SA99200725B1 - detergent tablet - Google Patents

Abstract

Abstract: A multi-phase detergent tablet for use in a washing machine, where the tablet consists of: a) a first phase in the form of a formed body with at least one mold inside, b) a second phase in the form of a compressed body present in an adhesive way inside this template. Where the tablet formulation contains one or more concentrated active detergents permanently, in the second phase, in which the second phase additionally contains a disintegrating agent. The multiphase tablets give improved dissolution and cleaning characteristics as well as excellent tablet adhesion and strength.

Description

Detergent tablet Full Description BACKGROUND: This invention relates to multi-phase detergent tablets. Detergent compositions in the form of tablets are well known in the industry. It is known that cleaning formulations in the form of tablets have several advantages over cleaning formulations in particulate form; Such as ease of dose estimation, use, transportation and storage. Detergent tablets are generally prepared by pre-mixing the components of the detergent composition and forming the mixed cleaning components Gre into a JSS tablet using any suitable machine; Al prefers pressing tablets. 0 | is formed Wed tablets by compressing the components of a detergent composition such that the resulting tablets are strong enough to withstand use and transportation without permanent damage. In addition to being powerful; The tablets must also dissolve quickly enough so that: The cleaning ingredients are released into the wash water as soon as possible at the start of the wash cycle. However, there is a clear division that the higher the compressive strength (V), the VO the rate of dissolution of the tablets is slower. And therefore; This invention seeks a way to find a balance between the strength of the tablet and the melting of the tablet. The solution to this problem was; in the past in the previous field; Includes compressing tablets by means of a low pressing (compression) pressure. Despite this, the tablets manufactured in this way, although they have a relatively fast melting rate, have the ability to oil and become unacceptable to the consumer. Other solutions include preparing the tablets using a large compressive stress, cl, in order to obtain the desired level of strength; contains melting aid; Like an effervescent agent.

The Multi-phase detergent tablets 41 described above were prepared by pressing a first composition in a tablet press to form a first, flat, basic layer. Then another cleaning compound was applied to the tablet press on top of the first layer. This second composition was then pressed to form another flat 0 base layer. Thus, the first layer is generally exposed to more than one compression, as it is pressed Lal during the compression of the second composition, and actually the first and second compressive forces are equal in amount, and the applicant found that when the situation is like this because the compressive force (compression) must be AES To bind the first and second structures together, the force used in both the first and second compression steps should be in the range from about 5.0060 to about 0 70.0000 kg (assuming the disk cross-sectional area is about 10 cm) and this results in a rate of Und for tablet melting and other multiphase tablets that have differential melting were prepared so that the second layer was compressed with a lower force than the first layer. In spite of this, although the rate of dissolution of the second layer has improved, the second layer is smoother compared to the first layer and thus is more susceptible to damage resulting from handling and transportation. Vo and European Patent No. BP-B-0,055,100 shows a cleaning block formed by combining a slowly melting preformed body with a tablet. The cleaning block is designed to be placed in the Jal cleaning vessel and left to thaw for several days; Preferably weeks. As a means of reducing the melt rate of the cleaning block, this description includes mixing one or more melt control agents. Examples of these dissolution control agents are para-dichlorobenzene, cparadichlorobenzene, and materials 01. Waxes, fatty acids, long-chain alcohols, esters derived from them, and fatty alkylamides. Detergent tablets (saad) for use in the laundry or automatic dishwashing machine (Ll) must be dissolved during the cycle. One for laundry or dishwasher in 15 to 51 minutes.

A general description of the invention: - Gi For the first embodiment in this invention, a multi-phase cleaning disc was provided for use in a washing machine, where the disc consists of: (a first phase in the form of a formed body with at least one mold inside it; and b) a second phase in the form of a particulate solid compressed inside this mold. and in favorite personifications; The first phase shall be a compressed formed body prepared at an applied compressive pressure of at least about 560 kg/cm, preferably at least about Z Yo kg/cm', and more preferably at least about Vou kg/cm (7.87 kg). Newton (pms [KN 0] and more and more preferably range from about 500 to about 009 and in particular from about 0 to about 17011 kg/cm” (compressive pressure here is the force exerted divided by the cross-sectional area of the disk in cross-sectional plane with the force exerted - al (the cross-sectional area of the die in a rotary press) and La preferably compressing the particulate solid of the second phase (this term is intended to include the possibility of multiple “roll shal”; denoted 5 in Sometimes here as 'optional subsequent phases' in this mold at a compressive stress exerted less than that of the first phase preferably at a compressive stress less than You kg/cm preferably in the range of about 550 kg/cm To about 0 kg/cm, preferably more than about 710 to about 70 kg/cm. These discs are preferred for use here in terms of giving the best cohesion and strength of the disc (measured for example Yo by Child Bite test For strength ([CBS]) and better dissolving characteristics of the product the tablets of the present invention CBS shall be at least about > kg; preferably greater than about A kg; more preferably greater than about 10 kg; In particular greater than about 11 kg and more particularly preferably greater than VE kg. CBS is measured by the US Consumer Product Safety Commission's testing specifications and also; Compressive stresses are exerted on the first and second phases

that generally in a ratio of at least about 1:0,7 and preferably at least about ?:1 and more preferably at least about 4:1 and therefore; hd for what came in another embodiment in this invention; A multi-phase cleaning tablet was obtained for use in a washing machine, where the disk consists of: ° a) sh a first phase in the form of a formed body pressed on (AE BY) and one inside it, where this formed body is prepared under compressive stress of at least about vo. kg/sm and b) sh a second phase in the form of a particulate solid compressed inside this mold; Where this second phase is pressed under pressure higher than about , kg / cm '. Yo. and in other favorite avatars. The second phase is a second phase in the form of a compressed or formed body that exists in an adherent manner. for example by physical adhesion or (Jesh) within at least one mold in the first body and Lad preferably the first and second phases in a high weight ratio Gat with respect to each other; For example, at least about 7: 1, and preferably at least about 1: 01, and it is also preferable that the tablet composition contain VO and one or more active cleaning agents (Jo) for example enzymes, enzymes, and bleaching agents. bleaches, activators 01866, cbleach catalysts, surfactants, chelating agents, etc.) that are permanently concentrated in the second phase; for example daw; at least by about +9058 and preferably by at least about 9670 and in particular 9680 by weight of the active substance (depending on the total weight 001 of the active substance in the tablet) in the second phase of the tablet and again; These formulations are the best for oe All binding, dissolving, cleaning and pH-regulating properties for; For example; on tablet formulations capable of dissolving in the wash solution giving at least 9650 and preferably at least 9660 and more preferably at least 9680 by weight of the detergent active substance to the wash solution within 01 or © or ; Or even GBT from the start of Yo Laundry.

0 so; Gil for another embodiment of this invention; Ad Detergent tablet multi-phase was obtained for use in a washing machine where the tablet consists of: a) a first phase in the form of a formed body with at least one template inside; and b) a second phase in the form of Ala particulate matter pressed into this © mold and where the disc contains at least one active detergent and is shaped so that it conducts at least 9650 and preferably ORI 9670 and more preferably At least 96850 of the weight of the active detergent to the laundry within 10 minutes, preferably during the first five minutes, and more preferably during the first three minutes of the washing process. . An additional benefit of this invention is the ability to obtain a 0-phase differential dissolution such that one phase of the tablet effectively dissolves before the second phase and can even completely dissolve completely before the other phase dissolves. This is particularly useful for differential delivery of detergent actives. and on cells according to the embodiment of AT in this invention; A multi-phase cleaning tablet was obtained for use in “A washing” and contains: yo a) sh a first phase in the form of a formed body with at least one mold inside; and b) a second phase in the form of a compact body conjoinedly present within this mold and wherein the tablet composition contains one or more permanently concentrated detergent active agents in the second phase and wherein the second phase additionally contains a disintegrating agent. Gaby For another embodiment in this invention a multi-phase cleaning disc 08 > consisting of: a) sh a first phase in the form of a molded body having at least one mold inside it; and b) a second phase in the form of a compact body conjoinedly present within this mold and wherein the tablet composition contains one or more permanently concentrated detergent active agents in the second phase and wherein the second phase additionally contains a binder.

d it is appropriate; That one or more effective cleaning enzymes, bleaches, bleach activators, bleaching catalysts 35 168660, surfactants, and chelating agents be selected; Crystalline cell inhibitors and mixtures thereof. It is preferable to use enzyme materials © especially effective enzymes to increase the cleaning performance during the initial cold water stage in the washing or cleaning process, and it is highly preferred to use Hana Jul. on one or more of the enzymes having induced or maximal activity in the temperature range from 7°C to 00°C and at a pH value of 011 in the range from 8 to 01 (Jia 01 natalase enzyme [2]. - 01 and accordingly; According to another embodiment of Lad in this invention; A multi-phase cleaning disc was obtained consisting of: (a first phase in the form of a formed body having at least one mold inside it; and b) a second sh a second phase in the form of a compressed body adherently located inside this The template and where the second phase additionally contains an enzyme Detailed description The aim of this invention is not only to obtain a cleaning tablet strong enough to withstand 0 use and transportation, but Lad has at least a large part of it that dissolves quickly in the washing water to obtain rapid delivery of the active detergent, preferably at least one phase of the tablet being dissolved in the wash water within the first 10 minutes; Preferably the five minutes and the best four minutes of the washing cycle in an automatic dishwashing machine or in the sink. Multiphasic detergent tablet dissolves or disintegrates in less than VO min in a dishwasher or washing machine depending on Ye's dissolution selection described herein. The time that ADA dissolves the multiphase tablet or its phase or an active detergent component thereof (Gk) for DIN44990 was determined using a dishwasher machine available from Bosch, set at the normal washing program at 2210 with a hardness of cle at H 918 using at least six multiples or a sufficient number to obtain Allie results

The multi-phase cleaning disc in this invention contains a Js phase, a second phase, and subsequent optional phases, and the first phase is in the form of a body formed for the cleaning composition containing one or more cleaning components as described later. Preferred cleaning ingredients include builder (a substance added to enhance cleaning performance), bleach, enzymes ©, and surfactants. The components of the cleaning formulation are mixed together by; She mixes dry ingredients by adding or mixing by sprinkling liquid ingredients; The components were then shaped into a first phase using any suitable machine; but preferably by compression; For example in a tablet press. Alternatively; The first phase may be prepared by extrusion or by molding; etc. The first phase can take many spatial shapes such as circles 0 and cubes; etc. but the preferred embodiments have a generally axially symmetric shape with circular cross-section; Or generally square or rectangular.

The first phase was prepared so that it contained at least one mold on the surface of the preformed body. The Load template or templates can vary in size, shape, location, orientation and position relative to the first phase, for example (JE) the template or templates can generally be V0 circular, square or oval in cross section and can be a gap related to Gals or cavity on the surface of the antibody or they can extend between unconnected regions of the surface of the body (eg axially opposite face surfaces) to form one or more "holes" in the formed body and they can be positioned symmetrically or axially with respect to phase The first or they can be placed in a non-Jide way, and in a preferred embodiment, the mold is made using a specially designed disc press Yo, where the surface of the pestle is in contact with the cleaning composition SSA so that when it contacts and compresses the cleaning composition, it presses a mold or multiple molds in the first stage of a multi-phase cleaning disc.It is preferable that the mold have a concave inward or concave surface in general to obtain good adhesion of the second stage.Alternatively, the mold can be made by pressing a formed body of the cleaning composition placed in an annular shape around a central mold, thus forming a body

YO is formed with a mold in the form of a cavity that extends axially between the opposite surfaces of the body.

The tablets of the present invention include one or more additional phases prepared from a composition or compositions containing one or more of the cleaning components described later and preferably at least one phase (hereinafter referred to as a second phase) taking the form of a particulate solid ( This term refers to powders, granules, agglomerates and other particulate solids© including mixtures thereof with liquid binders or infusion solids (ALG, infusion solids, ALE cil etc.) pressed into/through one or more dies in the first phase of a disc Cleaning so that the second phase itself takes the form of a formed body, and the other optional phases include one or more formulations in the form of a separate layer or layers, and the preferred cleaning components include building materials, coloring materials, binders, surface activators, disintegrating agents, and enzymes; in the form of proteases and amylase enzymes particularly enzymes 0 and in another preferred embodiment of this invention the second phase and the optional subsequent phases contain a disintegrating agent which may be selected from either a disintegrating agent or an effervescent agent and the disintegrating agents include Suitable agents that swell when in contact with water or facilitate the entry and/or removal of water by forming channels in the cleaning disc. Any known fizzing or fizzing agent for use in laundries or dishwashers has been envisaged for use here, and disintegrating agents include cis 5 natural starches; and modified; and pre-gelatinized such as those derived from starch (Jia) suitable starches (trade name Primojel s aul) U-Sperse Jie (corn, rice, potato) and starch derivatives, celluloses, microcrystalline celluloses, sole aul derivatives Trade) and 12010180 (trade name) are both available from Vivapurs (oles (brand name Arbocel cellulose_as) (trade name) Avicel (trade name) are available from Metsa-Sirla and Nymeels ain, Yo (trade name), alginate and acetate trihydrate (Hanfloc commercial) and a) LatticeNT, aqueous 5100 with a content of Na2CO3.H20, borkite and carbonate monohydrate formula polymers and polymers (CMC) phase 1 at least Approximately 9640, carboxymethyl cellulose, aluminum oxide, aluminum oxide, sodium acetate, sodium acetate CMC on, and suitable effervescent agents are those that produce gas when in contact with water and suitable effervescent agents 5

— and 1_ the substances that release oxygen, nitrogen dioxide, or carbon dioxide (Sas 28:000 . ahd) can be the appropriate effervescent agents from the group consisting of above borates and percarbonates “percarbonate” and “carbonate” and “bicarbonate” in union © with carboxylic acids or other acids Jie citric acid sulphamic sulphamic malic ( malic .maleic For example, the components of the cleaning formula, Law, are mixed by mixing the dry ingredients and by mixing or spraying the liquid ingredients, then the components of the second phase and the optional subsequent phases (Jala) were fed and held inside the mold provided by the first phase Yes the preferred embodiment of this invention contains sh first phase and second phase and the first phase normally consists of one mold and the second phase normally consists of one effective cleaning composition. More than one mold and the second phase is prepared from more than one effective cleaning formula. Furthermore; Lal envisioned that the second phase could contain more than one active cleaning formulation contained within a single block. Lal envisioned that multiple cleaning active formulations could exist in separate molds and in this way the sensitive cleaning components Les could be substantially separated in order to avoid any loss of performance caused by the reacting components Gp turning them substantially into inactive components. or stressful. In a preferred embodiment of this (cpl AY) the first, second, and/or optional subsequent Ye phases may contain a binder and when present the binder is chosen from the group consisting of organic polymers; For example polyethylene and/or polypropylene glycols especially those of 0060, 0660 and 0060 molecular weight, paraffins, polyvinyl pyrolindone PVP Aas diay (PVP) 4 by weight Geer ia, polyacrylates YO, sugars, csugar derivatives, and starch

11 hydroxy propyl methyl and starch derivatives, such as hydroxypropyl methyl cellulose (ml); carboxy methyl cellulose and carboxy methyl cellulose (HPMC) inorganic cellulose.hexametaphosphate; The binding is valuable for both tablet cohesion and assistance in obtaining differential melting of the first and second phases as described later. © In a preferred embodiment of this invention the first phase weighs more than about 7 g; g and it is more preferable that it be more than about 0 gm and it is more preferable that from gm to 15 gm and more preferably up to about 71 gm to about 01 gm the first stage weighs from about gm and the second stage weighs YE gm to About 18 gm and the most preferred of about Yo about And the following optional phases are less than; g. It is more preferable that the second instar and/or instars weigh 0 g, about 1 g, and about 7.9 g. 7 and the most preferred of about Te and in another embodiment of this invention; A separator layer was applied. The separator layer composition between the second and subsequent phases Glad first and second phases and/or the optional or facultative subsequent phases contains the separator layer composition containing at least one binder selected from the Yo group previously described. The advantage of having a separator layer is that it prevents or reduces the transition of components from, for example, from the first phase to the second phase and/or the following optional phases AY phase and vice versa. Optional under AJ force preferably compressed components The second phase and the phases in relation to the compressive strength usually used in the preparation of tablets, and therefore the fas is a low compression Yoo One of the advantages of this invention is that due to the use of a low compressive force, it is possible to use cleaning components that are sensitive to heat, force, or chemically inside a tablet Cleansing without sustaining the subsequent loss in performance that typically occurs when these components are used inside discs. Alternatively, The second phase or phases may be compressed under the same or greater compressive strength than the first phase in order to obtain a differential melting of the phases as described later. Yo

—and one of the other advantages of this invention is the better protection of the second phase against damage resulting from; For example; Use and transportation. As described by Gla, multi-phase cleaning tablets were prepared, where the second layer was compressed under a lower compressive force than the first layer, and despite the improvement in the dissolution rate, the second layer of these tablets becomes subject to damage and becomes friable or cracked upon use, and the compressed phases were protected The cleaning discs of this invention are lightly inserted into the mold provided by the first phase of the cleaning disc. Also, one of the other advantages of this invention is the ability to prepare a multi-phase cleaning tablet, where one phase can be designed so that it dissolves and is highly preferred before another phase. Preferred Preferred Gil Preferably first phase dissolves within 0 to 10 minutes and preferably over 10 to Ne minutes. The second phase and/or the optional subsequent phases dissolve in less than ½ minutes, more preferably less than 0.000 minutes, and most preferably less than ; minutes Alternatively; The second phase may dissolve after the first or other phases; For example (JOA) when the Bolle is obtaining cleaning or rinsing benefits at the end of the washing process and the time at which the first, second, and/or optional subsequent dissolving phases are independent of each other and thus in a particularly preferred embodiment of the present invention has been Obtaining differential solubility of the phases The advantage of being able to obtain a differential solubility of the multiphase detergent tablet is that it (Sa) separates a component that is chemically inactive when another component is present in a different phase, in which case it is preferable to place the component that has been deactivated in Ye The second phase and the optional following phases. Another advantage of this invention is the preferred adhesion between the phases of the polyphasic disc. It is proven that good adhesion can be obtained by lowering the exposure of the second phase compared to the polyphasic discs known in this field, leading to making the discs of this invention Less prone to breakage along the connection line between phases 58 Method Process

The multiphasic detergent tablets are prepared using any suitable tablet making machine; (Courtoy R253 «fi] Tablets are preferably prepared by compression in a tablet press capable of preparing a tablet containing a mold and in a particularly preferred embodiment in this invention. (pestles) in this tablet press so that the Gad surface which contacts the cleaning composition has a convex surface. The first cleaning composition was placed inside the tablet press mould, and the tamper was lowered to connect and then compress the cleaning composition to form a first phase, then the first cleaning composition was pressed using pressure applied generally at least about Yoo kg / Yau and preferably between about You and about Yau [aS 70000000 and more preferably about (Jove) about 150800 kg / You and more preferably about 010 to about 1701 kg / Yaw, then the pestle was raised after that and the first phase containing mold was revealed Then the second combination and optional following combinations cleaned were placed inside the moulds; then the specially designed tablet press ram was lowered again to lightly compress the second combination and optional following combinations to form the second phase and optional subsequent phases. Where an optional next phase is present, the optional Jul phase is prepared in an optional next pressing step essentially similar to the second pressing step previously described. about 500 to about 70010 kg/You and most preferably from about 71 to about 770 kg/Yau and after the second cleaning combination was pressed the tamper was raised once Te and the multi-phase cleaning disc was removed from the piston discs. Detergent Components The first, second, and/or optional subsequent phases of the multiphase cleaning tablet described herein are prepared by compressing one or more formulations containing the active cleaning ingredients and appropriately may include the formulations used in any of these phases. YO Many of Le Abad's cleaning ingredients contain building compounds and surfactants

16, enzymes, bleaching agents, alkaline-sources, coloring materials, aromatic substances, lime soap dispensers, organic polymeric compounds, including polymeric dye transfer agents, crystal growth inhibitors, heavy metal ion separators, metal ion salts, enzyme stabilizers, corrosion inhibitors, foam inhibitors, solvents, and fabric softening agents Optical polishes and hydrotropic materials.© More preferred cleaning ingredients in the first phase include builder, surfactant, enzyme and bleaching agent More preferred cleaning ingredients in the second phase include builder, enzyme, crystal growth inhibitors and disintegrating agents and/or binding materials

Builder Compound It is preferable that the tablets of this invention contain a builder compound; Effectively present at a level from Ve 96700 to 9670 by weight and most preferably from Ve 9000 by weight and preferably from % A to 561 to 9670 by weight for a formulation containing active cleaning ingredients.

