁₂ -C ₁₈ alkyl or hydroxyalkyl, M is H or a cation, e.g., an alkali metal cation (e.g. sodium, potassium, lithium), ammonium or Substituted ammonium (eg,
Quaternary ammonium cations such as methyl-, dimethyl- and trimethylammonium cations, tetramethylammonium and dimethylpiperidinium cations, and quaternary ammonium cations derived from alkylamines such as ethylamine, diethylamine, triethylamine, and the like. Mixtures). Typically, C ₁₂ -C ₁₆ alkyl chains have low wash temperatures (eg, about 50
C), and C ₁₆ -C ₁₈ alkyl chains are preferred at high wash temperatures (eg, above about 50 ° C.).

Other anionic surfactants useful for cleaning purposes can also be included in the granular bleach-containing laundry detergent compositions of the present invention. These include soap salts (including, for example, sodium, potassium, ammonium and substituted ammonium salts such as mono, di and triethanolamine salts), C ₈ -C ₂₂ primary or secondary alkane sulfonates, C ₈ -C _24. Olefin sulphonates, for example British Patent Specification 1,
No. 082,179, a sulfonated polycarboxylic acid produced by sulfonation of a pyrolysis product of an alkaline earth metal citrate, a C ₈ -C ₂₄ alkyl polyglycol ether sulfate (within 10 moles) Ethylene glycerol sulfonate, fatty acyl glycerol sulfonate, fatty oleyl glycerol sulfate, alkylphenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate such as acyl isethionate, N-acyl taurate,
Alkyl succinate cinnamate and sulfosuccinates, monoesters of sulfosuccinates (especially saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₂ diesters), acyl Sarcosinates, sulfates of alkyl polysaccharides such as the sulfates of alkyl polyglucosides (nonionic non-sulfate compounds are described below), branched primary alkyl sulfates, and the formula RO (CH ₂ CH ₂ O) _k -CH ₂ CO
O ^- M ⁺ (R is a _C 8 -C ₂₂ alkyl, k is an integer from 1 to 10, M is a soluble salt-forming cation) and alkyl polyethoxy carboxylates such as. Resin acids and hydrogenated resin acids, such as rosin, hydrogenated rosin, resin acids and hydrogenated resin acids, which are present in or derived from tall oil, are also suitable.

Another example is “Surface Active Agents and Detergents” (Vol. I and II, Schwart
z, Perry and Berch). Various such surfactants include 197
Laughlin et al., U.S. Pat. No. 3,929,678, issued Dec. 30, 5th, is also generally disclosed in column 23, line 58 to column 29, line 23 (for reference). Incorporated herein).

When included in the present compositions, the laundry detergent compositions of the present invention typically comprise from about 1 to about 40% by weight, preferably from about 3 to about 20%, of such an anionic surfactant. Contains.

Highly preferred anionic surfactants include those of the formula RO (A)_mSO₃Water solubility of M
There are alkylalkoxylated sulfate surfactants that are salts or acids,
And R is unsubstituted C_Ten-C_{twenty four}Alkyl or C_Ten-C_{twenty four}Hydro with alkyl moiety
A xyalkyl group, preferably C₁₂-C₂₀Alkyl or hydroxyalkyl, further
Preferably C₁₂-C₁₈Alkyl or hydroxyalkyl, wherein A is ethoxy
M is greater than zero, typically from about 0.5 to about
6, more preferably from about 0.5 to about 3, wherein M is H or a cation, such as a metal
Cations (eg sodium, potassium, lithium, calcium, magnesium
Etc.), ammonium or substituted ammonium cations. Alkyl ethoxy
Sulfated and alkylpropoxylated sulfates are contemplated in the present invention.
Can be Specific examples of the substituted ammonium cation include methyl, dimethyl, and trimethyl.
Ammonium cation, and tetramethylammonium and dimethylpi
Quaternary ammonium cations such as peridinium cations, and ethylamine
, Derived from alkylamines such as diethylamine, triethylamine
And mixtures thereof. Exemplary surfactants include C₁₂-C₁₈Alkyl
Polyethoxylate (1.0) sulfate (C₁₂-C₁₈E (1.0) M), C ₁₂ -C₁₈Alkyl polyethoxylate (2.25) sulfate (C₁₂-C₁₈E
(2.25) M), C₁₂-C₁₈Alkyl polyethoxylate (3.0) sulfate
(C₁₂-C₁₈E (3.0) M) and C₁₂-C₁₈Alkyl polyethoxyle
(4.0) sulfate (C₁₂-C₁₈E (4.0) M), where M is a convenience
It is selected from sodium and potassium.

The granular bleach-containing laundry detergent compositions of the present invention also contain cationic, amphoteric, zwitterionic and semipolar surfactants, as well as nonionic and / or anionic surfactants other than those already described above. May be.

[0066] Cationic cleaning interface suitable for use in the granular bleach-containing laundry detergent compositions of the present invention.
The activator has one long-chain hydrocarbyl group. Such a katio
Examples of surfactants include ammonium surfactants such as alkyltrimethyl.
There are ammonium halides and surfactants having the formula:²(OR³)_y] [R⁴(OR³)_y]₂R⁵N⁺X⁻ R in the above formula²Is an alkyl having about 8 to about 18 carbon atoms in the alkyl chain or
An alkylbenzyl group; each R³Is -CH₂CH₂-, -CH₂CH (CH₃ )-, -CH₂CH (CH₂OH)-, -CH₂CH₂CH₂-And their
Selected from the group consisting of mixtures; each R⁴Is C₁-C₄Alkyl, C₁-C₄Hi
Droxyalkyl, two R⁴Benzyl ring structure formed by linking groups, -CH ₂ CHOH-CHOHCOR⁶CHOHCH₂OH (R⁶Is about 1000 or less
Hexose or hexose polymer having a molecular weight), and y is 0.
R is selected from the group consisting of hydrogen; R⁵Is R⁴Is the same as R² + R⁵Is an alkyl chain having a total number of carbon atoms of about 18 or less;
0 and the sum of y values is from 0 to about 15; X is any suitable anion
It is.

A quaternary ammonium surfactant suitable for the present invention has the following formula (I):

Embedded image Wherein R ₁ is short chain length alkyl (C ₆ -C ₁₀ ) or alkylamidoalkyl of formula (II):

Embedded image Wherein y is 2-4, preferably 3 .; wherein R ₂ is H or C ₁ -C ₃ alkyl; x is 0-4, preferably 0-2, most preferably 0. Wherein R ₃ , R ₄ and R ₅ are the same or different and are a short-chain alkyl (C ₁ -C ₃ ) or an alkoxylated alkyl of the following formula III:

Embedded image (R ⁶ is C ₁ -C ₄ and z is 1 or 2) wherein X ⁻ is a counter ion, preferably a halide such as chloride or methyl sulfate.

Preferred quaternary ammonium surfactants are those of the formula wherein R ₁ is C ₈ , C ₁₀ or a mixture thereof, x = 0, R ₃ , R ₄ ＣＨCH ₃ and R ₅ ＣＨCH ₂ CH ₂ OH. I
As defined in

Highly preferred cationic surfactants are useful in the present compositions, having the formula:
Is a water-soluble quaternary ammonium compound: R₁R₂R₃R₄N⁺X⁻ (I) R in the above formula₁Is C₈-C₁₆Alkyl, R₂, R₃And R₄Are each independent
Then C₁-C₄Alkyl, C₁-C₄Hydroxyalkyl, benzyl and-
(C₂H₄₀)_xH (x has a value of 2 to 5) and X is an anion. R ₂ , R₃Or R₄At most one must be benzyl.

The preferred alkyl chain length for R ₁ is C ₁₂ -C ₁₅ , especially where the alkyl group is a mixture of chain lengths derived from coconut or palm kernel fat, or synthesized by olefin build-up or oxo alcohol synthesis. Induced by. R ₂ ,
Preferred groups for R ₃ and R ₄ are methyl and hydroxyethyl groups, and the anion X is selected from halide, methosulfate, acetate and phosphate ions. Examples of quaternary ammonium compounds of formula (i) suitable for use in the present invention are: coconut trimethylammonium chloride or bromide, coconut methyldihydroxyethylammonium chloride or bromide, decyltriethylammonium chloride, decyldimethylhydroxyethylammonium 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 (ethenoxy) ₄ ammonium chloride or bromide, choline Ester (R ₁ is CH ₂ —CH ₂ —OC ( ＝ O) -C _12-14 alkyl and R ₂ , R ₃ , R ₄ are methyl, compounds of formula (i), dialkylimidazolines (compounds of formula (i)).

Other cationic surfactants useful in the present invention are described in Cambre US Pat. No. 4,228,044, issued Oct. 14, 1980, and European Patent Application EP 0,028,027.
No. 00,224.

Typical cationic fabric softening components include water-insoluble quaternary ammonium fabric softening activators or their corresponding amine precursors, with dilong chain alkyl ammonium chloride or methyl sulfate being the most commonly used. I have.

Among these preferred cationic softeners are: 1) ditallow dimethyl ammonium chloride (DTDMAC) 2) dihydrogenated tallow dimethyl ammonium chloride 3) dihydrogenated tallow dimethyl ammonium methyl sulfate 4) dihydrogenated tallow dimethyl ammonium methyl sulfate Stearyl dimethyl ammonium chloride 5) Dioleyl dimethyl ammonium chloride 6) Dipalmityl hydroxyethyl methyl ammonium chloride 7) Stearyl benzyl dimethyl ammonium chloride 8) Tallow trimethyl ammonium chloride 9) Hydrogenated tallow trimethyl ammonium chloride 10) _C12-14 alkyl hydroxy Ethyl dimethyl ammonium chloride 11) C _{12-18 alkyldihydroxyethyl} methyl ammonium chloride 12) Di (stearoyl) Oxyethyl) dimethylammonium chloride (DS
OEDMAC) 13) di (tallowoxyethyl) dimethylammonium chloride 14) ditallow imidazolinium methyl sulfate 15) 1- (2-tallowyl amidoethyl) -2-tallowyl imidazolinium methyl sulfate

[0074] Biodegradable quaternary ammonium compounds have been provided as an alternative to the traditionally used dilong chain alkyl ammonium chloride and methyl sulfate. Such a quaternary ammonium compound has a long-chain alkyl (alkenyl) group in which a functional group such as a carboxy group is interposed. The above substances and fabric softening compositions containing them are described in EP-A-0,040,562 and EP-A-0,
It has been disclosed in numerous documents such as 239,910.

