DE69620003T3 - RELEASE SYSTEMS - Google Patents

Description

Field of the invention

The The present invention relates to glassy particles containing agents, which for laundry and cleaning products useful are, and laundry and cleaning products containing these glassy particles.

Field of the invention

laundry and cleaning products continue to evolve, not just one better cleaning, but also more benefits, such as color and fabric care and aesthetic Properties to provide. It can but new resources are being developed that provide such results often is the stability in the product or the releasability during washing for their use problematic. A big Variety of carrier systems and coating technologies has been developed to cope with this needs to react. Often such systems are generally unusable.

To the Example is continued to search for methods and compositions Which has effectively and efficiently a fragrance from a wash bath transferred to tissue surfaces. As can be seen from the literature, such as those mentioned below is, various methods of fragrance release are developed Service. U.S. Patent 4,096,072, Brock et al., Issued June 20, 1978, teaches a method of releasing tissue conditioning Means, including a perfume, over the washing and drying cycle with the aid of a fatty quaternary ammonium salt. U.S. Patent 4,402,856 Schnoring et al., Issued September 6, 1983, teaches a microencapsulation technique, which includes the formulation of a wrapping material, which the outward diffusion of a fragrance out of the capsule only allowed at certain temperatures. U.S. Patent 4,152,272, Young, issued May 1, 1979, teaches the inclusion of a perfume in waxy Particles to the perfume during storage in dry compositions and during the To protect washing process. The fragrance diffuses infiltrating in the dryer through the wax on the tissue. U.S. Patent 5,066,419, Walley et al., November 19 1991 teaches a fragrance which is water insoluble non-polymeric carrier material dispersed and in a protective wrapping by coating with a water-insoluble friable coating material encapsulated. U.S. Patent 5,094,761, Trinh et al., Issued to March 10th 1992, teaches a clay-protected fragrance / cyclodextrin complex, which perfume benefits for at least partially moistened textiles.

One another method of releasing a fragrance in the wash cycle includes combining the perfume with an emulsifying agent and a water-soluble polymers, forming the mixture into particles and adding them to a laundry detergent composition as disclosed in U.S. Patent 4,209,417, Whyte, issued June 24, 1980; U.S. Patent 4,339,356, Whyte, issued July 13, 1982; and US patent No. 3,576,760, Gould et al., Issued April 27, 1971 is.

Of the Perfume may also be on a porous carrier material, such as a polymeric Material, be adsorbed, as in the GB patent publication 2,066,839, Bares et al., Published on July 15, 1981. Scents are also on Clay or zeolite material is then adsorbed, which is then in particulate cleaning compositions is added. In general, the preferred zeolites were Type A or 4A with a nominal pore size of about 4 Angstrom units. It is now assumed that the Perfume adsorbed on zeolite A or 4A on the zeolite surface being relatively little of the perfume actually in the zeolite pores is adsorbed. Although the adsorption of a fragrance on zeolite or polymeric carriers possibly a certain improvement over the addition of an undiluted fragrance in admixture with cleaning compositions in the industry still looking for improvements in terms of Length of the Storage period of the laundry compositions without a loss of perfume properties with respect to intensity or the amount of a fragrance which is released on textiles, and the persistence of perfume fragrance on the treated tissue surfaces searched.

Combinations of fragrances, generally of the larger pore size zeolites X and Y, are also taught in the art. East German Patent Publication No. 248,508, published August 12, 1987, relates to perfume dispersing devices (eg, an air freshener) containing a faujasite-type zeolite (eg, zeolite X and Y) loaded with perfumes. It is noted that the critical molecular diameters of the perfume molecules are between 2 to 8 angstroms. East German Patent Publication No. 137,599, published September 12, 1979, also teaches compositions for use in powdered detergents to provide the thermoregulated release of fragrance. The zeolites A, X and Y are proposed for use in these compositions. These prior teachings are described in recently filed European Applications Publication No. 535,942, issued April 7, 1993, and Publication No. 536,942, published April 14, 1993, by Unilever PLC, as well as in US Patent No. 5,336,665, issued on May 9, 1993. August 1994 to Garner-Gray et al.

compositions for one effective fragrance release are disclosed in WO 94/28107 on December 8, 1994, by The Procter & Gamble Company. These compositions include zeolites having a pore size of at least 6 angstroms (e.g. Zeolite X or Y), wherein the fragrance is releasable in the pores of the zeolite and a matrix coated is with the perfumed zeolite, comprising a water-soluble (Removable by washing) composition, wherein the perfume essentially insoluble comprising from 0 to about 80% by weight of at least one solid polyol, containing more than 3 hydroxyl groups, and about 20 to about 100 Wt .-% of a fluid diol or polyol, wherein the perfume in essentially insoluble and wherein the solid polyol is substantially soluble.

US Patent 5,258,132, issued November 2, 1993; and U.S. Patent 5,230,822, issued July 27, 1993, both to Kamel et al., relate to solid Core particles which are encapsulated in a monolayer of paraffin wax, wherein the wax has a melting point of from about 40 ° C to about 50 ° C and the solids content is 100 to about 35% at 40 ° C and 0 to about 15% at 50 ° C. It will said that this coating the Extended period, while the encapsulated particles remain active in an aqueous environment. U.S. Patent 5,141,664 issued August 25, 1992 to Corring et al. relates to cleaning compositions comprising a clear gel with opaque particles of an active material, which in the Gel evenly dispersed and suspended. The active ingredient material is of a protective nature Substance, like an encapsulating layer, surrounded.

US Patent 2,809,895 issued to Swisher on October 15, 1957, relates to fixed, an essential oil containing compositions for use as an ingredient various foods, pharmaceuticals, fragrances, soaps and cosmetics are suitable. It is said that these are the formation of an emulsion lock in, consisting of a finely dispersed, essential oil and corn syrup, which is solidified and further treated to form a particulate, oxidation protected essential oil product to obtain. For the process becomes described that he emulsifying an essential oil to which an antioxidant and a dispersing agent have been added in the corn syrup solids solution and forming a particulate, includes solid emulsion.

US 3,971,852 describes a cellular Matrix having an aroma or fragrance oil in the cells thereof. It is said that one stability is achieved, so that the extractable oil essentially not over 5%, based on the wax of a glassy matrix with a plastic or flowable area, which oil spill, like cracks in the cell walls, prevented or sealed.

EP-A-57088 describes storage-sensitive cleaning additives which are in a water-soluble Matrix of amorphous phosphate are included.

In spite of such efforts There is still a need for particulate delivery systems which capable of perfumes in laundry and cleaning compositions, especially granular Cleaning compositions and granular cleaning compositions for automatic dishwashing include. Especially desirable are those particles which are under storage conditions of high heat and moisture are stable. Preferred for use are those Compositions also harmful to water-sensitive fragrances Protect water.

background of the field

U.S. Patent 4,539,135, Ramachandran et al., Issued September 3, 1985, discloses particulate laundry compositions comprising a clay or zeolite material which carries a fragrance. U.S. Patent 4,713,193, Tai, issued December 15, 1987, discloses a free-flowing particulate cleaning additive comprising a liquid or oily additive with a zeolite material. Japanese Patent HEI 4 [1992] -218583, Nishishiro, published August 10, 1992, discloses controlled release materials including perfumes plus zeolites. U.S. Patent 4,304,675, Corey et al., Issued December 8, 1981, teaches a method and composition comprising zeolites for deodorizing articles. East German Patent Publication No. 248,508, published August 12, 1987; East German Patent Publication No. 137,599, published September 12, 1979; European Applications Publication No. 535,942, published April 7, 1993, and Publication No. 536,942, published April 14, 1993, by Unilever PLC; U.S. Patent 5,336,665, issued August 9, 1994 to Garner-Gray et al .; WO 94/28107, published December 8, 1994; U.S. Patent 5,258,132, issued November 2, 1993, and U.S. Patent 5,230,822, issued July 27, 1993, both to Kamel et al .; U.S. Patent 5,141,664, issued August 25, 1992, to Corring et al .; and U.S. Patent 2,809,895, issued October 15, 1957 to Swisher.

Summary of the invention

The The present invention relates to a laundry or cleaning composition, as defined in claim 1.

Full Description of the invention

The The present invention relates to a cleaning composition comprising a release system in the form of a glassy particle, which Includes fragrances, which for laundry or cleaning compositions are useful. The glass is derived from one or more at least partially water-soluble Hydroxyl compounds, wherein at least one of the hydroxyl compounds a glass transition temperature, Tg, in anhydrous, not plasticized state of 0 ° C or higher. Furthermore, the glassy particle has a hygroscopicity value less than 80%. These release systems are in granular detergent compositions especially useful, especially about laundry scents release, which in small proportions in the compositions useful are.

• (i) alle natürliche oder synthetische Gummen, wie Alginatester, Carrageen, Agar-Agar, Pektinsäure, und natürliche Gummen, wie Gummi arabicum, Tragantgummi und Karaya-Gummi;
• (ii) Chitin; und
• (iii) Chitosan; sowie
• (iv) Cellulose und Cellulosederivate. Beispiele schließen ein: i) Celluloseacetat und Celluloseacetatphthalat (CAP); ii) Hydroxypropylmethylcellulose (HPMC); iii) Carboxymethylcellulose (CMC); iv) alle enterischen/aquatischen Überzüge; sowie Mischungen hiervon.

The at least partially water-soluble hydroxyl compounds useful herein are selected from the following classes of materials:

• (i) any natural or synthetic gums such as alginate esters, carrageenan, agar-agar, pectic acid, and natural gums such as gum arabic, gum tragacanth and karaya gum;
• (ii) chitin; and
• (iii) chitosan; such as
• (iv) cellulose and cellulose derivatives. Examples include: i) cellulose acetate and cellulose acetate phthalate (CAP); ii) hydroxypropyl methylcellulose (HPMC); iii) carboxymethylcellulose (CMC); iv) all enteric / aquatic coatings; and mixtures thereof.

materials within these classes which are not at least partially water-soluble and a glass transition temperature, Tg, below the lower limit of 0 ° C, are usable here only if in such quantities with the hydroxyl compounds useful here, which the required higher Tg are mixed, so that the produced glassy Particles have the required hygroscopicity value of less than 80% having.

The Glass transition temperature, usually abbreviated as "Tg", one is sufficient well-known and easy to determine property for glassy Materials. This transition is considered to be corresponding to the liquefaction a material in a glassy state to a material in the liquid state when warming over the Tg range described. It is not a phase transition like melting, evaporation or sublimation. [See. Brennan William P., "What is a Tg? A Review of the Scanning Calorimetry of the Glass Transition ", Thermal Analysis Application Study # 7, Perkin-Elmer Corporation, March 1973.] The measurement of Tg is made in a simple manner by using of a differential scanning calorimeter.

For the purpose In the present invention, the Tg of Hydroxylverbin applications for the anhydrous compound containing no plasticizer (the affected by the measured Tg of the hydroxyl compound). The glass transition temperature is also detailed described by Peyser P., "Glass Transition Temperatures of Polymers ", Polymer Handbook, Third Edition, Brandrup J. and Immergut E.H. (Wiley-Interscience, 1989), pp. VI / 209-VI / 277.

At least one of the hydroxyl compounds which in the glassy according to the invention Particles useful are, one must Tg in anhydrous, not plasticized state of at least 0 ° C, and for particles without a moisture barrier layer preferably at least 20 ° C, preferably at least 40 ° C, stronger preferably at least 60 ° C and most preferably at least about 100 ° C. It is also preferred that these Low temperature compounds, preferably in the range of 50 ° C to 200 ° C, and more preferably in the range of 60 ° C up to 160 ° C, are processable.

The "hygroscopicity value" as used herein indicates the degree of moisture absorption by the glassy Particles measured by the percentage increase in the weight of the particles according to the following Test methods. The for the glassy invention Particle required hygroscopicity value is determined by that 2 g of particles (with particle sizes of about 500 μm; without any moisture barrier layer) into an open Petri dish container Conditions of 32 ° C (90 ° F) and 80% relative humidity during a period of 4 weeks. The percentage increase the weight of the particles at the end of this period is the hygroscopicity value of the particles as used here. Preferred particles have a hygroscopicity value less than 50%, stronger preferably less than 10%, on.

The glassy according to the invention Particles typically comprise at least in part from 10 to 99.99% water-soluble Hydroxyl compounds, preferably 20 to 90%, and more preferably 20 to 75%. The glassy invention Particles also typically comprise from 0.01% to 90% of perfumes, which for laundry or cleaning compositions useful are, preferably 10 to 80% and more preferably 25 to 80%.

Of the Perfume is preferably in the perfume carrier material in such Extent included or is borne by him, that not more than 70% by weight, preferably not more than 45% by weight, of the entire fragrance material free from the fragrance carrier material available; and wherein the glassy particle has a moisture content, as produced, of not more than 10% by weight.

The The composition described in the preceding paragraph may be in the form a laundry detergent, Laundry detergent additive or fabric softener, wherein the hydroxyl compound or Hydroxyl compound mixture which forms the glass as a compressible fluid at temperatures in the range of 60 to 160 ° C is processable; no more as 40% of the total fragrance free of the fragrance carrier material available; the glassy particle has a moisture content as prepared, not more than 7%; and the glass transition temperature, Tg, at least a hydroxyl compound is at least 45 ° C.

method for producing the glassy particles of the invention derived from the field of sugar confectionery production. Such procedures shut down for example, in U.S. Patent 2,809,895, issued October 15 1957 to Swisher.

perfume

So As used here, the term "perfume" is used to refer to any fragrant To indicate material, which subsequently in the aqueous bath released and / or transferred to textiles coming into contact with it becomes. The perfume is predominant liquid at ambient temperatures. A big Variety of chemicals are for Fragrance applications, including materials such as aldehydes, Ketones and esters. Common ones are naturally occurring vegetable ones and animal oils as well as excreted products comprising complex mixtures of various chemical Components which are known for use as fragrances. The fragrances can be relatively simple in terms of their composition or can be highly differentiated complex mixtures of natural and synthetic chemical components, all of which are selected the existence desirable Scent is provided. Typical fragrances may be woody / earthy, for example Basic materials containing exceptional Materials such as sandalwood, civet and patchouli oil include. The perfumes can slightly flowery scents be, e.g. Rose extract, violet extract and lilac. The perfumes can also be formulated so that desirable fruity fragrances, e.g. Lime, lemon and orange, are provided. Each chemically compatible material, which is a pleasant or otherwise desirable Smell exudes, can be perfumed in the present Compositions are used.

fragrances shut down also pro-fragrances such as Acetal-Pro fragrances, Ketal-Pro fragrances, Ester-Pro fragrances (e.g., Digeranyl succinate), hydrolyzable, inorganic-organic Pro fragrances and mixtures thereof, a. These pro-fragrances can release the fragrance material as a result of simple hydrolysis or can pH-change-triggered Pro-fragrances (e.g., pH drop) or enzymatically-releasable pro-fragrances be.

preferred Perfume agents which are useful here are defined as follows.

For the purposes of the present invention, it is important for compositions which the aq The mediums of the laundry process are exposed to identify and define several characteristic parameters of fragrance molecules: their longest and widest dimensions; the cross-sectional area, the molar volume; and the molecular surface. These values are reported for the individual perfume molecules using the CHEMX program (from Chemical Design, Ltd.) for molecules in a least energy conformation, as determined by the CHEMX optimized standard geometry, and using the van der Waal standard atomic radii calculated. The definitions of the parameters are as follows:
"Longest dimension": the largest distance (in angstroms) between the atoms in the molecule, supplemented by their van der Waal radii.
"Widest dimension": the largest distance (in angstroms) between the atoms in the molecule, supplemented by their van der Waal radii, in terms of the projection of the molecule on a plane perpendicular to the "longest" axis of the molecule.
"Cross-sectional area": Area (in square Angstrom units) that is filled by the projection of the molecule onto a plane perpendicular to the longest axis.
"Molar Volume": the volume (in cubic Angstrom units) occupied by the molecule in its lowest energy configuration.
"Molecule surface": freely chosen units, which are scaled to square Angstrom units (for calibration purposes, the molecules methylbeta naphthyl ketone, benzyl salicylate, and camphor rubber have a surface area of 128 2, 163.5 ± 3, and 122.5 ± 3 units, respectively on).

