JP3169615B2 - Cellulase activity control by terminator - Google Patents

Description

Description: FIELD OF THE INVENTION The present invention is directed to a cellulase-stopping composition to prevent the loss of tensile strength that may be associated with the hydrolytic activity of cellulase on cellulosic substrates while maintaining the desired effects of using cellulase. Composition comprising a product and a cellulase.

BACKGROUND OF THE INVENTION Cellulase activity is the activity by which cellulosic fibers or substrates are attacked by cellulase, depending on the specific function of the cellulase, including endo- or exocellulase and each hemicellulase. Cellulose structures are depolymerized or cleaved into smaller, and thus better soluble or dispersible, fractures. This activity imparts cleaning, renewal, softening and usually improved feel characteristics to the structure, especially in fabrics.
This is due to fission of fibrils from the surface of the fiber, such that the main chain of the fiber is smooth, less likely to become a jacket, less likely to be entangled with other fibers, and less likely to be optically weakened in its light reflection and radiation. It was once thought to be.

Naturally, improvements have been made in the activity of particular cellulase compositions such that less use or shorter exposure times are required for similar effects. In the entire agent field, cellulases that work in a typical detergent wash environment are utilized with activity when desired cellulase performance is reached before the end of the wash cycle. However, cellulase continues to react even after exerting the desired performance, and the cleavage of cellulose will continue. Thus, there is a potential risk of tensile strength loss. However, the tensile strength loss of the fabric is also an unavoidable consequence of the mechanical action of use / wear, especially if the fabric is contaminated with metal compounds, which can further be attributed to damage by bleaching components in the washing process. It should be noted that

An obvious solution to the above problem is to use an appropriate amount of cellulase so that the time of the wash cycle is consistent with the time required for the desired cellulase performance, but no significant loss of tensile strength still occurs. It is. However, this may vary depending on local customs, washing machine equipment, soiling of clothing and garments to be washed, additional additives incorporated into the detergent for other unrelated reasons, and cellulase degradation during storage. It proved difficult due to the washing cycle. Therefore, a better method of preventing fabric damage while exerting the cellulase effect is desirable.

According to the present invention, this ensures that the desired cellulase activity is reached before the end of the wash cycle, while in such an amount that the cellulase terminator can provide a means for preventing the loss of tensile strength that may occur in that time. It can be carried out by including it.

Cellulases showing exceptionally high activity are described in WO 92-13057.
And EP-A-495554, and EP-A-495258 and EP-A-177165 in the context of softening clays in detergent compositions. Cellulases with exceptionally high activity are described in WO 91/172.
43 discloses itself. The recognition of possible tensile strength losses in cellulases has been reported in several publications. For example, Japanese Application J-62-310754 discloses a specific cellulase having a specific so-called non-degradation index. Japanese application J-63-134830 discloses a detergent composition for clothing containing a cellulase having a non-degrading index, and US 4,978,470 discloses a detergent composition for clothing containing a cellulase enzyme with a "non-degrading index" of less than 500 Is disclosed.

Attempts to fine-tune cellulase activity to eliminate the problems underlying the present invention as described above have been undertaken in the field of industrial cleaning where defined conditions, especially the length of fabric exposure to cellulase, can be assumed. It has many appeals. Due to the variety of individual situations encountered for typical household conditions, highly active cellulases combined with terminators ensure desirable cellulase activity, thereby preventing possible tensile strength losses in fabrics. That is a practically good approach.

SUMMARY OF THE INVENTION The present invention relates to the use of laundry detergent compositions in home textile processing machines and hand washing processes. The laundry detergent composition comprises
Surfactant system, preferably at least 10 CEVU /
A cellulase enzyme having liquid cellulase activity and a standardized cellulase activity standard test, such as a CMC viscosity reduction test and / or a cotton linter test.
comprising a cellulase terminator composition that meets the criteria for up to 10% residual activity in t). The cellulase terminator composition is contained in the laundry detergent composition in such an amount that the activity of the cellulase enzyme can be controlled. The terminator composition used is a bleach terminator that contains peroxidase with the bleaching system, thereby preventing possible tensile strength losses in the fabric. The terminator composition is preferably in a time delayed release laundry detergent composition.

DETAILED DESCRIPTION OF THE INVENTION Percentages used below are by weight unless otherwise indicated.

The activity of cellulase enzymes, especially the activity of cellulase enzymes, has been demonstrated in various applications by different assays. All of these methods attempt to provide a realistic assessment of expected in-service performance or a measure that is at least correlated with in-service performance.

Even if there are a variety of different test methods for cellulase activity, a commonly accepted requirement for cellulase is the lowest viscosity reducing activity in the CMC solution. Therefore, this method of measuring CMC endoase activity (in units of 1 CEVU) is used in the present invention for preferred cellulases, as explained below.

Particularly useful cellulase products in the compositions of the present invention are those that exhibit a CMC endoase activity of at least about 10, preferably at least about 20 CEVU /. In particular, preferred cellulases exhibit a CMC endoase activity of at least 25 CEVU /.

In the present context, the term "CMC endoase activity" refers to cellulose as measured by the viscosity reduction of a solution of carboxymethylcellulose (CMC) after incubation with the cellulase product of the invention, as described in detail below. The endoglucanase activity of the endoglucanase component with respect to its ability to degrade Glucose into glucose, cellobiose and triose.

CMC endoase (endoglucanase) activity is determined from the viscosity decrease of CMC as follows: 0.1 at pH 9.0
A substrate solution containing 35 g / CMC (Hercules7LFD) in M Tris buffer is prepared. The enzyme sample to be analyzed is dissolved in the same buffer. Substrate solution 10ml and enzyme solution 0.5m
l was mixed and kept at 40 ° C with a viscometer (eg, Haa
ke VT181, NV sensor, 181rpm). Viscometer readings are taken as soon as possible after mixing and again after 30 minutes. Under these conditions, the amount of enzyme that reduces the viscosity by half is 1 unit of CMC endoase activity, ie 1 CEVU /
Is defined as

Another suitable method for measuring cellulase activity is
Cotton lint method (see Example II).

Cellulases that can be used in the present invention include both bacterial and fungal cellulases. Preferably, they are 5-9.5
It has an optimum pH. Suitable cellulases are disclosed in US Pat. No. 4,435,307 to Barbesgoard et al., Which discloses a fungal cellulase produced from Humicola insolens. A suitable cellulase is GB-A
−2.075.028, GB-A−2.095.275 and DE-OS−2.247.
832 also discloses.

Examples of cellulase components that can be used in the present invention include Humicola
A cellobiohydrolase component that is immunoreactive with an antibody against highly purified ~ 70 kD cellobiohydrolase (EC 3.2.1.91) derived from insolens DSM1800, or a homologue or derivative of ~ 70 kD cellobiohydrolase that exhibits cellulase activity, or Humicola Highly purified from insolens DSM1800 ~ 50 immunoreactive with antibodies to 50 kD endoglucanase or showing cellulase activity ~ 50
An endoglucanase component that is a homolog or derivative of kD endoglucanase; preferred endoglucanase components have the amino acid sequence disclosed in PCT patent application WO 91/17244, or Fusarium oxysporum
Highly purified ~ 50 kD derived from DSM2672 (apparent molecular weight, amino acid composition equivalent to 45 kD with 2n glycosylation sites) Immunoreacts with an antibody to endoglucanase or exhibits ~ 50 kD endoglucanase homologue or derivative exhibiting cellulase activity Preferably, the endoglucanase component is PCT.
European Patent Application EP-A2-271,00 having the amino acid sequence disclosed in patent application WO 91/17244 or published
4. Any of the cellulases disclosed in 4 above, wherein the cellulase is a alkalophilic cellulase having a non-degrading index (NDI) of 500 or more and an optimum pH of 7 or more, or carboxymethylcellulose (CMC) When used as a substrate, the relative activity at a pH of 8 or more is more than 50% of the activity under optimal conditions, or the highly purified ~ 43k from Humicola insolens DSM1800
Immunoreacts with antibodies to D endoglucanase,
Or an endoglucanase component that is a homolog or derivative of a ~ 43 kD endoglucanase that exhibits cellulase activity; preferred endoglucanase components have the amino acid sequence disclosed in PCT Patent Application WO 91/17243 or are derived from Bacillus lautus NCIMB 40250. A highly purified ~ 60 kD endoglucanase is an endoglucanase component which is a homologue or derivative of a ~ 60 kD endoglucanase that immunoreacts with an antibody to 60 kD endoglucanase or which exhibits cellulase activity; preferred endoglucanase components are disclosed in PCT Patent Application WO 91/10732. The amino acid sequence.

Particularly suitable cellulases are those having a color care effect. An example of such a cellulase was found in 1991
A cellulase as described in European Patent Application No. 91202879.2 (Novo) filed on Nov. 6.

According to the present invention, preferred cellulases are as described in Danish patent application 1159/90 or PCT patent application WO 91/17243, and Novos No. in Bagsvaerd, Denmark.
Also known as Carezyme ^™ from rdisk A / S. The cellulase products described in these references and Carezyme ^™ consistent with this description are available from Humicola i
It immunoreacts with antibodies to highly purified 43 kD cellulase from nsolens DSM1800 or consists essentially of a homogeneous endoglucanase component that is homologous to its 45 kD endoglucanase. An alternative screening method for cellulases suitable for use in the laundry detergent compositions according to the present invention is EP-A-495258, or more particularly EP-A-495258.
-A-350098.

However, in the case of industrial production of cellulase products, it is preferable to use recombinant DNA technology or other techniques that adjust the fermentation or displacement of the microorganism as necessary to ensure overproduction of the desired enzyme activity. Such methods and techniques are known in the art and are readily performed by those skilled in the art.

