SA99200726B1 - 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 it, and b) a second phase in the form of a compressed body that is sticky inside this mold where The tablet formulation contains one or more cleaning actives that are permanently concentrated in the second phase, and where the second phase additionally contains a binding agent. Multiphase tablets give better dissolving and cleaning properties along with excellent tablet strength and consistency.

Description

Detergent tablet Full description Background of the invention:- This invention works on multi-phase .detergent tablets as well as cleaning formulations in the form of Tas 485 2a tablets in this field © It is pled that detergent formulations in tablet form have many advantages over particulate formulations Jia Ease of formation, use, transportation and storage. JS detergent tablets are prepared in general by pre-mixing the components of the cleaning formula and include the pre-mixed cleaning components in the form of a tablet using any suitable machine. Clean so that the resulting discs are strong enough to withstand handling and transportation without permanent damage. In addition to being strong, the tablets must also dissolve quickly enough so that the cleaning ingredients are released into the wash water as quickly as possible at the start of the wash cycle. On any ela, there is a clear division in that the higher the compressive strength, the . The rate of dissolving tablets is slower, and therefore this invention is looking for a way to find a balance between the strength of the tablet and the dissolving of the tablet, and the solution to this problem was; once upon a time; Compressing tablets includes tablets by pressing low pressure (compression) and despite this, the tablets manufactured in this way, although they have a rapid melting rate Gad, but they have the ability to crumble and become unfit and unacceptable 0 from the consumer and solutions include Others prepare the tablets using a high compression pressure (Lisi) in order to obtain the required level of strength and contain a dissolution aid such as an effervescent agent. XE

_Y-

Multi-phase detergent tablets The multi-phase detergent tablets described above were prepared by pressing a first composition in a 40-layer first basic level tablet press. Then another cleaning composition was applied to the tablet press on top of the layer to form a second flat layer. This second composition was then pressed into this second composition. Thus, the first layer is generally exposed to more than one compression, as the first and second compressive forces are equal. (the press) shall be sufficient to connect the first and second fittings together; The force applied in each of the first and second compression steps should be in the range from about 5.0060 to about 0.00 kg (assuming the disk cross-sectional area is about Yee 0) for the other polyphasic having tablets and tablets were prepared for dissolving the tablet Und differential melting so that the second layer is compressed with a lower force than the first layer. The first and therefore more susceptible to damage resulting from use and transportation. It shows a cleaning mold formed from EP-B-0,055,100 and European Patent No. yo by combining a formed body having a slow melt with a tablet and the cleaning mold is designed to be placed in Preferably weeks.As a means of reducing the rate of dissolution of the cleaning olf and leaving it to dissolve for several eles within the cleaning mould, this description includes mixing one or more dissolution control agents. In melting these para-dichlorobenzene chain ash alcohols and alcohols fatty acids Aaa and cwaxes Yo and the fatty alkylamides derived from them and fatty alkyl amides esters and esters for cleaning tablets intended for use should be dissolved Basically in a sink or dishwasher in up to 70 minutes. 11 single wash or dishwasher cycles in up to 70 minutes.

Ate

General Description AA A:- Wh is the first embodiment in this invention; A multi-phase cleaning disc is provided for use in a washing machine, where the disc consists of: a) a first phase in the form of a body formed with at least one lala mould, and 8 b) a second phase in the form of a solid particulate matter compressed into 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 56 kg/cm, preferably at least about Yo kg/cm, and more preferably at least about Tou kg/cm (©4.,© kilonewton (KN cm"), 0 and it is more and more preferable that it ranges from about 506 to about 00000 and in particular from about 0 to about 1701 kg / hour (the compressive pressure here is the force exerted divided by the cross-sectional area The disc is in a transverse plane with the force exerted - in the form of “AT” (the cross-sectional area of the die in a rotary press) and Gad prefers that the particulate solid of the second phase be compressed (this term is intended to include the possibility of having multiple “Rll” phases; indicated Ve (sometimes referred to here as 'optional later phases') in this mold at a compressive pressure exerted less than that of the first phase and preferably at a compressive pressure of less than YOu kg/h and preferably in the range of about Er kg / sqm to about 700 kg / sqm and preferably more from about 0 to about 170 kg / sqm and these discs are preferred for use here in terms of giving the best cohesion and strength of the disc (measured for example by Child Bite strength test (ICBS) ] 0 and better melting characteristics of the product. The tablets of this invention shall have CBS at least about 1 kg and preferably greater than about A kg and it is more preferable to be greater than about 10 kg and in particular greater than about 1 kg and preferably In particular more to be greater than VE kg and CBS was measured by the American Consumer Product Safety Commission test specifications lady The compressive stresses exerted on the first and second phases are generally in the proportion of at least Ye about 1 VY Preferably at least about ?: 1 and more preferably at least about .1: 4 AE.”

this and it; According to the embodiment of AT in this invention; A multi-phase cleaning tablet was obtained for use in a washing machine, where the disk consists of: a) sh first phase in the form of a compressed formed body with at least one mold inside it; Where this formed body is prepared under compressive pressure of at least about roo kg/name, and b) a second phase in the form of a particulate dda material compressed inside this mold; This second phase is compressed under a pressure higher than about 3250 kg/cm.” In the preferred embodiments (AY) the second phase is a second phase in the form of a compressed or formed conjoined body; for example for Gob 0 physical or chemical adhesion; within at least one mold in the first body and preferably also in the first and second phases in a relatively high weight ratio with respect to each other; for example at least about 7:1 and preferably at least about Lady 1:01 The composition of the tablet should preferably contain one or more active cleaning agents (Je) eg enzymes, bleaching agents, bleaching-activators, sines, surfactants, chelating agents 01... etc.) that are permanently concentrated in the second phase, for example (JB at least by about +965 and preferably at least by about 96780 and especially 9680 by weight of the active substance (depending on the total weight of the active substance in the tablet) in the second phase of the tablet and again These formulations are best for obtaining the cohesive, dissolving, cleaning and pH-regulating properties of the tablet to obtain, for example; on tablet formulations capable of dissolving in Yo wash solution giving at least +965 and preferably at least 96780 and preferably more than at least 0 by weight of the detergent active substance to the wash solution within 01 or © or ; or even ? minutes from the beginning of the washing process. And therefore; According to another embodiment of the present invention; A multi-phase detergent tablet was obtained for use in a washing machine, where the tablet consists of: Yo a) a first phase in the form of a formed body with at least one mold inside; and Ato

Ae in the form of a particulate solid compressed inside this a second phase b) a second phase of the mold and where the tablet contains at least one active cleaning agent and is shaped so that it is preferably more than at least 96860 of the weight of 00 connections on Less than 9606 and preferably at least minutes, preferably during the first five minutes and preferably 01 active detergent to the laundry during more than during the first three minutes of the washing process. One of the additional benefits of this invention is the ability to obtain differential solubility. of phases such that one phase of the tablet dissolves substantially before the second phase and can even essentially dissolve entirely before the other phase dissolves and this is particularly useful for the differential delivery of active detergents. For another embodiment of this invention; A multi cleaning tablet ad was obtained accordingly; and b) a second phase in the form of a compressed body located in a conjoined manner inside this mold and where the tablet composition contains one or more permanently concentrated active detergents in the second phase and where the second phase additionally contains a disintegrating agent. _- For another embodiment in this invention, a multi-phase cleaning disc was obtained, Tiss: It consists of, in the form of a molded body with at least one mold inside it; And the first phase dif a) a phase in the form of a compressed body located in an adherent manner inside a second phase b) a second phase of this mold and where the composition of the disc contains one or more concentrated effective cleaning materials 0 . permanently in the second phase and where the second phase additionally contains a binder and it is appropriate; To choose one or more of the effective cleaning enzymes, “bleach activators” and activators of bleaching materials “8m” bleaches and bleaching materials

GD), csurfactants, bleach catalysts, enzymes, crystal growth inhibitors and mixtures thereof. It is preferable to use enzymes Ye

No

1/- Particularly effective for increasing cleaning performance during the initial cold water stage of the washing process or

Vail enzymes are cleaning agents and it is highly preferred to use them here. Therefore, they are the detergent enzyme materials, especially enzymes and mixtures of enzymes that contain one or more of L200 enzymes that have induced or maximum activity in the temperature range from ©7 to [(Natalase Jia) 01 pH value 011 in the range from 4 to © and accordingly; According to another embodiment also in this invention; A multi-phase cleaning disc was obtained consisting of: a) 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 located in an adherent manner inside this mold and where the enzyme b "The second phase additionally contains an enzyme Detailed description: - The aim of this invention is to obtain a cleaning disc that is not only strong Sufficient washing sla to withstand use and transportation, but also with the least large part of it dissolves quickly in order to obtain a quick delivery of the effective detergent substance, and it is preferable to dissolve at least one phase in the washing water during the first ten minutes, and preferably five minutes, and preferably More than the first four pa Al VO minutes of the washing cycle in an automatic dishwasher or in the sink Multi Detergent Tablet 15 minutes in the dishwasher or in the washing machine Phases Dissolve or disintegrate in less than, depending on the dissolving option described Here, the time during which the multiphase tablet dissolves to 171844990 was determined using a Gia dishwashing machine or a phase of it or an active detergent component thereof available from Bosch, adjusted to the normal washing program at 15 “C with a water hardness of Ye using at least six multipliers or a sufficient number to obtain identical results. HVA The multi-phase cleaning disc in this invention contains a first phase, a second phase, and optional subsequent phases, and the first phase is in the form of a body formed for the cleaning composition that contains One or more cleaning components as described below. Favorite cleaning ingredients include enzymes, builder (a substance added to enhance cleaning performance), bleach, and YO enzymes.

AE»

_A- Mixing Se (by means of Gow) and surface activating materials and the residues of the cleaning composition - the dry ingredients are mixed in addition or mixed by spraying the liquid ingredients, then the ingredients are formed after that in the form of a first phase using any suitable machine; but preferably by compression; for example in a tablet press and alternatively; The first phase may be prepared by extrusion or by molding; etc. The first phase can take many spatial shapes such as circles © axially in general with a Ble section and cubes; etc. However, the preferred embodiments have a circular, square, or rectangular shape in general. The first phase was prepared so that it contains at least one mold on the surface of the body in size, shape, location, and direction of the formed lead. The mold or molds may vary. The template or templates in general (JED and their location relative to the first phase, for example 0) or a cavity on the Gals can be circular, square or oval in cross section and can be a vacuole attached to the surface of the antibody or they can extend between unconnected regions of the body surface (eg axially opposite facial surfaces) to form one or more 'holes' in the formed body and may be positioned symmetrically or axially with respect to the first instar or may be positioned symmetrically Unsymmetrical and in a preferred embodiment, the mold is made using a specially designed disc press 10 where the surface of the pestle adjacent to the cleaning composition is shaped so that when it contacts and compresses the cleaning composition, it presses a mold or multiple molds in the first phase of a disc, preferably The mold has a surface that is concave inwards or concave in general. Multi-phase cleaning is required to obtain good adhesion of the second phase. Alternatively, a mold may be made by compressing a molded body of the cleaning composition placed in an annular shape around a central mold thus forming a Ve molded body in the form of a cavity extending axially between opposite surfaces of the body. The discs of this invention include one or More than additional phases prepared from a composition or compositions containing at least one or more of the cleaning components described later and preferably at least one phase (referred to herein as a second phase) taking the form of a particulate solid (referring to This term refers to powders, granules, agglomerates and other particulate solids Ye

AE

including mixtures thereof with liquid binders, meltable solids, sprayable materials, etc.) is pressed into/through one or more of the molds in the first phase of the cleaning disc so that the second phase itself takes the form of a formed body and other optional phases include one or more of formulations in a layer or separate layers and preferred cleaning ingredients include 0 builders, pigments, binders, surfactants, disintegrating agents and enzymes; Particularly the enzymes enzymes amylase and protease

In another preferred embodiment of this invention it contains the second phase and the optional following phases

The disintegrating agent which can be selected from either disintegrating agent or effervescent agent includes agents

Agents that swell on contact with water or facilitate entry and/or removal of water

0 by creating channels in the cleaning disc and any known disintegrating or fizzing agent suitable for use in laundries or dishwashers is conceived for use here.

corn, rice and potatoes) and starch derivatives such as Primojels (glad pul) U-Sperse (trade name) Explotabs (trade name), celluloses, microcrystalline celluloses and derivatives

10 Cellulose such as Arbocel (trade_name) and Vivapur s (trade_name) are both available from Rittenmeyer; Nymcels (trade name) available from Metsa-Sirla Corporation, Avicel (aul) commercial, LatticeNT (pul) commercial, Hanfloc (esl) commercial, alginate, acetate trihydrate, borkite, carbonate monohydrate formula STPP 5 Na2CO3. Watery H20 with content

Phase 1 at least about 9646, carboxymethyl cellulose (CMC) and polymers

aluminum oxide and sodium acetate _and sodium acetate CMC on Ye and suitable effervescent agents are those which produce a gas when in contact with water and suitable effervescent agents

It can be - the substances from which oxygen is emitted (coxygen), nitrogen dioxide, or carbon dioxide (Ses carbon dioxide). Examples of suitable effervescent agents are chosen from the group consisting of perborate and perborate.

Yo carbonate “percarbonate,” carbonate “carbonate,” and bicarbonate in combination

Ag

Nae citric citric acid Jie or other 5 carboxylic acids with carboxylic acids .maleic cmalic sulfamic sulfamic acid; The maleic and the components of the cleaning formula are mixed together by, for example, mixing the dry components and by mixing or spraying the liquid components, then the components of the second phase and the following optional phases were fed into and held inside the mold provided by the first phase. 0 sec. shy and the preferred embodiment of this invention contains two phases; The first phase developed naturally on one mould, and the second phase naturally formed from one effective cleaning formula. Despite this, it was conceived that the first phase could contain more than one mold and that the second phase could be prepared from more than one effective cleaning composition. Moreover; It was also conceived that the second phase could contain more than one 0 active cleaning formulation contained within a single mould. It was also conceived that multiple effective cleaning formulations could exist in separate molds, and in this way the cleaning components could be substantially separated in order to avoid any performance loss resulting from the sensitive Giles components interacting together and essentially transforming them into components. ineffective or stressful.‎ In a preferred embodiment of the present invention; The first, second, and/or optional subsequent Vo phases may contain a binder and when present the binder is selected from the polyethylene and/or polyethylene Jud group of organic polymers; For example OSD 000 and especially those with a molecular weight “polypropylene glycols” polyvinyl pyrolindone and polyvinyl pyrrolidone eparaffing and 0658 paraffins Teva acrylates dally dene Ad 00s molecules that PVP especially Diay; (PVP) 0. “starch and create sugar derivatives, 5-saccharides, sugar derivatives, hydroxypropyl methyl polyacrylates, and starch derivatives, for example, hydroxypropyl methyl cellulose {(CMC) carboxy methyl cellulose} and carboxymethyl cellulose (HPMO) cellulose hexametaphosphate metaphosphate (inorganic alu Jie; polymers and polymers M0

-11- The binder is valuable for both disk cohesion and assistance in obtaining differential melting of the first and second phases as described later. from about; g, and it is more preferable that it be greater than about © g, and it is more preferable that the tor weighs

Yo g to about 15 g and more preferably up to about 71 g to about 10 1st of about g and the second and subsequent stages weigh TE to about 18 g and the most preferred from about facultative less than ; It is more preferable that the second stage and/or the following optional stages weigh less than g and more To g and about 1 g and about 5 g and preferably between about 1 g between about g. Yo g to about g VY in preference of about and in another embodiment of this invention; A separator layer has been placed The separator layer composition between Ve between the second phase and the following phases Ged The first and second phase and/or the optional or optional following phases The separator layer composition contains at least one binder selected from the components of Jum group previously described and the advantage of having a separator layer is that it prevents or reduces, for example, from the first phase to the second phase and / or the following optional phases Joc AY phase and vice versa. 10 It is preferable to compress the components of the second phase and phases The following is optional under force in relation to the compressive strength usually used in the preparation of tablets, and therefore the fan is low compression. One of the advantages of this invention is that due to the use of low compressive strength, 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. As an alternative Ys; 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. lila cleansing tablets for; For example; Use and transportation. And as described, multiphase where the second layer was compressed under lower compressive strength than the first layer and on YO

ANE

-17- In spite of the improvement in the rate of dissolution, the second layer of these tablets becomes vulnerable to damage and becomes subject to crumbling or cracking upon use. The lightly compressed phases in the cleaning tablets were protected in this invention inside the mold provided by the first phase in the cleaning disk. 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 greatly preferred before another phase. Min Ye Preferably the first phase is dissolved within © to Bila for the preferred weight range described Min. The second phase and/or subsequent optional phases dissolve in Vo to 01 preferably less than ½ min, more preferably less than 0.0 min, and most preferably less than ; minutes as a substitute for

JU that; The second phase may dissolve after the first or other phases; For example, when it is desired to obtain cleaning or rinsing benefits at the end of the washing process and the time at which the first, second, and/or optional subsequent phases dissolve is independent of each other and is therefore in a particularly preferred embodiment of the present invention Differential solubility of the phases was obtained. The advantage of being able to obtain a differential solubility of the multi-phase cleaned disc in Al phases is that a component that is chemically inactive can be separated when a Ni component of a different phase is present, in which case it is preferable to place the component which is inactivated in the second phase and the optional subsequent phases. Another advantage of this present invention is the improved adherence between the phases of the multiphase disc. It is well established that good adhesion can be obtained by lowering the exposure of the second phase compared to the multiphasic discs known in this field. This leads to making the discs of this invention - 0 less prone to fracture along the line of contact between the phases. In a tablet press Courtoy R253 capable of preparing mold containing slots and in a particularly preferred embodiment of this invention Ye

