SA99200727B1 - detergent tablet - Google Patents

Abstract

Abstract: This invention relates to a multi-phase detergent tablet consisting 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 present in an adherent manner inside this mold, where the second phase contains an enzyme Multiphasic tablets give better dissolving and cleaning properties with excellent tablet strength and cohesion.

Description

The Detergent tablet Full Description Background of the invention:- This invention relates to multiphasic Detergent tablet. It is also related to cleaning formulations in the form of tablets known in this field. It is known that cleaning formulations in the form of tablets have many advantages over cleaning formulations in particulate form, such as the ease of estimating the dose; use; transportation and storage. Detergent tablets are generally prepared by pre-mixing the components of the cleaning formula and forming the mixed cleaning components Gre into tablet form using any suitable A; A tablet press is preferred and Glad tablets are formed by compressing the ingredients of the cleaning formula so that the resulting tablets are strong enough to withstand use and transportation without permanent damage. 0 In addition to being strong; Lad tablets must 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. any way; There is a clear division in that the greater the compressive strength (pressing); The dissolving rate of the tablets will be slower. Thus this invention seeks a way to find a balance between the strength of the tablet and the melting of the tablet. yo was the solution to this problem; As shown in the previous field; It involves compressing the tablets by compression. Compression is low and despite this, the tablets manufactured in this way; Although it has a fast melting rate, Gad, it has the ability to be friable; It becomes invalid and unacceptable to the consumer. Other solutions include preparing the tablets using a large compressive pressure Laat in order to obtain the required level of dill and containing a dissolution aid; Yo is like an effervescent agent. The multi-phase cleaning tablets described above were prepared by pressing a first composition in a tablet press to form a completely flat first layer. Then a formula was put to clean 'yr's mouth

another to the tablet press on top of the first layer. This second composition was then pressed to form another flat second layer 0 Lila and thus the first layer is generally subjected to more than one compression since it is BERN compressed by the second composition. In fact, the first and second compressive forces are equal in magnitude. The applicant has found that when this is the case because the compressive force (compression) should be sufficient to bind the first and second fittings together, the force used in both the first and second compression steps should be in the range from about to about 70.0060 kgf (assuming that The cross-sectional area of the disk is about 10 cm). This results in a slower rate of dissolution of the tablet. Other multiphasic tablets with differential melting were prepared so that the second layer was compressed with a lower force than the first layer. 0 Despite this, although the rate of dissolution of the AEN layer has improved; The second layer will be

Smooth compared to the first layer and therefore more susceptible to damage resulting from use and transportation.

European Patent No. 0.055.100 EP shows a cleaning block (sink) formed by combining a slowly melting formed body with a tablet. The cleaning block is designed to be placed inside the cleaning container and left to dissolve for several days. Preferably weeks. And as a way to reduce the melting rate

QE Ye cleaning. This description includes the mixing of one or more dissolution control agents. Examples of dissolution control agents include paradichlorobenzene, waxes, fatty acids, long-chain alcohols, esters derived from them, and fatty alkylamides. intended for use in a laundromat or automatic dishwashing La in one cycle of Ye washing or in a dishwashing machine in vo to 171 minutes General description of the invention:- Gila for the first embodiment in this invention; Providing a multi-phase cleaning disc for use in a washing machine, as the disc has a weight of about 115 to 500 gm and consists of: (i) 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 located in an adhesive way inside this mould

And the second phase was formed from the solid microparticle; weighs less than 4 g and contains an enzyme and in preferred embodiments; The first phase shall be a compressed formed body prepared at an applied compressive pressure of at least about 0 lb/cm; Preferably at least about 150 kg / Cn and more preferably at least about You kg / TET) Com kN / (fp) and more and more preferably ranging from about 5060 to about Ten and especially From about 0 to about 1701 kg/sm (compressive pressure here is the force exerted divided by the cross-sectional area of the disc in a cross-sectional plane with the force exerted - al the cross-sectional area of the die in the rotary press). The particulate solid 0 of the second phase (this term is intended to include the possibility of multiple “Al” phases sometimes referred to here as “optional subsequent phases”) is compressed into this mold at compressive pressure applied lower than that exerted In the first phase, preferably at compressive pressure less than TO kg/cm, and preferably in the range from about Er kg/cm to about 706 kg/cm, and more preferably from about 01 to about YY kg/cm and be These discs are preferred for use here in that Ve gives the best disc adhesion and strength (measured for example by the Shield Pit strength test).

[685]) and better melting characteristics of the product. The discs of this invention shall have CBS at least of about 1 kg and preferably greater than about A kg; more preferably greater than about 10 kg; particularly greater than about 11 kg; It is particularly preferred that it be greater than VE kg; CBS is measured by US Consumer Product Safety Commission testing specifications. 0 Also, the compressive stresses exerted on the first and second phases are generally in a ratio of at least about ?,1: 1, preferably at least about ?: 1, and more preferably at least about 4: A, and accordingly; According to what came in another embodiment of this invention: a) a first phase is prepared at a compressive pressure of at least about You kg/Sm and YO __ b) a second phase is compressed at a pressure less than about You kg/Jos AYA

And the second phase is in the form of a compressed or shaped body that exists in an adherent manner. for example by physical or chemical adhesion; Within at least one mold in the first body, preferably also in the first two stages. the second is in a high weight ratio Gad relative to each other; ie at least about 1 : 1 and preferably at least about Ove Lady© It is preferable that the tablet formulation contain one or more active cleaning agents (eg 88m enzymes, (andl) and bleaching activators; and catalysts of materials (andl, surface activators, chelating agents, etc.) that are permanently concentrated in the eA phase, for example, JB, at least by about (Foo, preferably at least by about 9668, and in particular 96806 by weight of the material Abd (depending on total weight of active substance in 0 tablet) in the second tablet phase. Again, these formulations are the best for obtaining the properties of cohesion, dissolution, cleaning, and pH regulation of the tablet for, for example, tablet formulations. Able to dissolve in the washing solution so that it gives at least on and preferably at least STs and more preferably at least 9680 by weight of the detergent active substance to the washing solution within 01 or © or ; or until * minutes from the start of the washing process. Ve and preferably the tablet such that it is at least 0% and preferably at least S07 and more preferably at least 9680 by weight of the enzyme reaches the wash through; first 0 minutes; preferably within the first © minutes; More preferably during the first minutes of the washing process. An additional benefit of this invention is the ability to obtain a differential melting of 0 phases such that one phase of the tablet melts substantially prior to the AY phase) and Lela GS can even melt prior to the other phase melting. This is particularly useful for differential delivery of detergent actives. Accordingly; By another preferred embodiment of the invention the second phase additionally contains a binder. mouth

+ The enzyme's activities enhance cleaning during the initial cold water phase of the wash or cleaning process. For a more favorable use, therefore, an active enzyme-6 detergent, special enzymes, and enzyme mixtures contain enzymes with optimal or increased activity in a temperature range from #© to 2200 and at a pH value in the range © of M to 01 (eg. (Natalase) Description | For more details: - The aim of this invention is to obtain a cleaning tablet that is not only strong enough to withstand use and transportation, but Load has at least a large part of it that dissolves quickly in the washing water For rapid delivery of the active detergent. It is preferable that at least one phase 0 of the tablet be dissolved in the washing water during the first ten minutes, preferably five minutes. It is more preferable that the first four minutes of the wash cycle in an automatic dishwasher or in the sink. It is desirable that it be The washing machine is either a washing machine for dishwashing SGT a washing machine in the laundry The time during which the polyphasic tablet or phase of it or its active detergent component dissolves Gh to 0 was determined using a dishwasher available from Bosch set at Vo normal wash program at 710 with ele hardness at 918 H using on GY six multipliers or enough number to obtain identical results. The multi-phase cleaning disc in this invention contains a first phase, a second phase, and optional subsequent phases. The first phase is in the form of a body formed for the cleaning composition containing one or more cleaning components as described later. Includes 0 favorite cleaning ingredients. Building material (a substance added to strengthen the cleaning performance), bleaching agent, enzymes and surface activators. The components of the cleaning formula are mixed together by means of; ie Mix dry ingredients or mix by sprinkling liquid ingredients. The components were then formed into the Jf phase using any suitable machine; but preferably by compression; For example in a tablet press. Alternatively; The first phase can be prepared by extrusion; Or by pouring into cd Yo etc. The first phase can take many stereoscopic shapes, such as spheres and cubes. 4 pm

except etc. But the preferred embodiments have a generally axially symmetric shape with a generally circular, square or rectangular section. The first phase was prepared so that it contains at least one template on the surface of the formed body, and the template or templates (Lad) may differ in size, shape, and their location, orientation, and their location dually for the first phase. for example; The mold or dies can generally be circular; square or oval in section; They may be a Lal-related vacuole or cavity on the surface of the formed object; or they may extend between discontinuous regions of the surface of the body (eg JE, axially opposite facial surfaces) to form one or more 'holes' in the shaped body; They may be positioned symmetrically or axially with respect to the first prophase or they may be positioned asymmetrically. In a preferred embodiment the mold is made using a specially designed disc press (Cus) the surface of the pestle in contact with the cleaning composition is shaped so that when it contacts and compresses the cleaning composition it compresses a mould; Or multiple dies in the first phase of the multi-phase cleaning disc. preferably; The mold should have a concave inward or concave surface in general to obtain improved adhesion of the second phase. Alternatively; The die can be made by means of 59 body presses made of cleaning compound placed in an annular shape around a central die; Thus forming a molded body with a cavity in the form of a cavity that extends axially between the opposite surfaces of the body. The tablets of the invention include one or more additional phases prepared from a composition or compositions containing one or more of the described cleaning components Gay and preferably at least one phase (hereinafter referred to as a second phase) taking the form of a solid 0 particulate matter (this term refers to “powders” and granules; agglomerates; and other particulate solids with mixtures thereof with liquid binders; refractory solids and sprayables; etc.) pressed into/through one or more in-phase molds The first phase of the cleaning disc so that the second phase itself takes the form of a formed body. Optional other phases include one or more compositions in the form of a separate layer or layers. Preferred cleaning ingredients include builders, “asks,” binders, and surfactants; fragmentation agents and enzymes

aya

M

enzymes in particular amylase enzymes and proteases and in another preferred embodiment of this invention the second and subsequent optional phases contain a disintegrating agent which may be selected from either a disintegrating agent or an effervescent agent. Suitable dissolving agents include agents that swell on contact with water or facilitate the entry and/or exit of water by creating channels in the cleanout opportunities. Any known fizzing or fizzing agent suitable for use in laundries or dishwashers is conceptualized for use here. Suitable fizzing agents include starches (eg natural; modified; and cpregelatinized limes such as those derived from corn, rice and potato); starch derivatives – such as U-Sperse (trade name): Primojels (trade name); (sled aul) explotabs and celluloses”; microcrystalline cellulose Ye; cellulose derivatives Arbocel Jia (vivapurs (trade name) (sled) both available from Nymeely pul) are available from Metsa-Sirla Avicels (trade name); LatticeNT (trade name) and Hanfloc (trade name); alginate; acetate trihydrate; burkaite and carbonate monohydrate formula STEP NayCO3 HO aqueous with phase content [at least about 70580] and carboxymethylcellulose (CMC) Vo, CMCbased polymers CMC, sodium acetate, aluminum oxide Suitable fizzing agents are those that produce gas when in contact with water, and suitable fizzing agents can be materials that give off oxygen or nitrogen dioxide or carbon dioxide. Examples of suitable fizzing agents can be chosen from The group that consists of perborate, percarbonate, carbonate, and bicarbonate in combination with carboxylic acids or other acids, Umea Jie, citric acids, sulphamic acids, or malic or malic acid

maleic acid

AY 4

The Ge cleaning composition components are mixed by eg mixing the dry ingredients and by mixing or spraying the liquid ingredients. Then the components of the second phase and the optional tertiary phases were charged inside and trapped inside the mold provided by the first phase. The preferred embodiment of this invention contains a first-phase cosh and a second-phase cosh the first phase naturally consists of a single block and the second phase naturally consists of a single active cleaning composition. 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. In addition to ells, Lid envisaged that the second phase could contain more than one active cleaning formulation contained within a single mould. It was also envisaged that multiple Ye Ald cleaning formulations would be housed in separate molds and in this way the chemically sensitive cleaning components could be intrinsically separated in order to avoid any performance loss caused by the components reacting together and turning them substantially inactive or fatigued. In a preferred form of this invention; Optional first, second and/or subsequent phases may contain binder. Wherever the binder is present, it is selected from the group consisting of ce 0 organic polymers; For example polyethylene and/or polypropylene glycols, especially those with a molecular weight of 4000 Tove (Aen paraffins and polyvinyl pyrrolidone (PVP) polyvinyl pyrolindone in particular PVP, which has a molecular weight (dover), polyacrylates, polyacrylates, sugars, starch sugar derivatives and starch derivatives, for example, hydroxy propyl methyl cellulose (HPMO) and carboxy methyl cellulose cellulose (©010); and inorganic polymers 38 such as -hexametaphosphate and the binder is ded for both tablet cohesion and assistance in obtaining differential solubility for the first and second phases as described later. The first phase weighed more than about ½ g, and it is preferable to be greater than about ½ g.

1. g to 19 g. It is more preferable until about Tr g to about 10 g. The first instar weighs from about gm. The second phase weighs TE gm to about VA from about Saad gm and more to about Yo and the following optional phases are less than ; gm. It is more preferred that the second instar and/or instars weigh 1 g, about 1 g, and about 7.8 g. Preferably between about 11 optional following, between about gm to about 7.5 gm. 0.7 gm. and the most preferred of about ©,© 5 and in another embodiment of this invention; A separator layer containing a separator layer composition is placed between the first and second instars and/or facultative postphases or actually between the second instar and facultative postphases. The composition of the separating layer contains at least one binder selected from the previously described group. The advantage of having a separator layer is that it prevents or reduces the transition of, for example, from the first phase to the second phase and/or the AY phases of the optional subsequent 0-phase components and back. Preferably, the components of the second phase and the optional subsequent phases are compressed Under strength relative to the compressive strength usually used in the preparation of tablets. Therefore, the Tae has low compression. One of the advantages of this invention is that due to the use of a low compressive force, it is possible to use .. temperature, force or chemical sensitive cleaning components inside the cleaning disc without maintaining the VO following loss in performance which It usually occurs when these components join inside disks. Alternatively, The second phase or phases may be compressed under the same or greater compressive strength than the first phase in order to obtain a differential melting of the phases as described later. for example; Use and transportation. As previously described, multi-phase Te cleaning tablets were prepared, where the second layer was compressed under a lower compressive force than the first layer. or become chips upon contact.The lightly compressed phases in the cleaning discs of this invention are protected inside the mold provided by the first phase in the cleaning disc ©?ed.