The quaternary ammonium compound and its amine precursor are represented by the following formula (I) or (II)
)have:

Embedded image The formula Q is -O-C (O) -, - C (O) -O -, - O-C (O) -O-, -NR 4 -C (O) -, - C (O) - NR ⁴ - is selected from; ^{R 1} is _{(CH 2)} is n ^{-Q-T 2} or ^{T 3;} is ^{R 2} is _{(CH 2)} m ^{-Q-T 4} or ^{T 5} or ^{R 3,;} R ³ is C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl or H; R ⁴ is H, C ₁ -C ₄ alkyl or C ₁ -C ₄ hydroxyalkyl; T ¹ , T ² , T ³ , T ⁴ , T ⁵ are independently C ₁₁ -C ₂₂ alkyl or alkenyl; n and m are integers from 1 to 4; and X ⁻ is a softener compatible anion.

Non-limiting examples of softener compatible anions include chloride or methyl sulfate.

The alkyl or alkenyl chains T ¹ , T ² , T ³ , T ⁴ , T ⁵ are at least 11
And preferably at least 16 carbon atoms.
The chain may be straight or branched.

Tallow is a convenient and inexpensive source of long-chain alkyl and alkenyl materials. Compounds in which T ¹ , T ² , T ³ , T ⁴ , T ⁵ represent a mixture of long chain substances typical of tallow are particularly preferred.

Examples of quaternary ammonium compounds suitable for use in the present aqueous fabric softening composition include: 1) N, N-di (tallowyloxyethyl) -N, N-dimethylammonium chloride, 2) N N, N-di (tallowyloxyethyl) -N-methyl, N- (2-hydroxyethyl) ammonium methyl sulfate, 3) N, N-di (2-tallowyloxy-2-oxoethyl) -N, N- Dimethylammonium chloride, 4) N, N-di (2-tallowyloxyethylcarbonyloxyethyl) -N
, N-dimethylammonium chloride, 5) N- (2-tallowyloxy-2-ethyl) -N- (2-tallowyloxy-2-oxoethyl) -N, N-dimethylammonium chloride, 6) N, N , N-tri (tallowyloxyethyl) -N-methylammonium chloride, 7) N- (2-tallowyloxy-2-oxoethyl) -N- (tallowyl-
N, N-dimethylammonium chloride), 8) 1,2-ditaloyloxy-3-trimethylammoniopropane chloride and mixtures of the above substances.

When included in the present compositions, the granular bleach-containing laundry detergent compositions of the present invention typically comprise from 0.2 to about 25%, preferably from about 1 to about 8%, of such cations. Contains a surfactant.

[0081] Amphoteric surfactants are also suitable for use in the granular bleach-containing laundry detergent compositions of the present invention. These surfactants can be broadly described as aliphatic derivatives of secondary or tertiary amines, or aliphatic derivatives of heterocyclic secondary and tertiary amines,
Here, the aliphatic group may be linear or branched. One of the aliphatic substituents has at least about 8 carbon atoms, typically from about 8 to about 18 carbon atoms, and at least one has an anionic water-soluble group, such as carboxy, sulfonic acid, sulfuric acid. Group. Examples of amphoteric surfactants were issued on December 30, 1975
See Laughlin et al., U.S. Pat. No. 3,929,678, column 19, lines 18-35.

When included in the present compositions, the granular bleach-containing laundry detergent compositions of the present invention typically comprise from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such amphoteric. Contains a surfactant.

[0083] Zwitterionic surfactants are also suitable for use in laundry detergent compositions containing granular bleach. These surfactants can be broadly described as derivatives of secondary and tertiary amines, derivatives of heterocyclic secondary and tertiary amines, or derivatives of quaternary ammonium, quaternary phosphonium or tertiary sulfonium compounds. . See Laughlin et al., U.S. Pat. No. 3,929,678, issued Dec. 30, 1975, column 19, line 38 to column 22, line 48 for examples of zwitterionic surfactants.

When included in the present compositions, the granular bleach-containing laundry detergent compositions of the present invention typically comprise from 0.2 to about 15% by weight, preferably from about 1 to about 10% of such a bipolar electrode. Contains a surfactant.

The semi-polar nonionic surfactant comprises two alkyl moieties selected from the group consisting of one alkyl moiety of about 10 to about 18 carbon atoms, an alkyl group of about 1 to about 3 carbon atoms, and a hydroxyalkyl group. Water-soluble amine oxide having about 10 to about 1 carbon atoms
A water-soluble phosphine oxide having two alkyl moieties selected from the group consisting of one alkyl moiety of about 8 carbon atoms, an alkyl group of about 1 to about 3 carbon atoms, and a hydroxyalkyl group; one alkyl moiety of about 10 to about 18 carbon atoms. Particular categories of nonionic surfactants, including water-soluble sulfoxides having a moiety selected from the group consisting of alkyl and hydroxyalkyl moieties of about 1 to about 3 carbon atoms. Semi-polar nonionic detergent surfactants include amine oxide surfactants having the formula: ＯR ³ (OR ⁴ ) _x N (R ⁵ ) _{2 where} R ³ is from about 8 to about 22 alkyl having carbon atoms, hydroxyalkyl, alkyl phenyl group or mixtures thereof; R ⁴ is an alkylene, hydroxyalkylene group or mixtures thereof having from about 2 to about 3 carbon atoms;
x is 0 to about 3; each R ⁵ is an alkyl or hydroxyalkyl group having about 1 to about 3 carbon atoms, or a polyethylene oxide group having 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 include, in particular, C ₁₀ -C ₁₈ alkyldimethylamine oxides and C ₈ -C ₁₂ alkoxyethyldihydroxyethylamine oxides.

When included in the present compositions, the cleaning compositions of the present invention typically have a pH of 0.5.
It contains from 2 to about 15% by weight, preferably from about 1 to about 10%, of such semipolar nonionic surfactants.

The granular bleach-containing laundry detergent composition of the present invention may further comprise a cosurfactant selected from the group of primary or tertiary amines.

Primary amines suitable for use in the present invention include those of formula R₁NH₂Amine
Where R₁Is C₆-C₁₂, Preferably C₆-C_TenAlkyl chain, or R₄X (CH ₂ )_nAnd X is -O-, -C (O) NH- or -NH-, and R is₄Is C ₆ -C₁₂An alkyl chain, and n is 1 to 5, preferably 3. R₁Alkyl chain
May be linear or branched and may have an ethylene oxide of 12 or less, preferably less than 5.
A sid moiety may be interposed. Preferred amines according to the above formula are n-alkylamido
It is. Amines suitable for use in the present invention are 1-hexylamine, 1-octyl
Selected from amines, 1-decylamine and laurylamine. Other preferred
Primary amines include C₈-C_TenOxypropylamine, octyloxypropyla
Min, 2-ethylhexyloxypropylamine, laurylamidopropylami
And amidopropylamine.

[0090] Tertiary amines suitable for use in the present invention include tertiary amines having the formula R ₁ R ₂ R ₃ N, wherein R ₁ and R ₂ are a C ₁ -C ₈ alkyl chain or R ₅ | — (CH ₂ —CH—O) _x H, wherein R ₃ is a C ₆ -C ₁₂ , preferably C ₆ -C 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 -C ₁₂ and n is 1-5, preferably 2-3.
R ₅ is H or C ₁ -C ₂ alkyl, and x is 1-6. R ₃ and R ₄ may be linear or branched, and the R ₃ alkyl chain may have no more than 12, preferably no more than 5, ethylene oxide moieties.

A preferred tertiary amine is R₁Is C₆-C₁₂In the alkyl chain, R₂And R₃Is C ₁ -C₃Alkyl or R₅ ｜-(CH₂-CH-O)_xH (R in the above formula₅Is H or CH₃And x = 1 to 2).₁R₂ R₃N.

Also preferred are amidoamines of the formula: O ＯR ₁ -C-NH- (CH ₂ ) _n -N- (R ₂ ) _{2 where} R ₁ is C ₆ -C ₁₂ alkyl and n is 2 to 4, preferably n is 3, _{R 2} and _{R 3} is _C 1 -C _4.

The most preferred amines of the present invention include 1-octylamine, 1-hexylamine, 1-decylamine, 1-dodecylamine, C _8-10 oxypropylamine, N-
Coco-1,3-diaminopropane, coconut alkyldimethylamine, lauryldimethylamine, laurylbis (hydroxyethyl) amine, cocobis (hydroxyethyl) amine, 2 mol propoxylated laurylamine, 2 mol propoxylated octylamine, laurylamide dimethylamine, there is C _8-10 dimethylamine and C ₁₀ amidopropyl dimethylamine.

The most preferred amines for use in the present compositions are 1-hexylamine, 1-octylamine, 1-decylamine, 1-dodecylamine. Particularly desirable is n
-Dodecyl dimethylamine, bishydroxyethyl coconut alkylamine, 7
Ethoxylated oleylamine, laurylamidopropylamine and cocoamidopropylamine.

Conventional Detergent Enzymes In addition to the specific cellulases described above, the granular bleach-containing laundry detergent compositions may further comprise one or more enzymes that exert cleaning performance, fabric care and / or sanitary benefits. .

The above enzymes include other cellulases, hemicellulases, peroxidases, proteases, glucoamylases, amylases, xylanases, lipases, phospholipases, esterases, cutinases, pectinases, keratanases, reductases, oxidases, phenol oxidases, lipoxygenases, ligninases,
Pullulanase, tannase, pentosanase, malanase, β-glucanase,
There is an enzyme selected from arabinosidase, hyaluronidase, chondroitinase, laccase or a mixture thereof.

A preferred combination is a granular bleach-containing laundry detergent composition having a cocktail of conventional enzymes such as proteases, amylases, lipases, cutinases and / or other cellulases combined with one or more plant cell wall degrading enzymes. is there. The laundry detergent composition of the present invention is preferably derived from Humicola insolens, DSM1800
It also contains a 43 kD endoglucanase.

[0098] Other cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they have an optimum pH of 5-12 and 50 CEVU (Cellulose
Viscosity Unit). Suitable cellulases are described in US Pat. No. 4,435,307 to Barbesgoard et al., J61078384 and WO 96/0.
2653, wherein Humicola insolens, Trichoderma, Thie
A fungal cellulase produced from lavia and Sporotrichum, respectively, is disclosed. EP 739982 describes a cellulase isolated from a novel Bacillus species. Suitable cellulases are GB-A-2,075,028, GB-A-2,0
95,275, DE-OS-2,247,832 and WO 95/26398.