Ato

-11- (Gay) Preparation of the first phase using a specially designed tablet press following the method described. The pestle(s) in this tablet press have been modified so that the surface of the pestle that contacts the cleaning composition has a convex surface. The first cleaning composition has been placed inside The tablet press mould, and the tamper was lowered to connect and compress the cleaning composition to form a first phase, then the first cleaning composition was compressed using 0 and about You kg / cm', preferably between about You pressure exerted in general at least about kg/cm" and the most preferred Vor about done and more preferably about Spm kg/0 then the ram was raised after that and the first phase revealed Taw kg/1701 to about 0001 about the content On a die then the second combination and the cleaned optional following combinations were placed inside the dies and then the specially designed tablet press ram was lowered a second time to compress a light form-0 the second combination and the cleaned tertiary combinations thereof to form the second phase and the optional subsequent phases. Where an optional next phase is present, the Al phase and, in the form of the optional next, are prepared in an optional next pressing step essentially identical to the second pressing step previously described, and the second and subsequent optional detergent compositions are pressed under pressure, preferably less than kg/m. Sama and the most preferred from Ton kg / cm and preferably more than about 56 to about YOO VO times Gall to about 790 kg / cm and after pressing the second cleaning formula, about 1 second was raised and the multi cleaning disc was taken out The phases of the tablet press. Cleaning Components The first, second, and/or optional subsequent phases of the multiphase cleaning tablet described herein are prepared by pressing one or more formulations containing Ye cleaning active ingredients and appropriately. That the formulations used in any of these phases include building compounds, surface activating materials Led Le, many different cleaning components, enzymes, bleaching agents, alkaline sources, coloring materials, aromatic substances, lime soap dispensers, and organic polymeric compounds, including polymeric dye transfer inhibition agents. Crystal Growth Inhibitors, Heavy Metal Ion Separators, Metal Ion Salts, YO Stabilizers

AE

Ne Enzymes, Corrosion Inhibitors, Foam Inhibitors, Solvents, Fabric Softeners, Polishes, Agitators, Agile Optical Materials, Mostly Preferred First-Phase Cleaning Ingredients Include Builder, Surfactant, Enzyme, Bleaching Agent, More Preferred First-Phase Cleaning Ingredients The second includes the building compound, enzyme, crystal growth inhibitors, disintegrating agents and/or binding materials. The building compound (a compound added to enhance cleaning performance) It is preferable that the tablets of this invention contain a building compound; Actually present at a level from 9670 to 9670 by weight and the most preferred from 9600 to 906850 by weight and preferably from 01 to 9670 by weight of the formula containing the effective cleaning ingredients. Water-soluble building compound 0 include Water-soluble Monomeric Polycarboxylate Suitable Water-soluble Building Compounds; or their acid forms and monomeric polycarboxylates or copolymeric or conjugated polycarboxylic acids two-fold polycarboxylic acid salts in which the polycarboxylic acid contains at least two carbon atoms separated from each other; At most, carboxylic carboxylic VO, phosphate cborates, carbonates 05, borates, Ab carbonates, carbonates 88M, and mixtures of any of the aforementioned. Or _ poly. carboxylate carboxylate is __ carboxylate of Sa in kind although monomeric or oligomeric oligomeric 20170200718 is generally preferred over monomeric polycarboxylates of Te for reasons of cost and performance. Dial carboxylates include carboxylates

Jactic acid is one of the water-soluble salts of the carboxy group lactic acid, including polycarboxylate ether and ether derivatives glycolic acid glycolic acid containing two carboxy groups with water-soluble salts of Polycarboxylates

A yoo diacetic (ethylenedioxy succinic acid, diglycolic acid, maleic acid lull) P0180810; 420 tartronic acid, tartaric acid, ctartaric acid acid ether carboxylates in addition to fumaric acid and fumaric acid carboxylates, Jal., including 0. sulfinyl carboxylates of linevitsa and carboxylates © on the citrates, duals containing three carboxy groups, as soluble Polycarboxylates In water ALEY citraconates and acontrates 8+ and ccitrates carboxymethyloxysuccinate J succinate plus succinate derivatives 1,379,241 described in UK Patent No. 08 carboxymethyloxysuccinates and lactoxymethyloxysuccinates 08 described in UK Patent 0 described In the patent application, aminosuccinates and aminosuccinates 2 third Jie oxypolycarboxylate Dutch No. 3 and oxypolycarboxylate materials 2-oxa-1,1,3-propane tricarboxylates?-_propane 60 +1 carboxylate. ?- OXA- .1,387,447 described in British Patent No. 1 and includes _ polycarboxylate 5 containing four yo groups described in the patent Oxydisuccinates carboxy ethane and tetracarboxylate 06HL0”-1, 12,2 -7 XO) 10 British No. 1,261,829 and fourth 1,1,3,3-propane tetracar- ctetracarboxylates 1,1,2,3-propane and 0 « 3 ¥-Propane Tetracarboxylates 0071865 Containing Sulfosubstituted Polycarboxylates Including Polycarboxylates tetracarboxylates Patented 0. Sulfosuccinate Derivatives of Sulfosuccinate sulfo substituents

U.S.A. Pat. No. British No. 1,398,1 and 1,398,422 and in the US Patent No. 3,936,448 thermally solvated citrate described in sulfonated pyrolysed citrates and sulfonated citrates.

British Patent No. 1,439,000. British Patent No

AE

-1- and alicyclic polycarboxylates, including cyclic aliphatic 8m, tetracarboxylate and the fifth om coms cuss T pentane tetrahydrofuran-cis; cis; m0 4 oF cyclodianiide 5-tetrahydrofuran-cis, cis-tetrahydrofuran-cis, ciste tracarboxylates cis-tetracarboxylates tetrahydrofuran-tetrahydrofuran-cis mo 0 Yes Tetrahydrofuran _cis-dicarboxylates TO © 2.5 — tetra hydrofuran _cis-dicarboxylates, 2,2,5,5 - tetrahydrofuran - 1,2,3,4,5,6-hexane Hexacarboxylate = 0 4 FY B tetracarboxy lates of carboxymethyl alcohols and carboxymethyl derivatives hexane-hexacarboxylate “mannitol” and mannitol sorbitol 0177076 “aromatic polycarboxylates” alcohols include xylitol And xylitol 0 aes and derivatives of cpyromellitic acid and amellitic acid amellitic acid

Patent No. 1,425,343 Described in British Patent No. phthalic acid The preferred phthalates are polycarboxylates and the above; Polycarboxylates containing up to three hydroxycarboxylates groups are hydroxycarboxylates citrates for each molecule, especially citrates. or oligomeric monomeric citric acid / citrate or mixtures of citrates citric acid Jie their salts as useful building components. 418 Borate building materials can be used in addition to building materials containing sub Detergent storage or washing conditions but borate Substances forming borates that give borates “M” and in particular less than 460 then.0 0 unfavorably under washing conditions less than In it and carbonates containing two types of atoms and mixtures of sodium carbonate and sodium carbonate

AE»

VY

The very fine as described in order calcium carbonate from it with calcium carbonate

NAVY Nov 15 German Patent No. 2,321,001 published in The most preferred building compounds for use in the present invention are water-soluble building phosphates and specific examples of soluble building phosphates are alkali metal phosphates; and tripolyphosphates dl tripolyphosphate in © ammonium potassium sodium sodium phosphate Ue Js sodium and potassium orthophosphate ?1 degree of polymerization of + to Led ranging from sodium polymeta phosphate sodium phytic acid and phytic acid salts Partially soluble or insoluble Builder The building compound 0 The tablets of this invention may contain a partially soluble or Non or insoluble suitable in Goa soluble form. Soluble builders are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of partially water soluble builders include crystalline stratified silicates described as eg And the patent application (EP-A-0164514 in the European patent application No. Jud ve

DE-A3742043 and Danish Patent Application No. DE-A-3417649 Danish stratified crystalline generic formula: sodium silicates, preferably sodium silicate

NaMSix02+1.yH20 and * is hydrogen or sodium hydrogen where A is sodium preferably for Yo silicate up to ; nor is it a number from 0 to 1.5 a number of 0 stratified crystals of this type a two dimensional 'lamellar' structure such as sodium silicate EP 0 called stratified structure 58 as described in a patent European invention No. EP 0 293640 Silicate preparation methods are described and European patent No. 4

DE A-3417640 Crystal stratification of this type in Danish Patent Application No.

AE

M1 and the Danish patent application No. DE-A3742043 and for the purposes of this invention is in the general formula has a value? or 2 or; Preferably XY and the most preferred crystalline stratified sodium silicate compound having the formula -8 iy y=all (Na2Si205 as aul) NaSKS-6 commercial) available from Hoechst AG ° preferably a silicate material Sodium silicate is a crystalline stratified formulation present in granular cleaning formulations as particles in a cohesive mixture with a water-soluble ionic solid as described in Adsl Patent Application No. 17092/18594. The solid ionized material soluble in water was chosen from organic acids and salts of organic and inorganic acids and mixtures thereof with preference to citric acid 01. Examples of building materials that are highly insoluble in water include sodium aluminosilicates. Suitable aluminosilicates are aluminosilicate zeolites that have the single cellular formula AY Na2[(Al02)z(Si02)y].xH20 where 2 ey, the least is 6 and the molar ratio is between 7 nor range from 1 to 1.9 and be at least 6 © and preferably from V0 to 7176; Preferably more 05 .01 to TE and the formation of aluminosilicate material in the hydrated form and preferably crystalline containing from 96010 to 96748 and preferably more than 7018 to 9077 of water in linked form. Aluminosilicate zeolites can be materials found in nature, but it is preferable to be derived Lelia. Industrial crystal ion exchange materials a Yo aluminosilicate 06 are available under the name Zeolite A and Zeolite B. Zeolite B2, Zeolite X, Zeolite HS, and mixtures thereof. The preferred method for the manufacture of aluminosilicate zeolites is that described by Squeeman and colleagues (published in (Y) VE (V39¢) Zeolite and 10 _)111 Ye led by the author describing a method for preparing colloidal aluminosilicate zeolites. XE

-19- Preferably, the colloidal aluminosilicate zeolites should be 1 micrometer in diameter, so that no more than 0% of the particles have a size greater than 1 micrometer in diameter, preferably 106 of the J More than 965 particles have a size of 1 and for aluminosilicate zeolite particles the average diameter of a particle size is between 01 μm

CV micrometers, preferably between 05606 micrometers and 91 micrometers, and the most preferred between © micrometers. yy micrometers, and the zeolite A has the formula:

Nal2[(Al02)12(Si02)12].xH20 has the following formula X and the zeolite has YY and in particular 71 to Ye from x where the zeolite is MAB as described in the patent Na86[(AlO2)86(Si02)106) 276H20 0 EP No. 1270384070 is a preferred building zeolite here. Colloidal zeolites. Induced Structural Performance of Zeolite Aluminosilicate Colloid; A L zeolite is preferred

Cua from Lad where better stain removal is obtained and induced structural performance is observed 5 Reduced scale formation on fabric and improved fabric white retention which were problems believed to be associated with poorly constructive cleaning formulations. It was found that the cleaning formulations of colloidal aluminosilicate zeolite type 5 and zeolite 5 give separation performance of A ions mixtures containing commercially available zeolite. Cabal surprisingly, the compositions of DAD vs equal weight magnesium fons previously described give the separation performance of commercially available magnesium ions. A from zeolite.

AE

Neither are surfactants. Surfactants are preferred effective cleaning ingredients from the formulations described herein. Suitable surfactants are selected from hybrid anionic, cationic, ampholytic, nonionic ampholytic surfactants, and mixtures thereof. Products for automatic dishwashing machines are low foaming in nature and therefore foaming should be inhibited in the surfactant system for use in dishwashing liquids or better be low foaming and virtually non-ionic in nature and there is no need for foaming inhibition The resulting surfactant systems used in laundry detergents to the same degree necessary 0 in dishwashing and the surfactant is actually present at a level from 960.1 to BT by weight and preferably from 960.9 to 9600 by weight and more Preferably from 961 to 965 by weight of the formula's 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, 6 . A list of suitable cationic surfactants is given in USP 4,259,217. Filed in Murphy's name on March 71 VAY The list of surfactants used by Glad in cleaning formulations in automatic dishwashers is given in eg European Patent Application EP-A-0414549 and IPL 0 93/08876 WO and WO 93/08874 Basically nonionic surfactants Any surfactant can be used Non-ionic Useful for cleaning purposes In the cleaning tablet Preferred unspecified types of useful non-ionic surfactants are listed below: Age

Alcoholic surfactants, to which SU ethoxylated has been added ionic The alkyl ethoxylate - resulting from the condensation of aliphatic alcohols with 1 to 1 yo mol of ethylene oxide is suitable for use here. The alkyl chain of an aliphatic alcohol can be either straight © or dete primary or secondary; It generally contains from 1 to YY carbon atom, and it is especially preferred for alcohol condensation products that have an alkyl group containing from + to 71 carbon atoms with ? to 0 moles of ethylene oxide per mole of alcohol. Alkyl alkoxylate materials covered in their surface activated end The suitable alkyl alkoxylate material for the surface activated end is 0 polyalcohols (oxyalkyl) coated with epoxy represented by the following formula: R10[CH2CH(CH3)O]x[CH2CH20 ] [CH2CH(OH)R2] (I): where 181 is a straight or branched aliphatic hydrocarbon radical with 4 to 18 carbon atoms and R2 is a straight or branched aliphatic hydrocarbon radical from ? to TY a carbon atom; X is a number with an intermediate value from 1.5 to hie Ne preferably 11 and is a number with a value of at least 50; more often Shalt is at least .01 preferably with a surfactant of the formula [; at least 01 carbon atoms in the terminal epoxide [CH2CH(OH)R2] and suitable surfactants of formula lida of the present invention; It is the non-ionic surfactant type POLY- TERGENT®SLE-18B 00 of Olin Corporation; as described; For example; In the International Patent No. 70 WO published on October 11, 1994 in the name of the Olin Corporation Basia alcohols (oxyalkylated) covered with ether Jed The surfactants used here are polyalcohols (oxyalkyl) (oxyalkylated Yo covered with ether which has the following formula: Ago

YY.

R10 [CH2CH(R3)0x[CH2]k CH(OH) [CH2];OR2 aliphatic hydrocarbon is an aliphatic hydrocarbon radical R25 181 where it is carbon; Te to 1 or saturated or unsaturated aromatic straight or branched with 4 to 1 straight aliphatic hydrocarbon is 11 or an aliphatic hydrocarbon radical R3 and when it is “(Fr to 1 is a number with a mean value of X carbon atoms; if 5 is more then 183 can be the same or different and a and g are numbers with a value JY for © to 1 preferably from VY to 1 medium from and 181 and 82 are preferably aliphatic or aromatic hydrocarbon moieties saturated or non-VA atom carbon atom with preference having 8 to YY saturated straight or branched from + to is 11 or a straight aliphatic hydrocarbon moiety with from one atom to R3 carbon. Preferably 0 and preferably from A" Yo to 1 is a number with an average value of X two carbon atoms Preferably

Ne to when you are; in preferred embodiments; and * is greater than 7 then Gl (and as described or different that means; that 3 can vary between any of the Alles units can be 3 83 then oF is x alkyloxy As previously described, for example, if Vo propyleneoxy or (BO) ethlyeneoxy can be selected from ethyleneoxy (EO) (EO) 5 (EO) (EO) (PO) «(EO) (PO) (EO) and may vary in order from (PO) and of course; the number is chosen. (PO) (PO) (PO) (PO) (PO) (EO) «(PO) (EO) (PO) “(EO) only and the variety can be much greater than a larger numerical value of “ and include; eg multiple JAS Y (PO) and a very small number of (BO) lang units eg Yo include Particularly preferred surface activators as previously described are those that have a lower opacity + °F + surface activators can therefore be used in combination with higher opacity surface activators as It is described in detail later for superior grease cleaning benefits

At

YY

(oxyalkylated) and the alcoholic surfactants are multiple (oxyalkylated) so that the substance 1 and g is 1 covered with ether are those in which 16 is a surfactant with the following formula:

R10 [CH2CH(R3)O]x CH2CH (OH)CH20R2 as defined above. And * is a number with the value R35 R25 181 where it is °

Sanit and more VA to 1 preferably more than To 1 preferably Fe) medium of 83 is 14 ranging from 4 to R25 RT are the surfactants that are in it

No to 1 and range from ethlyeneoxy two-component ethyleneoxy H (oxyalkylated) and surfactants contain multiple alcohols (oxyalkyl is by name a straight or branched alcohol; and Ade oxide has three components ether covered with ether 0 An alkyl ether cap and a terminal cap of alkylene oxide serve as the terminal alkylene and the alcohol as the hydrophobic; oil-soluble part of the molecule where as the alkyl ether is the hydrophilic, water-soluble part of the alkylene oxide, an alkylene oxide group molecule. The alll surfactant layers significantly advance the characteristics of gall-of-formation and remove greasy substances when used in combination with surfactants with a higher opacity relative to the activators. (AS) Poly-alcohol surfactants (oxyple) and in form with the aliphatic alcohol of the present invention can be produced by reacting a second capped aliphatic alcohol (LHL) to form an ether which is reacted after This is done with a base to form a second epoxide (yo alkyl epoxide) to form compounds (ad) and then the second epoxide was reacted with an added alcohol, the new epoxide in this invention. Examples of methods for the preparation of ether-coated alcoholic (oxyalkyl 0”) surfactants are described as follows: poly alcohol

Ate

Prepare 612/14 alkyl glycidyl ether then mix 4 fatty alcohol pa 001( fatty alcohol 502.10_mol) and zinc chloride cea_.84((IV) tin chloride 7.77 _ml) available from Aldrich company (Aldrich) in a flask with a round bottom having three (lel) with a capacity of 50850 ml equipped with a condenser, an argon 0 inlet, an addition funnel, a magnetic stirrer and an internal temperature probe, then the mixture was heated to 10 m and epichlorhydrin (9) was added. ,70; 0.515 con mol; available from the Aldrich company drip so that the temperature is maintained between 19-758” C. After stirring s.d. an additional hour at 10 C, the mixture was cooled to room temperature The mixture was treated with 6 965 sodium hydroxide solution YA (sodium hydroxide G “Alone 0 mol 00%) with stirring OF and after completion of the addition; the mixture was heated to 00 C s.d. an hour and a half, then cooled and filtered with the help of ethanol ethanol was separated from the clear solution, and the organic phase was washed with water (Ja 001), dried on (MgSO4), filtered, and concentrated. After distillation of the oil at 1 (VY em ee mm Hg), the glycidyl ether was obtained. Je ether in the form of oil. VO Preparation of Covered Alcoholic Surfactant C12/14—;Alkyl-09/11 Ether ge Je +50 TAY Amg 0.10 ( Neodol®91-8 Added Alcohol A) was mixed Available ethoxyl from Shell Chemical Company (Shell chemical and zinc chloride tin chloride LT con 4.08) (AV) ml (Use in a flask with a round bottom with three necks of capacity YOu ml with a condenser and an inlet argon and an addition funnel; Yo min. After stirring, VA sad, for an hour at 10 m, the mixture was cooled to room temperature and dissolved in an equal part of dichloromethane. The solution was passed through a 1-inch layer of silica gel with rinsing with dichloromethane, and the clear solution was concentrated (At).