Water-soluble Builder Compound Suitable water-soluble builder compounds include water-soluble monomeric polycarboxylates; or its acid forms and monomeric polycarboxylates 0 or similar copolymeric or concomitant polymeric polycarboxylic acids two-fold polycarboxylic acid salts in which the polycarboxylic acid contains at least separated from each other by two carbon atoms »on Most carboxylic phosphates borates and borates <bicarbonates SB carbonates, carbonates, and mixtures of any of the above. cphosphates | 00 or _ polycarboxylate Se SH os . And can. That in kind although monomeric polycarboxylate oligomeric or monomeric polycarboxylates are generally preferred for reasons of cost and performance.

- ye —

Suitable carboxylates containing one carboxy group include the water-soluble salts of lactic acid, glycolic acid, and ether derivatives thereof, and include polycarboxylates containing two carboxy groups. It contains the water-soluble salts of succinic acid, malonic acid, ethylenedioxy acid, cdiacetic acid, cmaleic acid, and diglycolic acid, 0181700116

© tartronic acid, tartaric acid, tartaric acid ether carboxylates, in addition to fumaric acid and fumaric acid 0971 tons. They include _ polycarboxylates | carboxylates And carboxylate. sulfinyls containing three carboxy groups; In particular; Polycarboxylates | 0 Water soluble ALG citraconates, citraconates, caconitrates and aconitrates 5 Carboxymethyloxysuccinate Jie succinate In addition to succinate derivatives 1,379,241 described in British Patent No. 88 carboxymethyloxysuccinates and lactoxysuccinates (12010775000108) described In the British patent Patent No. sel py lb described_ in aminosuccinates and aminosuccinates 2 Yo tertiary Jie oxypolycarboxylate Dutch No. 7205873 and oxypolycarboxylate materials 2-oxa-1,1,3-propane tricarboxylates (ls = F 601 OXA-A-7 Telescope

Described in BR 1,387,447 and includes _ Polycarboxylate 8p201702:00<7181_containing four carboxy yo groups oxydisuccinate 077019000108188 described in BR 1,261,820 and IV 101 1 7 7- ethane-tetracarboxylate 1, 1,2,2-cthane 10 11 ctetracarboxylates 7- 7-propane tetracarboxylate-constriction61! 1,1,3,3-propane and 8a7 50 and 011 ?; =F Propane tetracarboxylates -1,1,2,3-propane tetracarboxylates Including polycarboxylates containing sulfo substituents Yo sulfosuccinate derivatives described in British patents Nos.

11 = - 1,1,398 and 1,398.,422 and in US Patent No. 3,936,448 U.S.

Pat.

No. and the thermally solvated sulfonated pyrolysed citrates described in British Patent No. 1,439,000 British Patent No. including polycarboxylates (asl) alicyclic and cyclic coum coum - pentane El _cis- _tetracarboxylate, fifthcarboxylate, cyclodianiadiene, and 7 8 m0 of tetrahydrofuran-cis; sis; cis-tetracarboxylates <2,3,4,5-tetrahydrofuran-cis, cis, ciste tracarboxylates and t©-tetrahydrofuran-cis-dicarboxylates and 7 7 0 m0 tetrahydrofuran -cis -dicarboxylates, 2,2,5,5 - tetrahydrofuran — 2,5 tetracarboxy lates 0 f cf (FY 0 = hexane-hexacarboxylate-12,3,4,5,6 hexane-hexacarboxylate and derivatives Carboxymethyl carboxymethyl alcohols Jie polyhydric alcohols sorbitol, mannitol and xylitol and include Aromatic polycarboxylates cmellitic acid and cpyromellitic acid and acid derivatives Vo phthalic acid described in British Patent No. 1,425,343 Patent No. And from the foregoing above; the preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule, especially the citrates and Aden0N. Gall the original monomeric polycarboxylate acids 10 oligomeric used as chelating agents or mixtures thereof with their salts such as citric acid or citrate mixtures [citric acid] as useful building ingredients . Borate-based materials as well as building materials containing borate-forming substances that give borates may be used under storage conditions or detergent washing but YO not preferably under washing conditions less than 0°C and particularly less than 40°C.

Examples of building carbonate materials are alkaline earth carbonates and alkali metals, including sodium carbonate, and carbonates containing two types of atoms and mixtures thereof with extremely fine calcium carbonate as described in German patent application No. 2,321,001 published in 15 NAVY NOVEMBEREN The most preferred building compounds for use in this invention are the water-soluble building phosphates 206 and specific examples of the eld-soluble All phosphates are alkali-metal tripolyphosphates; sodium and potassium orthophosphate _ and polyphosphate Use 0 sodium polymeta phosphate in which the degree of polymerization ranges from + to 1 and salts of phytic acid, the Partially Soluble or Insoluble Builder Compound. The tablets of this invention may contain a soluble Gia or an insoluble YO builder compound. Soluble or insoluble Gigs are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of water-soluble Goa builders include crystalline stratified silicates (described as Jud) in European patent application no. selcab. (EP-A-0164514 Danish Patent No. DE-A-3417649 and Danish Patent Application No. 08-43742043. 0 | Preferably crystalline stratified sodium silicates with the general formula: NaMSix02+1.yH20 where M is sodium or hydrogen and “is a number from VA up to 4 and not a number from zero up to 01 and it is preferred that sodium silicate have a crystalline layer of This type is a two-dimensional 'lamellar' structure such as Yo, which is called a lamellar § structure as described in European Patent No. 0 EP

VA = sel ny 164514 EP No. 293640 0 (EP). Methods for preparing crystalline stratified silicates of this type are described in Danish Patent Application No. DE-A-3417649 and Danish Patent Application No. 18- 3742043 and for the purposes of this invention * in the general formula has a value of ?, ©, or ; preferably 7. The most preferred crystalline stratified sodium silicate compound has the formula Al -8 5(e) known as NaSKS-6 (Name commercial) available from Hoechst AG preferably as stratified, crystalline sodium silicate present in granular cleaning formulations as particles in a cohesive mixture with an ionic solid AL in water as described in International Patent Application No. 17092 /18594. The water-soluble solid ionized substance Ye was chosen from organic acids and salts of organic and inorganic acids and mixtures thereof with preference to citric acid. Examples of building materials that are highly insoluble in water include sodium aluminosilicates. Suitable aluminosilicates are aluminosilicate zeolites that have the single cell formula Cus Na2[(Al02)z(Si02)y].xH20 Vo is 7 Ley, the least is 6 and the molar ratio is between 2 and ranges from 1 to 1.5 and X is at least © and preferably from ©#, to 7776; Preferably more than 01 to VTE and the formation of aluminosilicate material in the hydrated form and preferably crystalline containing from 9001 to 90748 and preferably more than 9018 to 9077 of water in a linked form. Yes, aluminosilicate zeolites can be materials found in nature, but it is preferable to be derived from Lelia, and the industrial crystal ion exchange materials of aluminosilicate are available under the name of Zeolite A and Zeolite. Zeolite B, Zeolite P, Zeolite X, Zeolite HS and mixtures thereof. The preferred method for the manufacture of aluminosilicate zeolites is the YO described by Skoemann et al. (published in “VV (Y) VE (154) Zeolite).

EP

The author is a method for preparing colloidal aluminosilicate zeolites cea led J (O00) and it is preferable that the colloidal aluminosilicate zeolites particles be aluminosilicate zeolites. micrometers in diameter and not more than 965 of the particles have a size less than the diameter, and it is preferable that the aluminosilicate zeolite particles have an average diameter of a particle size between 1 micrometer and 1 micrometer, preferably between 06 micrometers and 51 micrometers, and the most 0 micrometers and 71 micrometers 1.1 Preference is made between the formula: Zeolite A and the zeolite is

Nal2[(Al02)12(Si02)12].xH20 has the following formula X and in particular 77 and the zeolite has "00 to 010 of x where it is 0 and the zeolite is MAB as described in the patent NaS6[(AlO2)86(Si02)106].276H20 EC No. 20384070 is the preferred building zeolite here. The preferences are aluminosilicate zeolites (sina JV) and colloidal aluminosilicate zeolites when used as a component. In the cleaning formulation, colloidal zeolites give structural performance induced by Zeolite A colloidal aluminosilicates; Zeolite A 1 is preferred.

Cua from Lad Alll induced constructive performance is noted as better removal is obtained, reduced scale formation on the fabric and improved fabric whiteness retention which were problems believed to be associated with poorly constructive cleaning formulations. It has been found that cleaning formulations of the type of aluminosilicate zeolite ions old give colloidal Y and zeolite A mixtures containing commercially available Ye zeolite. Equal calcium A for equal weight of alumino zeolite Culp silicate) It is also surprising that cleaning formulations of type vs equal weight magnesium ions give the separation performance of magnesium ions (described as the commercially available lil . A from zeolite x.

Surfactant 3 sal Surfactants are the preferred effective cleaning ingredients from the formulations described herein. Suitable surfactants were selected from nonionic ampholytic, ampholytic, and ionic “cationic pO; Hybrid cations and mixtures thereof and products for automatic dishwashing machines should be of a low foaming nature and therefore foaming should be inhibited in the surfactant system for use in dishwashing liquids or better be of a foaming nature Low foaming and virtually non-ionic in nature and there is no need to inhibit foam formation resulting from surfactant systems used in laundry detergents to the same degree necessary in dishwashing and the surfactant is actually present at a level of 960.7 to 0 965 by weight and the most preferred from (%) to 96010 by weight, preferably from 960.8 to 90 by weight of the composition of the active detergent ingredients. The actual list of anionic, non-isd, ampholytic, and hybrid ionic species is given; And the varieties of these surface-activated materials in the US Patent No. USP. 3,929,678 yo deposited in the names of Laughlin and Heuring on December 01, 5 . Suitable cationic surfactants are listed in USP 4,259,217 (filed in Murphy's name March 71 NAA) and a list of surfactants used by Glad in cleaning formulations in automatic dishwashers For example, the European patent application EP-A-0414549 and the international Yo patent applications No. 93/08876 WO and No. 93/08874 WO. Basically nonionic surfactants can Any non-ionic surfactant useful for cleaning purposes is used in the cleaning tablet and the unspecified preferred types of useful non-ionic surfactants are listed below:

Nonionic Ethoxylated Alcohol Surfactant is the alkyl ethoxylate resulting from the condensation of aliphatic alcohols with 1 to 1 yo mol of ethylene oxide. 8 is appropriate for use here. The alkyl chain of an aliphatic alcohol can be either straight or branched; primary or secondary; It generally contains from 7 to TY carbon atoms, and it is especially preferred for alcohol condensation products that have an alkyl group containing 01 JA carbon atoms with ? to 0 moles of ethylene oxide per mole of alcohol. End-capped Alkyl Alkoxylate Surfactant \ Sale The appropriate surface activated alkyl alcohols are epoxy-capped polyalcohols represented by the following formula: R10[{CH2CH(CH3) O}x[CH2CH20][CH2CH(OH)R2] ( ) where 1 is a straight or branched aliphatic hydrocarbon radical from ; to 18 carbon atoms of which 82 is a straight or Y-branched aliphatic hydrocarbon radical of 77 to 77 carbons; * is a number with an intermediate value from 1.8 to 5, preferably 1; y is a number with a value of at least Vo, more preferably at least .01 and preferably .01 That the surfactant of formula 11 have at least 01 carbon atoms 0 in the terminal epoxide unit [0112011(01)182). The suitable surfactants of formula Wh of of this invention are the materials Olin Corporation's POLY-TERGENT®SLE-18B Nonionic Surfactant as Described by Jad in International Patent No. 22800/94 WO Published October 11 64 on behalf of the Corporation Olin

Ether-capped Poly( oxyalkylated) Alcohols The surfactants used herein include oxyalkylated poly(oxyalkylated) alcohols which have the following formula:

R10 [CH2CH(R3)0x[CH2]k CH(OH) [CH2]jOR2 ° where 11 R25 are straight or branched aliphatic hydrocarbon or aromatic saturated or unsaturated moieties 1 to Te carbon atom; R3 is [1] or a straight aliphatic hydrocarbon moiety having from 1 to ; carbon atoms And x is a number with an intermediate value from 1 to oF and when x is 0 for ? or more, 83 Ales can be or different and are 1 and g are numbers that have a value

Medium 1 to VY and preferably 1 to ©#. !1 and 02 are preferably straight or branched saturated or unsaturated aliphatic or aromatic hydrocarbon radicals having from “7 to TY carbon atoms with a preference of + to 18 carbon atoms. Preferably R3 is [11 or a straight aliphatic hydrocarbon radical with 1 to 2 carbons V0 preferably x is a number with an average value from 1 to Yeo and preferably +RE! LS is described previously; When you are in favorite embodiments; xy is greater than oY then R3 can be Allan or different that means; that R3 can vary between any of the alkyloxy units as previously described. for example; if x is ; R3 Yo can be selected from ethyleneoxy (EO) or propyleneoxy (PO) and can be varied in order from (EO) (EO) (PO) «(EO) ( PO) (EO) t (EO) (EO) (PO) (PO) (PO) (PO) (PO) (EO) «(PO) (EO) (PO) «(EO) and of course ; JUST THE NUMBER IS SELECTED AND THE VARIETY CAN BE MUCH MUCH GREAT THAN A LARGER NUMERICAL VALUE OF “ Include; For example, multiple EO units and a very small number of PO units

— swarm Particularly favored surfactants as described Gl include those with a low Opacity of less than 010"M. JUL can use these low O.S. surfactants in combination with high O.S. surfactants As described in detail later for superior grease cleaning benefits.8 The ether-encapsulated poly(oxyalkylated) alcoholic surfactants are those in which ko is 1 and g is 1 such that The surfactant has the following formula:

R10 [CH2CH(R3)0]x CH2CH (OH)CH20R2 is a number with value x as defined above. and is R35 R25 RI where the most preferred is NA and most preferred + to Ye to 1 preferred Fe to 1 medium from 0 ranging from 8 to 1; and 83 is R25 RI is the surface activated material in which they are

No from + to x and the ethlyencoxy ranges from two components ethylenoxy H (oxyalkylated) and polyalcoholic surfactants (oxyalkylated) have three general components; they are nominally straight or branched alcohols; and the ether-capped Je ether oxide An alkyl ether cap and a terminal cap of alkylene oxide alkyl ether © terminal and the alcohol act as the hydrophobic, oil-soluble part of the molecule while the alkyl ether is the hydrophilic, water-soluble part of the alkylene oxide These surfactants show significant advances in stain, film and greasy removal properties when used in combination with higher opacity Te surfactants than suitable surfactants. In general, poly(oxyalkyl) alcoholic surfactants with the ether-capped aliphatic alcohol of the present invention can be produced by reacting a second aliphatic alcohol to form an ether which is then reacted with a base to form an epoxide epoxide, then the second epoxide was reacted with an alcohol to which the alkoxyl was added to form compounds, epoxide YO