Examples of such cellulases include strains of Humicola insolens (Humicola grisea va
r. thermoidea), especially cellulase produced by Humicola strain DSM1800. Other suitable cellulases are those derived from Humicola insolens, having a molecular weight of about 50 KDa, an isoelectric point of 5.5, and containing 415 amino acids; derived from Humicola insolens, DSM 1800, which exhibits cellulase activity. ~ 43kD
Endoglucanase, a preferred endoglucanase component, has the amino acid sequence disclosed in PCT patent application WO 91/17243. 1994 September
Trichode as described in Genencor WO 94/21801 published on May 29.
EGIII cellulases from rma longibrachiatum are also suitable cellulases. Particularly suitable cellulases are those having a color care effect. Examples of such cellulases are described in European Patent Application No. 9120, filed Nov. 6, 1991.
No. 2879.2 (Novo). Carezyme and
Celluzyme (Novo Nordisk A / S) is particularly useful. See also WO 91/17244 and WO 91/21801. Other cellulases suitable for fabric care and / or cleaning properties are WO 96/34092, WO 96/17994 and WO
95/24471.

The other cellulases described above are usually incorporated into detergent compositions at a pure enzyme level of 0.0001 to 2% by weight of the detergent composition.

The peroxidase enzyme is a source of oxygen such as percarbonate, perborate,
Used in combination with phenolic substrates as persulfate, hydrogen peroxide, and the like, and as a bleach-enhancing molecule. They are used for "solution bleaching", i.e. to prevent dyes or pigments that have fallen off the substrate during the washing operation from migrating to other substrates in the washing liquor. Peroxidase enzymes are known in the art and include, for example, horseradish peroxidase, ligninase, haloperoxidases such as chloro and bromoperoxidase. Peroxidase-containing detergent compositions are described, for example, in PCT International Application WO 89/099813, and January 1991.
European patent applications EP 91202882.6 and 1996 filed on Jan. 6
It is disclosed in EP 968700133.8 filed on Feb. 20, 2008. Laccase enzymes are also suitable.

[0102] Enhancers are usually included at levels of 0.1 to 5% by weight of the total composition. Preferred enhancers are the substituted phenothiazines and phenoxazines 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (WO94 / 12621), and substituted syringates (
C3-C5 substituted alkyl siline gates) and phenols. Sodium percarbonate or perborate is the preferred source of hydrogen peroxide. The peroxidase is usually incorporated into detergent compositions at a pure enzyme level of 0.0001 to 2% by weight of the detergent composition.

[0103] Another preferred enzyme that may be included in the detergent compositions of the present invention is lipase.
Lipase enzymes suitable for detergents include those produced by microorganisms of the genus Pseudomonas, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034. Suitable lipases include the microorganism Pseudomonas fluorescent IAM1057, which shows a positive immune cross-reactivity with lipase antibodies.
Some are produced by This lipase is commercially available from Amano Pharmaceutical Co. Ltd. in Nagoya, Japan under the trade name Lipase P "Amano".
-P ". Other suitable commercially available lipases include Amano-CES, Chromobacter vis
cosum, e.g., Chromobacter viscosum var.lipo from Toyo Brewing Company in Tagakata, Japan
lipase from lyticum NRRLB 3673; Chromobacter viscosum lipase from USBiochemical Corp., USA and Disoynth Co., The Netherlands; Pseudomonas gl
There is a lipase from adioli. Particularly suitable lipases are M1 Lipase ^R and Lip
a lipase such as omax ^{R (Gist-Brocades)} and Lipolase ^R and Lipolase Ultra ^{R (Novo),} it was found that they are very effective when used in conjunction with the compositions of the present invention. Novo Nordisk EP258068, WO92 / 05249 and WO95 / 22615, Unilever WO94 / 03578, WO95 / 35
The lipolytic enzymes described in 381 and WO 96/00292 are also suitable.

Also suitable are a special kind of lipase, a cutinase [EC 3.1.1.50], which is considered a lipase that does not require surface activity. Addition of cutinase to the detergent composition,
For example, WO-A-88 / 09367 (Genencor), WO90 / 09446 (Plan
t Genetic System), WO94 / 14963 and WO94 / 14964 (Unil
ever).

The lipase and / or cutinase is present in an amount of 0.0001 to 2% by weight of the detergent composition.
At a pure enzyme level, typically in detergent compositions.

Suitable proteases are subtilisins (subtilisins BPN and BPN ') obtained from certain strains of B. subtilis and B. licheniformis. One suitable protease is obtained from the Bacillus strain and has a maximum activity in the pH range from 8 to 12,
Developed by Novo Industries A / S in Denmark and sold as ESPERASE ^R , hereinafter referred to as "Novo". Novo's GB
1, 243, 784. Other suitable proteases include Novo AL
CALASE ^R, DURAZYM ^R and SAVINASE ^R, as well as the Gist-Brocades MAXATASE ^R,
MAXACAL ^R, there is PROPERASE ^R and Maxapem ^R (protein engineered Maxacal). Proteolytic enzymes include modified bacterial serine proteases such as 1987
European Patent Application No. 87 / 303761.8 filed on April 28, 2008
(Especially pages 17, 24 and 98), and on October 29, 1986, for what is hereinafter referred to as "Protease B" and for the modified bacterial serine protease which is hereinafter referred to as "Protease A". One is described in published Venegas European Patent Application 199,404. Bacill where lysine was substituted for arginine at position 27, tyrosine was substituted for valine at position 104, serine was substituted for asparagine at position 123, and alanine was substituted for threonine at position 274.
A variant of the alkaline serine protease from us, hereinafter referred to as "protease C", is suitable. Protease C is described in EP 90915958: 4, corresponding to WO 91/06637 published May 16, 1991. In particular, genetically modified variants of protease C are also included in the present invention.

A preferred protease, designated “Protease D”, is a carbonyl hydrolase variant having an amino acid sequence not found in nature, which is described in WO 95/10591.
And USSN 08/3, filed October 13, 1994, by C. Ghosh et al.
According to the numbering of Bacillus amyloliquefaciens subtilisin as described in the patent application entitled "Bleaching Compositions Containing Protease Enzymes" at 22,677, preferably +99, +101, +103, +104, +107, +123.
, +27, +105, +109, +126, +128, +135, +156, +
166, +195, +197, +204, +206, +210, +216, +2
+7 in combination with one or more amino acid residue positions corresponding to those selected from the group consisting of 17, +218, +222, +260, +265 and / or +274.
At the position corresponding to position 6, it is derived from a precursor carbonyl hydrolase by using different amino acids instead of a plurality of amino acid residues in the carbonyl hydrolase.

[0108] Protease described in patent application EP251446 and WO91 / 06637, WO91 / 02792, protease BLAP ^R described, and WO
Those variants described in 95/23221 are also suitable for the present invention.

See also the high pH protease from Bacillus sp. NCIMB 40338 described in Novo WO 93 / 18140A. Enzyme detergents containing proteases, one or more other enzymes and a reversible protease inhibitor are available from Novo WO 92 / 03529A.
It is described in. If desired, proteases with reduced adsorptivity and improved hydrolyzability are available as described in Procter & Gamble, WO 95/07791. Recombinant trypsin-like proteases for detergents suitable for the present invention are described in Novo WO 94/25583. Other suitable proteases are described in Unilever, EP 516200.

The proteolytic enzyme is present in an amount of 0.0001 to 2% by weight of the composition, preferably 0.0
Pure enzyme levels of from 0.01 to 0.2%, more preferably 0.005 to 0.1%, are incorporated into the detergent compositions of the present invention.

Amylases (α and / or β) can be included for removal of carbohydrate-based soils. WO 94/02597 of Novo Nordisk A / S published February 3, 1994 describes a cleaning composition containing a mutant amylase. Novo Nordisk A / S W published on April 20, 1995
See also O95 / 10603. Other amylases known for cleaning compositions include both α- and β-amylases. α-amylases are known in the art and are described in US 5,003,257, EP 252,666, WO 91/00353.
, FR2,676,456, EP285,123, EP525,610, EP3
68,341 and British Patent Specification No. 1,296,839 (Novo). Other suitable amylases are WO94 / 18314 published August 18, 1994, and Genencor WO9 published February 22, 1996.
A stabilizing amylase described in 6/05295, and an amylase variant with additional modifications to the immediate parent of Novo Nordisk A / S, disclosed in WO 95/10603 published April 95. Amylases described in EP 277216, WO 95/26397 and WO 96/23873 (all Novo Nordisk) are also suitable.

Examples of commercially available α-amylase products include Genera's Purafect Ox Am^R, All Novo N
Termamyl commercially available from ordisk A / S Denmark^R, Ban^R, Fungamyl^Rand
 Duramyl^RIt is. WO 95/26397 describes other suitable amylases: Phadebas ^R As determined by the α-amylase activity assay, a temperature range of 25-55 ° C. and 8
At pH values in the range of -10, Termamyl^RHas a specific activity at least 25% higher than that of
An α-amylase characterized by the following is described. WO96 / 2
3873 (Novo Nordisk) are suitable. Active level
Have improved properties in terms of thermal stability and a combination of high activity levels
Other amylolytic enzymes are described in WO 95/35382. The amylolytic enzyme is present in an amount of 0.0001 to 2% by weight of the composition, preferably 0.001%.
018-0.06%, more preferably 0.00024-0.048% pure enzyme
At a level, it is incorporated into the detergent composition of the present invention.

The enzymes may be of any suitable origin, such as of plant, animal, bacterial, fungal and yeast origin. The origin may also be mesophilic or extremophilic (cryophilic, eutrophic, thermophilic, barophilic, alkaline, acidophilic, halophilic, etc.). Purified or unpurified forms of these enzymes may also be used. At present, it is customary to modify wild-type enzymes by protein / genetic engineering techniques to maximize performance efficacy with the cleaning compositions of the present invention. For example, variants are designed to increase the compatibility of the enzyme with the common components of such compositions. On the other hand, the optimal pH of the enzyme variant,
Variants may be designed such that bleed or chelant stability, catalytic activity, etc., are tailored to a particular cleaning application.