Yo. Mt 001 (Kugelohr) was dried by circular evaporation. It was then peeled in a Kugelohr kiln with turmeric to obtain the surfactant in the form of oil. Propoxyl | ethoxylated non-ionic ethoxylated fatty alcohol surfactant W0-M ethoxylated alcohols ethoxylated fatty alcohols Co-Cug is a fatty ethoxylated/propoxylated surfactant suitable for use here as surfactants; Especially the ones that are soluble in water. And the most preferred of them is the addition of ethoxyl from? to 0 from © to £0 preferably ethoxylated to ethoxylated with an ethoxylated 18 to 01 degree for ethoxylated/propoxylated fatty alcohols alkyl chain length from .01 to 1 and degree Addition of propoxyl of Tr carbon and degree of etoxylation of * to propylene glycol Condensate 1120/00 Ionic with propylene glycol with hydrophobic base formed by ethylene oxide The conjugate products of ethylene oxide Yo propylene glycol Propylene glycol se ethylene oxide The method of condensation of propylene oxide is suitable for use here, and it is preferable that the hydrophobic part of these compounds have a molecular weight of 18588 to 18588 and show insolubility in water. Examples of this type of compounds include 0 commercially marketed by Glas The available PluronicTM some surfactants of the type BASF 0 0. Diamine / propylene oxide non-ionic with propylene oxide compounds EO intercalated condensates ethylene diamine ethylene with the products formed from the reaction ethylene oxide The ethylene oxide condensate products are suitable for use ethylenediamine and propylene oxide Propylene oxide Reaction of ethylene diamine ali from gs The hydrophobic moiety is formed in these Jia Yo

At

ethylenediamine with an excess of propylene oxide and generally has a molecular weight of You to Fee Examples of this type of non-ionic surfactant include some commercially available TetronicTM compounds marketed by Lad BASF Mixed Non-ionic Surfactant System In a preferred embodiment of the invention the cleaning disc contains a mixed non-ionic surfactant system containing at least one non-ionic surfactant of low opacity and a non-ionic surfactant of high opacity at least one. opacity; As used here is a well-known property fam of anionic surfactants which is due to the decrease in the solubility of the surfactant as Ve rises dad and the temperature at which a second phase is observed is referred to as 'degree' alias (see Kirk Othmer's ud sh Encyclopedia of Chemical Refining; ed. AE No. YY p. 0) (PVA as used here) A 'low opacity' nonionic surfactant is defined as The original active ingredient of the nonionic surface activated system has a lower opacity VO . than Fe preferably less than Te and most preferably less than 10 M. Low opacity nonionic surfactants include the surfactants to which they are added Nonionic alkoxylated and in particular ethoxylates derived from primary alcohols QW ol ped sys primary alcohol reverse polyoxypropylene Js | polyoxypropylene oxyethylene J [polyoxyethylene oxypropylene (PO/EO/). PO) polyoxypropylene Y. These also include the low opacity anionic surfactant of gall; For example; Poly-Tergent® SLF-18 Ji) ethoxylated-propoxylated alcohol from Olin and slbaall (oxyalkylated epoxy Jie) Poly-Tergent® SLF-series 18B of non-ionics from Olin Corporation; as described as eg?Frying pans in IL No. 22800/94 (WO published October 1, 1544 as Ago

Olin 8NA0)_and poly(oxyalkylated) alcohol surfactants covered with ether The nonionic surfactants (Gos) can contain propylene oxide in an amount of up to 96159 by weight. Other preferred non-ionic surfactants may be prepared using methods described A US Patent No. 3 filed at VT Sept 15860 Building sks aul and cited herein by reference. Additional low opacity nonionic surfactants include dn cl oS oxyethylene . ms polyoxyethylene oxypropylene polyoxypropylene 0 polymeric The polyoxyethylene template compounds include polyoxypropylene polymeric those based on ethylene glycol, propylene glycol and glycerol glycerol, trimethylolpropane, and ethylenediamine as an active hydrogen compound as an initiator and some of the polymeric Ne template compounds are surface activated called REVERSED PLURONIC®; PLURONIC® and TETRONIC® of BASE-Wyandotte, Michigan are suitable in ADD 4 formulations of this invention. Preferred examples include REVERSED TETRONIC®702 5 PLURONIC®25R2 These surfactants are actually useful as non-ionic surfactants with low opacity. LS Yo is used here. A “high opacity” nonionic surfactant is defined as a component of the nonionic surfactant system having an opacity greater than +5°, preferably greater than 00, and preferably greater than 10"M. Preferably, The nonionic surfactant system contains surfactant added a) Etoxyl of Gude from Jeli monohydroxy alcohol or an alkylphenol containing A to Yo carbon atom; YO With 1 to Ve moles of ethylene oxide per mole of alcohol or alkylphenol Ago

_YA- On an average basis. These include non-ionic surfactants with a darkening degree

Rhodasurf and Carbide (available from Tergitol1559 “Jill High Carbide Consortium; e.g. from Shell lad) Neodol 91-85 (Rhone Poulenc) (available from Ron Poulenc) 5 shell to achieve the objectives of this The invention is to have a non-loading surfactant activated preferably 8 ionic with a high opacity degree hydrophilic-oleophilic balance (“11113”; refer Kirk to 11 preferably from Vo having a value within the range of 4 To Gls mentioned Kirk Othmer or Carbide (available from Carbide Union Tergitol 1559 for example; cal sal these include . and 91-8 11860001 (available from Rhone Poulenc) Available from Ron Polanc Rhodasurf-TMDS.5 5 (Shell from Shell 0) Another preferred high opacity anionic surfactant derived from

Co) 01 to 1 carbon atom straight and preferably branched secondary fatty alcohol containing of branched chain primary alcohols Mo alcohols); It includes secondary alcohols and primary alcohols. It is preferable that the non-ionic surface activators with a high degree of opacity are . Branched or secondary and preferably more alcohol ethoxylates Ve to 1 branched condensed medium from Crips or Corr alcohol ethoxylates alcohol ethylene oxide to 9 mol of ethylene oxide 1 mol ; more preferably VY to 1 mol; Preferably per mole of alcohol. It is preferable that the nonionic surfactant with ethoxylate added to it derived in the previous method has a narrow ethoxylate distribution relative to the medium. Anionic surfactants Yo for cleaning purposes is suitable Gla Any anionic surfactant useful sodium sodium (JEN for ded Ly) for use here and these materials include ammonium salts, cammonium ammonium salts, ammonium potassium, substances (di-triethanolamine salts, and substituted mono and triethanolamine Such as ole salts, carboxylate sarcosinate, carboxylate sulfonate, sulfate sulfate Yo M

00510168 Anionic surfactants. Anionic sulfate surfactants are preferred. Other anionic surfactants include Jie isethionates; N-acyl tau rates and 0-fatty acid amides for cmethyl tauride, alkyl succinates, csulfosuccinates, and monoesters of any sulfosuccinate (particularly Cpp-Cig monounsaturated and unsaturated esters) di-diesters Sf of sulfoxins (especially mm di-esters and sarcosinates [1- acyl 488 f-1]. _resin acids and acids are 0 - Hydrogenated resins are suitable for Jie liad rosin, hydrogenated rosin, resin acids, and hydrogenated resin acids contained in or derived from oud oil.

Anionic sulfate surfactants include Anionic sulfate surfactants suitable for use Ve here primary and secondary straight and branched alkyl sulfates; alkyl ethoxysulfates, fatty oleoyl glycerol sulfates, alkyl phenol ethylene oxide ether sulfates, Cs-Cp7 acyl -N- sulfates (latex- N-alkyl) Cs-Cy7 acyl-N-(C;-Cy4 alkyl) and aa) and 0-0 hydroxy (Js) glucamine “N-(C,-C, hydroxyalkyl) glucamine sulfates Ye and sulfates Alkyl polysaccharides Jie sulfates of alkylpolysaccharides Alkyl sulfate ls Glucoside sulfates of alkylpolyglucoside (Non-ionic non-sulphate compounds

nonionic nonsulfated (described later). It is preferable to choose the first straight and branched Cio-Crg sulfate surface activated alkyl sulfate materials; It is more preferred that the alkyl sulfate be branched,©0-

Yo: straight chain and 0-0 alkyl sulfate. Age

It is preferable to choose Alkyl ethoxysulfate surfactants from the group. which consist_ of (©-m,©) sulfate (JST) to which (Led) ethoxylated was added by 0.5 to 01 moles of ethylene oxide per molecule. Preferably more. that the alkyl ethoxysulfate surfactant is © 0-,,0-sulfate; More preferred is the ©0-,,© alkyl sulfate to which ethoxyl has been added by 0 to ; Preferably 1 to ¾ mole of ethylene oxide per molecule. A particularly preferred form in the present invention uses mixtures of preferred alkyl sulfate and preferred alkyl ethoxysulfate as a surfactant 0. These mixtures are described in International Patent Application No. 18124/117093. Anionic sulfonate materials (Jedd) surface-activated materials (Abid) Anionic sulfonate for surfactants suitable for use here Cs-Cyp sulfonate salts straight alkylbenzene sulfonates and calkyl ester sulfonates and U0 sulfonates -m6 primary alkane or secondary Vo; Co-Cog colefin sulfonated cpolycarboxylic acids alkyl glycerol sulfonates fatty acyl glycerol sulfonates oleyl glycerol sulfonates wah and any mixtures thereof. Anionic carboxylate surfactants 0 Suitable anionic carboxylate surfactants include Jas alkyl ethoxy carboxylates the alkyl polyethoxy polycarboxylate surfactants and soaps ("alkyl carboxylate") ("alkyl carboxyls' and in particular soaps as described herein. Suitable alkyl ethoxy carboxylates include those of Yo. 14 10.0(011:011.0(.0-11:.000 Cus R is the Cg group to mouth

+1 so that the ethoxylate and the distribution of 101 ethoxylates is from zero to X and ranges from “dS©

M is zero less than 9670 and x is; based on weight; The amount of the substance when it is alkyl and includes polycarboxylate materials polyethoxy alkyl cation is a cation

The RO-(CHR- suitable surface activated is that having the formula 1 x alkyl oxalate polyethoxy polycarboxylate; and Crp to Co is an R group where CHR-O)Rs© is a moiety chydrogen selected from the group consisting of hydrogen Ros Ry and be YO to the moiety “succinic acid mes” and the moiety amethyl acid methyl acid from group Ry and terminated mixtures were selected chydroxysuccinic acid substituted and unchanged hydrocarbon and hydrocarbon hydrogen of OSE and 8 carbon atoms; and mixtures thereof. 1 substituted with between Vo and suitable surface activated soaps include secondary activated soaps attached to a secondary carbon atom. The carboxyl surfactants containing the secondary surfactant saponified carboxylate unit preferred for use here are the water-soluble elements -1-lithem selected from the group consisting of the water-soluble salts of ?-2-ethyl acid. -1- ethyl-1-decanoic assy 2-methyl-1- undecanoic acid Ve and acid «2-propyl-1-nonanoic acid decanoic acid 2- *?- pentyl-1-heptanoic aes 2-butyl-l-octanoic acid octanoic -1<-litob -" and may also include some saponins as inhibitors -pentyl-1- Heptanoic acid for foaming. Alkaline metal surfactant sarcosinate Yo sarcosinate Other suitable anionic surfactants are sarcosinates of the R group being Cus (R-CON(RDCH,COOM) alkali metals of the formula is a straight or branched RY group; it is an alkenyl or alkyl alkyl Cs-Cyg alkyl and 14 is an alkali metal ion. Preferred examples are sarcosinates ©,-©

Ago vy as salts Je oleoyl methyl Jie and alloyl myristyl 488 of them. sodium salts Sodium (with dual charged ions) Amphoteric surfactants Suitable for use here Amphoteric surfactants and suitable alkyl amine oxide alkyl amphocarboxylic acids include those compounds having the following formula amine oxides and including hydroxy alkyl amine oxides selected from the alkyl group RY where_is RIORHNR) or alkyl phenyl alkylphenyl acylamidopropoyl acylamidopropyl hydroxyalkyl is an alkyl group RY carbon atom; And YU are terminator mixtures containing from 0 to 48 containing of ? to ? carbon atoms or hydroxyalkylene or hydroxyalkylene is 0 to © and preferably 0 to ; All d18 terms x are terminated mixtures and are to © or 1 containing of hydroxyalkyl or hydroxyalkyl of the alkyl group to ? 1 Ethylene oxide groups containing polyethylene oxide alkyl methylamine group JB alkyl © oxide preferably cthylene oxide 0 acylamido alkyl oxide and ©-and © acylamido alkyl dioxide cdimethylamine dimethylamine oxide concentrate Miranol(TM)C2M A suitable example for an alkyl dicarboxylic acid is New Jersey. One end and negative at the other end) surface activators YS formulations to clean from. Jah Lay Hybrid ionic surfactants can be introduced and the activators can be described more broadly as derivatives of amines and bonded to secondary and tertiary amines as derivatives of heterocyclic secondary and tertiary amines Or as quaternary ammonium derivatives or quaternary phosphonium compounds 4 quaternary ammonium

ago

A: Tertiary sulfonium, betaine, and sultaine surfactants are examples of hybrid ionic surfactants for use here. Suitable 5 betainees are those compounds with the formula 0272000 where R is a 0-0:hydrocarbyl group and each R is a ©tr R*s Js is a group and ©-,© Hydrocarbyl 097H 70:06. The preferred betaines are dimethyl-ammonio hexanoate, betaines, and jud acylamidopropane (or dimethyl Jfall 6 (ethane) or diethyl Complex surfactants betaines are suitable Lad for use here. Contains at least one ester (ie-000-) bond and at least a group with at least one cationic charge Other suitable surface-activated cationic ester have been described, including Ne, including the choline ester. Surface Activator US Patent Nos. U.S. Patent Nos. 2 Drew 4,239,660 and 4260,529 Suitable cationic surfactants include quaternary ammonium surfactants selected from 0-m0 materials; m0 is preferred. N-alkyl or alkenyl ammonium surfactants in which the remaining N-sites are replaced by 'hydroxyethyl' or 'hydroxypropyl ds' methyl groups." Enzymes The enzymes Enzymes are preferred scavenging components in prophase I and in particular fas in prophase II and/or other facultative phases. Levey be present These oe enzymes Sled) are selected TO _ the group. consisting of Clad AE veo cellulases or semi-cellulases; peroxidases; proteases; Gluco-cellulases enzymes <i sll xylanases xylanases camylases cgluco-amylases cesterases . Alsterases «phospholipases. Phospholipases. 5 reductases ckeratanases pectinases 485 keratanases ccutinases dipoxygenases for lipoxygenase 5 el Jaws of gill oxidases 5 el Jaws of gill oxidases 5 ctannases pullulanases or pullulanases ligninases liginases 3- glucanases Glucanases Lull: 85 malanases. 065 Chondromycin chyaluronidase arabinosidase 085 L Hyaluronidase: mixtures thereof. dJaccase lacase «chondroitinase

Jdipase, lipase amylase and amylase protease Preferred enzymes include protease 01 in combination cellulase and/or cellulase cutinase and peroxidase 08 + cutinase with one or more plant cell wall hydrolyzing enzymes. The cellulase enzymes used in this invention are both bacterial and fungal cellulase enzymes. Preferably, it should have an ideal pH between © and 1 and a higher potency (cellulose viscosity unit 086L 081101). The cellulase enzymes CEVU© .of 5 have been described by Barbsjord US. Patent 4,435,307 (USA no. gl fay) appropriate in patent and INT.P. No. 3 “that j 0 et al. 6 Malala 210 describe fungal cellulase enzymes produced respectively from Humicola inulinus, Trachodyderma, Sporotricum Thielavia, and Thielavia <Humicola insolens Trichoderma cellulases isolated from EP 739 982 describes Sporotrichum |. 0 new. Appropriate cellulases were described in the patent application Bacillus parts

GB-A2.095.275, UK Patent Application No. GB-A-2,075,028 and International Patent No. DE-OS-2.247.832 A, Danish Patent Application 8

Ao

RI

They are cellulases produced by a strain of cellulases, and examples of these cellulases are of the type Humicola grisea (Humicola insolens)