11 This other invention is the ability to prepare a multiple cleaning tablet Ue and from AT phases where one phase can be designed to dissolve and it is highly preferred before a phase and in this invention it is preferable to dissolve the second phase and the following optional phases before the phase the first.

Yo Preferably the first phase melts within © to Gils and according to the preferred weight range prescribed 1 minute and the second phase and/or optional subsequent phases melt within 15 to 10 minutes; preferably more than © in less than © minutes; More preferably less than 0.0lbs per minute; Most preferably less than 4 minutes. Alternatively, The second phase can dissolve after the first or other phases. For example, wherever cleaning or rinsing benefits are required at the end of the washing process. The time during which the first, second, and/or optional subsequent phases dissolve is independent of each other. Hence in a particularly favorable form in the present invention differential melting Ve of the phases has been obtained. The particular benefit of being able to obtain a differential dissolution of the multiphase detergent tablet is that a component which is chemically inactive can be separated out when another component of a phase is present in which case it is preferable to place the deactivated component in the second phase and the phase 0 is different Optional following (phases). Another feature of this invention is the improved adhesion between the phases of the polyphasic vo disc. It is established that improved adhesion can be obtained by reducing to Gage the exposure of the second phase compared to the multiphasic discs known in this field; making the discs of this invention less prone to fracture along the line of contact between the phases. Method a Making suitable tablets such as; AT multiphase cleaning tablets prepared using any Y. It is preferable that the tablets be prepared by pressing in a tablet press that Courtoy R253 is capable of preparing a tablet that contains a template. In a particularly preferred embodiment of this invention, the method described later was carried out. Canad peas The preparation of the first phase was done by using a tablet press, and the pestle(s) in this tablet press were modified so that the surface of the pestle that contacts the cleaning composition has a convex surface. .Ye m

17

The first cleaning composition was shot into the tablet press die and the tamper was lowered to contact and then compress the cleaning composition to form a first phase. then the first cleaning composition was compressed using a pressure exerted generally of at least about You kg/pm and preferably between about Tor and about 0001 kg/cm; Most preferably about 900 to about 1506 kg/cm, and most preferably about 01 to about 1701 kg/a, then Gad was removed after that and the first phase containing mold was revealed. Then the second compound and optional following cleaners were placed inside the mould. Then the specially designed disc press hammer was lowered again to lightly press the second assembly and optional following assemblies cleaned to form the second stage to form the second stage and optional following stages. In another embodiment of this invention where there is an optional next phase 0, the optional next phase is prepared in an optional next pressing step similar Ll to the previously described second pressing step, and the second and subsequent optional detergent compositions have been compressed under pressure preferably less than You kg / sama "and preferably more from about 56 to about 001 kg / sm and the most preferable from about 71 to about 770 kg / sam and after pressing the second cleaning formula

The tamper was raised a second time and the multiphase cleaning tablet was removed from the tablet press.

Vo cleaning ingredients Prepare the first, second and/or optional subsequent phases of the multi-phase cleaning tablet described here by pressing one or more formulations containing the active cleaning ingredients. appropriately; Compositions used in any of these phases may include several cleaning components (Le Asa) in which are building compounds; surfactants; 0, enzymes and whitening agents; sources of alkalinity; colored materials; aromatics, dime soaps, organic polymeric compounds 58 including polymeric dye transfer inhibitors; crystal growth inhibitors; ALE, metal ion salts 0601, enzyme stabilizers, corrosion inhibitors, foaming inhibitors

Q1 suds suppressors, solvents and fabric softeners; Optical polishing materials and hydrotropic materials. The more preferred first-stage cleaning ingredients include the builder and surfactant; enzyme; and whitening agent. The more preferred cleaning ingredients in phase_II include the builder; enzyme; crystal growth inhibitors, fragmentation agents and/or binders, and the enzyme is essential in the second phase. Builder compound (a compound added to enhance cleaning performance) It is preferable that the tablets of this invention contain a Builder compound present (lad at a level from 701 to 9680 by weight; preferably from 9600 to 9670 by weight and the most preferred Vo 9670 to 96700 by weight of the composition of the active cleaning ingredients.Water-soluble builderSuitable water-soluble builders include water-soluble monomeric polycarboxylates; or their acid forms; and isoforms polycarboxylic acids or copolymeric or 10 its salts in which polycarboxylic acid led contains at least two carboxylic moieties separated from each other by two carbon atoms at most, carbonates, bicarbonates, and borates borates, phosphates, cphosphates, and mixtures of any of the aforementioned. They can be carboxylate or asl polycarboxylate 0 | monomeric (monomeric) or oligomeric (small parts of origin) ) of their kind although monomeric polycarboxylates are generally preferred for reasons of cost and performance. Carboxylates include dial carboxylates containing one carboxy group Ye, the water-soluble salts of lactic acid and AY 4 yg-terminated acid, and include polycarboxylate ether and glycolic acid ether derivatives. Containing two water soluble carboxy groups Polycarboxylates 0016L02; And acid (ethylenedioxy acid) and malonic acid (csuccinic acid) of succinic acid, maleic acid, maleic acid 01866016 acetic acid (JU (aes (ethylenedioxy) oxy), tartaric acid, tartaric acid 11706 acid, and a secondary acid Glycolic © in addition to fumaric acid and fumaric acid tartronic acid include poly-sulfinyl carboxylates and styphenyl ether carboxylates _iY!, which contain three carboxy groups, in particular Polycarboxylates carboxylates and Citracones 0085 Soluble in caconitrates and aconitrates ccitrates citrates Methyloxysuccinate Sn Al Je succinate Succinate derivatives J Water_plus Ye

AYVAY EY describing the carboxymethyloxysuccinates GBP no. Dutch VY OAVY No. 2-oxa-1, 1,3-propane tricarboxylates Carboxylate ?-oxa-1a-1?-propane Ye

AYAVEEY Described in British Patent No. Containing Four Groups Polycarboxylates Including the Polycarboxylate Oxydisuccinate 85 Described in the Patent Carboxy Groups Ethane and Quaternary-7 FOO Telescope BR No. 771875 and IV ?- propane including poly(YA) ?- propane and tetracarboxylate (Fe) 11 carboxylate Ye succinate patented ll derivatives_ le carboxylate-containing substituents

U.S.A. British patent Nos. 1,7344471 and 1938577 and in US Patent No. thermally decomposed sulfonated pyrolysed citrates and sulfonated citrates Patent No. 3,936,448 1,439,000 described in British Patent No.

aya

M1 and include alicyclic and heterocyclic polycarboxylates (Tome come cme) cyclopentane-cis,cis,cis-tetracarboxylates and TY cyclopentadienide pentacarboxylates 4; m0 tetrahydrofuran-cis; comm © cis-tetracarboxylates Y §2,3,4,5-tetrahydrofuran- cis, cis, cis-tetracarboxylates ©- tetrahydrofuran- cis-dicarboxylate 2,5-tetrahydrofuran - cis - dicarboxy - and sane and Y; © 70 tetrahydrofuran 2,2,5,5 FY) ctetracarboxylates kah >-hexane-hexacarboxylates 1 chexane - hexacarboxylates and carboxymethyl derivatives of polyalcohols Vo hydroxy Jia Sorbitol, mannitol, and xylitol include aromatic polycarboxylates of millitic acid, pyromeilitic acid, and phthalic acid derivatives described in British Patent No. 1425343. From the above; The preferred polycarboxylates are hydroxycarboxylates containing up to three carboxy groups per molecule; Especially citrates. He also uses the original monomeric or oligomeric polycarboxylate acids 100066 used as chelating agents, or mixtures thereof with their salts such as citric acid or mixtures of citrates [citrate, citric acid, citric acid] as ingredients. Yo B is useful. Lind can use borate builders; In addition to building materials containing borate-forming substances that give borates under storage conditions or detergent washing, but not preferably under washing conditions less than 04 (and especially less than 40 then. Examples of carbonate materials are lig Sdn carbonate, alkaline earth, and metals, Ye Alkaline; La contains sodium carbonate and carbonates containing (AY SQ ye 438i) calcium carbonate on two types of atoms and mixtures thereof with calcium carbonate

Vo extremely as described in German Patent Application No. 2,321,001 published in

NAVY NOV The most preferred building compounds for use in this invention are water-soluble phosphates. Specific examples of alkali metal phosphates are aul phosphate; and tripolyphosphates for water solubility, which is the third polyphosphate and ammonium »; potassium orthophosphate and sodium pyrophosphate sodium polymeta/phosphate; potassium; And polymeta / sodium phosphate phytic acid and phytic acid salts YY to 1 in which the degree of polymerization ranges from Ga or insoluble Ga Builder 0 or not sa can The tablets of the present invention contain a soluble soluble builder compound. Partially soluble or insoluble building compounds are particularly suitable for use in tablets prepared for use in laundry cleaning methods. Examples of crystalline layered partially water soluble building materials include crystalline stratified silicate EP No. sel exemplary tiles; in dae described on 0 silicates lly DE-A-3417649 Danish Patent No. gl gay) sel lly EP-A-0164514 sodium silicates as pall preferably silicate DE-A-3742043 Danish patent Crystal stratification number with the general formula: 215102 10 or hydrogen “©70:08” and “sodium is sodium M where it is 9 and Ye silicate preferably has a number of 1, 1 through 4 and not a number from zero to stratified crystal of this type is a two-dimensional 'lamellar' structure, such as sodium sodium silicates which is called the stratified-58 structure as described in EP no. Description of methods of preparation EP 0 293640 and EP No. EP 0 4 - Crystalline stratified silicates of this type in Danish Patent Application No. complemented Ye

AY 4

1/7 Danish Patent Application No. 012-2-3742043. And for the purposes of this 9 the general form has a value of ? or or ; preferably ?. dx invention; The most preferred crystalline stratification is sodium silicate and the compound sodium silicate (trade name) has; Available from NaSKS-6 Corporation (known as 8-NapSH0s) the following version

Hoechst AG stratified crystalline present sodium silicate preferably as an ionic solid water soluble sodium silicate ale in granular cleaning formulations as particles in a cohesive mixture with 18594/177092. as described in the international patent application No. The solid ionized material soluble in water was selected from organic acids; salts of organic and inorganic acids and mixtures of terminators with preference to citric acid 0. Citric acid Examples of building materials that are highly insoluble in water include aluminosilicate The suitable aluminosilicates include aluminosilicates. sodium aluminosilicates, which have the following single cellular formula: aluminosilicate zeolites, aluminosilicate 7, the least 5, and the molar ratio is between dey, 2 (10 (.)5102(,1.11) .0e)] ا 11 Where it is | 0 to 7716 preferably V,0 to 0.5 and be at least 7 ©; preferably from 1 to a ranging from to 114. and the composition of the aluminosilicate material in the hydrated form and to be crystalline in the form of 01 more than preferably more than 90978 to 9077 of water in the form of SYA to 9000 preferred; Contains from related. Existing materials aluminosilicate zeolites AR aluminosilicate zeolites can be found in nature but it is preferable to be synthetically derived. Industrial crystalline ion exchange materials

Zeolite B and Zeolite A Zeolite A and aluminosilicates are available under Zeolite HS and Zeolite X and Zeolite © mixtures and Zeolite B ee

AY 4

CM-1 The preferred method for the manufacture of aluminosilicate zeolites is that described by Schoeman et al. (published in (Y44¢) Zeolite (MT) 0 ) in which the author describes a method for preparing aluminosilicate zeolites Colloidal silicates. The particles of zeolite should preferably be colloidal aluminosilicates such that not more than 900 of the particles have a size greater than 1 micrometer in diameter and not more than 965 particles have a size less than 105 micrometers in diameter. Aluminosilicate zeolites preferably have an average particle size diameter between 01 µm and 1 µm and most preferably between 06 µm and 5951 µm; The most Suni is between 01 µm and ,; micrometer. Ye and zeolite A has the formula: Naj2[(AlO02)12(S102)12}.xH20 where is 01 Geax to Fe and in particular YY and zeolite X has the formula Nags[( Al02)as(S102)106]-276H20 | Zeolites MAP; As described in European Patent No. EP384070-B is the preferred building zeolite here. Yo and the preferred aluminosilicate zeolite (oa) are colloidal aluminosilicate zeolites. When used as a component in the cleaning formulation, the aluminosilicate zeolites give cil gall and the colloidal Zeolite A is preferred; induced structural performance in terms of obtaining Better stain removal The structural performance of Cun Lad induced reduced scale formation on GILAD and improved fabric white retention which were problems 0 believed to be associated with poorly constructive cleaning formulations. Blended aluminosilicate zeolite cleaning formulations containing colloidal A zeolite and 7 zeolite give eld equal calcium ion separation for equal weight of commercially available A zeolite. The described Gila yields the separation performance of Yo for the magnesium ion against equal weight of commercially available A zeolite.