The Shape of the molecule is for the inclusion too important. For example, a symmetrically perfectly spherical molecule suitable for inclusion in the Zeolite channels is sufficiently small, no preferred orientation and will enclosed by each access direction. However, there are molecules for that exceed the pore size, a preferred "access direction" for inclusion. The calculation of the relationship from volume to surface of a molecule is used here to indicate the "shape index" for a molecule. The higher the value is the more bow-shaped the molecule.

For the purposes of the present invention, perfume agents are classified according to their ability to be entrapped in zeolite pores and therefore their usefulness as components for release from the zeolite carrier through an aqueous environment. The graphical representation of these agents on a plane in volume-to-surface area versus cross-sectional area area allows suitable grouping of agents according to their zeolite containment. In particular, for the zeolite X and Y carriers of the present invention, agents are included when they are below the limit (hereinafter referred to as the "inclusion limit") which is defined by the equation: Y = 0.01068x + 1.497 where x is the cross-sectional area and y is the volume-to-surface ratio. Agents below the inclusion limit are referred to herein as "releasable agents"; those means which are above the limit are referred to herein as "non-releasable means".

For containment during washing, releasable agents are retained in the zeolite carrier as a function of their affinity for the carrier relative to competing releasable agents. The affinity is affected by the size, hydrophobicity, functionality, volatility etc. of the molecule and can be affected by interactions between releasable agents within the zeolite support. These interactions allow for better enclosure during washing for the included mixture of releasable agents. More specifically, according to the present invention, the use of releasable agents having at least one dimension which closely matches the pore size of the zeolite carrier slows down the loss of other releasable agents in the aqueous wash environment. Releasable agents which are effective in this manner are referred to herein as "blocking agents" and are defined here in terms of the volume to surface area versus cross sectional area ratio as such releasable agents which fall below the inclusion limit (as defined above), but above the limit (referred to herein as the "blocker boundary") which is defined by the equation: y = 0.01325x + 1.46 where x is the cross-sectional area and y is the volume-to-surface ratio.

For compositions of the invention employing zeolites X and Y as carriers, all releasable agents below the "inclusion limit" can be delivered and released by the compositions of the present invention, the preferred materials being those described under the "Blo Mixtures of blocking agents and other releasable agents are also preferred Bleaching detergent bleach mixtures useful in the laundry particles of the present invention preferably comprise from 5 to 100% (preferably from 25 to 100%, more preferably from 50 to 100%). releasable agents; and preferably 0.1 to 100% (preferably 0.1 to 50%) of blocking agent, based on the weight of the laundry detergent composition.

It it is obvious that compositions according to the invention, whereby fragrance agent is released by the compositions will require a sensory perception, thus, to the consumer an advantage is evident. For the fragrance compositions of the invention have the most preferred perfume agents which are useful herein a perceptibility threshold (measured as odor threshold limits ("ODT") under carefully controlled GC conditions, as described in detail below) of less than or equal to 10 parts per trillion ("ppb") on. Medium with ODT values between 10 ppb and 1 part per million ("ppm") will be less prefers. Agents with ODT values above 1 ppm are preferred avoided. Fragrance mixtures for laundry washing, which for the Wäschewaschteilchen invention useful preferably comprise 0 to 80% of ODT release agents between 10 ppb and 1 ppm and 20 to 100% (preferably 30 to 100%; stronger preferably 50 to 100%) releasable agents with ODT values of less as or equal to 10 ppb.

Prefers are also fragrances which during carried the washing process and then into the air around the dried fabrics (e.g. as the space around the textiles during storage) is released become. This makes the transport of the fragrance from the zeolite pores out with a subsequent Distribution in the air around the textiles required. preferred Perfume agents are therefore based on their volatility further marked. The boiling point is here as a measure of volatility used, and preferred materials have a boiling point of less than 300 ° C on. Perfume mixtures for the laundry, which for the Wäschewaschteilchen invention useful preferably comprise at least 50% releasable agents a boiling point of less than 300 ° C (preferably at least 60%; stronger preferably at least 70%).

preferred laundry particle include in addition Compositions wherein at least 80%, and more preferably at least 90% the releasable funds have a "C1ogP value" greater than 1.0. ClogP values are obtained as follows.

Calculation of C1ogP

These Perfume ingredients are characterized by their octanol / water partition coefficient P marked. The octanol / water partition coefficient of a Perfume ingredient corresponds to the ratio between its equilibrium concentration in octanol and in water. Because the distribution coefficients of most Perfume ingredients are big, they become more suitable in the form of their logarithm to the base 10, logP, specified.

Of the logP value of many perfume ingredients has been described: to Example contains the Pomona92 database, available Daylight Chemical Information Systems, Inc. (Daylight CIS), many values together with references in the original literature.

The However, logP values are more suitably calculated by the "CLOGP" program, which is also calculated by Daylight CIS available is. This program also lists experimental logP values when they are available in the Pomona92 database. The "calculated logP value" (ClogP) is determined by the fragment approach of Hansch and Leo (see Leo A., in Comprehensive Medicinal Chemistry, Vol. 4, Hansch C., Sammens P.G., Tylor J.B. and Ramsden C.A., Eds., p. 295, Pergamon Press, 1990). The fragment approach Based on the chemical structure of each perfume ingredient and taken into account the number and type of atoms, the atomic compound and the chemical Binding. The ClogP values, which are the most reliable and most common used estimates for this physicochemical property, instead of the experimental logP values used in the selection of perfume ingredients become.

Determination of odor detection limits:

The gas chromatograph is characterized in that it determines the exact volume of material injected with the syringe, the exact split ratio, and the hydrocarbon reaction using a hydrocarbon standard of known concentration and chain length distribution. The air flow rate is accurately measured and, assuming that the inhalation time in humans is 0.2 minutes, the volume taken is calculated. Because the exact Concentration in the detector is known at any time, the inhaled mass per volume and therefore the concentration of a material is known. To determine if a material has a limit below 10 ppb, solutions are released in the recalculated concentration at the sniffer opening. A panelist sniffs at the GC outflow port and identifies the retention time when a scent is perceived. The average across all participants determines the limit of perceptibility.

• GC: 5890-Reihe II mit FID-Detektor
• 7673-Autosampler
• Säule: J & W Scientific DB-1
• Länge: 30 Meter; Innendurchmesser: 0,25 mm; Schichtdicke: 1 μm

The necessary amount of an analyte is injected into the column to achieve a concentration of 10 ppb in the detector. Typical gas chromatograph parameters for determining odor detection limits are listed below.

• GC: 5890 series II with FID detector
• 7673 autosampler
• Column: J & W Scientific DB-1
• Length: 30 meters; Inner diameter: 0.25 mm; Layer thickness: 1 μm

Method:

• Partial injection: distribution ratio 17/1
• Autosampler: 1.13 microliters per injection
• Column flow: 1.10 ml / minute
• Air flow: 345 ml / minute
• Inlet temperature: 245 ° C
• Detector temperature: 285 ° C

Temperature information:

• initial Temperature: 50 ° C
• Rate: 5 ° C / minute
• Final temperature: 280 ° C
• End time: 6 minutes

Leading assumptions:

• 0.02 minutes per sniff
• Carries GC air for sample dilution at

Perfume fixatives

Optional For example, the perfume may be combined with a perfume fixative. The perfume fixative materials used herein are Several criteria are identified, which they use in the implementation of this Make the invention particularly suitable. It will be dispersible, toxicological acceptable, non-irritating, fragrance-inert, degradable and / or from sources of renewable raw materials and relatively odorless additions used. It is believed that perfume fixative the evaporation of stronger volatile Slow down components of the fragrance.

Examples Close suitable fixative Representatives who are elected are from the group consisting of diethyl phthalate, musk and Mixtures thereof. If used, the perfume fixative comprises 10 to 50 wt .-%, preferably 20 to 40 wt .-%, of the perfume. In preferred glassy particles, the perfume comprises 50 to 100 % By weight releasable agent.

Perfume carrier materials

So as used herein, "perfume carrier materials" refers to any material which is capable a perfume agent for the inclusion in to carry the glassy particles. Such materials include porous solids one which is chosen are from the group consisting of amorphous silicates, crystalline non-layered silicates, layer silicates, calcium carbonates, Sodium carbonates, clays, zeolites, sodalites, alkali metal phosphates, macroporous Zeolites, chitin microspheres, Carboxyalkylcelluloses, carboxyalkylstars, cyclodextrins, porous starches and Mixtures thereof.

Preferred support materials have a surface area of at least 50 m ² / g and preferably not greater than 1700 m ² / g.

Preferred perfume carrier materials are zeolite X, zeolite Y and mixtures thereof. As used herein, the term "zeolite" refers to a crystalline aluminosilicate material. The structural formula of a zeolite is based on the crystalline unit cell, the smallest unit of a structure, which is represented by: Mm / n [(AlO2) m (SiO2y] · xH2O where n is the valency of the cation M, x is the number of water molecules per unit cell, m and y are the total number of tetrahedra per unit cell, and y / m is 1 to 100. Most preferably, y / m is 1 to 5. The cation M may represent group IA and group IIA elements, such as sodium, potassium, magnesium and calcium.

The Zeolite, which is useful here is a faujasite-type zeolite, including type X or zeolite Type Y zeolite, both with a nominal pore size of 8 Angstrom units, typically in the range of 7.4 to 10 Angstrom units.

The during execution useful in this invention Aluminosilicate zeolite materials are commercially available. Methods of making X and Y zeolites are good known and accessible in standard texts. Preferred synthetic crystalline aluminosilicate materials useful herein are available under the designation type X or type Y.

By way of illustration and not limitation, in one preferred embodiment, the crystalline aluminosilicate material is of type X and selected from the following: Na ₈₆ [AlO ₂ ] ₈₆ * (SiO ₂ ) ₁₀₆ ] xH ₂ O (I), K ₈₆ [AlO ₂ ] ₈₆ * (SiO ₂ ) ₁₀₆ ] xH ₂ O (II), Ca ₄₀ Na ₆ [AlO ₂ ] ₈₆ * (SiO ₂ ) ₁₀₆ ] xH ₂ O (III), Sr ₂₁ Ha ₂₂ [AlO ₂ ] ₈₆ • (SiO ₂ ] ₁₀₆ ] xH ₂ O (IV). and mixtures thereof, wherein x is 0 to 276. Zeolites of formulas (I) and (II) have a nominal pore size or aperture of 8.4 Angstrom units. Zeolites of formulas (III) and (IV) have a nominal pore size or aperture of 8.0 Angstrom units.

In another preferred embodiment, the crystalline aluminosilicate material is of type Y and selected from the following: Na ₅₆ [AlO ₂ ] ₅₆ * (SiO ₂ ) ₁₃₆ ] xH ₂ O (V), K ₅₆ [AlO ₂ ] ₅₆ * (SiO ₂ ) ₁₃₆ ] xH ₂ O (VI) and mixtures thereof, wherein x is 0 to 276. Zeolites of formulas (V) and (VI) have a nominal pore size or aperture of 8.0 Angstrom units. Zeolites used in the present invention are in a particulate form which preferably has an average particle size of 0.5 μm to 120 μm, preferably 0.5 μm to 30 μm, as measured by a standard particle size analysis technique.

The Size of zeolite particles allows that she in the textiles they come in contact with can. After setting on the tissue surface (with its coating matrix while washed away the washing process has been) the zeolites begin to release their trapped perfumes, especially when subjected to warm and humid conditions.

Inclusion of one Perfume in zeolite

The X or Y type zeolites useful herein preferably contain less than 10% desorbable water, more preferably less than about 8% desorbable water, and most preferably less than about 5% desorbable water. Such materials can be obtained by first by heating to about 150-350 ° C, optionally under reduced pressure (0.001 to 20 mm Hg (Torr)) are activated / dehydrated for at least 12 hours. After activation, the agent is slowly and thoroughly mixed with the activated zeolite and optionally heated to about 60 ° C for up to about 2 hours to accelerate the absorption equilibrium within the zeolite particles. The fragrance / zeolite mixture is then cooled to room temperature and is in the form of a free-flowing powder.

The Amount of in the zeolite carrier enclosed perfume is less than 20%, typically less than 18.5%, based on the Weight of the loaded particle, determined by the limits of the Pore volume of the zeolite. It should be noted, however, that the particles of the invention this Exceed proportion of perfume based on the weight of the particle can, however, it is known that excess portions of the perfume are not included in the zeolite, too if only releasable agents are used. Therefore, the particles according to the invention more than 20% by weight of perfume. Because any excess perfumes (as well as any existing non-releasable funds) not in The zeolite pores become trapped become these materials probably immediately after contact with the aqueous wash medium released.

In addition to Its function is to retain the fragrance in the zeolite particles protect, The glassy particle also suitably serves several perfumed zeolite particles to agglomerates having a total particle size in the range of 200 to 1000 microns, preferably 400 to 600 μm, to agglomerate. Dustiness is reduced in this way. In addition, will thereby reducing the tendency of the smaller, individually perfumed zeolites, down to the bottom of containers to relocate with granular Cleaning agents filled which are typically themselves particle sizes in the range of 200 to 1,000 μm exhibit.

detergent surfactants

Detergent surfactants, which are provided in the inventions Completely include formulated cleaning compositions preferably at least 1%, preferably 1 to 99.8%, based on the weight of the cleaning composition, depending on the individual used Surfactants and the desired Effects. In a particularly preferred embodiment, the detersive surfactant comprises 5 to 80% by weight of the composition.

The Detersive surfactant may be nonionic, anionic, ampholytic, zwitterionic or cationic. Mixtures of these surfactants can also be used. Preferred cleaning compositions comprise anionic detergent surfactants or mixtures of anionic surfactants with other surfactants, especially nonionic surfactants.

Nonlimiting examples of useful surfactants include the conventional C ₁₁ -C ₁₈ alkylbenzenesulfonates and primary, secondary and random alkyl sulfates, the C ₁₀ -C ₁₈ alkyl alkoxy sulfates, the C ₁₀ -C ₁₈ alkyl polyglycosides and their corresponding sulfated polyglycosides, alpha sulfonated C ₁₂ -C ₁₈ fatty acid esters, C ₁₂ -C ₁₈ alkyl and alkylphenol alkoxylates (especially ethoxylates and mixed ethoxy / propoxy), C ₁₂ -C ₁₈ betaines and sulfobetaines ("sultaines") and C ₁₀ -C ₁₈ amine oxides one. Other conventional, useful surfactants are listed in standard texts.

A Class of a nonionic surfactant, which in the cleaning compositions according to the invention especially useful is included Condensates of ethylene oxide with a hydrophobic group to form a surfactant with an average hydrophilic-lipophilic balance (HLB) in the range of 5 to 17, preferably 6 to 14, more preferred 7 to 12, provide. The hydrophobic (lipophilic) group can be more aliphatic or aromatic nature. The length of the polyoxyethylene group, which is condensed with a certain hydrophobic group, can be easily adapted be a water-soluble Connection with the desired Balance between hydrophilic and hydrophobic elements to obtain.

Particularly preferred nonionic surfactants of this type are the C ₉ -C ₁₅ primary alcohol ethoxylates containing from 3 to 8 moles of ethylene oxide per mole of alcohol; especially the primary C ₁₄ -C ₁₅ alcohols containing 6 to 8 moles of ethylene oxide per mole of alcohol; the primary C ₁₂ -C ₁₅ alcohols containing from 3 to 5 moles of ethylene oxide per mole of alcohol; and mixtures thereof.

Another suitable class of nonionic surfactants includes the polyhydroxy fatty acid amides having the formula: R ² C (O) N (R ¹ ) Z (I) wherein R ^{1 is} H, C ₁ -C ₈ hydrocarbyl, 2-hydroxyethyl, 2-hydroxypropyl or a mixture thereof, preferably C ₁ -C ₄ alkyl, more preferably C ₁ - or C ₂ alkyl, most preferably C ₁ -Alkyl (ie methyl); and R ^{2 is} a C ₅ -C ₃₂ hydrocarbyl group, preferably straight chain C ₇ -C ₁₉ alkyl or alkenyl, more preferably straight chain C ₉ -C ₁₇ alkyl or alkenyl, most preferably straight chain C ₁₁ -C ₁₉ alkyl or alkenyl, or a mixture thereof; and Z is a polyhydroxyhydrocarbyl group having a linear hydrocarbyl chain wherein at least 2 (in the case of glyceraldehyde) or at least 3 hydroxyl groups (in the case of other reducing sugars) are directly attached to the chain or an alkoxylated derivative (preferably ethoxylated or propoxylated) thereof. Z is preferably derived from a reducing sugar in a reductive amination reaction; more preferably, Z is a glycityl group. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and xylose as well as glyceraldehyde. As starting materials, high dextrose corn syrup, high fructose corn syrup and high maltose corn syrup may be used as well as the individual sugars listed above. These corn syrups may yield a mixture of Z sugar components. It should be understood that it is by no means intended to exclude other suitable starting materials. Z is preferably selected from the group consisting of -CH ₂ - (CHOH) _n -CH ₂ OH, -CH (CH ₂ OH) - (CHOH) _n-1 -CH ₂ OH, -CH ₂ - (CHOH) ₂ - (CHOR ') (CHOH) -CH ₂ OH, wherein n is an integer from 1 to 5, inclusive, and R' is H or a cyclic mono- or polysaccharide, and alkoxylated derivatives thereof. Most preferred are glycityls wherein n is 4, especially -CH ₂ - (CHOH) ₄ -CH ₂ OH.