In particular, attention should be paid to amino acids that are susceptible to oxidation in terms of bleach stability and surface charge in terms of surfactant compatibility. The isoelectric point of such enzymes may be modified by substitution of some charged amino acids, for example, increasing the isoelectric point helps to improve compatibility with anionic surfactants. Enzyme stability can be further enhanced, for example, by forming additional salt bridges and reinforcing calcium binding sites to increase the stability of the chelants. Special attention should be paid to cellulases, as most cellulases have a separate binding domain (CBD). The properties of such enzymes can be altered by modifying these domains.

The enzymes are usually incorporated into detergent compositions at a pure enzyme level of 0.0001 to 2% by weight of the detergent composition. Enzymes may be separate components (eg, globules, granules, stabilizing liquids, etc. containing one enzyme) or as a mixture of two or more enzymes (eg,
(Co-granules).

Another suitable detergent ingredient that can be added is an enzymatic oxidation scavenger, which comprises 1
Co-pending European Patent Application No. 92870018, filed Jan. 31, 992.
No. 6 is described in the specification. An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

The various enzyme substances and their means of incorporation into synthetic detergent compositions are also described in Genencor I.
WO 9307263A and WO 9307260A from nternational, WO from Novo
89086694A, and US 3,553, McCarty et al.
139. The enzyme was purchased from Place et al., US Pat.
U.S. Pat. No. 4,507,219 to Hughes, 101,457 and March 26, 1985.
However, it is further disclosed. Enzymatic substances useful in liquid detergent formulations and their incorporation into such formulations are described in US Pat. No. 4,261, April 14, 1981 to Hora et al.
868. Enzymes useful in detergents can be stabilized by various techniques. Enzyme stabilization technology is described in US Pat.
319, October 29, 1986, EP 199,405 and EP of Venegas.
200,586. Enzyme stabilization systems, for example, US3
519,570. A useful Bacillus sp. AC13 that provides proteases, xylanases and cellulases is described in Novo WO9401532A.

Color Care and Fabric Care Effects Technologies that exert a type of color care effect can also be included. Examples of these technologies are metal catalysts for color maintenance. Such metal catalysts are described in co-pending European Patent Application No. 92870181.2. Dye fixing agent, polyolefin dispersant for preventing wrinkles and improving water absorption, fragrance,
Amino-functional polymers for color care treatment and perfume retention are another example of color care / fabric care technology and are described in co-pending patent application No. 96870140.9, filed November 7, 1996. Have been.

[0119] Fabric softeners can also be incorporated into the bleach-containing laundry detergent compositions according to the present invention. These agents may be inorganic or organic in type. The inorganic softener is GB-A-1,4
00,898 and U.S. Pat. No. 5,019,292. Organic fabric softeners include GB-A1,514,276 and E
Water-insoluble tertiary amines as disclosed in P-B 0,011,340, EP-B-
Mono-C ₁₂ -C ₁₄ quaternary ammonium salts disclosed in U.S. Pat. Nos. 0,026,527 and EP-B-0,026,528 and combinations thereof, and EP-B-0,242,
There are dilong chain amides as disclosed in 919. Other useful organic components of the fabric softening system include high molecular weight polyethylene oxide materials such as those disclosed in EP-A-0,299,575 and 0,313,146.

The level of smectite clay is usually 2 to 20% by weight, more preferably 5 to 15%.
%, The substance being added as a dry mix component to the rest of the formulation. Organic fabric softeners, such as water-insoluble tertiary amines or di-long chain amide materials, may be used in aqueous solutions.
5 to 5% by weight, usually 1 to 3% by weight, high molecular weight polyethylene oxide substance and water-soluble cationic substance 0.1 to 2% by weight, usually 0.15 to 1%
. Added at the 5% level. These substances are usually added to the spray-dried portion of the composition, but in some cases, they may be added as dry mix particles or sprayed as a molten liquid onto other solid components of the composition. Is convenient.

Builder System The composition according to the present invention may further comprise a builder system. Aluminosilicate materials, silicates, polycarboxylates, alkyl or alkenyl succinic acids, and fatty acids, materials such as ethylenediaminetetraacetic acid, diethylenetriaminepentamethyleneacetic acid, sequestering agents such as aminopolyphosphonates,
Any conventional builder system is suitable for use in the present invention, including especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid. Phosphate builders may also be used in the present invention. Suitable builders include inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, and more particularly hydrated synthetic zeolites such as hydrated zeolites A, X, B, HS or MAP. Other suitable inorganic builder materials are laminated silicates, such as SKS-6 (Hoechs
t). SKS-6 is a crystal laminated silicate made of sodium silicate (Na ₂ Si ₂ O ₅ ).

Suitable polycarboxylates having one carboxy group include lactic acid, glycolic acid and There are those ether derivatives. 2
Polycarboxylates having two carboxy groups include succinic acid, malonic acid, (
Water-soluble salts of ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, and German Patent Publication No. 2,446,686;
No. 2,446,687 and U.S. Pat. No. 3,935,257, and sulfinyl carboxylate described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates, as well as carboxymethyloxysuccinates described in GB 1,379,241, Netherlands application 72050873. And oxypolycarboxy such as 2-oxa-1,1,3-propanetricarboxylate described in GB 1,387,447. There are rate substances.

The polycarboxylates having four carboxy groups are described in GB 1,26
Oxydisuccinate, 1,1,2,2-ethanetetracarboxylate, 1,1,3,3-propanetetracarboxylate and 1,1,2,3-propane disclosed in 1,829 There are tetracarboxylates. Polycarboxylates having sulfo substituents include those described in GB 1,398,421,
398,422 and U.S. Pat. No. 3,936,448, and the sulfonated pyrolytic citrate described in GB 1,082,179; Polycarboxylates having substituents are disclosed in GB 1,439,000.

Cycloaliphatic and heterocyclic polycarboxylates include cyclopentane-cis,
Cis, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-dicarboxylate, 2,
2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4
There are 5,6-hexane-hexacarboxylate and carboxymethyl derivatives of polyhydric alcohols such as sorbitol, mannitol and xylitol. Aromatic polycarboxylates include melitic acid, pyromellitic acid, and the phthalic acid derivatives disclosed in GB 1,425,343. Among the above preferred polycarboxylates are hydroxycarboxylates having up to 3 carboxy groups per molecule, more particularly citrates.

[0125] Preferred builder systems for use in the present compositions include a water-insoluble aluminosilicate builder or laminated silicate (SKS-6) such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. There is a mixture.

Another preferred builder system is a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid. Preferred builder systems for use in the liquid detergent compositions of the present invention are soaps and polycarboxylates.

Other builder substances that can form part of the builder system on use in the granular composition include inorganic substances such as carbonates, bicarbonates, alkali metal silicates, and organic phosphonates.
There are organic substances such as aminopolyalkylene phosphonates and aminopolycarboxylates.

Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acid has at least two carboxyl groups separated from each other by no more than 2 carbon atoms. I have. This type of polymer is GB-A-1,596
, 756. Examples of such salts are polyacrylates with a MW of 2000 to 5000 and copolymers thereof with maleic anhydride, such copolymers having a molecular weight of 20,000 to 70,000, in particular of about 40,000. The washing builder salt is usually contained in an amount of 5 to 80%, preferably 10 to 70%, most usually 30 to 60% by weight of the composition.

Chelating Agents The granular bleach-containing laundry detergent compositions of the present invention may also optionally include one or more iron and / or manganese chelating agents. Such chelators can be selected from the group consisting of aminocarboxylates, aminophosphonates, polyfunctionally substituted aromatic chelators and mixtures thereof, all as described below. Without being bound by theory, it is believed that the effects of these materials are due in part to their exceptional ability to remove iron and manganese ions from the wash liquor by the formation of soluble chelates.

Aminocarboxylates useful as optional chelating agents include ethylenediaminetetraacetic acid, N-hydroxyethylethylenediaminetriacetic acid, nitrilotriacetic acid,
There are ethylene diamine tetrapropionic acid, triethylene tetraamine hexaacetic acid, diethylene triamine pentaacetic acid and ethanol diglycine, their alkali metal, ammonium and substituted ammonium salts, and mixtures thereof.

Aminophosphonates are also suitable for use as chelating agents in the compositions of the present invention when at least low levels of total phosphorus are acceptable in the detergent composition, and include ethylenediaminetetrakis (methylenephosphonate) such as DEQUEST. including. Preferably,
These aminophosphonates do not contain alkyl or alkenyl groups of about 7 or more carbon atoms.

[0132] Polyfunctionally substituted aromatic chelators are also useful in the present compositions. May 2, 1974
See U.S. Pat. No. 3,812,044 issued to Connor et al. A preferred compound of this type is a dihydroxydisulfobenzene, such as 1,2-dihydroxy-3,5-disulfobenzene, in the acid form.

A preferred biodegradable chelator for use in the present invention is Har
Ethylenediaminedisuccinic acid ("EDDS"), particularly the [S, S] isomer, as described in US Pat. No. 4,704,233 to tman and Perkins. The composition may also contain a water-soluble methylglycine diacetate (MGDA) salt (or acid form) as a cobuilder useful as an insoluble builder, such as zeolites, laminated silicates, and the like, or as a chelant. If utilized, these chelating agents will usually be from about 0.1 to about 15% by weight of the detergent composition. More preferably, if utilized, the chelating agent will be from about 0.1 to about 3.0% by weight of such a composition.

Foam Inhibitors Another optional ingredient is a foam inhibitor, exemplified by silicones and silica-silicone mixtures. Silicones are typically represented by alkylated polysiloxane materials, and silica is commonly used in finely divided form, exemplified by silica airgel, xerogels and various types of hydrophobic silica. These materials can be formulated as particles, and the suds suppressor is advantageously formulated to be released in a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. . Alternatively, the foam control agent may be applied by dissolving or dispersing in a liquid carrier and spraying on one or more other components.

Preferred silicone suds suppressors are described in US Pat. No. 3,933,6, Bartollota et al.
No. 72. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor, which is disclosed in German Patent Application DT published April 28, 1977.
OS 2,646,126. Examples of such compounds are
DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Particularly preferred suds suppressors are silicone oils and 2-
A foam suppressant system consisting of a mixture of alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyloctanol, sold under the trade name Isofol 12R.

Such a suds suppressor system is described in co-pending European Patent Application N 92870174.7, filed November 10, 1992. Particularly preferred silicone suds suppressors are co-pending European Patent Application No. N # 9220.
1649.8. The compositions may comprise silicone / silica mixture in combination with a molten nonporous silica such as Aerosil ^R. The above-mentioned suds suppressor is present in an amount of 0.001 to 2% by weight, preferably 0.02% by weight of the composition.
Usually used at a level of 1 to 1% by weight.