The new d in this invention. Examples of methods for preparing ether-encapsulated poly-alcohol surfactants are described as follows: Preparation of 012/14 Alkyl Glycidyl Ether 14/012 was mixed can 001 ( fatty alcohol 5501591_mol) and zinc (IV) tin chloride (54_v 7.77 FA (Je de) of Aldrich in a 3-neck, round-bottom flask with a capacity of 5081 ml was equipped with a condenser, an argon inlet, an addition funnel, a magnetic stirrer, and an internal temperature probe, then the mixture was heated to 0 and epichlorhydrin (can €V,V.) Epichlorhydrin 919 mol available from Aldrich was added drip so that The temperature was maintained between 0-210 and after 0 sad stirring an additional hour at 10°C the mixture was cooled to room temperature and the mixture was treated with 906681 sodium hydroxide solution (TYLA) G YYY © filler 9650) with stirring (JG) and after completing the addition, the mixture was heated to 180”C for an hour and a half, then cooled and filtered with the help of ethanol [601800]. Then the clear solution was separated and the organic phase was washed with water (de 001) and dried on ( MgSO, its filtration and concentration. After distillation (am 0) mt 171-0011 ode cud 05 _ hg) glycidyl ether was obtained in the form of oil. Preparation of Alcoholic Surfactant Covered with 14/01 Alkyl-09/11 Ether Preparation of 12/14 Alkyl-C9/11 Ether Capped Ge Jse +0 TAY aa 01 (Neodol®91-8) Alcohol Added Jans gy Yo available from Shell Chemical Company (Shell chemical and zinc chloride tin chloride aa 1.04 (IV) 7.77 mmol) in a round bottom flask with three necks capacity You ml Equipped with a capacitor and an Argon input «8800; add funnel; magnetic stirrer, and an internal temperature sensor. The mixture was heated to 2°10 at which 14/01 alkyl glycidyl ether 1.0747 can VY (alkyl glycidyl ether mol) was added by distillation over Vo min. After stirring VA sad Yo for 1 hour at 1 m the mixture was cooled to room temperature and dissolved in an equal portion

AG of dichloromethane. The solution was passed through a 1-inch layer of silicagel gel 511168 _rinsed with dichloromethane and the clear solution was concentrated by ofall and then exfoliated in a Kugelrohr oven (100 m; 15 mmHg) to obtain the surfactant in the form of oil. © Ethoxylated Fatty Alcohol Surfactant | Nonionic Ethoxylated/Propoxylated Fatty Alcohol Surfactant Ce-Cig Cp-Cg 5 ethoxylated Jus sul are ethoxylated/propoxylated fatty alcohols suitable for use here as surfactants; Particularly the water soluble ones. The preferred ethoxylated fatty alcohols are C-Cyg fatty alcohols are ethoxylated OY aS with an ethoxylated degree of © to ©0; The most Saad of them are ,0-02 ethoxylated fatty alcohols with an ethoxylated degree of ? to 56 and preferably Vo for ethoxylated/propoxylated fatty alcohols with alkyl chain length of 01 to 18 carbons and an ethoxylation degree of ? Nonionic EO/PO Condensates with Propylene Glycol Condensates are ethylene oxide with hydrophobic base formed For 0 - by condensing propylene oxide with propylene glycol suitable for use here and it is preferable that the hydrophobic part of these compounds have a molecular weight of 18080 to 18080 and show insolubility in water and examples of this type of compounds include some Commercially available 100010111 type surfactant commercially marketed by BASF Yer A.

oy — nonionic EO ESS products with propylene oxide / ethylene diamine intercalated compounds The conjugate products of ethylene oxide with the products formed from the reaction of propylene oxide and diamine Ethylene ethylenediamine is suitable for use © here. The hydrophobic moiety in these gs is formed from the product of the reaction of ethylenediamine diamine with excess propylene oxide and has a molecular weight generally from Youu to 70805. Examples of this type of surfactant include non Ionic Certain Compounds 7600012114 Available Glad Marketed lad by BASF Mixed Nonionic Surfactant System 0 In a preferred embodiment of this invention the cleaning disc contains a mixed nonionic surfactant system containing On a nonionic surfactant with at least one low Opacity and on a nonionic surfactant with at least one high Opacity. dad opacity; As used here is a well-known property fam of nonionic surfactants which is a result of the decrease in the solubility of the surfactant with increasing Ve temperature; The temperature at which a second phase is observed is referred to as the 'aiid degree' (see Kirk Othmer's adil encyclopedia of chemical purification; CAE edition YY pp. 379-7160). Definition of the non-ionic surfactant “IY low opacity” as the original effective component of the non-ionic surfactant system has a opacity less than 0 than PY and preferably less than Fe and most preferably less than 10 M. Nonionic surfactants with low opacity include nonionic alkoxylated surfactants, particularly ethoxylates derived from QE Gedy primary alcohol reversed polyoxypropylene /_polyoxyethylene [polyoxyethylene polyoxypropylene Yo (00/20/00). And also; These include non-ionic surfactants

Low Opacity” e.g. (Jud) Poly-Tergent® SLF-18 Ji ethoxylated-propoxylated alcohol from Olin and polyalcohols (oxyalkylated) epoxy-coated Jie) Poly-Tergent® 5172-8 series anionics from ly Corporation as described” eg © in International Patent No. 94/22800 (WO published in 1) October 1946 as Jelly Olin surfactant poly(oxyalkylated) alcohol capped with ether. Nonionic surfactants may optionally contain propylene oxide in an amount up to 9019 by weight. Other preferred non-ionic surfactants may be prepared using the methods described in US Patent No. 3 filed at ab 980 adi 11 Builloty and cited herein by reference. The actives include andl Extra Low Opacity Nonionic CS Mold SH ss polyoxyethylene oll SH Je propylene polymeric eds polyoxypropylene 5 Jal ld compounds include polyoxyethylene - polyoxypropylene polymeric those dud Contains ethylene glycol, propylene glycol, glycerol, trimethylolpropane, and ethylenediamine as a hydrogen compound as a precursor, and some compounds of the polymeric template 0 are activated for the surface called REVERSED PLURONIC® 3; PLURONIC® and TETRONIC® of BASF-Wyandotte, Michigan dali in the ADD formulations of this invention. Preferred examples include the REVERSED TETRONIC®702 5 PLURONIC®25R2 585 These surfactants are actually useful as non-ionic surfactants with a low opacity.

The “high opacity” nonionic surfactant as used herein is defined as a component of the nonionic surfactant system having an opacity greater than 0?m; Preferably greater than 00’M; preferably greater than 010’M. Preferably, the nonionic surfactant activator system contains an added chal activator A etoxyl derived from deli monohydroxy alcohol© or an alkylphenol alkylphenol Yeo JA contains a carbon atom with 1 to Vo mole of ethylene oxide per mole of alcohol or alkylphenol on an average basis. These include high opacity anionic surfactants; For example Tergitol1559 “Jia (available from Rhodasurf TMDS8.5 Carbide Consortium 5) (available from Rhone Poulenc 5 91-8 1160001 (available from Shell ye. Preferred) Also, to achieve the objectives of this invention, the nonionic surfactants with a high degree of opacity should have a hydrophilic-oil-loving balance (CHLB?) Refer to Kirk Othmer mentioned above (Wha has a value within the range from 9 to 10, preferably from 11 to .These include col pall eg 1559 Tergitol (available from Carbide Consortium) and Rhodasurf-TMD8.5 (available from Rhone Poulenc), 91-8 Neodol (available VO from Shell) Another preferred high opacity nonionic surfactant is derived from a straight and preferably branched secondary fatty alcohol containing from +1 to Yo carbon atom Ce (mil alcohol); includes branched chain secondary and primary alcohols. Nonionic surfactants with high opacity are preferably Ye branched or secondary alcohol ethoxylates and more preferably alcohol ethoxylates Con alcohol ethoxylates or cross-branched condensates with an average of “ to Vo mol; 1 to 1" mole is preferred; more preferably 1 to 4 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant derived in the aforementioned manner should have a narrow etoxylate distribution relative to average.

Anionic Surfactant Any anionic surfactant useful for cleaning purposes (Lilo) is suitable for use here. These substances include salts (including lead, for example, sodium potassium 20018351017070, ammonium salts, ammonium salts 0 substituted Jie, mono J salts, and di- and triethanolamine (di-). triethanolamine salts sulfates, sulfonates, carboxylates, sarcosines ©8016 Anionic surfactants Anionic sulfate surfactants are preferred Other anionic surfactants include Jie isethionates 0 Cacyl isethionates, N-acyl tau rates !1-7, fatty acid amides for amethyl tauride, 45-alkyl succinate, sulfosuccinate, and monoesters. 90110500010818 Sulfosuccinates (especially Cpp-Cig monounsaturated and polyunsaturated esters) (JU) esters. oe diesters Sulfosuccinates (especially Cops) 5-di-esters and 17-acyl sarcosinates 2071-21 Resin acids and hydrogenated resin acids are also suitable for Jie rosin, hydrogenated rosin, resin acids and hydrogenated resin acids contained in or derived from wodwood oil. Anionic Sulfate Surfactant Ye Anionic sulfate surfactants suitable for use here include primary and secondary straight and branched alkyl sulfates; alkyl ethoxysulfates, fatty oleoyl glycerol csulfates, alkyl phenol ethylene oxide ether, and (Ci-Cq -N- dad Cs-Cp7 alkyl sulfate) ) B©-R)-Iradh Badi and- ‎C-Cy)N- | 8-hydroxyalkyl)glucamine “N-(C;-C, hydroxyalkyl) glucamine sulfates

Jie sulfates of alkylpolysaccharides Js sulfates of alkylpolyglucoside Jie sulfates of alkylpolysaccharides Jie sulfates of alkylpolyglucoside (nonionic nonsulfated compounds described later). It is preferable to choose alkyl sulfate surfactants from 00-sulphate 0© primary straight and branched alkyl; it is more preferable to be branched-chain alkyl sulfate CppCrs and straight-chain ,0-en© alkyl sulfate. Alkyl ethoxysulfate activated mall is preferably selected from the group consisting of sulfate ©-,© alkyl to which Ll) has been ethoxylated by 18 to 10 moles of ethylene oxide per molecule. preferably 0 more; that the alkyl ethoxysulfate surfactant is a ,0-,© sulfate; More preferred is a 5-t© alkyl sulfate to which it has been ethoxylated by 16 to 1 oF and preferably 1 to 1 mol of ethylene oxide per molecule. A particularly preferred form in the present invention uses mixtures of preferred alkyl sulfate 0 and preferred alkyl ethoxysulfate as a surfactant. These mixtures are described in International Patent Application No. 18124/117093. Anionic sulfonate surfactant materials Anionic sulfonate surfactants suitable for use here include 0-.m-alkyl benzene sulfonates, 0-alkylbenzene sulfonates, alkyl ester sulfonates, and sulfonates. Cg-Cpp primary or secondary alkane; and sulfonates M©-M0 colefin and sulfonated polycarboxylic acids and alkyl glycerol sulfonates | alkyl glycerol csulfonates, fatty acyl glycerol sulfonates, ofatty oleyl glycerol sulfonates, and any mixtures thereof. Yo

Lhasa Anionic Carboxylate Surfactant Suitable anionic carboxylate surfactants include Jas alkyl ethoxy carboxylates the alkyl polyethoxy polycarboxylate surfactant and soaps © (alkyl carboxylate) carboxyls' 1 carboxylates'); particularly the soaps as described herein. Suitable alkyl ethoxy carboxylates include those of the formula 174 10(011:011:0(,011:000 Cua) being R is “Cg Ae sane to Cig alkyl” and the x ranges from zero to 101 and the distribution of ethoxylate is such that it is based on the weight of the amount of the substance when x is zero is less than 96700 M 0 is a ce cation and includes alkyl polyethoxy-polycarboxylate materials suitable for surfactants having the formula ua RO-(CHR;-CHR2-O) -Rs R is a group of Cs to Cig alkyl and x is from 1 to Yo and Ros Ry is selected from the group consisting of hydrogen chydrogen and moiety methyl anethyl acid, succinic acid, 58 hydroxysuccinic acid, and mixtures thereof. between 1 and 8 carbon atoms; and mixtures thereof. Suitable surfactant soaps include secondary surfactant soaps that contain a carboxyl unit attached to a secondary carbon atom. The preferred secondary surfactant yo saponins for use here are the water-soluble elements selected from the group consisting of the water-soluble salts of 2-methyl-1- undecanoic acid and 7? - ethyl-1-decanoic 2-ethyl-1-decanoic acid, ~Y propyl-1-nonanoic acid, 2-propyl-1-nonanoic acid, and —Y-1-butyl 2-butyl-1-octanoic acid and ~Y-pentyl-1-heptanoic acid

— L. Pentyl-1-heptanoic acid. Gad may include some soaps as foam inhibitors. Alkali Metal Sarcosinate Surfactant Other suitable anionic surfactants are © sarcosinate Alkali metals with formula 7011:0001 2-0011 Cua where R is straight or branched Cs-Cyg alkyl or alkenyl group; !18 is ic gana SU CHC 14 is an alkali metal ion. Preferred examples are myristyl sarcosinate 0065 and oleoyl methyl Jie as sodium salts thereof. Surfactant Jali Amphoteric surfactants suitable for use here Amine and amine oxide surfactants and alkyl amphocarboxylic acids Suitable amine oxides include those compounds with the following formula Cua RIORHN'RY), Vo RY is selected from the alkyl hydroxyalkyl group acylamidopropoyl Jus' alkyl phenyl or terminator mixtures containing from A to 77 carbon atoms ; And RY is an alkylene or hydroxyalkylene group containing of ? to ? carbon atoms” or mixtures of terminators and x is 0 to 5; Preferably from zero to “oF and each RY is a Yo of an alkyl or hydroxyalkyl group containing from 1 to ?” Or a polyethylene oxide group containing 1 to ? Ethylene oxide groups. It is preferred to be the ©-,,©_alkyl oxide “dimethylamine” and the ©-,© acylamido-alkyl amine acylamido alkyl .dimethylamine oxide.

SRAM - The appropriate example of an alkyl dicarboxylic acid is Miranol(TM)C2M Concentrate manufactured by Miranol Corporation 21:2001; Dayton, New Jersey. Hybrid Ionic Surfactants (positive charge at one end, negative charge at the other) Zwitterionic Surfactant © Lad Zwitterionic Surfactant can be introduced into formulations to clean from. The activators can be described more broadly as derivatives of secondary amines (AEN) as derivatives of heterocyclic secondary and tertiary amines; Quaternary ammonium derivatives, quaternary phosphonium, or tertiary sulfonium compounds, betaine 0, and sultaine surfactants are examples of hybrid ionic surfactants for use here. Suitable betaines are those compounds with the formula R(R);N'R*COO" Cua where R is a 0-6,0 hydrocarbyl group and each of 18 is an RY Jl Ci-Cs is a group Ci-Cs hydrocarbyl betaine Yo 5 Preferred oa hexanoate Cig Dimethyl-ammonium dimethyl-ammonio hexanoate Cros betaines acylamidopropane acylamidopropane (or JU (ethane) dimethyl (or diethyl) complex surfactants betaines are also suitable for use here. Cationic surfactants Yaa are esters Cationic ester surfactants preferably used in the present invention are water dispersible compounds having surface active properties containing at least one (ie-000-) ester bond and at least a group with at least one cationic charge 0 Other suitable cationic surface-activated esters, including the surfactant-activated kaolin ester, are described in US Patent No.s. .

Pa suitable surfactants for quaternary ammonium cationic materials including cationic materials

Preferably N and 0m “Ce-Crg” surfactant selected from quaternary ammonium materials. The Cus surfactant is replaced by alkenyl ammonium or alkenyl ammonium by N-alkyl Jil or hydroxyethyl by cmethyl Jie. The remaining 1 sites are in 'hydroxypropyl Jus' © groups

The enzymes laa Enzymes are preferred cleaning components in the first phase and especially in the second and/or other facultative phases. And when it is present, this is chosen from the group that . It consists of cellulase enzymes (clad) peroxidases. proteases; Gluco oY eld or semi-cellulases enzymes 0 jal xylanases amylases 07165 ._xylanases cgluco-amylases amylases chythanases esterases. “phospholipases . Phospholipases 5 reductases keratanases keratanases pectinases pectinases +8 lipoxygenases phenoloxidases 48.R. The phenoloxidases, the pentosanases, the ctannases, the tanases, the cpullulanases, or the pullulanases, the ligninases, the lignases, the Yo 3- glucanases. 8 Chondromycin hyaluronidase Arabinosidase 85 L Hyaluronidase Mixtures thereof Jaccase Allacase cchondroitinase

Jipase, lipase, amylase, and protease. Preferred enzymes include cellulase and/or cellulase, cutinase, and Yo-015 peroxidases with one or more plant cell wall hydrolysing enzymes. The cellulases used in this invention are either bacterial or fungal cellulase enzyme. Preferably, it should have an ideal pH between © and 1 and a higher potency (cellulose viscosity unit 081101088). CEVU 860 cellulase enzymes were described by Barbsjord US. Patent 4,435,307 5, American gl fay) sel pn Occasion_ in Yo

Doss 1 and colleagues: M. Lamla (sel ny) 0 International Patent No. W0O96/02653 describing the enzymes of fungal cellulases produced respectively from Humicola insolens Trichoderma and Humicola insolens 48 or Sporotrichum. The patent describes EP No. 982 739 Cellulases Isolated from New Bacillus © Fragments The appropriate cellulases are described in GB-A-2,075,028 and GB-A2.095.275 and patent application Danish No. DE-0S-2.247.832 and International Patent No. 117095/26398. Examples of these cellulases are cellulases produced by a strain of Humicola insolens (Humicola grisea type 0 thermoidea). Du als diary “(thermoidea humicola DSM 1800 Humicola and appropriate cellulases AY) are cellulases from Humicola inulinase 585 having a molecular weight of 0 kDa; an electroequilibrium point of 0.0 and containing $10 amino acids 43kD camino acids from endoglucanase, Suid endoglucanase from Humicola. Insolens J (DSM 1800 Humicola insolens) exhibits cellulase 0 activity and the preferred component of endoglucanase 06 has the amino acid sequence described in the international patent application No. AV AVY EY and the suitable cellulases Lad are cellulase 11 from Trichoderma longibrachiatum described In International Patent No. Genencor Sula aul (WO094/21801) Published Sept. 75 V9 Particularly suitable cellulases are LY cellulases that have color-preserving benefits. Examples of such cellulases are the cellulases described in EP Application No. 747 /4,7 9170 Filed November 1, 1891 Novo Carezyme and Celluzyme (Novo Nordisk A/S) are particularly useful. See Lad International Patent No. 17244 / WOOL and International Patent No. 17091/ 21801. Other suitable cellolases for their preservative properties

on cloth and/or cleaning agents are described in International Patent Nos. WO96/34092, 710964, and W095/24471.