In formula (I), R ¹ may be, for example, N-methyl, N-ethyl, N-propyl, N-isopropyl, N-butyl, N-isobutyl, N-2-hydroxyethyl or N-2-hydroxypropyl. For very high foaming, R ^{1 is} preferably methyl or hydroxyalkyl. If less foaming is desired, R ^{1 is} preferably C ₂ -C ₈ alkyl, especially n-propyl, iso-propyl, n-butyl, iso-butyl, pentyl, hexyl and 2-ethylhexyl.

R ² -CO-N <may be, for example, cocamide, stearamide, oleamide, lauramide, myristamide, capricamide, palmitamide or tallow amide.

Soap (i.e., salts of fatty acids) can also be used as is for a portion of the cleaning surfactant is desired.

Low foaming nonionic Surfactants are useful in automatic dishwashing to facilitate cleaning support, the defoaming of food foams, especially of proteins and to support the control of stains / film formation, and are desirable in the present cleaning compositions in proportions of 0.1 to 20% of the composition included. In general, be Bleach-stable surfactants are preferred. Inventive ADD (Automatic Dishwashing Detergent) compositions preferably comprise low-foaming nonionic Surfactants (LFNIs). LFNIs can in amounts of 0 to 10 wt .-%, preferably 0.25 to 4 wt .-%, are present. LFNIs are used more typically in ADDs because of the improved Water-separating effect (especially of glass) they add to the ADD product to lend. They also include polymeric non-silicone, non-phosphate materials, which are further illustrated below, of which known is, that you in automatic dishwashing Defoaming food contaminants.

preferred Close LFNIs nonionic alkoxylated surfactants, especially derived from primary alcohols Ethoxylates, and mixtures thereof with more complicated surfactants, such as the polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) reverse block polymers, one. Surfactants of the PO / EO / PO polymer type are well known to have a suds suppressors or defoaming Effect, especially in the context of common food soil constituents, like egg, own.

The Invention preferred embodiments, wherein an LFNI is present and wherein this component is at 95 ° F (35 ° C), more preferred at 77 ° F (25 ° C), is fixed. To facilitate the production, has a preferred LFNI has a melting point between 77 ° F (25 ° C) and 140 ° F (60 ° C), more preferably between 80 ° F (26.6 ° C) and 110 ° F (43.3 ° C).

In a preferred embodiment For example, LFNI is an ethoxylated surfactant derived from the Reaction of a monohydroxy alcohol or alkylphenol containing 8 to 20 carbon atoms, with 6 to 15 moles of ethylene oxide per mole Alcohol or alkylphenol based on an average basis.

A particularly preferred LFNI is derived from a straight-chain fatty alcohol containing from 16 to 20 carbon atoms (C ₁₆ -C ₂₀ -alcohol), preferably a C ₁₈ -alcohol having an average of 6 to 15 moles, preferably 7 to 12 moles, and more preferably 7 to 9 moles of ethylene oxide per mole of alcohol is condensed. Preferably, the thus-derived ethoxylated nonionic surfactant has a narrow ethoxylate distribution as compared to the average.

The LFNI can optionally contain propylene oxide in an amount of up to about Contain 15 wt .-%. Other preferred LFNI surfactants can by those described in U.S. Patent 4,223,163, issued September 16, 1980 to Builloty Processes are produced.

Especially preferred ADDs wherein the LFNI is present utilize an ethoxylated one Monohydroxy alcohol or an ethoxylated alkyphenol and include additionally a polyoxyethylene-polyoxypropylene block polymer compound; wherein the ethoxylated monohydroxy alcohol or alkylphenol fraction of LFNI comprises 20 to 100%, preferably 30 to 70%, of the total LFNI.

Suitable polyoxyethylene-polyoxypropylene block polymer compounds meeting the above-described requirements include those based on ethylene glycol, propylene glycol, glycerin, trimethylolpropane and ethylenediamine as the reactive hydrogen starter compound. Polymeric compounds prepared by sequential ethoxylation and propoxylation of starter compounds with a single reactive hydrogen atom, such as C _12-18 aliphatic alcohols, generally do not provide satisfactory foam control in the instant ADDs. Certain of the called PLURONIC ^® and Tetronic ^® block polymer surfactant from BASF-Wyandotte Corp., Wyandotte, Michigan, are suitable in ADD compositions of the invention.

One contains particularly preferred LFNI 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend, comprising about 75%, based on the weight of the mixture, of one Reverse block copolymers of polyoxyethylene and polyoxypropylene containing 17 moles of ethylene oxide and 44 moles of propylene oxide; and about 25% on the weight of the mixture, a block copolymer of polyoxyethylene and polyoxypropylene which is started with trimethylolpropane and 99 moles of propylene oxide and 24 moles of ethylene oxide per mole of trimethylolpropane contains.

to Use as LFNI in the ADD compositions are suitable LFNIs, which have relatively low cloud points and a high hydrophilic-lipophilic Balance (HLB). Cloud points of 1% solutions in Water are for optimal foaming control over the entire range of Water temperatures typically below 32 ° C and preferably below, e.g. 0 ° C.

LFNIs, which may also be used, include a C ₁₈ -alcohol polyethoxylate having a degree of ethoxylation of about 8, commercially available as SLF18 from Olin Corp., and any biodegradable LFNI having the melting point properties discussed above.

enzymes

enzymes can in the present cleaning compositions because of a variety of purposes, including the removal of proteinaceous, carbohydrate-containing or triglyceride-containing Stains from surfaces, such as textiles or tableware, to prevent transmission volatile Dyes, for example, during washing, and for tissue care included be. Suitable enzymes include proteases, amylases, Lipases, cellulases, peroxidases and mixtures thereof each of suitable origin, such as plants, animals, bacteria, fungi and yeast, a. Preferred choices are made by factors such as pH activity and / or Stability optima, Thermal stability, stability across from active cleaning agents, builders and the like. In this Regard bacterial or fungal enzymes are preferred, such as bacterial amylases and proteases and fungal cellulases ,.

"Detersive enzyme" as used herein means any enzyme which has a cleansing, stain removing or otherwise beneficial effect in a laundry composition, hard surface cleaning composition or personal care cleansing composition. Preferred purification enzymes are hydrolases, such as proteases, amylases and lipases. Preferred enzymes for laundry use include, but are not limited to, proteases, cellulases, lipases and peroxidases. Particularly preferred for automatic dishwashing are amylases and / or proteases, including both currently commercially available types and improved types which, although becoming more and more bleach compatible despite incremental improvements, have a remaining degree of susceptibility against deactivation by bleaching agents.

enzymes are usually added in cleaning or cleaning additive contained in sufficient proportions to provide a cleaning effect Quantity ". The term "cleaning effective Quantity "refers to any amount that is capable of providing a cleansing, stain-removing, Dirt-removing, whitening, deodorizing or freshness improving effect on substrates such as textiles, dishes and the like, cause. In practical terms, typical amounts are currently in the Commercially available Preparations up to 5 mg, by weight, more typically 0.01 to 3 mg, active enzyme per gram of cleaning composition. In other words the compositions typically comprise from 0.001 to 5% by weight, preferably 0.01 to 1 wt .-%, one commercially available Enzyme preparation. Protease enzymes are usually in such commercial Preparations in sufficient proportions, 0.005 to 0.1 Anson units (AU). activity per gram of composition. For certain cleaning agents, as with automatic dishwashing, may be desirable be to increase the active enzyme content of the commercial preparation in order the total amount of non-catalytic materials a minimum and thus reduce the stains / film formation or to improve other end results. Higher levels of active ingredient can be found in highly concentrated cleaning formulations also desirable be.

Suitable examples of proteases are the subtilisins obtained from certain strains of B. subtilis and B. licheniformis. One suitable protease is obtained from a strain of Bacillus, having maximum activity throughout the pH range of 8-12, developed and sold as ESPERASE ^® sold by Novo Industries A / S of Denmark, hereinafter "Novo". The preparation of this enzyme and analogous enzymes is described in GB 1,243,784 to Novo. Other suitable proteases include Alcalase ^® and SAVINASE ^® from Novo and MAXATASE ^® from International Bio-Synthetics, Inc., The Netherlands; and Protease A as disclosed in EP-130,756 A, January 9, 1985, and Protease B as disclosed in EP-303,761 A, April 28, 1987, and EP-A-130,756, January 9, 1985. See also an effective at high pH protease from Bacillus sp. NCIMB 40338, which is described in WO 93/18140 A to Novo. Enzymatic detergents comprising a protease, one or more other enzymes, and a reversible protease inhibitor are described in WO 92/03529 A to Novo. Other preferred proteases include those of WO 95/10591 A to Procter & Gamble. Optionally, a protease is available which has reduced adsorption and increased hydrolysis, as described in WO 95/07791 to Procter & Gamble. A recombinant trypsin-like protease for detergent, which is suitable here, is described in WO 94/25583 to Novo.

More accurate is a particularly preferred protease, termed "protease D", a carbonyl hydrolase variant with a non-naturally occurring amino acid sequence which is derived is from a precursor carbonyl hydrolase by substituting a plurality of amino acid residues with another amino acid in a position in carbonyl hydrolase corresponding to position +76, preferably also in combination with one or more amino acid residue positions, which correspond to those selected from the group consisting from +99, +101, +103, +104, +107, +123, +27, +105, +109, +126, +128, +135, +156, +166, +195, +197, +204, +206, +210, +216, +217, +218, +222, +260, +265 and / or +274, according to the numbering of subtilisin from Bacillus amyloliquefaciens, as in the patent applications of Baeck A. et al. titled "Protease-Containing Cleaning Compositions ", U.S. 5,679,630, and Ghosh C. et al., Bleaching Compositions Comprising Protease Enzymes, U.S. 5,677,272, both filed on October 13, 1994.

Amylases useful herein, particularly, but not limited to, for machine dishwashing purposes include, for example, α-amylases described in GB-1,296,839 to Novo; RAPIDASE ^®, International Bio-Synthetics, Inc .; and TERMAMYL ^®, Novo, one. FUNGAMYL ^® from Novo is especially useful. The targeted modification of enzymes for improved stability, eg oxidation stability, is known. See, for example, J. Biological Chem., Vol. 260, No. 11, June 1985, pp. 6518-6521. Certain preferred embodiments of the present compositions may amylases having improved stability in detergents such as automatic dishwashing types for, especially improved oxidative stability as measured against a reference-point of TERMAMYL ^® in a commercial application in 1993 use. These preferred amylases share the property of being "stability-enhanced" amylases characterized at least by a measurable improvement in one or more of the following properties:
Oxidation stability, eg to hydrogen peroxide / tetraacetylethylenediamine in a buffered solution at pH 9-10; Thermal stability, eg at usual washing temperatures, such as 60 ° C; or alkaline stability, eg at a pH of about 8 to about 11, measured against the amylase designated as a reference above. The stability can be measured using any of the technical tests disclosed in the art. See, for example, the references disclosed in WO 94/02597. Stability-enhanced amylases can be purchased from Novo or Genencor International. One class of particularly preferred amylases has the commonality that, using site-directed mutagenesis, they are derived from one or more of the Bacillus amylases, particularly the Bacillus α-amylases, whether one, two or more amylase strains are immediate precursors. Amylases which have improved oxidation stability compared to the above-identified reference amylase are preferred for use in cleaning compositions, especially bleaching, more preferably oxygen bleaching, which is different from chlorine bleaching. Such preferred amylases include: (a) an amylase according to WO 94/02597, Novo, February 3, 1994, supra, as further illustrated by a mutant wherein, using alanine or threonine, preferably threonine, a substitution of the position 197 located methionine residue of the alpha-amylase B. licheniformis, known as TERMAMYL ^®, or the homologous position variation of a similar parent amylase, such as B. amyloliquefaciens, B. subtilis, or B. stearothermophilus is introduced; (b) stability-enhanced amylases as described by Genencor International in a publication entitled "Oxidatively Resistant alpha-amylases" presented at the 207th American Chemical Society National Meeting, 13-17. March 1994, by Mitchinson C. It is noted that bleaches in automatic dishwashing detergents inactivate alpha-amylases, but that amylases with improved oxidation stability have been prepared by Genencor from B. licheniformis NCIB8061. Methionine (Met) was identified as the most suitable residue for modification. Met was simultaneously substituted at positions 8, 15, 197, 256, 304, 366, and 438, yielding specific mutants, of which M197L and M197T are particularly important, with the M197T variant being the most stable expressed variant. Stability was measured in CASCADE ^® and SUNLIGHT ^®; (c) particularly preferred amylases include amylase variants having additional modification in the immediate precursor, as described in WO 9510603 A and are available from the assignee, Novo, as DURAMYL ^®. Another particularly preferred amylase having improved oxidation stability includes those described in WO 94/18314 to Genencor International and WO 94/02597 to Novo. Any other oxidative stability-enhanced amylase can be used, such as those derived by site-directed mutagenesis of known chimeric, hybrid or simply mutant parent forms of obtainable amylases. Other preferred enzyme modifications are available. See WO 95/09909 A to Novo.

Useful cellulases include both bacterial and fungal types, which preferably have a pH optimum between 5 and 9.5. U.S. 4,435,307, Barbesgoard et al., March 6, 1984, discloses suitable fungal cellulases from Humicola insolens or Humicola strain DSM-1800 or a cellulase 212 producing fungus of the genus Aeromonas and one extracted from the midgut gland of marine mollusk Dolabella auricula solander cellulase. Suitable cellulases are also disclosed in GB-A-2,075,028; GB-A-2,095,275; and DE-OS 2,247,832. CAREZYME ^® (Novo) is especially useful. See also WO 91/17243 to Novo.

Suitable lipase enzymes for use in detergents include those produced by microorganisms of the Pseudomonas group, such as Pseudomonas stutzeri ATCC 19.154, as disclosed in GB-A-1,372,034. See also the lipases in Japanese Patent Application 53,20487, which was published on February 24, 1978. This lipase is available from Amano Pharmaceutical Co., Ltd. of Nagoya, Japan, under the trade names Lipase P "Amano" or "Amano-P." Other suitable commercial lipases include Amano-CES, lipases from Chromobacter viscosum, eg Chromobacter viscosum Var. lipolyticum NRRLB 3673 from Toyo Jozo Co., Tagata, Japan; Chromobacter viscosum lipases from US Biochemical Corp., USA, and Disoynth Co., The Netherlands; and lipases from Pseudomonas gladioli. The Humicola lanuginosa derived and commercially available from Novo LIPOLASE ^® enzyme, see. also EP 341,947, is a preferred lipase for use herein. Lipase and amylase variants which are stabilized against peroxidase enzymes are described in WO 94/14951 A to Novo. See also WO 92/05249 and RD 94/359044.

to suitable cutinase enzymes herein are described in WO 88/09367 A to Genencor.

Peroxidase enzymes can be used in combination with oxygen sources, eg, percarbonate, perborate, hydrogen peroxide, etc., for "bleaching in solution" or to prevent the transfer of dyes or pigments removed from substrates during washing to other substrates present in the wash solution , Known peroxidases include horseradish peroxidase, ligninase and haloperoxidases, such as chloro or bromo peroxidase. Peroxidase-containing cleaning composition Compositions are disclosed in WO 89/099813 A, Oct. 19, 1989 to Novo, and WO 89/09813 A to Novo.