-1- SURFACE ACTIVITIES Surfactants are effective cleaning ingredients preferred from the formulations described herein. The suitable surfactants were selected from nonionic ampholytic, ampholytic, cationic, and anionic hybrids and mixtures thereof, and the products of automatic dishwashing machines should be of low foaming nature and therefore should Foaming is inhibited in the surfactant system for use in dishwashing liquids or better yet it is of a low foaming nature and is virtually non-ionic in nature. There is no need to inhibit foaming from surfactant systems used in laundry detergents to the same degree at the level of Glad that is necessary in dishwashing. The surfactant is present in 0 by weight; the most preferred of 9001 by weight; Preferably 960.5 to WY to 7 to 905 by weight of the active detergent formulation. 9611 ampholytic Actual list of anionic species given; non-ionic; hybrid amphoteric and ionic; Classes of these surfactants are in US Patent No. December 01 in Heuring and Heuring and Laughlin filed as Laughlin USP. 3,929,678 Yo Suitable cationic surfactants are listed in the US Patent March 5, 1581 List 71 is mentioned in Murphy's USP. 4,259,217 No. of cleaning formulations in Glad dishwashers with surfactants used and patent applications EP-A-0414549 eg European patent application

WO 93/08874 and ISBN WO 93/08876 _-0 Nonionic Surfactants Any useful nonionic surfactant may be included in the cleaning tablet. Lila mentioned the non-specific types of useful non-ionic surfactants as follows: 4m

For nonionic ethoxylated surfactants, the alkyl ethoxylate resulting from the condensation of aliphatic alcohols with 1 to 1 yo mole of ethylene oxide is suitable. for use here. The alkyl chain of an aliphatic alcohol can be either straight or branched. primary or secondary; It generally contains from 6 to YT carbon atoms, and it is especially preferred for alcohol condensation products that have an alkyl group containing from 4 to 71 carbon atoms with ? to 0 moles of ethylene oxide per mole of alcohol. Alkyl alkoxylate material covered at its surface activated end The alkyl alkoxylate material covered at its surface activated end 0 The appropriate polyalcohols (oxyalkyl 10) covered with epoxy are represented by the following formula: R,0[CH, CH(CH;)0],[CH,CH,0],[CH,CH(OR,] (I) dua Rp is a straight or branched aliphatic hydrocarbon moiety from ; to VA is a carbon atom and Ry is a straight or branched aliphatic hydrocarbon radical ve or branched from ? to 7? a carbon atom and X is a number with an average value from 5 to 5 and it is more preferable to be 1; And Boley is about a number with a value of at least V0 and more so Saad to be at least .01 preferably with a surface activator of the formula [; at least 01 carbon atoms in the epoxide unit Terminal [D211:011)011(18). The suitable surfactant 0 of formula Gh J of the present invention is Olin Corporation's POLY-TERGENT®SLE-18B nonionic surfactant, as shown. Described”; eg in WO 94/22800 published on October 1, 0994 in the name of the Olin Corporation

Poly(oxyalkylated) ether-encapsulated alcohols Preferred surfactants for use here include poly(oxyalkylated) ether-encapsulated alcohols having the formula [CH,CH®R* O) [CH J CH(OH) [CH,}OR' ml ° where any d12 is aliphatic hydrocarbon or aromatic, saturated or unsaturated, straight or branched from 1 to Te atom carbon; p[ is 11 or a straight aliphatic hydrocarbon moiety with 1 to ; carbon atoms; XSi is a number with an average value from 1 to Fs and when x is For * or more then 187 can be the same or different and jak are numbers having a mean value of ye from 1 to 11 preferably from 1 to © and 18 and 12 preferably aliphatic or aromatic hydrocarbon radicals Saturated or unsaturated straight or branched with from + to YY carbon atom with preference having + to VA carbon atom Preferably 18 is 11 or a straight aliphatic hydrocarbon radical having from one to two carbon atoms preferably x is a number with an average value from 1 to 71 preferably from 1 0 to Ae and as described above; when you are; in preferred embodiments; and « greater than ?; The R’ can be the same or different that is to say; That 183 can be varied between any of the alkylenooxy units as previously described. for example; If x is oF then 183 can be selected from ethyleneoxy (EO) or propyleneoxy oS sida (PO)Yo and can be varied in order from (EO) (EO) (PO) «(EO) (PO) (BO) t (EO) (EO) (PO) (PO) (PO) (PO) (PO) (EO) «(PO) (EO) ( PO) «(EO) and of course; Only the number JAS T is chosen and the variety can be much greater than an integer value greater than x and includes; For example (EO) las go JB and a very small number of (PO) units Particularly preferred surfactants as described include Gl those with a low YO opacity of less than 1*m. Thus, these AYA surfactants can be used

The lower opacities in combination with the higher opacity surfactants as detailed by Gal for superior grease cleaning benefits. More specifically, spall ether-encapsulated poly(oxyalkyl) alcoholic surfactants are those in which k is 1 and g is 1 such that the © surfactant has the following formula: [CH, CH(R*)O]x CH,CH (011) 003 mL where RY and 18 RY are defined as le and * is a number with an average value from 1 to 7; preferably from 1 to Ye and more preferred even from 6 to OA and more preferred are surfactants for which the RPGR ranges from 4 to RD VE is 0 out of 11 ethlyeneoxy components and ranges from * 1 to No Ether-encapsulated oxyalkylated surfactants have three general components; they are by name a straight or branched alcohol; an alkylene oxide and a terminal cap of alkyl ether. The terminal alkyl ether cap and alcohol act as the hydrophobic, oil-soluble part of the molecule where NO is the alkylene oxide group, the hydrophilic, water-soluble part of the molecule. Notable for the advantages of stain and film formation and the removal of greasy dirt; When used in conjunction with surfactants with a higher opacity than suitable surfactants. 6l and in general; The ether-coated poly(oxy-alkylene) alcoholic surfactants in this invention can be produced by reacting an aliphatic alcohol with an epoxide to form an ether which was then reacted with a base to form a second epoxide and then The reaction of the second epoxide with an alkyl alcohol to form the new compounds in the present invention. Examples of methods for preparing YO ether-capped poly(oxyalkylated) alcohol surfactants are described as follows: AYS

JssS pans ether Juli alkyl glycidyl ether JssS Crone (Use +,0V0 can Vor) fatty alcohol and zinc chloride AY (IV) 8 g 7.77 mmol mixed; available from Aldrich in a 9560 mL three neck round bottom flask fitted with a condenser; argon + argon inlet and 8 addition funnel; magnetic stirrer and internal temperature probe. The mixture was then heated to OTe and epicyclohedrin was added. Epichlorhydrin (70/70; edge 1,819 can available from Aldrich) drip so that the temperature is maintained between 219-758 °C. After stirring for an additional hour at PT then the mixture is cooled to Room temperature The mixture was treated with 6 965 TVA sodium hydroxide solution (sodium hydroxide c?la.; mol; 0% 0) with GF Ye stirred and after completion of the addition the mixture was heated to 0°C for an hour and a half; then Cooled and filtered with the help of ethanol 6018001. Then the clear solution was separated and the organic phase was washed with water (Vo (ml)); Preparation of the glycidyl ether in the form of oil Preparation of the alcoholic surfactant covered with Berr© alkyl-Cong ether Ga Jse +0 TAT cpa 110 (Neodol®91-8) alcohol added Available ethoxyl mechanism from Shell chemical and zinc chloride 0 OA (IV) C 77,? mmol) in a You ml three-necked round-bottom flask with condenser; an argon inlet and an addition funnel; magnetic stirrer; And an internal temperature sensor. The mixture was heated to 10"C, at which point Cire 11 alkyl glycidyl ether (0 g 07957 mol) was added dropwise for 0V0min. After stirring for VA 1 hour at 10C The mixture was cooled to room temperature and dissolved in an equal part of dichloromethane and the solution was passed through a 1 inch layer of silica gel with rinsing with dichloromethane and the clear solution was concentrated by evaporation It was then exfoliated in a Kugelrohr kiln (ae 5 2° ev) kugelrohr hyacinth) Yo to obtain the surfactant in the form of oil.

On the fatty alcoholic surfactant to which ethoxylated has been added Non-ionic propoxylates being 0-M0 ethoxylated fatty alcohols and 0-M0 ethoxylated/propoxylated fatty alcohols are suitable for use here as surfactants; In particular, the ones that are soluble in water. The preferred ethoxylated fatty alcohols are fatty alcohols Cio-Cig as ethoxylated are ethoxylated day alcohols with an ethoxylated degree of * to con and the most preferred of them are (-0) added fatty alcohols It is ethoxylated with a degree of ethoxylated addition from “to £0.” It is preferred that fatty alcohols mixed with ethoxylated/propoxyl have a 0-alkyl chain length from 01 to 18 carbon atoms, a degree of ethoxylation from to Yo, and a degree of propoxylation 1 to .01 EQO/PO nonionic condensates with propylene glycol are condensates of ethylene oxide with a hydrophobic base formed by condensation of propylene oxide with propylene Propylene glycol Adie 05 for use here preferably the hydrophobic part of these compounds have a molecular weight of 0 to 18586 and show insolubility in water Examples of this type of compounds include some Pluronic™ surfactants Available Glas marketed by Glad by BASF. EO J non-ionic products with propylene oxide / ethylene diamine close-ups form ethylene oxide condensates With the products formed from the reaction of propylene oxide and ethylenediamine diamine suitable for use here, the hydrophobic part in these products is formed from the product of the reaction of ethylenediamine diamine with the surplus of -propylene oxide and is It has a molecular weight of m

generally from 7500 to Fees Examples of this type of non-ionic surfactant include some commercially available Tetronic™ compounds marketed {lad by BASF A system of non-ionic surfactants mixed in a preferred embodiment of this invention containing The cleaning disc is based on a mixed nonionic surfactant© system containing at least one low Opacity nonionic surfactant and at least one high Opacity nonionic surfactant. f'degree of opacity; As used here is a well-known property (Tam) of nonionic surfactants which is due to the decrease in the solubility of the surfactant with increasing temperature; The temperature at which a second phase is observed is indicated as 0 “pied degrees.” (See Kirk Othmer's Ales Encyclopedia of Purification) ed. GA No. YY p. TVA and as 'Low Opacity' Nonionic Surface Activator is defined as the parent active ingredient of the nonionic surfactant system having opacity less than OT preferably less than OV and most Sain less than 10"M. Non-ionic surfactants with low opacity include non-ionic alkoxylated surfactants, particularly ethoxylates derived from primary alcohols and polyoxypropylene /_polymers. Js [polyoxyethylene oxypropylene Lad 5 (PO/EO/PO) polyoxypropylene These include the low opacity nonionic surfactants of gall; for example Jad ethoxylated alcohol ethoxylated-propoxylated alcohol (eg 512-18 (se Poly-Tergent® Olin «NA©”); and poly(oxyalkylated) epoxy-coated alcohols (such as the Poly-Tergent® SLF-18B series of non-ionics from Olin Corporation; as described, for example, in International Patent No. 94/22800 (WO) Posted on October 1, 0994 as M

Olin and poly(oxyalkylated) alcohol capped .ether db. The non-ionic surfactants may optionally contain propylene oxide in an amount up to 9619 by weight Other preferred preparation of Sars anionic surfactants using Gohl described_ in US Patent No. 3 filed of September 16 al VIAL Builloty and cited herein by reference. These include anionic surfactants with significantly lower opacity Additional dB oS Poly. Ams polyoxyethylene (ld Si oxy-propylene polyoxypropylene 0 Jedis polymeric polyoxyethylene - polyoxypropylene polymeric those based on ethylene glycol propylene glycol, glycerol, trimethylolpropane Obs, and ethylenediamine as an active hydrogen precursor and some of the template compounds are REVERSED PLURONIC®; PLURONIC® polymeric surface-activator named yo

Michigan (BASF-Wyandotte) TETRONIC®

REVERSED EXAMPLES INCLUDE THIS (THE GLAY 3 ADD SUITABLE IN FORMULATIONS WHICH SURFACE ACTIVES ARE ACTUALLY USEFUL) TETRONIC®702 5 PLURONIC®25R?2 as a non-ionic surfactant with a low opacity. 0. As used herein, a “high opacity” nonionic surfactant is defined as a component of the nonionic surfactant system having an opacity greater than 60 µm; preferably greater than 1200 µm, preferably greater than 10”* M. It is preferable that the non-ionic surfactant system contain a surfactant - with added ethoxylation derived from the reaction of a monohydroxy alcohol or an alkylphenol containing Ye JA carbon atom YO with 1 to Vo moles of ethylene oxide per mole of alcohol or alkyl phenolphide

It's on an average basis. These include high opacity anionic surfactants; For example; Tergitol1559 (available from Carbide Consortium) and Rhodasurf 5a (available from Rhone Poulenc) and 91-8 Neodol (available from Shell °) are also preferred for achieving targets This invention is that non-ionic surfactants with a high degree of opacity have a hydrophilic-oleophobic balance (CHEB) (see Kirk Othmer previously mentioned) has a value within the range from 9 to Ve, preferably from 11 to 5 These include ool salt eg 1559 Tergitol (available from Carbide Union Rhodasurf-TMD8.5 5 (available from Rhone Poulenc) and 91-8 Neodol ( Available 0 from Shell Another preferred non-ionic surfactant with a high opacity was derived from a straight chain, preferably branched, secondary fatty alcohol containing from 1 to 1 carbon atom Co) mm alcohols); these include branched-chain secondary and primary alcohols. Preferably, nonionic surfactants with a high opacity are Ve ethoxylates 1"0501e_branched or secondary, and more preferably alcohol ethoxylates Po or Wu-branched condensates averaged from + to Vo mol; preferably +” to 11 mol; And more preferred “7 to 4 moles of ethylene oxide per mole of alcohol. Preferably, the ethoxylated nonionic surfactant derived in the above manner should have a narrow ethoxylate distribution relative to the medium. 0 Anionic surfactants Any anionic surfactant (Gla sade) for cleaning purposes is suitable for use as lia. These materials include ded Wy salts, for example (JED, sodium, potassium). And ammonium cammonium and ammonium salts replaced by Jia first mono salts, second and third ethanolamine salts (di-triethanolamine salts) Yo materials sulfate, sulfonate, carboxylate, and sarcosinate 4m

sya

Anionic sulfate is an anionic surfactant. Anionic surfactants, sarcosinate sulfates, are preferred