Cellulase Terminator Composition The cellulase terminator composition comprises a peroxidase, an enhancer and a hydrogen peroxide source and is used in combination to irreversibly terminate cellulase activity after a certain time. The cellulase terminator composition is referred to below as CTC.

The function of CTC is that cellulase activity is greater than 90% within 5 minutes of the start of the wash cycle, cellulase activity is less than 50% within 5-10 minutes of the start of the wash cycle, and less than 10% residual cellulase. Activity requires a wash cycle
The goal is to control the activity of cellulase to reach after 15 minutes. The characteristic of CTC in the absence of a controlled release agent is that it reduces cellulase activity to 10% of initial cellulase activity in a standardized cotton litter test within 15 minutes of a wash cycle.
%, Preferably 3%.

A preferred approach to characterize CTC is to incorporate one or more compounds of CTC into the release agent. The release agent is an agent that releases the compounded CTC compound into the cleaning environment in a controlled manner.

For example, peroxidase is formulated in a release agent such that the activity level of the peroxidase within 5 minutes of a wash cycle is less than 10%. Activity levels of greater than 50% of the peroxidase are reached within the first 5-10 minutes from the start of the washing cycle.

Alternatively, the enhancer and / or the hydrogen peroxide source may be independently incorporated into the release agent according to the present invention.
In this case, the enhancer and / or the hydrogen peroxide source are preferably independently formulated in a release agent. More preferably, the peroxidase and the enhancer are formulated together in a release agent according to the invention, and the hydrogen peroxide source is independently formulated in another release agent according to the invention.

Preferably, the peroxidase is in the form of peroxidase-containing granules (hereinafter sometimes referred to as "peroxidase granules" or "peroxidase-containing granules"). The peroxidase granules may further suitably contain various granulating auxiliaries, binders, fillers, lubricants and the like. Examples include cellulose (eg, cellulose in fibrous or microcrystalline form), dextrin (eg, yellow dextrin), polyvinylpyrrolidone, polyvinyl alcohol, cellulose derivatives (eg, CMC or hydroxypropylcellulose), gelatin, salts (eg, There are sodium sulfate, sodium chloride, calcium sulfate or calcium carbonate), titanium dioxide, talc and clay (eg, kaolin or bentonite). Other substances relevant for incorporation into granules of the type in question are described, for example, in EP0304331B1, and are well known to those skilled in the art. The enhancer and the hydrogen peroxide source may also be in the form of granules. As a preferred option, when the enhancer is formulated in a release agent, the peroxidase and the enhancer are granulated together to form a co-granule incorporated in the release agent. Alternatively, independent enhancer granules and (hydrogen peroxide source) granules are also contemplated in the cleaning composition according to the present invention.

Methods and devices for making enzyme-containing granules are also well known to those skilled in the art (see, for example, EP0304331B1). For example, US
Compact granules made using a device including a knife as described in Example 1 of Patent No. 4,106,991 are very suitable granules (co-granules) in the context of the present invention.

The release agent may be, for example, a coating. The coating protects the granules (cogranules) in a washing environment for a period of time. The coating is applied to the granules (co-granules) in an amount ranging from 0 to 50% by weight, preferably 5 to 40% by weight (calculated on a weight basis of uncoated dry granules).
Usually applied to The amount of coating applied to the granules depends to a large extent on the nature and composition of the coating desired and the type of protection that coating should provide to the granules. For example, the thickness of the coating or multilayer coating applied to any of the granules determines the period over which the contents of the granules are released. Possible multilayer coatings are, for example, coatings in which a fast release coating is coated over a slow release coating.

Suitable release coatings are those which allow the release of the contents of the peroxidase- and / or enhancer (cogranulate) and / or (hydrogen peroxide) -granules according to the invention under the conditions common during their use. is there. Thus, for example, if the product of the present invention is a detergent (eg, 1
When introduced into a cleaning solution containing a surfactant (typically containing more than one type of surfactant), the coating ensures the release of the contents of the granules from the release agent when it is introduced into the cleaning medium. Should be something.

Preferred release coatings are coatings that are substantially insoluble in water. Suitable release coatings in the cleaning medium are suitably: tallow; hydrogenated tallow; partially hydrolyzed tallow; natural and synthetic source fatty acids and fatty alcohols;
Di- and triesters (e.g., glycerol monostearate); ethoxylated fatty alcohols; latex; hydrocarbons with melting points in the range of 50-80C; Melt coatings are a preferred class of fast or slow release coatings and can be used without dilution with water. For information on slow release coatings, see Controlled Release Systems: Fabri.
Reference is made to cation Technology, Vol. I, CRC Press, 1988.

The coating may suitably further comprise materials such as clay (eg, kaolin), titanium dioxide, pigments, salts (eg, calcium carbonate), and the like. Those skilled in the art are aware of other coating components associated with the present invention.

The following describes the production of peroxidase granules to be incorporated in a release agent.

Granulated cellulose fiber (Arbocel ^TM BC200) 2.0 kg, kaolin
0.9 kg, yellow dextrin (TACKIDEX ^™ G155) 1.2 kg and sodium sulfate 10.1 kg (all dry ingredients) were mixed in a Lodige mixer.

2.1 kg of liquid peroxidase concentrate to which 0.5 kg of sucrose and 0.8 kg of water were added (dissolved) while continuously mixing the above mixed dry ingredients.
(Enzyme protein 71 mg / g; Coprinus peroxidase made as described in Example 1 of EP505311)
Sprayed.

During and after spraying, the compact peroxidase granules were formed with the knife described in Example 1 of US Pat. No. 4,106,991.

After granulation, the peroxidase granules were dried in a fluid bed. Sieve the dried peroxidase granules,
Product fractions of 300-1000 mm size were separated for coating.

Coating The peroxidase granules incorporated in the fast release agent are:
For example, uncoated peroxidase granules. Peroxidase granules incorporated in a slow release agent are made as follows. The peroxidase granules to be incorporated into the slow release agent were heated to 60 ° C. in a Lodige mixer and 5% glycerol monostearate (heated to 60 ° C.) was added under continuous mixing. After the glycerol monostearate was dispensed, the peroxidase granules were powdered with 6.7% organoclay (Claytone ^™ AF) and 6.7% titanium dioxide under continuous mixing. All percentages are weight percentages based on dry uncoated peroxidase granules. After cooling, the coated peroxidase granules, ie, the peroxidase granules incorporated in the slow release agent, were sieved and fractions in the 300-1100 mm size range were collected for use.

CTC is used in the laundry detergent composition in an appropriate amount, preferably 10% by weight or less. Of course, the "suitable amount" is strongly dependent on the potency of the CTC, the activity of the cellulase, the detergent system and its interaction with the cellulase. Thus, the amount of CTC correlates with other compounds of the detergent composition and the cleaning conditions. The amount according to the invention is selected such that, for example, under European washing conditions, the cellulase activity of the selected cellulase is reduced to 10% of the initial cellulase within 15 minutes from the start of the washing cycle.

CTC Composition The CTC composition according to the present invention contains a peroxidase, an enhancer and a source of hydrogen peroxide.

Peroxidase enzymes used in the context of the present invention (EC
1.11.1) is very suitably, for example, the enzyme class EC1.11.
Any peroxidase contained in 1.7, including peroxidase fragments exhibiting peroxidase activity, and synthetic or semi-synthetic peroxidase derivatives (e.g., having a porphyrin ring system) or microperoxidases (e.g., US 4,077,768, EP 0537381, WO 91/05858 and WO 92/16634) are also relevant in the context of the present invention.
Suitable peroxidases are known from microbial, plant and animal sources. Other possible peroxidase enzymes are derived by protein engineering methods, in which one or several amino acids of the native peroxidase enzyme are replaced by other amino acids.

Preferably, the peroxidase used in the method of the invention is produced by a plant (eg, horseradish or soybean peroxidase) or a microorganism such as a fungus or bacterium. Some preferred fungi include Deuteromyc
otina subphylum, Hyphomycetes class, e.g. Fusarium, Humicol
a, Tricoderma, Myrothecium, Verticillum, Arthromyc
es, Caldariomyces, Ulocladium, Embellisia, Cladosp
strains belonging to rorium or Dreschlera, especially Fusarium oxy
sporum (DSM2672), Humicola insolens, Trichoderma
resii, Myrothecium verrucana (IFO6113), Verticill
um alalboatrum, Verticillum dahlie, Arthromyces ra
mosus (FERM P-7754), Caldariomyces fumago, Ulo
cladium chartarum, Embellisia alli or Dreschlera
There are halodes.

Other preferred fungi include Basidiomycotina subphylum, Basid
Class iomycetes, such as Coprinus, Phanerochaete, Coriol
strains belonging to us or Trametes, especially Coprinus cinereus
f.microsporus (IFO 8371), Coprinus macrorhizus,
Phanerochaete chrysosporium (eg NA-12) or T
rametes (formerly called Polyporus), eg T.ve
rsicolor (for example, PR428-A). Other preferred fungi include Zygomycotina subphylum, Mycoraceae, such as Rh
There are strains belonging to izopus or Mucor, especially Mucor hiemalis.

Some preferred bacteria include Actinomycetales strains,
For example, Streptomyces spheroides (ATTC23965), Strept
omyces thermoviolaceus (IFO12382) or Streptover
There is ticillum verticillium ssp.verticillium. Other preferred bacteria include Bacillus pumilus (ATCC12905), B
acillus stearothermophilus, Rhodobactersphaeroide
s, Rhodomonas palustri, Streptococcus lactis, Pseu
domonas purrocinia (ATCC15958) or Pseudomonas f
luorescens (NRRL B-11). Another preferred bacterium is Myxococcus, for example a strain belonging to M. virescens.