A Selection of enzyme materials and agents for their incorporation into synthetic Cleaning compositions are also disclosed in WO 93/07263 A and WO 93/07260 A to Genencor International; WO 89/08694 A to Novo; and US 3,553,139, January 5, 1971 to McCarty et al. Enzymes are still in U.S. 4,101,457, Place et al., July 18, 1978, and U.S. 4,507,219; Hughes, March 26th 1985, disclosed. For liquid Cleaning preparations useful Enzyme materials and their incorporation into such preparations in U.S. 4,261,868, Hora et al., Apr. 14, 1981. enzymes for use in detergents can be prepared by various techniques be stabilized. Enzyme stabilization techniques are described in US-3,600,319, 17. August 1971, Gedge et al., EP 199,405 and EP 200,586, October 29 1986, Venegas, discloses or exemplified therein. Enzyme stabilization systems are also described, for example, in US 3,519,570. The useful Bacillus sp. AC13, which provides proteases, xylanases and cellulases, is described in WO 94/01532 A to Novo.

Enzyme stabilization system

enzyme-containing Compositions, including, but not limited to, liquid Compositions, can 0.001 to 10 wt%, preferably 0.005 to 8 wt%, most preferably 0.01 to 6 wt .-%, of an enzyme stabilization system. The enzyme stabilization system may be any stabilizing System that is compatible with the cleaning enzyme. One such system can be inherent be provided by other formulation agents or be added separately, e.g. from the supplier or from a manufacturer of detergent-ready enzymes. Such stabilizing Systems can for example, calcium ions, boric acid, Propylene glycol, short chain carboxylic acids, boronic acids and Mixtures thereof include and are designed to be different Stabilization problems in dependence on the type and physical form of the cleaning composition speak to.

One Stabilization approach is the use of water-soluble Sources for Calcium and / or magnesium ions in the finished compositions, which such ions for provide the enzymes. Calcium ions are generally more effective as magnesium ions and are preferred herein when only one type of cation is used. Typical cleaning compositions, especially Liquids, include 1 to 30, preferably 2 to 20, more preferably 8 to 12 millimoles Calcium ions per liter of finished cleaning composition, though Variations in dependence of factors including the multiplicity, the type and the proportions of the admixed enzymes, possible are. Preferably, water-soluble calcium or magnesium salts used, including for example, calcium chloride, calcium hydroxide, calcium formate, calcium malate, Calcium maleate, calcium hydroxide and calcium acetate; more generally calcium sulfate or magnesium salts containing the exemplified calcium salts to be used. Even higher levels of calcium and / or Magnesium can Naturally useful be, for example, for promotion the greasing efficiency of certain surfactant types.

One Another stabilization approach is the use of borate species. See Severson, U.S. 4,537,706. Borate stabilizers can, if used in proportions of up to 10% by weight or more of the composition although more typical proportions of up to 3% by weight of boric acid or other borate compounds, such as borax or ortho borate, for use in liquid Detergents are suitable. Substituted boric acids, such as phenylboronic Butane boronic acid, p-bromo or similar, can instead of boric acid and reduced total boron levels in cleaning compositions can despite the use of such substituted Borderivaten be possible.

Stabilizer systems of certain cleaning compositions, for example, automatic dishwashing compositions, may further comprise from 0% to 10%, preferably from 0.01% to 6% by weight of chlorine bleach scavengers which are added to prevent the in many Water supplies present chlorine bleaching species attack and inactivate the enzymes, especially under alkaline conditions. Although chlorine levels in water may be low, typically in the range of 0.5 ppm to 1.75 ppm, the available chlorine is in the total water volume that comes into contact with the enzyme, for example during dishwashing or washing of textiles, relatively large; accordingly, enzymatic stability to chlorine may sometimes be problematic in use. Since perborate or percarbonate, which have the ability to react with chlorine bleach, may be present in certain of the present compositions in amounts which are separate from the stabilizing system, the use of additional stabilizers against chlorine generally may not generally be necessary, though their use gives better results. Suitable chlorine radical scavenging anions are well known and readily available, and if used, salts, containing ammonium cations, with sulfate, bisulfite, thiosulfide, thiosulfate, iodide, etc. Antioxidants such as carbamate, ascorbate, etc .; organic amines such as ethylenediaminetetraacetic acid (EDTA) or an alkali metal salt thereof; and monoethanolamine (MEA) and mixtures thereof may also be used. Specific enzyme inhibition systems may also be included so that different enzymes have maximum compatibility. Other conventional radical scavengers such as bisulfate, nitrate, chloride, sources of hydrogen peroxide such as sodium perborate tetrahydrate, sodium perborate monohydrate and sodium percarbonate, as well as phosphate, condensed phosphate, acetate, benzoate, citrate, formate, lactate, malate, tartrate, salicylate, etc., and mixtures thereof, may optionally be used. Since the chlorine radical scavenging function can generally be carried out by components listed separately under better known functions (eg, hydrogen peroxide sources), it is not absolutely necessary to add a separate chlorine radical scavenger, unless there is no compound in an enzyme-containing embodiment of the invention, which is effective to the extent desired; even then the radical scavenger is added only to obtain optimal results. In addition, the manufacturer will employ the ordinary skill of a chemist to avoid the use of any enzyme radical scavenger or stabilizer which, as formulated, is predominantly incompatible with other reactive ingredients, if used.

in the With regard to the use of ammonium salts, such salts can easily be used the cleaning composition are mixed; but they tend to, while the storage to adsorb water and / or release ammonia. Accordingly, become such materials, if any, desirably in one Particles such as that described in U.S. 4,652,392, Baginski et al. protected.

Bleaching compounds - bleaching agents and bleach activators

The Cleaning compositions can optionally bleaching or bleaching compositions containing a bleaching agent and one or more bleach activators. If present, the bleaching agents are typically in proportions from 1 to 30%, more typically 5 to 20%, of the cleaning composition, especially for washing clothes, in front. If available, amounts to the amount of bleach activators typically 0.1 to 60%, more typically 0.5 to 40% of the bleaching composition comprising the bleaching agent plus the bleach activator.

The bleaching agents used here may any of the bleaching agents which are useful in cleaning compositions in textile cleaning, cleaning hard surfaces or useful for other cleaning purposes are and which are now known or become known. These include oxygen bleach as well other bleach. Perborate bleach, e.g. sodium (e.g., mono- or tetrahydrate) used here.

A other bleach category, which is used without restriction can be included Percarboxylic bleach and salts thereof. Suitable examples of this class of agents shut down Magnesium monoperoxyphthalate hexahydrate, the magnesium salt of metachloroperbenzoic acid, 4-nonylamino-4-oxoperoxybutyric acid and diperoxydodecanedioc one. Such bleaching agents are disclosed in U.S. Patent 4,483,781, Hartmann, issued on November 20, 1984; U.S. Patent Application 740,446, Burns et al., filed June 3, 1985; in the European patent application 0,133,354, Banks et al., Published on February 20, 1985; and in U.S. Patent 4,412,934, Chung et al on November 1, 1983, disclosed. Particularly preferred bleaching agents shut down also 6-nonylamino-6-oxoperoxycaproic acid, as in U.S. Patent 4,634,551 issued January 6, 1987 to Burns et al., is disclosed.

Peroxygen bleach can also be used. Suitable peroxygen bleach compounds shut down Sodium carbonate peroxyhydrate and equivalent "percarbonate" bleach, sodium pyrophosphate peroxyhydrate, Urea peroxyhydrate and sodium peroxide. Persulfate bleach (e.g., OXONE, commercially manufactured by DuPont) may also be used become.

One preferred percarbonate bleaching agent comprises dry particles having a average particle size in the range from 500 to 1,000 μm, wherein not more than 10 wt .-% of the particles are smaller than 200 microns, and not more than about 10% by weight of the particles are greater than 1250 μm. Optional The percarbonate can be made with silicate, borate or water-soluble Surfactants coated be. Percarbonate is available from various sources, such as FMC, Solvay and Tokai Denka, available.

mixtures of bleaching agents also be used.

Peroxygen bleach, the perborates, percarbonates, etc. are preferably bleach activators combined, resulting in aqueous solution (i.e. while the washing process) for in situ production of the bleach activator corresponding peroxyacid leads. Various nonlimiting examples of activators are disclosed in U.S. Patent 4,915,854, issued April 10, 1990 to Mao et al., And U.S. Patent 4,412,934. The nonanoyloxybenzenesulfonate (NOBS) and tetraacetylethylenediamine (TAED) activators are typical and mixtures thereof may also be be used. See also US 4,634,551 for other typical bleaching agents and Activators, which are useful here are.

Particularly preferred amido-derived bleach activators are those having the formulas: R ¹ N (R ⁵ ) C (O) R ² C (O) L or R ¹ C (O) N (R ⁵ ) R ² C (O) L wherein R ^{1 is} an alkyl group having from about 6 to about 12 carbon atoms, R ^{2 is} an alkylene group having from 1 to about 6 carbon atoms, R ^{5 is} H or alkyl, aryl or alkaryl having from about 1 to about 10 carbon atoms, and L is a suitable leaving group , A leaving group is any group that is displaced from the bleach activator by the perhydrolysis anion as a result of the nucleophilic attack on the bleach activator. A preferred leaving group is phenylsulfonate.

preferred examples for Bleach activators of the above formulas include (6-octanamidocaproyl) oxybenzenesulfonate, (6-nonanamidocaproyl) oxybenzenesulfonate, (6-decanamido-caproyl) oxybenzenesulfonate and mixtures thereof as described in U.S. Patent 4,634,551 is.

Another class of bleach activators includes the benzoxazine-type activators described in Hodge et al. in U.S. Patent 4,966,723, issued October 30, 1990. A particularly preferred benzoxazine-type activator is:

worin R⁶ H oder eine Alkyl-, Aryl-, Alkoxyaryl- oder Alkarylgruppe mit 1 bis etwa 12 Kohlenstoffatomen ist. Besonders bevorzugte Lactam-Aktivatoren schließen Benzoylcaprolactam, Octanoylcaprolactam, 3,5,5-Trimethylhexanoylcaprolactam, Nonanoylcaprolactam, Decanoylcaprolactam, Undecenoylcaprolactam, Benzoylvalerolactam, Octanoylvalerolactam, Decanoylvalerolactam, Undecenoylvalerolactam, Nonanoylvalerolactam, 3,5,5-Trimethylhexanoylvalerolactam und Mischungen hiervon ein. Vgl. auch US-Patent 4,545,784, erteilt an Sanderson, 8. Oktober 1985, welches Acylcaprolactame, einschließlich Benzoylcaprolactam, adsorbiert in Natriumperborat offenbart.Another class of preferred bleach activators includes the acyl lactam activators, especially acyl caprolactams and acyl valerolactams having the formulas:

wherein R ^{6 is} H or an alkyl, aryl, alkoxyaryl or alkaryl group having from 1 to about 12 carbon atoms. Particularly preferred lactam activators include benzoyl caprolactam, octanoyl caprolactam, 3,5,5-trimethylhexanoyl caprolactam, nonanoyl caprolactam, decanoyl caprolactam, undecenoyl caprolactam, benzoyl valerolactam, octanoyl valerolactam, decanoyl valerolactam, undecenoyl valerolactam, nonanoyl valerolactam, 3,5,5-trimethylhexanoyl valerolactam, and mixtures thereof. See also U.S. Patent 4,545,784, issued to Sanderson, October 8, 1985, which discloses acyl caprolactams, including benzoyl caprolactam, adsorbed in sodium perborate.

Bleach, which are different from oxygen bleaches are on the Specialty also known and can used here. A type of non-oxygen bleach of particular interest light-activated bleaching agents, such as the sulfonated zinc and / or Aluminum phthalocyanines, a. See U.S. Patent 4,033,718 on July 5, 1977 to Holcombe et al. If used, contain cleaning compositions typically about 0.025 to about 1.25 weight percent of such bleaches, especially sulfonate zinc phthalocyanine.

Optionally, the bleaching compounds may be catalyzed by a manganese compound. Sol These compounds are well known in the art and include, for example, the manganese-based catalysts described in US Patent 5,246,621; U.S. Patent 5,244,594; U.S. Patent 5,194,416; U.S. Patent 5,114,606; and in European Patent Applications Publication Nos. 549,271A1, 549,272A1, 544,440A2 and 544,490A1. Preferred examples of these catalysts include Mn ^IV ₂ (uO) ₃ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (PF ₆ ) ₂ , Mn ^III ₂ (uO) ₁ (u-OAc) ₂ ( 1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₂ , Mn ^IV ₄ (uO) ₆ (1,4,7-triazacyclononane) ₄ (ClO ₄ ) ₄ , Mn ^III Mn ^IV ₄ (uO) ₁ (u-OAc) ₂ (1,4,7-trimethyl-1,4,7-triazacyclononane) ₂ (ClO ₄ ) ₃ , Mn ^IV (1,4,7-trimethyl-1,4, 7-triazacyclononane) (OCH ₃ ) ₃ (PF ₆ ) and mixtures thereof. Other metal-based bleach catalysts include those disclosed in U.S. Patent 4,430,243 and U.S. Patent 5,114,611. The use of manganese together with various complex ligands to enhance bleaching is also reported in the following U.S. Patents: 4,728,455; 5,284,944; 5,246,612; 5,256,779; 5,280,117; 5,274,147; 5,153,161; and 5,227,084.

Out practical reasons and not to the limit the present compositions and methods are adapted, by an order of magnitude at least one part per 10 million of active bleach catalyst species in the aqueous wash liquor and preferably 0.1 to 700 ppm, more preferably 1 to 500 ppm, to provide the catalyst species in the wash liquor.

The automatic dishwashing compositions and methods of the present invention may use cobalt (III) bleach catalysts having the formula: [Co (NH ₃ ) _n (M) _m (B) _b T _y wherein cobalt is in the +3 oxidation state; n is 4 or 5 (preferably 5); M represents one or more ligands coordinated to the cobalt via a site; m is 0, 1 or 2 (preferably 1); B is a ligand coordinated to the cobalt over two sites; b is 0 or 1 (preferably 0), and if b = 0, then m + n = 6, and if b = 1, then m = 0 and n = 0; and T represents one or more suitably selected counteranions present in a number of y, where y is an integer, to obtain a charge balanced salt (preferably, y is 1 to 3, most preferably 2, when T is one) -1-charged anion); and wherein the catalyst further has a base hydrolysis rate constant of less than 0.23 M ^-1 s ^-1 (25 ° C).

Preferred groups T are selected from the group consisting of chloride, iodide, I ₃ ^- , formate, nitrate, nitrite, sulfate, sulfate, citrate, acetate, carbonate, bromide, PF ₆ ^- , BF ₄ ^- , B (Ph) ₄ ^-, phosphate, phosphite, silicate, tosylate, methanesulfonate, and combinations thereof. Optionally, T may be protonated if more than one anionic group is present in T, eg, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^-, etc. Further, T may be selected from the group consisting of unusual inorganic anions such as anionic surfactants (For example, linear alkyl benzene sulfonates (LAS), alkyl sulfates (AS) or Alkylethoxysulfonate (AES)) and / or anionic polymers (eg polyacrylates or polymethacrylates) may be selected.

The M groups include, but are not limited to, F ^-, SO ₄ ^-2, NCS ^-, SCN ^-, S ₂ O ₃ ^-2, NH _3, PO ₄ ^3-, and carboxylates (which preferably are mono-carboxylates, but more than one carboxylate in the group may be present, as long as the attachment to the cobalt is via only one carboxylate per group, in which case the other carboxylate may be protonated in the M group or in its salt form). Alternatively, M may be protonated if more than one anionic group is present in M (eg, HPO ₄ ^2- , HCO ₃ ^- , H ₂ PO ₄ ^- , HOC (O) CH ₂ C (O) O-, etc.). Preferred M groups are substituted and unsubstituted C ₁ -C ₃₀ carboxylic acids having the formula: RC (O) O wherein R is preferably selected from the group consisting of hydrogen and unsubstituted and substituted C ₁ -C ₃₀ (preferably C ₁ -C ₁₈ ) alkyl, unsubstituted and substituted C ₆ -C ₃₀ (preferably C ₆ -C ₁₈ ) aryl and unsubstituted and substituted C ₃ -C ₃₀ (preferably C ₅ -C ₁₈ ) heteroaryl, wherein substituents are selected from the group consisting of -NR ' ₃ , -NR' ₄ ⁺ , -C (O) OR ', - OR 'and -C (O) NR' ₂ , wherein R 'is selected from the group consisting of hydrogen and C ₁ -C ₆ groups. Such substituted radicals R therefore include the groups - (CH ₂ ) _n OH and - (CH ₂ ) _n NR ' ₄ ⁺ wherein n is an integer from 1 to 16, preferably 2 to 10 and most preferably 2 to 5 ,

Most preferably, the M groups are carboxylic acids having the above formula wherein R is selected from the group consisting of hydrogen, methyl, ethyl, propyl, straight or branched C ₄ -C ₁₂ alkyl, and benzyl. Most preferably, R is methyl. Preferred carboxylic acid M groups include ant, Benzoic, octanoic, nonane, decane, dodecane, malonic, maleic, succinic, adipic, phthalic, 2-ethyllibanic, naphthenic, oleic, palmitic, triflate, tartaric, Stearic, butter, citric, acrylic, asparagine, fumar, lauric, linoleic, lactic, malic and especially acetic acid.