These cellulases were introduced naturally into the cleansing formula when

Levels from 960.0001 to 967 active enzyme by weight of the cleansing formula. © Peroxidase enzymes were used in association with oxygen sources, Jie oxygen, percarbonate, perborate, persulfate, chydrogen peroxide, etc. It can be used in apd solution bleaching, i.e. aie, the transfer of pigments or colored materials removed from the substrates during the washing process to the other substrates in the washing solution. Yo peroxidase enzymes are known in this field. Jay for example; In the international patent application No. WOB9/09813 and in the European patent application No. \o 20-84-64 ._filed .in + November 19511 or sel patent duo EP No. 96870013.8 deposited on 01 February 1947 and it is also appropriate to use an enzyme

Lactase enzyme and preferred tonics a phenthiazine and phenoxasine substituted Jia 10-Phenothiazinepropionicacid Yo and 01-ethylphenothiazine- 10-ethylphenothiazine-4-carboxylic acid (EPC), 10-phenoxazinepropionic acid (POP) and 10-Jie 10-methylphenoxazine (described in a patent Int. 12621/94 ©70)_substituted syringates. (0-0 substituted alkyl syringates) and phenols and are sodium percarbonate

the name

Sodium percarbonate or sodium Oe Gs are the preferred sources of Gail oxide

hydrogen peroxide (na sad peroxidases) and/or peroxides cellulases and these cellulases enzyme oe 907 were used naturally in the cleaning formula at levels from 960,0001 to

enzymes© effective by weight cleansing formula. Other preferred enzymes that can be used in the cleaning formulations in this invention include lipase 1:08568. Lipase enzymes suitable for use as a detergent include those produced by microorganisms of the group Pseudomonas such as Pseudomonas stotzeri 19,154 LATCC described in UK Patent No. 17977074. Suitable lipases include those that exhibit positive cross-reactivity with the antibody to the lipase. Produced by the organism Gaal pseudomonas fluorescent JAMIOST and this lipase is available from Amano Pharmaceutical Formulations; Nagoya Japan under the brand name Lipase © “Amano” referred to here by Ga as “©-00p0talmh”. Other suitable commercial lipases include “Amano-CES and ASL ga SI lipases (Chromobacter viscosum) (oe)-like (Chromobacter viscosum var) 0 lipolyticum type NRRLB3673 from Toyoguzu Corporation 010020 Tagata.” Tagata of Japan and Chromobacter viscosum lipases from _ the _ American _ Foundation for Biochemical Materials; USA and Disoynth _ Company The Netherlands and lipases ex Pseudomonas gladioli and particularly suitable lipases are lipases 00 such as Lipomax s MI LipaseR (Gist-Brocades Gist-Brocades) and Lipolase Ultra (Novo) which were found to be effective when used in combination with the formulations of this invention. The appropriate materials Diag are the lipolytic enzymes described in European Patent No. EP 258068 and Adsl Patent No. 92/05249 WO and International Patent No. WO 95/22615 by Novo Nordisk and in International Patent No. Yer A

WO 94/03578 and International Patent No. 94/03578 WO and International Patent No. WO 96/00292 by Unilever and the appropriate materials are also the enzymes of cutinases [EC] cutinases 0 7,1, 1,9]_ which can be considered as a special type of lipase Glad dipase Lipases that do not require activation of the interface 0 surface. The addition of lipase chitinases to cleaning formulations is described in, for example; WO-A-88/09367 WO-A-88/09367 WO 90/09446 (Genetic System of Plants) WO 94/14963 WO 90/09446 (Plant Genetic System) 94/14964 WO (Unilever).

Naturally occurring lipases and/or cutinases were introduced into the clean-up formulation

Ye at levels from 60,0001 to 967 active enzyme by weight of the cleaning formula. The appropriate proteases are subtilising proteins obtained from a specific strain of B. subtilis B. subtilis and b. Lycineformis B. licheniformis (BPN 5 BPN subtilisin) One suitable protease is obtained from a strain of Bacillus which has maximum activity over the pH range of “A 119 Yo (5-12;” shall and sold ESPERASE® aul by Novo factories [I x in Denmark; referred to herein as 'Novo'). The preparation of this enzyme and similar enzymes is described in Aula ll Patent No. Jelly Lge aul VYETVAE Appropriate Proteases The others are SAVINASE®; DURAZYM® (ALCALASE® (KANNASE®) by Novo and MAXAPEM® (PROPERASE® MAXACAL® MAXATASE® (Maxacal Vo _ for _ protein _ engineering) _ from Gist-Brocades.

Proteolytic enzymes include proteolytic enzymes modified bacterial serine proteases; such as those described in European Patent Application No. 57251446 filed on January 7 (dia) 1988 pp. TE, 117 and 38); which are called here "Protease B"; and in EP 850199404 Venegas; published TA Oct 0987 which refers to a bacterial proteolytic modified serine YO enzyme called "Protease A" here. that

f - here it is called “protease c; Which is a type of alkali serine protease 56006 from Bacillus, in which lysine was replaced by arginine at position 7, tyrosine replaced by valine at position 014, and serine 96 _ replaced asparagine at position VY and substituting alanine in place of threonine (wig ill © at position 4/a?). Protease G is described in WO 91/06637 and published May 11. NAY and modified species Ly and in particular protease C are also used herein. The preferred protease referred to as “protease D” is a carbonylhydrolase with an amino acid sequence not found in nature; derived from carbonylhydrolase 0 > primary by substituting a different amino acid with several amino acid residues at the position of this carbonyl hydrolase equivalent to the +771 position and preferably Lad in combination with one or more amino acid moiety positions equivalent to those selected from the group consisting of +15 and +a And +710 and +; Wah and Jalaka VO and Yl YYY+, and +15? Gls 74 + Ss for the numbering of Bacillus subtilisin amyloidoliquivashiar; As described in International Patent No. 17095/10591 and patent application pub C. Ghosh .0 and associates under 'Bleaching Compositions Containing Protease Enzymes' US Patent Serial No. 322,677/08 U.S.

Ser.

No. filed on Oct 11, 56 in Existing US Patent No. 5,677,65 U.S.

Pat.

No. Yo 272 and also appropriate to be used in this invention are the proteases described in EP No. 446 251 EP and INTERNATIONAL PATENT No. 91/06637 WO and the BLAP® protease described in INTERNATIONAL Patent No. 02792/17091 and its types described in International Patent No. 95/23221 WO

L and see Lad High pH Protease from Bacillus sp NCIMB 40338 described in International Patent No. WO 93/18140 A for Novo. Enzymatic cleaners containing proteases have been described; and one or more other enzymes” and a reverse protease inhibitor in WO 92/03529 A for Novo. When © is required, proteases with low adsorption and high hydrolysis are available as described in International Patent No. 95/07791 ash WO Procter and Gamble A recombinant protease similar to trypsin has been described for use in Detergent JS is suitable here in WO 94/25583 Novo. Other suitable proteases are described in EP 200 516 EP Unilever Ve. Other preferred protease enzymes include proteases that are It is a type of carbonyl hydrolase which has an amino acid ud sequence not found in nature and is derived by replacing several amino acid residues of the precursor carbonyl hydrolase with different amino acids; Where this multiple amino acid residue has been substituted in the coenzyme precursor at position 7001+ in conjugation with one or more of the following residues: 8 +7, +17 Veet Vids AVE, +PDA, +710, and +; 10, +la, +7a, +7a, VT, +177, +e91, VIVE YT VTE VoA+, 10th, +a, joe, +61? YIA4S VIVE, and +77;_where the numbered_positions correspond to the naturally occurring subtilisin in Bacillus amyloliquefaciens or an equivalent amino acid residue in carbonyl hydrolases or subtilising subtilisins | The other 0 (Jie) is Bacillus lentus subtilisin. Preferred enzymes of this type include those with the +7001, +1, A+ 101, and +10 A+ 4100 locus changes.

Proteolytic enzymes have been used in the cleaning formulations of the present invention at a level from 960,000 to BY and preferably from 960,001 to 960,7; Preferably more than one

Pee YO up to 960.1 pure enzyme by weight of the formula.

1

Amylase enzymes (alpha and/or beta) can be used to remove stains

resulting from sugars. It describes International Patent No. 17094/02597 in the name of Novo Nordisk

Novo Nordisk A/S ofl Published Feb 7 1444 Cleaning formulations containing hybrid 85-amylase. And refer to sel Lad International Patent No. WO95/10603 under the name

© Novo Nordisk Novo Nordisk A/S (fl Published April 01, 1986) Other amylases known to be used in cleaning formulations include alpha and beta amylases and alpha-amylases known in the industry include these Described in US Patent No. 5,003,257, European Patent No. 252,666 EP, International Patent No. 1770/91/00353, French Patent No. 2,676,456 FR, Patent

0 > EP No. 285,123 EP, EP No. 525,610 EP, EP No. 368,341 EP, BR No. 17934749 (Novo). The proper amylases (AY) are the _increasingly stable amylases described in ISBN WO94/18314 published VA Aug 1454 and ISPM ask WO96/05295 Genencore Genencor published in YY

Vo February 1997 and the types of amylases further modified in the direct parent compound available from Novo Nordisk fl Nordisk described in WO 95/10603 published April 8. A suitable material is Lay amylases amylase described in EP No. 216 277 EP and International Patent 17095/26397 International Patent No. WO96/23873 (all from Novo Nordisk

Y. Examples of commercial a-amylases are Purafect Ox Am® from Genencor, Fungmyl® Ban® 5 Termamyl® and Natalase® 5 Duramyl® are all available from Novo Nordisk A/S Denmark. WO 95/26397 describes 6 other suitable amylases: alpha-amylases characterized as having a specific potency of at least 96705 greater than the specific potency of Termamyl® at a temperature range of 220 to 200

YO and at a pH value in the range A to 01 measured using the alpha potency test

d" Phadebas® amylase and the appropriate use of the different types of the foregoing enzyme described in International Patent No. 96/23873 WO (Novo Nordisk 21070). Other amylose-degrading enzymes that have improved properties in terms of activity level, thermal stability union and higher activity level are described in International Patent No. 35382/17095. ° Preferred amylase enzymes include those described in International Patent No. 77 and International Patent 96/23873 se al WO Nordisk Novo Nordisk. Amylose degrading enzymes were used in the cleaning formulations in this invention at a level from 960,0001 to 967 preferably from 960.00018 in 960,073 preferably from See YE 0 to 900.048 pure enzyme by formula weight. In a particularly preferred embodiment, the Detergent tablets in this invention contain amylase enzymes, in particular those described in WO 96/26397 and WO 96/23873 under the name of Novo Nordisk by association With complement amylase. By 'complementary' we mean the addition of one or more amylases suitable for cleaning purposes. Examples of complementary amylases (alpha and/or beta) are described below. Cleaning formulations containing hybrid amylases. Other amylases known to be used in cleaning formulations include both alpha and beta-amylases; alpha-amylases known in the Yo field include those described in US Patent No. 5,003,257 5L1; and European Patent No. 252,666.” EP, INTERNATIONAL PATENT No. 170/91/00353, French Patent No. 2,676,456 (FR), EP No. 285,123, EP No. 525,610 EP, EP No. 368,341 EP, Written Description of the British Patent No. 17578749 (Novo).Other suitable amylases are the yo-amylases with increased stability described in International Patent No. 17094/18314

s

and International Patent No. Genencor Sua aul WO096/05295 and the different types of amylases having an additional modification in the direct parent compound available from Novo Nordisk fl and described in International Patent No. 95/10603 WO It is appropriate to Lad the described amylases In European Patent No. 216 277 EP (Novo Nordisk). Examples of © brand alpha-amylase products are Purafect Ox Am® from Genencor, Termamyl®, Ban® and 00880078 5 Duramyl® all available from Novo Nordisk A/S Denmark. 26397/17095 describes other suitable amylases: Alpha-amylases characterized as having a specific potency of at least 9675 greater than the specific potency of Termamyl® at a temperature range of V0 to 200 and at a pH value of 011 in the range of 8 to 01 Ys measured using the appropriate lS yall Phadebase® alpha-amylase potency assay are the variants of the foregoing enzymes described in International Patent No. 23873/17096 (Novo Nordisk). Other amylose-degrading enzymes that have improved properties in terms of level of activity, thermal stability union, and greater level of activity are described in International Patent No. A International Patent Ay 4 170 and International_Patent No. W096/05295 sold by Genencor and ©! Natalase® 3 Ban® y Fungamyl® 3 Termamy and Duramyl® are all available from Novo

Nordisk Maxamyl® 5 afl by Gist-Brocades. Complementary amylase is generally interfered with in the cleaning formulations of this invention at Yo level (Yorn) through BY preferably from 960.000148 to 960.05 More than 60,004 to 960,044 pure enzymes are preferred by formula weight. It is preferable that the ratio of the pure enzyme weight of the specific amylase to the complement amylase be between 9: 0 up to 1: 9 and more preferably between 4: 1

up to:1; Preferably between 7:1 and 1: ?. The aforementioned enzymes can be from any suitable source such as YO plant, animal, bacterial, fungal and yeast source. The source, Lal, may be thermophilic

Medium or high temperature (hygrophilous; hygrophilous; hygrophilous; lal hydrophilic; alkaline-loving; acid-loving; salt-loving, etc.). Pure or impure forms of these enzymes were also used, and hybrids of endogenous enzymes were used. Se hybrids can be obtained by protein engineering and/or genetic engineering and chemical and/or physical modifications of endogenous enzymes. It is common Glee enzyme gene expression by family organisms in which a brat product of the genetic material responsible for the production of the enzyme .enzyme has occurred. These enzymes were used naturally in the cleansing formula at levels from 60006 to 907 active enzyme by weight of the cleansing formula. Enzymes 0 may be added as separate single active ingredients (pills, granules, stabilized liquids, etc... containing one enzyme) or as mixtures of two or more enzymes (such as conjugate granulocytes). Enzyme oxidation activators described in EP 607 553 filed in August NAST Examples include tetraethylene polyamides 01 to which ethoxylated has been added. Numerous_ of enzyme substances and means of their use in industrial cleaning formulations in International Patent No. WO 9307263 A, International Patent No. WO 9307260 awh Genencor «806000©_International and Patent WO 8908694 A for Novo. and US Patent No. 3,553,139 US. © January 19720 on behalf of McCarty and associates. Enzymes are also described in US Patent No. 4,101,457 1.8 by Plass et al. in VA July VAVA or US Patent No. 4,507,219 1.5 Hogg in YT March NIAC Beneficial enzymes are described in liquid detergent formulations. ; And their interference in those formations in US Patent No. 4,261,868 US. On behalf of Hora and his colleagues in VE April 1981 The © enzymes used in detergents can be stabilized by several techniques. Enzyme immobilization techniques and examples are described

Mind you - in US Patent No. 3,600,319 .17.5 on Aug 117 199779 aul Gedge and colleagues EP 199,405 EP EP 200,586 in ?? Oct. 187 MVenegas” and Lad enzyme stabilization systems (JE) are described in © US Patent No. 3,519,570 JUS. Beneficial bacillus of the type ACIS that gives proteases and xylanases is described. and cellulases in International Patent No. WO 9401532 A as Novo. Bleaching agent One of the most favored ingredients in detergent formulations is the bleaching agent. Suitable bleaching agents include chlorine and chlorine bleaching agents. 0xygen, and in one of the preferred forms, the oxygen-producing bleaching agent contains a source of hydrogen peroxide and a precursor bleaching compound of an organic peroxy acid. Hydrogen Preferred sources of hydrogen peroxide include inorganic bleaching agents perhydrate, and in one of the alternative forms of overlapping organic peroxy acid treated directly in the formula, formulas containing mixtures of a source of hydrogen peroxide and peroxy acid were imagined. Primary organic peroxyacid in combination with treated organic peroxy acid. Yo Inorganic Bleaching Agents Perhydrate Detergent ingredient formulations preferably include a source of hydrogen peroxide; and an oxygen-exporting bleaching agent. Suitable sources of hydrogen peroxide include inorganic perhydrate salts.