Other related peroxidases are "haloperoxidases" (see, for example, US Pat. No. 4,937,192), such as chlorine peroxidase (EC1.11.1.10), bromine peroxidase and iodine peroxidase (EC1.11.1.8). Another possible source of useful peroxidase is BCSaun
ders et al., Peroxidase, London, 1964, pp. 41-43.

The peroxidase further comprises, in a medium, a DNA sequence encoding the peroxidase and a DNA encoding the peroxidase under conditions capable of expressing peroxidase.
It may be produced by a method comprising culturing a host cell transformed with a recombinant DNA vector having a DNA sequence encoding a function capable of expressing the sequence and recovering peroxidase from the culture. In particular, the peroxidase produced by the recombinant technique is a peroxidase obtained from Coprinus po., Especially C. macrorhizus or C. cinereus according to WO 92/16634.

As already mentioned to some extent earlier, the term peroxidase used in the context of the present invention refers to substances having peroxidase activity, such as cytochrome, hemoglobin or peroxidase active fragments obtained from peroxidase enzymes, and synthetic or semi-synthetic derivatives thereof. For example, iron porphine, iron porphyrin and iron phthalocyanine and their derivatives. The peroxidase used in the production of the invention is very suitably, in most cases, Coprinus peroxidase, Myxococcus peroxidase or horseradish peroxidase.

Enhancer The enhancer may be any suitable peroxidase enhancer. Examples of enhancers include halide ions (eg, chlorine and bromine); certain metal ions (eg, Mn ²⁺ ); phenol species (eg, 2,4-dichlorophenol p-hydroxycinnamic acid, vanillin, 7-hydroxy). Coumarin, 6-hydroxy-2-naphthoic acid and p-hydroxybenzenesulfonate); 2,2-azino-bis (3-ethylbenzothiazoline-6-sulfonate) (ABTS; see, for example, WO 94/12620); 10-methyl- ,
There are 10-ethyl- and 10-propyl-phenothiazine (see, for example, WO 94/12621). Numerous other enhancers or enhancers are described in WO94 / 12619, WO94 / 12620 and WO94 / 126
21.

Preferred enhancers in the context of the present invention are 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP), 10-methylphenoxazine (WO94 /
No. 12621), and the dye transfer inhibiting cogranulate products of the invention containing such enhancers have good storage stability (shelf life) and are very satisfactory in fabric washing. Dye transfer inhibition can be performed (see below).

Hydrogen peroxide source Bleach suitable for the present invention includes a source of peroxygen bleach. Examples of suitable sources of peroxygen bleach include hydrogen peroxide releasing agents, such as hydrogen peroxide,
Perborates such as perborate monohydrate, perborate tetrahydrate, persulfate, percarbonate,
There are peroxydisulfate, perphosphate and peroxyhydrate. Preferred bleach is percarbonate and perborate.

Hydrogen peroxide releasing agents include tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS, described in US Pat. No. 4,412,934), and 3,5,5-trimethylhexanoloxybenzenesulfonate (ISONOBS, EP12
05991) or pentaacetylglucose (PAG)
These can be used in conjunction with bleach activators, such as these, which are perhydrolyzed to form peracids as active bleaching species, for improved bleaching effects.

It is also desirable to utilize an enzymatic process for hydrogen peroxide formation. To this end, the process according to the invention may additionally comprise an enzyme system capable of producing hydrogen peroxide during the washing process (ie the enzyme and its substrate).

One such category of hydrogen peroxide generating systems includes enzymes that can convert molecular oxygen and organic or inorganic substrates into hydrogen peroxide and oxidized substrates, respectively. Although these enzymes only produce low levels of hydrogen peroxide, they are used with considerable advantage in the process of the present invention since the presence of peroxidase can ensure efficient utilization of the hydrogen peroxide produced. Can be

Preferred hydrogen peroxide producing enzymes are those that act on inexpensive and readily available substrates conveniently contained in detergent compositions. An example of such a substrate is glucose utilized for the production of hydrogen peroxide by glucose oxidase. Suitable oxidases include those that act on aromatic compounds such as phenols and related substances. Other suitable oxidases are uric acid oxidase, galactose oxidase, alcohol oxidase, amine oxidase, amino acid oxidase, amyloglucosidase and cholesterose oxidase.

Preferred enzyme systems are alcohol and aldehyde oxidase. A more preferred system for granular detergents has a solid alcohol, such as glucose, whose oxidation to glucuronic acid is catalyzed by glucose oxidase to form hydrogen peroxide. Further preferred systems for liquid detergents include, for example, liquid alcohols, which also act as solvents. An example is ethanol / ethanol oxidase. Such an enzyme system is disclosed in EP Patent Application No. 91202655.6, filed Oct. 9, 1991.

Other peroxygen bleach suitable for the present invention include organic peroxy acids such as percarboxylic acids.

Detergent components The detergent compositions of the present invention may also contain additional detergent components. The exact nature of these additional ingredients and their compounding levels
It depends on the physical form of the composition and the nature of the cleaning operation in which it is used.

The compositions of the present invention include, for example, hand and machine laundry detergent compositions, including laundry liquor compositions, compositions suitable for pretreatment use of soiled fabrics, rinsing liquor added fabric softener compositions, and It is formulated as a composition for use in home hard surface cleaning operations.

When formulated as a composition suitable for use in a machine wash process, the compositions of the present invention preferably comprise both a surfactant and a builder compound, and preferably an organic polymer compound,
It further contains one or more detergent components selected from bleaching agents, additional enzymes, foam inhibitors, dispersants, lime soap dispersants, soil suspending and redeposition inhibitors, and corrosion inhibitors. Laundry compositions can also contain softening agents as additional detergent components.

If necessary, the density of the laundry detergent composition can be from 550 to 1000 g /, preferably 600 to 950 g / at the composition measured at 20 ° C.
It is. The “compact” form of the composition includes density,
In terms of composition, it is best reflected by the amount of inorganic filler salt;
Inorganic filler salts are a conventional component of detergent compositions in powder form; for a conventional detergent composition, 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 is
It is present in an amount not exceeding 15% by weight, preferably not exceeding 10% of the composition, most preferably not exceeding 5%.

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

 A preferred filler salt is sodium sulfate.

Surfactant system The detergent composition according to the invention is characterized in that the surfactant can be selected from nonionic and / or anionic and / or cationic and / or amphoteric and / or zwitterionic and / or semipolar surfactants. Agent system.

Surfactants are typically present at a level of 0.1-60% by weight. Further preferred levels of loading are from 1 to 35% by weight, most preferably from 1 to 20% by weight in the case of the machine dishwashing, laundering and rinsing liquid-containing fabric softener compositions according to the invention, by hand according to the invention. Is 5 to 60% by weight, more preferably 15 to 45% by weight.

Preferably, the surfactant is formulated to be compatible with the enzyme components present in the composition. For liquid or gel compositions, it is most preferred that the surfactant be formulated such that it promotes the stability of the enzymes in these compositions or does not degrade the enzymes at least.

Preferred non-alkylbenzene sulfonate surfactant systems for use in accordance with the present invention include, as surfactants, one or more of the nonionic and / or anionic surfactants described herein.

Polyethylene, polypropylene and polybutylene oxide condensates of alkylphenols are suitable for use as the nonionic surfactant of the surfactant system of the present invention;
Polyethylene oxide condensates are preferred. These compounds have from about 6 to about 14 carbon atoms in a straight or branched configuration,
Preferably, there is a condensation product of an alkylphenol and an alkylphenol having an alkyl group of from about 8 to about 14 carbon atoms. In a preferred embodiment, ethylene oxide is
It 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 Igepal ^™ CO-6 sold by GAF Corporation.
30 and Trit, all sold by Rohm & Haas Company
on ^TM X-45, X-114, X-100 and X-102. These surfactants are commonly referred to as alkylphenol alkoxylates (eg, alkylphenol ethoxylates).

The condensation products of primary and secondary aliphatic alcohols with about 1 to about 25 moles of ethylene oxide are suitable for use as nonionic surfactants in the nonionic surfactant systems of the present invention. The alkyl chain of the aliphatic alcohol is straight or branched, primary or secondary, and usually has about 8 to about 22 carbon atoms. Preferred are condensation products of an alcohol having an alkyl group of from about 8 to about 20, more preferably from about 10 to about 18, carbon atoms with about 2 to about 10 moles of ethylene oxide per mole of alcohol. About 2 to about 7 moles, most preferably 2 to 5 moles, of ethylene oxide are present in the condensation product per mole of alcohol. Examples of commercially available nonionic surfactants of this type include Tergitol ^™ 15-S-9 (condensation product of a C ₁₁ -C ₁₅ linear alcohol and 9 moles of ethylene oxide), both sold by Union Carbide Corporation. Tergitol
^TM 24-L-6NMW (with C ₁₂ -C ₁₄ primary alcohol with 6 mol of ethylene oxide, the condensation product of narrow molecular weight distribution; Shell
Neodol ^™ 45-9 (C ₁₄
-C ₁₅ linear alcohol with condensation product of 9 moles ethylene _{^{oxide), Neodol TM 23-3 (C 12}} -C 13 condensation product of linear alcohols with ethylene oxide 3.0 moles), Neodol
^TM 45-7 (C ₁₄ -C ₁₅ condensation product of linear alcohol with 7 mol ethylene _{^{oxide), Neodol TM 45-5 (C 14}} -C 15 condensation product of linear alcohol with 5 moles of ethylene oxide); The Ky sold by Procter & Gamble Company
ro ^TM EOB (C ₁₃ -C ₁₅ condensation products of alcohols with 9 moles ethylene oxide); Genapol LA sold by Hoechst
There are O5O (C ₁₂ -C ₁₄ condensation products of alcohols with 5 moles of ethylene oxide). HLB in these products
Is preferably from 8 to 11, and most preferably from 8 to 10.

