EP1911833B1

EP1911833B1 - Dosed or dosable washing agent

Info

Publication number: EP1911833B1
Application number: EP07019771.0A
Authority: EP
Inventors: Rudolf Gitzi; Ivan Hübscher; Karin Kleeli; Hans Eggenschwiler; Hartmut Kilian
Original assignee: Mifa AG Frenkedorf
Current assignee: Mifa AG Frenkedorf
Priority date: 2006-10-11
Filing date: 2007-10-10
Publication date: 2013-07-03
Anticipated expiration: 2027-10-10
Also published as: EP1911833A1

Description

The present invention relates to a dishwashing agent in form of dosed pieces, in particular a washing agent for use in machines (such as dishwashers), especially dosed pieces, wherein the stability of the wash active substances (in particular enzymes and the bleaching system) is secured by a specific composition and production method; to production processes thereof and to the use of such washing agents.
In dishwashers, in general a predetermined amount of washing agent is needed to get the desired cleaning result. For washing agents in powder form and for liquid washing agent, the recommended amount is indicated on the package. However, since many people do not well read the recommendation, the result may be unsatisfactory or the environment may be unnecessarily burdened with excess agent. In addition, for convenience, more and more people prefer pre-portioned washing agents, e.g. tablets. Hitherto - due to insufficient stability of some of the active ingredients, especially in humid and hot environment as it exists during hot washing cycles in most sections of the dishwasher or the washing machine - the washing agent has to be added for each washing cycle. It is therefore much desirable to have a composition that can easily be formed into solid dosing units and that is storage stable, preferably also in humid environment, much preferred in humid and hot environment.
Further, conventional washing agents, such as disclosed in WO98/30674 , have a high content of alkaline compounds (e.g. NaOH; Na2CO3) and are therefore considered "aggressive" towards the items to be cleaned and the environment. It is thus a further aim of the present invention to provide washing agents which enable a less aggressive, "gentler", treatment of the items to be cleaned.
Further, conventional washing agents are faced with the problem of "incompatible" active ingredients, such as enzymes and bleaching systems. This issue is addressed, e.g. by providing solid chemical concentrate systems of at least two cooperative shapes, e.g. as disclosed in WO 92/20774 . While this approach may be suitable in certain cases, the manufacturing and handling of such articles is considered difficult and / or inconvenient.
Solid detergent compositions are well known. For example, US4219435 discloses detergent tablets with a coating; US 5698513 discloses urea-based solid cleaning compositions; US 6060444 discloses solid cleaning compositions that may comprise additives and hardening agents; WO92/20774 discloses a solid chemical concentrate system of at least two cooperative shapes; WO98/30674 discloses stable solid block detergent compositions.
Thus, it is an aim of the present invention to provide dishwashing agents that overcome the limitations and disadvantages of the currently known washing agents. Further, it is an aim of the present invention, to provide processes for obtaining such washing agents and uses for the washing agents provided.
While there are shown and described presently preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practiced within the scope of the following claims. Further, it is understood that the various ranges, embodiments, and preferences provided in this specification may be combined at will. Also, specific embodiments or preferences may not apply.
It has now surprisingly be found that a suitable solid dishwashing agent comprises a carrier, a surfactant, and therein incorporated active substances; wherein said dishwashing agent is in the form of tablets or granules or beads; wherein said carrier is a solid, water-soluble matrix (1), (i) said matrix (1) being tight against water and humidity, this property being obtained by an open porosity below 25 vol-%, (ii) said matrix (1) comprising polymers selected from the group consisting of polyethylene glycols, polypropylene glycols, methoxypropylene glycols (M-PEGs), block copolymers thereof and mixtures thereof, and optionally low-foaming, non-ionic surfactants with a melting point >40°C; wherein said surfactant (i) is a low-foaming, non-ionic EO/PO adduct having a melting point >40°C, (ii) being selected from the group consisting of EO/PO adducts of carboxylic acids and EO/PO adducts of fatty alcohols; wherein said active substances (i) at least comprise a builder, (ii) further comprise at least one enzyme and/or at least one bleaching agent or bleaching system and/or at least one corrosion protecting agent and/or at least one perfume and/or at least one coloring agent, (iii) are present in at least one separate phase (2).
The term "washing agent" as used herein encompasses washing agents for dish washing. Although one of the advantages obtainable with the present invention is a high stability of critical active substances even in not only humid but also hot environment, the inventive agents can be used for any cleaning application where dosed or easily dosable forms are desired, preferably such forms that are also storage stable at least in humid environment. In an advantageous embodiment, the invention relates to washing agents as described herein that are dishwashing agents. In a further advantageous embodiment, the invention relates to washing agents as described herein that are laundry washing agents. The term dishwashing agent and laundry washing agent is known to the skilled person and implies the presence of suitable active substances, which are also further explained below.
Due to their sensitivity to water, in particular to water in combination with high temperature during the dish washing cycle, problematic ingredients in solid dosable washing agents are in particular the enzymes and the bleaching system.
An improved washing agent is obtained if it furthermore comprises at least one corrosion protecting agent, (for dishwashing agents e.g. a silver protecting agent), and bleaching agents. In order to improve the acceptance of the consumer or for security reasons perfumes (fragrances) and/or coloring agents (dyes) may be added.
In order to have a very fast effect of the active substances, the size of the particles incorporated into a water soluble matrix preferably is below 500µm.