The Close B groups Carbonate, di- and higher Carboxylates (e.g., oxalate, malonate, malic acid, succinate or maleate), picolinic and alpha and beta amino acids (e.g., glycine, alanine, beta-alanine, or phenylalanine).

Useful cobalt bleach catalysts are known and are described, for example, together with their base hydrolysis rates in Tobe ML, Base Hydrolysis of Transition-Metal Complexes, Adv. Inorg. Bioinorg. Mech. 2 (1983), pages 1-94. For example, Table 1 at page 17, provides the base Hydrolysengeschwindigkeiten (designated therein as k _OH) for cobalt pentaamine of catalysts which with oxalate (k _OH = 2.5 x 10 ^-4 M ^-1 s ^-1 (25 ° C) ), NCS ^- (k _OH = 5.0 x 10 ^-4 M ^-1 s ^-1 (25 ° C)), formate (k _OH = 5.8 x 10 ^-4 M ^-1 s ^-1 (25 ° C ) and acetate (k _OH = 9.6 × 10 ^-4 M ^-1 s ^-1 (25 ° C.)). The preferred cobalt catalyst useful herein has the formula [Co (NH ₃ ) ₅ OAc] T _y wherein OAc represents an acetate group, and more particularly cobalt pentaamine acetate chloride [Co (NH ₃ ) ₅ OAc] Cl ₂ (here " PAC "); and [Co (NH ₃ ) ₅ OAc] (OAc) ₂ ; [Co (NH ₃ ) ₅ OAc] (PF ₆ ) ₂ ; [Co (NH ₃ ) ₅ OAc] (SO ₄ ); and [Co (NH ₃ ) ₅ OAc] (BF ₄ ) ₂ .

These Cobalt catalysts can be prepared in a simple manner by known methods, such as for example, in the above article by Tobe and in it cited References; and in U.S. Patent 4,810,410 to Diakun et al on the 7th of March 1989; J. Chem. Ed. 66 (1989) (12), 1043-1045; The Synthesis and Characterization of Inorganic Compounds, Jolly W.L. (Prentice-Hall, 1970), pp. 461-463; Inorg. Chem. 18 (1979), 1497-1502; Inorg. Chem. 21 (1982), 2881-2885; Inorg. Chem. 18 (1979), 2023-2025; Inorg. Synthesis (1960), 173-176; and Journal of Physical Chemistry 56 (1952), 22-25.

These Cobalt catalysts can processed together with additional materials, if necessary the color impairment in terms of aesthetic Properties of the product, or the composition can be made so that they Contains catalyst "stains".

Out practical reasons and not as a limit adapting the compositions and methods of automatic dishwashing, by an order of magnitude of at least 1 part per 100 million of the active cobalt catalyst species in the aqueous wash medium and preferably 0.1 ppm to 50 ppm, more preferably 1 ppm to 25 ppm, and most preferably 2 ppm to 10 ppm of the cobalt catalyst species Provide in the wash liquor. To such shares in the wash liquor Typical compositions include 0.04 to 1%, more preferably 0.08 to 0.36% based on the weight of the compositions.

Builder

Detergent builder can optionally included in the present compositions, to control the mineral hardness to support. Inorganic and organic builders can be used. Builder are typically used in laundry detergent compositions used to aid in the removal of particulate contaminants.

Of the Builder share can be dependent the purpose of the composition and its desired vary greatly in physical form. If available, include the Compositions typically at least 1% builder. Liquid formulations typically comprise 5 to 50% by weight, more typically 5 to 30% by weight, a detergent builder. Granular formulations include typically about 10 to 80% by weight, more typically 15 to 50% by weight, of the detergent builder. Lower or higher builder proportions are intended but be excluded.

inorganic or P-containing detergent builders include, but are not limited to on, the allcalcium, ammonium and alkanolammonium salts of Polyphosphates (exemplified by the tripolyphosphates, Pyrophosphates and the glassy polymeric metaphosphates), phosphonates, phytic acid, Silicates, carbonates (including bicarbonates and sesquicarbonates), Sulfates and aluminosilicates. However, in some regions Non-phosphate builder required. Importantly, the compositions are surprising are well-effective, even in the presence of so-called "weak" builders (compared with phosphates), such as citrate, or in the so-called "under-adjusted" situation at Zeolite or layered silicate builders.

Examples of silicate builders are the alkali metal silicates, especially those having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1, and layered silicates, such as those described in U.S. Patent 4,664,839, issued 12 May 1987 to Rieck HP, described sodium layer silicates. NaSKS-6 is the trademark for a crystalline layered silicate marketed by Hoechst (commonly abbreviated as "SKS-6" herein). Unlike zeolite builder, the NaSKS-6 silicate builder does not contain aluminum. NaSKS-6 has the morphological delta-Na ₂ SiO ₅ form of a layered silicate. It can be prepared by methods such as those described in German DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a particularly preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi _x O _{2x + 1} x yH ₂ O, wherein M is sodium or hydrogen, x is an integer of 1.9 to 4 , preferably 2, and y is a number from 0 to 20, preferably 0, can be used here. Several other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as alpha, beta and gamma forms. As noted above, the delta-Na ₂ SiO ₅ (NaSKS-6 form) is most preferred for use herein. Other silicates may also be useful, such as magnesium silicate, which is effective as a solidifying agent in granular formulations, as a stabilizer for oxygen bleach, and as a component of foam control systems.

Examples for carbonate builder are the alkaline earth and alkali metal carbonates, as described in the German patent application No. 2,321,001, published on November 15, 1973, are disclosed.

Aluminosilicate builders are useful in the present invention. Aluminosilicate builders are of great importance in most of the granular universal cleaning compositions currently on the market and may also be a significant builder ingredient in liquid cleaning formulations. Aluminosilicate builders include those having the empirical formula: M _z (zAlO _{2) y]} .xH ₂ O wherein z and y are integers of at least 6, the molar ratio of z to y is in the range of 1.0 to 0.5, and x is an integer of 15 to 264.

Useful aluminosilicate ion exchange materials are commercially available. These aluminosilicates may have a crystalline or amorphous structure and may be naturally occurring aluminosilicates or may be synthetically derived. A method of making aluminosilicate ion exchange materials is disclosed in U.S. Patent 3,985,669, Krummel et al., Issued October 12, 1976. Preferred synthetic, crystalline aluminosilicate ion exchange materials useful herein are available under the designations Zeolite A, Zeolite P (B), Zeolite MAP and Zeolite X. In a particularly preferred embodiment, the crystalline aluminosilicate ion exchange material has the formula: Na ₁₂ [(AlO ₂ ) ₁₂ (Sio ₂ ) ₁₂ ] xH ₂ O where x is 20 to 30, especially about 27. This material is known as zeolite A. Dehydrated zeolites (x = 0-10) can also be used here. Preferably, the aluminosilicate has a particle size of 0.1-10 μm in diameter.

organic Detergent builder, which for the purposes of the invention are suitable, close, but are not limited to a wide variety of polycarboxylate compounds one. As used herein, "polycarboxylate" refers to compounds having a variety of carboxylate groups, preferably at least 3 carboxylate groups. Polycarboxylate builder can but may be added to the composition in the acid form in general also be added in the form of a neutralized salt. at when used in the salt form, alkali metal salts, such as sodium, Potassium and lithium salts, or alkanolammonium salts are preferred.

The Close polycarboxylate builder a variety of categories more useful Materials. An important category of polycarboxylate builders comprises the ether polycarboxylates, including oxydisuccinate as in Berg, U.S. Patent 3,128,287, issued April 7, 1964, and Lamberti et al., U.S. Patent 3,635,830, issued January 18, 1972 is. See also the "TMS / TDS" pictures of US Patent 4,663,071, issued to Bush et al. on May 5, 1987. Suitable ether polycarboxylates shut down also cyclic compounds, especially alicyclic compounds, such as those disclosed in U.S. Patents 3,923,679; 3,835,163; 4,158,635; 4,120,874; and 4,102,903.

Other useful detergent builders include the ether hydroxypolycarboxylates, copolymers maleic anhydride with ethylene or vinyl methyl ether, 1,3,5-trihydroxybenzene-2,4,6-trisulfonic acid and carboxymethyloxysuccinic acid, the various alkali metal, ammonium and substituted ammonium salts of polyacetic acids such as ethylenediaminetetraacetic acid and nitrilotriacetic acid, and polycarboxylates such as mellitic acid, succinic acid, Oxydisuccinic acid, polymaleic acid, benzene-1,3,5-tricarboxylic acid, carboxymethyloxysuccinic acid and soluble salts thereof.

Citrate builders, e.g. citric acid and soluble Salts thereof (especially the sodium salt) are polycarboxylate builders, the for liquid Universal cleaner preparations because of their availability from renewable resources and their biodegradability are particularly important. Citrates may also be in granular compositions used, especially in combination with zeolite and / or layered silicate builders. Oxydisuccinates are in such compositions and combinations also especially useful.

Also useful in the cleaning compositions of the present invention are the 3,3-dicarboxy-4-oxa-1,6-hexanedioates and the related compounds disclosed in U.S. Patent 4,566,984, Bush, issued January 28, 1986. Useful succinic acid builders include the C ₅ -C ₂₀ alkyl and alkenyl succinic acids and salts thereof. Specific examples of succinate builders include: laurylsuccinate, myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred), 2-pentadecenylsuccinate, and the like. Lauryl succinates are the preferred builders of this group and are described in European Patent Application 86200690.5 / 0,200,263, published November 5, 1986.

Other suitable polycarboxylates are disclosed in U.S. Patent 4,144,226, Crutchfield et al., issued Mar. 13, 1979, and U.S. Patent 3,308,067, Diehl, issued Mar. 7, 1967, disclosed. See also Diehl, U.S. Patent 3,723,322.

Fatty acids, eg C ₁₂ -C ₁₈ monocarboxylic acids, may also be included in the compositions alone or in combination with the above-mentioned builders, especially citrate and / or succinate builders, to provide additional builder activity. Such use of fatty acids generally results in a reduction in foaming, which should be considered by the manufacturer.

In Situations where phosphorus-based builders can be used, and especially in the formulation of pieces, which are for hand washing can be used the various alkali metal phosphates, such as the well-known sodium tripolyphosphates, Sodium pyrophosphates and sodium orthophosphates can be used. Phosphonate builders such as ethane-1-hydroxy-1,1-diphosphonate, and others known Phosphonates (see, for example, U.S. Patents 3,159,581, 3,213,030; 3,422,021; 3,400,148 and 3,422,137) can also be used.

polymer soil

Known polymeric soil release agents, hereinafter "SRA", can optionally in the cleaning compositions according to the invention be used. If used, SRA's generally comprise from 0.01 to 10.0% by weight, more typically 0.1 to 5 wt%, preferably 0.2 to 3.0 wt% of Compositions.

preferred SRA's typically own hydrophilic segments around the surface of hydrophobic fibers how to hydrophilize polyester and nylon, and hydrophobic segments, to deposit on hydrophobic fibers and then to completion of washing and rinsing cycles stick to it, thereby acting as an anchor for the hydrophilic segments serve. In this way it is possible that stains, which occur after treatment with the SRA, in later washing processes flushed out more easily can be.

SRA's can be one Variety of charged, e.g. anionic or canonical species, see. U.S. 4,956,447, issued September 11, 1990 to Gosselink et al., and uncharged monomeric groups, and their structures can be linear, branched or star-shaped. They can be protective groups lock in, which in controlling the molecular weight or the change the physical or surface active Properties are particularly effective. The structures and charge distributions can be used for Application on different fiber or textile types and for different types Cleaning or cleaning additive products are adapted.

Preferred SRA's include oligomeric terephthalate esters which are typically prepared by methods which involve at least one transesterification / oligomerization, often with a metal catalyst such as Ti tanium (IV) alkoxide. Such esters can be prepared using additional monomers that can be incorporated into the ester structure via one, two, three, four, or more positions without, of course, forming a highly crosslinked overall structure.

suitable SRA's include sulfonated product of a substantially linear ester oligomer, which consists of an oligomeric ester backbone of recurring terephthaloyl and oxyalkyleneoxy groups and allyl-derived, sulfonated end groups, which covalently bind to the backbone consists, as for example in US-4,968,451, November 6th 1990 to Scheibel J.J. and Gosselink E.P., is described. Such Ester oligomers can prepared by: (a) ethoxylating an allyl alcohol; (b) reacting the product of (a) with dimethyl terephthalate ("DTM") and 1,2-propylene glycol ("PG") in a two-stage Transesterification / oligomerization procedure; and (c) reacting the product from (b) with sodium metabisulfite in water. Other SRA's include the nonionic end-capped 1,2-propylene / polyoxyethylene terephthalate polyester from U.S. 4,711,730, December 8, 1987 to Gosselink et al. for example those obtained by the transesterification / oligomerization of poly (ethylene glycol) methyl ether, DMT, PG and poly (ethylene glycol) ("PEG") getting produced. Other examples of SRA's include: the partially or fully anionically end-capped, Oligomeric esters of U.S. 4,721,580, January 26, 1988 to Gosselink, such as oligomers of ethylene glycol ("EG"), PG, DMT and Na-3,6-dioxa-8-hydroxyoctanesulfonate; the nonionic capped, oligomeric block polyester compounds of U.S. 4,702,857, October 27, 1987 to Gosselink, which, for example, from DMT, methyl (Me) -capped PEG and EG and / or PG or a combination of DMT, EG and / or PG, Me-capped PEG and Na-dimethyl-5-sulfoisophthalate getting produced; and the anionic, especially sulfoaroyl, end-capped Terephthalate esters of U.S. 4,877,896, October 31, 1989 to Maldonado, Gosselink et al .; the latter being typical of SRA's used in both laundry and as well as fabric care products are an example of this an ester composition consisting of m-sulfobenzoic acid monosodium salt, PG and DMT, optionally, but preferably, further comprising added PEG, e.g. PEG-3400.

SRA's also include: simple copolymeric blocks of ethylene terephthalate or propylene terephthalate with polyethylene oxide or polypropylene oxide terephthalate, cf. U.S. 3,959,230 to Hays, May 25, 1976, and U.S. 3,893,929 to Basadur, July 8, 1975; Cellulose derivatives such as the hydroxyether cellulose polymers available as METHOCEL from Dow; the C ₁ -C ₄ -alkylcelluloses and C ₄ -hydroxyalkylcelluloses, cf. U.S. 4,000,093, December 28, 1976 to Nicol et al .; and the methyl cellulose ethers having an average degree of substitution (methyl) per anhydroglucose group of from about 1.6 to about 2.3 and a solution viscosity of from about 80 to about 120 centipoise measured at 20 ° C as a 2% aqueous solution. Such materials are available as METOLOSE SM100 and METOLOSE SM200, which are the trade names for methyl cellulose ethers manufactured by Shin-Etsu Kagaku Kogyo KK.

Suitable SRA's characterized by hydrophobic poly (vinyl ester) segments include graft copolymers of poly (vinyl ester), eg, C ₁ -C ₆ vinyl ester, preferably poly (vinyl acetate) grafted to polyalkylene oxide bases. See European Patent Application 0 219 048, published April 22, 1987 by Kud et al. Commercially available examples include SOKALAN-SRA's, such as SOKALAN HP-22, which is available from BASF, Germany. Other SRA's are polyesters having repeating groups containing 10-15% by weight of ethylene terephthalate together with 80-90% by weight of polyoxyethylene terephthalate derived from a polyoxyethylene glycol having an average molecular weight of 300-5,000. Commercial examples include ZELCON 5126 from Dupont and MILEASE T from ICI.