As the nonionic surfactant of the surfactant system of the present invention, about 6 to about 30 carbon atoms, preferably about 10 to about carbon atoms are used.
16 hydrophobic groups and about 1.3 to about 10, preferably about 1.3 to about 3,
Most preferably a polysaccharide having from about 1.3 to about 2.7 saccharide units,
For example, having a polyglycoside hydrophilic group, January 21, 1986
Also useful are the alkyl polysaccharides disclosed in Llenado U.S. Pat. No. 4,565,647, issued on the date. 5 or 6
For example, glucose, galactose and galactosyl moieties can be used in place of the glucosyl moieties (optionally a hydrophobic group is attached at position 2, 3, 4 etc. to form glucoside or galactoside). Not glucose or galactose). For example, an intersugar linkage may exist between one position of the new sugar unit and positions 2, 3, 4, and / or 6 of the previous sugar unit.

Preferred alkyl polyglycosides have the formula: R ² O (C _n H _2n O) _t (glycosyl) _{x where} R ² is alkyl, alkylphenyl, hydroxyalkyl, hydroxyalkylphenyl and mixtures thereof. (Alkyl groups are from about 10 to
Has 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 from about 1.3 to about 3, most preferably from about 1.3 to about 2.7. Glucosyl 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.

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
It preferably has a molecular weight of about 1500 to about 1800 and is insoluble in water. The addition of a polyoxyethylene moiety to this hydrophobic moiety tends to increase the overall water solubility of the molecule, resulting in a total condensation product corresponding to condensation with ethylene oxide having a polyoxyethylene content within about 40 moles. About weight
By 50%, the liquidity of the product is retained. Examples of compounds of this type include certain commercially available Pluronic ^™ surfactants sold by BASF.

As the nonionic surfactant of the nonionic surfactant system of the present invention, a condensation product of ethylene oxide with a product obtained from the reaction of propylene oxide with ethylenediamine is also suitable for use. The hydrophobic portion of these products consists of the reaction product of ethylenediamine and excess propylene oxide and usually has a molecular weight of about 2500 to about 3000. The hydrophobic portion contains about 40 to about 80% by weight of the condensation product.
And to a degree having a molecular weight of from about 5000 to about 11,000. Examples of this type of nonionic surfactant include BASF
There are certain commercially available Tetronic ^™ compounds, marketed by the Company.

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

Highly preferred nonionic surfactants are polyhydroxy fatty acid amide surfactants of the formula: In the above formula, 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, and Z is A polyhydroxyhydrocarbyl having a linear hydrocarbyl chain and at least three hydroxyls directly attached to the chain, or an alkoxylated derivative thereof. Preferably, R ¹ is methyl and R ² is a linear C
_{An 11-15} alkyl or C _16-18 alkyl or alkenyl chain, such as coconut alkyl, or a mixture thereof, wherein Z is derived from a reducing sugar such as glucose, fructose, maltose, lactose in a reductive amination reaction.

When included in such laundry detergent compositions, the nonionic surfactant systems of the present invention act to improve the fat / oil stain removal of such laundry detergent compositions under a wide range of laundry conditions. I do.

Highly preferred anionic surfactants include the formula RO
(A) _m SO _{3 M} has an alkyl alkoxylated sulphate surfactant is water-soluble salts or acids, hydroxyalkyl wherein R has the same unsubstituted C ₁₀ -C ₂₄ alkyl or C ₁₀ -C ₂₄ alkyl moiety, group, preferably a C ₁₂ -C ₂₀ alkyl or hydroxyalkyl, more preferably C ₁₂ -C
_{18 is} an alkyl or hydroxyalkyl, A is an ethoxy or propoxy unit, m is greater than zero, typically from about 0.5 to about 6, more preferably from about 0.5 to about 3, and M is H or a cation; For example, metal cations (eg, sodium, potassium, lithium, calcium, magnesium, etc.), ammonium or substituted ammonium cations. Alkyl ethoxylated sulfates and alkyl propoxylated sulfates are contemplated herein. Specific examples of substituted ammonium cations are derived from methyl, dimethyl, trimethyl-ammonium cations, quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, and alkylamines such as ethylamine, diethylamine, triethylamine. And mixtures thereof. Exemplary surfactants are C ₁₂ -C ₁₈
Alkyl polyethoxylate (1.0) sulfate (C _{12
-C 18 E (1.0) M)} , C 12 -C 18 alkyl polyethoxylate (2.25) sulfate _{(C 12 -C 18 E (2.25} ) M), C
₁₂ -C ₁₈ alkyl polyethoxylate (3.0) sulfate _{(C 12 -C 18 E (3.0} ) M) , and C ₁₂ -C ₁₈ alkyl polyethoxylate (4.0) sulfate _{(C 12 -C 18 E (4} .
0) M), where M is conveniently selected from sodium and potassium.

Suitable anionic surfactants used are “The Jo
urnal of the American Oil Chemists Society ", 52 (19
75), C ₈ sulfonated with gaseous SO ₃ according to pp. 323-329
-C ₂₀ carboxylic acids (i.e., fatty acids), including straight-chain esters of an alkyl 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 alkyl ester sulfonate surfactants of the following structural formula: Wherein R ³ is C ₈ -C ₂₀ hydrocarbyl, preferably alkyl, or a combination thereof, R ⁴ is C ₁ -C ₆ hydrocarbyl, preferably alkyl, or a combination thereof, and M is an alkyl ester sulfonate. And a cation that forms a water-soluble salt with the cation. Suitable salt-forming cations include metals such as sodium, potassium and lithium, and 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 is especially 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 C _10- C ₂₀ alkyl or hydroxyalkyl having an alkyl moiety, more preferably a 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 ( For example, methyl, dimethyl, trimethyl-
Ammonium cations and quaternary ammonium cations such as tetramethylammonium and dimethylpiperidinium cations, ethylamine, diethylamine,
Quaternary ammonium cations derived from alkylamines such as triethylamine, and mixtures thereof)
It is. Typically, C _12-C16 alkyl chains lower wash temperatures (e.g., about 50 ° C. or less) Preferred preferably at, C ₁₆ -C ₁₈ alkyl chains are higher wash temperatures (e.g., about 50 ° C. or higher).

Other anionic surfactants useful for cleaning purposes,
It can be contained in the laundry detergent composition of the present invention.
These include soap salts (eg, 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 sulfonates, such as alkaline earth metal citrates as described in GB 1,082,179 sulfonated polycarboxylic acids prepared by sulfonation of the pyrolyzed product, (including ethylene oxide within 10 mole) C ₈ -C ₂₄ alkyl polyglycol ether sulfates, alkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfates , Alkylphenol ethylene oxide ether sulfate, paraffin sulfonate, alkyl phosphate, isethionate such as acyl isethionate, N-acyl taurate, alkyl succinate and sulfosuccinate , Monoester (particularly saturated and unsaturated C ₁₂ -C ₁₈ monoesters) and diesters of sulfosuccinates (especially saturated and unsaturated C ₆ -C ₁₂ diesters) sulfosuccinates, acyl sarcosinates, alkyl polyglycosides alkyl polysaccharide sulfates, such as sulfates (nonionic non sulfate compounds are described below), and branched primary alkyl sulfates of the formula _{RO (CH 2 CH 2 O)} k -CH 2 COO - M + (R is
C ₈ -C ₂₂ alkyl; k is an integer from 1 to 10;
Are soluble salt-forming cations). Also suitable are rosins, hydrogenated rosins, and resin acids and hydrogenated resin acids, such as resin acids and hydrogenated resin acids present or derived from tall oil.

An example is “Surface Active Agents and Detergent
s "(Vol. I & II, Schwartz, Perry & Berch). Various such surfactants are described in December 1975.
Laughlin et al., U.S. Pat.
No. 23, line 58 to column 29, line 23 of the specification are also generally disclosed (incorporated herein by reference).

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 40% by weight.
Contains 20% of such anionic surfactants.

CTC was found to be very efficient at anion / nonion ratios of 10: 1 to 1: 2.

The laundry detergent compositions of the present invention may also contain cationic, amphoteric, zwitterionic and semipolar surfactants, and nonionic and / or anionic surfactants other than those previously described.

Cationic detersive surfactants suitable for use in the laundry detergent compositions of the present invention are those having one long-chain hydrocarbyl group. Examples of such cationic surfactants include ammonium surfactants, such as alkyltrimethylammonium halides, and surfactants having the formula: [R ² (OR ³ ) _y ] [R ⁴ ( oR ³⁾ _{y] 2} R ⁵ N ⁺ X ^- the formula R ² is an alkyl or alkyl benzyl group having from about 8 to about 18 carbon atoms in the alkyl chain; each R ³ is -CH ₂ CH ₂ - _{, -CH 2 CH (CH 3)} -, - CH 2 CH (CH 2 OH) -,
Selected from the group consisting of —CH ₂ CH ₂ CH ₂ — and mixtures thereof; each R ⁴ is formed by linking C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, two R ⁴ groups Benzyl ring structure, —CH ₂ CHOH—CHOHCOR ⁶ CHOHCH ₂ OH (R ⁶ is about
A hexose or hexose polymer having a molecular weight of less than 1000) and hydrogen when y is non-zero; R ⁵ is similar to R ⁴ or R ² + R
^An alkyl chain having a total number of carbon atoms of ⁵ or less; no more than about 18; each y is 0 to about 10; the sum of y values is 0 to about 15; X is any compatible anion is there.