Drawings:

The invention will be better understood and objects other than those set forth above will become apparent when consideration is given to the following detailed description thereof. Such description makes reference to the annexed drawings, wherein:

Figure 1 shows a washing agent in tablet form and comprising within a matrix homogeneously distributed active substances (not shown since homogeneously distributed and not forming a second phase), wherein Figure 1a is a top-view, Figure 1b a cross section along line b-b and Figure 1c is a cross-section through the tablet along line c-c.
Figure 2 shows a washing agent in tablet form and comprising within a first phase forming a matrix a second phase incorporating sensitive ingredients, wherein said second phase can be a homogeneous second phase or an inhomogeneous second phase incorporating different ingredients shown by different hatchings, and wherein Figure 2a is a top-view, Figure 2b a cross section along line b-b and Figure 2c is a cross-section through the tablet along line c-c.
Figure 3 shows a washing agent in tablet form and comprising within a first phase forming a matrix beads forming a therein distributed second phase, wherein said second phase can be a homogeneous second phase or an inhomogeneous second phase incorporating different ingredients shown by different hatchings, and wherein Figure 3a is a top-view, Figure 3b a cross section along line b-b and Figure 3c is a cross-section through the tablet along line c-c
Figure 4 is a flow diagram schematically showing the manufacturing of a washing agent according to this invention.

Matrix:

In the scope of the present invention it has now been found that it is possible to incorporate humidity sensitive compounds into a matrix that combines the properties of being "tight", "temperature stable", and "soluble". The matrix is "tight", i.e. does not comprise voids or cavities or pores or capillaries etc. through which water might penetrate into the solid washing agent composition. This property may be obtained by a matrix having an open porosity below 25 vol-%, preferably below 20 vol-%. The open porosity is calculated based on the apparent density of the solid (g/cm*; He-pycnometry) and the bulk density (calculated based on weight and volume). This low porosity is in contrast to conventional dishwashing agents which posses a high porosity, typical values are in the range of 40 vol-%, to ensure fast dissolving during the washing cycle. It is also noted that coated tablets for dishwashing are not "tight" in the context of this invention, as such coating aims to improve handling and to ensure fast dissolving. Further, the matrix is "soluble", i.e. said matrix must have a good, fast, preferably within 1 to 5 minutes, solubility even in cold water. Further, the matrix is "temperature stable", in particular if the washing agent is intended for use in a container large enough to receive an amount sufficient for several washing cycles, said matrix results in a washing agent that remains solid at the highest possible temperature to which the washing agent comprising container might be subjected The matrix in general has a melting point in the range of 45 - 85°C, dependent on the positioning of the storage container and the further (high melting) ingredients. If the agent shall be applicable independent of an specific use, a melting point of about 80°C is preferred.
Thus, a washing agent of the present invention comprises a carrier and therein incorporated active substances, wherein said carrier is a solid, water-soluble matrix that is tight against water and humidity, wherein said washing agent is dimensionally stable at the highest temperature in the storage container during a washing cycle, wherein said wash active substances at least comprise a builder, and wherein said washing agent is in the form of tablets or granules or beads.
In general, said highest temperature is in the range of about 70 to 80°C. Consequently said washing agent melts above at least 70 °C, preferably said washing agent melts above about 75°C, in particular at or above about 80°C. However, in particular, when washing agents are concerned that are intended for being stored outside the washing machine and dosed for each washing cycle, or washing agents that are especially designed for low temperature washing, the dimensional stability is less critical, i.e. needs only to be present at such low temperatures.
Further, the matrix of said washing agent has a turbidity/cloud point of above about 18°C, preferably above 25°C.
A matrix suitable for an inventive washing agent is obtainable from polymers selected from the group consisting of polyethylene glycols, polypropylene glycols, methoxypropylene glycols (M-PEGs), block copolymers thereof, or low-foaming non-ionic surfactants with a melting point above 40°C, in particular ethylene oxide (EO)/propylene oxide (PO) adducts, optionally in the presence of one or more further/other solid or liquid surfactants selected from the group of low-foaming non-ionic surfactants such as e.g. one or more fatty alcohol alkoxylates, one or more fatty alcohol ethylene oxide (EO)/propylene oxide (PO) adducts, one or more EO/PO block copolymers, one or more fatty alcohols such as stearyl alcohols, and/or one or more co-builders such as polycarboxylates, e.g. copolymers of acrylic acid and maleic acid.
The average molecular weight of the polymers preferably forming the matrix and the optionally also present surfactants and co-builders each can vary in a broad scope, as long as a matrix is formed that together with the further ingredients results in the desired melting point of the washing agent and preferably also in the desired turbidity. Preferred ranges of the average molecular weights of the preferred polymers, surfactants and preferred optional co-builders are:

polyethylene glycols MW: 6000-35000
polypropylene glycols MW: 2000-4000
methoxypropylene glycols (M-PEGs) MW: 950-5600
EO/PO adducts (e.g. Aduxol^®) MW: 1000-8000
EO/PO block copolymers (e.g. Pluronic^®) MW:1000-8000
polycarboxylates MW: about 70000
Incorporated into said matrix are active substances, namely at least one builder, preferably also at least one surfactant, and at least one enzyme. The dishwashing agent may also comprise a combination of at least one low-foaming non-ionic surfactant and at least one cationic surfactant and/or at least one amphoteric surfactant. For laundry washing agents anionic surfactants, optionally in the presence of further surfactants, are preferred
Main ingredients of the matrix are consistency providing agents, in particular
one or more polymers selected from the group consisting of polyethylene glycols, polypropylene glycols, methoxypropylene glycols (M-PEGs), block copolymers thereof, and/or one or more low-foaming, non-ionic surfactants with a melting point >40°C, in particular EO/PO adducts, all, the polymers and the surfactants, with different molecular weights ranging from 200 to 40000 as well as mixtures thereof and mixtures of polymers with different molecular weights, and optionally
one or more further/other surfactants selected from low-foaming non-ionic surfactants such as e.g. one or more fatty alcohol alkoxylates, one or more fatty alcohol ethylene oxide (EO)/propylene oxide (PO) adducts, one or more EO/PO block copolymers, one or more fatty alcohols such as stearyl alcohols (e.g. Lorol C18™, obtainable from Cognis), and/or optionally
one or more co-builders such as polycarboxylates, e.g. copolymers of acrylic acid and maleic acid with molecular weights up to 70000.

Such mixtures are suitable to adjust the melting point.
The matrix 1 essentially consists of a water soluble medium that is water-tight as well as humidity-tight such that it serves as a sealing and protection medium for critical substances and preferably results in a washing agent that is dimensionally stable at the temperatures to be expected in washing machines. The matrix 1 is preferably formed by polyethylene glycols (PEG) and/or polypropylene glycols (PPG) and/or polyethylene glycol-polypropylene glycol block-copolymers, and/or EO/PO adducts with a melting point above 40°C, optionally and preferably together with further/other surfactants, in particular low-foaming non-ionic surfactants. Much preferred high molecular weight polyethylene glycols and/or polypropylene glycols are used as polymers.
The substances intended to form the matrix 1 are chosen with regard to their average molecular weight and combined such that the mixture, or the final solid washing agent, respectively, has the desired physical properties, in particular the desired water and humidity tightness, dimensional stability and dissolution rate.
If a several phase composition is chosen it is not absolutely necessary that the carrier of each phase (phase matrix) is identical. For example an active substance comprising phase 2 might lack a surfactant while the basic matrix 1 might incorporate one. In addition, for some uses it might even be preferred that the matrixes have different dissolution rate.
For optimal long time stability, in particular in wet and hot environment, core-shell tablets, granules or beads are preferred with a core comprising the sensitive ingredients either in the form of a second phase 2 or as second phases 2 incorporated into a matrix 1. The shell is formed by a matrix 1 around said core.
If the use of the washing agent in washing machines with a washing agent container comprising a storage compartment and a dosing compartment is intended, for the dimensional stability, the melting point of the matrix 1 should be such that the maximal temperatures expected in washing machines, in particular at the site of the storage compartment/dosing compartment, does not lead to a sticking together of the tablets or granules or beads or their adherence to the container walls. In order to be on the safe side, variations and inaccuracies of the temperature regulation, in general assumed to be about ±5°C, have to be included in the melting point considerations.
As already shortly addressed above, the positioning of the storage/dosing compartment influences the temperature at the container comprising the solid washing agent and might be taken into consideration for determining the needed melting point. Preferably, however, the maximal temperature expected in proximity to the dosing unit is chosen.
In addition to the desired dimensional stability obtained by adjusting the melting point, also the turbidity/cloud point of the surfactants in water is preferably adjusted, namely to above about 18°C, preferably above 25°C.

Shape / Size:

The geometric shape of the washing agent in general is in form of granules, beads or tablets. While granules and beads offer the possibility to adapt the dosed amount to e.g. the water hardness, the tablet form is much preferred since it allows easy and constant dosing and the possibility to better incorporate the sensitive ingredients, e.g. by formulating a core-shell tablet with the most sensitive substances in the core or in core compartments, provided that specific agents shall be separated from each other. The size and shape of the tablets is not crucial.
While the above mentioned geometric shapes have been defined as tablets, granules or beads that in general have round shape at least in one cross section, in the scope of the present invention also similar forms, i.e. forms with at least one rectangular or triangular or hexagonal etc. cross-section can be used. Preferred forms are symmetric forms such as circles, ovals, squares or rectangles. Presently preferred are shapes with at least one round and/or oval cross-section. Suitable tablets may have any size known in the field; typically they have a weight between 10 - 30g, e.g. 20 g.