Inorganic superhydrate salts naturally occur in the form of sodium salt at a level from 901 to 96460 by weight. More Sain from 967 to 0 by weight and more preferably from 966 to 9675 by weight of combinations. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate, and persilicate ©0©5111681. The naturally occurring inorganic superhydrates are salts of the alkali metals. Inorganic perhydrate salts may be included as a crystalline solid without additional protection. and for some perhydrate salts; The preferred use of these granular formulations necessitates a coated form of the material which gives better storage stability of 0 perhydrate salt in the granular product. Sodium borate can be in the form of the monohydrate which has the nominal formula aul 11280211202 or the tetrahydrate 11250211202.31120. The metal percarbonates (Ald) and in particular sodium percarbonate are the preferred superhydrates for use in the formulations of this invention. GA is sodium carbonate which is an additive compound with the following_formula 2 and is available as Lad as a crystalline solid. and have sodium percarbonate; Being a compound adding hydrogen peroxide, a hydrogen peroxide, the ability when dissolved to release hydrogen peroxide quickly enough that can increase the ability to obtain high concentrations of the bleaching agent in certain places. It is preferable to use 0 percarbonate in these formulations in a covered form, which gives stability to the product. Suitable covering materials that give stability to the product include a mixture of water-soluble alkali metal sulfate and carbonate salt. These coating materials with coating methods were previously described in British Patent No. 1,466,799 under the name Antiroxi of March 9th NAVY. The weight ratio of the coating mixture to percarbonate is in the range from 1: Yee YO to 1: ; Preferred from:1 99 to:1 9 Preferred from:1 9; to 9:1 preferably

Ald GS is a mixture of Ge sodium sulphate and sodium carbonate, which has the general formula Cus Na2S04.n.Na2CO3 from 1.1 to F preferably from 17 to 1, preferably 17 Gan to co. Other suitable covering materials that give stability to the product include sodium silicate © which has a ratio of 11820 : 5102 from 1 VA to ?: 1 Preferably 1 A up to ??.?: 1 and/or sodium metasilicate preferably at a level from %Y to (sale) 9001 of 967 to (Wo of 51:02 oe weight of inorganic perhydrate salt Say that magnesium silicate is also used for coating Covering materials that contain Ve silicate salts and borates or boric acids or inorganic materials Other organics are suitable for use here as well.Sas that other covering materials that contain waxes, oils, and greasy soaps are used as distinctive in this invention.Potassium peroxymonopersulfate 9 is a salt perhydrate Another inorganic perhydrate salt is of use in the formulations described here as well. The raw material for the peroxy acid bleaching agent The raw materials for the bleaching peroxy acid agents are compounds that react with hydrogen peroxide in a hydrolysis reaction to obtain peroxy acid Yo. In general, the raw materials for the peroxy acid bleaching agent can be represented by the following formula: 4 1 la a where a is a leaving group and # is any functional group such that when perhydrolysis is carried out the structural composition of the resulting peroxy acid is: 0 N— ! — Al

Glossy - It is preferable to use the compounds of the raw material for peroxy acid bleaching at a level from to BY by weight, preferably from 901 to 90010 by weight, and preferably from 961.5 to 59 by weight of the formulations. Actually suitable peroxy acid feedstock compounds contain one or more © of the JN groups 0-acyl 0-28©71; These raw materials can be selected from a wide range of sections. Appropriate sections include anhydrides, esters (Sue) esters 001065_lactams, imidazoles derivatives, and oximes with an acyl added Aig. acylated. Description of examples of materials used in these sections in the application sels of the invention Aula nll No. GB-A-1586789 and the appropriate esters are described in 0 UK Patent Application “GB-A-836988 864798; 1147871 (2143231, EP-A-0170386 EP-A-0170386 Abandoning groups The leaving group, herein referred to as group 1, must be sufficiently active for the epihydrolysis reaction to occur within the maximum time range Sa) of the wash cycle) Despite this yo if 1, it is very effective it is difficult to cul this activator for use in a whitening formula. The preferred I groups are selected from the group consisting of:

7 R? ry

LO. AF we -© 0 ] A 1 poison —N N —~N--C—CH—R*

Re LJ Re Y

Y

0 E ~O-CH=C—CH=CH, —O—CH=C—CH=CH, 0 0 1 7 3 ° CHC Cu 1 Fr, + Swe

O—C~—R! Noo NRE ~~ 'i & 6

R3 oY 1 or aryl aryl is an alkyl group of aryl compounds R1 and mixtures thereof where 1 is an alkyl chain containing R3 carbon atom”; And the VE to 1 contain from alkaryl

Jal is RS 083 Series or H Carbon; And 84 is an SA to an [1] or solvent group. and can y to 4 carbon atoms and be 1 contain from alkenyl functional group chosen from; For example sb Lila and 1014 R35 181 that any of the alkoxy ("hydroxy halogens hydrated, for example" calkyl groups) be replaced by alkyl groups or ammonium and ammonium nitrosyl amide 0100571 and amide camine amine chalogen .alkyl ammonium alkyl ammonium The preferred solvent groups are 50:11-, 14,00- and 5011, and more preferably 50:14- and 00274-00274, where 183 is ONRY)s 5 N(R) X is 0

The ALL alkyl group contains 1 to ; carbon atoms 34 is a cation that gives solubility to the bleaching activator and 3 is an anion that gives solubility to the bleaching activator. Preferably 1,4 is alkali metal; ammonium or ammonium cation substituted; With sodium and potassium © being preferred; And x is a chalide, Jie hydroxide, methylsulfate sulfate, or acetate anion. The starting material for perbenzoic acid gives the compounds of the starting material for perbenzoic acid. perhydrolysis after hydrolysis.

0- to 0-acyl Glad The compounds of the starting material for perbenzoic acid 1 and other suitable non-benzoyl oxybenzene sulfonates include substituted 0-oxybenzoyl sulfonates, which include, for example, oxybenzoyl sulfonate:

0 OO and the suitable compounds Lad are the products of benzoyl addition benzoylation of sorbitol \o glucose “glucose” and all the saccharides by Jol se benzoyl addition OAc which include, for example: = OAC OAc 082 COCHs; = AC and 37-benzoyl and the compounds of the starting material for perbenzoic acid of the amide type include each of the -N Ye succinimide (N-benzoyl succinimide), tetrabenzoyl ethylene diamine and the substituted N-benzoyl ureate N-benzoyl substituted 5. Suitable imidazole-type perbenzoic acid precursors include N-benzoyl imidazole and N-benzoyl imidazole.

1 — M Jediy N-benzoyl benzimidazole Perbenzoic acid precursors containing -N acyl group 2181 Other useful N-benzoyl pyrrolidone and dibenzoyl taurine and benzoyl pyroglutamic acid 2. The raw materials for other perbenzoic acid include the benzoyl diacyl peroxides and the benzoyl tetraacyl peroxides, and the compound has the following formula : l 1 0 SN oro 0™"cooH and phthalic anhydride is a precursor compound for perbenzoic acid) + al is suitable for use here. Perbenzoic acid of the type ASU lactam with N-acyl N-acylated in the appropriate formula: Q q Gorn R6—C — Neri; In \o Where it is “from zero to A and preferably from zero to; and 85 is a benzoyl group Yor A

The raw materials for perbenzoic acid derivatives The raw materials for perbenzoic acid derivatives prepare substituted perbenzoic acids after hydrolysis. Suitable substituent perbenzoic acid derivatives precursors include any of the perbenzoic precursors described herein in which the benzoyl group is sb-substituted with a non-cationic Aad functional group and includes (eg (Ji) The hydroxy alkyl groups, the alkoxy calkoxy, the halogen, the amine, the camine, the nitrosyl, and the amide. And in a preferred section of the substituted perbenzoic acid starting material compounds are the compounds 0 substituted with an amide which has the following general formula: a-st RI —N—g sn o o w oO RS 0 a RS © 0 where RY is an aryl alkaryl group of 1 to VE carbon atom and RY is 71606: arylene group; or an alkarylene has 1 to VE carbon atom; 18 is 11 or an aryl calkyl group Or 'Ye' the alkaryl contains from 1 to 10 carbon atoms and can be .1 is absolutely any leaving group. RY preferably contains from 7" to VY carbon atoms. It has 182 forms Preferably from ; to 4 carbon atoms. RY can be a aryl-substituted dit or an alkyl aryl containing a branched substitution; or both and can be obtained from either synthetic or natural sources which include for example; Friendly fat. Various synthetic species similar Yo are suitable for ROD and the substitution may include alkyl groups, caryl, halogen, nitrogen, sulfur and other substituent groups or other substituent organic compounds. And 187 is an 11 or a Jie and L and A must not contain more than VA carbon atoms in total. The amide-substituted (andl) factor-activating compounds of this type are described in European Patent No. EP-A-0170386.

— Age of cationic peroxy-acid feedstocks The cationic peroxy-acid feedstock compounds prepare peroxy-cationic acids after ultrahydrolysis. Lady The cationic peroxy acid precursor was formed by substituting the © part of the peroxy acid in a suitable peroxy acid precursor with a positively charged functional group; Jie ammonium group or alkyl ammonium aise, preferably ethyl group or methyl ammonium, and the raw materials for cationic peroxyacid are present in the formulations as a salt with anion. appropriate”; Jie is the halide ion jon or the methylsulfate ion methylsulfate jon for example 01. In order for the compound to be the starting material for a cationic substituted peroxy acid, it can be a starting material compound for a perbenzoic acid; or a substituted derivative thereof; As described here previously. Alternatively the peroxy acid precursor compound may be an alkyl percarboxylic acid precursor compound or the 05 substituted peroxyalkyl acid precursor with an amide described herein below. The starting materials for cationic peroxy-acid are described in US Patent Nos. 4,904,406 4,751,015 4,988,451 4,397,757 5,269,962 127,852 ¢5,093,022 5,106,528 and English Patent 1,382,594 (UK). And the European patent (EP 475,512 Hj 458396 & 284,292_and in_Japanese_patent No. JP 87 -318,332 0 The starting materials for the cationic peroxy acid include any benzoyl oxybenzene sulfonates or alkyl ammonium alkyl benzoyl and caprolactams to which 17-Neacylated has been added. ‎monobenzoyltetraacetyl glucose benzoyl peroxides Yo

_— 4 0 — The preferred cation-substituted benzoyl oxybenzene sulfonates is a 4-(trimethyl ammonium) methyl derivative of benzoyl oxybenzene sulfonate. 0 Om Nt VA ° The preferred substituted alkyl oxybenzene sulfonate Gi pols has the following formula: So. 3 7( 0 \ 1 a ee N___~ 0 ~ Preferred cationic peroxyacid feedstocks include 0-type carrolactams to which N-acylated caprolactams are added, especially trimethylammonium methylenebenzoyl caprolactams. .trimethyl ammonium methylene benzoyl caprolactam © b Hy ~ 1 3 a i 1 / “, a ben ~N emsa r sahal and include the preferred cationic peroxyacid starting materials 0 The other type of caprolactam added dud -N al caprolactam N-acylated caprolactam “trialkyl ammonium methylene alkyl 0 b Ay ~ 1 7 3 1 \ — Ne 10 > m where is “ from zero to OT and in particular from 1 to 0 of 01

so — - The other preferred cationic peroxy acid precursor is ?- (-N, N,N)trimethylammonium) ethyl sodium chloride; Sulfonyl chloride carbonate. 2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride Raw materials for bleached alkyl percarboxylic acid o Raw materials for bleached alkyl percarboxylic acid work on the preparation of percarboxylic acids after hydrolysis and the materials work The preferred precursor of this type is based on the preparation of peracetic acid after epihydrolysis. The preferred over-carboxylic alkyl precursor compounds of the amide type include the alkylene diamines to which the 177, 11, 11, 11-N added tetra acetylated alkylene Cua diamines 0. The alkylene group contains an alkylene of 1 to 76 carbon atoms and in particular those compounds in which the alkylene group contains 1 and ? and 1 carbon atom. Tetraacetyl ethylene diamine (TAED) is particularly preferred. Primary preferred alkyl percarboxylic acid feedstocks—e 5 oF ter V0 include sodium 3,5,5-tri-methyl hexanoyloxybenzene sul- (150-NOBS) fontate and sodium nonanoyloxybenzene sulfonate (NOBS) sodium nonanoyloxybenzene sulfonate, sodium acetoxybenzene sulfonate (ABS) and penta acetyl glucose .glucose Yer A

C - Amide Substituted Alkyl Peroxyacid Precursors The compounds of the amide-substituted alkyl peroxy acid precursors are also suitable, including those that have the following general formula: a where RY is an alkyl group with 1 to VE carbon atom” and RY is an alkyl group with 1 to VE carbon atom; 187 is an 11 or an alkyl group containing from 1 to 10 carbon atoms; .a can be a leaving group. RY preferably contains + to VY carbon atoms; It contains 8 preferably of ; 0 to +8 carbon atoms. RY can be a branched or straight-chain alkyl containing branched, substituent, or both and can be obtained from synthetic or natural sources. Including, for example, fat Alwadak. Various similar structural types are suitable for R?, and Joly can substitute alkyl groups, halogen, nitrogen, sulfur, and other substituent organic compounds or groups, and RS is in the form of VO. preferred is 1 or an instance. 18A should not contain more than 18 carbon atoms in total. The amide-substituted bleaching agent activator compounds are described in the European patent application EP-A-0170386 Benzoxazin Organic Peroxyacid Precursors Y. The appropriate compounds Lad are feedstock compounds of the type LS Benzoxazine are described for example in European Patent Application No. EP-A-332,204 and European Patent Application No. EP-A-482,807 In particular, those with the following formula: 0 , OL solution:

the parent including benzoxazines 560207082108 substituted of the following kind: rd Ry ~ 8 Ry od Ry where Ry is an alkyl cH; carel; ef aryl “JS where Ry (Ry Ry and Rs are same or different substituents selected from 11 and halogen alkyl halogen © calkenyl aryl hydroxyl calkoxyl camino alkyl amino M0005 (where Re is 11 or an alkyl group) and carbonyl .One particularly preferred starting material of the benzoxazine type is: 0 006 ~~O Vo Preformed Organic Peroxyacid The Organic Peroxyacid System may contain anal in addition to, or as a substitute for, the preformed Organic Peroxy Acid Bleach + Preformed Organic Peroxy Acid Compound Effectively at a level from 900.8 to 9675 by weight and more preferably from 961 to 9601 by weight of the composition. 1 Bamide, which has the general formula ANN o RS 0 OOH M SS C - - AG RS © 0 Yeo A

RH - where RI is a cAlkyl aryl alkaryl group with 1 to VE carbon atom; R2 is an alkylene group [carylene [carylene] [carylene] containing from 1 to VE carbon atom and [RS] is [1] or [J] aryl or caryl group contains 1 to 10 carbon atoms. RT contains preferably from + © to 17 carbon atoms. It contains 82 preferably of; to A carbon atoms. 1 can be a straight-chain or a branched alkyl; An aryl or alkyl aryl substituted containing a branch; substitute or both and can be obtained from artificial or natural sources including eg. Friendly fat. Multiple similar structural species are suitable for RZ and the substitution may include an ase group (Jl DSU N; sulfur and other substituting organic 0 groups or compounds. RS is preferably an 11 or methylation and shall not contain RI and RS contains more than VA a carbon atom in total.An organic peroxyacid acid substituted with an amide of this type has been described in European Patent Application No. EP-A-0170386 and includes acids other organic peroxyacid peroxides VO diacyl and ctetraacyl Ja) and in particular peroxydodecanedoic acid [0106:0*37000868060106]”; Diperoxytetradecanedioc acid and ddiperoxytetradecanedioc acid and diperoxyhexadecanedioc acid. The preferred organic peroxy acid here is benzoyl dioxide. Diperazelaic acid, dal-Ye acid, diperbrassylic acid, and N-phthaloylamineoperoxicaproic acid are also suitable for use here. Controlled Rate of Release-means (Sa) Provides a means of controlling the rate of release of a bleaching agent, in particular oxygen bleaching agent, to the wash solution.

A means may be provided to control the rate of release of the bleaching agent for the uniform release of peroxide materials into the wash solution. These methods may include; For example; Control the release of any inorganic perhydrate salt that acts as a source of hydrogen peroxide to the washing solution. ° One way to control the rate of release of the anal agent is by covering the bleaching agent with a cap designed for uniform release. The coating (lL for example) can contain a material that is poorly soluble in water or be a coating of such thickness as SS such that the melting kinetics of the thick coating give a uniform rate of release. The covering material can be applied using several methods. Any coating material actually present 0 with a weight ratio of coating agent to bleaching agent from 994:1 to:1?; preferably from 1:4 in 0:1 Suitable coating materials include She triglycerides Wa) hydrogenated vegetable oil, soybean oil, cottonseed oil), mono or diglycerides, microcrystalline waxes, gelatin, cellulose Yo, fatty acids, fatty acids, and mixtures thereof. Other suitable covering materials may include sulphates, silicates and carbonates 8g2:00021; Lead Lay -calcium carbonate and silicas The preferred covering material contains; In particular for the source of bleaching agent from inorganic yo perhydrate salt; on sodium silicate with a ratio of SiO; Level from 967 to 9001 (usually 907 to 0%) of 5102 by weight of the inorganic superhydrate. Magnesium silicate may also be used for coating.

+420

Any covering materials of inorganic salt can be combined with organic binding materials to obtain a coating composition of inorganic salt / organic binder. Suitable binding materials include the following cthoxylates etoxylates and ©-,© sas containing *e- 100 moles of ethylene oxide per mole of alcohol preferably Cre-Cao ethoxylates © primary alcohol ethoxylates containing from 001-7071 moles of ethylene oxide

.alcohol moles of alcohol JS oxide Other preferred binders include some polymeric materials, polyvinylpyrrolidones up to 7,000,000 and poly 17,0000 having an average molecular weight of 008 having an average molecular weight of 060 to ( PEG) polyethylene glycols Ethylene glycols are examples of these 00001 to 0001 to 4000060 preferably over 0001 preferably 101xe with ethylene maleic anhydride polymeric materials. Conjugated copolymers of maleic anhydride “methacrylic acid” or “methacrylic acid” methylvinyl ether cethylene mol per cent of the polymer represent at least 01 maleic anhydride with maleic anhydride being other examples of useful polymeric materials as binding agents. These materials can use water and propylene glycol Jie as is or in combination with polymeric solvents VO —e containing alcohol ethoxylates Cip-Cap alcohol and propylene glycol ethoxylates per mole above. The remembrance. Examples of binders include ethylene oxide 0 mol as well as other mono- and diglycerol ethers as well as other mono- and diglycerol ethers

0-00 fatty acids.

P and cellulose derivatives such as methyl cellulose 060171261101086, carboxymethylcellulose, hydroxyethyl eellulose, and similar or conjugated polycarboxylic acids (Goals) or their salts are other examples of binders suitable for use here.

One method of using a coating material for granules includes; Preferred granulation methods for Yo include the use of any organic binders described herein and Ble, and any component may be used.