Highly preferred cationic surfactants are a useful water-soluble quaternary ammonium compounds in the present composition has the _{formula: R 1 R 2 R 3 R} 4 N + X - (i) In the above formula, R ₁ is C ₈ -C ₁₆ alkyl, and R ₂ , R ₃ and R ₄
Are independently C ₁ -C ₄ alkyl, C ₁ -C ₄ hydroxyalkyl, benzyl and — (C ₂ H ₄₀ ) _x H (having a value of 2 to 5), and X is an anion . R ₂ , R ₃ or
No more than one of R ₄ should 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 synthetically derived by olefin build-up or OXO alcohol synthesis. You.

Preferred groups for R ₂ , R ₃ and R ₄ are methyl and hydroxyethyl groups and the anion X is selected from halide, methosulphate, 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 -C 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 esters (R ₁ is CH ₂ - CH ₂ -OC (= O) -C
Compounds of formula (i) which are _12-14 alkyl and R ₂ , R ₃ , R ₄ are methyl) Dialkylimidazolines (compounds of formula (i)) Other cationic surfactants useful in the present invention include: 1980
U.S. Patent No. 4,228,044 to Cambre, issued October 14,
And European Patent Application EP 000,224.

When included in the present compositions, the laundry detergent compositions of the present invention typically comprise from about 0.2 to about 25% by weight, preferably from about 1 to about 25% by weight.
It contains about 8% of such cationic surfactants. The combination of cationic surfactant, cellulase and CTC,
It has been found that softening and cleaning provide a synergistic improvement.

Amphoteric surfactants are also suitable for use in the 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, where the aliphatic group is linear or branched. It may be. 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. For examples of amphoteric surfactants, December 1975
Laughlin et al., U.S. Pat.
See column 19, lines 18-35 of the specification.

When included in the present compositions, the laundry detergent compositions of the present invention typically comprise 0.2 to about 15% by weight, preferably about 1 to about 1%.
It contains 0% of such amphoteric surfactants.

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

When included in the present compositions, the laundry detergent compositions of the present invention typically comprise 0.2 to about 15% by weight, preferably about 1 to about 1%.
Contains 0% of such zwitterionic surfactants.

Semipolar nonionic surfactants have about 10 to about 18 carbon atoms.
A water-soluble amine oxide having one alkyl moiety of the formula and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of about 1 to about 3 carbon atoms; one alkyl of about 10 to about 18 carbon atoms A water-soluble phosphine oxide having a moiety and two moieties selected from the group consisting of alkyl and hydroxyalkyl groups of from about 1 to about 3 carbon atoms; one alkyl moiety of from about 10 to about 18 carbon atoms and a carbon atom A specific category of nonionic surfactants, including water-soluble sulfoxides, having from about 1 to about 3 moieties selected from the group consisting of alkyl and hydroxyalkyl groups.

Semi-polar nonionic detersive surfactants include amine oxide surfactants having the formula: Wherein R ³ is alkyl having about 8 to about 22 carbon atoms;
Hydroxyalkyl is an alkyl phenyl group or mixtures thereof; R ⁴ is a mixture of alkylene, hydroxyalkylene group, or those having from about 2 to about 3 carbon atoms; x is from 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
_{There are 18} alkyl dimethylamine oxide and C ₈ -C ₁₂ alkoxyethyl dihydroxyethylamine oxide.

When included in the present compositions, the laundry detergent compositions of the present invention typically comprise 0.2 to about 15% by weight, preferably about 1 to about 1%.
It contains 0% of such semi-polar nonionic surfactants.

Optional Detergent Components Preferred detergent compositions of the present invention may further include enzymes that exert cleaning performance and / or fabric care benefits. The enzyme is selected from protease, glucoamylase, amylase, lipase, cutinase, pectinase, reductase, oxidase, phenol oxidase, lipoxygenase, ligninase, pullulanase, tannase, pentosanase, malanase, β-glucanase, arabinosidase or a mixture thereof. There are enzymes that are used.

A preferred combination is a cleaning composition having a cocktail of conventionally applied enzymes such as proteases, amylases, lipases, cutinases along with one or more plant cell wall degrading enzymes.

Preferred commercially available protease enzymes include Novo Nordisk A
/ S (Denmark) from Alcalase, Savinase, Prim
What is sold as ase, Durazym and Esperase, Gi
Trade names Maxatase, Maxacal and Maxap from st-Brocades
sold as em, sold from Genencor International, and Solvay Enzyme under the trade name Opticlean
And one sold as Optimase. Proteases described in our co-pending application USSN 08 / 136,797 can also be included in the detergent compositions of the present invention. The protease enzyme is incorporated into the composition according to the present invention at an active enzyme level of 0.0001 to 2% by weight of the composition.

The combination of protease, cellulase and CTC has been found to produce an improved wool and silk regrowth effect due to the CTC effect on the protease.

Other preferred enzymes that can be included in the detergent compositions of the present invention include lipases. Lipase enzymes suitable for detergents include Pseu, such as Pseudomonas stutzeri ATCC 19.154 disclosed in GB 1,372,034.
Some are produced by microorganisms of the genus domonas. Suitable lipases include those produced by the microorganism Pseudomonas fluorescent IAM1057, which show a positive immune cross-reactivity with lipase antibodies. This lipase is trade name Lipa
se P “Amano” Amano Pharmaceutic in Nagoya, Japan
It is commercially available from Al Co. Ltd. and is referred to hereafter as "Amano-P". Particularly suitable lipases are M1 Lipase ^R and Lipoma
x ^R (Gist-Brocades) and a lipase such as Lipolase ^R (Novo), it was found to be very effective when used in combination with the compositions of the present invention.

Also suitable is a special type of lipase, a cutinase [EC3.1.1.50], which is considered a lipase that does not require surface activity.
Addition of cutinase to the detergent composition is described, for example, in WO-A-88.
/ 09367 (Genencor).

The lipase and / or cutinase may be present in the detergent composition.
It is usually incorporated into detergent compositions at an active enzyme level of 0.0001 to 2% by weight.

Amylases (α and / or β) can be included for removal of carbohydrate-based soils. Suitable amylases are Termamyl ^R (Novo Nordisk), Pungamyl ^R and BAN ^R (Novo Nordisk). The enzymes may be of any suitable origin, such as vegetable, animal, bacterial, fungal and yeast sources. The enzyme is 0.0001 of the detergent composition.
It is usually incorporated into detergent compositions at levels of ~ 2% active enzyme. Other suitable detergent ingredients that can be added are January 1992
Co-pending European Patent Application No. 92870018.6 filed on 31st
Enzymatic oxidation scavenger described in the specification.
An example of such an enzymatic oxidation scavenger is ethoxylated tetraethylene polyamine.

The composition according to the invention may further comprise a builder system. Aluminosilicate materials, silicates, polycarboxylates, fatty acids, materials such as ethylenediaminetetraacetic acid, sequestering agents such as aminopolyphosphonates, especially ethylenediaminetetramethylenephosphonic acid and diethylenetriaminepentamethylenephosphonic acid, including any conventional Builder systems are also suitable for use in the present invention. Although less preferred for obvious environmental reasons, phosphate builders can also be used in the present invention.

Suitable builders are inorganic ion exchange materials, usually inorganic hydrated aluminosilicate materials, and more specifically hydrated synthetic zeolites, such as hydrated zeolites A, X, B, HS or MA
P.

Another suitable inorganic builder material is a laminated silicate, such as SKS-6 (Hoechst). 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 their ether derivatives as disclosed in Belgian Patent Nos. 831,368, 821,369 and 821,370. Suitable polycarboxylates having two carboxy groups include:
Water-soluble salts of succinic acid, malonic acid, (ethylenedioxy) diacetate, maleic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid and German Patent Publication No. 2,446,686
No. 2,446,687 and U.S. Pat. No. 3,935,257, and the sulfinyl carboxylate described in Belgian Patent 840,623. Polycarboxylates having three carboxy groups include, in particular, water-soluble citrates, aconitrates and citraconates and GB 1,379,241.
Carboxymethyloxysuccinate, succinate derivatives such as lactoxysuccinate described in Netherlands Application No. 7205873, and 2-oxa-derivatives described in GB 1,387,447. There are oxypolycarboxylate materials such as 1,1,3-propanetricarboxylate.

Polycarboxylates having four carboxy groups include oxydisuccinate, 1,1,2,2-ethanetetracarboxylate and 1,1,3,3-propane disclosed in GB 1,261,829. There are tetracarboxylate and 1,1,2,3-propanetetracarboxylate.
Polycarboxylates with sulfo substituents include British Patent Nos. 1,398,421, 1,398,422 and U.S. Pat.
There are sulfosuccinate derivatives disclosed in 936,448 and sulfonated pyrolytic citrates described in GB 1,082,179, and polycarboxylates with phosphon substituents are described in GB 1,439,000. It has been disclosed.

Alicyclic and heterocyclic polycarboxylates include:
Cyclopentane-cis, cis, cis-tetracarboxylate, cyclopentadienidepentacarboxylate, 2,3,4,5-tetrahydrofuran-cis, cis, cis-tetracarboxylate, 2,5-tetrahydrofuran-cis-di Carboxylates, 2,2,5,5-tetrahydrofuran-tetracarboxylate, 1,2,3,4,5,6-hexane-hexacarboxylate and carboxymethyl of polyhydric alcohols such as sorbitol, mannitol and xylitol There are derivatives. 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 specifically citrates.

Preferred builder systems for use in this composition include a mixture of 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. .