Use:

If the laundry or dish washing machine has a suitably equipped washing agent container for the washing agent, washing agent may be placed therein for several washing cycles. Such a container may e.g. be a large container with a storing compartment and a dosing compartment. The storing compartment can be so dimensioned that it has room for washing agent in an amount sufficient for up to about 30 washing cycles. The dosing compartment has room for the amount of washing agent needed or recommended for one washing cycle. The dosing compartment is placed between the storage compartment and the washing agent supply, e.g. a tube supplying fresh water or water from the washing compartment to the dosing compartment for washing out the washing agent comprised in said washing compartment and for supplying said washed out washing agent to the washing compartment. The dosing compartment is separated from both the storing compartment and the washing agent supply by movable separations, e.g. sliders, that preferably are automatically opened or closed. For filling the dosing compartment, the movable separation separating the dosing compartment from the washing agent supply has to be in the closed position prior to opening the movable separation separating the storing compartment and the dosing compartment. As soon as the amount washing agent needed to fill the dosing compartment, i.e. the tablet or a sufficient number of granules and/or beads has fallen or been pushed into the dosing compartment, the movable separation between the dosing compartment and the storing compartment is closed. For supplying the dosed amount of washing agent, the movable separation between the dosing compartment and the washing agent supply is opened and the dosed amount of washing agent is washed out with water and supplied to the washing compartment.
If a different amount of washing agent is preferred for pre-washing and main washing steps, two separate washing agent containers as described above may be provided or one washing agent container with two different dosing compartments.
The dosing compartments can be filled directly after having been emptied or - for reducing the contact with humidity and thus enhancing the storage stability - directly at the beginning of a washing cycle.
The agent of the present invention can also be used in ordinary washing machines with one or more washing agent containers and a washing agent supply, the containers and supply being designed for only one washing cycle, optionally with a pre-washing step. In this case, for easy dosing, tablets are much preferred.

Homogenity:

The inventive washing agent comprises a matrix 1 and active substances, examples of which are further described herein. The active substances can either be homogeneously distributed throughout the matrix 1 (Figure 1) or they can be present in separate second phases 2 (Figures 2 and 3) or part of the active substances can be homogeneously mixed with the matrix 1 and part can be present in separate second phases 2 (Figures 2 and 3). The separate second phase 2 can be formed from different beads or bars, e.g. beads with one basic composition but different sensitive ingredients, e.g. ingredients that shall be kept separately until the washing process starts, or the second phase 2 may encompass areas, e.g. beads or bars, with different solubility so that ingredients may have optimal effect at different stages of the washing process. Second phases with e.g. different ingredients or compositions or different solubility are marked in the Figures by different hatchings.
In one embodiment, the washing agent isa homogeneously mixed composition or it may comprise phases with higher concentrations of specific, e.g. especially humidity sensitive, compounds, or phases wherein compounds that might interact with each other are separated. Such different phases lead to an additional protection of active substances from chemical reactions with each other and/or the environmental humidity.
In an alternative embodiment, , all or part of the ingredients may be incorporated into the matrix in coated form. This fother enhances stability. In particular enzymes and bleaching agents are preferably incorporated in coated form. They can either be homogeneously mixed with the matrix or incorporated in additionally protected "inner" phases of the washing agent, e.g. forming a core-shell tablet.

Manufacturing:

In the production of such a washing agent, in general first the matrix is mixed and then the (further) active substances are added. Dependent on the kind of homogeneity, i.e. homogeneously mixed or active substance(s) rich phases incorporated, different production methods may be preferred such as casting or pressing or (co)extrusion etc.

Active substances

Preferred parameters and examples for presently preferred ingredients / components (surfactants, builders, bleaching agents, enzymes, corrosion inhibitors, perfumes, colorants) are described in further detail below. Components for dishwashing agents are described first, components for laundry washing agents are described afterwards.
In order to have a very fast effect of the active substances, the size of the particles incorporated into a water soluble matrix 1 preferably is below 500µm.

Dishwashing agents:

Surfactants:

In general all low-foaming non-ionic surfactants and cationic and/or amphoteric surfactants or polymers, respectively that can be combined with the low-foaming non-ionic surfactants can be used. Cationic and/or amphoteric surfactants or polymers, respectively, can be added in order to get specific cleaning effects on the goods to be washed. It was found that a total surfactant content of the inventive dishwashing composition between 5 - 20 wt-%, preferably between 8 - 20 wt-% ensures positive results. The surfactants as described herein, in particular the low-foaming, non-ionic surfactants with a melting point >40°C may be part of the matrix 1 and optionally be present in the second phase 2.
Suitable examples of surfactants in the context of the present invention include:

Low-foaming, non-ionic surfactants with a melting point >40°C:

low-foaming esters of carboxylic acids, in particular EO/PO adducts
fatty alcohols EO/PO adducts (e.g. Aduxol^®)

Further/other non-ionic surfactants:

alkyl polyglycol ethers
- -- fatty alcohol polyglycol ether with 3-25 ethoxy units (EO), e.g. Dehypon E124™ (obtainable from Cognis)
- -- oxoalcohol polyglycolether
mixed alkyl/aryl polyglycolethers
low-foaming alkyl polyglucosides (APGs)
fatty alcohols, e.g. stearyl alcohols (e.g. Lorol C18™)

Further/other non-ionic polymeric ethoxylate and/or propoxylate (EO/PO) adduct surfactants:

alcohol EO/PO adducts
- -- fatty alcohol EO/PO adducts
- -- oxo alcohol EO/PO adducts
EO/PO block-copolymers
ethylene diamine ethylene oxide-propylene oxide (EO/PO) block-copolymers
endcapped (fatty) alcohol EO adducts and EO/PO adducts(e.g. butyl endcapped)
low-foaming esters of carboxylic acids, in particular EO/PO adducts
Especially preferred are alkoxylated fatty alcohols, in particular those that are ethoxylated and/or propoxylated. Also especially preferred are alkyl polyglycolethers, EO/PO-blockpolymers, endgroup capped (fatty) alcohol EO adducts, low foaming esters of carboxylic acids, in particular EO/PO adducts, and mixtures thereof. The used non-ionic surfactants in general have a turbidity/clouding point in the range of 18 - 65°C.