Jie isethionates Other anionic surfactants include N-acyl taurates and N-acyl taurates; alkyl isethionates and cmethyl tauride for methyl acid fatty acid amides Fatty 0 to any monoesters, mono-esters, sulfosuccinates, sulfosuccinates 85 (particularly, 2-0 monounsaturated and unsaturated esters), sulfosuccinate (di-esters, Cora, se-esters, 35). of sulfoxins (particularly resin acids and N-acyl sarcosinates are acyl -N and hydrogenated sarcosinates such as rosin 0810 and hydrogenated rosin Load). Anionic sulfate surfactants suitable for use as anionic sulfate include primary, secondary, straight and branched anionic sulfates; and ethoxy-alkyl sulfates herein alkyl sulfate Vo fatty oleoyl glycerol Fatty alkyl ethoxysulfates alkyl phenol ethylene oxide ether sulfates - 3 05-017 acyl-N-(C1-C4 alkyl) (J-0 alkyl) - N- and 0-mL-acyl csulfates “N-(C1-C2 hydroxyalkyl) glucamine sulfates No (0-:0© hydroxyalkyl) glucamine Alkyl sulfates Jie sulfates of alkylpolysaccharides and alkyl polysaccharides 0 (The nonionic sulfates of alkylpolyglucoside are described later.) Nonionic nonsulfated

Cio-Crs surface activated alkyl sulfate materials are preferably selected from straight and branched Cpp-Cps first alkyl sulfate; It is more preferable to be straight chain alkyl sulfate and straight chain 2-0 alkyl sulfate. Yo 9m

It is preferable to choose alkyl ethoxysulfate surfactants from the group consisting of (©-m,©) sulfate (JST) to which (Led) ethoxylated by © has been added to 10 moles of ethylene oxide for each molecule. preferably more; that the alkyl ethoxysulfate surface activator is © R©-N© sulfate; More preferred is the ©-,© alkyl sulfate to which it has been ethoxylated by 15 to 7; Preferably 1 to ¾ mole of ethylene oxide 686 per molecule. A particularly preferred form in the present invention uses mixtures of preferred alkyl sulfate and preferred alkyl ethoxysulfate as a surface-activated Ve. These mixtures were described in International Patent Application No. 7093/18124?. Anionic sulfonate surfactants Jods Anionic sulfonates dhiidl Anionic sulfonate surfactants _ suitable for use here Mo0-© straight alkyl benzene sulfonates “alkylbenzene sulfonates”, alkyl ester sulfonates, Cg-Cop sulfonates primary alkane or secondary VO; and U©-M0 olefin sulfonates and sulfonated polycarboxylic acids inan<001702:00; Calkyl glycerol sulfonates, fatty acyl glycerol sulfonates, fatty oleyl glycerol sulfonates, and any mixtures thereof. Anionic carboxylate surfactants L Suitable anionic carboxylate surfactants include Jay calkyl 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 .having the formula Aull '10(011,011:0(.011.00014) where R is About M© Group to Qom

Alc Cig Alkyl; It ranges * from zero to 010 and the distribution of ethoxylate is such that it is; based on weight; The amount of material when x is zero is less than %Y and M is a cation Jp includes alkyl polyethoxy polycarboxylate suitable surface activated those of the formula RO-(CHR|- CHR,-O)-R3© where R is an m© group to an alkyl Crs and x is from 1 to Yo and is Ry Ry is selected from the group consisting of hydrogen, the methyl acid moiety, the succinic acid moiety, the hydroxysuccinic acid moiety, and terminated mixtures, and Ry was selected from the group consisting of hydrogen and the substituted and unsubstituted hydrocarbon Vs having between 1 and 48 carbon atoms; and mixtures thereof. Suitable surfactant soaps include secondary surfactant soaps that contain a carboxyl unit attached to a secondary carbon atom. The preferred secondary surface-activated soaps for use here are the water-soluble elements selected from the group consisting of the water-soluble ALE salts of ?-methyl-1-undecanoic acid (aes 2-methyl-1- undecanoic acid? - Ethyl-1-decanoic 2-ctyl-1- “decanoic acid and ?- propyl-1-nonanoic acid and “- butyl-1-octanoic acid 2-butyl-1-octanoic acid and ?- Pentyl-1-heptanoic acid. Other suitable anionic surfactants are alkali metal sarcosinates of the formula (R-CONRHCH,COOM where 1 is ic gana Cs-Cy alkyl or alkenyl straight or branched; RY is an alkyl group CHC and 34 is an alkali metal ion. Preferred examples are aphid sarcosinate

DRESEM 485 myristyl enrafti_and oleoyl methyl oleoyl in the form of sodium salts thereof. Amphoteric (double-charged ions) surfactants Suitable for use here include amphoteric surfactants oo Alii amine oxide surfactants and .alkyl amphocarboxylic acids include amine oxides Suitable oxides are those compounds having the following formula (RAORDN'R), where RO is selected from the calkyl hydroxy group OSI acylamidopropoyl Jus sual Jud hydroxyalkyl alkyl phenyl or 0 dete mixtures contain from 8 to 77 carbon atoms; RY is an alkylene or hydroxyalkylene group containing from 7 to “*” carbon atoms; or mixtures of terminations where x is zero to ©; preferably from zero to; Each 85 is an alkyl or hydroxyalkyl group containing 1 to - or a polyethylene oxide group containing 1 to ? Ethylene oxide groups 01 preferably ASH Cue-Cis oxide dimethylamine chloride and Yemen acylamide oxide AST acylamido alkyl dimethylamine oxide and the appropriate example of an alkyl dicarboxylic acid Miranol(TM)C2M is a concentrate manufactured by Miranol Inc. (Dayton, NJ. 0) - Hybrid ionic surfactants (positive charge at one end and negative charge at the other end) Hybrid ionic surfactants can be introduced The activators can be described more broadly as derivatives of GED Au amines, as derivatives of secondary and tertiary heterocyclic amines, or as derivatives of quaternary ammonium, quaternary phosphonium, or AY 4 compounds.

vy — Betaine tertiary sulfonium and sultaine surfactants are examples of hybrid ionic surfactants for use here. Suitable betaines are those compounds of formula 107201782000 where R is a 0-06 hydrocarbyl group and each RY is a peralkyl RY, is a Ci-Cs Ae gene Hydrocarbyl 5 (7:70:06 th. And the preferred betaines are hexanoate 0 Crag sec..methyl- Dimethyl ethane (or diethyl) and complex surfactants betaines are also suitable for use here. Cationic surfactants are the cationic ester surfactants used in this invention. Preferably they are water dispersible compounds with surface-activated properties containing at least one (ie-000-) ester bond and at least one cationic moiety group.Other suitable cationic ester surfaceactivators have been described. La Vo has kaolin ester as an adil choline ester for the surface; in US Patent Nos. C and 1232 Roh 74 1 suitable cationic surfactants include quaternary ammonium surfactants selected from “Cg” materials. -Crg preferably 2-0 17 N-alkyl or alkenyl ammonium surfactants where the Vo remaining N sites are replaced by Jie 61 hydroxyethyl or hydroxypropyl groups The enzymes Enzymes are the preferred scavenging components in the first phase and in particular fas in the second and/or other facultative phases. And when they are present, these enzymes are selected TO. enzymes .from the group that consists of ge cellulase enzymes AYA

Ta quasi-cellulases; peroxidases » proteases; Glucose «cellulases enzymes» lipases cxylanases amylases 7165 10160-200. oxygenases Oxidases 85 :;: phenoloxidases 600101065 lipoxy 0 pentosanases ctannases tanases cpullulanases or pullulanases ligninases lignases B- glucanases malanases #aunt “Mullah” _ beta- . Glucanases 85 Chondromycin hyaluronidase zadinoroiolaiella _. 015 Arabinosidases, mixtures thereof. Jaccase, chondroitinase lipase, camylase, and amylase protease. Preferred enzymes include Ya-conjugate cellulase and/or cutinase lid SH peroxidases and peroxidases.

ASL with one or more cell wall lysing enzymes. The cellulase enzymes used in this invention include both bacterial and fungal cellulase enzymes. Preferably, it should have an ideal pH between © and 71 and a higher potency. Cellulose enzymes have been described (Cellulose dn) (CEVU ov unit of 5 in the name of_Barbsjord USS. Patent 4,435,307 No. Ekirmala gl ay) appear in the appropriate patent and INT.P. 02653/7096_ that [0 no a Barbesgoard describe fungal cellulase enzymes produced respectively from Sporotrichum inulines and Sporotrichum inulines 728. insolens Trichoderma isolated from parts of Bacillus <1 3Y LuEP 739 982 describes the new EP No. Ye. Suitable cellulases are described in British Patent Application No. Bacillus, Patent Application GB-A2.005.275, UK Patent Application No. GB-A-2,075,028 .17095/26398 and International Patent No. DE-OS-2.247.832. Danish invention No. Cellulases produced by a strain of a cellulases. These cellulases are Al of the type Humicola grisea (Humicola insolens) Yo

aya

Diary (thermoidea) especially Ds Humicola DSM 1800 Humicola and other suitable cellulases are cellulases from Humicola inulinase Humicola 05 having a molecular weight of ON kDa; an electroequilibrium point of 0.0 and containing lbs. 10 amino acids 43kD camino acids of endoglucanase derived from 0_ Adel ln J (DSM 1800 Humicola insolens cellulase) and the preferred component of endoglucanase is the amino acid described in the application International Patent No. ET 91/1977. Also suitable cellulases are Cellulase 26111 ge Trichoderma longibrachiatum described in International Patent No. 21801/7094;_as Genencor Sia.

0 Published in YA Sept. 0544 Particularly suitable cellulases are cellulases, which have color-preserving benefits. Examples of these cellulases are the cellulases described in European Patent Application No. 9917578974,7 filed on November 6, 1591 (Novo), Carezyme and Celluzyme (Novo Nordisk A/S). Special, and see Lad International Patent No. 17244/ (WOOL) and patent

Vo IN 21801/ WOOT and other suitable cellulases for their fabric preserving and/or cleaning properties are described in INT 17096/34092 and 4 and 24471/095 7 .

These cellulases in the anh form were introduced into the cleaning formula at levels from 960,000 to 967 active enzyme by weight of the cleaning formula.

0 Peroxidase enzymes were used in combination with oxygen sources, Jie oxygen, percarbonate, perborate, persulfate, chydrogen peroxide, etc. And they can be used in (ans) 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 enzymes

Yo peroxidase is known in this field; include; For example; plant peroxidase

reply

And

Watercress ligninase Xanengilao 0880180 peroxidase and Jie haloperoxidase chloro and bronoperoxidase -brornoperoxidase. Cleaning compositions containing peroxidase, for example, are described in International Patent Application No. 09813/17089 And in the European patent application No. 1541 dg Vd posal EP-A-540784 ° or _European_patent No. EP 2106.8 filed on February 01, 1597 Lads it is appropriate to use an enzyme

Lactase is the Jaccase enzyme and the preferred tonics are phenthiazine and substituted phenoxasine such as 10-Phenothiazinepropionicacid (PPT) 10-Phenothiazinepropionicacid Ns and 10-ethylphenothiazine- ;- crboxylic acid 10-ethylphenothiazine-4-carboxylic acid (EPC) and 10-phenoxazinepropionic acid (POP) and 10-methylphenoxazine (described in International Patent No. WO 94/12621 and substituted syringates (substituted ©- and ©- and ©-alkyl syringates) and phenols are sodium carbonate 34

Sodium percarbonate 0 or sodium perborate are the preferred sources of hydrogen peroxide

These naturally occurring cellulases and/or peroxidases were used in the cleansing formula at levels from 960,0001 to BY of the active enzymes by weight of the cleansing formula.

Other preferred enzymes that may be used in the cleaning formulations of this invention include lipases 11085688. Lipases suitable for use as a detergent include those produced by microorganisms of the group Pseudomonas such as Pseudomonas stotzeri 19.154 AATCC described in UK Patent No. 177074 Suitable lipases include those that show a positive cross-immunoprecipitation reaction to the antibody to the lipase. produced by the object

Yo Flour Pseudomonas Fluorescent JAMIOST This loll is available from Amano Formulation Company

mouth

Las Pharmacy; Nagoya Japan under the trade name Lipase © “Amano” referred to here by Gay as “Amano-P” Other suitable commercial lipases include (Amano-CES and Shige SH lipases. Chromobacter viscosum) .”)_as eo (Chromobacter viscosum var) lipolyticum species NRRLB3673 from Toyoguzu Corporation © 10701020 oll Tagata and Chromobacter viscosum lipases J0001:i) from the American Biomaterials Corporation Gilat USA United States of America AS dy Disoynth The Netherlands and lipases ex Pseudomonas gladioli Particularly suitable lipases are Lipomax s M1 LipaseR Jia (Gist-Brocades lipolase Ultras 0) Novo, which has been found to be effective when used in combination with the formulations of this invention. The suitable materials, Lay, are the lipolytic enzymes described in EP No. 258068, INTERNATIONAL Patent No. 05249/92, and INTERNATIONAL Patent No. 5 170 by Novo Nordisk and in INT 94/03578 WO and INT 94/03578 WO 10 and INT 96/00292 WO by Unilever Suitable substances for Lad are the enzyme ketase1 (ECL cutinases), which Sa (Sa) considers as a special type of Glad dipase, a lipase that does not require activation of the boundary surface. The addition of lipase chitinases to cleaning formulations is described in, for example; WO-A-88/09367 WO-A-88/09367 (Genencor) 0_ WO 90/09446 (Plant Genetic System) WO 94/14963 and International Patent No. 14964/94 170 (Unilever).Lipases and/or cutinases were introduced naturally into the cleaning formulation at levels from 960,000 to 967 active enzyme by weight of the cleaning formulation.The appropriate proteases are subtilisins 9051118108 which Obtained from a specific strain of B. subtilis 3. and B. licheniformis 4m vs.

Subtilisin (BPN; BPN subtilisin) One suitable protease is obtained from a strain of Bacillus, which has maximum potency over the pH range from A to B-12) 1 developed and sold as ESPERASE® by Novo A/S Factories in Denmark; herein referred to as 'Novo'. The preparation of this enzyme and similar enzymes is described in OE_UK_patent 8 175477284_as_Novo. Other suitable proteases include SAVINASE®; DURAZYM® (ALCALASE® (KANNASE® via Novo MAXAPEM® (PROPERASE® MAXACAL® MAXATASE®) (Maxacal Cums (a) Nutrpla_Sdenhill_Maxacal Gist-Brocades.