Others Other ingredients used in granular bleach-containing laundry detergent compositions, such as soil suspending agents,
Soil release agents, optical brighteners, abrasives, disinfectants, haze inhibitors, colorants and / or encapsulated or unencapsulated fragrances may also be used. A particularly suitable 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 suitable water-soluble encapsulating materials include, but are not limited to, those described in US Pat.
It consists of a dextrin derived from a non-gelatinized starch ester of a substituted dicarboxylic acid. These acid ester dextrins are preferably made from starches such as waxy maize, waxy sorghum, sago, tapioca and potato. A suitable example of the encapsulating material is N-Lok from National Starch.
The N-Lok encapsulant consists of modified maize starch and glucose. Starch is modified by adding a monofunctional substituent such as octenyl succinic anhydride. Antiredeposition and soil suspending agents suitable for the present invention include cellulose derivatives such as methylcellulose, carboxymethylcellulose and hydroxyethylcellulose, and homo- or copolymer polycarboxylic acids or salts thereof. Polymers of this type include polyacrylates and maleic anhydride-acrylic acid copolymers already described as builders, and copolymers of maleic anhydride with ethylene, methyl vinyl ether or methacrylic acid, where maleic anhydride is at least one of the copolymers. Accounts for 20 mol%. These materials are generally used at levels of 0.5 to 10%, more preferably 0.75 to 8%, most preferably 1 to 6% by weight of the composition.

Preferred optical brighteners are anionic in nature, examples of which are 4,4′-bis (2
-Diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate disodium, 4,4'-bis (2-morpholino-4-anilino-s-triazin-6-ylamino ) Stilbene-2,2'-
Disodium disulfonate, disodium 4,4'-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate,
', 4 "-bis (2,4-dianilino-s-triazin-6-ylamino) stilbene-2-sulfonic acid monosodium salt, 4,4'-bis [2-anilino-4- (
N-methyl-N-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonate disodium, 4,4'-bis (4
-Phenyl-2,1,3-triazol-2-yl) stilbene-2,2'-disulfonate, 4,4'-bis [2-anilino-4- (1-methyl-
2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-2,2'-disulfonate disodium salt, 2-stilbyl-4 "-(naphtho-1
', 2', 4,5) -1,2,3-Triazole-2 "-sodium sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Highly preferred brighteners are Certain brighteners from pending European Patent Application No. 95201943.8.

Other useful polymeric substances are polyethylene glycols, especially molecular weights between 1000 and 1
0000, more specifically 2000-8000, most preferably about 4000. These are used at a level of from 0.20 to 5% by weight, more preferably from 0.25 to 2.5%. These polymers, and the previously described homo or copolymer polycarboxylate salts, provide whiteness maintenance, fabric ash adhesion (fabric ash).
deposition) and in the presence of transition metal impurities to improve cleaning performance on soil, proteins and oxidative soils.

Soil release agents useful in the compositions of the present invention are conventionally copolymers or terpolymers of terephthalic acid and ethylene glycol and / or propylene glycol units in various configurations. Examples of such polymers are disclosed in commonly assigned U.S. Patent Nos. 4,116,885 and 4,711,730 and European Patent Application 0,272,033. EP-A-0,272,03
A particularly preferred polymer according to 3 has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 [(T-PO) _2.8 (T-PEG) _0.4 ] T (POH) _0.25 ((PEG) ₄₃ CH ₃ ) _{0.75 wherein} PEG is — (OC ₂ H ₄ ) O—, PO is (OC ₃ H ₆ O), and T is (pcOC ₆ H ₄ CO).

Modified polyesters are also very useful as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol, with the end groups being mainly sulfobenzoate, and secondarily ethylene glycol and / or Or it consists of a monoester of propanediol. The purpose is to obtain a polymer capped at both ends by sulfobenzoate groups, in the present context most of the copolymers being "mainly" end-capped with sulfobenzoate groups. However, some copolymers are not completely capped, so their end groups may consist of monoesters of ethylene glycol and / or propane-1,2-diol,
"Secondary" consists of such species.

The polyester selected in the present invention comprises about 46% by weight dimethyl terephthalic acid, about 16% by weight propane-1,2-diol, about 10% by weight ethylene glycol, about 13% by weight dimethyl sulfobenzoic acid And about 15% by weight of sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their methods of manufacture are described in detail in EPA 311,342.

It is well known in the art that free chlorine in tap water rapidly inactivates enzymes contained in detergent compositions. Thus, when a chlorine scavenger such as perborate, ammonium sulfate, sodium sulfite or polyethyleneimine is used in a formulation at a level of 0.1% or more by weight of the total composition, an improved through-the-wash of detergent enzymes ( throuth the wash) Demonstrate stability. Compositions containing chlorine scavengers are described in European Patent Application No. 9 filed January 31, 1992.
No. 2,780,18.6.

[0145] Alkoxylated polycarboxylates, such as those made from polyacrylates, are useful in the present invention to provide additional fat removal performance. Such materials are described in WO 91/08281 and PCT, which are incorporated herein by reference.
90/01815, pages 4 et seq. Chemically, these substances are 7
Consists of a polyacrylate having one ethoxy side chain for every ~ 8 acrylate units. Side chain of the formula _- consists _{(CH 2 CH 2 O) m} (CH 2) n CH 3, wherein m is 2 to 3, n is 6-12. The side chains are esterified to the polyacrylate “backbone” to form a “comb” polymer type structure. Molecular weights vary, but typically range from about 2000 to about 50,000. Such alkoxylated polycarboxylates represent from about 0.05 to about 10% by weight of the composition.

Dispersants The granular bleach-containing laundry detergent compositions of the present invention can also contain dispersants:
Suitable water-soluble organic salts are homo- or copolymeric acids, or salts thereof, wherein the polycarboxylic acid has at least two carboxyl groups separated from each other by no more than two carbon atoms. This type of polymer is disclosed in GB-A-1,596,756. Examples of such salts are polyacrylates of MW 2000-5000, and their copolymers with maleic anhydride, such copolymers having a molecular weight of 1000-100,000. In particular, copolymers of acrylates and methyl acrylates such as 480N having a molecular weight of 4000 can be added to the granular bleach-containing laundry detergent compositions of the present invention at a level of 0.5-20% by weight of the composition.

The compositions of the present invention may contain a lime soap peptizer compound, which has a lime soap dispersing power (LSDP) of 8 or less, preferably 7 or less, and most preferably 6 or less. Is preferred. The lime soap peptizer compound is preferably present at a level of 0-20% by weight.

A numerical measure of the effectiveness of the lime soap peptizer is the lime soap dispersive power (LSD).
P), HCBorghetty and CA Bergman, J. Am. Oil. Chem. Soc., Volum
e 27, pages 88-90 (1950) Measured using a lime soap dispersion test as described in the article. This lime soap dispersion test method is widely used by those skilled in the art,
For example, the following review literature: WNLinfield, Surfactant Science Series, Volume 7,
p.3; WNLinfield, Tenside Surf.det., volume 27, pages 159-161 (1990);
K. Nagarajan, WFMasler, Cosmetics and Toiletries, volume 104, pages 71-73 (
1989). LSDP is 333 ppm CaCo ₃ (Ca: M
g = 3: 2) Percent by weight of dispersant to sodium oleate required to disperse the lime soap precipitate formed by 0.025 g of sodium oleate in 30 ml of water of equivalent hardness. Surfactants that have good lime soap peptizer capabilities include certain amine oxides, betaines, sulfobetaines, alkyl ethoxy sulfates and ethoxylated alcohols.

Exemplary surfactants having an LSDP of 8 or less for use according to the invention include C ₁₆ -C₁₈Dimethylamine oxide, C having an average ethoxylation degree of 1 to 5₁₂-C₁₈Al
Kill ethoxy sulphate, especially C with ethoxylation degree 3₁₂-C_FifteenAlkyl ethoxy
Cisulfate surfactant (LSDP = 4), and trade name from BASF GmbH
Average ethoxylation sold in Lutensol A012 and Lutensol A030 respectively
Degree 12 (LSDP = 6) or 30 C₁₄-C_FifteenThere is ethoxylated alcohol
. Polymer lime soap peptizers suitable for use in the present invention include Cosmetics an
d. Toiletries, volume 104, pages 71-73 (1989), M.K.Nagarajan, W.F.
It is described in a paper by Masler.

4- (N-octanoyl-6-aminohexanoyl) benzenesulfonate,
4- (N-nonanoyl-6-aminohexanoyl) benzenesulfonate, 4-
Hydrophobic bleach, such as (N-decanoyl-6-aminohexanoyl) benzenesulfonate and mixtures thereof; Nonanoyloxybenzenesulfonate combined with hydrophilic / hydrophobic bleach formulation is also used as lime soap peptizer compound it can.

Discoloration Inhibition The granular bleach-containing laundry detergent compositions of the present invention are used to inhibit the transfer of dye from one fabric with dissolved and suspended dye to another encountered during a fabric washing operation with a colored fabric. Can also be contained.

Polymer Discoloration Inhibitor The granular bleach-containing laundry detergent composition according to the present invention comprises 0.001 to 10% by weight,
Preferably it also contains 0.01 to 2%, more preferably 0.05 to 1% of a polymeric transfer dye inhibitor. The polymeric transfer dye inhibitor is commonly incorporated into granular bleach-containing laundry detergent compositions to prevent dye transfer from the colored fabric onto the washed fabric. These polymers have the ability to complex with or adsorb free dye washed off from the colored fabric before the dye has a chance to adhere to other objects in the wash liquor.

Particularly suitable polymeric dye transfer inhibitors are polyamine N-oxide polymers, copolymers of N-vinylpyrrolidone and N-vinylimidazole, polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole, or mixtures thereof. The addition of such a polymer also enhances the performance of the enzyme according to the invention.

A) Polyamine N-Oxide Polymers Polyamine N-oxide polymers suitable for use comprise units having the following structural formula:

Embedded image In the above formula, P is a polymerizable unit, to which an R—N—O group can be bound, or the R—N—O group forms part of the polymerizable unit, or a combination of both A is NC (= O), C (= O) O, C = O, -O-, -S-, -N-;
x is 0 or 1; R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, alicyclic group or a combination thereof, to which the nitrogen of the NO group can be attached, or The nitrogen of the NO group is part of these groups. The NO group can be represented by the following general structure:

Embedded image Wherein R1, R2 and R3 are an aliphatic group, an aromatic, a heterocyclic, an alicyclic group or a combination thereof, wherein x or / and y or / and z is 0 or 1, where N The nitrogen of the -O group is attached, or the nitrogen of the NO group forms part of these groups.