Cationic surfactants or polymers:

Dialkyldimethylammonium chlorides such as e.g. distearyldimethylammonium chloride, bis (partially hydrogenated nortalow carboxyethyl)-(2-hydroxyethyl)-methyl ammonium methosulfate and diquarternary polydimethylsiloxans

Amphoteric surfactants or polymers:

caprylic glycinate, cocamidopropylbetain and disodium cocoampho diacetate.

Builders:

Suitable builders are inorganic builders, optionally together with one or more co-builder, and organic builders.

Inorganic builders:

Preferred inorganic builders are selected from the group consisting of zeolites, silicates, phosphates, alkali carriers and mixtures thereof.
Examples of preferred zeolites are zeolite A and zeolite P.
Examples of preferred silicates are alkaline metal silicates, in particular sodium silikates, sodium disilikates, sodium metasilicates, and mixtures thereof.
Examples of preferred phosphates are alkaline metal phosphates, especially preferred pentasodium triphosphate, pentapotassium triphosphate (sodium tripolyphosphate or potassium tripolyphosphate) and mixtures thereof.
Examples of preferred alkali carriers are alkaline metal hydroxides, alkaline metal carbonates, alkaline metal bicarbonates (alkaline metal hydrogencarbonates), alkaline metal silicate, alkaline metal metasilicate and layered silicates and mixtures thereof.

Builder systems (comprising inorganic builder(s) and organic co-builder(s)):

Inorganic builders:

A preferred inorganic builder system for use together with an organic co-builder or a system of organic co-builders comprises at least one of the compounds listed below, preferably a mixture comprising all compounds, namely compounds selected from the group consisting of tripolyphosphates, sodium carbonate, alkaline metal silicates, in particular disilicates, layered silicates and zeolites.

Organic co-builders:

Organic co-builders are preferably selected from the group consisting of: homologue polymeric polycarboxylates/polycarboxylic acids and copolymeric polycarboxylates/polycarboxylic acids, polymeric amino dicarboxylic acids, polyacetales, dextrines, phosphonates and mixtures thereof.
Examples for homologue polymeric polycarboxylates are polyacrylic acids, alkaline metal salts of polyacrylic acid, polymethacrylic acids, alkaline metal salts of polymethacrylic acid, and mixtures thereof.
Examples for copolymeric polycarboxylates and copolymeric polycarboxylic acids are the acids or alkaline metal salts of acrylic acid and methacrylic acid, acrylic acid and maleic acid, methacrylic acid and maleic acid, acrylic acid and sulfonic acid, and mixtures thereof.
Examples for polymeric amino dicarboxylic acids preferably are polyaspartic acids, their salts and derivatives.
Examples for phosphonates are hydroxyalkane phosphonates, preferrably 1-hydroxyethane-1,1-diphosphonate (HEDP), and aminoalkane phosphonates, preferrably ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriamine pentamethylenephosphonate (DTPMP), and mixtures thereof
The co-builders are preferably present as powders.

Organic builders:

Suitable organic builders are polycarboxylic acids and their salts, in particular the sodium salts. Examples for organic builders are citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, their salts and derivatives, amino carboxylic acids, nitrilo triacetic acid (NTA), methyl glycine diacetate and mixtures thereof.

Bleaching agents:

Suitable bleaching agents are compounds that in contact with water form hydrogen peroxide. Such compounds are used in combination with bleaching activators and optionally boosters and/or catalysts. Further suitable bleaching agents are inorganic or, preferably, organic bleaching agents, especially peracids.

H₂O₂ liberating compounds:

Examples for compounds that in water liberate H₂O₂ are sodium percarbonate, sodium perborate tetrahydrate, sodium perborate monohydrate, peroxypyrophosphates, citrateperhydrates, and mixtures thereof.

Bleaching activators:

Suitable bleaching activators are compounds comprising one or more N-acyl groups and/or O-acyl groups, such as compounds selected from the groups consisting of anhydrides, esters, imides, acylated imidazoles, oximes and mixtures thereof, preferably compounds selected from the following group of examples:

multiply acylated alkylenediamines, in particular tetraacetylethylenediamine (TAED),
acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT),
acylated glycole uriles, in particular tetraacetyl glycole urile (TAGU),
N-acylimides, in particular N-nonanoylsuccinimide (NOSI),
acylated phenolsulfonates, in particular n-nonanoyloxy benzenesulfonate, isononanoyloxybenzenesulfonate (n-NOBS bzw. isoNOBS) and mixtures thereof,
anhydrides of carboxylic acids, in particular phthalic acid anhydride,
n-methyl morpholine acetonitrile methylsulfate (MMA)
acylated sugar derivatives, in particular pentaacetylglucose (PAG),
N-acylated lactames, in particular N-benzoylcaprolactame, acetylcaprolactame,
decanoyloxybenzoic acid (DOBA), and
mixtures thereof

Further possible activators for use in the inventive dishwashing agent are nitriles and so called nitrile quats. Some examples are 4-morpholinecarbonitrile, (cyanomethyl)diethylmethylammoniumtosylate, and mixtures thereof.
In addition, combinations of usual bleaching activators can be used. Examples for preferred combinations are: TAED/NOBS etc.