Proteolytic enzymes include proteolytic enzymes modified bacterial serine proteases; such as those described in EP251446 (filed in YA April 19897 (in particular TES pp. 17-38); which Lede here calls “protease B”); and in the EP251446 application 4 Venegas" published on October 79 AAT which refers to a modified bacterial serine proteolytic enzyme called "protease A" here. Appropriately called here "Cr protease which is a type of serine protease Alkaline Vo protease from Bacillus in which lysine was substituted for arginine at position (TY), tyrosine was substituted for valine at position 001, and serine was substituted serine replaces asparagine at position OYY and replaces ola alanine with threonine at position 774. Protease G is described in WO 91/06637 and published on NAY 11 and species Transgenic;

0 and in particular of protease c; It is also used here. The preferred protease referred to as "D-protease" is a carbonyl hydrolase type with an amino acid sequence not found in nature; It is derived from a primary carbonyl hydrolase by substituting a different amino acid with several amino acid residues at the position of this carbonyl hydrolase equivalent to the +71 position and preferably Lad in combination with one or more TO positions of the amino acid moieties equivalent to those chosen from the group constituting from +19

m

Sr and +1a1a and +710 and +410 and +la1a and +71 and +la? and +ka0a and +a and almighty 5 VYAF and +10, +721 and +17a, +40 and +laca and +; and +A Thay and +C no 5 YAVAH and +/1? and +777 Ylods hud and/or +7724 Gla for the numbering of Bacillus amyloidocivaciar subtilisin ; As described in International Patent No. WO95/10591 and patent application © for the invention in the name of C. Ghosh Cl Ghosh and colleagues under the title “OLS Whitening Containing Protease Enzymes” which has serial number 8/777,79/71_USA filed on 0 Oct N48 and is appropriate to use in this invention Lad These are the proteases described in EP No. 446 251 EP and INTERNATIONAL PATENT No. 91/06637 WO and the 0©8140 protease described in IPL No. 17091/02792 and its species described in IPL No. 95/23221 TWO 0 and see Lal protease with pH Je of Bacillus sp NCIMB 40338 described in the international patent No. WO 93/18140 A for Novo. protease and one or more enzymes (ws AY)0 and a reverse protease inhibitor in Novo WO 92/03529 A. When required, low adsorption and high hydrolysis proteases are available as described in International Patent No. 07791/95 WO in the name of Procter and Gamble A recombinant protease similar to trypsin for use in detergents is appropriately described here in Novo WO 94/25583 Described Proteases 0 - Other Appropriate in EP 200 516 EP Unilever Other preferred proteases include proteases which are a type of carbonyl hydrolase that has an amino acid covalent acid not found in nature and derived by replacing several amino acid residues of the precursor carbonyl hydrolase with different amino acids; Where this multiple YO-amino acid residue has been substituted in the corresponding preenzyme material at position 7001+ in combination with one or more of the following residues: M

And

+ and +17 and +l7a1 Vid and +a.0 and +a Yoh Vary and +la10 and +m1 and +17 VF tg and +771 and +e1 ro+ So YOA+, +14 a r + Hatha Wet VIVA, +o.0+, +51?, +la1”_, +/1” and +7?; Cus numbered positions correspond to the subtilisin found in nature in Bacillus amyloliquefaciens or equivalent amino acid residues in carbonyl hydrolases or other subtilisins (Jie) (Bacillus lentus subtilisin) Preferred enzymes of this type include those with +001, +1, or +710 and +510 locus changes.

A+ 0+ and proteolytic enzymes are used in the cleaning formulations of this invention at Ve level from 960,0001 to HY and preferably from 960,001 to 960,7; Preferably over M up to 760.1 pure enzyme by formula weight. Amylase enzymes (alpha and/or beta) can be used to remove stains caused by sugars. International Patent No. WO94/02597 under the name of Novo Nordisk ASS published © February 1994 describes cleaning formulations containing hybrid amylases. Vo Load see NOVO 10603/17095 International Patent No. 17095 in the name of Novo Nordisk A/S published 01 April 1490 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 Vo and Patent EP No. 285,123, EP No. 525,610 EP, EP No. 368,341 EP, BR No. 179571874 (Novo). WO94/18314 published Aug 18, 1544 and IPO No. WO96/05295 in the name of Genencor published YY Feb 1957 and types of Yo-amylases- further modification of the direct parent compound available From Novo Nordisk 99m

Why of! Nordisk is described in International Patent No. 95/10603 WO published in dad 5. Suitable materials include Lad amylases described in EP 277 6 EP and INT 7095/26397_PAT 73 (all from Novo Nordisk).

° Examples of commercial alpha-amylases o-amylases are Purafect Ox Am® from Genencor and Fungmyl® Ban® 5 Termamyl® and Natalase® 3 Duramyl® are all available from Novo Nordisk A/S Denmark. WO 26397/95 describes other suitable amylases: Alpha-amylases characterized as having a specific potency of at least 9675 greater than the specific potency of Termamyl® at a temperature range from OVO to 2200 and at a value of

0 pH in the range 8 to 01 measured using the Phadebas® Alpha Amylase Potency Test and suitable for use of the different enzyme variants described in International Patent No. 96/23873 WO (Novo Nordisk). Other amylose-degrading enzymes that have improved properties in terms of activity level, thermal stability union and higher activity level are described in International Patent No. 35382/17095.

yo Preferred amylase enzymes include those described in International Patent No

7 And in the provisional application in the name of Novo Nordisk for International Patent No. 20-3

The amylose-degrading enzymes in the cleaning formulations of this invention were mixed at a level from 960,000 to 967 preferably from Yor, VA up to .960.05 preferably from

Tha, eee YE 0 to 960,048 pure enzyme by weight of the formula.

In a particularly preferred embodiment; The cleaning tablets in this invention contain the enzymes Dala Phospho Oded described in Lal invention sel No. 7 and Novo Nordisk provisional patent application No. 23873/96 WO in combination with complement amylase. mouth

1

And by "complementary" we mean the addition of one or more amylases suitable for cleaning purposes.

AB complement amylases (alpha and/or beta) are described later. It describes the international patent

No. WO94/02597 and International Patent No. WO95/10603 in the name of Novo Nordisk A/S

Cleaning formulations containing hybrid amylases. Other known amylases include

0 by using in its cleaning formulations both alpha and beta amylases; Alpha amylases are known

This field includes those described in United States Patent No. 5,003,257 (US Patent

European Invention No. 252,666 “EP” and International Patent No. 170/91/00353; and innocence

French invention No. 2,676,456 sel uy (FR European invention No. 285,123 EP and patent

European Patent No. 525,610 EP and European Patent No. 368,341 EP and Description

0 writing uk patent number 17954749 (tofu). Other suitable amylases are

Amylases with increased stability described in International Patent No. WO94/18314

And the international patent No. aus WO96/05295 Genencor and types of amylase

The different modifications that have an additional modification in the direct original compound are available from Novo Nordisk ofl

and described in International Patent No. 95/10603 WO. Amylases are also appropriate.

VO described in European Patent No. 216 277 BP (Novo Nordisk). Examples of products

The commercial alpha-amylase is Purefect Ox Am® from Genencor 5 Ban® 5 Termamyl®

Duramyl® 5 Fungamy® 5 are all available from Novo Nordisk a/o Denmark. Describes innocence

Int. W095/26397 Other suitable amylases: Distinguished alpha-amylases

That it has a specific activity of at least 9675 greater than the specific activity of the compound Termomyl® at

Yo Temperature range from Ye to dey foo pH value 011 in the range + to

0 measured using the Phadebas® Alpha Amylase Potency Test and suitable compounds are the types

The different enzyme profiles described in International Patent No. WO96/23873 (Novo Nordisk). Other amylose-degrading enzymes that have improved properties in terms of activity level, thermal stability union, and greater level of activity are described in International Patent No.

WO95/35382 Yo The preferred complementary amylases in this invention are the amylases sold under

4 m

Trade name ‎play) sel 8 Adyeasdl Purafect Ox Am® International A, WO 94/18314 and International Patent No. 7096/05295 Sold by Genencor and ©1 Termamy R Fungamyl® and Ban® , Natalase® and Duramyl® all available from Novo Nordisk (ofl and Maxamyl® by Gist-Brocades).

° and complementary amylase is generally interfered with in the cleaning formulations of this invention at a level of Torre) up to 967; Preferably from 960.00014 to 960.05; More than 94 to 700,048 pure enzymes by weight of the formula are preferred. Preferably the weight ratio of the pure enzyme of the limiting amylase to the complemented amylase is between 4:1 to 1:5 and more preferably between 4:1 to:1; Preferably between Yoyo: 1

Ve and the aforementioned enzymes can be from any suitable source such as plant, animal, bacterial, fungal and yeast sources. The Lad source can be medium thermophilic or hyperthermophilic (hygrophilic; hygrophilic; allophilic; hydrophilic; alkaline-loving; acid-loving; Od-loving etc.). Pure or non-pure forms can be used. Pure Lad enzyme hybrids were used.Se hybrids can be obtained by protein engineering and/or genetic engineering and chemical and/or physical modifications of the endogenous enzymes.It is common for Glee enzyme gene expression by Glee organisms Membership of a family in which a non-brat product of the genetic material responsible for the production of the enzyme .enzyme has been used naturally in the Chil formula at levels from ee) 0 up to 967 active enzyme by weight of the cleansing formula. Enzymes may be added as separate single active ingredients (pills, granules, stabilized liquids, etc. containing one enzyme) or as mixtures of two or more enzymes (eg concomitant granulocytes). Other suitable original cleaning active substances that can be added are the enzyme oxidation activators described in the provisional European patent application filed at 5m

SS, January 1, 1997. It includes abd, the activating materials for the oxidation of this enzyme, enzyme oxidation, tetraethylene polyamines lied Jolt, p “obedience 0, to which ethoxylated has been added, and many enzyme materials and means of their use have been described in formulations © Industrial Cleaning in International Patent No. WO 9307263 A and International Patent No. sub WO 0 Genencor. Adsl Genencor and International Patent No. WO 8908694 A for Novo. and US Patent No. 3,553,139 (USS.VAY) on behalf of McCarty and colleagues. Lad enzymes are described in US Patent No. 4,101,457.11.5 in the name of Plass and colleagues in YA July 1978 or US Patent No. 0 4,507,219 11.5 in the name of Hogg in YT March VAS The enzyme substances are described useful in liquid cleaning formulations; And their overlap in those formations in US Patent No. 8.1.5 in the name of Hora and his colleagues on April 14 NIA The enzymes used in detergents can be stabilized by many techniques 0 OLE enzyme fixation and its examples are described in US Patent No. 3,600,319 .17.8 on 117 August 0971 in the name of V0 Gedge et al. EP No. 199,405 sel uy BP EP No. EP 6 in 4? Oct 14871 Venegas enzyme stabilization systems Lal eg are described; In US Patent No. 3,519,570 11.5. The useful Bacillus 8013, which produces proteases, xylanases, and cellulases, is described in International Patent 0 __ No. 9401532 WO in the name of Novo. Bleaching agent One of the most popular ingredients in detergent formulations is the bleaching agent. Suitable bleaching agents include chlorine and oxygen-permitting chlorine bleaching agents 6p.

In one of the preferred forms, the oxygen-release bleaching agent contains a hydrogen peroxide source and an organic peroxy acid primary bleaching compound. An organic peroxy acid is produced at the site of the reaction of the initial compound with a source of hydrogen peroxide. Preferred sources of hydrogen peroxide include the inorganic bleaching agents© inorganic perhydrate, and in one of the alternative forms of the interaction of organic peroxy acid treated directly in the composition, compositions containing mixtures of a source of hydrogen peroxide and peroxyacid were envisaged. Primary organic in combination with treated organic peroxy acid. Jal ge Inorganic Bleach Perhydrate Ve perhydrate Detergent ingredient formulations preferably include a source of hydrogen peroxide; and an oxygen-exporting bleaching agent. Suitable hydrogen peroxide sources include inorganic perhydrate salts. Inorganic superhydrate salts naturally occur in the form of sodium salt at a level from 901 to 90460 by weight. More preferably from 907 to Vo 9660 by weight and more preferably by 965 to 9672 by weight of the fittings. Examples of inorganic perhydrate salts include perborate, percarbonate, perphosphate, persulfate, and persilicate. Inorganic perhydrate salts are naturally They are salts of alkali metals. Jal can form inorganic superhydrate 0 salts as a crystalline solid without additional Ales. and for some perhydrate salts; The preferred use of these granular formulations necessitates a coated form of the material which gives better storage stability of the superhydrate salt in the granular product. Sodium borate can be in the form of the monohydrate with the nominal formula 11080211207 or the tetrahydrate NaBO,H;0,.3H;0 AYA

and are percarbonates of the alkali metals; In particular, sodium percarbonate is the preferred superhydrate for use in the formulations of the present invention. Sodium percarbonate is an addition compound with the following formula: 28200.31 and it 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 the ability to obtain high concentrations of 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 salt mixed from 0 sulfate and water-soluble alkali metal carbonate. These coating materials with coating methods (Bla) are described in British Patent No. 1,466,799 under the name Antiroxi of March 9 NAVY. The weight ratio of the coating salt mixture to percarbonate is in the range from 1:5 to 1:1. ; preferably from :1 a 99 :1 9 preferably from :1 5 ?; To 1: 15 it is preferably the mixed salt of Geo sodium sulphate and sodium carbonate 0, which has the general formula NapSO04nNa,CO, where it is 0.1 en to oF, preferably from 1.7 to 1 and preferably “ from 0.7 to 0.8 . Other suitable covering materials that give stability to the product include; Sodium silicate, which has a SiO ratio; OY. 9097 to 9000 (usually from 909 to 510 (%o) by weight of the inorganic perhydrate salt. Say that Hadi) magnesium silicate Lad Magnesium silicate Covering materials that contain silicate and borate salts or boric acids or other inorganic materials are also suitable for use here.