DSM 1800 Humicola Diu in particular “(thermoidea (suse Humicola insolens oe) and other suitable cellulases are cellulases yielding 0.0 kDa; EBP on has a molecular weight J) Humicola insolens © _ From_ endoglucanase 43 kD camino acids, 405 amino acids, which contain “DSM 1800 Humicola insolens sid sud” which is derived from humicola 06. The preferred sequence is endoglucanase, and the component of endoglucanase has cellulase that shows cellulase activity. 7091/ 17243 The amino acid described in International Patent Application No. 26111 Cellulases _from_Trichoderma longibrachiatum Load and the appropriate Cellulases 0 are described in International Patent No. 17094/21801; Trichoderma longibrachiatum Sept. 1594. The appropriate cellulases as YA Publication In Genencor, in particular, there are cellulases that have color-preserving benefits. Examples of these cellulases are the cellulases described in European Patent Application No. 495057 published in Novo Nordisk Celluzyme and Carezyme. The charismatic 0 (pea) 144Y alg 11 No. ip. sel is particularly useful. See also Novo Nordisk A/S, IPO 21801/ 87091. Other suitable cellulases (WOOL / 17244) for their fabric-preserving and/or cleaning properties are described in IPOs 17095/24471 and W0O96. / 17994 5 2 numbers f and these 5 cellulases were naturally introduced into the cleaning formula at levels from 9760,000 up to 967 active enzyme by weight of the cleaning formula Peroxidase enzymes were used in combination with oxygen sources above Carbonates «percarbonate», perborate, persulfate, hydrogen peroxide, etc. It can be used YO in and solution bleaching, that is, to prevent the transfer of dyes or colored materials removed from the

substrates during the washing process to the other substrates in the washing solution. and peroxidase enzymes are known in this dedi clad for example; Watercress peroxidase <horseradish peroxidase and ligninase ©01088p11 and Jie haloperoxidase sis ms chloro peroxidase 00000016 © 4.228,042 Substituted Jie-01 phenothiazine propionic acid

(PPT) 10-Phenothiazinepropionicacid, 1-0-ethyl phenothiazine-acid; - Carboxylic acid “(EPC) 10-ethylphenothiazine-4-carboxylic acid and Jie “Vey (POP) 10-phenoxazinepropionic acid 10-methylphenoxazine (described in International Patent No. 94/ 12621 (WO 0 and substituted syringates (substituted C3-Cs alkyl syringates) and phenols are sodium percarbonate or perborate

Sodium is the preferred source of hydrogen peroxide and these naturally occurring cellulases and/or peroxidases were used in the cleansing formulation at levels from 96,0001 to 967 of the enzyme.

enzymes | 0 effective by weight of the cleaning formula. Other preferred enzymes that may be used in the cleaning formulations of this invention include lipase 1108888. The lipase enzymes suitable for use as a detergent include those producing Aaa the microorganisms of the group Pseudomonas Jie and Pseudomonas stotzeri 19.154 ATCC described in UK Patent No. 1372034. Ye suitable lipases include those that show a positive cross-reactivity with the antibody to the lipase. Produced by the microorganism Pseudomonas fluorescent TAMIOST. This lipase is available from Amano Pharmaceutical Formulation Company; Nagoya Japan under the trade name Lipase P “Amano” hereafter referred to as “Amano-P” Other suitable commercial lipases include Amano- “CES” and lipases of Chromobacter viscosum Jie (ex Chromobacter viscosum) YO Viscosum si (so (Chromobacter viscosum var) ¢ Lipolyticum NRRLB3673 from Age Corporation

for Toyoguzu. 10700020 (Tagata Wal _ Japan and duwsall ge (Chromobacter viscosum lipases) _ American Biochemical Materials; USA Ady Disoynth Netherlands and lipases ex Pseudomonas gladioli and particularly suitable lipases are Lipomax 3 M1 LipaseR Ja © Gist-Brocades Lipolase Ultras (Novo) which was found to be effective when used in combination with the formulations of this invention. The appropriate materials for Loaf are hydrolytic enzymes For the fats described in EP No. 258068 EP, INT. Patent No. 92/05249 WO, and INT. Patent No. 95/22615 WO by Novo Nordisk.

0 - International No. 94/03578 WO and Patent International No. 94/03578 WO and Patent

I.S. 96/00292 WO by Unilever The appropriate substances Lad are the enzymes EC [cutinases [1,0,0]_ which can be considered as a special type of lipase Sl) are actually lipases that do not Requires separator surface activation. The addition of lipase chitinases to cleaning formulations is described in, for example;

5 International Patent Application No. WO-A-88/09367 (Genencor) & International Patent 90/09446 WO (Plant Genetic System) & International Patent No. 94/14963 WO & International Patent No. 94/14964 WO (Unilever).

Lipases and/or cutinases were introduced naturally into the cleanse formulation at levels of (yor eve) up to 7 of the active enzyme by weight of the cleanse formulation.

Y. The appropriate 8 proteins are Al subtilisins obtained from a specific strain of B. subtilis .13 and b. Lycineformis B. licheniformis (BPN' 5 BPN subtilisin and one of the suitable proteases is produced from a strain of Bacillus, which has maximum activity over the pH range of 8- B-12) 01 developed and sold as ESPERASE® by Novo Factories A/C in

Yo Denmark; referred to here as ''novo''. The preparation of this enzyme and similar enzymes is described in a patent

Ag

BR No. aul 175497484 nouveau. Other suitable proteases include

SAVINASE®; DURAZYM® (ALCALASE® (KANNASE®) by Novo

MAXAPEM® “PROPERASE® MAXACAL® MAXATASE®

Jains Gist-Brocades.

Proteolytic (protein engineering) from Maxacal Gypsum Brocades

38 gum gall 8 Proteolytic Enzymes Modified Bacterial Serine Proteases; like that oo

In European Patent Application No. 50,251,446 filed on January 7, 19848 (as

especially TEs pp. 17 and 48); which is called here Sod by " and in the patent application

European Invention 50199404 Venegas. Published 79 Oct AAT referring to

A bacterial serine enzyme modifies a protein that is called "protease A" here. And appropriate

serine protease which is a type of serine protease Cz is what is called here 'protease' 0 © arginine in place of arginine lysine in which lysine has been substituted Bacillus alkali of bacillus

in position YY and replacing tyrosine in place of valine in position Vet

And substituting serine for asparagine at position 1" and substituting alanine

alanine in place of threonine at position 7/4a7. C proteases have been described in the patent

Yee Patent International WO 91/06637 and published on May 0 N99) and genetically modified species;

in particular protease c; It is also used here.

The preferred protease (ad) referred to as "d protease" is a carbonyl type

A hydrolase has an amino acid sequence not found in nature; It is derived from carbonyl hydrolase

primary by replacing a different id-acid with several amino acid residues at the

0 This carbonyl hydrolase is equivalent to position +771 and Lad is preferred in combination with one or more of

The positions of the amino acid moieties equivalent to those selected from the group consisting of +4

And +aa and +710 and 10 and alaa and +771 and +la and +t10 and +0 and +711 5 YYA+

YAVAHG YVTHg Yh 0A+W 0.+W 1AQ+W W+A W+5 A Volt 1757W

And 6717 and 7777 Yet, and +15? and/or +7714 Gib for the numbering of Bacillus subtilisin

Yo amyloliquivashiar; As described in International Patent No. 7095/10591 and Patent Application Ag

Ya. and colleagues under the title 'Bleaching formulations containing ©. Ghosh C. Josh pub Patent filed with U.S. Ser. No. 08/322,677 "Protease Enzymes" US Patent Serial No. in Patent. Current US No. 6 0114 RoboCA 17 in .U.S. Pat. No. 5,677,65 272 It is appropriate to use it in this invention as well. They are the proteases described in Applications ° and the proteases WO 91/06637 and INTERNATIONAL PATENT No. EP 251 446 EP No. 446 and its types described in WOO1/02792 described in INTERNATIONAL PATENT No. BLAP®

WO 95/23221 in International Patent No

Bacillus sp, a strain of Bacillus Me pH; see also the de novo protease. Novo. And when WO 92/03529 A reverse protease in the international patent No. Lia as low lie and high hydrolysis is gala), the protease that has sla and Procter Gamble is named WO 95/ 07791 Described in ISPM No. 1 for use in detergents trypsin The recombinant trypsin-similar protease -Gamble Ve is described by Novo and the protease WO 94/25583 is appropriately described here in ISPM No.

Unilever EP 516 200 Other appropriate in European Patent No. Other preferred protease enzymes include proteases which are an amino acid type whose amino acid sequence carbonyl hydrolase is present in nature and derivative by replacing several amino acid residues of the carbonyl _0 precursor hydrolase with different amino acids; Where this multiple amino acid residue has been replaced by conjugation with one or more of the following residues: +7001 in the corresponding preenzyme at position 17, +F1, +M701L+F, +0.4F +017, +01a, +0..+, Vid, +17, +1 YY, +No, VIVES, +178, +DA, +A/DA, +114, +113 1774, 11+, and subtilisin, where the numbered positions correspond to subtilisin (YY regi 1?a+r 11+ and 8

Age

found in nature in Bacillus amyloliquefaciens or equivalent amino acid residues in carbonyl hydrolases or other subtilisins (Jie) subtilisin Bacillus lentus subtilisin preferred enzymes of this type include those which have repositioned Yabo Val VI 7001+

A+ Yo o and proteolytic enzymes are used in the cleaning formulations in this invention at levels from 700,800 to 967; preferably from 960.009 to 960.,7; Preferably over 58 up to 960.1 pure enzyme by weight of the formula. Amylase enzymes (alpha and/or beta) can be used to remove stains caused by sugars. 0 INT.P. No. 02597/17094 in the name of Novo Nordisk ASS published * February 19494 describes cleaning formulations containing hybrid amylases. See also International Patent No. 10603/77095 in the name of Novo Nordisk A/S published in Ye April 19985 Other amylases known to be used in cleaning formulations include alpha and beta-amylases. Known alpha-amylases in this field include those described in US Patent No. 5,003,257 (US Patent No. 252,666 EP), International Patent No. 00353/170/91, French Patent No. 2,676,456 FR, and European Patent No. 2,676,456 EP No. 285,123, EP No. 525,610 EP, EP No. 368,341 EP, UK Patent No. 17456874 (Novo).Other suitable amylases are the increased stability amylases described in Ye International Patent No. WOO4 /18314 published August 18, 1994 and INT.P. No. 5 in the name of Genencor published YY February 1997 and the types of amylases further modified in the direct parent compound available from Novo Nordisk of!Nordisk described in WO 95/10603 published April 8. A suitable material for Lad is the amylases described in EP No.

Ag

AW

Intn sels WOO95/26397 and intn EP 277 216 (all from Novo Nordisk). 3 of the Purafect Ox Am® brand o-amylases and examples of alpha-amylase products are all available from Natalase® 5 Duramyl®, Fungmyl® Ban® Termamyl® Genencor, Amylase WO 95/26397 Denmark. The international patent Novo Nordisk © ofl describes other suitable: alpha-amylases characterized as having a specific potency of at least 96725 greater than at a temperature range of 7°C to 2200°C and at a Termamyl® value of the compound's specific potency Measured using an alpha-amylase activity tester pH 01 01 in the range from 8 to appropriate using the different types of the above enzyme described in the Phadebas® patent. (Novo Nordisk). Other amylose-degrading enzymes WO 96/23873 INT. he that have improved properties in terms of level of activity, thermal stability union, and higher level of activity WO 96/35382. 7095/35382 are described in PI. 7095/35382. These preferred amylase enzymes include Described in International Patent No. Nordisk sig aly WO 96/23873 Yellow_ and Patent _ Novo Nordisk Yo 7. Amylose-degrading enzymes were used in the cleaning formulations in this invention at a level from 960.0001 to 967, preferably from 960, 00014 up to 960.07 preferably up to 960.044 pure enzymes by weight of the formulation. 64 In a particularly preferred embodiment the cleaning tablets of this invention contain amylase enzymes and in particular those described in International Patent No. 7774987/Ye Patent In combination with complementary amylase.‎ 1070 Nordisk on behalf of Novo Nordisk WO 96/23873 International Patenting By "complementary" we mean the addition of one or more amylases suitable for cleaning purposes. Examples of complement (alpha and/or beta) amylases are described in PL LEY 17095/10603 in the name of Novo Nordisk A/S 7 Cleaning formulations containing hybrid amylases. Other known amylases include Yo

ago

By using in cleansing formulations both alpha and beta amylases; Known alpha-amylases in this field include those described in US Patent No. 5,003,257 (US Patent No. 252,666 “EP” and International Patent No. 170/91/00353; French Patent No. 2,676,456 (FR) and EP No. 2,676,456 EP No. 285,123, EP No. 525,610 EP, EP No. 368,341 EP, Written Description BR No. 1,797,874 (Novo).Other suitable amylases are the increased stability amylases described in International Patent No. 7094 /18314?and ISPM No. 05295/177096_in the name of Genencor and various amylases further modified in the direct parent compound available from NovoTordisk ofl 0 and described in ISPM No. 10603/95 WO and appropriately Load The amylases are described in EP No. 216 277 BP (Novo Nordisk).Examples of commercial alpha-amylase products are Purafect Ox Am® - Genencor 5 Ban® 3 Termamyl® and Duramyl® 5 Fungamy® All available from Novo Nordisk A/S Denmark. 26397/17095 describes other suitable amylases: Alpha-amylases marked No have a specific potency of at least 9675 greater than the specific potency of Termomyl® at a temperature range from #?”C to 200 and at a pH value pH in the range + to 0 measured using the Phadebas® Alpha Amylase Potency Test and the appropriate compounds 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 yo level of activity, thermal stability union, and greater level of activity are described in International Patent No. nb Invention Adel No. WO 4, International Patent No. WO96/05295 Sold by Genencor, Fungamyl® 5 Termamy®1, Ban®, Natalase® and Duramyl® are all available from Novo Gist-Brocades by Maxamyl® Guest Brocades and of! Nordisk Yo

Ae

Complementary amylase is generally crosslinked in the cleaning formulations of the present invention at a level from 960.0001 to TY preferably from 960.00014 to 960.07; More than 984 to 960,047 pure enzymes by weight of the formulation are preferred. Preferably, the weight ratio of the pure enzyme for specific amylase to complement amylase should be between 4:0 up to 9:1 and more preferably between Vf© up to:1; Preferably between ?:1 and :1?. The aforementioned enzymes can be from any suitable source such as plant, animal, bacterial, fungal and yeast sources. The source, Lad, can be medium thermophilic or hyperthermic (hygrophilic; hygrophilous; thermophilic; high atmospheric pressure; alkaline; acid-loving; salt-loving; etc.). Pure or impure forms of these enzymes can also be used, and hybrids of endogenous enzymes were used. He hybrids can be obtained by protein engineering and/or genetic engineering and chemical and/or physical modifications of endogenous enzymes. It is common for Glee gene expression of the enzyme by Alle organisms in which a brat product of the Add genetic material has been produced from the production of enzyme 0216. Vo these enzymes were used naturally in the cleaning formula at levels from 960,060 to 907 active enzyme per weight of the cleaning formula. Enzymes 485 can 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 concomitant granulocytes). Other suitable cleaning ingredients that may be added are the enzyme Z oxidation activators described in EP 607 553 filed at; Aug *19. Examples include the materials activating the oxidation of this enzyme are tetraethylene polyamides to which ethoxylated has been added. Many of the enzyme materials and means of their use in industrial cleaning formulations have been described in the International Patent No. WO 9307263 and the International Patent No. WO 9307260 Yo _ in the name of _ Genencor «680600_international and patent dy Adsl AE

WO 8908694 A for Lenovo. and US Patent No. 3,553,139 US. © January 11 on behalf of McCarty and colleagues. Lad enzymes are described in US Patent No. 4,101,457 U.S. Plass et al. in VA Jul 15978 or US Patent No. 4,507,219 U.S. Hogg in TT Mar 588. © Enzymes are described Useful in liquid detergent formations and their interference in those formations in US Patent No. 4,261,868 US. In the name of Hora and colleagues in VE April NAA The enzymes used in detergents can be stabilized by many techniques 0 Enzyme stabilization techniques and their examples are described in U.S. Patent No. 3,600,319 USS. August 17th VAVY in the name of Gage & Associates EP No. 199,405 EP EP No. 0 200,586 20 october 79th 1085 Venegas “Load enzyme stabilization systems, for example” are described in US Patent No. 3,519,570. The useful bacillus species ACIS that give rise to proteases, xylanases and cellulases are described in WO 9401532 A In the name of Novo.

Bleaching agent 0 One of the most favored ingredients in detergent formulations is the bleaching agent. The oxygen-permeable chlorine Suitable bleaching agents include chlorine and 0-Xygen bleaching agents. And a primary bleaching compound of an organic peroxy acid. Preferred sources of hydrogen peroxide include bleaching agents, and in one of the alternative forms of interference perhydrate acid, inorganic organic oxy superhydrate treated directly in the formulation, and formulations containing mixtures have been envisaged.

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From a source of hydrogen peroxide and a primary organic peroxyacid in combination with a treated organic peroxyacid. Inorganic bleaching agents perhydrate

Detergent ingredient combinations preferably include a source of hydrogen peroxide; And factor

Oxygen outlet bleaching. Suitable hydrogen peroxide sources include perhydrate salts

inorganic.

Inorganic superhydrate salts naturally occur in the form of sodium salt at a level from 501 to 9640 by weight. More preferably from 967 to 50 by weight and more preferably by 965 to 9675 by weight of the formulations.

01 Examples of salts 38 include inorganic perhydrate salts perborate, percarbonate, perphosphate, persulfate, and persilicate 06:51116816. The naturally occurring inorganic superhydrates are salts of the alkali metals. The inorganic superhydrate salts may be included as a crystalline solid without additional Ales. and for some perhydrate salts; the

1 The preferred use of these granular formulations entails a coated form of the material which gives better storage stability of the superhydrate salt in the granular product.