Suitable chelants for inclusion in the detergent composition according to the present invention are ethylenediamine-N, N'-succinic acid (EDDS) or its alkali metal, alkaline earth metal, ammonium or substituted ammonium salts, or mixtures thereof. . Preferred EDDS compounds are the free acid form and its sodium or magnesium salt. Examples of such preferred sodium salts of EDDS include Na ₂ EDDS and Na ₄ EDDS. Examples of such preferred magnesium salts of EDDS, there is MgEDDS and Mg ₂ EDDS. Magnesium salts are most preferred for inclusion in the composition according to the invention. The chelants have been shown to synergistically improve cleaning performance when combined with cellulase and CTC.

Preferred builder systems include a mixture of a water-insoluble aluminosilicate builder such as zeolite A and a water-soluble carboxylate chelating agent such as citric acid.

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

Other suitable water-soluble organic salts are homo- or copolymeric acids or salts thereof, wherein the polycarboxylic acids have at least two carboxyl groups separated from one another by no more than two carbon atoms. Combinations of cellulase, CTC and the above polymers significantly reduce the inorganic envelope.

This type of polymer is disclosed in GB-A-1,596,756. Examples of such salts are MW 2000-5000 polyacrylates and their copolymers with maleic anhydride, such copolymers being 20,000-70,000,
In particular, it has a molecular weight of about 40,000.

The detergent builder salt is usually contained in an amount of 10-80%, preferably 20-70%, most preferably 30-60% by weight of the composition.

Another optional ingredient is a suds suppressor 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 and xerogels and various types of hydrophobic silica. These materials can be formulated as particles that are formulated such that the suds suppressor can be advantageously released in a water-soluble or water-dispersible, substantially non-surfactant, detergent-impermeable carrier. On the other hand, the foam control agent can be dissolved or dispersed in a liquid carrier and applied by spraying on one or more other components.

Preferred silicone suds suppressors are disclosed in Bartollota et al., US Pat. No. 3,933,672. Another particularly useful suds suppressor is a self-emulsifying silicone suds suppressor, which is disclosed in German patent application DT published April 28, 1977.
It is described in OS 2,646,126. An example of such a compound is DC-544, commercially available from Dow Corning, which is a siloxane-glycol copolymer. Particularly preferred suds suppressors are silicone oils and 2
A suds suppressor system comprising a mixture of alkyl-alkanols. A suitable 2-alkyl-alkanol is 2-butyloctanol, sold under the trade name Isofol 12R.

Such suds suppressor systems are described in co-pending European Patent Application N92870174.7, filed November 10, 1992.

Particularly preferred silicone suds suppressors are described in co-pending European Patent Application No. N92201649.8.
The compositions may comprise silicone / silica mixture in combination with molten porous silica such as Aerosil ^R.

The above foam control agents are usually used at a level of 0.001 to 2% by weight, preferably 0.01 to 1% by weight of the composition.

Other ingredients used in the detergent composition, such as soil suspending agents, soil releasing agents, optical brighteners, abrasives, bactericides, fade 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 consist of dextrins derived from non-gelatinized starch esters of substituted dicarboxylic acids as described in US Pat. No. 3,455,838. 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. N-Lok
The encapsulating material 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 (maleic anhydride is at least 20 moles of the copolymer). %). These substances are usually 0.5% of the composition
%, More preferably from 0.75 to 8%, most preferably from 1 to 6% by weight.

Preferred optical brighteners are anionic in nature, an example being 4,4'-bis (2-diethanolamino-4-anilino-s-triazin-6-ylamino) stilbene-
Disodium 2,2'-disulfonate, 4,4'-bis (2-
Morpholino-4-anilino-s-triazin-6-ylamino) stilbene-2,2'-disulfonate disodium salt, 4,4'-bis (2,4-dianilino-s-triazine-
6-ylamino) stilbene-2,2'-disulfonate disodium salt, 4 ', 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'-
Disodium disulfonate, 4,4'-bis (4-phenyl-2,1,3-triazol-2-yl) stilbene-2,
Disodium 2'-disulfonate, 4,4'-bis [2-anilino-4- (1-methyl-2-hydroxyethylamino) -s-triazin-6-ylamino] stilbene-
Disodium 2,2'-disulfonate, 2-stilbyl-
4 "-(naphth-1 ', 2', 4,5) -1,2,3-triazole-2" -sodium sulfonate and 4,4'-bis (2-sulfostyryl) biphenyl. Highly preferred brighteners are the specific brighteners of co-pending European Patent Application No. 95201943.8.

Other useful polymeric substances are polyethylene glycol,
In particular, the molecular weight is 1000-10000, more specifically 2000-8000,
Most preferably it is of the order of 4000. These are 0.20-5
%, More preferably at a level of 0.25 to 2.5%. These polymers and the previously described homo- or copolymer polycarboxylate salts improve whiteness maintenance, fabric ash adhesion, and cleaning performance of soil, proteinaceous and oxidative soils in the presence of transition metal impurities. It is useful.

Soil release agents useful in the compositions of the present invention conventionally include terephthalic acid and ethylene glycol and / or in various configurations.
Or a copolymer or terpolymer with propylene glycol units. Examples of such polymers are disclosed in commonly assigned US Pat. Nos. 4,116,885 and 4,711,730 and EP-A-0,272,033. E
A particularly preferred polymer according to PA-0,272,033 has the formula: (CH ₃ (PEG) ₄₃ ) _0.75 (POH) _0.25 (T-PO) _2.8 (T-PEG) _0.4 T (POH) ₀₂₅ (( PEG) ₄₃ CH ₃ ) _{0.75 In the} above formula, PEG is — (OC ₂ H ₄ ) O—, PO is (OC ₃ H ₆ O), and T is (pcOC ₆ H ₄ CO).

Modified polyesters as random copolymers of dimethyl terephthalate, dimethyl sulfoisophthalate, ethylene glycol and 1,2-propanediol are also very useful, with the end groups being mainly sulfobenzoate,
It consists secondarily of monoesters of ethylene glycol and / or propanediol. The goal is to obtain a polymer capped at both ends by sulfobenzoate groups, and "mainly", in this context, most of the copolymers are end-capped with sulfobenzoate groups. However, some copolymers are not completely capped, so their terminal groups may consist of monoesters of ethylene glycol and / or propane-1,2-diol and are "secondarily"
Consist 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. It contains by weight sulfoisophthalic acid and has a molecular weight of about 3000. Polyesters and their method of manufacture are described in detail in EPA 311,342. The combination of cellulase, CTC and polyester has been found to synergistically improve whiteness and color retention.

Fabric softeners Fabric softeners can also be incorporated into the laundry detergent compositions according to the present invention. These agents may be inorganic or organic in type. The inorganic softener is GB-A-1,400,898
And the smectite clay disclosed in US Pat. No. 5,019,292. Organic fabric softeners include GB-A-1,514,
Water-insoluble tertiary amines as disclosed in EP-B-0,011,340, EP-B-0,026,527 and EP-B-0,02
And combinations thereof with mono C ₁₂ -C ₁₄ quaternary ammonium salts disclosed in 6,528, there is a di-long-chain amides as disclosed in EP-B-0,242,919. Other useful organic components of the fabric softening system include high molecular weight polyethylene oxide materials as disclosed in EP-A-0,299,575 and 0,313,146.

The level of smectite clay is usually 5-15% by weight,
More preferably in the range of 8 to 12% by weight, the substance is 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 are incorporated at levels of 0.5-5% by weight, usually 1-3% by weight, while high molecular weight polyethylene oxide materials and water-soluble cationic materials are 0.1-2% by weight, usually 0.15
It is added at a level of ~ 1.5% by weight. These substances are usually added to the spray-dried portion of the composition, and in some cases it is more convenient to add them as dry mix particles or spray them as a molten liquid on other solid components of the composition is there. The flexibility performance of the combination of cellulase, smectite clay and CTC was found to be synergistically enhanced.

Dye Transfer Inhibition The present invention also relates to a process for inhibiting dye transfer from one fabric with dissolved and suspended dye to another encountered during a fabric washing operation involving a colored fabric.

The combination of cellulase, polymeric dye transfer inhibitor and CTC has been found to provide a synergistic improvement in whiteness and maintenance of color.

Polymer Dye Transfer Inhibitor The detergent composition according to the present invention also contains 0.001 to 10% by weight, preferably 0.01 to 2%, more preferably 0.05 to 1% of a polymer dye transfer inhibitor. The polymeric dye transfer inhibitor is typically incorporated into detergent compositions to prevent the transfer of dye from the colored fabric onto the fabric washed therewith. These polymers have the ability to complex 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-vinyl pyrrolidone and N-vinyl imidazole,
Polyvinylpyrrolidone polymers, polyvinyloxazolidone and polyvinylimidazole or mixtures thereof. Addition of such a polymer also enhances the performance of the enzyme.

a) Polyamine N-oxide polymers Polyamine N-oxide polymers suitable for use comprise units having the structural formula: In the above formula, P is a polymerizable unit, to which an R-NO group can be bonded, or the R-NO group forms a part of the polymerizable unit, or a combination of both. A is NC (= O), C (= O) O, C = O, -O-,-
R is an aliphatic, ethoxylated aliphatic, aromatic, heterocyclic, cycloaliphatic group or a combination thereof, wherein N is S-, -N-, and x is 0 or 1.
The nitrogen of the -O 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: In the above formula, R1, R2, R3 are an aliphatic group, aromatic, heterocyclic,
An alicyclic group or a combination thereof, wherein x or / and y or / and z is 0 or 1, and the nitrogen of the NO group can be bonded to them, or the nitrogen of the NO group is Forms part of the group.