Other covering materials that contain waxes, oils and greasy soaps (Lind) can be used distinctively in this invention. Potassium peroxymonopersulfate is another inorganic perhydrate salt used in the formulations described 0 also herein. Feedstock for Peroxy Acid Bleaching Agents The starting materials for peroxy acid bleaching agents are compounds that react with hydrogen peroxide in a hydrolysis reaction to yield peroxy acid. In general, the peroxy acid precursors can be represented by the following formula: 0,01 ahm where a is a leaving group and “ is any functional group; So that when performing superhydrolysis, the structural composition of the resulting peroxy acid is: 0 X = d - QOH. It is preferable that the compounds of the raw material of bleached peroxy acid overlap at a level from Ne 960.8 to 9671 of co. ) preferably from 901 to 96010 by weight; More than 961.5 to yo of the weight of the fittings is preferred. Suitable peroxy acid feedstock compounds (Glad) contain one or more JN©-acyl <O-acyl groups and these starting materials can be selected from a wide range of classes. Appropriate classes include the anhydrides, the esters, the lage! esters lactams LUO dmides | 0 and derivatives of imidazoles and oximes with an acylated addition. Examples of the materials used in these sections are described in the British patent application No. GB-A-1586789. The appropriate esters are described in Ed.

UK Patent Application No. 3-4-8 864798 1147871” 2143231 and EP-A-0170386 EP-A-0170386 The leaving group “as Hall” referred to here must be a sufficiently active A group of 0 for the decomposition reaction to occur above Jl within the maximum time range (eg wash cycle) and although dia .1 is highly effective it will be difficult to stabilize this activator for use in a bleaching formulation. Wim choose I.

Ole gana Favorites from the set consisting of: ‎LY R3 RY‎ ‎Fw +©‎ 0 ‎i 1 N\ 2‎ ‎—N—-C—R —N N ~~ N—C—CH~—F} 1 Re y a a Re Y / 1 ~0~CH=C—CH=CH, —0—CH=C—CH=CH; b 0 i YY, | Ct Edam 2 : NR : No , + God it 1 ! 0 0 2 between Sale and | 0-0-0147 RYO AY SQ

cm ;- and mixtures thereof in which RY is an alkyl aryl or an alkaryl group containing from 1 to 14 carbon atoms; 183 is an alkyl chain containing 1 to A carbon atoms; 187 is an H or 183 187 is an alkenyl chain with 1 to 8 carbons and y is an 11 or solvent group. © and RPS RY 87 can be completely replaced by any functional group chosen from; For example; alkyl groups hydroxy alkoxy halogen amine agnostic; _nitrosyl, amide, ammonium or -alkyl ammonium the preferred solvent groups are -SOsM', 0:147- 50,247 Ve and ONR)ss -N'R)X More preferred -S0 MT and 00:124- where RY is . an alkyl chain containing 1 to ; carbon atoms 14 is a cation that gives solubility to the bleaching activator and 3 is an anion that gives solubility to the bleaching activator. Preferably 101 is alkali metal; ammonium or ammonium cation substituted; With sodium and potassium Vo being the favourites; And x is a chalide hydroxide methylsulfate or anion . acetate anion <A The starting material for perbenzoic acid gives the compounds of the starting material for perbenzoic acid perbenzoic acid Benzoic perhydrolysis after hydrolysis. The compounds of the starting material of perbenzoic acid added to it ©0- Jud 0-8 that are suitable include benzoyl oxybenzene sulfonates and unsubstituted which include, for example, oxybenzoyl sulfonate: 0 mouthwash

The compounds suitable for Load are the benzoylation products of sorbitol 1101i:50; glucose cglucose and all saccharides by means of benzoyl addition agents which include, for example: AcO 0 OAc GAC OBz COCH; = AC© and 57-benzoyl. The amide precursor compounds of perbenzoic acid include N-benzoyl succinimide, tetrabenzoyl ethylene diamine, and N-benzoyl ureate. N-benzoyl substituted ureas. The starting materials for perbenzoic acid of the appropriate imidazole type include: 0-imidazole to N-benzoyl imidazole and benzimidazole. <-. N-benzoyl benzimidazole Other useful perbenzoic acid precursors containing the Neacyl did -N Ae gene include pyrrolidone 7<-N-benzoyl pyrrolidone, dibenzoyl taurine, and benzoyl pyroglutamic acid benzoyl pyroglutamic acid yo. The raw materials for perbenzoic acid include other perbenzoic acid cthe benzoyl diacyl peroxides and the cbenzoyl tetraacyl peroxides, and the compound has the following formula: 0 0 0-4 ~~ 600 m << 0 © or Phthalic anhydride is a precursor compound of perbenzoic acid 00 which is another suitable for use here. : 0 0 m

Mg and the raw materials of perbenzoic acid, oe Perbenzoic acid, have the lactam type, to which the -N acyl L-17-8071816 is added, and the appropriate formula is: 1 and O-N 7 R&—~C—N__ | CHy~{CH , In where is « from zero to A and preferably from zero to 7; And 18 is a benzoyl group Precursors for Perbenzoic acid Derivatives Feedstocks for perbenzoic acid derivatives prepare substituted perbenzoic acids after perhydrolysis. Suitable substituent perbenzoic acid derivative precursors include any of the perbenzoic precursors described herein that are led by a substituted benzoyl group (sb) of a non-cationic functional group and include; eg. For example; chydroxy alkyl and alkoxy groups halogen 13108860 amine camine and nitrosyl and amide .amide and in a preferred section of the compounds of the precursor of substituted perbenzoic acid are amide-substituted 1 compounds that have The following general formula is: ar 82 aj 0 ar sq sa 1j 0 © km » 05 m o where RY is an aryl or an alkaryl group with 1 to VE carbon atom and 182 is a carylene or alkarylene group containing from 1 to VE carbon atom; R is 11 or a co-alkyl group; aryl or Ys alkaryl contains from 1 to 10 carbon atoms and can be .1 is absolutely any leaving group .RY preferably contains from 1 to 11 carbon atoms .R? preferably contains of ; to 8 carbon atoms. RY can be an aryl; Substituted aryl or alkyl m

-1e- aryl containing branching; substitute” or both and can be obtained from either artificial or natural sources which include, for example; Friendly fat. Various similar structural types are appropriate. RAD and dod can substitute for alkyl groups aryl dN, halogen, nitrogen, sulfur and other substituent groups or 0 other substituent organic compounds. 187 is an 11 or die and for RT 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. 0170386-M-5. Peroxy-Cationic Acid Precursors Compounds of peroxy-cationic acid precursors prepare peroxy-cationic acids after hydrolysis. Indeed; Cationic peroxy-acid precursors were formed by substituting the peroxy-acid moiety in a suitable peroxy-acid precursor with a positively charged functional group; Such as the ammonium group or calkyl ammonium, preferably the ethyl group or Jie methyl ammonium, and the starting materials for the cationic peroxyacid yo acid are actually present in the formulations as a salt with an anion suitable anion” such as the halide ion jon or the methylsulfate ion cmethylsulfate fon for example. In order for the compound to be the starting material for a cationic substituted peroxy acid, it can be a starting material compound for a perbenzoic acid; or a substituted derivative thereof; As described here previously. 0 Alternatively the peroxy acid precursor compound may be an alkyl percarboxylic acid precursor compound or the amide-substituted peroxy acid precursor described herein later. The starting materials for cationic peroxy acid are described in US Patent No. 4,904,406 « 4,751,015 » 4,988,451 4,397,757 269,962, Y 5,127,852 (Ye 5,093,022 5,106,528) and English Patent 1,38 2,594 UK. Patent AYA

_ 7 0— European No. 475,512 “EP 458,396 and 284,292 and in Japanese Patent No. JP 87-318,332. Suitable cationic peroxy-acid precursors include benzoyl oxybenzene sulfonates, alkyl-substituted alkylammonium or ©benzoyl and N-acyl caprolactams and benzoyl tetraacetyl benzoyl monosulfate peroxides. The preferred substituted oxybenzoylbenzoyl sulfonate (Gen) is the methylated −(trimethylammonium) derivative of benzoyl oxybenzoyl sulfonate. The preferred cationic substituted alkyl oxybenzene sulfonate has the following formula: so, 3 © 0 / 0 d + TNT TNT Kha N LAN 0 7 * M and materials include Preferred cationic peroxy-acid type added carrolactam Jud -17 a) N-acylated caprolactam trialkylammonium methylbenzoyl; In particular ole is trimethylammonium methylenebenzoyl. For NT m or _/ 1 p & + 2 p and includes _ other preferred cationic peroxy acid feedstocks of the type caprolactam with added N-acylated caprolactam trikyl ammonium methylene alkyl 0 0 i 1 1 ! N UL 1 cm \ N,._CHn 3) 0 ~~ Ye where « from zero to OY and in particular from 1 to © AYA

To The other preferred cationic peroxy-acid precursor is (N,) = F (N,N tri-Jie) ethyl sodium chloride;-(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 the preferred raw materials of this type work on the preparation of peracetic acid after the hydrolysis. . The preferred overcarboxylic alkyl precursor compounds of the amide type include the added alkylene diamines (N°, N, Nl), 117-_ NI tetra 11,111 acetylated alkylene diamines 0 where the alkylene group contains An alkylene is 1 to 1 carbon atoms and in particular those compounds in which the alkylene group contains 1, 1, and 1 carbon atoms. Tetraacetyl ethylene diamine (TAED) is particularly preferred. Primary preferred alkyl percarboxylic acid feedstocks include co ov #- tert Veo 3,5,5-tri-methyl hexanoyloxybenzene sulfonate and sodium nonanoyloxybenzene sulfonate. (NOBS) sodium nonanoyloxybenzene sulfonate and sodium acetoxybenzene sulfonate (ABS) sodium acetoxybenzene sulfonate and penta acetyl glucose © .glucose _precursors of the substituted alkyl acid peroxyamide and the precursor compounds of the substituted alkyl peroxybenzene sulfonate Amides suitable for Lal, including those with the following general formula: RI —N—C—RZ—C—1 ag u ss ss l or 5 1 1 a 5 1 m

and e where RY is an alkyl group with 1 to VE carbon atoms; R? is an alkylene group containing from 1 to 1 carbon atom; 187 is an 11 or an alkyl group containing from 1 to 10 carbon atoms; .a can be a leaving group. RY contains preferably 1 to VY carbon atom; It contains 18 preferably of; 0 to SIMA carbon. RY can be a branched or straight-chain alkyl containing branched, substituent, or both and can be obtained from synthetic or natural sources. Including, for example, fat Alwadak. Various similar structural species are suitable for 1. The substitution may include alkyl groups, halogen, nitrogen, sulfur, sulfur, and other substituent organic compounds or groups and are 187 in the preferred Vo form of 11 or methyl. RPGR shall not contain more than 18 carbon atoms in total and the amide-substituted bleaching agent activator compounds are described in the European patent application EP-A-0170386 Raw Materials Benzoxazine Organic Peroxy Acid and Appropriate Compounds Lad are Ad Bald compounds of the benzoxazine type 0 as described for example in EP-A-332,294 and BP-A-482,807 and as Especially those with the following formula: 0 Mar QOL Led Lay Substituted benzoxazines of the following kind: 0 Ry 0 > 0 Ya mh where Ry is 1]; alkyl carel; ariel; Aryl JS where Ry is a mg of Ry and Rs are same or different substituents selected from 11 and an alkyl halogen alkyl halogen AYA

Coo alkyl amino camino amino alkoxyl alkoxyl chydroxyl hydroxyl caryl aryl alkenyl or alkyl group) and carbonyl H is Rg (where COORg is God amino .carbonyl is: benzoxazine and one of the particularly preferred feedstocks is the benzoxazine type

A

1 2 That © : Processed Organic Peroxy Acid The bleaching organic peroxy acid system may contain in addition to; or as a substitute for; Organic Peroxy Acid Bleach Raw Material Complex; treated peroxy acid;‎ 96010 by weight; More preferably from 901 to YO at a level from 960.9 to Glad .0 of the formula weight. One of the preferred divisions of organic peroxy acid compounds are amide-substituted compounds having the following general formula:

R1—G-—N—RZ—¢c— OOH kd 2G J-YZB 2-00 A 0 VE atom to 1 karyl atom of cdi is an alkyl group; RY where a VE atom is to 1 karelene containing from eb carbon; and “18 is an alkyl group; No 01 to 1 is 11 or an alkyl group; An aryl or karyl has an RT carbon and is a carbon atom. It contains 182 preferably 11 to 1 preferably of RY carbon atoms. It is a straight-chain or branched alkyl; RY contains carbon atoms. and can be A of ; to an aryl or alkyl aryl substituent containing a branch; substitute or both and can be obtained from artificial or natural sources including but not limited to; Friendly fat. The synthetic types are 0 5 m

1e Similar multiples are suitable RP and substitution may include oS aryl group; halogen Nitrogen; Sulfur and other substituted organic groups or compounds. 85 is preferably 11 or 1 and RGR! must not contain more than 18 carbon atoms in total. Amide-substituted peroxy-acid compounds of this type are described in © European Patent Application No. EP-A-0170386

Other organic peroxy acids include diacyl and tetraacyl peroxides; In particular, Diperoxyhexadecanedioic acid, Diperoxyhexadecanedioic acid, Diperoxyhexadecanedioic acid, Diperoxyhexadecanedioc acid, and the preferred organic peroxy acid here is Dibenzoyl peroxide. and be acid

0 mono- and diperazelaic acid and mono- and diperbrassylic acid sud dis Naess diperbrassylic acid per oxycaproic acid N-phthaloylaminoperoxicaproic acid are also suitable for use here. Regular rate of launch vehicle

A means may be provided to control the rate of release of the anil agent and in particular the 15 oxygen bleaching agent to the wash solution. A means may be provided to control the rate of release of the bleaching agent for the uniform release of peroxide substances to the wash solution. Such means may include; For example, controlling the release of any inorganic perhydrate salt that serves as a source of hydrogen peroxide to the wash solution.

i One way to control the rate of release of the bleaching agent is by covering the bleaching agent with a cap designed for uniform release. The cover can thus contain; For example JB on ALE has poor solubility in water or a cover of sufficient thickness such that the melting kinetics of the thick cover give a uniform rate of release.