Sodium borate can be in the form of the monohydrate which has the following nominal formula 11880211202 or the tetrahydrate 11230211202.31120. They are percarbonates of the alkali metals; In particular percarbonate

0 Sodium percarbonate is the preferred superhydrate for use in the formulations of the present invention. Sodium percarbonate is a compound added to it, AU deal 2, which is commercially available as a crystalline solid. and have sodium percarbonate; Being a hydrogen peroxide addition compound, the ability, when dissolved, to release hydrogen peroxide quickly enough that can increase

‎AE

The ability to obtain high concentrations of the bleaching agent in certain places. It is preferable that the percarbonate be used 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 © _ previously described in British Patent No. 1,466,799 under the name of ANTROXY of March 9th NAVY The weight ratio of the coating salt mixture to percarbonate is in the range from 0:1 to 1:4 Preferably from:1 59 to:1 9 and preferably from:1 9; to 1:04 preferably mixed salt Ge sodium sulphate and sodium carbonate having the general formula Cua Na2S04.0.Na2CO03 being 0.1 Gen to 0 © It is preferred from 1.7 to 1, and it is more preferable to be 0.9 en to cao. Other suitable covering materials that give stability to the product include sodium silicate, which has a ratio of 11820:5102. 1:8:1 up to “: 1 preferably 1:8:1 up to 1 4 or sodium metasilicate and preferably used at a level from 6” to 9600 (usually from “96 to %0) of 58102 _ weight_ of Sued Gb salt, perhydrate salt, inorganic 0. Sas, that magnesium silicate is also used for coating. Covering materials that contain silicate salts, borates, or boric acids shall be boric acids or other inorganic substances are also suitable for use here.Other covering materials which contain waxes, oils, 0 and Lad greasy soaps are characteristically used in this invention.Potassium peroxymonopersulfate Another organic perhydrate salt is used in the formulations described here as well. AE

AVA

Raw material for bleaching peroxy acid The raw materials for bleaching peroxy acid agents are compounds that are combined with hydrogen peroxide in a hydrolysis reaction to obtain peroxy acid Joli. In general, the raw materials can be represented as peroxy acid bleached by the following formula: , ° is a leaving group and “is any functional group so that L where is when perhydrolysis is performed, the structural composition of the resulting peroxy acid is: 0 fac ‎ ! — 0H It is preferable to use compounds of the raw material of peroxy acid bleach at a level of weight, preferably from 961.5 to 9600 to 070 of weight, and preferably from 961 to 900.9 Ne of weight of the formulations. 5 The compounds of the materials contain Primary peroxy acid that is actually appropriate on one or more Selection of these raw materials from a wide range of (Says < O-acyl acyl -0 JN from groups of imides cesters esters anhydrides sections. Sections include Appropriate anhydrides, oximes, oximes, imidazoles, and derivatives of imidazoles, lactams, dimides, and examples of substances used in these sections are described in the request for appropriate acylated acylated esters, and esters are described in GB-A-1586789 British Patent No. 2143231 “1147871” 864798 “GB-A-836988” British Patent Application No.

EP-A-0170386 EP No. Ya residues are sufficiently effective (LL must be the residue; herein referred to as the wash cycle group) despite ia) of the occurrence of a hydrolysis reaction within the maximum time range

ago

- 2 A is very effective, so it is difficult to install this activator for use in Lo than this if it is a bleaching formula. Preferred 1 groups are chosen from the group consisting of: 7 5 g RS

SOF +O 0 © - A —N—C—R ~N N —~N—C—CH—F

R® LJ 'ke y

Y

8 7 ~O-CH=C—CH=CH, Om CH=C—CH=CHs 0 No 1 excels. / Someone is ducking to bring it ~N___ AR . ; G 0 0 3 G 0 1 1 : or caryl aryl alkyl alkyl dc gana 1 is Cua and mixtures thereof 1 is an alkyl chain containing an R3 carbon atom; It is VE to 1 containing from © alkaryl of the alkenyl chain RS 183 of 11 or RE to 8 carbons; and be, or group, a solvent. H can be y carbon atoms and A to 1 can be completely alkenyl in any functional group chosen from; For example R45 R35 RI to replace any of the casi) calkoxy hydroxy hydroxy alkyl JS cle seas (JU

AEs

The amine chalogen is nitrosyl, amide, ammonium, or alkyl ammonium. The preferred solvent groups are 11, .50-SO My -COMYs and -N'R (X and Cua) for -2108-+0 and more preferably -50:247 and -0021247 Cua be 83 is an alkyl chain © containing from 1 to ; carbon atoms; be 24 is a cation that gives solubility to the bleaching activator Xs is an anion that gives solubility to the bleaching activator. Preferably 14 is an alkali metal; ammonium or an ammonium cation substituted with sodium and potassium being the preferred ones.” And x is a hydroxide chalide methylsulfate 0 or acetate anion. The precursor to perbenzoic acid aad Compounds of the precursor to perbenzoic acid Perbenzoic acid 5 after hydrolysis The precursor compounds of perbenzoic acid to which the 0- acylated 0-acylated VO has been added include suitable benzoyl oxybenzene sulfonates and unsubstituted which include, for example, oxybenzoyl sulfonate: 0 The relevant Load compounds are products of the addition of benzoylation Jas jill to Sorbitol 001?; Glucose and all saccharides by Jal se Addition of benzoyl 0 which includes, for example: AcO Tre CAC OAc OBz COCH3 = AC and 37 - benzoyl Age one Compounds of the raw material of perbenzoic acid of the amide type, each of Jad tetrabenzoyl oped second olds (N-benzoyl succinimide No deminiscs

N-benzoyl substituted N- benzoyl urease Suitable tetrabenzoyl ethylene diamine imidazole Starting materials include imidazole-ureas perbenzoic acid Lm17 and benzimidazole <7 benzoyl imidazole benzoyl -N oo imidazole © Perbenzoic Acid Raw Materials Containing Jedi; N-benzoyl benzimidazole

5 AY! perbenzoic acid The raw materials for perbenzoic acid include 01 the cthe benzoyl diacyl peroxides diacyl benzoyl peroxides and the compound has the following formula: benzoyl tetraacyl peroxides 1 oR 0 © 07-00 is a raw material compound Perbenzoic acid Phthalic anhydride and phthalic anhydride are another suitable for use here. : -N genitive lactam 1 0 C—CHy—CH,

RO-—C—N._

CHy~{CH, I and 18 is of, preferably from zero to A where « from zero to 1 benzoyl is a benzoyl group

ago

Precursors for Perbenzoic Acid Derivatives Precursors for Perbenzoic Acid Derivatives prepare substituted perbenzoic acids after perhydrolysis. Suitable substituted perbenzoic acid derivative precursors include any of the perbenzoic precursors described herein in which the benzoyl group is substituted with any non-cationic functional group and includes, for example, cationic alkyl groups The hydroxy and the alkoxy halogen <halogen the amine and the nitrosyl and the amide .amide and in a preferred section of the precursor compounds of the substituted perbenzoic acid are the amide-substituted 0 compounds that have the general formula Next: Sn 2c Hs Wg R1—¢—N-—RZ—C—L SN where RY is an aryl or alkaryl group with 1 to VE carbon atom and 182 is a carylene or alkarylene group containing 1 to VE carbon atom; 187 is an 11 or an aryl or 0-calkyl group alkaryl contains from 1 to 01 carbon atoms and can be a. is any group leaving Lala and contains 18 preferably from 1 to VY carbon atoms and contains 182 preferably from 4 to / atoms carbon. RY can be an aryl; Substituted aryl or alkyl aryl containing branched; replacing; 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, aryl, halogen, nitrogen, sulfur and other substituting groups or other substituting organic compounds. And 185 is 11 or so and it must not contain more than 18 carbon atoms in total. Activating compounds for amide-substituted bleaching agents of this type are described in European Patent No. EP-A-0170386 At

07 Peroxy Cationic Acid Raw Materials Peroxy cationic acid feedstock compounds prepare peroxy cationic acids after hydrolysis. Indeed; Cationic peroxy-acid precursors were formed by substituting the © part of the peroxy-acid in a suitable peroxy-acid precursor with a positively charged functional group; Such as an ammonium group or alkyl ammonium, preferably an ethyl group or methyl ammonium, and the raw materials for a cationic peroxyacid (lad) are present in the formulations as a salt with an anion suitable" such as the halide ion or the amethylsulfate ion for example ye. For the precursor compound of a cationic substituted peroxy acid, it can be a precursor compound of perbenzoic acid, or a substituted derivative thereof; As described herein previously.Alternatively the peroxy acid feedstock complex may be an alkyl percarboxylic acid precursor or the V0 amide precursor alkyl percarboxylic acid precursor described herein. Cationic peroxy acid in US Patent Nos. 6 4,751,015« 4,988,451 4,397,757 5,269,962 5,127,852« 5,093,022 8 and English Patent 1,382,594 sel uy UK. European Patent (EP 4755) 12 HB) 458396 & 284,292_in_Japanese Patent No. JP 87-318,332 Y » Suitable peroxy-cationic acid starting materials include benzoyl oxybenzene sulfonates, alkyl substituted with alkyl ammonium or Jy all and caprolactams with added 17-Jud and monobenzoyl tetraacetyl benzoyl glucose peroxides. millimeter

_oY- substituted benzoyl oxybenzene sulfonates Ga and form 4-(trimethyl ammonium) oxy-sulfonate; methyl 0

Os Yale + . Name of the substituted alkyl oxybenzene sulfonate The alkyl oxybenzene sulfonate has 5 oO A Pi cationic mnie / 0 0 preferred cationic peroxyacid The raw materials for the cationic peroxy acid include N-acylated caprolactam of the carrolactam type with added 11-acylcaprolactamate alkylammonium methylenebenzoyl; In particular caprolactam, trimethyl ammonium methylene benzoyl 0 0".

N-acylated caprolactams dud Nad Type of caprolactam added Ge Other 9 0 Co trialkyl ammonium methylene alkyl Trialkylammonium| Methyleryl alkyl caprolactam Vo da mrl 2 00 to 1 especially from OY where 8 is from zero to

N,N, ) =Y The other preferred cationic peroxyacid feedstock is trimethylammonium chloride) ethyl sodium 4-sulfonylcarbonate 1

Ato

2-(N,N,N-trimethyl ammonium) ethyl sodium 4-sulphophenyl carbonate chloride Raw materials for bleached alkyl percarboxylic acid Raw materials for bleached alkyl percarboxylic acid work on the preparation of percarboxylic acids after hydrolysis and work The preferred starting materials of this type are based on the preparation of peracetic acid after hydrolysis. The preferred overcarboxylic alkyl raw material compounds of the amide type include the added alkylene diamines ad “N°, N°, N, N lg acetyl N, N, NI NI tetra Cua acetylated alkylene diamines containing An alkylene group has 1 to + 0 carbon atoms, especially those compounds in which the alkylene group contains 1, 7, and 7 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. Favorite primary alkyl percarboxylic acid feedstocks include ?; 0(=o) sodium nonanoyloxybenzene sulfonate 3,5,5-tri-methyl hexanoyloxybenzene sul- (is0-NOBS) fontate Vo, NOBS sodium nonanoyloxybenzene sulfonate, and sodium acetoxybenzene sulfonate (ABS) sodium acetoxybenzene sulfonate and penta acetyl glucose .glucose Precursors for peroxyalkyl acid substituted amide A Precursor compounds for peroxyalkyl acid substituted with amide are suitable Lid, including those of the general formula The following: RY is the center of an algyl group having 1 i to ond i. 82 is an alkylene group containing 1 to VE carbon atoms; RY is of 1] or an alkyl group containing from 1 to 10 carbon atoms; a. can be an AE group

_oo- a carbon atom; It contains 182 preferably from; 11 leaves. It contains 18 preferably from + to is a branched or straight-chain alkyl containing RY to 4 carbons. It can be branched, substituted, or both, and it can be obtained from industrial or natural sources

R? Including, for example, ghee. Various similar structural species are suitable for (nitrogen < halogen calkyl halogen The substitution may include alkyl groups © and other substituent organic compounds or compounds and are 187 in the form of sulfur sulfur a carbon atom in VA A and 85 should not contain more than H Preferably is the total Bleaching agent activator compounds substituted with amide are described in the European patent application EP-A-0170386. Raw materials for benzoxazine 0 peric acid Organic Oxy 0-type_benzoxazine AN SD Se is Lal Auld SS,

EP- As described for example in EP-Application No. Benzoxazine and in particular EP-A-482,807 and EP-Application No. 4-4 having the following formula: D OL ml \o Including the following type of substituted benzoxazines 85H:

Ry03

O.L., 5

Ry

Rj Ry aryl » aryl alkyl ; where “dash is an alkyl; Hoe is Ry where alkyl is an alkyl halogen identical or different substituents selected from 11 halogens Rs and Ra alkyl amino camino sud calkoxyl alkoxyl hydroxyl aryl hydroxyl aryl calkenyl 0 or an alkyl group) and the carbonyl H is Re 00 (where it is “alkyl amino .carbonyl

AE

One particularly preferred feedstock of 2 benzoxazine is: © ~O Co Treated organic peroxy acid The organic peroxy acid system may contain a canal in addition to; or as a substitute © for; Organic Peroxy Acid Bleach Raw Material Complex; treated peroxy acid; lad at 960.5 to 9675 wt.; more preferably from 961 to 96100 by weight of the formulation. One of the preferred divisions of peroxyorganic acid compounds is the amide-substituted compounds which have the following general formula: R'—C-—N-—R2—C— OOH 0 ) | From 00g Sg ZO: L where 181 is an alkyl aryl alkaryl group having from 1 to VE carbon atom; R2 is an alkylene group “carylene” an alkarylene containing from 1 to VE carbon atom and RS is 11 or a dist aryl or caryl group containing from 1 to 10 carbon atoms. And RT preferably contains from +Ye to 117 carbon atoms. And 102 contains preferably 4 to 4 carbon atoms. 1 can be a straight-chain or a branched alkyl; An aryl or alkyl aryl substituted containing a branch; Substitution or both and may be obtained from industrial or natural sources including for example (JU) luteum. Several similar synthetic species are suitable for 82. The substitution may include an alkyl group; (Jil) halogen; nitrogen; sulfur and groups or compounds other substituent organic Vo.RS is preferably 11 or Jie and RI and RS shall not contain more than VA carbon atom in total.Ago acid compounds are described

_ov- of this type in a patent application, organic peroxy-amide 40 substituted with an amide. EP-A-0170386 EP No. EP-A-0170386 Other organic peroxyacids include peroxyacids, especially peroxyacids. dtetraacyl, diacyl SG peroxides, diperoxydodecanedioc acid, diperoxydodecanedioc acid, cdiperoxytetradecanedioc acid wll, and the preferred organic peroxy acid here It is above the diperoxyhexadecanedioc acid and monobenzoyl diperazelaic acid. Mono- and di-pyrazylic acid, [<- phthaloylamine peroxycaproic acid and diperbrassylic acid and di-peracyric acid are suitable for use here as well. N-phthaloylaminoperoxicaproic 2610 0 Regular rate of release medium A means of controlling the rate of release of the bleaching agent; In particular, the oxygen bleaching agent into the washing solution. A means can be provided to control the rate of release of the bleaching agent for the uniform release of peroxide materials into the washing solution. These methods may include; For example; Control of the inorganic Vo that serves as the source of the perhydrate salt The release of any perhydrate salt into the wash solution chydrogen peroxide Hydrogen One way to control the rate of release of the bleaching agent is by capping the bleaching agent Cap designed for regular firing. The cover can thus contain; on On a material that is poorly soluble in water or a coating of sufficient thickness JE Sabil Yo such that the dissolution kinetics of the thick coating give a uniform rate of release. The coating material can be applied using several methods. Any coating material present shall be 1: preferably from oF:1 up to 59:1 of ¼ by weight of coating material to Glad factor 3.1 in 4.

At

© - Suitable covering materials include triglycerides (eg Gia hydrogenated vegetable oil, soybean oil, cottonseed oil), mono or diglycerides 1766:1066g01; microcrystalline waxes and gelatin #NADAA; Cellulose, fatty acids, and mixtures thereof. ° Other suitable mulching materials may include sulphates, silicates, and carbonates of the alkali earth metals and the alkali metals Lay containing calcium carbonate and silicas. In particular for the source of bleaching agent from inorganic salt perhydrate; on sodium silicate with a ratio of NapO: SiO; from 1.8:1 to ?:1

0 (preferably 1 LE Sa) VA and/or sodium metasilicate preferably applied at a level from 907 to 96080 (sale 565 to 0%) of 02:5 by weight of the inorganic perhydrate Magnesium silicate can also be used for coating.

Any inorganic salt covering materials may be combined with organic binders

0 For a covering composition of inorganic salt / organic binder suitable binders include the following Cpo-Coo sthoxylates alcohol containing 100 moles of ethylene oxide per mole of alcohol preferably M ethoxylate Primary alcohol ethoxylates containing from 0001-""1 mole of ethylene oxide per mole of alcohol.alcohol

0 Other preferred binders include some polymeric materials, polyvinylpyrrolidones having an average molecular weight of 17001 to 70000060 and polyethylene glycols (PEG) polyethylene glycols having an average molecular weight of 001 to 111 x 0 preferably 0001 up to +5000 and more preferably 0001 up to 0.001 are examples of such polymeric materials. and copolymers of maleic anhydride with ethylene

“methacrylic acid” methylvinyl ether ethylene Vo

Age

With maleic anhydride comprising at least 01 mol per cent of the polymer are other examples of polymeric materials useful as binding agents. These polymeric materials may be used as is or in combination with cold Jia solvents, propylene glycol and Cio-Cao alcohol ethoxylates containing 001 mol ethylene oxide. ethylene oxide per mole of the aforementioned. Examples of other binders include Cip-Cop mono- and diglycerol ethers and Cpo-Cap fatty acids. Derivatives of cellulose such as cmethyleellulose, carboxymethylcellulose, hydroxyethylcellulose, and homologous or conjugated polycarboxylic acids (Gonads) or their salts are other examples of binders suitable for use herein. One method of using a coating material for granules includes; Preferred pelleting methods include the use of any organic binders described here previously. Any common granule/mixer ingredient Lay may be used in it but without limitation; Fryer; Rotary mill and types of tuner No. Vertical. Fused covering compositions may be applied either by pouring in; Or spray it as a mist inside a moving layer of bleaching agent. Other methods of obtaining a uniform release include automated means of altering the physical properties of the bleach to control its solubility and release rate. Appropriate methods may include compression; automated injection; manual injection; Adjust the bleaching ability to 0 solubility by selecting the molecular size of any particulate component. While the choice of molecular size depends on both the composition of the particulate component and the desirability of obtaining the desired systemic release compounds; A The particle size is desirable to be greater than 501 μm; Preferably, it has an average molecular diameter of 80,860 to 1,701 µm. ANE ae Other methods for obtaining uniform release media include the appropriate selection of any other components in the fabric of the cleaning composition so that when the composition is introduced into the washing solution, the ionic strength environment in it enables the required uniform release kinetics to be obtained. Metal Bleach Catalysts Compositions described herein that contain a bleaching detergent ingredient may additionally contain a preferred ingredient which is a metal bleaching catalyst. It is preferable that it be a bleaching catalyst that contains a transition metal; A bleaching agent catalyst is a heavy metal cation-containing catalyst with specific bleaching catalytic activity; such as copper and iron cations and on the Ve bleaching metal cation little or no; such as zinc or aluminum cations; a sold additive with catalytic activity and a separator with specific stability coefficients for the catalyst and additional metal cations; In particular, aes and tetra-ethylenediamine tetra acetic acid (methylenephosphonic acid (aan) ethylenediaminetetra) and its water-soluble salts. These catalysts are described in U.S. Pat. 0.11.5. No. Preferred examples of such catalysts include JUS Pat 5244594 Ekirmala No. 3 cyclosanone = Y 7- 3 methyl = 4; V) (172)0-003ma | 0 ter -7 4 oY) Mnlll2(u-0)1(u-OAc)2 “—Y (trimethyl-1,4,7-triazacyclononane ter-aza —Y ( MnIV4@u-0)6¢ (0104(2 ~Y) dla tertiary aza noonan =V 4 ;0-lithium and mixtures thereof. Others described <MnIlIMnIV4(u-0)1(u-OAc)cyclo-noonan); - 0104( 2); in EP Application No. 549,272 other suitable binding molecules include 1,59-trimethyl-1 trimethyl-1; 0 = triazodecano-4 oo) for use here Yo

AE

,5,9-triazacyclododecane = methyl- 1 4 7”- tertiary aza noonane 2-methyl-1,4,7- —Y 120701006 methylha ff 7- tertiary aza noonan 2-methyl-1,4,7-tri- ef (F<) cazacyclononane ,7-triazacyclononane and mixtures thereof. ° It is possible to choose catalysts for the useful bleaching substance in the formulations here in the appropriate manner for this invention. Examples of suitable bleaching catalysts see US Patent No.