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 N-O groups form part of the polymerizable unit include those polyamine N-oxides in which R is selected from aliphatic, aromatic, cycloaliphatic or heterocyclic groups.
There are oxides. One class of polyamine N-oxides is the polyamine N-oxide group, wherein the nitrogen of the NO group forms part of the R group. Preferred polyamine N-oxides are when R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine, quinoline, acridine and derivatives thereof. Another class of polyamine N-oxides is the polyamine N-oxide group, wherein the nitrogen of the NO group is attached to the R group.

Other suitable polyamine N-oxides are those in which the N-O groups are attached to the polymerizable units. A preferred class of these polyamine N-oxides is the general formula (I) wherein R is an aromatic, heterocyclic or alicyclic group and the nitrogen of the NO functional group is part of the R group. Is a polyamine N-oxide. 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 functionality is attached to the R group. ).

Examples of these classes are polyamine oxides where 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 inhibition properties. Examples of suitable polymer backbones are polyvinyl, polyalkylene, polyester, polyether, polyamide, polyimide, polyacrylate, and mixtures thereof.

The amine N-oxide polymer of the present invention typically comprises
It has a ratio of amine to amine N-oxide of 10: 1 to 1,000,000. 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 2: 3 to 1: 1000000, more preferably 1: 4 to 1: 1000000,
Most preferably, it is 1: 7 to 1: 1000000. The polymers of the present invention actually include random or block copolymers where one monomer type is amine N-oxide and the other monomer type is amine N-oxide or otherwise. The amine oxide units of the polyamine N-oxide have a pKa <10, preferably a pKa <7, more preferably a pKa <6. Polyamine oxides can be obtained at 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 in the range of 500 to 1,000,000, preferably 1000 to 50,000, more preferably 2000 to 30,000, most preferably 3000 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 range of 5,000 to 1,000,000, preferably 20,000 to 200,000.

Highly preferred polymers for use in the detergent compositions according to the present invention are those selected from N-vinylimidazole N-vinylpyrrolidone copolymers, the polymers being 5000 to 50,000, more preferably 8000 to 30,000, most preferably 10,000. It has an average molecular weight range of 20,00020,000. Average molecular weight range, Barth HG & Mays JWChemi
cal Analysis, Vol. 113, “Modern Methods of Polymer C
haracterization ". Highly preferred N-vinylimidazole.
The N-vinylpyrrolidone copolymer is between 5000 and 50,000, more preferably between 8000 and 30,000, most preferably between 10,000 and 20,000.
It has an average molecular weight range of 00.

N characterized by having the above average molecular weight range
-Vinylimidazole N-vinylpyrrolidone copolymers exhibit excellent dye transfer inhibition while not adversely affecting the cleaning performance of the detergent compositions formulated therewith. The N-vinylimidazole N-vinylpyrrolidone copolymer of the present invention has a ratio of 1: 0.2, more preferably 0.8: 0.3,
Most preferably 0.6: 0.4 N-vinylimidazole to N
It has a molar ratio of vinylpyrrolidone.

c) Polyvinylpyrrolidone In the detergent compositions of the present invention, from about 2500 to about 400,000, preferably from about 5000 to about 200,000, more preferably from about 5000 to about 5
Polyvinylpyrrolidone ("PVP") having an average molecular weight of from 0,000, most preferably from about 5000 to about 15,000 may also be utilized. A suitable polyvinylpyrrolidone is the product name PVP K-1
5 (viscosity molecular weight of 10,000), PVP K-30 (average molecular weight of 40,000), PVP K-60 (average molecular weight of 160,000) and
ISP Corpor as PVP K-90 (average molecular weight of 360,000)
ation, New York, NY and Montreal, Canada. Other suitable polyvinylpyrrolidones commercially available from BASF Corporation include Sokalan HP165 and Soklan
alan HP12; polyvinylpyrrolidone known to the detergent industry (see, for example, EP-A-262,897 and EP-A-256,696).

d) Polyvinyl oxazolidone In the detergent composition of the present invention, polyvinyl oxazolidone may also be used as a polymer dye transfer inhibitor. The polyvinyl oxazolidone is present in an amount of about 2500 to about 400,000, preferably about 5000 to about 200,000, and more preferably about 5000 to about 5
It has an average molecular weight of from 0,000, most preferably from about 5000 to about 15,000.

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

Washing Method The process described herein consists of contacting a fabric with a washing liquid 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 5
It is carried out at 9595 ° C., especially at 10-60 ° C. The pH of the treatment liquid is preferably 7 to 11, particularly 7.5 to 10.5. Highly preferred p
H is 9-10.5.

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.

LAS: Sodium linear C ₁₂ alkylbenzene sulfonate TAS: Sodium tallow alkyl sulfate XYAS: Sodium C _1X -C _1Y alkyl sulfate SAS: C ₁₂ -C ₁₄ secondary (2,3) alkyl sulfate in the form of sodium salt APG: Formula C ₁₂ - (glycosyl) _{x (x} is a is 1.5) alkylpolyglycoside surfactants AEC: formula C ₁₂ ethoxy (2) carboxylate of alkyl ethoxy carboxylates surfactant SS: secondary of formula 2-butyl octanoic acid Soap surfactant 25EY: C ₁₂ − condensed with an average Y mole of ethylene oxide
Primary alcohols mainly linear in C ₁₅ 45EY: Average Y moles of ethylene oxide condensed with C ₁₄ -
C ₁₅ primarily straight chain primary alcohol XYEZS: mole per average Z moles of ethylene oxide condensed with C _1X -C _1Y sodium alkyl sulfate nonionic: from BASF Gmbh sold under the trade name Plurafax LF404, average ethoxylation degree 3.8 and the average propoxylation degree 4.5 of C ₁₃ -C ₁₅ mixed ethoxylated / propoxylated fatty alcohols CFAA: C ₁₂ -C ₁₄ alkyl N- methyl glucamide TFAA: C ₁₆ -C ₁₈ alkyl N- methyl glucamide silicate: Amorphous sodium silicate (SiO ₂ : Na ₂ O ratio =
2.0) NaSKS-6: Crystal-laminated silicate of the formula Na ₂ Si ₂ O ₅ Carbonate: anhydrous sodium carbonate phosphate: sodium tripolyphosphate MA / AA: 1: 4 maleic / acrylic acid copolymer,: average molecular weight about 80,000 polyacrylate: BASF GmbH and sold under the trade name PA30 from an average molecular weight of about 8000 of polyacrylate homopolymer zeolite a: hydration of formula _{Na 12 (AlO 2 SiO 2)} 12 · 27H 2 O having a primary particle size of 1~10μm range Sodium aluminosilicate zeolite MAP: zeolite P type alkali metal aluminosilicate having a silicon to aluminum ratio of 1.33 or less citrate: trisodium citrate dihydrate citrate: citric acid perborate: empirical formula NaBO ₂ · H ₂ O ₂ anhydrous Sodium perborate monohydrate bleach PB4: anhydrous sodium perborate tetrahydrate percarbonate: empirical formula 2Na ₂ CO ₃ · 3H ₂ O ₂ in anhydrous sodium percarbonate bleach TAED: tetraacetylethylenediamine Paraffin: Paraffin oil amylases sold under the tradename Winog 70 from Wintershall: Novo Nordisk A / S starch sold under the tradename Termamyl from degradation Enzyme Lipase: Novo Nordisk A / S from Lipolase, Lipol
Lipolytic enzyme sold by ase Ultra Peroxidase: Peroxidase enzyme POD Cellulase: Cellulolytic enzyme sold by Novo Nordisk A / S under the trade name Carezyme or Celluzyme Carezyme1T (1000CEVU / g) Celluzyme 1T (1000CEVU / g) CMC : Sodium carboxymethylcellulose HEDP: 1,1-hydroxyethanediphosphonic acid DETPMP: diethylenetriaminepenta (methylenephosphonic acid) sold by Monsanto under the trade name Dequest 2060 PVP: polyvinylpyrrolidone polymer EDDS: ethylenediamine-N in sodium salt form , N'-disuccinic acid (S, S) isomer Foaming inhibitor: 25% paraffin wax Mpt 50 ° C, 17% hydrophobic silica, 58% paraffin oil Granular foaming inhibitor: Granular 12% silicone / silica, 18
% Stearyl alcohol, 70% starch SCS: Sodium cumene sulfonate CTC: Coprinus cinereus peroxidase 0.3POXU / ml 4M PPT, 0.5% PB1 + release agent (glycerol stearate coating) CTCI: 0.5% PB1 POD (2PODU / ml) 50M phenol sulfonate Sulfate: anhydrous sodium sulfate HMWPEO: high molecular weight polyethylene oxide PGMS: polyglycerol monostearate having the trade name of Radiasurf248 TAE25: tallow alcohol ethoxylate (25) PEG-6: polyethylene glycol having a molecular weight of 600 Example 1 Example of a granular detergent Manufactured according to the 6d composition without CTCI.
POD granules in CTCI were applied without release agent. The following washing tests were performed: Conditions: Miele washing machine W756 40 ° C washing cycle Water hardness: 15 grains / US gallon Detergent used: 120 g / washing pH = 8.5 (in washing liquid) Input composition: 2 kg cotton / polycotton fabric Tracer to assess regeneration (tracer was a piled cotton fabric) WFK11A test fabric to determine tensile strength loss Cellulase concentration: 165CEVU / Carezume IT Wash fabric in 12 wash cycles, then regenerate color and pull The strength was evaluated. The CTCI system was added to the cleaning solution after 0 min (Treatment B), 5 min (Treatment C), and 10 min (Treatment D).

The tests demonstrate that treatments A, C, and D produce similarly high color reproduction effects, but treatment B is inadequate.

However, treatment A has a significantly higher tensile strength loss than treatments C and D. Therefore, the optimal release profile for the CTCI system is 5-10 min,
No significant increase in tensile strength loss relative to cellulase-free treatment E while exerting an effect equal to A.