4 m

Because the covering material can be applied using several methods. Any coating material is actually present with a weight ratio of coating material to bleaching agent from 1:94 up to oF:1 preferably from 1:9 pounds in L400. Suitable coating materials include triglycerides (Sh) partially hydrogenated vegetable oil©, soybean oil, and cottonseed oil) or mono- or diglycerides; microcrystalline waxes, gelatin, cellulose, fatty acids and mixtures thereof. Other suitable covering materials may include sulphates, silicates, carbonates of the alkali earth metals, and alkali metals including calcium carbonate and silicate. Preferred covering material; In particular for the source of bleaching agent from the inorganic 0 perhydrate salt; on sodium silicate with ratio SIO;:1120 from 1 A to VY preferably 1 0) A up to 4, ?:1 and/or sodium metasilicate” preferably applied at a level of % Y to 9601 (usually 962 to 0%) of 8102 by weight of the inorganic superhydrate salt. Lad: Magnesium silicate can be used for coating. Any inorganic salt coating materials can be combined with other materials. No organic binder for an inorganic salt coating/organic binder formulation.Suitable binders include the following M-0,©-alcohol ethoxylates containing 001-mole of JS ethylene oxide. alcohol Preferably Min-Y alcohol ethoxylates JI alcohol ethoxylates containing 100-71 moles of ethylene oxide per mole of alcohol Other preferred binders include some polymeric materials and Polyvinylpyrrolidones |0 which have an average Molecular weight from 1,000 to 70.0660 and polyethylene glycols (PEG) polyethylene glycols having an average molecular weight of 01 to Toxo preferably 0001 to 45000060850 and preferably more than 0001 to 00001 are examples of these polymeric materials. Conjugated polymers of maleic anhydride with ethylene of methylvinyl ether methacrylic acid YO with maleic anhydride representing at least Yo mol per cent of Polymer 95m

—oA— are other examples of polymeric materials useful as binding agents. These materials and propylene glycol celal Jia may be used as is or in combination with polymeric solvents —o containing alcohol ethoxylates Cio-Coo alcohol and propylene glycol ethoxylates per mole above. The remembrance. Examples of binders include ethylene oxide 0 mol, as well as mono- and diglycerol ethers, other Cio-Cyp ethers of fatty acids, and carboxymethyl cellulose. Cellulose derivatives such as methyl cellulose, chydroxyethyleellulose, carboxymethylcellulose, similar or polymerically conjugated acids, or their salts are polycarboxylic acids, other examples of binders suitable for use here. for granules; Preferred pelleting methods include the use of any organic binders described herein previously. Any component can be used without limitation; Fryer; Roller mill and blender types (Sly in Lay granules/standard mixer or vertical daly spray. Molten coating formulations can be applied either by pouring as a spray into a moving layer of bleaching agent. V0 Other methods for obtaining a uniform release include automated means of altering the physical properties of the bleach to control its solubility and rate of release Suitable methods may include squeezing, mechanical injection, manual injection, and adjusting the solubility of the bleach By selecting the molecular size of any particulate constituent. While the choice of molecular size depends on both the composition of the particulate constituent and the desire for Y. to obtain the desired uniform release compounds, it is desirable that the molecular size be µm. 1701 µm. Preferably, it has an average molecular diameter of 8080 to 0000 © greater than Other methods for obtaining uniform release media include 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 present In it, it is possible to obtain the required regular release kinetics. AL Yo M

These are metal-based bleaching catalysts. Compositions described herein that additionally contain a cleaning-ingredient bleaching agent may contain a preferred ingredient, a metal-based bleaching catalyst. preferably a transition metal bleaching catalyst; © It is more preferable to have a bleaching catalyst containing manganese or cobalt. One suitable type of bleaching agent catalyst is a heavy metal cation-containing catalyst with a specific bleaching catalytic activity; Jie copper and iron cations and an additional metal cation have little or no bleaching catalytic activity; Jie zinc or aluminum cations; a separator having specific stability coefficients for the catalyst and additive metal cations; and in particular 0 ethylenediaminetetraacetic acid; and ethylenediaminetetramethylphosphonic acid) and their water-soluble salts. These catalysts are described in US Patent No. 4,430,243 Pat. .11.5. Preferred types of bleaching catalysts include the manganese-based complexes described in US Patent No. 5,246,621.

Pat. and US Patent No. 5,244,594 (US.

Pat. preferred examples of such catalysts include (1) -17 ct trimethyl-0;4; 7- Three azanonan “(ila) yut wa l (must-mil and la’th-m, rman) malaz (dy) 7- a third trimethyl jie ha cf = v a third aza noonan 4 (u-0) g¢(ClO); = v 0 tertiary aza nonan cyclo) +- and (e0!0) and mixtures thereof and others are described in EP No. 549,272 Other binding molecules suitable for use herein included (© ab -4 methyl-1; 0 * - tertiary aza gl-5,9, 59-trimethyl-1 1 —Y «triazacyclododecane methyl- -V ot a) tertiary aza_nonan cyclo 2-methyl-1,4,7- 26006 '- capped around #- tertiary aza noonan cyclic 2-methyl-1,4,7-tri- 4m

for Vf 7 1 223076100076 4th instance-A; =V cf triazyanonan Gila -2,4,7,1 ctetramethyl-1 ,4,7-triazacyclononane and mixtures thereof. The selection of catalysts for the useful bleaching agent in the formulations herein may be made as appropriate to the present invention. Examples of suitable bleaching catalysts see US Patent No.

Pat. © 4,246,612 and US Pat. No. 5,227,084 Pat. 17.5. See also US Pat. No. 5,194,416 Pat. 11.5 describing complex mononuclear (IV) manganese compounds OV) Mn Jie 4; = third instance--; cf 7- tertiary aza noonan cyclo) -4,7, 1).(PF¢)3-(OCH3); trimethyl-1,4,7-triazacyclononane) and another bleaching catalyst; As described in US Patent 0 No. 14,606 5.1 US.

Pat. is a water-soluble complex of manganese (IID and/or (AV) with a binding molecule that is a non-carboxylate polyhydroxy Ss ied having at least three 0-011 consecutive groups Preferred binding molecules include sorbitol, esorbitol, dditol, cdulsitol, mannitol, emannitol, xylitol, carabitol Js JY exylithol, adiwinthol, sal cadonitol, ariritol, cmeso-erythritol, VO, meso-inositol, cmeso-inositol, and lactose. clactose and mixtures thereof, US Patent No. 5,114,611 US.

Pat. Bleach Catalyst containing a complex complex of transition metals which include Mn, CO, Fe or Cu with a non-(large)-cyclic binder. These binding molecules have the following formula: rR? has =N-RY AR where JSR RY RMR is selected from H and alkyl and aryl groups substituted so that each RIN=CR? .13-07-85 is a pentagonal or hexagonal ring. This ring can also be replaced. and 3 is a bide bond group of SiO as 1187 “C=0¢” group of which 87 R% and SRT is an alkyl JH; or an aryl group; Including substituted and non-replaced groups. The binding molecules include the AYA rings

07108208 + pyridine nitro chalide 0100 and the binding moiety 7 ?'-pyridylamine-bis 2,2© bispyridylamine is particularly preferred. Preferred bleaching catalysts include complex compounds of Mn: cue Co + -pyridylmethane -bispyridylmethaneSe and pyridylamine bis .bispyridylamine daly catalysts_preferred . As TX) Co aS bispyridylamine 220 Cl (bispyridylamine and isothiocyanato bispyridylamine bispyridylam ine-cobalt (11); trisdipyridylamine-cobalt perchlorate ([01) Co 0 (7 “-bispyridylamine”(bispyridylamine 010:02 perchlorate bis- NYY) bispyridylamine (bispyridylamine copper(11) perchlorate; Tris(di-) ?- pyridylamine (di-2-pyridylamine iron (11) and mixtures thereof. Favored examples include diatomic Mn complexes with N-terminal tetrameric-1<7-Z-linking molecules parties; they include NMn™(w-0),Mn VN)" and [BiPy,Mn"(u-0),Mn"bipy,] 1° While the catalytic complex manganese compound compositions of the Bleach in this invention, it can be conceived in terms of that it includes chelates or complex symmetrically hydrated compounds that result from the interaction of the carboxyl and nitrogen atoms of the lipid (binding molecule) with the manganese cation (Jills manganese cation). The oxidation states of the Mn 0 cation during catalysis are not known specifically for AR and the valence states can be (+I) or (+I) Ar (+1V) or (HV) due to the presence of Six possible points of contact in the bonding molecules with the manganese cation; It is reasonable to conclude that polynucleated species and/or "cage" structures can be present in the bleaching medium Uy were the active Mn-binding molecule species actually present it acts in a clear preparative manner to obtain better bleaching performance against stubborn YO stains Such as stains of tea, ketchup, coffee, wine, juice and the like. mouth

l Other bleaching catalysts have been described; For example did in European Patent Application No. 408,131 (complex cobalt compound catalysts); and EP Applications No. 53, 306,089 (metallic porphyrin catalysts) and US Patent No. 4,728,455 US. (manganese agents / binding molecule © multilateral catalysts) and US Patent No. 4,711,748 US. EP No. 224,952 dele (manganese pated on aluminosilicate catalyst) and US Patent No. 4,601,845 US. (aluminosilicate support ao aluminosilicate manganese and zinc or salt Magnesium (magnesium salt, US Patent No. 4,626,373 dale) US. manganese/soa0 catalytic binding) US Patent No. 4,119,557 (Ferric complex catalytic agent) and written description of German Patent No. 2,054,019 (cobalt grating catalyst), Canadian Patent No. 866,191 (transition metal-containing salts), and US Patent No. gl aay! US. 4,430,243 (Materials ae BOS manganese cations and metal_cations 20800) and US Pat. No. Ve 4,728,455 (Manganese gluconate catalysts). Other preferred examples include Jal se cobalt ( I) The catalyst having the formula: for 81M CO[(NH3),M where the cobalt is in the oxidation state TH and “is a number from zero to 0 (preferably; or © and more preferably #) 10 represents one-terminal ligands” and : 0 0 is a number from zero to © (preferably 1 or ? and more preferably 1); BY represents two-terminal binding molecule; b is represents a number from 0 to ; is 7' is a three-sided joining member; t is a 0 or a 1; © is a four-sided joining; and is either a zero or 11 and © is a five-sided joining ; Up is zero or 1 and 5p + 40 +31 + 20 +“ +“ < 1 is “one or more carefully chosen anti-Yo anions present by a number where y is A number from 1 to ? (preferably 1 to ? 4m

S and prefer more? When obey is about the anion with a charge of -1); to obtain a neutral salt, it is preferable to choose 57 from the group consisting of chloride, nitrite, <u fill «nitrate, sulfate, and citrate The acetate cacetate carbonate and terminating conjugates, and in which at least one of the coordination sites connected to 0 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 cobalt reduction effort (TID) to cobalt (11) under alkaline conditions less than 154 volts (preferably less than 1" volt) against a normal hydrogen electrode, and the preferred cobalt catalysts of this type shall have the following formula : [Co(NH3)n(M)m]Yy Ve where 0S is a number from ? to © (preferably more; or 0 is preferred) and M' is a free-moving harmonic slit; preferred is chosen From the group consisting of chlorine bromine cbromine hydroxide water and (when it is greater than 1) cede unions (mixtures) and m is a number from 1 to ? (preferably 1 or 17 and more preferably) 1 Ve, which is N= nam and is a carefully chosen anti-anion numbered 7; which number is from 1 to ? (preferably ? to; and more preferably ? when y is an anion with charge 1-) to obtain a balanced salt. The preferred cobalt catalysts of this type used here are cobalt pentaamine chloride salts having the formula [Co(NH3)sClYy and in particular [Co(NH;3)sCl]Cly" M. The preferred AST formulations are This invention uses cobalt bleaching agent (TIT) catalysts having the formula: 1M (1.8). One or more cobalt-coordinating bonding molecules in one position and be 8 zero or 1 ye or * ? (preferably 1) and the 8 is a cobalt-coordinating bonding moiety in two positions and be a 4m i b and when 1 - nam zero then b = (preferably zero) and when 1 is zero or and 1 is one or more anti-anions chosen as € =n =m zero then 1 = It is a number to obtain a balanced salt y where y is suitable in a number where 1 is a Laie anion to 7 and preferably more? 1 is a y (preferably In the base is a constant less than ?7,. Sle, and where this catalyst has a decomposition rate (1- charge) © mol 'sec' (15 m).