Pat. 4,246,612 and US Patent No. 5,227,084 USS.

Pat. See also US Patent No. 5,194,416.

Pat. describing complex mononuclear manganese (IV) compounds Mn Jie (1-4 7-trimethyl-—V 4 01 tertiary aza-nonan) (PF¢)3-(OCHa)3). 1 ,4,7-trimethyl-1 ,4,7-triazacyclononane) 01 and a bleaching catalyst ce AY! as described in US Patent No. 5,114,606 U.S.

Pat. is a water-soluble complex of manganese (AV) 4/5 (ID) manganese with a binding molecule that is a non-carboxylate polyhydroxy Ss nell having at least three consecutive 6-011 groups. These molecules include Favorite Links Ve sorbitol sorbitol edulsitol 01 dalcitol cdulsitol mannitol xylitol carabitol Jd,Y xylithol sal cadonitol ariritol meso-erythritol cmeso-inositol lactose clactose and mixtures thereof. It describes US Patent No. 5,114,611 US.

Pat is a bleaching catalyst containing a complex complex of transition metals which include Mn, CO, 18, or Cu with a non-(large)-cyclic bonding Te moiety. These binding molecules have the following formula: it RY J fms me | where are 8 182 RY RP each selected from H and substituted alkyl and aryl groups so that each 07-21 is a pentagonal or hexagonal ring ribs. This ring can also be replaced. And B is a bond group selected from 0 Sc AE”.

“C=O: NR’” CR’R% group being 187 R% and 187 each being an 11, alkyl or aryl group; Including substituted and non-replaced groups. The binding molecules include cpyridine rings pyridazine pyrimidine pyrazine imidazole wll (Js) pyrazole and triazole P8201; Optionally ofa that © replaces these rings with Jie substituents the alkyl aryl caryl _alkoxy allel alkoxy 06 + nitro and the binding molecule oY is particularly preferred ?- pyridylamine bis 2,2 cbispyridylamine Preferred bleaching catalysts include complex compounds of M0 (CuFe «Mn -_pyridyl obispyridylmethane Se fe and pyridyl Se pd .bispyridylamine]. Most preferred catalysts include Co (7?-pyridylamine-bis). Cl (2,2-bispyridylamine 0) and di(isothiocyanato) bispyridylamine-cobalt (1); Y bispyridylamine (0,010,000 bispyridylamine perchlorate bis-(7); = bispyridylamine (bispyridylamine copper (ID) copper perchlorate; Tris(II-)

—Y pyridylamine (di-2-pyridylamine iron (11) and mixtures thereof. Yo) Preferred examples include dinuclear Mn complexes with N-terminal and di-17 tetramer bonding molecules Parties” including (C10) NMn “(u-0)MnVNg”.

bipy2] “Tamatu (0M M-malormen 8). While the compositions of complex manganese compounds catalysts for bleaching materials are not specified in this invention, it can be conceived in terms that they include chelates or complex symmetrically quenched compounds (Ye) that produce From the interference of the carboxyl and nitrogen atoms of the lipid (binding molecule) with the manganese cation (cation 0000887688), similarly; the Ala oxidation of the manganese cation during the catalysis process is not known precisely; and the SS states could be (10+) or (1+) or (+IV) ar L(+V) and due to the presence of six possible contact points in the bonding molecules with the manganese cation, it is reasonable to conclude that the species are polynuclear and/or structures " Cage "Yo" can be present in aqueous bleaching medium. Uy was the form of active Mn-binding molecule types M ye present (Glad) it works in a clear preparative manner to obtain better bleaching performance against stubborn stains such as tea and ketchup stains coffee, wine, juice, etc. Bleach catalysts (cs AY) are described, for example, in EP No. 408,131 (Complex Cobalt Compound Catalysts); and EU0 Patent Applications No. 384,503 5 306,089 (metallic porphyrin catalysts) and US Patent No. 4,728,455 (manganese agents/multilateral binding molecule catalysts) and US Patent No. 4,711,748 US. and patent application EP No. 224,952 dele) manganese adsorbed on aluminosilicate (LSD) and US Patent No. 4,601,845 US. (magnesium aluminosilicate support or zinc manganese salt with manganese aluminosilicate 0 (Manganese agent/catalytic binding molecule) U.S. 4,626,373 U.S. Patent No. (salt complex ferric catalyst) dole) 17.5.4,119,557 U.S. Patent No. 2,054,019 written description (Cobalt grapple agent) catalytic), CAN 866,191 (transition metal-containing salts) and manganese cations (208 materials with US. 4,430,243 manganese cations Ne and non-catalytic_metal_cations) and US 4,728,455 ...11.5 (manganese gluconate catalysts). Other preferred examples include cobalt catalysts (TID) having the formula: for the characteristic 1 010115 1 where cobalt is in the + oxidation state and “ is a number from 0 to © ( He prefers ; OR © (preferably 0) represents 14 one-sided bonding molecules and 0 is a number from zero to 0 (1 is preferred or * is more preferred 1) BY is a two-terminal bonding molecule; 0 is a number from zero to oF is "7 a three-terminal bonding molecule; t is a 0 or a 1; © is a four-terminal bonding molecule; and © is either a zero or a 1; © is a five-terminal bonding part; m is either zero or 1

ANE fe is if one or more anti-anions 1 = “+ m+ 2b + 31+ 4g + 5p and Cr is to ? (preferably ? to 1 is a number of carefully chosen y's that are in a number of not where is an anion with a -1 charge); To obtain a neutral salt y when the charge is X, it is more preferable to nitrate, the chloride charge, and it is preferable to choose 5 from the group consisting of chloride, carbonate, acetate, acetate, citrate, sulfate, sulfate nitrite © nitrate and terminator unions, where at least one of the coordination sites connected to the carbonate with the cobalt is free to move under the conditions of using an automatic dishwasher, and the remaining coordination sites stabilize the cobalt under the conditions of automatic dishwashing so that the reduction effort is volts (preferably less than 1.4 under alkaline conditions less than (ID) cobalt to (ID) cobalt normal hydrogen 7 e volts) in exchange for an electrode (electrode) ordinary hydrogen 00 and have factors Preferred catalytic cobalt of this type has the following form: [00011 (04 Pa Le) is a number from ? to © (preferably more; or 0 is preferred) and [a n is a free coordination crack Mobility; preferably selected from the group consisting of chlorine (1 hydroxide 00106 water and) when 00 is greater than bromine 0 oF or more preferably chlorine 0 oF or 1 to * (preferably 1 and be 00 is a number of cle conjugates (mixtures) of which cy is a carefully selected anti-anion having a nocto number <1 = ma and being 0 (preferably ? When f is an anion of oF to * (preferably ? to 1 number of to obtain a balanced salt.) with a 1- charge The preferred cobalt catalysts of this type used here are chloride salts 0 especially dha, [Co(NH3)SCHYy asad lf cobalt, which originates from [Co(NH3)5C1]CI2). More preferred are the formulations of this invention that use bleaching catalysts of the formula: (ITD) Cobalt [Co(NH3)n(M)m(B)b]Ty Yo

AE

+5 where cobalt is in the +3 oxidation state and «either ; or © (preferably 0) where M is one or more cobalt-coordinating binding moieties in one position and © is zero or 1 YJ (preferably 1) where 3 is a cobalt-coordinating binding moiety in two positions b is zero or 1 (preferably zero) and when b = zero then 0+ = 1 and when 0 is > 1 mm then mm is zero and “ is 4 and T is one or more than suitably selected anti-anions present by the number y where a is a number to obtain a balanced salt (preferably y is 1 to ? and more preferably ? when T is an anion with charge 1- Where this catalyst has a constant base hydrolysis rate less than ?7, mol-1 sec-1 (11 m).

Ve and the preferred 1' is chosen from the group consisting of chlorides; Iodide F-13 formate nitrate nitrate nitrite sulfate csulfate sulfite csulfite citrate BF4- (PF6- bromide am sdl “carbonate “lis SU cacetate MAW” citrate B(ph)4 - Phosphate Phosphite P11 CT 0105_silicates silicate tosylate methane sulfonate cmethanesulfonate and conjugates thereof optionally 0 _ protons can be added to it if_ there is SS of one anionic group present in © such as &l HyPOs- « HCO;-HPO4,- and also can TES from the group consisting of unconventional inorganic anions such as anionic surfactants Jia) straight alkylbenzene sulfonates (LAS) and alkyl sulfates (AS ) alkyl sulfates and alkyl ethoxysulfonates (255)...._etc) and/or Yu-L (Jie) anionic polymers polyacrylates and polymethacrylates

polymethacrylates, etc.). Including moieties 24 but without cand, for example, Tel 042y (SCN- (NCS- PO43- (NH3 «S203-2]) carboxylates are preferably emono-carboxylates but can More than one carboxylate is present in the YO radical as long as the cobalt bond is by only one carboxylate per radical, in which case

ANE

A proton may be added to other carboxylates in moiety 34 or its salt) and optionally (Se) add a proton (10 if GS there is more than one anionic group present in 34 Ba) (HOC(O)CH2C(0)O - <H2PO4- (HCO3- <HPO42- etc.) The decimated M moieties are the ,0-,6-substituted and unsubstituted carboxylic acids having the following formula: -10(0)0 where R is preferentially selected from the group which consist of hydrogen, 0©-,© (preferably:©-,) unsubstituted and substituted alkyl and Co-Cap (preferably unsubstituted and substituted aryl Co-Crg) 0 (preferably 0©-) unsubstituted aryl Substituted and substituted Cua The substituents are : selected from the set consisting of -C(O)OR' "-NR'4 +" NR'3 nap -C(O)NR'2 0 where " 18 selected from the group consisting of hydrogen and m©-,© moieties and these substituted R thus include the 011(.011)- (CHR) NR'4+ moieties where « is a number from 1 to 11 preferably from ? to 01 and preferably from ? to #. 14 preferably are carboxylic acids having the previous formula where 1 is selected from the group consisting of hydrogen (hydrogen 0. methyl cmethyl ethyl cethyl propyl and denatured-e alkyl straight or branched and benzyl and the more preferred 14 is methyl and includes carboxylic acid moieties M preferred formic benzoic coctanoic and nonanoic 007016 and decanoic dodecanoic, maleic, succinic, adipic, phthalic, 2-cthylhexanoic, cnaphthenoic 00, and coleic palmitic terephthalate ctriflate tartrate 10707816 stearic butyric ccitric <b full butyric acrylic and aspartic caspartic fumaric lauric dauric linoleic dinoleic lactic ddactic malic p1l0; Especially acetic acid. It includes the 3-carbonate moieties (carbonate - second - and higher) 'Yo carboxylate' (Mie) oxalate (coxalate) malonate (malic) malic succinate (succinate) malic Ago

(maleate, picolinic acid, epicolinic acid, and alpha-helite amino acids (such as glycine (phenylalanine) for alanine © anine and beta-alanine glycine and cobalt catalysts for the bleaching material used 285523 and described for example) Base Hydrolysis of Compounds 14 1. Tobe Example plus rates of base hydrolysis in 1-5 pp. 7 (1147) “Adv. Inorg. Bioinorg. Mech. Complex Transition Metals” © © Base hydrolysis rates (referred to as 117 on page 1 for example; the table gives compounds with cobalt pentaamine for cobalt pentaamine catalysts (in which KOH is x & KOH) NCS m) and with Y0) 1 sec 1-lom 4-01 * ¥,0 = kOH) oxalate 1-Ovo-oxalate 1-lom 4-01 X 0A KOH) (H “m) ) and with formate 1-enath 1-lum 0 (75 "m)) and the more preferred cobalt catalyst 17 eneath 10-lum 4-01 XAT KOH) and with acetate (pV where [Co( NH3)SOACITY here is the salt of cobalt pentaamide acetate having the formula cobalt pentaamine acetate which is as especially dba;oda moiety OAc [00)01113 (5 plus 2 0)[ed] Co(NH3)50ACc]CI2 (JCo(NH3)50Ac](BF4)2 ([Co(NH3)50Ac](S04) [Co(NH3)SOACc](PF6)2 (“PAC”) [Co(NH3)SOACI(NO3)2 0

ago

These cobalt catalysts were readily prepared using known methods such as those described for example in the article referenced herein by Gil and references therein and US Patent 4,810,410.

Patent No. on behalf of Dayakun et al. published March 1 HEY (VY) 1 “(Y3A4) J.

Chem.

Ed. 74 © 1970 W.L.

Jolly (prentice-Hail; pages )£1—¥¢ ‎(YA «norg.

Chem.

Chem.c (Y3AY) YAAS=YAAY (YY dnorg.

Chem. (Yava) M. “Inorg.

Synth (YAY) YL YoY YY (+471}) « Chemistry journal of (Y40Y) Yo YY «o1 cphysical In addition to the preparation examples mentioned here EY Cobalt catalysts suitable for use in cleaning tablets can be produced in This invention Ve by following the preparation methods described in the US Patent Nos. U.S.

Patent Nos. ¢5,559.26 ¢5,581,005 5,597,936 which are cited as references in this invention. These catalysts can be concomitantly treated with adjuvants to reduce the color effect if required by product descriptions or used in enzyme-containing molecules as represented herein or (Sa) manufacture formulations to contain catalyst "patches". Organopolymeric Compound Organopolymeric compounds may be added as preferred ingredients in the cleaning tablets of this invention, and by Lila organopolymeric compound is meant any organic polymeric compound commonly found in cleaning formulations that have dispersing agents, anti-re-sedimentation, dirt removal, or other cleaning properties. The organic polymeric compound was actually used in the cleaning formulations of this invention at a level from 960.1 to 9670 preferably from 960 ©,960 to 9615 preferably from 961 to 96100 by weight of the formulations Examples of the organic polymeric compounds include polycar- Co-polymeric organic boxylic acids or Aled soluble in YO water and modified polycarboxylates or their salts in which the polycarboxylic acid contains Ago

It has at least two carboxyl radicals separated from each other by at most two carbon atoms. Polymers of this latter type are described in GB-A-1 patent application 6. Examples of these salts are polyacrylates with a molecular weight of 001 and their copolymers conjugated with any other suitable monomer units, including acrylic acids, cacrylic, fumaric, maleic, itaconic, caconitic, cmesaconic ccitraconic, modified cmethylenemalonic acid or its salts, maleic anhydride, acrylamide, cacrylamide, alkylene, vinyl methyl ether, styrene, and any mixtures thereof, preferably polymers Conjugates of wll SY 0 acid and maleic anhydride having a molecular weight of 0000 to Noreen. Preferred and commercially available acrylic acid-containing copolymers having a molecular weight of less than 15,000 include those sold under the trade name PA20. PA30 Solcalm CP10 PA10 PAILS “Molded by Dell oli; BASF under the trade name 45N Acusol :4827 :46011 by Rohm and Haas. vo Preferred acrylic acid-containing copolymers include those containing monomer units: a ) from 96650 to 9600 preferably from 9680 to 9670 by weight acrylic acid or its salts and b) from 9600 to 9690 preferably from 9670 to 9680 by weight substituted acrylic monomer or its salts having the general formula -[(082-081)00 -0-3]- where at least one of the alternatives is 181 or 182 or R3 and preferably RI or R2 is a 0 dS of 1 to ; carbon or hydroxyalkyl group 81 or R2 can be hydrogen and R3 can be hydrogen or an alkali metal salt most preferably a substituted acrylic monomer where 181 is methyl and 82 is hydrogen (ie methacrylic acid monomer (methacrylic acid monomer) and the most preferred concomitant polymer of this type has a molecular weight of Ton and contains from 9660 to 9680 by weight vo-acrylic acid Bot to 96710 by weight methacrylic acid p