+1 = ! Granules/Standard Mixer including, but not limited to; Fryer; Roller Mill and Vertical Tuner Types. Fused covering compositions may be applied either by pouring in; Or mist it into a moving layer of bleaching agent. Other methods for obtaining a uniform release include automated means of altering the physical properties of the bleach to control its solubility and release rate. (Say that appropriate methods include compression, automatic injection; manual injection; and adjusting the solubility of the bleach by selecting the molecular size of any particulate component. Whereas, the choice of molecular size depends on both the composition of the particulate component and the desirability of obtaining On desired systemic release compounds it is desirable to have a molecular size of 0 greater than 900 µm;preferably an average molecular diameter of 6060 to 01101 µm.Other methods for obtaining systemic release media include appropriate selection of any other components in the texture of the cleaning composition so that when the composition is introduced into the wash solution the ionic strength environment in which it is present enables the desired uniform release kinetics to be obtained.Metal-containing Bleach Catalyst Vo Bleaching of a cleaning ingredient additionally over a preferred ingredient which is a metal bleaching catalyst Preferably a metal bleaching catalyst is a transition metal bleaching catalyst;more preferably a manganese or cobalt bleaching catalyst .cobalt One suitable type of sale catalyst for bleaching is a heavy SY cation catalyst with specific bleaching catalyst potency; such as copper and iron cations and an additional metal cation having little or no bleaching catalytic activity; such as zinc or aluminum cations; a separator having specific stability coefficients for the catalyst and additive metal cations; In particular, ethylenediamine tetra acetic acid and ethylenediaminetetra acetic acid (aes) methylenephosphonic

+1 and its water soluble salts. These catalysts are described in the patent (40

U.S.A. Pat. 4,430,243 Preferred species_ of bleaching catalysts Jali manganese-based complex compounds described in US Pat. No. 5,246,621 1.8.284 and Pat. US 5,244,594 .© 3rd cycloanosan -7 of = 3rd SY cE 0(0172)0-3 3rd -v of (MT112)-0(10-02) —Y(trimethyl-1,4,7-triazacyclononane triaza-7 cf) MnlV4(u-0)6e )0104(2 triaza nonanne)7-17-4 methyl-; and chelates Others have been described (MnlTIMnIV4(u-0)1(u-OAc) cyclic noon); - 0104(2); in EP Application No. 549,272 other suitable binding molecules include 1 0 ,59-trimethyl-1 ter azacyclodecane (4 co = e ter -4 co) for use here 2-methyl-1,4,7- triazanonane cyclo-7 cf methyl-1; - “,5,9-triazacyclododecane 2-methyl-1,4,7-tri- 7- _methyl-a 1 7- triazacyclononane 1,2,4,7- triazacyclononane 1,2,4,7- triazacyclononane = v of tetramethyl-a -17 cf YY) cazacyclononane and mixtures thereof. ctetramethyl-1 , 4,7-triazacyclononane |0 Catalysts for the useful bleaching agent in the formulations herein may be selected as appropriate to this invention. Examples of suitable bleaching agent catalysts refer to US Patent No. See also US. Pat. 5,227,084 and patent US Pat. 4,246,612 complex (IV) describing manganese compounds US Pat. 5,194,416 US Pat. sel (Gila gus tri-aza 7 cf trimethyl-1-YE) ( Mn ie mononuclear 0.(PF¢)3-(OCH3); (1 ,4,7-trimethyl-1 ,4,7-triazacyclononane) other; as described in the US patent anil and a catalyst of a material manganese is a water-soluble complex of manganese US. Pat. 1 14,606 non-polyhydroxy Ss ued with a binding molecule that forms a poly(IV) Ss 0 preferred binding molecules include Allie C-OH carboxylates with at least three groups 8 y= xylitol cmannito [l mannitol dulsitol dito] edetol sorbitol sorbitol 111650-6-101 ariritol sual adonitol 711001 “””_arabitol [Nt7”_ adonitol and mixtures thereof. lactose and lactose cmeso -inositol, misanositol, catalyst - bleaching agent, USS. Pat 5,114,611 describes US Patent No. 00 or 00 with a fraction of Fe, CO, or Mn containing a complex complex of transition metals which include the non-(large)-cyclic bond ©. These binding molecules have the following formula:

RZ Qim Do Yag each selected from 11 substituted alkyl and aryl groups 871822 RAR! Where it is a pentagonal or hexagonal ring. Could it be 82-07-84, RI-N=C-R? so that all

S¢ 0 This loop is also replaced. and 3 is a Ye-selected bonding group and 87 each is an 11-alkyl or R% 185 group being “C=O: 7 labeled as an aryl group; Including substituted and non-replaced groups. The linking molecules include pyrazine rings, pyrimidine, pyridazine, pyridine, and optionally triazole, triazole, imidazole, imidazole, ued alkoxy, aryl anhydride;_alkoxy. calkyl alkyl Jie These rings are replaced by Jas Ye 2,2 pyridylamine bis = GY nitro 0100 and the linking molecule halide is particularly preferred

Mn «Cu «Co. The preferred bleaching catalysts include the complex compounds of «bispyridylamine -bispyridylamine and pyridylamine-bispyridylmethane-2 0 2,2-bis (od ds YY) Co pS Jl . preferred_catalysts des, bispyridylamine (bispyridylamine) isothiocyanato and di(isothiocyanate) Cl (bispyridylamine 0)

Co tris dipyridylamine-cobalt perchlorate (01); (ID) bispyridylam ine-cobalt bis YY) perchlorate bis-10,02 v(bispyridylamine ?-bispyridylamine) perchlorate ; Tris (di-?- (I) copper (bispyridylamine (pel ia yu) and mixtures thereof. (ID) iron (di-2-pyridylamine)

+ Favored examples include the dinuclear Min complexes with N-terminal and 8-terminal <4-terminal binding molecules" and include 7-lyl banana NM-(C104) [and the [Bipy2Mn"(u-) 0),Mn" While the compositions of complex manganese compounds catalysing bleaching materials are not specified in the © of this invention; It can be conceived in terms that it includes chelates or complex symmetrical compounds that result from the interaction of the carboxyl and nitrogen atoms of the lipid (binding molecule) with the manganese cation. Likewise, the oxidation state of the manganese cation during The catalytic process is unknown on the A side and the PS states can be (l+), (+1), (HIV) or (HV) and due to the presence of six possible contact points in the binding molecules of Ye With the pail cation it is reasonable to conclude that polynuclear species and/or "cage" structures can be present in the aqueous bleaching medium. Visible for better whitening performance against stubborn stains such as tea stains, ketchup, coffee, wine, juice, etc. AY Gand 5 catalysts (eg) are described in European Vo Patent Application No. 408,131 (Cobalt complex agents) fs lad and EP Applications No. 3, 306,089 (metallic porphyrin catalysts) and US Patent No. 4,728,455 U.S. (manganese agents/multilateral binding molecule catalysts) and US Patent No. 4,711,748 US. And European Patent Application No. 224,952 dale) manganese absorbed on aluminosilicate sels) American patent Ye 8, 4,601,845 US. (support gues) aluminosilicate with manganese and zinc zinc or magnesium salt sel ny (salt US Pat. No. 4,626,373 U.S. (manganese agent/catalytic binding molecule) & US Patent No. 4,119,557 (dale US. complex ferric catalyst) and written description of the German patent YO No. 2,054,019 (Cobalt Chloride Catalyst) and Canadian Patent No. 866,191 (Transition Metal Containing Salts) and Patent

f - US No. 4,430,243 US. (chelating agents with manganese cations and non-catalytic ll cations) and US Patent No. 4,728,455 US. (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (TID) having the formula:

CO[(NH3)uM'mBs T'QqP,] Yy ° Cua cobalt is cobalt in the +7 oxidation state and n is a number from 0 to © (preferably; or © more preferably 0) MY is a one-terminal binding molecule, 0 is a number from zero to © (preferably 1 or 7 is more preferable 1) and BY is a two-terminal binding molecule; 5 is a number from zero to oF 1 represents a three-terminal binding molecule;

q is “bY, © is a four-part 10, + is a zero or 1 0, and © is a five-terminal; © is either zero or 10 either zero or and is not one or more anti-anions 11 = “+ “+ 265 + 32 + 4 + Sp and is to * (preferably * to ? 1 for the number of carefully selected sole nocts present in a number where (preferably more ?when 57 is an anion with a charge of -1); to obtain a neutral salt

V is the charge; It is preferable to choose 57 from the group consisting of chloride, nitrate, nitrate, nitrite, sulfate, citrate, acetate, carbonate, and terminating unions, where Ld is at least one of the coordination sites. The cobalt connected to the cobalt is free to move under the conditions of using an automatic dishwasher, and the remaining coordinating sites stabilize the cobalt under the conditions of automatic dishwashing so that the reduction effort of Ye cobalt (II) to cobalt (I) cobalt under alkaline conditions is less than 1. 4 volts (preferably less than oY volts) versus a normal hydrogen electrode The preferred cobalt catalysts of this type have the formula: [Co(NH3)a(M)m]Yy where « is a number from © to © (preferably more; or ©; more preferably 0) YO and 14 is a free-moving harmonic split; preferably chosen from the set consisting of

++ - chlorine “chlorine bromine hydroxide chydroxide water and (when 07 is greater than 1) terminated unions (mixtures) and m is a number from 1 to 7 (preferably 1 or ?; and most preferable) 1; and is 0 +” = 6 and y is a carefully chosen anti-anion that exists in the number no which is a number from 1 to ? (oF JY is preferred and more preferably ? when y is an © anion with charge) 1- to obtain a balanced salt. The preferred cobalt catalysts of this type used herein are the cobalt pentaamine chloride salts of the formula [Co(NH3)SCI]Yy' and in particular 000113(501[1012]). The compositions of the present invention using sale catalysts are more preferred The bleaching of cobalt (111) has the formula: [Co(NH3)n(M)m(B)b] Ty 1 where cobalt is in the + oxidation state and is either ; or © (preferably 0) and is M One or more cobalt coordinating bonding molecules in one position and 8 is a zero or 1 or ¥ (preferably 1) and 38 is a cobalt coordinating bonding moiety in two positions and b is a zero or 1 (preferably zero) and when 5 = zero then 0 + 0 < 1 and when b > 1 yo then m = zero = n ; T is one or more anions Appropriately selected antigen present by the number y where y is a number to obtain a balanced salt (preferably y is 1 to ? and more preferably ? when 1 is an anion with charge 1) - where this catalyst has a constant base hydrolysis rate less than 1mol-1sec-1(pY0)ve CYT and the preferred T is chosen from the group consisting of chlorides; Iodide and -13 formate formate nitrate enitrate nitrite sulfate sulfite sulfite citrate citrate acetate carbonate bromide PF6- bromide B(ph) 4- <BF4- Phosphate “phosphate” phosphite cphosphite silicate tosylate methane sulfonate cmethanesulfonate and conjugates thereof optionally to which Yo proton can be added 13 There was JS of one anionic group Found in !© eg

B” - (H2PO4- (HCO3- (HPO42-) etc. Lady 17 can be selected from the group consisting of unconventional inorganic anions such as anionic surfactants (such as straight alkylbenzene sulfonates (LAS) ) and alkyl sulfates (AS) alkyl sulfates and alkylethoxysulfonates (25e).... Sadat ifs (A©) anionic polymers (such as polyacrylates, polymethacrylates, etc. M moieties include, but are not limited to, e.g. SCN- (NCS- 5804-2 (F- PO43- 21133 » 52027) and carboxylates (preferably cmono-carboxylates). But more than one carboxylate can be present in the 0 radical as long as the bond to the cobalt is by only one carboxylate per radical, in which case z a proton can be added to the other carboxylates in radical 14 or its salt (and optionally a proton M) can be added if There is more than one anionic group present in M (eg -110042; HOC(O)CH2C(0)0- <H2PO4- (HCO3- etc) and the preferred 14 moieties are the substituent Mo,©-.0 carboxylic acids and unsubstituted having the following formula: RC(0)O- yo where R is preferably selected from the group consisting of the hydrogens of the n- (preferably ©-,©) alkyl unsubstituted and 66-00 (preferably e:©-m0) unsubstituted and substituted aryl C3-Cags (preferably ©-0) unsubstituted and substituted aryl where the substituents are selected from the group consisting of 01803 -C(O)NR'2 -OR' -C (O)OR' -NR'4+Yo where '8' is selected from the group consisting of hydrogens and C-Co moieties and this +1 thus substituted includes moieties 0112(0017)- ++0112(07184) Where 8 is ne from 1 to 11 preferably from 01 (IY and preferably from ? to #. 14 are preferably carboxylic acids having the previous formula, where they are © selected from the group consisting of chydrogen methyl Jie Yo ethyl cethyl propyl Co-Cray propyl straight or branched alkyl and benzyl

The 14 most favored are methyl and include the 14 preferred carboxylic acid moieties: formic benzoic coctanoic, nonanoic 000016, and decanoic dodecanoic 0006680016_malonic p21001; maleic, succinic, adipic, phthalic, and 2-ethylhexanoic cnaphthenoic | © and oleic palmitic terephthalate ctriflate tartrate stearic butyric citric acrylic and aspartic caspartic fumaric lauric linoleic dinoleic lactic dactic malic 01 and in particular acetic acid .acetic acid Jediy radicals 8 carbonate carbonate and second- and higher carboxylates (Sie) Ye oxalate oxalate malonate malic amalonate Succinate ©5060103; Maleate, picolinic acid, alpha and beta amino acids (such as glycine, alanine, and beta-alanine, Judd § cbeta-alanine, phenylalanine). Cobalt catalysts for the bleaching agent used here are known They are described for example as well as their rates of base decomposition in Jail 34. 1. Tobe hydrolytic-base for complex transition metal Vo compounds Inorg.

bioinorg.

Mech. cited FY ((VAAY) pages AE) as JO Table 1 on page 117 gives base hydrolysis rates (denoted by KOH) for pentamine catalysts Cobalt pentaamine synthesized with oxalate (a°Y0) 1-ynath-1-lom 4-01 X = 3.5 kOH) oxalate and with x © KOH) NCS 40 mol-1sec-1 (©7 "m)) and with formate (Y0°) 1-yenath (1-lom 1-01 X 0,A KOH) To am) and with acetate X 5.7 KOH) 10-mol -1sec-1 (©7”m)) The most preferred cobalt catalyst here are cobalt penta-acetate salts having the formula Cua [Co(NH3)SOACITy OAc is the day; oda moiety, especially achloride Cobalt pentaamine acetate which is [Co(NH3)50Ac]CI2 plus {Co(NH3)50Ac}(OAc)2 {Co(NH3)50Ac](BF4)2 JCo(NH3)50Ac]( S0O4) (Co(NH3)50Ac](PF6)2 [Co(NH3)SOAC)(NO3)2 Yo (4) herein referred to as “PAC”

- vq —

These cobalt_catalysts were uma Als using the Ge Aged methods described for example in the article referenced herein la and references therein and US Patent No. 4,810,410 Patent No. 17.5 on behalf of Diacon et al. published in 1 March P 019 (VY) 6(165) J.

Chem.

Ed.; and Synthesis and Characterization of Organic Compounds © 1970 Jolly (prentice-Hail; 97.1 pp. 1551-?; Chem. VA Inorg.

Chem.c (Y3AY) YAAe—YAAY (YY dnorg.

Chem.c (037/9) Yo.Y=)eay ml Chemistry journal of ¢ (Y47+) YYI=1VY (Inorg.

Synth ¢«(14Y4)YYoY.

YY

(Y40Y) YoY Y (oT (physical) in addition to examples of preparation mentioned herein later. The cobalt catalysts suitable for use in the cleaning tablets of the present invention Vo can be produced by following the preparation methods described in US Patent Nos. U.S.

Patent Nos

5,559,26 < 5,581,005 5,597,936; which are mentioned as references in this invention.

Concomitant treatment of these catalysts with auxiliaries can be carried out to reduce the color effect if required in product descriptions or used in enzyme-containing particles.

As represented hereinafter or formulations may be manufactured to contain catalyst "patches".

Organic Polymeric Compound 1 Organic polymeric compounds can be added as preferred ingredients in cleaning tablets in this invention and an organic polymeric compound is meant exactly any organic polymeric compound usually found in cleaning formulations that have dispersing and anti-re-sedimenting agents and remove

Dirt or other cleaning properties. 9 The organic polymeric compound was actually used in the cleaning formulations in this invention at a level from 960.1 to 90700 preferably from 900.9 to 906159 preferably from 901 to 7001 by weight of the formulations. Examples of organic polymeric compounds include polycarboxylic acids, co-polymeric or water-soluble Yo-likes, and modified polycarboxylates or their salts in which the polyacid contains

— and a carboxyl has at least two carboxyl moieties separated from each other by at most two carbon atoms. Polymers of this latter type are described in the British patent application GB- Ally LA-1 6 These salts are polyacrylates with a molecular weight of 000101-“001 and their copolymers with any other monomer units © Suitable Lo containing acrylic fumaric acids (fumaric maleic) etachonic 806 caconitic mesaconic 76588062 ccitraconic and methylenemalonic acids (Aad) cmethylenemalonic acid or Wadd and maleic anhydride anhydride acrylamide calkylene lS acrylamide and vinyl_ether Jie styrene (pond! “vinylmethyl ether” and any mixtures ie preferably _ copolymers 000.001 to 0050069A of acrylic acid; and maleic anhydride having a molecular weight of 0 Preferred commercially available acrylic acid-containing copolymers with a 20-pack of PA30 Sokalan include those sold under the 15,0080 molecular weight less than dell brand name and those sold by BASF by sokalan 0010 PA10 (PALS

Haas and Rohm 46017. 481] 45N Acusol Preferred ones include acrylic acid 1-containing copolymers preferably 97080 to 90010 a) and monomer 96960 to 96960 containing Monomer units to 0960 preferably 9000 of its salts and b) of acrylic acid by weight substituted 0 acrylic acid or its salts which acrylic monomer from 9670 to 9680 by weight acrylic monomer where at least one of the substitutes is 11 or —[CR2-CR1(CO-O-R3)]- has the general formula 1 to ; Carbon or group 1 is an alkyl with R2 and preferably 1 or RI or 82 YS is hydrogen and 183 can be R2 hydroxy alkyl and can be 181 or acrylic monomer is Acrylic monomer Shall about hydrogen or an alkali metal salt and the most and 12 is hydrogen (ie the substituted die acid monomer where 81 is and the most preferred conjugate polymer of this (methacrylic acid monomer) is methacrylic Yer A

vy - — type molecular weight 3000 and contains 9670 to 9680 by weight acrylic acid and 9640 to 9071 by weight methacrylic acid. Polyamines and modified polyamines are useful here as including those derived from aspartic acid Ji that are described in EP-A-© 305282, EP-A-305283 and EP-A-351629. Other optional polymers may be alcohols, JS polyvinyl alcohols, modified and unmodified, cellulosics, modified celluloses, polyoxyethylenes, cpolyoxypropylenes | 0 and copolymers, ie copolymers, both modified and unmodified, and terephthalate esters of ethylene, propylene glycol, or mixtures thereof with polyoxyalkylene units. Appropriate examples are described in the patents. US Patent Nos. 55,591,703 5,597,789 4,490,271 VO Soil Release Agents Suitable polymeric soil release agents include those soiling agents having: a) one or more non-ionic hydrophilic constituents primarily of (1) polyoxyethylene fractions having a degree of polymerization of at least 7 or (7) oxypropylene or polyoxypropylene parts having a degree of polymerization of Y 0 to 01 Whereas these hydrophilic parts do not contain any oxypropylene unit unless they are linked to the adjacent moieties at each end by ether bonds or (7) a mixture of oxyalkylene units containing oxyethylene and 1 to Vo oxypropylene unit and preferably These hydrophilic parts ©9670 contain at least coxyethylene units and more preferably for those components having at least 01 to Yo oxypropylene unit YO 96006 oxyethylene unit or b) one more than Hydrophobic components containing (1).