The NO group may be part of the polymerizable unit (P), attached to the polymer backbone, or a combination of both. Suitable polyamine N-oxides in which the NO group forms part of the polymerizable unit include those polyamine N-oxides in which R is selected from aliphatic, aromatic, cycloaliphatic or heterocyclic groups. is there.

One class of polyamine N-oxides consists of a group of polyamine N-oxides in which the nitrogen of the NO group forms part of the R group. Preferred polyamine N
An oxide is where R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof.

Another class of polyamine N-oxides consists of a group of polyamine N-oxides in which the nitrogen of the NO group is attached to the R group. Other suitable polyamine N-oxides are polyamine oxides in which the NO groups are attached to polymerizable units.

A preferred class of these polyamine N-oxides is the general formula (R) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the above R group. It is a polyamine N-oxide having I). Examples of these classes are polyamine oxides, where R is a heterocyclic compound such as pyridine, pyrrole, imidazole and derivatives thereof. Another preferred class of polyamine N-oxides is the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO function is attached to the R group. ).

Examples of these classes are polyamine oxides, wherein the R groups are aromatic, such as phenyl. Any polymer backbone may be used as long as the amine oxide polymer formed is water-soluble and has dye transfer inhibiting properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate and mixtures thereof.

The amine N-oxide polymers of the present invention typically comprise 10: 1 to 1: 1000
It has a ratio of amine to amine N-oxide of 000. However, the amount of amine oxide groups present in the polyamine oxide polymer can be varied by suitable copolymerization or by moderate N-oxidation. Preferably, the ratio of amine to amine N-oxide is from 2: 3 to 1: 1,000,000, more preferably from 1: 4 to 1: 1,000,000, and most preferably from 1: 7 to 1: 100,000.
0. The polymers of the present invention actually include random or block copolymers in which one monomer type is an amine N-oxide and the other monomer type is or is not an amine N-oxide. The amine oxide units of the polyamine N-oxide have a pKa <10, preferably a pKa <7, more preferably a pKa <6.

[0161] Polyamine oxides can be obtained with almost any degree of polymerization. The degree of polymerization is not critical as long as the material has the desired water solubility and dye suspending power. Typically, the average molecular weight is between 500 and 1,000,000, preferably 1000
~ 50,000, more preferably 2000 to 30,000, most preferably 30
It is in the range of 00 to 20,000.

B) Copolymer of N-vinylpyrrolidone and N-vinylimidazole The N-vinylimidazole N-vinylpyrrolidone polymer used in the present invention has an average molecular weight of 5000 to 1,000,000, preferably 5000 to 200,000. Having a range.

Highly preferred polymers for use in the detergent compositions according to the invention are those selected from N-vinylimidazole N-vinylpyrrolidone copolymers, the polymers being from 5000 to 50,000, more preferably from 8000 to 30 000
And most preferably has an average molecular weight range of 10,000 to 20,000.

The average molecular weight range is described in Barth HGand Mays JW, Chemical Analysis, Vol. 113, "M
odern Methods of Polymer Characterization ". Highly preferred N-vinylimidazole N-vinylpyrrolidone copolymers are 5,000-50,000, more preferably 8,000-30,000, most preferably It has an average molecular weight range of 10,000 to 20,000 N-vinylimidazole N-vinylpyrrolidone copolymer, characterized by having the above average molecular weight range, is formulated with it while exhibiting excellent dye transfer inhibition properties. Does not adversely affect the cleaning performance of the detergent composition.

The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention comprises:
0.2, more preferably 0.8: 0.3, most preferably 0.6: 0.4 N-
It has a molar ratio of vinylimidazole to N-vinylpyrrolidone.

C) Polyvinylpyrrolidone In the detergent compositions of the present invention, from about 2500 to about 400,000, preferably about 50
Polyvinylpyrrolidone ("PVP") having an average molecular weight of from about 00 to about 200,000, more preferably from about 5000 to about 50,000, and most preferably from about 5000 to about 15,000 may also be utilized. Suitable polyvinylpyrrolidone is available under the product name PV
PK-15 (viscosity molecular weight of 10,000), PVP K-30 (40,000
Average molecular weight), PVP K-60 (average molecular weight of 160,000) and PV
As PK-90 (average molecular weight of 360,000), ISP Corporation, New
Commercially available from York, NY and Montreal, Canada. Other suitable polyvinylpyrrolidones commercially available from the BASF Cooperation include Sokalan HP165 and Sokalan HP12; polyvinylpyrrolidone known to the detergent industry (eg, E
Nos. PA-262,897 and EP-A-256,696).

D) Polyvinyloxazolidone In the detergent composition of the present invention, polyvinyloxazolidone may also be used as a polymer transfer inhibitor. The above polyvinyl oxazolidone is used in an amount of about 2500 to about 400.
000, preferably from about 5000 to about 200,000, more preferably about 500
It has an average molecular weight of from about 0 to about 50,000, most preferably from about 5000 to about 15,000.

E) Polyvinylimidazole In the detergent composition of the present invention, polyvinylimidazole may also be used as a polymer dye transfer inhibitor. The above polyvinyl imidazole is used in an amount of about 2500 to about 400,0.
00, preferably about 5000 to about 200,000, more preferably about 5000 to about 200,000.
It has an average molecular weight of about 50,000, most preferably from about 5000 to about 15,000.

F) Crosslinked Polymers Crosslinked polymers are polymers in which the backbone is linked to some extent, these links may be of chemical or physical nature, with the possibility that the active groups may be on the backbone or It may be on the side chain, and the crosslinked polymer can be found in Journal of Polymer Science, volum
e 22, pages 1035-1039. In one embodiment, the cross-linked polymer is made to form a three-dimensional rigid structure, allowing the pores formed by the three-dimensional structure to trap the dye. In another aspect, the crosslinked polymer captures the dye by swelling. Such crosslinked polymers are described in co-pending patent application 94870213.9.

Cleaning Methods The compositions of the present invention may be used in essentially any cleaning or cleaning method, including dipping, pre-treatment, and methods involving a rinsing step in which another rinse aid composition may be added. Is also good.

[0171] The process described herein involves contacting a fabric with a wash liquor in a conventional manner, and is exemplified below.

The process of the present invention is conveniently performed during the cleaning process. The cleaning method is preferably performed at 5 to 95 ° C, particularly 10 to 60 ° C. The following examples are meant to illustrate the compositions of the present invention and do not necessarily limit or limit the scope of the present invention.

In detergent compositions, enzyme levels are expressed as pure enzyme by weight of the total composition.
And detergent components are given by weight of the total composition unless otherwise stated.
The abbreviated component designations have the following meanings: LAS: sodium linear C_11-13Alkylbenzene sulfonate, TAS: sodium tallow alkyl sulfate, CxyAS: sodium C_1X-C_1YAlkyl sulfate, CxySAS: sodium C_1X-C_1YSecondary (2,3) alkyl sulfate,
 CxyEz: C condensed with an average z mole of ethylene oxide_1X-C_1YMainly directly
CxyEzS: C condensed with an average of z moles of ethylene oxide_1X-C_1YNatori
Um alkyl sulfate, QAS: R₂N⁺(CH₃)₂(C₂H₄OH) (R₂= C₁₂-C₁₄), QAS1: R₂N⁺(CH₃)₂(C₂H₄OH) (R₂= C₈-C₁₁), APA: C_8-10Amidopropyldimethylamine, soap: sodium derived from an 80/20 mixture of tallow and coconut fatty acids
Linear alkyl carboxylate, STS: sodium toluene sulfonate, CFAA: C₁₂-C₁₄Alkyl N-methylglucamide, TFAA: C₁₆-C₁₈Alkyl N-methylglucamide, silicate: amorphous sodium silicate (SiO₂: Na₂O ratio = 1.6-3.
2) Zeolite A: Formula Na having a primary particle size in the range of 0.1 to 10 μm₁₂(AlO₂S
iO₂)₁₂・ 27H₂O hydrated sodium aluminosilicate (on anhydrous basis)
Weight)), NaSKS-6: Formula δ-Na₂Si₂O₅Buffer citrate, citrate, carbonate to pH 7.5-10, and
And / or bicarbonate combinations. Citrate: has a particle size distribution of 425 to 850 μm
86.4% trisodium citrate dihydrate / citric acid: citric anhydride
/ Carbonate: anhydrous citric acid / bicarbonate: anhydrous carbonic acid having a particle size distribution of 400 to 1200 μm
Sodium hydrogen, borate: sodium borate, sulfate: anhydrous sodium sulfate, magnesium sulfate: anhydrous magnesium sulfate, STPP: sodium tripolyphosphate, TSPP: tetrasodium pyrophosphate, MA / AA: 4: 1 acrylate / maleate random copolymer average molecule
Amount of about 70,000 to 80,000, MA / AA 1: 6: 4 acrylate / maleate random copolymer average content
AA: sodium polyacrylate polymer having an average molecular weight of 4500, PB1: empirical formula NaBO₂・ H₂O₂Of anhydrous sodium perborate monohydrate, PB4: empirical formula NaBO₂・ 3H₂OH₂O₂Sodium perborate tetrahydrate
Material, percarbonate: empirical formula 2Na₂CO₃・ 3H₂O₂Anhydrous sodium percarbonate
TAED: Tetraacetylethylenediamine, NOBS: Nonanoyloxybenzenesulfonate in sodium salt form, NACA-OBS: (6-Nonamidocaproyl) oxybenzenesulfonate
DTPA: diethylenetriaminepentaacetic acid, HEDP: 1,1-hydroxyethanediphosphonic acid, DETPMP: diethyl ester sold by Monsanto under the trade name Dequest 2060
Riaminpenta (methylene) phosphonate, EDDS: ethylenediamine-N, N'-disuccinic acid in its sodium salt form (
S, S) Isomer, Photoactivated Bleach: Sulfonated Bleach Encapsulated in Dextrin Soluble Polymer
Lead phthalocyanine, photoactivated bleach 1: sulfonation encapsulated in dextrin soluble polymer
Aluminophthalocyanine, Protease: from Novo Nordisk A / S under the trade names Savinase, Alcalase, Durazym
Proteolytic enzyme sold; Maxaca sold by Gist-Brocades
l, Maxapem; and patents WO 91/06637 and / or WO 95/10
Amylase: Purafact Ox Am from Genencor under the trade name of 591 and / or EP 251446.^RWO94 for sale in
/ 18314, amylolytic enzymes described in WO 96/05295;
votermamyl commercially available from Nordisk A / S^R, Fungamyl^RAnd Duramyl^R;
And WO95 / 26397, lipase: sold by Novo Nordisk A / S under the trade names Lipolase, Lipolase Ultra
Lipolytic enzymes, and Lipomax by Gist-Brocades, Cellulase: Cellulose degradation sold by Novo Nordisk A / S as Endolase
Enzymes, other cellulases: cells sold by Novo Nordisk A / S under the trade name Carezyme
Loose-degrading enzyme, CMC: sodium carboxymethylcellulose, PVP: polyvinyl polymer with an average molecular weight of 60,000, PVNO: polyvinylpyridine-N-oxide with an average molecular weight of 50,000, PPVVI: vinylimidazole and vinylpyro with an average molecular weight of 20,000
Ridone copolymer, Brightener 1: disodium 4,4'-bis (2-sulfostyryl) biphenyl,
 Brightener 2: 4,4'-bis (4-anilino-6-morpholino-1,3,5-to
Liazin-2-yl) stilbene-2,2'-disulfonate disodium silico
Defoamer: a foam control agent to dispersant ratio of 10: 1 to 100: 1 with a dispersant
Polydimethylsilyl containing siloxane-oxyalkylene copolymer
Xan foam regulator, foam inhibitor: granular, 12% silicone / silica, 18% stearyl alcohol
, 70% starch, SRP1: anionic end-capped polyester, QEA: bis [(C₂H₅O) (C₂H₄O)_n] (CH₃) -N⁺-C₆H ₁₂ -N⁺-(CH₃) Screw [(C₂H₅O) (C₂H₄O)]_n(N = 20-3
0), PEI: average molecular weight of 1800 and average ethylene oxide residue of 7 ethyleneoxy residues per nitrogen.
Polyethyleneimine having a degree of toxylation, HMWPEO: high molecular weight polyethylene oxide, PEGx: polyethylene glycol with molecular weight x, PEO: polyethylene oxide with an average molecular weight of 5,000.