Polyamines and modified polyamine compounds are useful here, including those derived from Ju-aspartic acid described in EP-A-2, EP-A-305283 and EP-A-305283 European Invention No. 20-8-351629 [. Other optional polymers may be modified and unmodified JS polyvinyl alcohols 30 polyvinyl alcohols and acetates, cellulosics, modified celluloses, cpolyoxyethylenes, cpolyoxypropylenes, and lie copolymers, both modified and unmodified terephthalate esters of ethylene, propylene glycol, polyoxyalkylene, or mixtures thereof with propylene glycol units (0 numbers, please play). The appropriate FE patents ABN 4490,271 5,597,789 and US patent Nos. 5,591,703 Dirt-removing agents Suitable polymeric dirt-removing agents include those dirt-removing agents having: (1(a) parts one or more anionic hydrophilic components consisting primarily of ve oxy parts (Y) or 1 having a polymerization degree of at least polyoxyethylene polyoxyethylene having a polymerization degree of ? polyoxypropylene or oxypropylene where these hydrophilic parts do not contain any oxy unit propylene unless 01 to is linked to the adjacent cracks at each end by ether bonds or (?) a mixture of oxy units an oxypropylene unit and preferably these contain 01 to 1 alkylene containing oxyethylene and from At least 0 oxyethylene units and more preferably especially for these hydrophilic fractions %Yo% oxyethylene unit or at least 0 oxypropylene units 00 to 71 components having 3© oxyalkylene parts (1(b) one more hydrophobic component containing oxyethylene Lad terephthalate; where; If these hydrophobic components contain terephthalate, then the ratio of oxyethylene terephthalate to 3© oxyalkylene terephthalate units is ?: Yo

Ato

VY

(¥) or less or (7) parts 4-6 alkylene or oxy 04-06 alkylene or mixtures thereof or 1 parts poly(vinyl ester) preferably polyvinyl acetate having at least a degree of polymerization? or 8) (©-,©-alkyl ether substituents or 4©-hydroxyalkyl ethers or mixtures thereof, where these are hydroxy-alkyl or Cy substituents present in the form of cellulose derivatives ©-,© alkyl ether or mixtures thereof or combination of (a) and (b). 0 degree of polymerization (1) in (a) polyoxyethylene the polyoxyethylene moieties have lady 6 preferably from 1091 of 706 although higher levels may be used; Preferably from * to OXY 64-06 hydrophobic alkylene parts include but not limited to; caps 001 to M where MO3S(CH2)NOCH2CH20- Jie terminal of polymeric descaling agents is sodium and is a number of ;-1 as described in Patent 0 by the name of GoSelink Jan 0988 YT in sind) US. Patent US 4,721,580 Gosselink. The polymeric descalers used here also include cellulosic derivatives and templates <hydroxyether cellulosic polymers such as propylene or ethylene terephthalate conjugated to 1 ethylene terephthalate or polyethylene oxide, aa terephthalate, and the like, and such agents are commercially available, polypropylene oxide terephthalate, propylene, dirt removal agents include METHOCEL (Dow), and include hydroxy ethers of cellulose such as alkyl CC The celluloses used here are those selected from the group consisting of cellulose

U.S.A. Patent See US Patent No. hydroxyalkyl and b-hydroxyalkyl To et al. Nicol As Dec 1997/76 VA published in 53 Polyhydrophobic (vinyl ester) soiling agents distinguished by fractions ( Vinyl ester, preferably (CoCo acetate for water, copolymers associated with polyvinyl ester such as multiple polyalkylene esters that have been grafted into the polyalkylene oxide structure (vinyl ester vinyl Ate

7 No Jie oxide structure of polyethylene oxide lb gal, polyethylene oxide EP No. 0.219.048 EP published YY April 1987 as Code Kud et al. Another suitable descaling agent is a polymer conjugate with polyethylene terephthalate and terephthalate (PEO) polyethylene oxide© The molecular weight of this polymeric descaler in ad is from 75,000 to 8 _See_American patent, U.S.

Patent pi) 0 by Hays published YO May 59/76 and US Patent No. U.S.

Patent 3,893,929 as Basadur published in Jul A 975 Another suitable polymeric dirt removing agent is a polyester having repeated Vo units of ethylene terephthalate units containing 9615-01 by weight ethylene terephthalate units together with BATT by weight polyoxyethylene terephthalate units derived from polyoxyethylene glycol having an average molecular weight opr 0-700 Another suitable polymeric desulfurizing agent is the sulfonated product of a completely straight ester oligomer consisting of a basic terephthaloyl isl sill oligomeric ester structure 1, oxyalkyleneoxy repeat units and terminal moieties covalently attached to the structure and these dirt removing agents are fully described in US Patent No.

Patent 4,968,451 published + November 1946 Scheibel and EP. awk 11. Gosselink Other suitable polymeric dirt-removing agents include polyterephthalate esters in US Patent #4,711,730 Patent 11.5 published December A VAAY Yo on behalf of Gosselink associates and oligomeric esters capped by Lah Anionics in US Patent No. 580, 4,721 U.S.

Patent published January 76, 988 as Gosselink and Oligomeric Polyester Compounds in US Patent No. 4,702,857 U.S.

Patent published 71?Oct 87 1_as Gosselink Other polymeric dirt-removing agents include dirt-removing agents in US Patent #4,877,896 U.S.

Patent Ag

Lala, published on Oct 71 4 Maldonado pals 10 and colleagues describe anionic terminally capped terephthalate esters, particularly sulfaroyls. Another degreasing agent is an oligomer with terephthaloyl repeat units, csulfoisoterephthaloyl units, oxyethyleneoxy units, and oxy-Yo-2-oxy-1 propylene repeat units being the basic structure of the oligomer. Preferably terminated with end caps of modified isethiones and the particularly preferred degreasing agent of this type contains one sulfoisophthaloyl unit ©5 terephthaloyl units and one oxy-ethylenoxy and oxy-0a-7-propylencoxy ,2-propylencoxy 07-1 0 ratio ranging from 1.7 to VA and two end capping units of 7-(7-hydroxyethoxy)-ethanesulfonate sodium 2-(2-hydroxyethoxy)-ethanesulfonate heavy metal ion separator containing tablets This invention is preferred over an optional component which is a heavy Sl ion separator. The heavy metal ion separation material here means components that work on separating (forming a chelate Ve complex) the heavy metal ions. These components can have the ability to form chelates with calcium and magnesium, but preferably they have selectivity for binding to heavy metal ions, Ce, iron, manganese and copper. Heavy metal ion separators are generally present at level from 960.005 to 0 preferably from 960.1 to 90010 preferably from 960.709 to 967.5 preferably from 960.9 to 9609 Ye of the weight of the formulations. Heavy metal ion separators can exist; which are acidic in nature; which have for example a phosphonic acid or a carboxylic acid as functional groups; either in its acid form or as a complex compound/salt with a suitable counter cation such as an alkali metal ion, an alkali, ammonium, a substituted ammonium ion, or any other Neo

Vi- It is soluble in water. Preferably ALG mixtures thereof. Preferably any complex salts/compounds

A) The molar ratio of this antication to the heavy metal ion separator is at least

Jie Suitable heavy metal ion separators for use here include organophosphates; 1-hydroxydihydroxy-polyaminoalkylene, alkylene phosphonates, and ethane 1-hydroxy disphosphonates. © 0010 T. The preferred of the previous types are the fifth, trimethylene phosphonates, nitrilo, ethylene diamine, methylene phosphonate, fourth (methylene phosphonate) and third (methylene phosphonate) Diphosphonate -1 Vg methylene phosphonate .hydroxy-ethylene 1,1diphosphonate hydroxyethylene-0 Other suitable heavy metal ion separators for use here include nitrilo polyaminocarboxylic acid Polyaminocarboxylic acids, nitrilotriacetic acid, tri-acetic acid, cethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, ethylenediaminetetraacetic acid, jie acids, and ethylene-diamine pentacetic acid. GY) succinic; And SB amine 1 RE 2-hydroxypropylenediamine disuccinic acid is salts thereof. Alkali or earth metal (EDDS) ethylenediamine-N,N'-disuccinic acid, ammonium substituted for this acid, or mixtures thereof. and compounds or a complex compound thereof. magnesium

ago

Vo. Crystal growth inhibitor ingredient Cleaning tablets preferably contain a crystal growth inhibitor ingredient; An organic %o component is preferably used at a level from 960.01 to lished second acid, preferably from 960.1 to 967 of the formulations weight.

8 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.

An organic diphosphonic acid is a 0-0 diphosphonic acid

“ethylene diphosphonic acid C2 diphosphonic acid, preferably diphosphonic acid 0

Such as ethylene diphosphonic acid or more preferably 1-hydroxy-1-GAY = ethane 1-hydroxy-1, 1-diphosphonic acid (HEDP) can exist In ionized form Toa or in whole and in particular as a salt or compound VO water soluble sulfate salt

The cleaning tablet optionally contains a water-soluble sulfate salt. And if it is present, the water-soluble sulphate salt is at a level from 960.1 to © and more preferably from 961 to 9070 and preferably more than 9659 to 9675 from the weight of the formulations.

x The water soluble sulfate salt can be any sulfate salt with any antication. The preferred salts were selected from the alkali metal sulfates and alkaline earth metals, especially sodium sulfate. Alkali metal silicate

One of the preferred ingredients in the tablet of the present invention is alkali metal silicate. and silicate

11220: 5102 which has a ratio of sodium silicate The preferred alkali metal is sodium silicate Yo

M0

-Y- and Xie is more preferably VE and more preferably from 1.8 to oF up to 1.8 oF at a level less than 9670 and preferably from 961 to Junie Sodium silicate is present in form up to 9617 of weight 9:02. The metal silicate BY and more preferably the alkali FeO can be in the form of either an anhydrous salt or a hydrated salt. as a component of a base system. Thanks to the fact that Lad and alkali metal silicate 8 can be present at the level of sodium silicate, the base system also contains sodium metasilicate by weight. JY sodium meta silicate has a Si02 64 and the weight ratio of this sodium silicate to meta .1 is a nominal ratio of 1820 : 2 of ; ro up to 1 10h that sodium silicate; measured as 5102; preferably from

Yoo to 1 :01 preferably over 1 to ?: 1 :109 more preferably than 0 Colorant The term 'colourful' as used here means any substance that absorbs certain wavelengths From the optical spectrum of the visible light. These colored materials, when added to the cleaning composition, have the effect of causing a change in the visible color and thus the shape of the cleaning composition. The colored materials can be, for example, either dyes or pigments. It is preferable that the colored materials be Ve is stable in the formulation in which it will be used, and therefore, in a formulation with a high pH, it is preferable that the dye be stable alkaline, and in a formulation with a low pH, the dye must be acidic: it may contain The first phase and/or the second phase and/or the following optional phases contain A ghd--a colored substance or a mixture of colored substances or colored particles or a mixture of particles 01 The different phases have different visible shapes. One of either the first or second phases contains a pigment.When both the first and second phases and/or subsequent phases contain a pigment it is preferable for the pigments to have different visible appearances. Examples of suitable dyes include active dyes, direct dyes and pigments azo. : preferred dyes include phthalocyanine dyes, anthraquinone dyes, and quinoline dyes; and mono YO m0

_VVeo anthraquinone dyes; Suni azo, diazo and polyazo. Most common dyes include 96180 SANDOLAN E-HRL, quinoline and monoazo. Favorite dyes include the following

TURQUOISE ACID (trade name) SANDOLAN MILLING BLUE (trade name) (trade name) All available SANDOLAN BRILLIANT GREEN and BLUE HEXACOL QUINOLINE YELLOW 5 from Clariant UK” 5 (trade name) both available from Pointings; KINGDOM HEXACOL BRILLIANT BLUE

LEVAFIX (commercial) available from Holiday or pul) ULTRA MARINE BLUE; (United States commercial) available from the United States of America. pul) TURQUISE BLUE EBA The pigment can be introduced into the phases by any suitable means. Appropriate means include mixing all or some of the cleaning components with the coloring matter in a grinder or spraying all or some of them with the coloring matter in a rotating mill. When the coloring matter is present as a component in the first phase, it is present at a level from 760,001 to 901.9, preferably 960.01 to 961; Preferably over 960.1 even the Lad and when present as a component in the second and/or elective phases. The coloring matter is generally present at a level from 960.001 to 960.1, preferably from Ye .96 0.07 to 960.09, preferably from 960.001 to 5. The corrosion inhibitor compound The tablets of this invention suitable for use in dishwashing methods may contain selected corrosion inhibitors from organic silvering agents; in particular paraffin; in particular MID salts) and nitrogen-containing corrosion inhibitor compounds; And compounds for organic ligand binding molecules. (MnCl) and organic silver coating agents were described in the international patent application No. and the provisional European patent application 690122--50. 7 compounds are described

EP-A- Nitrogen-Containing Provisional European Patent Application No. KH Inhibitor M

VA-10001 compounds were described for use in corrosion inhibition in the patent application.8

EP-A-672.749 European Temporary No. 96100 The organic silver coating agent can be introduced at a level from 960.06 to preferably from 960.1 to 965 of the total composition weight. The functional role of the silver coating agent is to form a protective coating layer during °o use" or any silver components in the laundry load in which the compositions of the present invention are placed. The silvering agent must therefore have a high attraction bond to the solid silver surfaces; particularly when in the form of a component of the aqueous wash and bleaching solution with which solid silver surfaces have been treated. Suitable organic silvering agents include fatty esters of monoalcohols or Ye carbon atoms in the hydrocarbon chain. Ee to 1 polyhydroxyl fatty acid fraction in the fatty ester can be obtained from mono-acid or to 56 300 carbons in the hydrocarbon chain 1 polycarboxylic fatty acid 'hydrocarbon monocarboxylic fatty' Suitable examples of fatty acids include monocarboxylate yo, oleic acid, estearic acid, behenic acid, behenic acid, cmyristic acid, palmitic acid, coleic acid “propionic acid,” cacetic acid, and acetic acid Cauric acid, cisobutyric acid, isobutyric acid, glycolic acid, glycotic acid 1802 acid SLi, and valerie acid 0. Examples include dihydroxyisobutyric acid. BP isobutyric acid and succinic acid Suitable polycarboxylic acids maleic acid maleic acid citric acid dsocitric acid succinic acid maleic acid succinic acid cacid

Ao

The fatty alcohol moiety of the fatty ester can be represented by mono or polyhydric alcohols having a 1 to Er carbon in the hydrocarbon chain. Examples of suitable fatty alcohols include cbehenyl, carachidyl, and cocoyl-71; vinyl alcohol, diglycerol, xylitol©, sucrose, erythritol, erythritol, sorbitol or sorbitan, preferably with a fatty acid group and/or a fatty alcohol The lipid ester catalyst 1 to YE has a carbon atom in the alkyl chain. The preferred fatty esters, Ua, are ethylene glycol esters; 0 and glycerol; and sorbitan, where the fatty acid fraction of the ester sale contains selected varieties of behenic acid, stearic acid, coleic acid, palmitic acid, or myristic acid. Glycerol esters are also highly preferred. These are the mono-, di-, or tri-esters of the glycerols and fatty acids described earlier. Specific examples of esters of fatty alcohols used include cla, by cstearyl acetate, palmityl di-tactate, cocoyl isobutyrate, JG coleyl maleate, coleyl dimaleate, and talyl propionate. tallowyl proprionate Esters of the fatty acid used here include: xylitol monopalmitate, ye pentaerythritol monostearate, sucrose monostearate, glycerol monostearate, ethylene monostearate Cethylene glycol monostearate and sorbitan esters, including sorbitan Cl. Aid) sorbitan esters sorbitan monostearate sorbitan palmitate sorbitan monolaurate yo sorbitan monostearate Ago

sorbitan monomyristate sorbitan monobehenate sorbitan mono-oleate sorbitan dilaurate JSG sorbitan stearate 0101180; Sorbitan “sorbitan dioleate” and also the esters

0 mono- and di-alkyl sorbitan blended. glycerol esters; The favorites here are glycerol monostearate, glycerol mono-oleate, and glycerol palmitate. glycerol monopalmitate and mono. Glycerol behenate

.glycerol distearate and glycerol distearate “glycerol monobehenate

Suitable organic silvering agents include triglycerides, mono- or diglycerides and their hydrogenated derivatives, GIS or Goa, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable oils, fish oils, and animal fats. Suitable vegetable oils include soybean oil, cottonseed oil, castor oil, olive oil, peanut oil, yarrow oil, sunflower oil, rapeseed oil, grapeseed oil, and palm oil.

Ne and corn oil.

The waxy materials are; Lay contains fine crystalline waxy materials, suitable organic silver covering agents here, and the preferred waxy materials have a melting point in the range from 2270 to 0 C, and usually contain 11 to 10 carbon atoms. Long-chain saturated hydrocarbons.

Y. Alginate and gelatin are suitable organic silvering agents here. Diakylamine oxides such as Cpp-Cop methylamine oxide and quaternary dialkyl ammonium compounds and its salts Jia halides Cpp-Cop methylammonium are also suitable here.