Performance "boosters":

Examples for suitable performance "boosters" for activated bleaching systems are imines and imine quats (oxazaridine precursors) such as N-methyl-3,4-dihydroisochinoliniumtosylate.

Catalysts:

Suitable catalysts that may assist in the activation of oxygen are organic metal complexes, in particular complexes with Fe, Mn, Cu or Co as central atom. Specific examples of suitable catalysts are salen complexes and saltren complexes, in particular a tris(2-salicylideneamino)ethylamine manganese (III) saltrene complex obtainable as Tinocat™, from Ciba Speciality Chemicals.
Further suitable catalysts are manganese complexes with 1,4,7-trimethyl-1,4,7-triazacyclononane ligands (MnTACN)as described in EP 458397 to Unilever, or pentaamine acetatocobalt(III) nitrate (PAAN) (see US patent 5,804,542 (1998 )).

Organic and inorganic bleaching agents:

Organic bleaching agents, especially peracids:

As an alternative or in addition to the bleaching agents that in contact with water liberate H₂O₂, organic bleaching agents, especially peracids may be added either alone or together with a bleaching activator (Suitable bleaching activators are e.g. those described above for the H₂O₂ liberating bleaching agents). Such organic bleaching agents are:
Organic bleaching agents, in particular bleaching agents selected from the group consisting of diacylperoxides, substituted or unsubstituted arylperoxy acids and their salts, substituted or unsubstituted aliphatic peroxyacids and their salts, peroxydicarboxylic acids and their salts, as well as mixtures of all aforementioned bleaching agents.
As an alternative to the bleaching agents that in contact with water liberate H₂O₂, chlorine liberating bleaching agents and their salts may be used.

Inorganic bleaching agents:

As an alternative to the bleaching agents that in contact with water liberate H₂O₂, also inorganic bleaching agents, especially peracids and their salts may be used.
An example for diacylperoxides is dibenzoylperoxide.
Examples for arylperoxy acids and their salts are peroxybenzoic acid and their derivatives comprising one or more substituents in the aromatic ring, in particular substituents selected from alkyl, aryl, Cl, COOH, especially magnesium monoperphthalate.
Examples for aliphatic or substituted aliphatic peroxyacids and their salts are peroxylauric acid, peroxystearic acid, o-carboxybenzamide peroxycapronic acid, N-nonenylamidoperadipic acid, N-nonenylamido persuccinate, much preferred E-phthalimido peroxyhexanoic acid (PAP), and mixtures thereof.
Examples for peroxy dicarboxylic acids and their salts are 1,9-diperoxyazelaic acid, diperoxysebacic acids, diperoxododecanic acid (DPDDA), diperoxyphthalic acids.
Examples for chlorine liberating compounds are heterocyclic N-chloroamides such as trichloroisocyanuric acid, dichloroisocyanuric acid (DICA), their salts and mixtures thereof.
Examples for inorganic peracids and their salts, respectively are peroxomonosulfuric acid, prevailingly as potassium monopersulfate triple salt, also known as (caroic acid).
Examples of preferred bleaching systems are tetraacetylethylenediamine (TAED)/sodium perborate monohydrate and 4-morpholinecarbonitrile/sodium perborate monohydrate.
A much preferred bleaching system comprises an organic peracid, in particular phthalimido peroxohexanoic acid (PAP). The organic peracid preferably is used in form of small particles, in general particles of 200 - 1000 µm, preferably 300 - 700 µm. In order to enhance the stability in the matrix, the PAP may be used in coated form.

Enzymes:

Enzymes are used to digest some of the food leftovers on the dishes. Preferred enzymes are hydrolases, in particular hydrolases such as proteases, esterases, lipases, amylases, mannanases and much preferred mixtures of said enzymes.

Examples for proteases are Alcalase™ , Esperase™ , Savinase™, Everlase™, Ovozyme™, Purafect OX™, ProperaseTM
Examples for amylases are Termamyl™, Duramyl™, Purastar OxAm™
An example for lipases is Lipolase™

Much preferred are enzyme mixtures comprising proteases and amylases.
The enzymes can be used adsorbed on carriers or embedded into a coating in order to additionally protect them from disintegration.
A preferred particle size distribution for the enzymes is 200 - 1000 µm.

Corrosion protecting agents:

In many applications it might be desirable to also have a corrosion protecting agent, in particular a silver protecting agent incorporated.
Examples for silver protecting agents are triazoles, such as benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles, and mixtures thereof
Especially preferred are benzotriazol and/or alkylaminotriazoles.
It is also possible and within the scope of the present invention to add zinc salts or organo zinc compounds in order to prevent corrosion of the articles to be cleaned such as dishes, cutlery and glasses.

Perfumes:

Suitable perfumes for dishwashing agents are known in the field and may be used in the context of this invention accordingly. Perfumes may be added as such or adsorbed on or incorporated in a carrier.