— Lua parts C3 oxyalkylene terephthalate “lua coxyalkylene terephthalate” If these hydrophobic components Lad goad oll on oxyethylene terephthalate, then the percentage of oxyethylene terephthalate is C3 oxy units oxyalkylene terephthalate being 7:1 or less or (7) parts C4-© 66 alkylene or C4-C6 oxy alkylene or mixtures thereof or (TY) Polyvinyl ester parts, preferably polyvinyl acetate, which have at least a degree of polymerization? Or (;) Substitutes 01-04 alkyl ether ©4 hydroxyalkyl ether or Mixtures thereof where these substituents are present in the form of cellulose derivatives 04-61 alkyl ether or 04 hydroxyalkyl ether cellulose 0 or mixtures thereof or a union of (a) and (b). Polyoxyethylene at (a) (1) degree of polymerization of 0000 although eel levels may be used preferably from ? to 151 preferably from + to 001 and include 064-06 oxy-alkylene hydrophobic parts waterproof but without yaad end caps of polymeric dirt removing agents MO3S(CH2)nOCH2CH20- Jie where M NO is sodium ny is a number of -1 as described in US Patent No. 4,721,580 US. Patent published January 76, 1188 as Gosselink. The polymeric dirt removing agents used here also include cellulosic derivatives and templates chydroxyether cellulosic polymers such as propylene or ethylene terephthalate associated with terephthalate Ethylene-0 or polyethylene oxide with polyethylene terephthalate and the like and such agents are commercially available 0017010071006 oxide terephthalate propylene dirt removal agents include METHOCEL(Dow) die including hydroxy ethers of cellulose The celluloses used here are those selected from the group consisting of B©-,0 alkyl cellulose

Yoo A

vy — Cys hydroxy alkyl sly asl, chydroxyalkyl US Invention No. U.S.

Patent 4,000,093 posted on YA Dec 19977 on behalf of Nicol and colleagues. Dirt-removing agents characterized by hydrophobic polyvinyl ester fractions include polyvinyl ester conjugate copolymers Jie esters and 0-,:©0 vinyl and preferably polyvinyl acetate grafted into the oxide structure. Polyalkylene Jie oxide Structure of polyethylene oxide alla sal polyethylene oxide EP No. 0.219.048 EP published in YY April VAAY Code Kud et al. Another dirt-removing agent The suitable polymer is a conjugate polymer with polyethylene terephthalate and terephthalate polyethylene oxide (PEO) 0. The molecular weight of this polymeric dirt removal agent in ad is from 70,000 to 25,000 pl ARYL sel asl. US Patent 3,959,230 .11.5 Hayes Published Yo May 1576 US Patent No. 3,893,929 U.S.

Patent as Basadur published in A July 5978. Another suitable polymeric dirt removing agent is a polyester with repeated VO units of ethylene terephthalate units containing 9019-01 by weight ethylene terephthalate units together with 9580-90 by weight Polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight of 00-700 8,0. Another suitable polymeric deagent is the sulfonated product of a completely straight ester oligomer consisting of a basic oligomeric ester structure of terephthaloyl Yo, repeating oxyalkyleneoxy units and terminal moieties covalently attached to the structure. These deagents are fully described in the patent. US No.

Patent 4,968,451 Published + November 1590 As J.J.

Scheibel and EP. Gosselink Other suitable polymeric dirt removing agents include polyterephthalate polyesters in US Patent No. 4,711,730.

Patent published December 1989 A YO on behalf of Gosselink colleagues and the oligomeric esters covered by the anionic Ld pla in the patent

American DG No. 580, 4,721 US.

Patent published Jan 71 148 as Gosselink and Oligomeric Polyester Compounds in US Patent No. 4,702,857 U.S.

Patent published in 1987 gl YY as Gosselink Other polymeric dirt-removing agents include Jose's dirt-removing agent in US Patent #4,877,896 U.S.

Patent © published October 31, 1984 Maldonado aul and colleagues describing terephthalate esters capped with Ud jh are anionic and in particular -sulfoarolyl Another deagent is an oligomer with terephthaloyl repeat units terephthaloyl and sulfoisoterephthaloyl units 59011015016:©01018101; and oxy units. Ethyleneoxy | oxyethyleneoxy and oxy-1;-”-propylene 0-2 oxy-1 The repeating units are the basic structure of the oligomer and are preferably terminated with end caps of modified isethiones. A particularly preferred degreasing agent of this type contains a sulfo unit One sulfoisophthaloyl and © terephthaloyl units and units. oxy. Ethyleneoxy | and oxy-0;-TT oxy-1,2-propyleneoxy with a ratio of 117 to 1,8 and two terminal capping units of 7-(7-hydroxyethoxy)-(2-sodium)ethanesulfonate 2-hydroxyethoxy)--ethanesulfonate Heavy Metal Ion Sequestrant The tablets of this invention preferably contain an optional component which is a heavy metal ion sequestrant. The heavy metal ion separation material here means components that separate (formation of a chelate Yo compound) the heavy metal ions. These components can have the ability to form chelates with calcium and magnesium, but preferably they have selectivity to bind to heavy metal ions such as iron, manganese, and copper -copper. The heavy metal ion separation materials are generally present at a level of 760.005. to 70 preferably from 960.1 to 96100 preferably from 960.78 to 967.5 preferably from 960.5 to ee Yo the weight of the fittings.

ve — — heavy metal ion separators can exist; which are acidic in nature; which have for example a phosphonic acid or a carboxylic aes (0) as functional groups; either in their acid form or as a complex/salt compound with a suitable counter cation such as an alkali metal ion, alkali, ammonium ion or Substituted ammonium or any © mixtures thereof Preferably any water soluble complex salts/compounds Preferably the molar ratio of this antication to the heavy metal ion separator is at least 1:1 Include suitable heavy metal ion separators For use here are organic phosphates, such as polyamino alkylene phosphonates (alkylene phosphonates) and -1-hydroxydioxyethylene phosphonates, Sl ethane 1-hydroxy disphosphonates, alkali and nitrilo trimethylene phosphonates, and the preferred types The former are methylene phosphonate ethylene diamine, methylene phosphonate ethylene diamine, 4 ale (methylene phosphonate) methylene diamine and 1a-1s Hydroxy-ethylene 1,1diphosphonate Vo Other suitable heavy metal ion separation materials for use here include nitrilotriacetic acid and polyaminocarboxylic acids 5 such as ethylenediaminetetraacetic acid ethylenediaminetetraacetic acid, cethylenetriamine pentaacetic acid, ethylene diamine disuccinic acid, ethylene diamine diglutaric acid, TY yopropylene diamine disuccinic acid, or any salts thereof. Particularly preferred is GAY diamine GB NL No succinic acid (EDDS) ethylenediamine-N,N'-disuccinic acid, salts of the alkali metal, the alkaline earth metal, ammonium 5 substituted for this acid, or mixtures Of which. Yar A

Lal and the 2018 favorite compounds are free acids, sodium salt, magnesium or a complex of them. Crystal growth inhibitor component Cleaning tablets preferably contain a crystal growth inhibitor component; The component of © is an organic diphosphonic acid used preferably at a level from 960.01 to 765 and preferably from 900.9 to 967 of the compositions weight. Organic diphosphonic acid here means an organic diphosphonic acid that does not contain nitrogen as part of its chemical composition. This definition thus excludes organo-aminophosphonates which nonetheless can be used in formulations of this invention as components of heavy metal ion separators. The organic diphosphonic acid is 0-04 diphosphonic acid, preferably C2 diphosphonic acid, fia ethylene diphosphonic acid, or more preferably ethane acid. 1,0-Discordia-1-Diphosphonic ethane 1-hydroxy-1, 1-diphosphonic acid (HEDP) 0 may exist in a partially ionized form or WS and particularly as a salt or a soluble sulfate salt compound Water-soluble sulfate salt The cleaning tablet optionally contains a water-soluble sulfate salt. And if it is present, the sulfate salt that is soluble in water is at a level from 96001 to Yo 9640 and more preferably from 961 to 9670 and more preferably more than 965 up to BVO of the Cos formulations. The water soluble sulfate salt may be any sulfate salt having any antication. The preferred salts were chosen from the alkali metal sulfates and alkaline earth metals, especially sodium sulfate.

— Alkali Metal Silicate Alkali Metal Silicate is one of the preferred ingredients in the tablet of this invention. The preferred alkali metal silicates are sodium silicate having a ratio of 11820:2:5 from 1.8 to 17 and more preferably from 1.8 to 7.4; Preferably © over at ?. Sodium silicate is present preferably at a level below 9670 and preferably from 961 to 90615; Preferably over 969 up to 9617 by weight 5102. The alkali metal silicate may be in the form of either an anhydrous salt or a hydrated salt. The Lal alkali metal silicate can be present as a component of an alkaline system. It is preferred that the Lal base system contain sodium metasilicate at a Ve level of at least 960.4 SiO; by weight. Gad is sodium metasilicate nominal ratio of 11850 : 510.7 of 1. The weight ratio of this sodium silicate to that sodium metasilicate is; Measured as (SiO; preferably from 1 100 to 10 cf. and more Saal from 1 V0 up to 7:1 and preferably more than 1:01.© Aa: Vo Colourant The term 'colorant' as used here means any sala that absorbs certain wavelengths of light from the visible light spectrum. These colourants, when added to a cleaning formula, have the effect of causing A change in the visible color and thus the shape of the cleaning formula, and the colored materials can be, for example, either dyes or pigments.It is preferable that the material be BBG Ald, the composition in which it will be used.Therefore, in a formula that has a high pH, it is preferable that the material The pigment is stable Gla and in a formulation with a low pH the pigment must be acid stable The first phase and/or the second phase and/or optional subsequent phases may contain a pigment or a mixture of pigments or pigment particles Or a mixture of colored particles such that the Yo of different phases has different visible shapes.It is preferable that one of the first two phases contain

No - or two on colored matter. When both the first and second phases and/or subsequent phases contain a pigment it is preferable that the pigments have different visible shapes. Examples of suitable dyes include active dyes, direct dyes, and azo dyes. Preferred dyes include phthalocyanine, anthraquinone, quinoline, monoazole, diazole and polyazo. The most common dyes include anthraquinones, quinoline and mono-azo. Favorite dyes include SANDOLAN E-HRL 96180 (trade name) 5 aul) SANDOLAN MILLING BLUE (trade name) TURQUOISE ACID (aul BLUE) and SANDOLAN BRILLIANT GREEN (trade name) all of which are available from Clariant UK » HEXACOL QUINOLINE YELLOW; (trade name) available from Bayer, USA. Sa It is present at a level from 960.001 to 961.9, preferably from 960.01 to 961 and more preferably from 960.1 to 7. When present as a component in the second and/or optional lead phases, the pigment is generally present at a level from 900.001 to 7. 960.1 preferably from 0.10.5060 to 90.05 preferably from 90.0097 to 960.07 Corrosion Inhibitor Compound The tablets of this invention suitable for use in dishwashing methods may contain corrosion inhibitors selected from the coating agents with organic silver, especially paraffin, nitrogen-containing JON inhibitor compounds, 11 (0/1) compounds, and especially Mn(ID) yo salts for organic ligands.

~via - Organic silver coating agents are described in International Patent Application No. 7 and European Provisional Application 87-8-690122. The nitrogen-containing OSH inhibitor compounds are described in provisional European patent application No. EP-A-8. Mill compounds for use in corrosion inhibition are described in European Patent Application © Provisional No. 20-4-672.749. The organic silver coating agent may be introduced at a level from 900.06 to Ve and preferably from 960.1 to 960 of the total composition weight. The functional role of the silver coating agent is to form a protective coating "during use" or any silver components in the wash load in which the compositions of this invention are placed. The Jalal must be silver-coated and therefore highly attractive by binding to solid silver surfaces; Particularly when it is in the form of an ingredient for the aqueous washes and bleaching solutions with which solid silver surfaces have been treated. Suitable organic silvering agents include fatty esters of mono or polyhydric alcohols having from 1 to 50 carbon atoms in the hydrocarbon chain. Yo The fatty acid portion of the fatty ester can be obtained from mono or polycarboxylic acids (GY) with from 1 to 50 carbon atoms in the hydrocarbon_chain Suitable examples of monocarboxylic fatty acids include monocarboxylic fatty acids cbehenic acid, stearic acid, oleic acid Vo, palmitic acid, myristic acid 20771511, lauric acid, acetic acid, propionic acid propionic acid, butyric acid, dsobutyric acid, valerie acid, dlactic acid, glycolic acid, and 8,8]-dihydroxyisobutyric acid. They include Examples Yo Suitable Polycarboxylic Acids “n-butyl-malonic acid”

CA. = dsocitric acid, citric acid, maleic acid 10, malic acid, and succinic acid. The fatty alcohol moiety of the fatty ester can be represented by A polyhydric alcohols. From 1 to 40 carbon atoms in the © hydrocarbon chain Examples of auld fatty alcohols include behenylalcohol 06060, carachidyl, ccocoyl, vinyl alcohol Bs “vinyl alcohol” glycerol, xylitol, and sucrose erythritol, erythritol pentaerythritol, sorbitol or sorbitan preferably with the fatty acid group and/or the fatty alcohol of the fatty ester cofactor 0 ester from 1 to Y carbon atom in chain The alkyl-chain and fatty esters preferred here are ethylene glycol, glycerol, and cus sorbitan esters. The fatty acid portion of the ester usually contains Selected varieties of behenic acid or stearic acid or oleic acid and yo palmitic acid or myristic acid and glycerol esters are preferred Alle also. These are the mono, di, or tri esters of the glycerol and fatty acids described above. Specific examples of the esters of the fatty alcohol used here include stearyl acetate, cpalmityl di-lactate, and lls ccocoyl isobutyrate. Gy coleyl maleate coleyl dimaleate and tallowyl proprionate .tallowyl proprionate The fatty acid esters used here include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate 22020516781 cglycerol monostearate, cethylene glycol monostearate, sorbitan esters

AY - - suitable sorbitan esters include sorbitan monostearate 0000166 sorbitan palmitate sorbitan monolaurate sorbitan monomyristate sorbitan monobehenate sorbitan mono-© 016816; _ The second Hel sorbitan “sorbitan dilaurate” and the second sorbitan distearate “sorbitan dibehenate” and the second sorbitan “Lad sorbitan dioleate” mono- and di-alkyl sorbitan esters mixed. The preferred glycerol esters here are glycerol monostearate 0, glycerol mono-oleate, glycerol behenate 000001011816 goals glycerol behenate 200006606 and glycerol distearate Covering agents are included With suitable organic silver triglycerides, mono- or di-glycerides and their hydrogenated derivatives, GIS or Lisa, and any mixtures thereof. Suitable sources of 0 fatty acid esters include vegetable oils, fish oil, and animal fats. Suitable vegetable oils (cn) include soybean, cottonseed oil, castor oil, olive oil, peanut oil, yaf oil, sunflower oil, rapeseed oil, grapeseed oil, palm oil, and corn oil. And the waxy materials are; Including fine-crystalline waxy materials, organic Yo-silver coating agents are suitable here. The preferred waxy materials have a melting point in the range from 270 to 00C. They usually contain 11 to 11V carbon atoms. Wax petroleum materials of the type of paraffin and microcrystalline are preferred. It consists of long-chain saturated hydrocarbons. Alginate and gelatin are suitable organic silvering agents here. Diakylamine oxides such as Cpp-Coo methylamine oxide and quaternary alkyl ammonium compounds Yo and its salts such as Cpp-Cp methylammonium halides are also suitable here.