Example 1 The following high-density laundry detergent composition was prepared according to the present invention: I II III IV V LAS 8.0 8.0 8.0 6.0 6.0 TAS -0.5-1.0 0.1 C46 (S) AS 2.0 2.5---C25AS-- -4.5 5.5 C68AS 2.0 5.0 7.0--C25E5--3.4 4.6 4.6 C25E7 3.4 3.4 1.0--C25E3S---5.0 4.5 QAS-0.8---QAS1---0.5 1.0 Zeolite A 18.1 18.0 14.1 20.0 18.1 NaSKS-6- ---10.0 Silicate 1.4 1.4 3.0 0.5 0.3 Buffer 19.1 20.1 30.0 10.0 15.5 Sulfate 20.0 20.0 21.1--Mg sulfate 0.3---0.2 MA / AA 0.3 0.3 0.3 1.0 1.0 CMC 0.2 0.2 0.2 0.4 0.4 PB4 9.0 9.0 5.0-- Percarbonate---15.0 15.0 TAED 1.5 0.4 1.5 3.9 4.2 NACA-OBS-2.0 1.0--DETPMP 0.25 0.25 0.25--SRP1----0.2 EDDS-0.25 0.4 0.5 0.5 CFAA-1.0---HEDP 0.3 0.3 0.3 0.4 0.4 QE A----0.5 Cellulase 0.005 0.008 0.01 0.003 0.0005 Protease 0.009 0.009 0.01 0.05 0.03 Amylase 0.002 0.002 0.002 0.008 0.008 Other cellulases 0.0007--0.0007 0.0007 Lipase 0.006--0.01 0.01 Light activated bleach (ppm) 15 15 15 20 20 PVNO / PVPVI-----Brightener 1 0.09 0.09 0.09 0.09 0.09 Perfume 0.3 0.3 0.3 0.4 0.4 Silicone defoamer 0.5 0.5 0.5 0.3 0.3 Density g / L 850 850 850 850 850 Others up to 100%

Example 2 The following granular laundry detergent compositions particularly useful under European-style machine wash conditions were prepared in accordance with the present invention: I II III IV LAS 5.5 7.5 6.0 7.0 TAS 1.25 1.9 0.4 0.3 C24AS / C25AS-2.2 5.0 2.2 C25E3S-0.8 3.0 1.0 C45E7 3.25--3.0 TFAA----C25E5-5.5--QAS 0.8---QAS1-0.7 1.0 0.7 STPP 19.7---Zeolite A-19.5 20.0 17.0 NaSKS-6 / citric acid (79: 21)-10.6--NaSKS-6--5.0 5.0 Silicate 6.8-0.5-Buffer 15.9 23.4 15.0 25.0 Sulfate 30.0--12.0 Mg sulfate--0.2-MA / AA 0.5 1.6 1.0 1.0 CMC 0.2 0.4 0.4 0.4 PB4 5.0 12.7 --Percarbonate--18.0 15.0 TAED 0.5 3.1 5.0-NACA-OBS 1.0 3.5-2.5 DETPMP 0.25 0.2-0.2 HEDP-0.3 0.3 0.3 QEA--1.0-Cellulase 0.0008 0.005 0.006 0.003 Protease 0 .009 0.03 0.05 0.02 Lipase 0.003 0.003 0.006 0.004 Other cellulase 0.0006 0.0006 0.0007 0.0007 Amylase 0.002 0.002 0.01 0.003 PVNO / PVPVI----PVP 0.9 1.3-0.9 SRP1--0.2-Light activated bleach (ppm) 15 27 20 20 Photoactivated bleach (1) (ppm) 15---Brightener 1 0.08 0.2 0.09 0.15 Brightener 2-0.04--Fragrance 0.3 0.5 0.4 0.3 Silicone defoamer 0.5 2.4 0.3 2.0 Density g / L 750 750 750 750 Others up to 100%

Example 3 The following detergent compositions which are particularly useful under European machine wash conditions were prepared in accordance with the present invention: I II III IV Blown Powder: LAS 6.0 5.0 11.0 0 TAS 2.0--2.0 Zeolite A 24.0--20.0 STPP-27.0 24.0-Sulfate 4.0 6.0 13.0-MA / AA 1.0 4.0 6 2.0 2.0 silicate 1.0 7.0 3.0 3.0 CMC 1.0 1.0 0.5 0.6 Brightener 1 0.2 0.2 0.2 0.2 Silicone defoaming 1.0 1.0 1.0 0.3 DETPMP 0.4 0.4 0.2 0.4 Spray-on: Brightener 0.02 --- 0.02 C45E7 --- 5.0 C45E2 2.5 2.5 2.0-C45E3 2.6 2.5 2.0-Fragrance 0.5 0.3 0.5 0.2 Silicone defoamer 0.3 0.3 0.3-Dry additive: QEA---1.0 EDDS 0.3---Sulfate 2.0 3.0 5.0 10.0 Buffer 13.5 13.0 15.0 16.0 QAS1 0.5--0.5 NaSKS-6 5.0----Percarbonate 18.5---PB4-18.0 10.0 21. 5 TAED 2.0 2.0-2.0 NACA-OBS 3.0 2.0 4.0-Cellulase 0.005 0.001 0.006 0.0004 Protease 0.03 0.03 0.03 0.03 Lipase 0.008 0.008 0.008 0.004 Amylase 0.003 0.003 0.003 0.006 Brightener 1 0.05 ---0.05 Others up to 100%

Example 4 The following granular detergent composition was prepared in accordance with the present invention: III III IV VVI Blown powder: LAS 23.0 8.0 7.0 9.0 7.0 7.0 TAS----1.0-C45AS 6.0 6.0 5.0 8.0--C45AES- 1.0 1.0 1.0--C45E35----2.0 4.0 Zeolite A 10.0 18.0 14.0 12.0 10.0 10.0 MA / AA-0.5---2.0 MA / AA1 7.0------AA-3.0 3.0 2.0 3.0 3.0 Sulfate 5.0 6.3 14.3 11.0 15.0 19.3 Silicate 10.0 1.0 1.0 1.0 1.0 1.0 Buffer 15.0 20.0 10.0 20.7 8.0 6.0 PEG 4000 0.4 1.5 1.5 1.0 1.0 1.0 DTPA-0.9 0.5--0.5 Brightener 2 0.3 0.2 0.3-0.1 0.3 Spray-on: C45E7-2.0--2.0 2.0 C25E9 3.0------C23E9--1.5 2.0-2.0 Fragrance 0.3 0.3 0.3 2.0 0.3 0.3 Aggregate: C45AS-5.0 5.0 2.0-5.0 LAS-2.0 2.0--2.0 Light A-7.5 7.5 8.0-7.5 Buffer-4.0 4.0 5.0-4.0 PEG4000-0.5 0.5--0.5 Other (water, etc.)-2.0 2.0 2.0-2.0 Dry additives: QAS----1.0-Citric acid---- -2.0-PB4----12.0 1.0 PB1 4.0 1.0 3.0 2.0--Percarbonate-----2.0 10.0 Buffer-5.3 1.8-4.0 4.0 NOBS 4.0-6.0--0.6 Methylcellulose 0.2------NaSKS-6 8.0------STS--2.0-1.0-Cumenesulfonic acid-1.0---2.0 Cellulase 0.005 0.01 0.0004 0.0005 0.005 0.005 Protease 0.02 0.02 0.02 0.01 0.02 0.02 Lipase 0.004-0.004-0.004 0.008 Amylase 0.003-0.002-0.003- Other cellulases 0.0005 0.0005 0.0005 0.0007 0.0005 0.0005 PVPVI-----0.5 0.1 PVP-----0.5-PVNO--0.5 0.3--QEA- ----1.0-SRP1 0.2 0.5 0.3-0.2-Silicone defoamer 0.2 0.4 0.2 0.4 0.1-Mg sulfate--0.2-0.2-Others up to 100%