Another preferred SRA is an oligomer having the empirical formula (CAP) ₂ (EG / PG) ₅ (T) ₅ (SIP) ₁ , which comprises terephthaloyl (T), sulfoisophthaloyl (SIP), oxyethyleneoxy and oxy-1, 2-propylene (EP / PG) groups and which is preferably terminated with end caps (CAP), preferably modified isethionates, such as in an oligomer having one sulfoisophthaloyl group, five terephthaloyl groups, oxyethyleneoxy and oxy-1,2-propylene groups in a defined ratio, preferably about 0.5: 1 to about 10: 1, and two endcap groups derived from sodium 2- (2-hydroxyethoxy) ethanesulfonate. This SRA preferably further comprises from 0.5% to 20% by weight of the oligomer of a crystallinity-reducing stabilizer, for example, an anionic surfactant such as linear sodium dodecylbenzenesulfonate, or a member selected from xylene, cumene and toluenesulfonates, or mixtures thereof, these Stabilizers or modifiers are introduced into the synthesis vessel, as taught in US Pat. No. 5,415,807, Gosselink, Pan, Kellett and Hall, issued May 16, 1995. Suitable monomers for the above SRA include Na-2- (2-hydroxyethoxy) ethanesulfonate, DMT, Na-dimethyl-5-sulfoisophthalate, EG and PG.

Another group of preferred SRA's are oligomeric esters comprising:
(1) a backbone comprising (a) at least one moiety selected from the group consisting of dihydro xysulphonates, polyhydroxysulphonates, a moiety that is at least trifunctional, thereby forming ester bonds that yield a branched oligomer backbone, and combinations thereof; (b) at least one moiety which is a terephthaloyl group; and (c) at least one unsulfonated moiety which is a 1,2-oxyalkyleneoxy group; and (2) one or more capping units selected from nonionic capping units and anionic capping units such as alkoxylated, preferably ethoxylated, isethionates, alkoxylated propanesulfonates, alkoxylated propanedisulfonates, alkoxylated phenolsulfonates, sulfoaroyl derivatives and mixtures thereof. Preference is given to esters having the empirical formula: {(CAP) x (EG / PG) y '(DEG) y''(PEG)y''' (T) z (SIP) z '(SEG) q (B) m} wherein CAP, EG / PG, T and SIP are as defined above; (DEG) represents di (oxyethylene) oxy groups; (SEG) represents groups derived from the sulfoethyl ether of glycerin and related group units; (B) branching groups which are at least trifunctional, thereby forming ester bonds to give a branched oligomer backbone; x is about 1 to about 12; y 'is about 0.5 to about 25; y '' is 0 to 12, y '''is 0 to about 10; y '+ y''+y''' is about 0.5 to about 25 in total; z is about 1.5 to about 25; z 'is 0 to about 12; z + z 'is about 1.5 to about 25 in total; q is about 0.05 to about 12; m is about 0.01 to about 10; and x, y ', y ", y"', z, z ', q and m represent the average number of moles of the respective groups per mole of ester, and wherein the ester has a molecular weight in the range of about 500 to about 5,000.

Preferred SEG and CAP monomers for the above esters include Na-2- (2,3-dihydroxypropoxy) ethanesulfonate ("SEG"), Na-2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate ("SE3") and its homologs, as well as mixtures thereof, and the products of ethoxylation and sulfonation of allyl alcohol. Preferred SRA esters in this class include the product of transesterification and oligomerization of sodium 2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate and / or sodium 2- [2- {2- (2-hydroxyethoxy) ethoxy} ethanesulfonate, DMT, sodium 2- (2,3-dihydroxypropoxy) ethanesulfonate, EG and PG using a suitable Ti (IV) catalyst and can be described as (CAP) ₂ - (T) ₅ (EG / PG) _{1, 4} (SEG) _2.5 (B) _0.13 , wherein CAP is (Na + O ₃ S [CH ₂ CH ₂ O] _3.5 ) - and B is a unit of glycerol, and the molar ratio of EG / PG is about 1.7: 1 as measured by conventional gas chromatography after complete hydrolysis.

additional Classes of SRA's include: (I) nonionic terephthalates using diisocyanate coupling agents for linking of polymeric ester structures, cf. U.S. 4,201,824, Violland et al., And U.S. 4,240,918, Lagasse et al .; and (II) SRA's with carboxylate end groups, which were prepared are converted to hydroxyl end groups by addition of trimellitic anhydride to known SRA's convert to trimellitate ester. With the right catalyst selection forms the trimellitic anhydride Bonds with the ends of the polymer via an ester of the isolated carboxylic acid of trimellitic anhydride instead of opening of the anhydride bond. It can either nonionic or anionic SRA's are used as starting materials as long as they have hydroxyl end groups which are esterified can be. See US-4,525,524, Tung et al. Other classes include: (III) terephthalate-based anionic SRA's the urethane-linked Variant, cf. U.S. 4,201,824, Violland et al .; (IV) Poly (vinyl caprolactam) - and related copolymers with monomers such as vinylpyrrolidone and / or Dimethylaminoethyl methacrylate, including both nonionic as well as cationic polymers, cf. U.S. 4,579,681, Ruppert et al .; (V) graft copolymers, in addition to the SOKALAN types from BASF, which are manufactured by the Grafting of acrylic monomers onto sulfonated polyesters. For this SRA's is claimed made that she a similar Soil repellency and anti-redeposition activity such as known cellulose ethers have: cf. EP-279,134 A, 1988, to Rhone-Poulenc Chemie. Yet other classes include: (VI) graft polymers of vinyl monomers like acrylic acid and vinyl acetate to proteins such as caseins, cf. EP-457,205 A to BASF (1991); and (VII) polyester-polyamide SRA's, which are prepared by condensation of adipic acid, Caprolactam and polyethylene glycol, especially for the treatment of Polyamide weave, cf. Bevan et al., DE-2,335,044 to Unilever N.V., 1974. Other useful SRA's are in the U.S. Patents 4,240,918; 4,787,989; and 4,525,524.

complexing

The Cleaning compositions can also optionally one or more iron and / or manganese complexing Contain funds. Such complexing agents may be selected from the group consisting of Aminocarboxylates, aminophosphonates, polyfunctionally substituted, aromatic chelating agents and mixtures thereof, all as follows Are defined. Without being bound to a theory, one assumes that the The advantage of these materials, in part due to their exceptional ability to recover iron and manganese ions from washing solutions through the formation more soluble Remove complexes.

When optionally complexing agents useful Close aminocarboxylates Ethylenediaminetetraacetates, N-hydroxyethylethylenediaminetriacetates, Nitrilotriacetates, ethylenediamine tetrapropionates, triethylenetetramine hexaacetates, Diethylene triamine pentaacetates and ethane diglycines, alkali metal, Ammonium and substituted ammonium salts thereof and mixtures one of them.

Amino phosphonates are for use as complexing agents in the compositions of the invention also suitable if at least small amounts of phosphorus in total in cleaning compositions, and include ethylenediaminetrakis (methylenephosphonates) like DEQUEST. Preferably, these amino phosphonates contain no Alkyl or alkenyl groups of greater than about 6 carbon atoms.

polyfunctionally substituted aromatic complexing agents are present in the present Compositions also useful. See U.S. Patent 3,812,044, issued May 21, 1974 to Connor et al. Preferred compounds of this type in the acid form are dihydroxydisulfobenzenes such as 1,2-dihydroxy-3,5-disulfobenzene.

One preferred biodegradable complexing agent to the present Use is ethylenediamine disuccinate ("EDDS"), especially the [S, S] isomer, as in U.S. Patent 4,704,233, November 3, 1987 Hartman and Perkins, is described.

If When used, these complexing agents generally comprise from 0.1 to 10% by weight of the cleaning compositions. More preferably, if used, For example, the chelating agents comprise from 0.1% to 3.0% by weight of such compositions.

Clay soil removal / antiredeposition agents

The Compositions of the invention can also optional water-soluble ethoxylated amines with clay soil removal and anti-redeposition properties contain. granular Cleaning compositions containing these compounds, typically contain from 0.01% to 10.0% by weight of the water-soluble ethoxylated amines; liquid Cleaning compositions typically contain from 0.01 to 5%.

The most preferred soil release and anti-redeposition agents is ethoxylated tetraethylene pentamine. Exemplary ethoxylated Amines are further described in U.S. Patent 4,597,898, Vander Meer, issued July 1, 1986. A another group of preferred clay soil removal / anti redeposition agents are the cationic compounds described in the European patent application 111,965, Oh and Gosselink, published on June 27, 1984. Other clay soil removal / anti redeposition agents which can be used shut down the ethoxylated amine polymers disclosed in the European patent application 111,984, Gosselink, published on June 27, 1984; the zwitterionic polymers disclosed are in the European Patent Application 112,592, Gosselink, published July 4, 1984; and the amine oxides disclosed in U.S. Patent 4,548,744, Connor, issued October 22, 1985. Other clay soil removal / anti redeposition agents, which are known in the art can be used in the present compositions also be used. Another type of preferred anti redeposition agent includes the carboxymethylcellulose (CMC) materials. These materials are well known in the art.

Polymeric dispersants

polymers Dispersants can advantageously in proportions of 0.1 to 7% by weight in the compositions, especially in the presence of zeolite and / or layered silicate builders, be used. Suitable polymeric dispersants include polymers Polycarboxylates and polyethylene glycols, although others which are known in the art, can also be used. Without to be bound by theory, it is believed that polymeric Dispersant the total detergent builder power by crystal growth inhibition, Release of particulate Increase pollutants by peptization and anti redeposition when they in combination with other builders (including low molecular weight Polycarboxylates).

Polymeric polycarboxylate materials can be prepared by polymerizing or copolymerizing suitable unsaturated monomers, preferably in their acid form. Unsaturated monomeric acids that can be polymerized to form suitable polymeric polycarboxylates include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesacon acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments in the polymeric polycarboxylates which do not contain carboxylate radicals, such as vinylmethyl ether, styrene, ethylene, etc., is suitable; with the proviso that such segments do not constitute more than 40% by weight.

Especially suitable polymeric polycarboxylates can be derived from acrylic acid be. Such acrylic acid-based polymers, which are useful here are, are the water-soluble Salts of polymerized acrylic acid. The average molecular weight of such polymers in the acid form is preferably in the range of 2,000 to 10,000, more preferably 4,000 to 7,000, and most preferably 4,000 to 5,000. Water-soluble salts such acrylic acid polymers can for example, the alkali metal, ammonium and substituted ammonium salts lock in. soluble Polymers of this type are known materials. The usage of Polyacrylates of this type in cleaning compositions is for Example in Diehl, U.S. Patent No. 3,308,067, issued March 7, 1967, been revealed.

copolymers on acrylic / maleic acid basis can also as a preferred component of the dispersing / antiredeposition agent be used. Such materials include the water-soluble ones Salts of copolymers of acrylic acid and maleic acid one. The average molecular weight of such copolymers in the acid form is preferably in the range of 2,000 to 100,000, more preferred 5,000 to 75,000, most preferably 7,000 to 65,000. The ratio of Acrylate to maleate segments in such copolymers is generally in the range of 30: 1 to 1: 1, stronger preferably 10: 1 to 2: 1. water-soluble Salts of such acrylic acid / maleic acid copolymers can for example, the alkali metal, ammonium and substituted ammonium salts lock in. soluble Acrylate / maleate copolymers of this type are known materials, which are described in the European patent application no. 66915, published on December 15, 1982, and in EP-193,360, published on September 3 1986, which also describes such polymers which hydroxypropyl acrylate include. Other useful Close dispersant the maleic acid / acrylic acid / vinyl alcohol terpolymers one. Such materials are also disclosed in EP-193,360, including, for example the 45/45/10 terpolymer of acrylic acid / maleic acid / vinyl alcohol.

One other polymeric material that may be included is polyethylene glycol (PEG). PEG can improve the performance of a dispersant and as a clay soil removal / anti redeposition agent be effective. Typical molecular weight ranges for these Purposes are in the range of 500 to 100,000, preferably 1,000 up to 50,000, stronger preferably 1,500 to 10,000.

Polyaspartate and polyglutamate dispersants can also be used especially in connection with zeolite builders. Dispersants such as Polyaspartate preferably have a molecular weight (average) from 10,000 on.

brighteners

Any optical brighteners or other whitening or bleaching agents, which are known in the art can be used in proportions of typically from about 0.01% to about 1.2% by weight in the cleaning compositions be included. commercial optical brighteners, which may be useful in the present invention, can be used in Subgroups, including, but not necessarily limited to, derivatives of stilbene, pyrazoline, coumarin, carboxylic acids, methine cyanines, Dibenzothiophene-5,5-dioxide, azoles, 5- and 6-membered ring heterocycles and other various means. Examples of such brighteners are in "The Production and Application of Fluorescent Brightening Agents, "Zahradnik M., published by John Wiley & Sons, New York (1982).

specific Examples of optical brighteners which in the present compositions are useful are those described in U.S. Patent 4,790,856 issued to Wixon on December 13, 1988. These brighteners close the PHORWHITE series from brighteners of Verona. Others disclosed in this reference Close Brightener a: Tinopal UNPA, Tinopal CBS and Tinopal 5BM, available from Ciba-Geigy; Artic White CC and Artic White CWD; the 2- (4-strylphenyl) -2H-naphthol [1,2-d] triazoles; 4,4'-bis- (1,2,3-triazol-2-yl) stilbenes; 4,4'-bis (stryl) biphenyls; and the aminocoumarins. Specific examples of these brighteners include 4-methyl-7-diethyl-aminocoumarin; 1,2-bis (benzimidazol-2-yl) ethylene; 1,3-diphenyl-pyrazolines; 2,5-bis (benzoxazol-2-yl) thiophene; 2-Styrylnaphtho- [1,2-d] oxazole; and 2- (stilben-4-yl) -2H-naphtho [1,2] triazole. See also US patent 3,646,015 issued to Hamilton on February 29, 1972.

Suds suppressors

Compounds for reducing or suppressing the formation of foam can be found in the be included in the compositions according to the invention. Foam suppression may be of particular importance in the so-called "high concentration cleaning process" as described in US-4,489,455 and 4,489,574, and in European front-loading washers.

A size Variety of materials can be used as suds suppressors, and Suds suppressors are well known to the professionals. See, for example, Kirk Othmer's Encyclopedia of Chemical Technology, Third Edition, Volume 7, pages 430-447 (John Wiley & Sons, Inc., 1979). A category of suds suppressor of particular interest comprises Monocarboxylic fatty and soluble Salts thereof. See U.S. Patent 2,954,347, issued September 27 1960 to Wayne St. John. The monocarboxylic fatty acids used as suds suppressors and their salts typically have hydrocarbyl chains of 10 to 24 Carbon atoms, preferably 12 to 18 carbon atoms, on. Close suitable salts the alkali metal salts, such as sodium, potassium and lithium salts, and Ammonium and alkanolammonium salts.

The cleaning compositions may also contain non-surfactant foam depressants. These include, for example: high molecular weight hydrocarbons such as paraffin; Fatty acid esters (eg fatty acid triglycerides); Fatty acid esters of monohydric alcohols; aliphatic C ₁₈ -C ₄₀ ketones (eg stearone), etc. Other suds inhibitors include N-alkylated amino triazines such as tri- to Hexaalkyhnelamine or di- to tetra which are formed as products of cyanuric chloride with 2 or 3 moles of a primary or secondary amine containing 1 to 24 carbon atoms; propylene oxide; and monostearyl phosphates such as monostearyl alcohol phosphate ester; and monostearyldialkali metal (eg, K, Na, and Li) phosphates and phosphate esters. The hydrocarbons, such as paraffin and halogen paraffin, can be used in liquid form. The liquid hydrocarbons are liquid at room temperature and atmospheric pressure and have a pour point in the range of about -40 ° C to about 50 ° C and a minimum boiling point of less than about 110 ° C (atmospheric pressure). The use of waxy hydrocarbons, preferably having a melting point below 100 ° C, is also known. The hydrocarbons are a preferred category of suds suppressor for cleaning compositions. Hydrocarbon suds suppressors are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al. Finally, the hydrocarbons will eventually include aliphatic, alicyclic, aromatic and heterocyclic, saturated or unsaturated hydrocarbons having from about 12 to about 70 carbon atoms. The term "paraffin" as used in this suds suppressor discussion is intended to include mixtures of pure paraffins and cyclic hydrocarbons.

A Another preferred category of non-surfactant suds suppressor includes silicone suds suppressor. These Category closes the use of polyorganosiloxane oils, such as polydimethylsiloxane, dispersions or emulsions of polyorganosiloxane oils or resins and combinations of polyorganosiloxane with silica particles, wherein the polyorganosiloxane is chemisorbed or fused to the silica is a. Silicone suds suppressors are well known in the art and are described, for example, in U.S. Patent 4,265,779, issued May 5, 1981 to Gandolfo et al., And in U.S. Pat European Patent Application No. 89307851.9, published on February 7, 1990, by Starch M.S, revealed.