Other suitable organic silvering agents include some polymeric materials. Polyvinylpyrrolidones, which have a molecular weight of

1.1 05 to 0.8586 and polyethylene glycols (PEG) which have

m

SAY - 0s Rusk molecular Oe 300 to 000001 and ND polyamine oxide polymers (N-oxide polymers _and copolymers. Jad -N) copolymers Pyrrolidone 11-01017011008 .L2-._vinyl N-vinylimidazole and its cellulose derivatives Jie cellulose, Jie arboxymethylcellulose©, and hydroxyethylcellulose are examples of such polymeric materials. And some aromatic substances are; Especially those that show high stability on metallic surfaces; Also useful as an organic silvering material here. (Say) using Lad polymeric silvering agents as organic silvering agents. Z 0 The preferred organic silvering agent is paraffin oil which is actually a branched aliphatic hydrocarbon with a number of carbon atoms in the range 0 to + 9 The preferred paraffin oil was chosen from the 025-45 permanently branched species having a ratio of cyclic to acyclic hydrocarbons from 01:1 to ?:1 and preferably from 1:5 to .1. 1: Paraffin oil, which has these characteristics, and which has a ratio of cyclic hydrocarbons (Ye) to LA (TA YY Agha) is sold by Wintershall Salzburg, Germany under the trade name WINOGT70 Corrosion Inhibitor Compounds Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and its derivatives Jie benzimidazole and 7-heptadecyl imidazole 2-heptadecyl imidazole and imidazole derivatives 0 those described in Czech Patent No. 139,279 and UK Patent Application No. 137,741 GB-A-1, which describes Lad method for the preparation of imidazole compounds .: The suitable nitrogen-0-containing corrosion inhibitor compounds for Lad are benzotriazole compounds and their derivatives, particularly those which are substituted with pyrazole In Yo any of the positions 1 or ? or; or © with alternatives 141 R35, 184 and 1805 where RI is any of 11 or Ato

CONH3 sl CH20H or COCH3 and R55 R3 are any of the “and ©-,© alkyl or hydroxyl and 184 are any of the H, NH2 or NO2 dedi corrosion inhibitor compounds containing Other suitable nitrogens are benzo triazoles 02008206—Y-mercaptobenzothiazole “2-mercaptobenzothiazole and \— phenyl-#k-© mercapto-E FX ;- tetrazole ¢1-phenyl-5-mercapto-1, 2,34-tetrazole, cthionalide, amorpholine, melamine, cdistearylamine, cstearoyl stearamide, cyanuric acid, caminotriazole, and aminotetrazole and indazole. Ammonium sulphate or diammonium hydrogen citrate is suitable for use here. VO corrosion inhibitor compounds (11:001 cleaning tablets can contain corrosion inhibitor compound Mn(ID) and MID compound can be used preferably at a level from 960.005 to 968 by weight and preferably from 966.51 to 961 preferably_from 960.07 to 960.4 lbs. of combination weight. It is preferable to use the MIT compound) at a level to obtain 1 ppm until You are ppm Yo a million and preferably from 15 ppm up to 50 ppm and preferably from 1 ppm Up to Te ppm by weight of Mn(ID) ions in any bleaching solution. Mn(TD) may be an inorganic salt in anhydrous or hydrated forms. Suitable salts include manganese sulphate 08080656, manganese carbonate, and manganese phosphate. nitrate YO, manganese acetate, and manganese chloride. Age

_AY-

The MID compound can be a salt or a complex of an organic fatty acid such as manganese acetate or manganese stearate.

The Mn(lD) compound can be a salt or a complex of an organic binding molecule. In one preferred embodiment the organic binding molecule is an LED metal ion separator

© In another preferred embodiment, the organic binding molecule is a crystal growth inhibitor.

Other corrosion inhibitor compounds

Other suitable additive hie compounds include .mercaptans and diols, particularly mercaptans with ; To a carbon atom including lauryl mercaptan and 1-thiophenol [sampled; And Althiongul «thionapthol

0, thionalides 2006 and the appropriate thioanthranol. Lad are Cip-Cop saturated or unsaturated fatty acids or their salts, in particular aluminum tristearate, which are: © hydroxy fatty acids or its salts are also suitable. An octadecane phosphanate and other antioxidants such as gall hydroxytoluene (BHT) betahydroxytoluene are also suitable here.

yo Conjugated polymers of butadiene and maleic acid, particularly those obtained under reference name YAY by Polysciences Inc., have been found to be particularly useful as corrosion inhibitors. Hydrocarbon oils Another favorite cleaning ingredient to use in this invention is oil.

aliphatic hydrocarbons aaa and actually hydrocarbons chydrocarbon oil Ve or to 00 carbon in the range from permanently long-chain ld that has a number of the preferred hydrocarbons are saturated and/or branched and the preferred hydrocarbon oil was selected 01:1 having a cyclic to acyclic hydrocarbon ratio of Ll of 025-45 branched species and the preferred hydrocarbon oil is paraffin. And oil 1:1 to #5:1 and preferably from 1:1 to #5

‎Ate

“AE- paraffin that meets the above descriptions and that has a ratio of cyclic to acyclic hydrocarbons WINOGT70 Germany in the name of Salzbergen “Wintershall” is that sold by TA 7 water soluble bismuth compounds can The cleaning tablets in this invention that are used in water-soluble washing-up liquids, preferably in dishes with bismuth, contain bismuth compound EO 960.1 at a level of 760.005 to 9670, preferably from 960.01 to 0%, preferably more than From the weight of the formulations. 901 up to any salt or lala, and the water-soluble bismuth compound can be a complex compound of bismuth with any inorganic or organic counter anion, and bismuth salts and bismuth nitrate were chosen The preferred inorganic bismuth trihalides are bismuth trihalides. Bismuth phosphate and bismuth nitrate are the preferred salts with an organic anti-anion 2. Bismuth acetate and citrate are the enzyme stabilization system.

Golo Preferred enzyme-containing formulations can contain 960,001 up to and preferably 960.006 up to 968 and preferably 960.01 up to 967 by weight of an enzyme stabilization system. detergent. These stabilized systems can contain carboxylic acid, propylene glycol, boric acid, and chlorine bleach; and mixtures thereof. Mises cboronic acid short chain; and boronic acid protease inhibitors Jie contain Lal reversible enzyme inhibitors These stabilization systems can contain reverse Yo. The lime soap dispersant The tablets of this invention may contain the lime soap dispersant preferably 961 It is present at a level from 960.1 to 96460 by weight; more preferably than of the weight of the fittings. 90010 of the weight; Preferably over 9167 to Ye to TO

XE

_Ao- and lime soap dispenser is a substance that prevents precipitation of alkali metal salts, ammonium, or amines of fatty acids by calcium or magnesium ions. The compounds 08877/17093. preferred lime soap dispensers are described in the international patent application No. foaming inhibition system preferably containing cleaning tablets subject of this invention; when configured for use in ° machine-washing formulations; on foam inhibition system located at level from 960.01 up to 0% by weight of the formulation. 960.1 preferably from 9060.09 up to 01096; More than 0 is preferred and suitable antifoaming systems for use herein may include any antifoaming antifoaming compound; silicone silicone compounds (eg JB led as Ll is known) and alkanol 1 antifoaming. Inhibition systems for 2-alkyl alkyl —Y and No. 0 Adel pl fal foam compounds are described in the salad patent application for preferred foams and compounds.

EP-A-705 324 and EP No. 6 Polymeric Dye Transfer Inhibitors Preferably from 9600 Cleaning tablets here can also contain from 960.01 up to 960.0 by weight of Transfer Inhibitors Polymeric Dye.‎ 960,05 Ve

N polymeric dye preferably from JE polymers and inhibiting agents for copolymers and conjugate polymers “polyamine N-oxide polymers” (N-vinylimidazole vinyl imidazole -Ny N-vinylpyrrolidone pyrrolidone dad -N) or combinations thereof polyvinylpyrrolidonepolymers and polyvinylpyrrolidone copolymers optical brighteners Yo Detergent tablets suitable for use in laundry washing methods specified Hana optionally contain 960,006 to 968 by weight Certain types of optical brighteners Hydrophilic. Hydrophilic photoluminescent materials used here include those that have the structural formula:

Ao = S Hy SOM HRM Rr!

Where 181 collage anilines are selected; ~V-N-bis-hydroxyethyl-11-2-018 –Y-NH; hydroxyethyl dug (NH-2-hydroxyethyl R2 choice of 1-?-bis-hydroxyethyl —Y-Ny N-2-bishydroxyethyl hydroxy N-Jfl methyl© amino «N - 2-hydroxyethyl-N -methyl amino, cmorfilino, chloro, amino 00l; M is a cation forming the salt Jie sodium or potassium .and in the formula the previous; when 11 is a canilino and R2 is -2-bis-hydroxyethyl N-2-bishydroxyethyl and 14 is a cation such as 0 sodium the polish is acid 4;;'bis[(4-anilino-7-(10 -7-bis-hydroxyethyl)-5-triazine-?-yl)amino]-7;7"-disulfonic stilbenes[-bis[(4) -anilino-6-(N -2-bis-hydroxyethyl)-s triazine-2-yl)amino ]-2,2'- "4.4 stilbenedisulfonic acid and disodium salt This special polishing material was marketed Traded under the trade name \o Tinopal-UNPA-GX by Ciba-Geigy Corporation, Tinopal-UNPA-Gx is the preferred hydrophilic photoluminescent polishing agent for use in cleaning formulations here. And in the previous formula when RI is an anilino and 2 is “YN hydroxyethyl —Y-N-methylamino My N-2hydroxyethyl-N-2-methylamino is a Jie cation sodium, the polishing agent is the disodium salt of 8(40-bis[(4?-anilino-11-7-?-hydroxyethyl-17-methylamino)-5-triazine-?-yl)YY iad stilbene disulfonic acid 4,4'-bis[(4-anilino-6-(N-2-hydroxyethyl- N -methyl amino )-s-triazine-2- yl)amino] 2,2'stilbenedisulfonic acid disodium salt AE».

_AV- Trade name This particular Cad is commercially welll Bale qiust and Ciba-Geigy was developed by Ciba-Geigy Corporation. Tinopal-3BM-Gx and 2 are anilino anilino RI be Laie In the previous formula, the sodium substance as the sodium cation is an M cation and is a morphilino morpholino ;'-but [(©-anilino-7-morpholino-5-: of of an acid sodium salt Polishing forms the sodium salt 5 triazine-?- yl)amino]-? ; '- Stilbene disulfonic. 4,4'-bis[ ) 4-anilino-6- morphilino-s- triazine- 2-y I) amino ]2,2'stilbenedisulfonic acid. by Tinopal-AMS-Gx and this special polishing material is commercially marketed under the trade name Ciba Geigy 0 Baby Smoothing System Detergent tablets suitable for use in laundry detergents may contain a Smoothing System Clay that contains a clay mineral compound and an optional clay agglomerating agent. Smectite

U.S.A. Pat. Nos. The loess smectite materials were described in US patent numbers NO. European patent applications describe 4,062,647 3,954,632 3,948,790 8 Gamble factors and Procter EP-A-313,14 5 EP-A-299,575 Suitable organic polymeric agglomerate numbers. Cationic Fabric Softener Jul go Cationic Fabric Softeners can be used in the compositions described in this invention Y. Suitable for use in laundry washing methods Suitable cationic fabric softeners include Amines The water-insoluble ternary or long-chain diamine substances described in GB-A-1 514276 Application No. EP-B-O 011 340.

AE

-AA-

Cationic fabric softeners were actually used at total levels from 960.5 to 959 wt and usually from 961 to 968 wt. Other optional components

Other optional ingredients suitable for use in formulations of the present invention include:

0 Aromatics and shall salts with sodium sulfate being a filler salt. Ag

pH 011 for formulations The cleaning tablets in this invention are not preferably prepared to have an excessively high pH but rather have a pH measured as a solution of 01 in a distilled substance from A to VY 0 preferred from 9 to OVA preferable from 4.59 to 1.9. One of the favorite ways to wash dishes in a machine includes the handle of dirty items chosen from crockery; and vitreous; silverware; And metal tools, knives, and mixtures thereof by means of an aqueous liquid with an effective amount of the cleaning tablet dissolved or disintegrated in it, and it means an effective amount of 0 cleaning tablet from A g to 260 g of the product dissolved or dispersed in a washing solution whose volume is from © to ‎ 10 liters in Ulad product dosing or washing solution volumes commonly used in standard machine dishwashing methods. Vo cleaning tablets are preferably from 0g to 56g in weight and preferably from 01g to 2g in weight. Vo Laundry Method The washing methods herein include treating the soiled clothes with an aqueous rinsing solution in a washing machine with an effective quantity of dissolved or crushed laundry detergent tablet in the machine described in this invention and an effective quantity of detergent composition a is from 560 g to 0g of product dissolved or dispersed in the wash solution which is dana from © to 65 liters in the form of actual product doses and wash solution volumes typically used in standard Yo Yo machine wash 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 before the start of the washing cycle. It will be used in the usual washing method. Ago

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 drum rotation shall be started cyclically and the release device shall be designed to prevent the dry cleaning product from spreading. However, this product is then allowed to be released during the wash cycle as a response to its vibration 0 whenever the drum is rotated and also as a result of its contact with the wash water. To allow the cleaning product to be released during washing, the machine may have a number of holes through which the product can pass. Alternatively; The device can be made of ale that is idl permeable but impermeable to the solid product, which will allow the release of the dissolved product. It is preferable that the cleaning product be released quickly at the start of the washing cycle, thus obtaining 0 temporary local high concentrations of the product in the drum. in the washing machine 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. Alternatively; The release device may be a flexible container (Jie bag or Ne bag) and the bag may be of fibrous construction and covered with an impermeable material which retains the contents such as that described in EP No. 0018678. Alternatively; They may consist of a non-ALE water-soluble synthetic polymeric material with an end plug or sealing device designed to rupture in aqueous media such as those described in EP Nos. 0011500 0011501 0011502 0011968. The usual form consists of say 08 collapsible A water-soluble adhesive applied across a hose seals one edge of a pouch consisting of a water-repellent polymeric film such as polyethylene or polypropylene Examples Abbreviations used in examples: Yo in formulations Cleaning The abbreviated component definitions have the following meanings: F /

STPP Sodium tri polyphosphate lig S Sodium hydrogen carbonate Bicarbon Anhydrous Citric acid Citric acid Anhydrous sodium carbonate Carbonate Amorphous Sodium Silicate Silicate (Y = Na20: Si02) Crystalline layered silicate of formula SKS-6 5112251205 Sodium perborate monohydrate PB1 Anhydrous sodium perborate monohydrate 5-or) Jay alcohol to which an ethoxylated / | Non-ionic propoxylated has an average ethoxylate grade of FA and an average propoxyl grade of £0.0 Sold under the trade name plurafac by BASF TAED Tetraacetyl ethylene diamine -1-ethane acid 0-Discordia-1-diphosphonic HEDP Ethane 1-hydroxy-1,1-diphosphonicacid Pentaamine cobalt acetate PAAC (I) Pentaamine acetate cobalt (III) salt Paraffin oil Sold under the brand name 70 Winog by Paraffin Wintershall Proteolytic enzyme Protease Amylolytic enzyme Amylase BTA Benzotriazole Sodium sulfate anhydrous Anhydrous sodium sulphate Sulphate AE

Polyethylene Glycol Molecular Weight PEG3000 | Lf all Yoo from Hoechst Polyethylene Glycol with a molecular weight of approx. | PEG6000 0 available from Hoechst was measured as a solution of 961 in distilled water at 0 then pH and all levels in the following examples were estimated as parts by weight. Examples 1-17 The following shows examples of the cleaning tablets in this invention suitable for use in dishwashers. L « ale w rrp ln STPP 7 7 0 q,0V q,0V 1Y,8V Yo Ye Y, 6s mira L 84 silicate Y,Yo A6 5 SKS-6 6 P 04 ¥ M L L G CARBONATE HEDP SYA YA SYA +, YA +, YA +, YA M A M M M M PB1 Y,¢0 Lenk K MM L "YH L PAAC SAR SA YoY AY GATT amylase ved ved vd tam tyre protease 0 ra 1% Gia “A A” non-ionic PEG6000 of +11 +, v1 +, YA va “Ya m BTA vet ot ef ve m Vo) VA eh Vo RY paraffin oY GY VY VY a oY aromatic substance Ate

Lay

Coes ||| Teer] ee Dea GM sting Amylase 0 "5 P" CY "8 P Protease 8 YY OY VY YY VY Citric Acid LY oY A SA L L Sulfamic acid Qm bicarbonate 8 fo s bitter “to 5 H 0 silicate carbonate Vg VE

CaCl2oY ov

PEG3000 oe ved el vel FER passed The multiphase disc assemblies were prepared as follows. The cleaning composition was prepared by mixing the granular and liquid components and then passing them inside the mold in a 1-phase effective piston.

XY is a regular rotary. The piston includes a hammer shaped to form a mould. The mold section is approximately mm and the composition was then subjected to a compressive force of 460 kg/cm. Then the tamper was lifted to expose the first phase TA in the disc containing a mold on its upper surface. The effective cleaning composition 5 was prepared in the phase ? In an inclined manner and passed it into the mold, then the effective particulate composition was subjected to a multi-phase piston of pa ll kg name, then the pestle was raised and 176 was extracted to the compressive strength

VY through Gil the tablets and the resulting tablet dissolved or crumbled in a washing machine as described min; Whereas phase 7 of the tablets dissolves within minutes. The tablets are given excellent dissolution and cleaning properties as well as good cohesion and tablet strength. 0 b

Claims (1)

-q0- protection_elements 1-1 multi-phase detergent tablet A multi-phase for use in a machine A washing that consists of: ” ) Ji phase having a formed body having at least one die in it; the formed body is prepared at pressure ; Compression from about 400 km/cm to about 0001 kg/cm W 25b A second phase in the form of a compressed body is present in a sticky manner inside this mold and then pressed a Second stage at a pressure from about 2 kg/cm Y to less than You kg/cm L Y where the tablet composition has one or more cleaning actives concentrated as A permanently in the second phase; and where the second phase additionally has the binder. 1 “- multi-phase detergent tablet A multi-phase as in claim Y 3 where one or more effective cleaning agents are selected from the group consisting of: andl ¢ ¥sa cbleach activators —bleaches bleaching agents 1 “chelating agents Ja so surfactants J sell bleach catalysts ¢ and mixtures thereof crystal growth inhibitors sail retardants © 1 ?- A multi-phase detergent tablet A multi-phase as in claim 1 1E where the binder is selected from the group composed of: sugar and csugar derivatives ¥ starch ostarch, starch derivatives, organic and inorganic polymers jad 4-1 The multi-phase detergent tablet should be cleaned as in the protective element Y-1 where it contains In addition, there is a separator phase between the first and second phases. Ag 1 *- Detergent tablet A multi-phase as in the protective element EY, where the separating layer contains a binder that has been placed in the liquid form. 1 >< A method for washing dirty clothes or table linens in a washing machine that includes feeding X the washing machine one or more multi-phase cleaning tablets according to item 1. 1 7- Method as in item 1 where The Y multi-phase detergent tablet dissolves or disintegrates in as little as 11 minutes in a dishwasher or washing machine. AE