Example 5 The following detergent composition was prepared according to the present invention: III III IV Base granules: Zeolite A 30.0 22.0 24.0 10.0 Sulfate 10.0 5.0 10.0 7.0 MA / AA 3.0---AA-1.6 2.0-MA / AA1 -12.0-6.0 LAS 14.0 10.0 9.0 20.0 C45AS 8.0 7.0 9.0 7.0 C45AES-1.0 1.0-Silicate-1.0 0.5 10.0 Soap-2.0--Brightener 1 0.2 0.2 0.2 0.2 Buffer 6.0 9.0 10.0 10.0 PEG4000-1.0 1.5-DTPA- 0.4--Spray-on: C25E9---5.0 C45E7 1.0 1.0--C23E9-1.0 2.5-Fragrance 0.2 0.3 0.3-Dry additives: Buffer 5.0 10.0 18.0 8.0 PVPVI / PVNO 0.5-0.3-Cellulase 0.0005 0.006 0.0008 0.002 Protease 0.03 0.03 0.03 0.02 Lipase 0.008--0.008 Amylase 0.002--0.002 Other cellulases 0.0002 0.0005 0.0005 0.0002 NOBS -4.0-4.5 PB1 1.0 5.0 1.5 6.0 Sulfate 4.0 5.0-5.0 SRP1-0.4--Foaming inhibitor-0.5 0.5-Others up to 100%

Example 7 The following granular detergent composition was prepared in accordance with the present invention: I II III Blown powder: Zeolite A 20.0-15.0 STPP-20.0 Sulfate 5.0 Buffer -5 1.0 TAS--1.0 LAS 6.0 6.0 6.0 C68AS 2.0 2.0-Silicate 3.0 8.0-MA / AA 4.0 2.0 2.0 CMC 0.6 0.6 0.2 Brightener 1 0.2 0.2 0.1 DETPMP 0.4 0.4 0.1 STS --- 1.0 Spray-on: C45E7 5.0 5.0 4.0 Silicone Foaming agent 0.3 0.3 0.1 Fragrance 0.2 0.2 0.3 Dry additive: QEA--1.0 Buffer 14.0 9.0 10.0 PB1 1.5 2.0- PB4 18.5 13.0 13.0 TAED 2.0 2.0 2.0 QAS--1.0 Light-activated bleach 15 ppm 15 ppm 15 ppm NaSKS-6--3.0 Cellulase 0.005 0.0006 0.003 Protease 0.03 0.03 0.007 Lipase 0.004 0.004 0.004 Amylase 0.006 0.006 0.003 Other cellulases 0.0002 0.0002 0.0005 Sulfate 10.0 20.0 5.0 Density (g / L) 700 700 700 700 Others up to 100%

Example 6 The following detergent composition was prepared in accordance with the present invention: I II III Blown powder: Zeolite A 15.0 15.0 15.0 Sulfate-5.0-LAS 3.0 3.0 QAS-1.5 1.5 DETPMP 0.4 0.2 0.4 EDDS-0.4 0.2 CMC 0.4 0.4 0.4 MA / AA 4.0 2.0 2.0 Aggregate : LAS 5.0 5.0 5.0 TAS 2.0 2.0 1.0 silicate 3.0 3.0 4.0 Zeolite A 8.0 8.0 8.0 Buffer 8.0 4.0 Spray-on: Fragrance 0.3 0.3 0.3 C45E7 2.0 2.0 2.0 C25E3 2.0 --- Dry additive: Buffer 13.0 18.0 12.0 TAED 6. 0 2.0 5.0 PB1 14.0 7.0 10.0 PEO -0.2 Bentonite clay--10.0 Cellulase 0.005 0.01 0.005 Protease 0.03 0.03 0.03 Lipase 0.008 0.008 0.008 Other cellulase 0.001 0.001 0.001 Amylase 0.01 0.01 0.01 Silicone defoamer 5.0 5.0 5.0 Sulfate -3. 0-Density (g / L) 850 850 850 Others Up to 100%

Example 8 The following detergent composition was prepared according to the present invention: I II III IV LAS 18.0 14.0 24.0 20.0 QAS 0.7 1.0-0.7 TFAA-1.0 --C23E56.5--1.0-C45E7-1.0--C45E3S 1.0 2.5 1.0-STPP 32.0 18.0 30.0 22.0 Silicate 9.0 5.09 0.0 8.0 Buffer 11.0 15.0 10.0 5.0 PB1 3.0 1.0--PB4-1.0--NOBS 2.0 1.0--DETPMP-1.0- -DTPA 0.5-0.2 0.3 SRP1 0.3 0.2-0.1 MA / AA 1.0 1.5 2.0 0.5 CMC 0.8 0.4 0.4 0.0. 2 PEI--0.4-Sulfate 20.0 10.0 20.0 30.0 Mg sulfate 0.2-0.4 0.9 Cellulase 0.0005 0.008 0.008 0.005 Protease 0.03 0.03 0.02 0.02 Amylase 0.008 0.007-0.004 Lipase 0.004-0.002-Other cellulase 0.0003--0.0001 Light activated bleach 30 ppm 20 ppm 20 ppm 10 ppm Fragrance 0.3 0.3 0.1 0.2 Brightener 1/2 0.05 0.02 0.08 0.1 Others Up to 100%

Example 9 The following granular fabric detergent composition exhibiting "softening by washing" capability was prepared in accordance with the present invention: II C45AS-10.0 LAS 7.6-C68AS 1.3-C45E7 4.0. -C25E3-5.0 cocoalkyldimethylmethyl-hydroxyethylammonium chloride 1.4 1.0 Buffer 17.0 19.0 NaSKS-6-5.0 Zeolite A 15.0 15.0 MA / AA 4.0 0 DETPMP 0.4 0.4 PB1 15.0-Percarbonate-15.0 TAED 5.0 5.0 Smectite clay 8.0 10.0 HMWPEO-0.1 Cellulase 0.005 0.01 Protease 0.02 0.01 lipase 0.02 0.01 amylase 0.03 0.005 other cellulase 0.0 1 - silicate 3.0 5.0 foam control agent 1.0 to 4.0 CMC 0.2 0.1 Others 100%

──────────────────────────────────────────────────続 き Continuation of front page (81) Designated country EP (AT, BE, CH, DE, DK, ES, FI, FR, GB, GR, IE, IT, LU, MC, NL, PT, SE), OA (BF, BJ, CF, CG, CI, CM, GA, GN, ML, MR, NE, SN, TD, TG), AP (GH, KE, LS, MW, SD, SZ, UG, ZW) , EA (AM, AZ, BY, KG, KZ, MD, RU, TJ, TM), AL, AM, AT, AU, AZ, BA, BB, BG, BR, BY, CA, CH, CN, CU, CZ, DE, DK, EE, ES, FI, GB, GE, GH, HU, IL, IS, JP, KE, KG, KP, KR, KZ, LC, LK, LR, LS , LT, LU, LV, MD, MG, MK, MN, MW, MX, NO, NZ, PL, PT, RO, RU, SD, SE, SG, SI, SK, SL, TJ, TM, TR, TT, UA, UG, US, UZ, VN, YU, ZW (71) Applicant ONE PROCTER & GANBLE PLAZA, CINCINNATI, OHIO, UNITED STATES OF AMERICA (72) Inventors Christian, Arthur, Jack, Kamier United States Ohio, West, Chester, Rap, Farm, Drive, 8485

Claims (14)

[Claims] 1. A granular bleach-containing laundry detergent composition comprising a fungal cellulase having a 1% solution pH of 7.5 to 10, an optimal pH of 4 to 10 and no cellulose binding domain. . 2. The method according to claim 1, wherein the cellulase is Humicola insolens, Trichoderma longibrachiatum, Trichode.
The granular bleach-containing laundry detergent composition according to claim 1, which is derived from rma reseei and / or Trichoderma viride. 3. Cellulase having the following properties: (a) derived from Humicola insolens DSM1800; (b) an estimated molecular weight of about 50 kDa; (c) an isoelectric point of about 5.5; and (d) possession of 415 amino acids. The granular bleach-containing laundry detergent composition according to claim 1 or 2, further characterized. 4. The cellulase has the following properties: (a) derived from Trichoderma sp. (B) estimated molecular weight of 22-27 kDa (c) isoelectric point of 7.2-8.0, and (d) 5.5-6 The granular bleach-containing laundry detergent composition according to claim 1 or 2, further characterized by exhibiting an optimum pH of 0.0. 5. Cellulase comprising 0.0001 to 0.1% by weight of the total composition, preferably 0.000 to 0.1%.
5. The granular bleach-containing laundry detergent composition according to any one of claims 1 to 4, wherein the composition is present at a pure enzyme level of 5 to 0.05%, more preferably 0.001 to 0.01%. 6. The laundry detergent composition according to claim 1, wherein the pH is obtained by means of a buffer system. 7. The buffer system comprises an acid selected from citric acid, succinic acid, oxalic acid, muconic acid, aspartic acid, luronic acid, glutaric acid, malic acid, diglycolic acid, malonic acid and / or maleic acid. 7. The granular bleached laundry detergent composition of claim 6, comprising the composition. 8. The alkaline earth, wherein the buffer system comprises a mixture of a monomeric or oligomeric polycarboxylate agent with a parent acid or a salt thereof, a carbonate builder such as sodium carbonate, bicarbonate and sesquicarbonate and mixtures thereof. 7. The granular bleach-containing laundry detergent composition according to claim 6, wherein the detergent composition is selected from the group consisting of alkali metals and carbonates of alkali metals. 9. The granulated bleach-containing composition according to claim 8, wherein the monomeric or oligomeric polycarboxylate agent is selected from citric acid, citrate and mixtures thereof, and the carbonate builder is selected from carbonate, bicarbonate and mixtures thereof. Laundry detergent composition. 10. The method according to claim 6, wherein the buffer system is present at a level of from 1 to 40% by weight of the total composition, preferably from 1.5 to 35%, more preferably from 2 to 30%. A laundry detergent composition containing the granular bleach according to claim 1. 11. The granular bleach-containing laundry detergent composition according to claim 1, further comprising a conventional detergent enzyme selected from other cellulases, proteases, amylases and / or lipases. object. 12. The granular bleach-containing laundry detergent composition according to claim 11, wherein the other cellulase is a ４３43 kD endoglucanase derived from Humicola insolens, DSM1800. 13. The laundry detergent composition according to claim 1, which is in the form of an additive. 14. An optimum pH of 4 to 10 in a granular bleach-containing laundry detergent having a 1% solution pH of 7.5 to 10 to achieve excellent cleaning and whiteness performance effects.
Use of a fungal cellulase having no cellulose binding domain.