Other Silicone suds suppressors are disclosed in U.S. Patent 3,455,839, which discloses compositions and method of defoaming of aqueous solutions the inclusion lower Amounts of Polydimethylsiloxanfluids relates.

mixtures of silicone and silanized silica are, for example, in the German Patent Application DOS-2,124,526. Silicone defoaming agent and foam control agents in granular detergent compositions are disclosed in U.S. Patent 3,933,672, Bartolotta et al., and U.S. Patent 4,652,392 Baginski et al., Issued Mar. 24, 1987.

• (i) einem Polydimethylsiloxanfluid mit einer Viskosität von 20 cs bis 1.500 cs bei 25°C;
• (ii) 5 bis 50 Teilen pro 100 Gewichtsteilen von (i) einem Siloxanharz, bestehend aus (CH₃)₃SiO_1/2-Einheiten und SiO₂-Einheiten in einem Verhältnis von (CH₃)₃SiO_1/2-Einheiten zu SiO₂-Einheiten von 0,6:1 bis 1.2:1; und
• (iii) 1 bis 20 Teilen pro 100 Gewichtsteilen von (i) einem festen Silicagel.

An exemplary silicone-based suds suppressor for use herein is a suds suppressing amount of a suds controlling agent consisting essentially of:

• (i) a polydimethylsiloxane fluid having a viscosity of from 20 cs to 1500 cs at 25 ° C;
• (ii) 5 to 50 parts per 100 parts by weight of (i) a siloxane resin consisting of (CH ₃ ) ₃ SiO _1/2 units and SiO ₂ units in a ratio of (CH ₃ ) ₃ SiO _1/2 units to SiO ₂ units of 0.6: 1 to 1.2: 1; and
• (iii) 1 to 20 parts per 100 parts by weight of (i) a solid silica gel.

In the preferred silicone suds suppressor used herein, the solvent for a continuous phase consists of certain polyethylene glycols or polyethylene-polypropylene glycol copolymers or mixtures thereof (preferred) or polypropylene glycol. The primary silicone foam below pusher is branched / crosslinked and preferably not linear.

Around To further illustrate this point, typical liquid laundry detergent compositions include with a controlled foaming, optionally from 0.001 to 1% by weight, preferably 0.01 to 0.7% by weight, most preferably 0.05 to 0.5 wt%, of the silicone suds suppressor, comprising: (1) a non-aqueous emulsion a primary Antifoam which is a mixture of (a) a polyorganosiloxane, (b) a resinous siloxane or a silicone resin generating agent Silicone compound, (c) a finely divided filler material, and (d) a Catalyst to control the reaction of the mixture components (a), (b) and (c) to accelerate to produce silanolates; (2) at least a nonionic silicone surfactant; and (3) polyethylene glycol or a copolymer of polyethylene-polypropylene glycol having a solubility in water at room temperature of more than 2% by weight; and without polypropylene glycol. Similar Quantities can in granular Compositions or gels are used. See also US patents 4,978,471, Starch, issued December 18, 1990, and 4,983,316, Starch, issued on January 8, 1991; 5,288,431, Huber et al., Issued to February 22, 1994; and U.S. Patents 4,639,489 and 4,749,740 to Aizawa et al., col. 1, line 46 to col. 4, line 35.

Of the Silicone suds suppressors comprises preferably polyethylene glycol and a copolymer of polyethylene glycol / polypropylene glycol, all with an average molecular weight of less than 1,000, preferably between 100 and 800. The polyethylene glycol and the polyethylene / polypropylene copolymers have a solubility in water at room temperature of more than 2% by weight, preferably more than 5 wt .-%, on.

The preferred solvents is polyethylene glycol having an average molecular weight of less than about 1,000, stronger preferably between about 100 and 800, most preferably between 200 and 400, and a copolymer of polyethylene glycol / polypropylene glycol, preferably PPG-200 / PEG-300. Preference is given to a weight ratio between about 1: 1 and 1:10, most preferably between 1: 3 and 1: 6, of Polyethylene glycol to the copolymer of polyethylene / polypropylene glycol.

The preferred silicone suds suppressor used herein contain no polypropylene glycol, especially with a molecular weight from 4,000. They also preferably do not contain block copolymers of ethylene oxide and propylene oxide, such as PLURONIC L101.

Other suds suppressors which are useful herein include the secondary alcohols (eg, 2-alkylalkanols) and mixtures of such alcohols with silicone oils, such as the silicones disclosed in US 4,798,679 and 4,075,118 and EP-150,872. The secondary alcohols include the C ₆ -C ₁₆ alkyl alcohols having a C ₁ -C ₁₆ chain. A preferred alcohol is 2-butyloctanol available from Condea under the trademark ISOFOL 12. Mixtures of secondary alcohols are available under the trademark ISALCHEM 123 from Enichem. Mixed suds suppressors typically comprise mixtures of alcohol + silicone in a weight ratio of 1: 5 to 5: 1.

For any Cleaning compositions used in laundry washing machines they are supposed to be not to the extent foam that they should make flood the washing machine. Suds suppressor, if used are preferably in a "foam suppressing amount". By the term "foam-suppressing amount" is meant that the manufacturer the composition can choose a quantity of this foam control agent, which controls the foam sufficiently to produce a low foaming laundry detergent for use in automatic laundry washing machines.

The compositions generally comprise 0 to 5% suds suppressor. When monocarboxylic fatty acids and their salts are used as suds suppressors, they are typically present in amounts of up to 5% by weight of the cleaning composition. Preferably, 0.5 to 3% fat monocarboxylate suds suppressor is used. Silicone suds suppressors are typically used in amounts of up to 2.0% by weight of the cleaning composition, although larger amounts may be used. This upper limit is of a practical nature, due mainly to the interest in keeping costs to a minimum, and the effectiveness of small amounts for effective control of foaming. Preferably, 0.01 to 1% silicone suds suppressor, more preferably 0.25 to 0.5%, is used. As used herein, these weight percentages include any silica that may be used in combination with polyorganosiloxane, as well as any adjunct materials that may be used. Monostearyl phosphate suds suppressors are generally used in amounts ranging from 0.1% to 2% by weight of the composition. Hydrocarbon suds suppressors are typically used in amounts ranging from about 0.01 to 5.0%, although higher levels are used can be. The alcohol suds suppressors are typically used in 0.2 to 3% by weight of the finished compositions.

fabric softeners

Different about that Washing effective fabric softeners, especially the very fine smectite clays of U.S. Patent 4,062,647, Storm and Nirschl, issued December 13 1977, as well as other plasticizer clay known in the art, can optionally, typically in proportions of 0.5 to 10% by weight, in The present compositions can be used simultaneously to provide fabric softening benefits with fabric cleaning. Clay plasticizers can used in combination with amine and cationic plasticizers as described, for example, in U.S. Patent 4,375,416, Crisp et al. March 1983, and U.S. Patent 4,291,071, Harris et al., issued September 22 1981, is disclosed

Dye transfer inhibitors

The Compositions of the invention can also include one or more materials which are in inhibition the transmission from dyes from one fabric to another during the Cleaning process are effective. In general, such include Dye transfer inhibitors polyvinylpyrrolidone polymers, polyamine N-oxide polymers, Copolymers of N-vinylpyrrolidone and N-vinylimidazole, manganese phthalocyanine, Peroxidases and mixtures thereof. If used, include these agents typically about 0.01 to about 10%, based on the weight of the composition, preferably about 0.01 to about 5% and stronger preferably about 0.05 to about 2%.

More specifically, the polyamine N-oxide polymers preferred for use contain units having the following structural formula: RA _x -P, where P is a polymerizable moiety to which an NO group may be attached, or the NO group may be part of the form a polymerisable unit, or the NO group may be bonded to both units; A is one of the following structures: -NC (O) -, -C (O) O-, -S-, -O- or -N =; x is 0 or 1; and R is aliphatic, ethoxylated aliphatic, aromatic, heterocyclic or alicyclic groups, or any combination thereof, to which the nitrogen of the NO group may be attached, or the NO group is a part of these groups. Preferred polyamine N-oxides are those wherein R is a heterocyclic group such as pyridine, pyrrole, imidazole, pyrrolidine, piperidine and derivatives thereof.

worin R₁, R₂ und R₃ aliphatische, aromatische, heterocyclische oder alicyclische Gruppen oder Kombinationen hiervon sind; x, y und z 0 oder 1 sind; und der Stickstoff der N-O-Gruppe an irgendeine der vorstehend erwähnten Gruppen gebunden sein kann oder einen Teil hiervon bildet. Die Aminoxidgruppe der Polyamin-N-oxide weist einen pKa < 10, vorzugsweise einen pKa < 7 und stärker bevorzugt einen pKa < 6 auf.The NO group can be given by the following general structures:

wherein R ₁ , R ₂ and R _{3 are} aliphatic, aromatic, heterocyclic or alicyclic groups or combinations thereof; x, y and z are 0 or 1; and the nitrogen of the NO group may be attached to or form part of any of the aforementioned groups. The amine oxide group of the polyamine N-oxides has a pKa <10, preferably a pKa <7, and more preferably a pKa <6.

each Polymer backbone may be used as long as the amine oxide polymer formed is water-soluble and dye transfer inhibiting Owns properties. Examples of suitable polymeric backbones are. Polyvinyls, polyalkylenes, polyesters, polyethers, polyamide, polyimides, Polyacrylates and mixtures thereof. These polymers close randomly or block copolymers wherein one type of monomer is an amine N-oxide and the other monomer type is an N-oxide. The amine N-oxide polymers have typically a ratio from amine to amine N-oxide from 10: 1 to 1: 1,000,000. however For example, the number of amine oxide groups present in the polyamine oxide polymer by suitable copolymerization or by a suitable degree the N-oxidation can be varied. The polyamine oxides can be used in virtually any degree of polymerization can be obtained. typically, the average molecular weight is in the range of 500 up to 1,000,000; stronger preferably 1,000 to 500,000; most preferably 5,000 to 100,000. This preferred class of materials may be referred to as "PVNO".

The most preferred polyamine N-oxide used in the cleaning compositions useful is poly (4-vinylpyridine-N-oxide), which is an average Molecular weight of about 50,000 and a ratio of amine to amine N-oxide of about 1: 4.

copolymers of N-vinylpyrrolidone and N-vinylimidazole polymers (designated as a class as "PVPVI") become the present Use also preferred. Preferably, the PVPVI has an average Molecular weight in the range of 5,000 to 1,000,000, more preferred 5,000 to 200,000, and most preferably 10,000 to 20,000. (The average molecular weight range is determined by light scattering determined as described in Barth et al., Chemical Analysis, Volume 113, "Modern Methods of Polymer Characterization ", the disclosures of which are hereby incorporated by reference Reference). The PVPIV copolymers are typically a molar ratio from N-vinylimidazole to N-vinylpyrrolidone of 1: 1 to 0.2: 1, more preferred 0.8: 1 to 0.3: 1, and most preferably 0.6: 1 to 0.4: 1. These Copolymers can be either linear or branched.

The Compositions of the invention can also a polyvinylpyrrolidone ("PVP") with an average Molecular weight of about 5,000 to about 400,000, preferably about 5,000 to about 200,000 and stronger preferably use about 5,000 to about 50,000. PVP's are the professionals known in the detergent field; see. for example EP-A-262,897 and EP-A-256,696. PVP-containing compositions may also Polyethylene glycol ("PEG") with an average Molecular weight of about 500 to about 100,000, preferably about 1,000 to about 10,000, included. Preferably, the ratio of PEG to PVP based on ppm, released into the wash solutions, about 2: 1 to about 50: 1 and stronger preferably about 3: 1 to about 10: 1.

The Cleaning compositions can also optionally from 0.005 to 5% by weight of certain types of hydrophilic optical brighteners which also contain a dye transfer inhibiting Provide effect. If used, the compositions include preferably 0.01 to 1 wt .-% of such optical brightener.

worin R₁ gewählt ist aus Anilino, N-2-Bis-hydroxyethyl und NH-2-Hydroxyethyl; R2 gewählt ist aus N-2-Bis-Hydroxyethyl, N-2-Hydroxyethyl-N-methylamino, Morphilino, Chlor und Amino; und M ein salzbildendes Kation ist, wie Natrium oder Kalium.The hydrophilic optical brighteners useful in the present invention are those having the structural formula:

wherein R _{1 is} selected from anilino, N-2-bis-hydroxyethyl and NH-2-hydroxyethyl; R2 is selected from N-2-bis-hydroxyethyl, N-2-hydroxyethyl-N-methylamino, morphilino, chloro and amino; and M is a salt-forming cation, such as sodium or potassium.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-bis-hydroxyethyl and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6- (N-) 2-to-hydroxyethyl) -s-triazine-2-yl) amino] -2,2'-stilbene disulfonic acid disodium salt. This particular brightener species is commercially available under the tradename Tinopal-UNPA-GX from Ciba-Geigy Corporation. Tinopal-UNPA-GX is the preferred hydrophilic optical brightener useful in the cleaning compositions.

In the above formula, when R _{1 is} anilino, R _{2 is} N-2-hydroxyethyl-N-2-methylamino and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6 - (N-2-hydroxyethyl-N-methylamino) -s-triazine-2-yl) amino] 2,2'-stilbenedisulfonic acid disodium salt. This particular brightener species is commercially available under the trade name Tinopal 5BM-GX from Ciba-Geigy Corporation.

In the above formula, when R _{1 is} anilino, R _{2 is} morphilino and M is a cation such as sodium, then the brightener is 4,4'-bis - [(4-anilino-6-morphilino-s-triazin-2-yl ) amino] 2,2'-stilbene disulfonic acid sodium salt. This particular brightener species is commercially available under the tradename Tinopal AMS-GX from Ciba-Geigy Corporation.

The specific optical brightener species selected for use in the present invention provide particularly effective performance advantages in dye transfer inhibition when used in combination with the selected polymeric dye transfer inhibiting agents described above. The combination of such selected polymeric materials (eg, PVNO and / or PVPVI) with such selected optical brighteners (eg, Tinopal UNPA-GX, Tinopal 5BM-GX, and / or Tinopal AMS-GX) provides significantly better dye transfer inhibition in aqueous solution wash solutions as one of these two detergent composition components when used alone. Without wishing to be bound by theory, it is believed that such brighteners are effective in this manner because they have a high affinity for fabrics in the wash solution and therefore deposit relatively quickly on these fabrics. The extent to which the brighteners deposit on the fabrics in the wash solution can be defined by a parameter called the "exhaustion coefficient". The exhaustion coefficient is generally defined as the ratio of a) the brightener material deposited on the fabrics to b) the initial brightener concentration in the wash liquor. Brighteners with relatively high exhaustion coefficients are the most suitable in the context of the present invention for inhibiting dye transfer.

of course is recognizable that others conventional Connection types of optical brighteners optionally in the present Compositions can be used to conventional Tissue "luminosity" advantages instead a true dye transfer inhibition effect provided. Such use is common for detergent formulations and well known.

pH and buffering variation

Lots Automatic dishwashing detergent compositions buffered, i. they are against a pH drop in the presence of acidic contaminants relatively stable. However, other compositions may an exceptionally low buffering capacity have or can be essentially unbuffered. Techniques for control or change of the pH at the recommended use levels close more generally not only the use of buffers, but also of additional ones Alkali, acids, pH-spanning systems or two-chamber containers and are the experts well known.

• (i) Natriumcarbonat oder -sesquicarbonat;
• (ii) Natriumsilicat, vorzugsweise wäßriges Natriumsilicat mit einem SiO₂:Na₂O-Verhältnis von 1:1 bis 2:1, und Mischungen hiervon mit begrenzten Mengen von Natriummetasilicat;
• (iii) Natriumcitrat;
• (iv) Citronensäure;
• (v) Natriumbicarbonat;
• (vi) Natriumborat, vorzugsweise Borax;
• (vii) Natriumhydroxid; und
• (viii) Mischungen von (i)–(vii).