— L. Other suitable organic silvering agents include some polymeric materials. Jud polyvinylpyrrolidones having an average molecular OS of 0 to 70001 and polyethylene glycols (PEG) polyethylene glycols having an average molecular weight of 09 to 00,000 and <-1 polymers. Multiple amine oxide (N-oxide cpolymers ©) and copolymers (N-) copolymers Vinyl pyrrolidone N-vinylpyrrolidone Ng phenylimidazole “N-vinylimidazole” and cellulose derivatives such as methylcellulose and carboxymethyl cellulose arboxymethylcellulose and hydroxyethyl. Hydroxyethylcellulose cellulose are examples of these polymeric materials. And some aromatic substances are; Especially those that show high stability on metallic Ys surfaces; Also useful as an organic silvering material here. Lad polymeric dirt-removing agents can be used as organic silvering agents. dale favorite organic silver coating is paraffin oil; Actually, it is an aliphatic hydrocarbon branched with a number of carbon atoms in the range from 71 Ye to 50. The preferred paraffin oil was chosen from the types 025-45 permanently branched, which have a ratio of cyclic hydrocarbons to no. Toroidal from 1:01 to 10:7, preferably from ©1:1 to 1:11, and paraffin oil that has these qualities; Which has a ratio of cyclic to acyclic hydrocarbons JA TY Sold by Wintershall Lilall (Salzbergen under any commercial WINOGT0 Yo Nitrogen-containing Corrosion Inhibitor Compounds Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and its derivatives such as benzimidazole and 7-heptadecyl imidazole and 2-heptadecyl imidazole and imidazole derivatives described in Czech Patent No. 139, 279 and patent application

Anam - British No. 137,741 , 08-4-1 describing Lad method for the preparation of Se imidazole and suitable nitrogen-containing corrosion inhibitor compounds Lia are pyrazole compounds 060200382016 and their derivatives, especially those that are in which pyrazole is substituted in any of the positions 1 or ? or; OR © with alternatives 181, 83, 84 and 85 where 81 is any of JH CONH3 4 CH20H R COCH3 and 183 RS is any of C=C alkyl or hydroxyl and 124 is any of NO, § NH , of H Other suitable nitrogen-containing JSEI inhibitor compounds include a tertiary benzo—Y benzotriazole Js) 2-mercaptobenzothiazole and 1-phenyl-5-De-mercapto-A FY-four Azole si 5 «1-phenyl-5-mercapto-1,2,34-tetrazole 4 «thionalide, cmorpholine, melamine (Sb cmelamine), cdistearylamine, cstearoyl stearamide, cyanuric acid cyanuric acid, the amino triazole caminotriazole, the amino tetrazole aminotetrazole, and indazole Yo. The nitrogen-containing compounds are Jie Nitrogen amines 8001068, especially cdstearylamine and ammonium compounds such as Ammonium chloride, cammonium bromide, ammonium sulphate, or diammonium hydrogen citrate are suitable for use here. Ye Corrosion Inhibitor Compounds Mn(Il) Cleaning Tablets may contain Corrosion Inhibitor Compound (14011). Compound (1/001 can be used preferably at level from 960.005 to 965 by weight; preferably from 960.01 to 961 preferably _ From 960.07 to 960.4 of the weight of the formulations.It is preferable to use compound (148)11 at a level to obtain 0.1 ppm up to Yor ppm

— gm-preferably from 159 ppm up to or ppm preferably 1 ppm up to 10 ppm by weight (AMID ions) i.e. bleaching solution. Compound (10)01 may be an inorganic salt in anhydrous or hydrated forms. Suitable salts include manganese sulphate, manganese carbonate©, manganese phosphate, and manganese nitrates. Manganese nitrate and manganese acetate (manganese acetate and manganese chloride. It can be a compound MID) is a salt or a complex of an organic fatty acid such as manganese acetate or manganese stearate. It can be a compound MIT) is a salt or complex compound of an organic binding molecule. 0 In one preferred embodiment the organic binding molecule is a heavy metal ion dissociator and in another preferred embodiment the organic binding molecule is a crystal growth inhibitor. Other JSG inhibitor compounds Other Corrosion Inhibitor Compounds Jodi JS inhibitor compounds Other suitable addition .mercaptans and diols especially mercaptans with 4 to 70 carbon atoms including VO mercaptan lauryl mercaptan, thionapthol J sai sills cthiophenol, thionalide, thioanthranol suitable La. Cip-Cyy are saturated or unsaturated fatty acids or their salts, in particular aluminum tristearate -tristearate and enameled hydroxy fatty acids whose salts are also suitable. The octadecane plus phosphanate and the other antioxidant Jia betahydroxytoluene (BHT) are appropriate here as well. It was found that the conjugated polymers of butadiene and maleic acid 421 »; Particularly those obtained under reference name 1797897 by Polysciences Inc. are particularly useful as corrosion inhibitor compounds.

Ab - - Hydrocarbon oils Another preferred cleaning ingredient to use in this invention is chydrocarbon oil and actually long-chain aliphatic hydrocarbons ah JSG that have a number of carbon atoms in the range of 000 to on © and the preferred hydrocarbons are saturated and/or branched, and the preferred hydrocarbon oil was chosen from the 025-45 branched Wa types that have a cyclic to acyclic hydrocarbon ratio of 01:1 up to ?:1; preferably From 1:1 to 1:1 and the preferred hydrocarbon oil is paraffin. And the paraffin oil that meets the previous characteristics and that has a ratio of cyclic to acyclic hydrocarbons TA 7 is that sold by (Salzbergen “Wintershall” Germany under the name 117/1<10670. 0. Water-soluble bismuth compounds soluble Bismuth Compound The cleaning tablets of the present invention used in dishwashing liquids may contain a water-soluble bismuth preferably present at a level from 960.065 to 90670; preferably from 900.01 to 965 and preferably more than 96001 to 96001 901 by the weight of the formulations.Yo The water soluble bismuth compound Lila can be any salt or a complex compound of bismuth with any inorganic or organic counter anion The preferred inorganic bismuth salts were selected from bismuth trihalides Bismuth nitrate, bismuth phosphate, and bismuth acetate and citrate are the preferred salts with an organic counter anion. Preferably enzyme-containing 960.001 to + oY preferably 960.005 to 968 preferably 960.01 to 967 by weight for enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is Gg with the cleaned enzyme. These stabilized systems may contain calcium ion, jon, and boric acid, YO, from ah; And propylene glycol, and carboxylic acid

AT - - short chain; And boronic acid ‎acid 50:0016;_and chlorine materials ‎land! and mixtures thereof. These stabilization systems may also contain reversible enzyme inhibitors such as reverse protease inhibitors. Lime Soap Dispersant Compound ° The tablets of this invention may contain a lime soap dispersant compound preferably at a level from 960.1 to 90460 by weight; more preferably from 9611 to 90710 by weight” and more preferably from 967 to 9600 by weight of the combinations. Lime soap dispenser is a substance that prevents precipitation of alkali metal salts, ammonium or amine of fatty acids by calcium or magnesium ions. The preferred lime soap dispersing compounds 0 are described in International Patent Application No. 08877/117093. Suds Suppressing System Preferably containing cleaning tablets subject of this invention; when configured for use in machine-washing formulations; On foam inhibition system found at level from 960.01 to 959 preferably from 960.06 to 0090; more preferably from 96009 to 965 formulation weight. Vo and anti-foaming systems suitable for use herein may include any well-known anti-foaming compound including, for example, JED silicone anti-foaming compounds; Y=2-alkyl and alkanol anti-foaming compounds 2168001. The preferred foam inhibiting systems and foam salad compounds are described in Adsl pay sel pn lb No. 6 and EP Application No. 324 EP-A-705a. Polymeric Dye Transfer Inhibiting Agents can Here, the cleaning tablets contain Lad from 960.01 to 96010, preferably from 65 to 960.9 by weight, for polymeric dye transfer inhibition agents. oxide polymers and copolymers

— M - Jug -N) pyrrolidone -Ng N-vinylpyrrolidone vinyl imidazole “N-vinylimidazole” and polyvinylpyrrolidonepolymers or combinations thereof. Optical Brighteners Detergent tablets suitable for use in the laundry methods described © Hana optionally contain 960.065 up to 965 by weight of certain hydrophilic optical brighteners. The hydrophilic photoluminescent materials used herein include those with the following structural formula. mA bo nopt we SU 54150 135 Ye where 181 is selected from the Y-Nj “bis-hydroxyethyl anilino” N-2-bis-Jal 111- ? © NH-2-hydroxyethyl and R2 is chosen from - !> - bis-hydroxyethyl -Y-Ny N-2-bishydroxyethyl hydroxyethyl-1<- die amino N -2 -hydroxyethyl-N -methyl amino and a related morpholino, chloro and camino, and M is a salt-forming cation such as sodium or yo-potassium. previous; When RL is an aniline R2 < anilino is -N2-bis-hydroxy Ms N-2-bishydroxyethyl Js) is a Jie cation sodium the polish is acid 4 4'bis[(4-anilino-N)-1-7-bis-hydroxyethyl)-5-triazine-?-yl)amino]-a-7-stilbene disulfonic _-bis[(4) -anilino-6-(N -2-bis-hydroxyethyl)-s triazine-2-yl)amino 1-2,2'- Yo 44 stilbenedisulfonic acid and disodium salt This special polishing material was marketed Commercially promoted under the trade name Tinopal-UNPA-Gx by Ciba-Geigy Corporation, Tinopal-UNPA-Gx is the preferred hydrophilic optical brightener for use in cleaning formulations here.

AA - - and in the previous formula when 11 is a synthetic aniline and 22 is ~Y-N hydroxyethyl -Y-N-methylamino My N-2hydroxyethyl-N-2-methylamino is a Jie cation sodium, the polishing material is the disodium salt of acid 4; ¢'—bis[(?-anilino-21-7-?-hydroxyNod)methylamino)-5-triazine-7-yl)0amino]-7; TY stilbene disulfonic. 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N -methyl amino )-s-triazine-2- yl)amino] 2,2'stilbenedisulfonic acid disodium salt and This special adil is commercially marketed under the trade name Tinopal- 3BM-Gx by Ciba-Geigy Corporation. morphilino and M is a sodium Jia cation, the polishing material is the sodium salt of acid Ef only [(?-anilino-7-morpholino-5-triazine-?-yl (amino)-?-?'- stilbene disulfonic. 4,4'-bis[ ( 4-anilino-6- morphilino-s- triazine- 2-7 I) amino ]2,2'stilbenedisulfonic acid. 0 This special polishing material was commercially marketed under the trade name Tinopal-AMS-Gx by Ciba Geigy Corporation. Clay Softening System Detergent tablets suitable for use in laundry detergents may contain Ye The infant softening system containing a mineral clay complex and an optional clay bulking agent. It is preferable that the mineral clay compound be a smectite clay compound. The clay materials, a smectite clay, were described in US patent numbers “U.S.

Pat.

Nos. 3,862,058 3,948,790; 3,954,632 4,062,647. European patent applications Nos. aul BEP-A-313,145 EP-A-299,575 Procter YO and Gamble describe suitable organic polymeric clay agglomerates.

Cationic Fabric Softening Agents (Se) The use of cationic fabric softening agents in the formulations described in this invention suitable for use in laundromat methods. Suitable cationic fabric softening agents include water-insoluble tertiary amines or amine substances. A second long chain described in © BR 514276 GB-A-1 and EP-B-0 011 340 . Cationic Fabric Softeners (lad) were used at total levels from 960.5 to 9 by weight and usually from 961 to 965 by weight.Other Optional ComponentsYe Other optional ingredients suitable for use in formulations of this invention include aromatics and filler salts with sodium sulfate being a pH salt for formulations not preferred. That the cleaning tablets in this invention are prepared so that they have an excessively high pH, but it is preferable that they have a pH measured as a solution of 61 in a distilled substance from A to 1.59, preferably from 1 to OVA, preferably from 4.0 to 11.8. Dishes washing method in a machine A suitable method for washing or cleaning dirty cutlery in a machine has been envisioned. One of the favorite ways to wash dishes in Te Select's dirty utensil handler includes crockery; and vitreous; silverware; And metal tools, knives, and mixtures thereof by means of an aqueous liquid having an effective amount of cleaning tablet dissolved or disintegrated in it, and it means an effective amount of cleaning tablet from + g to To g of the product dissolved or dispersed in a washing solution of a volume of * to 01 liters Glad product doses or washing solution volumes commonly used in standard machine dishwashing methods. Preferably Vo TO cleaning tablets are from 46 g to 46 g in weight and preferably from 51 g to Yo g in weight.

0 Laundry method The laundry methods herein include treating the soiled clothes with an aqueous rinse solution in a washing machine with an effective amount of dissolved or crumbled laundry detergent tablet in the machine described in this invention. 0 g of product dissolved or dispersed in a washing solution of a volume of © to 18 liters in the form of actual product dosing and washing solution volumes typically used in standard machine washing methods. In an embodiment of a preferred use, a release device was used in the washing method, where the release device was loaded with the detergent product and extracted to deliver the product directly to the drum of the washing machine 0 before starting the washing cycle, and its volumetric capacity should be sufficient to be able to contain the cleaning product sufficiently As if it was going to be used in the usual washing method. Once the washing machine was loaded with clothes, the release device containing the cleaning product was placed inside the drum, and when the washing cycle started in the washing machine, water was entered into the drum. The Loge drum is rotated and the release device must be designed to prevent the spread of Ye dry cleaning product. However, this product is then allowed to be released during the wash cycle as a response to its vibration as the drum is turned and also as a result of contact with the wash water. To allow the cleaning product to be released during washing, the machine may contain a number of holes through which the product can pass. Alternatively; The device can be made of a material that is permeable to the liquid but not impermeable to the solid product, which will allow the release of the dissolved product 0. It is preferable that the cleaning product be released quickly at the start of the washing cycle, thus obtaining temporary local Alle concentrations of the product in the drum in the machine washing at this stage of the wash cycle. The preferred ALE release devices are for reuse and are designed in such a way that container consistency is maintained both in the solid state and during the wash cycle.

41 - - As an alternative to that; The release device may be a flexible container such as a bag or pouch and the bag may be of fibrous construction and covered with an impermeable material such that it retains the contents J described in EP No. 0018678. Alternatively; It may consist of a non-ALS water soluble synthetic polymeric material with an end © seal or a sealer designed to rupture in aqueous media such as those described in EP Nos. 0011500 0011501 0011502 0011968. The usual form of the sealer is A water-soluble adhesive applied across the hook that seals one edge of a pouch consisting of a water-repellent polymeric film such as polyethylene polypropylene Ve Examples Abbreviations used in examples: In cleaning formulations it is The abbreviated component definitions have the following meanings: STPP Sodium tri polyphosphate Bicarbonate 1 Bicarbonate Sodium hydrogen carbonate Citric acid Anhydrous Citric acid Carbonate 1 Carbonate Sodium carbonate Anhydrous Anhydrous sodium carbonate Silicate Amorphous Sodium Silicate (Y = 20: Si02) SKS-6 Crystalline layered silicate of formula §-Na2Si205 Crystalline layered silicate of formula PBI Anhydrous sodium perborate monohydrate Non-ionic Ci3-Cis Fatty alcohol added a) Ethoxylated propoxylated mixture having Aas Jassie Addition of ethoxyl FA and average degree of propoxylation £0 sold under the brand name

plurafac by BASF TAED Tetraacetyl ethylene diamine HEDP Ethane-1,0-iscordia-1-diphosphonic acid Ethane 1-hydroxy-1,1-diphosphonicacid | PAAC Pentaamine acetate cobalt (III) salt Paraffin Paraffin oil sold under the trade name 70 Winog by Wintershall Protease Proteolytic enzyme Proteolytic enzyme Amylase Amylolytic enzyme BTA Benzotriazole Benzotriazole Sulphate Anhydrous sodium sulphate Anhydrous sodium sulphate PEG3000 Polyethylene glycol with weight LS Jas available from Hoechst PEG6000 Polyethylene glycol with a molecular weight of approximately 0 Available from Hoechst pH measured as a solution of 901 in distilled water at AY and estimated All levels in the following examples are given as parts by weight.

DSO EXAMPLES TV-T The following shows examples of detergent tablets in this invention suitable for use in dishwashers. D10 1 1 read 0 7 7 VI VY, EV i,0V q,0V Va, 60 q,1Y 4,7 STPP silicate .0' a p miera each SKS-6 m 0 m Y,Yo AA carbonate Yo Ye YY 04,¥ p °o,Yo CAA CAA CVA HEDP m d PB1 m Y, to 6 YA brain trap PAAC "Yi" PIN | Yen RE Cont Macyl amylase AY Ay YoY l 0 0 protease ved v4 0 al ca oe non-ionic 0 VY 0 VA vA CE LY GY 0 PEG6000 d 1" f" ce ve oat oof ef BTA Paraffin Yo Yo +10 Ye Ye 1 + Fragrance GAY | ay GY oY VY VY Sulfate Tim 00 As R Amylase “Yo Yo Ye Yo Yo OY Protease YY LYo GY YY Yo P

Citric acid LY oY OY M acid ¥, ov sulfamic acid 8 M "6" 48 0 in 6 bicarbonate 00,. 00,” CE Gg carbonate silicate no el vet vo ve CaCl yt vo PEG3000 g The multi-phase disc is prepared as follows: The effective cleaning composition of the first phase is prepared by mixing the granular and liquid components and passing them in a mold with a piston traditional roundabout. The piston contains a pestle shaped appropriately to form the die. The cross-section of the mold is approximately PAX Fo mm. The components are subjected to a compressive force of 40 1 kg / sqm, after which the hammer lease lifts the disc to the first © phase, which contains a mold on its upper surface. The second phase cleaning active composition is prepared in the same way and passed into the mould. The effective particulate composition gal 6 is subjected to a pressure of 1171 kg/cm and the pestle is raised; The multiphase disc is ejected from the eccentric piston. The tablets dissolve or disintegrate in the washing machine as described above within 171 minutes; (Phase 1 tablets dissolve within minutes) The tablets give excellent solubility and cleanliness together with good Ve tablets in strength and purity.

Claims (1)

A9 — Elements_of protection pa -1 1 A multi-phase detergent tablet consists of: Y 1 is a first phase in the form of a compressed formed body with at least one mold inside it; The formed body, Y, is prepared at a compressive stress of about 506 kg/sqm to about 00000 kg/sqm. Samaoo © b) a second phase in the form of a compact body contiguously contained within this 1 mould; The second phase is compressed at a pressure from about 50 kg/sqm to less than Tou kg/1 md 0 The tablet composition contains one or more permanently concentrated active detergents in the second phase A; And so that the second phase contains the fragmentation factor. 1 7 ?- Ga A multi-phase detergent tablet of element 1 in which the second phase Y is compressed at a pressure from about 400 kg/cm to about 3000 kg/cm" . <TD A multi-phase detergent tablet Gh A multi-phase detergent tablet for waist 1 where Y phase 2 dissolves faster than phase 1. 1- A multi-phase detergent tablet as in Element 1 where TY dissolves the second phase in the Jue dishwashing machine in © minutes. 1 *- A multi-phase detergent tablet as in item 1; where “one or more detergents are selected from the group including bleaches V and bleach activators bleaching agent ¢15 catalysts, csurfactants, chelating agents, crystal growth inhibitors © and mixtures thereof. 1-1 Gila A multi-phase detergent tablet for element 1 where Y is selecting agent (Cand) from the group that includes theftite agents, effervescent agents and mixtures thereof. TY 1 A multi-phase detergent tablet A multi-phase detergent tablet As in item 1 where " _the first and/or second phase contains a binder. ga fA A multi- phase detergent tablet as in item 1 where “the binder is selected from the group consisting of sugar, csugar derivatives 1 cstarch, starch derivatives, organic polymers ¢ and others Atsaqa membership 100. 1 4- A multi-phase detergent tablet da A multi-phase detergent tablet for waist 1 where Y additionally includes a phase separator between the first and second phases. 0 1 Gia A multi-phase detergent tablet for element 5 where Y includes the separator phase on a binder applied to a liquid. -1 1 way to wash 1 of laundry dirt or table linens in a washing machine included Charging machine Y washing with one or more multi-phase detergent tablets Wha tablet V for protection element 1. IY 1 method as in claim 11 whereby A multi-phase detergent tablet Y dissolves or disintegrates in less than ve a minute in a dishwasher or a washing machine YF.