Example 2 The following washing machine test was performed. The first process is 10CEVU /
Cellulase levels correspond to control treatments tested in the absence of CTC. Treatment 2 consists of the same level of cellulase and CTC (3
Described). Process 3 is similar to process 2 except that CTC is not released in a controlled manner. Cellulase activity is monitored during the test by the method described in (2).

⁽¹⁾ Cellulase is Carezyme ^™ supplied by Novo Nordisk. The activity of the enzyme granules is 1000 Cevu / g.

⁽²⁾ Cellulase is quantified in the detergent matrix (5) by a two-step operation. The β- 1-4 glycosidic bond of insoluble cellulase (cotton lint) is randomly hydrolyzed by cellulase in the presence of cellobiase to give D-
Get glucose. The concentration of D-glucose, which is proportional to cellulase activity, is determined indirectly by spectral analysis at 340 nm using Abbott commercial enzyme test kits (hexokinase and glucose-6-phosphate dehydrogenase) in the presence of NAD ⁺ . Standard Carezyme ^™ was used for calibration, and results are expressed as% of standard Carezyme ^™ .

⁽³⁾ Description of CTC system: Peroxidase from Coprinus cinereus is supplied by Novo Nordisk. The concentration of peroxidase enzyme in the washing solution is 0.3 POXU / ml. The peroxidase enzyme is delivered in the form of controlled release granules (granule activity is 30 KPOXU / g). The enhancer is PPT (phenothiazine-10-propionic acid). The concentration of the PPT promoter is 4 μM, and the concentration of PB1 in the washing solution is 35 ppm. The source of hydrogen peroxide is perborate monohydrate (PB1).

⁽³⁾ Test conditions: Granule detergent is added to Miele washing machine as small granules. The detergent ⁽⁶⁾ concentration in the cleaning solution is 8000 ppm. The washing conditions are as follows: water temperature is 40 ° C., water hardness is 8 grains / US gallon. The test runs without input.

⁽⁵⁾ The composition of the detergent used in the test is described in the following table. The nonionic surfactant system used is Marlip
al24 / 50 (C24EO5) and C16 / C18 glucose amide 2.
7: 1 mixture. The HLB of these surfactants was determined to be ≧ 10. The pH of the detergent was determined to be 9.5 in the wash liquor.

% By weight of total formulation 45AS 8.5 25E3S 2.1 24E5 7.1 C16 / C18 glucose amide 2.6 zeolite 23.1 citrate 7.7 citric acid 5.3 Na-SKS-6 7.5 carbonate 3.1 bicarbonate 4.0 sulfate 5.94 polyacrylate 5.1 CMC 0.36 PVNO / PVPVI 0.19 protease 0.87 lipase 0.24 amylase 0.8 EDDS 0.5 suds suppressor 0.41 water and the rest The test results show that control treatment 1 has relatively stable cellulase activity in the wash liquor. Controlled release
Treatment 2 with CTC shows sufficient cellulase activity in the first 5 minutes of washing. After 5 minutes, CTC is released, inactivating cellulase. However, processing 3
Shows a significant loss of cellulase activity immediately after the start of washing. Consequently, process 3 is inadequate. Therefore, Treatment 2 containing controlled release CTC is highly desirable because it shows the best cellulase activity during washing.

Example 3 The following multi-cycle washing machine test was performed under the washing conditions described in (5). The first treatment corresponds to a control treatment in which a cellulase level of 10 CEVU / is tested in the absence of CTC. Treatment 2 contained 5 times higher levels of cellulase and CTC (3
Described). Treatment 3 is the same as treatment 2, but without CTC. The tensile strength loss and depile effect on the cotton fabric is monitored during the test.

⁽¹⁾ Cellulase is Carezyme ^™ supplied by Novo Nordisk. The activity of the enzyme granules is 1000 Cevu / g.

⁽²⁾ Description of CTC system: Peroxidase from Coprinus cinereus is supplied by Novo Nordisk. The concentration of peroxidase enzyme in the washing solution is 0.3 POXU / ml. The peroxidase enzyme is delivered in the form of controlled release granules (granule activity is 30 KPOXU / g). The enhancer is PPT (phenothiazine-10-propionic acid). The concentration of the PPT promoter is 4 μM, and the concentration of PB1 in the washing solution is 35 ppm. The source of hydrogen peroxide is perborate monohydrate (PB1).

⁽³⁾ Depilling benefits are determined by visual grading performed on cotton socks prewashed 10 times with detergent to make pills on the surface. Depilation is measured after 6 washing cycles. Depilation is measured on a scale from 1 (complete pill removal) to 5 (high level pill). Pilgrade differences of ≧ 1 are considered significant.

^{(4) The} standardized tensile strength loss (TSL) is measured with an Instron apparatus using a standard cloth. In the above example, treatment 1 was the control (100), which was washed 30 times (ie, 3
The force required to tear a piece of fabric (of the 0 wash cycle). The washing conditions are described in (5). Differences> 10% are considered significant.

⁽⁵⁾ Test conditions: Granule detergent is added to Miele washing machine as small granules. The detergent ⁽⁶⁾ concentration in the cleaning solution is 8000 ppm. The washing conditions are as follows; the water temperature is 40 ° C. and the water hardness is 8 grains / US gallon. The test runs in the presence of a 3 kg charge of clean fabric (polyester, cotton, polycotton).

⁽⁶⁾ The composition of the detergent used in the test is described in the following table. The nonionic surfactant system used is Marlip
al24 / 50 (C24EO5) and C16 / C18 glucose amide 2.
7: 1 mixture. The HLB of these surfactants was determined to be ≧ 10. The pH of the detergent was determined to be 9.5 in the wash liquor.

% By weight of total formulation 45AS 8.5 25E3S 2.1 24E5 7.1 C16 / C18 glucose amide 2.6 zeolite 23.1 citrate 7.7 citric acid 5.3 Na-SKS-6 7.5 carbonate 3.1 bicarbonate 4.0 sulfate 5.94 polyacrylate 5.1 CMC 0.36 PVNO / PVPVI 0.19 protease 0.87 lipase 0.24 amylase 0.8 EDDS 0.5 suds suppressor 0.41 water and the rest The test results show that control treatment 1 has a relatively low level of effect. The effect profile of Treatment 1 is poor compared to the high level effects seen in Treatments 2 and 3. However, treatment 3 shows a significant level of TSL as compared to treatments 1 and 2. Consequently, process 3 is inadequate. Thus, Treatment 2 containing CTC is highly desirable in terms of effectiveness, as it is not inadequate in the risk area.

Example 4 A granular fabric cleaning composition according to the present invention was prepared as follows: Example 5 A granular fabric cleaning composition according to the present invention was prepared as follows: Example 6 A granular fabric cleaning composition according to the present invention, which is particularly useful in washing colored fabrics, was prepared as follows: Example 7 A granular fabric cleaning composition according to the present invention was prepared as follows: Example 8 A compact granular fabric cleaning composition according to the present invention was prepared as follows: Example 9 “Softening Through the Wash” (soften
A granular fabric cleaning composition according to the present invention, which exerts the ability to ing through the wash, was prepared as follows: Example 10 A heavy liquid fabric cleaning composition suitable for use in pretreatment of a stained fabric and for use in a machine washing process according to the present invention was prepared as follows: Example 11 A granular heavy liquid cleaning composition according to the present invention was prepared as follows: Example 12

──────────────────────────────────────────────────続 き Continued on the front page (72) Inventors André, Christian, Convents Ohio, Cincinnati, Humphrey, Rhode, USA, 9696 (72) Inventor Olivier, Pakat, Belgium 1853, Strombeek-Bevel, Bus, 6, Belgrade, 2 (56) references US Pat. No. 5,445,755 (US, A) US Pat. No. 5,451,337 (US, A) US Pat. No. 5,460,747 (US, A) WO 93/9224 (WO, A1) WO 94/12621. (WO, A1) (58) Field surveyed (Int. Cl. ⁷ , DB name) C11D 3/386 C11D 3/39 C11D 3/395

Claims (12)

(57) [Claims] (1) cellulase; (ii) a) peroxidase, b) 10-phenothiazinepropionic acid (PPT), 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) And c) a cellulase terminator composition comprising a hydrogen peroxide source, wherein the cellulase activity is within 5 minutes of the start of the wash cycle. The cellulase activity is controlled so that the cellulase activity is less than 50% within 5-10 minutes from the start of the wash cycle and less than 10% of the residual cellulase activity reaches 15 minutes after the wash cycle. A detergent composition characterized in that: 2. The detergent composition according to claim 1, wherein at least one of the compounds a), b) and c) is incorporated in a release agent. 3. The cellulase is Humicola insolens DSM1800.
3. The detergent composition according to claim 1, which is a 43 kD endoglucanase derived from. 4. The hydrogen peroxide source is peroxygen bleach containing percarbonate and perborate.
The detergent composition according to claim 1. 5. The detergent composition according to claim 1, further comprising an anionic surfactant and a nonionic surfactant. 6. The weight ratio of anion to nonion is from 10: 1 to 1: 2.
The detergent composition according to claim 5, which is: 7. The detergent composition according to claim 1, which has a pH of 8 to 10. 8. The method of claim 1, further comprising a protease.
The detergent composition according to any one of claims 1 to 7. 9. The detergent composition according to claim 1, further comprising a clay. 10. The detergent composition according to claim 1, further comprising a cationic surfactant. 11. The detergent composition according to claim 1, which is in the form of a liquid, granule, gel, paste or solid product. 12. A detergent additive comprising the detergent composition according to claim 1.