The preferred ADD compositions comprise a pH adjusting component selected from water-soluble, alkaline, inorganic salts and water-soluble, organic or inorganic builders. The pH adjusting components are chosen so that when the ADD is dissolved in water at a concentration of 1,000-5,000 ppm, the pH remains in the range of above about 8, preferably about 9.5 to 11. The preferred non-phosphate component for pH adjustment according to the invention is selected from the group consisting of:

• (i) sodium carbonate or sesquicarbonate;
• (ii) sodium silicate, preferably aqueous sodium silicate having a SiO ₂ : Na ₂ O ratio of 1: 1 to 2: 1, and mixtures thereof with limited amounts of sodium metasilicate;
• (iii) sodium citrate;
• (iv) citric acid;
• (v) sodium bicarbonate;
• (vi) sodium borate, preferably borax;
• (vii) sodium hydroxide; and
• (viii) mixtures of (i) - (vii).

Preferred embodiments contain low levels of silicate (ie, 3 to 10% SiO ₂ ).

Illustrative for special Preferred pH adjusting components are binary mixtures of granular sodium citrate with anhydrous sodium carbonate and three-component mixtures of granular Sodium citrate trihydrate, citric acid monohydrate and anhydrous Sodium.

The Amount of pH adjusting component in the present ADD compositions is preferably 1 to 50%, based on the weight of the composition. In a preferred embodiment is the component for pH adjustment in the ADD composition in an amount of 5 to 40% by weight, preferably 10 to 30 wt .-%, before.

For compositions especially with a pH between 9.5 and 11 of the initial wash solution preferred ADD embodiments, based on the weight of the ADD, 5 to 40%, preferably 10 to 30%, most preferably 15 to 20%, sodium citrate together with about 5 to 30%, preferably 7 to 25%, most preferably 8 to 20%, sodium carbonate.

The essential pH-adjusting system can be supplemented with other optional detergent builder salts (ie for improved hard water sequestration) selected from non-phos phat detergent builders known in the art, comprising the various water-soluble alkali metal, ammonium or. substituted ammonium borates, hydroxysulfonates, polyacetates and polycarboxylates. Preference is given to the alkali metal salts, especially the sodium salt, of such materials. Other water-soluble organic nonphosphorus builders can be used for their sequestering properties. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraacetic acid, nitrilotriacetic acid, tartrate monosuccinic acid, tartrate disuccinic acid, oxydisuccinic acid, carboxymethoxysuccinic acid or mellitic acid and sodium benzene polycarboxylate salts.

(a) Water-soluble silicates

The present automatic dishwashing detergent compositions may further water-soluble Include silicates. water-soluble Silicates are any silicates which are soluble to the extent that that she the stains / filming properties of the ADD composition are not unfavorable influence.

Examples of silicates are sodium metasilicate and, more generally, the alkali metal silicates, especially those having a SiO ₂ : Na ₂ O ratio in the range of 1.6: 1 to 3.2: 1, and layered silicates, such as the sodium layer silicates described in U.S. Patent 4,664,839 , issued May 12, 1987 to Rieck HP ^® NaSKS-6 is a crystalline layered silicate marketed by Hoechst (commonly abbreviated herein as "SKS-6"). Unlike zeolite builders, NaSKS-6 and other useful water-soluble silicates do not contain aluminum. NaSKS-6 is the 6-Na ₂ SiO ₅ form of a layered silicate and can be prepared by methods such as those described in DE-A-3,417,649 and DE-A-3,742,043. SKS-6 is a preferred layered silicate for use herein, but other such layered silicates, such as those having the general formula NaMSi _x O _{2x + 1} x yH ₂ O, wherein M is sodium or hydrogen, x is a number from 1.9 to 4, preferably 2, and y is a number from 0 to 20, preferably 0, may be used. Several other layered silicates from Hoechst include NaSKS-5, NaSKS-7 and NaSKS-11 as α, β and γ forms. Other silicates may also be useful, such as magnesium silicate, which may serve as a granulating agent in granular formulations, as a stabilizer for oxygen bleaching and as a component of foam control systems.

Silicates are particularly useful in applications for automatic dishwashing (ADD) applications include granular aqueous silicates having a ratio of 2.0 a, as BRITESIL ^® H20 from PQ Corp. and usually ver as starting material employed BRITESIL ^® H24 though liquid grades of various silicates can be used when the ADD composition is in liquid form. Within certain limits, sodium metasilicate or sodium hydroxide alone or in combination with other silicates may be used in conjunction with an ADD to increase the wash pH to a desired level.

Materialpflegmittel

The present ADD compositions may contain one or more material care agents which are used as corrosion inhibitors and / or anti-tarnish aids are effective. Such materials are preferred components of Automatic dishwashing compositions, especially in certain European countries where the use of galvanized nickel silver and sterling silver in household cutlery is still relatively common, or if aluminum protection is of importance and the composition is low in silicic acid. In general shut down such material care agents metasilicate, silicate, bismuth salts, manganese salts, Paraffin, triazoles, pyrazoles, thiols, mercaptans, aluminum fatty acid salts and mixtures thereof.

If present, such protective materials are preferably included in minor amounts, eg, 0.01 to 5% of the ADD composition. Suitable corrosion inhibitors include paraffin oil, typically a predominantly branched aliphatic hydrocarbon having a number of carbon atoms in the range of from 20 to 50, with a preferred paraffin oil being predominantly branched C _25-45 species having a ratio of cyclic to noncyclic hydrocarbons of about 32:68 is selected. A paraffin oil which fulfills these characteristics is sold by Wintershall, Salzbergen, Germany, under the trade name WINOG 70. In addition, the addition of small amounts of bismuth nitrate (ie Bi (NO ₃ ) ₃ ) is also preferred.

Other corrosion inhibitor compounds include benzotriazole and comparable compounds; Mercaptans or thiols, including thionaphthol and thioanthranol; and finely divided aluminum fatty acid salts, such as aluminum tristearate. The manufacturer is aware that such materials are generally to be used judiciously and in limited amounts to avoid any tendency to stain or film glassware or to affect the bleaching performance of the compositions. For this reason, mercaptan anti-tarnish aids, which are very reactive to the bleach, and conventional fatty carboxylic acids, which precipitate especially with calcium, are preferably avoided.

Other ingredients

A wide variety of other ingredients useful in cleaning compositions can be included in the compositions, including other active ingredients, carriers, hydrotropes, processing aids, dyes or pigments, solvents for liquid formulations, solid fillers for bar shaped compositions, etc. If heavy foaming foam boosters, such as the C ₁₀ -C ₁₆ alkanolamides, may be included in the compositions, typically in proportions of from 1 to 10%. The C ₁₀ -C ₁₄ monoethanol and diethanolamides illustrate a typical class of such suds boosters. The use of such suds boosters together with high sudsing adjunct surfactants, such as the amine oxides, betaines and sultaines mentioned above, is also advantageous. Optionally, soluble magnesium salts such as MgCl ₂ , MgSO ₄ and the like can be added in proportions of typically 0.1 to 2% to provide additional foam and enhance grease removal performance.

Various Detergent ingredients used in the present compositions can be used optionally by absorption of the components to a porous hydrophobic Substrate, then coating of the substrate with a hydrophobic coating, further stabilized become. Preferably, the detergent component with a Surfactant mixed before it is adsorbed to the porous substrate. In use, the detergent ingredient is removed from the substrate released into the aqueous wash liquor, where he fulfills his intended cleaning function.

To more fully illustrate this technique, a porous hydrophobic silica (trademark SIPERNAT D10, DeGussa) is mixed with a proteolytic enzyme solution containing 3-5% of a nonionic surfactant in the form of an ethoxylated (EO 7) C _13-15 alcohol. Typically, the enzyme / surfactant solution accounts for 2.5 times the weight of the silica. The resulting powder is dispersed in silicone oil with stirring (various silicone oil viscosities ranging from 500 to 12,500 can be used). The resulting silicone oil dispersion is emulsified or otherwise added to the final detergent matrix. By this method, ingredients such as the aforementioned enzymes, bleaches, bleach activators, bleach catalysts, photoactivators, dyes, fluorescers, fabric care agents, and hydrolyzable surfactants may be "protected" for use in cleaners, including liquid laundry detergent compositions.

Liquid cleaning compositions can Water and other solvents as a carrier contain. Low molecular weight, primary or secondary alcohols, exemplified by methanol, ethanol, propanol and Isopropanol, are suitable. Monohydric alcohols become solubilizing of the surfactant, but polyols such as those of 2 to about 6 Carbon atoms and 2 to about 6 hydroxyl groups (e.g., 1,3-propanediol, Ethylene glycol, glycerol and 1,2-propanediol) may also be used. The Compositions can 5 to 90%, typically 10 to 50%, of such carriers.

The Cleaning compositions are preferably prepared so that during the Application in aqueous cleaning processes the wash water has a pH between about 6.5 and about 11, preferably between about 7.5 and about 10.5.

Liquid product formulations for washing dishes preferably have a pH between about 6.8 and about 9.0. Laundry products are typically at pH 9-11. Techniques to control the pH at the recommended use levels shut down the use of buffers, alkali, acids, etc. and are the Well known to professionals.

Granular cleaning composition high density

The Delivery systems in the form of a glassy particle can in granular Both low density (below 550 Grams / liter) as well as high density, wherein the density of the granules is at least 550 grams / liter, be used. Such high density cleaning compositions typically comprise 30 to 90% of a cleaning surfactant.

compositions low density can by usual Spray-drying process getting produced. Various means and equipment are available to granular To prepare cleaning compositions with high density. The current commercial practice in the field used spray towers to granular laundry detergent which often have a density of less than 500 g / l. Accordingly, if a spray-drying As part of the overall process, the resulting spray-dried must be applied Particles using the means described below and equipment be further compressed. In another embodiment, the manufacturer may spray-drying the use of a mixing, compacting and granulating apparatus, which are commercially available is, exclude. The following is a non-limiting description of one of the present Use suitable equipment.

In in the present method High speed mixer / compressor can be used. For example, the under the trademark "Lodige CB30 "recyclers sold Device a static, cylindrical mixing drum with a central, rotating axis, whereupon mixing blade / cutting knife attached are. Another such apparatus includes those sold under the trademark "Shugi Granulator" and under the trademark "Drais K-TTP 80" one. Appliances, like those under the trademark "Lodige KM600 mixer ", can be used for further compaction.

at a procedure, the compositions are prepared and passing through two mixing and compacting devices, which work in series, condensed. In this way, the desired Ingredients of the composition are mixed and mixed through a Lodige mixer passed using residence times of 0.1 to 1.0 minutes and then through a second Lodige mixer using Residence times of 1.0 minute to 5 minutes are passed.

at Another method will involve an aqueous slurry the desired Ingredients of the formulation into a fluidized bed of particulate surfactants sprayed. The resulting particles can passing through a Lodige device as noted above be compacted. The glassy particles are mixed with the cleaning composition in the Lodige device mixed.

The Finished density of the particles can be achieved by a variety of simple techniques which are typically dispensing a lot of the granular Detergent in a container with known volume, measuring the weight of the detergent and representing the density in grams / liter.

To the production of granular Detergent "base" composition low or high density becomes the release system of the present invention in the form of a glassy particle by a suitable dry mixing method added to it.

The Process for washing textiles and separating a fragrance on it contacting the textiles with an aqueous wash liquor comprising at least about 100 ppm conventional Detergent ingredients as described above, as well as at least about 1 ppm of the above disclosed fragrance release system. Preferably comprises the aqueous liquor 500 ppm to 20,000 ppm of conventional Detergent ingredients and 10 ppm to 200 ppm of the fragrance release system.

The Release system in the form of a glassy particle is among all conditions effective, but is particularly useful Fragrance scent benefits on textiles during storage, drying and drying ironing provided. The method comprises contacting the textiles with an aqueous liquor containing at least 100 ppm conventional Detergent ingredients and at least 1 ppm of the composition for releasing the fragrance, so that the perfumed zeolite on be carried along with the textiles, storing the on the clothesline dried fabrics under ambient conditions with a moisture of at least 20%, drying the textiles in a conventional automatic dryer or the supply of heat to the textiles, which at low heat (less than 50 ° C) on the clothesline dried or machine dried by conventional ironing facilities (preferably with steam or with prior wetting).

The The following nonlimiting examples illustrate the invention used according to Parameters and compositions. All percentages, parts and ratios are by weight unless otherwise stated.

Example I

1. Production a perfume laden zeolite

10 g activated zeolite Na-X (<5% Residual moisture) are in a simple mixer or a mixer of the type of a coffee grinder brought in. For this purpose, 1.5 g of perfume are added dropwise. The mixer is moved about 10 minutes, with a postcode (a fragrance laden Zeolite) with a loading of 15% w / w. is obtained.

2. Preparation of a sucrose syrup low humidity (Tg = 57 ° C)

75 g of sucrose are mixed with 25 g of distilled water. The The system is heated with continued stirring until sufficient water is removed to a 2-5% To obtain water-containing syrup. Under atmospheric Pressure results in such low water content boiling points of the viscous Syrups in the range of 150-160 ° C.

3. combination the postcode and the sucrose syrup with low humidity

The Low-moisture sucrose syrup is allowed to stir while stirring about 90 ° C cooling down, at this time, the post code is added to the syrup. typically, will be a share of 20-30 Wt .-% postcode added, with higher Shares a greater effort required (such as the use of a mixer or extruder with high torque) to cope with increases in viscosity.

4. Education / Shredding a glassy particle

The Postcode dispersion in the sucrose syrup is allowed to reach ambient temperature cooling down. When the temperature of the system is below the glass transition temperature of sucrose falls a glassy system is obtained which is ground and different Particle sizes sorted can be.

5. Combination of particulate glass from step (4) with the detergent base

2.22% the glassy particles can added to a detergent formulation by 0.67% ZIP and 0.1% perfume release.

Example II

The execution takes place in a similar As in Example I but using an 80:20 mixture of sucrose / maltodextrin (DE = 10). Such systems can also a mixture of sucrose or another oligosaccharide with low MW and a polysaccharide or starch with a DE value of less as 15, preferably <10, in a proportion of at least 10% w / w include. A typical one Sucrose / maltodextrin melt comprised 80% sucrose and 20% LoDex 5 (from American Maize) containing 2% water. The melt is then charged to a ZSK 30 twin screw extruder from Werner & Pfleiderer, wherein the postal code in a proportion of 20% w / w. into the seventh zone of the extruder is introduced. The extrudates are cooled to 90 ° C and comminuted to particles of 500-1,000 microns and sorted.

The Examples I and II do not fall within the claimed scope.

Claims (9)

A laundry or cleaning composition comprising: at least one non-soap detergent active material and glassy particles comprising perfume, a perfume carrier material carrying the perfume by absorption on the surface of the carrier material or by adsorption in the pores of the carrier material, and a glass derived from one or more at least partially water-soluble hydroxyl compounds selected from the group consisting of: (i) natural or synthetic gums; or (ii) chitin; or (iii) chitosan; or (iv) cellulose and derivatives thereof; wherein at least one of the hydroxyl compounds has a glass transition temperature, Tg, in anhydrous, not plasticized state of 0 ° C or higher, and wherein the glassy particles have a hygroscopicity value of less than 80%. A composition according to claim 1, wherein the perfume includes a pro-fragrance. A composition according to claim 1 or 2, wherein said Fragrance carrier material a porous one Solid is selected from the group consisting of amorphous silicates, crystalline non-stratified Silicates, layered silicates, calcium carbonates, sodium carbonates, Clays, zeolites, sodalites, alkali metal phosphates, macroporous zeolites, chitin, Carboxyalkylcelluloses and mixtures thereof. A composition according to claim 3, wherein the perfume carrier material is a porous solid having a surface area of at least 50 m ² / g. A composition according to claim 3 or 4, wherein the support material selected is made of zeolites and macroporous Zeolites, and more preferably selected from zeolite X, zeolite Y and mixtures thereof. A composition according to claim 4, wherein the perfume in the perfume carrier material contained to such an extent or is borne by him, that not more than 70% by weight, preferably not more than 45% by weight, of the total perfume material free from the fragrance carrier material and wherein the glassy particle has a moisture content, as produced, of not more than 10% by weight. Composition according to at least one of the preceding Claims, which further comprises a crystallinity modifier in one portion from 0.0001% to 1% by weight of the glassy particle, preferably potassium bitartrate, includes. A composition according to claim 6, wherein the glassy Particles no longer have a moisture content as produced as 10% by weight, preferably not more than 7% by weight, especially preferably not more than 5% by weight. Composition according to at least one of the preceding Claims, wherein the glassy particle comprises an external coating, preferably a salt, selected borates, silicates, citrates, carbonates, bicarbonates, sulphates, waxy coatings, polymer, as well as mixtures thereof.