Coloring agents:

Any coloring agent suitable for the use in dishwashers may be used.
Specific ranges and compositions are listed in Table 1 on the next pages

Alkaline Compounds:

The use of such compounds is known in the field. Typically Alkalisilkates, Alkalicarbonates, Alkalihydroxides are used. In the context of this invention, typically less than 33 wt-% are used, preferably, 5 - 25 wt-%, particularly preferably 10 - 20 wt-%. Futher, dishwashing agents require higher amounts of alkaline compounds, while in laundry washing agents such compounds may be lower or even absent.

Table 1:

Function	Material used	Range of use [%]	Pref. range of use [%]	Specific compositions [%]
		Range of use [%]	Pref. range of use [%]	1	2	3	4	5	6	7	8	9
Matrix	PEG 6000 - 35000	5-60	5-30	30	15	10		5	10	20	5	15
	PPG	5-40	5-30			5	5	5	15	10	5	5
	Surfactants*	5-40	5-25	5	10	15	25	20	15	10	25	16.7
Builder	Tripolyphosphate	5-60	10-50	35	30	25	30	20	10	-	41	28
	Copolymers**	2-20	5-15	9	9	14	12	10	10	15	9	12
	Trisodiumcitrate								5	5
Alcaline compound	Metasilicate	1-10	4-8	5	5	8	8	5	5	5	2.7	10
	Disilicate	1-25	5-20			8.3			15	19.5
	Layered silicate				10		3.8	19.8
	Soda				4.1
	NaOH	1-5	2-3		2
Bleaching agent	Na-perborate monohydrate	2-20	4-10	8					4
	Na-perborate tetrahydrate	2-20	5-15		8
	PAP	1-20	5-15			10	10	10	3.4	10	9	10
Bleaching activator	TAED	1-10	3-6	4	3				2
Enzyme	Protease			2.0	1.5	2.0	2.5	2.5	3.0	3.0	2	2
	Amylase			1.3	1.3	1.5	1.5	1.5	2.0	2.0	1	1
	Mannanase				0.5
Ag prot.		0.1-1	0.2-0.4	0.2	0.1	0.2	0.2	0.2	0.1	0.1	0.1	0.1
Corr. prot.		0.1-5	0.2- 5	0.5	0.5	1.0	2.0	1.0	0.5	0.4	0.2	0.2

In Table 1, the notes and abbreviations mean:

* surfactant = low-foaming EO/PO block copolymers ; m.p. > 40°C
** copolymers = maleic acid/acrylic acid copolymer with molecular weight of about 70000 and acrylic acid/sulfonic acid copolymer with molecular weight of about 12000 (Acusol 588G, obtainable from Rohm & Haas)
Pref. = preferred
Ag prot. = silver protecting agent = 1,2,3-benzotriazol
Corr. prot. = General corrosion protecting agent = zinc acetate

Laundry washing agents:

Usual ingredients for laundry washing agents are anionic, non-ionic, cationic and/or amphoteric surfactants, organic and/or inorganic builder substances (e.g. alkaline washing agents, pH adjusting agents, complexing agents, ion-exchanging agents, enzymes (e.g. proteases, lipases and glycosidases, in particular amylases, cellulases, glucosidases and mannanases) agents for stabilizing the enzymes (e.g. 4-formylphenyl boronic acid), bleaching agents, auxiliary substances such as soil-release agents, graying inhibitors, colour transfer inhibitors, re-soiling inhibitors, corrosion inhibitors, optical enhancers, rheology modifiers, conserving agents,foam regulators, UV-absorber, photocatalytic systems, antioxidants, excited state quenchers, aromatics and colorants.

Specific compounds for the above mentioned ingredients are as mentioned above, wherein in laundry washing agents anionic surfactants are preferred over the low foaming non-ionic surfactants preferably used in dishwashing agents. Differences and similarities in preferred laundry washing and dishwashing agents are shown in the Table 2 below:

Table 2

Laundry washing agents:	Dishwashing agents:
Anionic surfactants	---
Nonionic surfactants	Low foaming nonionic surfactants
Cationic surfactants	Cationic surfactants
Amphoteric surfactants	Amphoteric surfactants
Builders	Builders
Alkaline agents	Alkaline agents
Complexing agents	Complexing agents
Ion exchanging compounds	Ion exchanging compounds
Bleaching agents	Bleaching agents
Enzymes (e.g. proteases, lipases, amylases, cellulases, mannanases)	Enzymes (e.g. proteases, amylases)
Soil antiredeposition agents and/or soil repellent and/or soil release agents	---
Foamregulators	---
Corrosion inhibitors (e.g. silicates)	Corrosion inhibitors (e.g. silicates and/or benzotriazoles)
Fluorescent whitening agents (FWA's)	---
Dye transfer inhibitors	---
Fragrances	Fragrances
Dyes	Dyes
Formulation aids	---

Manufacturing:

The washing agents of the present invention can easily be prepared using methods known to the skilled person in the art. Dependent on the embodiment to be produced, one or the other method may be preferred (see Figure 4).
For example if all ingredients are homogeneously mixed, the active substances may first be mixed with each other and then incorporated into a molten, also premixed matrix 1. The resulting melt can then be casted. In an alternative method, the melt is solidified in form of flakes or other small particles and then pressed or extruded to get its final form.
In yet another method that is not shown in Figure 4, the matrix is formed into granules, then mixed with the optionally partially or preferably totally coated further ingredients and then pressed, preferably without active heating, such that a tablet with a water and humidity tight, capillary-free matrix 1 is formed. Such a pressure usually is in the range of 10 to 30 tons, dependent on the size of the tablet to be formed.
If the active substances or part thereof are incorporated in separate phases 2, the optionally part of the active substances comprising matrix 1 melt can be produced as described above and formed into extrudable particles. The further phases 2 are produced in an analogue manner and then the matrix 1 and all the phases 2 are co-extruded to form a tablet or bead shaped body that, in a subsequent step, preferably is coated by a shell of matrix 1 material.
A suitable matrix that can be used for all above described block forming methods is mainly made of e.g. polyethylene glycols, polypropylene glycols, methoxypropylene glycols (M-PEG's), low-foaming, non-ionic surfactants with a melting point of >40°C, and EO/PO block copolymers having different molecular weights and fatty alcohols such as stearyl alcohol (Loriol C18). These matrix forming substances and further ingredients are mixed such that the melting point of the matrix or the washing agent, respectively, is above 75°C and the turbidity point/cloud point in water is above 25°C.

Use:

These washing agents can be used in dish washing or laundry washing machines with washing agent containers intended for one washing cycle only, or they may be used with dishwashers or laundry washing machines provided with a storage container suitable for storing washing agent in an amount sufficient for several washing cycles. Such a storage container is divided into a storage compartment and a dosing compartment. Such dosing compartment may have such a volume as to allow the placement therein of just the amount of washing agent needed for one washing step, e.g. the respective volume of granules or beads or one tablet. For a pre-washing step, either two identical volumes may be measured or two dosing compartments with different volumes may be provided either connected to the same storage compartment or as two separate storing containers.
While there are shown and described presently preferred embodiments of the invention, it is to be distinctly understood that the invention is not limited thereto but may be otherwise variously embodied and practiced within the scope of the following claims.

Claims

A dishwashing agent comprising a carrier, a surfactant, and therein incorporated active substances,
■ wherein said dishwashing agent is in the form of tablets or granules or beads;

■ wherein said carrier is a solid, water-soluble matrix (1),
o said matrix (1) being tight against water and humidity, this property being obtained by an open porosity below 25 vol-%, this property obtained by an open porosity below 25 vol-%, the open porosity being calculated based on the apparent density of the solid (He pycnometry) and the bulk density (calculated based on weight and volume),

o said matrix (1) comprising polymers selected from the group consisting of polyethylene glycols, polypropylene glycols, methoxypropylene glycols (M-PEGs), block copolymers thereof and mixtures thereof, and optionally low-foaming, non-ionic surfactants with a melting point >40°C;

■ wherein said surfactant
o is a low-foaming, non-ionic EO/PO adduct having a melting point >40°C,

o being selected from the group consisting of EO/PO adducts of carboxylic acids and EO/PO adducts of fatty alcohols;

■ wherein said active substances
o at least comprise a builder,

o further comprise at least one enzyme and/or at least one bleaching agent or bleaching system and/or at least one corrosion protecting agent and/or at least one perfume and/or at least one coloring agent,

o are present in at least one separate phase (2).
The dishwashing agent of claim 1, in the form of core-shell tablets, granules or beads
■ wherein said core comprises sensitive ingredients either in the form of a second phase (2) or as second phases (2) incorporated into a matrix (1) and

■ wherein said shell is formed by the matrix (1) around said core.
The dishwashing agent of anyone of the preceding claims, wherein said matrix (1) has a turbidity / cloud point of above 18°C.
The dishwashing agent of anyone of the preceding claims wherein said matrix (1) comprises a further / other surfactant, selected from the group consisting of fatty alcohols.
The dishwashing agent of anyone of the preceding claims wherein said matrix (1) comprises a co-builder selected from the group consisting of polycarboxylates.
The dishwashing agent of anyone of the preceding claims, wherein said active substances further comprise at least one enzyme and at least one bleaching agent or bleaching system and at least one corrosion protecting agent and at least one perfume and at least one coloring agent.
The dishwashing agent of claim 6, wherein said bleaching agent or bleaching system comprises an organic peracid, in particular phthalimido peroxohexanoic acid (PAP).
The dishwashing agent of claim 6 that comprises a bleaching agent or bleaching system selected from tetraacetyl-ethylenediamine (TAED) /sodium perborate monohydrate or 4-morpholinecarbonitrile / sodium perborate monohydrate.
The dishwashing agent of anyone of the preceding claims, wherein the total content of tensides is at least 5 wt%.
The dishwashing agent of anyone of the preceding claims that additionally comprises at least one cationic and / or at least one amphoteric surfactant.
The dishwashing agent of anyone of the preceding claims that additionally comprises at least one substance selected from the group consisting of alkaline agents, complexing agents and ion exchanging compounds.
The dishwashing agent of anyone of the preceding claims, wherein part of the active substances are present homogeneously admixed with the matrix (1) and part of the active substances are present in at least one separate phase (2).
A method for manufacturing a dishwashing agent according to any of claims 1 to 12 comprising the steps of (i) mixing a matrix as defined in any of claims 1 to 12 and (ii) adding one or more active substances as defined in any of claims 1 to 12.
A method according to claim 13 which is selected from the group consisting of casting, pressing and (co)extrusion.