The preferred T is chosen from the group consisting of chlorides; Iodide Tyg formate Nitrate cnitrate nitrite sulphate sulfate sulfite citrate citrate acetate carbonate bromide B(ph)s'“ BFs“ PFs bromide 0 phosphate phosphate phosphite silicate silicate tosylate methane sulfonate emethanesulfonate and consortia thereof [Gola] a proton can be added to it if there is more than one anionic group present in 7 Such as Baume H110 “20# etc. Also, 7 can be selected from the group consisting of non-traditional inorganic anions, Je, anionic surfactants (such as alkyl benzene sulfonates (LAS) daiwa alkylbenzene sulfonates 0 and alkyl sulfates (AS) alkyl sulfates and alkyl ethoxysulfonates (AES) 3-alkylethoxysulfonates and/or (Jie) anionic polymers polyacrylates 001780718188 and polymethacrylates

polymethacrylates, etc.). M-notches include but not limited to; eg NCS 80,326 F 507 S,05% Y”a 1 and carboxylates (preferably monocarboxylate 0000-0:00721018 but more than one carboxylate can be present in the moiety as long as the cobalt bond is Only one carboxylate pathway per moiety, in which case a proton can be added to the other carboxylate in moiety 14 or its salt (and optionally a YM proton can be added) there was more than one anionic group present in 14 (such as HPO

4 m

and 11606 “b0ta (HOC(O)CH,C(0)0-¢ etc.) The preferred M moieties are substituted and unsubstituted O©-,© carboxylic acids having the following formula: RC(O)O - where R is preferably selected from the group consisting of Ci-Caos© hydrogen (preferably 0,6) unsubstituted and substituted alkyl and 0-m© (preferably unsubstituted and substituted aryl CoCr) C3-Cags (preferably unsubstituted mixed aryl (C5-Cig) where the substituents are selected from the group consisting of -NR's"¢ NR3r) - _C(O)NR'5¢ -OR'¢ where RY is selected from the group consisting of hydrogen and m©-,© moieties and this substituted R thus includes moieties 0110(,011)- 0112(018476)- Cua where « is a number of 1 0 to 11 and preferably from 01 JY and preferably from 1 to # 14 is preferably carboxylic acids having the previous formula where R is selected from the group consisting of hydrogen methyl cethyl propyl and ©-«© straight or branched alkyl and benzyl and the most preferred 14 is methyl and includes carboxylic acid moieties 14 preferred formic Ye benzoic octanoic coctanoic, cnonanoic, dodecanoic, malonic, maleic, succinic, adipic 016, phthalic, 7- Jf 2-ethylhexanoic naphthenoic, oleic, palmitic terephthalate, ctriflate, tartrate, stearic, butyric, citric, acrylic, and caspartic | 0 fumaric, lauric, dauric, linoleic, dinoleic, lactic, dactic, malic, especially acetic acid. oxalate malonate malic cmalonate succinate succinate maleate (maleate picolinic acid acid 0100101 alpha and beta amino acids Jie) glycine yo alanine alanine and beta-alanine cbeta- alanine and phenylalanine (phenylalanine AY 4

The -1 + and cobalt catalysts for the bleaching agent used herein are known and described for example as well as their base degradation rates in MLL.

Tobe “Basic hydrolysis of complex transition metal compounds oF (087) (Adv.

Inorg.

bioinorg.

Mech. pp. 1-4 5. For example; Table 1 on page VV gives the base hydrolysis rates (denoted by © as kop) for cobalt pentaamine catalysts complexed with oxalate 1-4” V0 = kon) oxalate mol ' (2°V0) aul mercury 01” 0 kop) NCS mol ‘sec’ (©7”m)) and with formate “Use 701 X 8.8 Kop) sec’ (2°70) and with acetate ‎ TY x 4,1 Ko) mol “al (©””m)) The most preferred cobalt catalyst here are cobalt penta-acetate salts having the formula [Co(NH3)sOACITy where OAC is the acetate moiety and as 0 especially cobalt pentaamine acetate chloride which is [Co(NH3)sOACIClL plus [Co(NH;3);s0AC] (504) «[Co(NH3)sOAc](PFe)2 «[Co] (NH;)sO0Ac](OAc), [Co(NH3)sOACKNO3), ([Co(NHz3)sOAC)(BF4), (denoted here as PAC?) These cobalt catalysts were easily prepared Using known methods (Jia) those described for example in the article referenced (ad) herein earlier and referenced therein and US Patent 0 4,810,410 Patent No. 11.5 . by Dayacon et al. published on March 1 EF (VY ( TT A (1 A3) J.

Chem.

Ed. 14 10-; and the synthesis and characterization of organic compounds with the name (1970) (WL.

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

Chem. dnorg.

Chem.c (Y4AY) YAAS—YAAY T1 norg.

Chem.c (V4V4) 51437 Y+ YoY YT (1A (anklets) dnorg.

Synth of Hekla (+147) « Chemistry journal of (V40Y) Yo-YY (01 physical 00) in addition to the preparation examples mentioned herein later. Cobalt catalysts suitable for use in the cleaning tablets in this invention can be produced by following the preparation methods described in US Patent Nos. 5,559,26; ¢5,581,005 6 which are cited as references in this invention.

These catalysts can be concomitantly treated with adjuvants to reduce the effect of color if required by product descriptions or used in enzyme-containing molecules as represented here, or formulations can be manufactured to contain catalyst 'patches'. Organopolymeric Compound Organic polymeric compounds may be added as preferred ingredients in the cleaning tablets in this invention. Organopolymeric Compound Ld means any organic polymeric compound commonly found in cleaning formulations that have dispersing agents, anti-re-deposit, dirt-removing, or other cleaning properties. The organic polymeric compound was actually used in the cleaning formulations in this invention at a level from 900.1 to 9670 preferably from 900.8 to 9615 preferably from 961 to 9600 by weight of the formulations. Examples of organic polymeric compounds include co-polymeric or similar water-soluble polycarboxylic acids and modified polycarboxylates or their salts in which the polycarboxylic acid (Ne) contains at least two carboxyl moieties separated from each other by two carbon atoms On: the most. Polymers of the latter type are described in the British patent application GB-A-1,596,756. Examples of these salts are polyacrylates with molecular weight 000011-7”7001 and their conjugations with any other suitable monomer units. Including acrylic acids, cacrylic, fumaric, emaleic, itaconic, 0 atsamma; aconitic caconitic cmesaconic ccitraconic and methylenemalonic acids Alaeddl “methylenemalonic acid” or its salts and maleic anhydride related to “alkylene oS acrylamide” and “vinyl methyl ether” styrene and any mixtures thereof and preferably acrylic acid conjugated copolymers; and maleic anhydride having a molecular weight of 70,000 to Aen

CA

Preferred and commercially available acrylic-acid-containing polymers that have

PA20 PA30 Solcalm those sold under the brand name 15,0080 molecular weight less than those sold under the brand name dell and those sold under the BASF dhuls sokalan CP10 (PALO “PAILS” by Rohm and Haas. 4601: 4811. 45N Acusol incl. Preferable copolymers containing acrylic acid are those containing acid by weight 96700 preferably from 9680 to 96010 on monomer units: a) from 9640 to 96560 preferably from 9670 to 96860 by weight 9001 acrylic or Its salts and b) of a substituted acrylic monomer or its salts having the general formula -[(F-082-08,)00-0]- where is Ry or Ry and preferably Ry or Ry or Ry is at least one of the alternatives Ry or Ry to ; Carbon or hydroxy alkyl group and can be 1 alkyl of 0 is hydrogen or an alkali metal salt and most preferably is Ry from hydrogen and can be from hydrogen (i.e. Ros is an methylation of Ry Substituted acrylic monomer where it is and the most concomitant polymer has (methacrylic acid monomer) methacrylic acid monomer and contains from 9670 to 96860 by weight acid 79000 preferably of this type molecular weight methacrylic acid ell Sle by weight acid 96700 acrylic and 9640 to and polyamines and modified polyamine compounds are useful here including those derived No. Ano patent sel balt (8 those described J from aspartic acid and patent application EP- A-305283 and European Patent Application No. EP-A-305282

EP-A-351629 EC No. Other optional polymers can be poly alcohols and acetates Ye cellulosics of modified and unmodified celluloses JS polyvinyl alcohols vinyl and modified celluloses and polyoxyethylenes 0017076017160©5» Polyoxypropylene Of which both modified and unmodified copolymers and copolymers cpolyoxypropylenes or propylene glycol ethylene terephthalate esters modified and polyoxyalkylene terephthalate esters or mixtures thereof with polyoxyalkylene units propylene glycol ~~ Yo

aya

-4+- Suitable examples are described in US Patent Nos. 55,591,703 5,597,189 4,490,271 Dirt-removing agents Suitable polymeric dirt-removing agents include those soiling agents having: 6) one or more non-ionic hydrophilic components that Consist primarily of (1) polyoxyethylene parts having a degree of polymerization of at least 1 or (Y) oxypropylene parts 087010071606 or polyoxypropylene having a degree of polymerization from Y to 01 where these hydrophilic parts do not contain any oxypropylene unit unless they are joined to adjacent moieties at each end by ether bonds or (7) a mixture of 0-alkylene oxy-units containing oxyethylene and 1 to To an oxypropylene unit and it is preferable that these hydrophilic parts contain at least 9675 oxyethylene units and preferably more especially for those components which have at least 01 to 01 oxypropylene units + 960 oxyethylene units or b) one more of the hydrophobic components containing (1) oxyalkylene terephthalate and © oxyalkylene terephthalate parts; where; If these hydrophobic components Lad contain oxyethylene terephthalate V0 then the ratio of oxyethylene terephthalate to Cy oxyalkylene terephthalate units is ?: 1 or less or (1) parts m©-m© alkylene or M©-,© alkylene oxy or mixtures thereof or (7) poly(vinyl ester) parts and preferably polyvinyl acetate having a degree of polymerization of at least (£) alkyl ether substitutes (£) or b-hydroxyalkyl ether or Mixtures thereof where these substituents are present in the form of cellulose derivatives CC alkyl ether or © hydroxyalkyl ether or Yo mixtures thereof or a union of (a) and (b). in (a) (1) a degree of polymerization of 70000 although higher levels may be used; * preferably to Vou and preferably from + to 01 include the hydrophobic M0m©alkylene oxy moieties but without limitation; The end caps of Cua MOsS(CHoROCH,CHy0- Jie) polymeric dirt removing agents are M Be YO for sodium and “is a number of 1-4 as described in the patent M

Ve GoSelink aus VAAA January YT in ial US. Patent 4,721,580 US No. Gosselink Cellulosic Derivatives Lal The polymeric dirt removing agents used herein and templates include chydroxyether cellulosic polymers such as propylene ethylene terephthalate associated with ethylene terephthalate © or polyethylene oxide with polyethylene oxide terephthalate and the like and such agents are commercially available cpolypropylene oxide terephthalate propylene dirt removing agents include METHOCEL(Dow) ie include hydroxy ethers of alkyl cellulose CoC The celluloses used here are those selected from the group consisting of cellulose

U.S.A. Patent See US Patent No. chydroxyalkyl Cay 0 et al. Nicol VEY Dec YA Published 3 Polyhydrophobic (vinyl ester) Including soiling agents distinguished by (vinyl ester) fractions Waterproof copolymers associated with polyvinyl ester such as ©-,© vinyl esters preferably (polyalkylene acetate) that have been grafted into a polyalkylene oxide structure (vinyl ester vinyl) invention soln request asl polyethylene oxide as a structure Polyethylene oxide 0 as Code 1600 et al. 1987 Apr YY Published in EP 0.219.048 Euro 0.219.048 Another suitable soiling agent is a polymer conjugated with polyethylene oxide templates. terephthalate and ethylene terephthalate The molecular weight of this polymeric dirt removing agent is in (PEO) polyethylene oxide U.S. Patent. No. sel aly Coes to Yeo Range. From May 0, 19977 and Patent Invention Yo published in Hays as Hays US Patent 3,959,230 978 sls A published in Basadur as Basadur U.S. Patent US 3,893,929 Another suitable polymeric dirt removing agent is a polyester having units by weight 9015-01 repeated_ ethylene terephthalate units containing ADD

Except ethylene terephthalate together with 9680-4360 by weight Polyoxyethylene terephthalate units Derived from polyoxyethylene glycol having an average molecular weight Orman Another suitable polymeric descaling agent is the sulfonated product of the straight oligomer (jiu) Lad consisting of A basic oligomeric ester structure of terephthaloyl©, oxyalkyleneoxy repeat units and terminal moieties covalently attached to the structure and these degreasing agents are fully described in US Patent No.

Patent 1 Published + November 1986 IJ.

Scheibel and E.P. aul Gossellink Gel se and other suitable polymeric dirt removal include polyterephthalate esters in US Patent No. 4,711,730 US.

Patent published Dec. A VAAY 0 on behalf of Gosselink colleagues and the anionic terminally capped oligomeric esters in US Patent No. 580, 4,721 US.

Patent published at 1488 ly YT as Gosselink and Oligomeric Polyester Compounds in US Patent No. 4,702,857 U.S.

Patent published Oct 77 15897 as Gossellink Other polymeric dirt-removing agents include dirt-removing agents in US Patent #4,877,896 U.S.

Patent Ne published on 1?October 0984 on behalf of Maldonado and colleagues describing anionic terminally capped terephthalate esters and in particular a sulfaroyl. Another degreasing agent is an oligomer with terephthaloyl repeat units, sulfoisoterephthaloyl units, oxyethyleneoxy units, and oxy-0 7-_propylene-2 oxy-1 propylene 0 and the repeat units are structured oligomeric base and preferably terminated with end caps of modified isethiones. A particularly preferred descaling agent of this type contains one sulfoisophthaloyl unit, © terephthaloyl units, ethyleneoxy and 0-oxy;7-propyleneoxy,2-propyleneoxy units. 07-1 with a ratio of 1.7 to 1.8 and two end capping units of 7-(?

The heavy metal ion separator (a) The tablets of the present invention preferably contain an optional component, a heavy metal ion separator. The heavy metal ion separation material here means components that work on separating (forming a chelating compound) the heavy metal ions. These constituents may have the ability to form chelates with 0 calcium and magnesium but preferably have selectivity for binding to heavy metal ions such as iron, manganese and copper. The heavy metal ion separators are generally present at a level from 960.005 to SY, preferably from 960.1 to 9600, preferably from 960.75 to 967.5, preferably from 960.9 to 8 of the compositions weight. Ve and can be Heavy metal ion separators that are acidic in nature having for example a phosphonic acid or a carboxylic acid 0 as functional groups exist either in their acid form or as a complex/salt complex with a suitable counter cation such as a metal ion Alkali or alkali or ammonium or substituted ammonium ion or any mixtures thereof Preferably any water soluble salts/compounds Preferably Yo The molar ratio of this anti cation to the heavy metal ion dissociator is at least AY Suitable heavy metal ion separators for use here include organophosphates, such as polyaminoalkylene alkylene phosphonates, alkali metal ethane 1-hydroxy disphosphonates, and trimethylene phosphonates gb jill. The preferred of the previous types is the fifth (methylene phosphonate) ethylene diamine Cult (methylene phosphonate) and fourth (methylene phosphonate) Diamine and 1-1-dihydroxy-ethylene 1,1diphosphonate Other suitable heavy metal ion separators for use here include nitrilo-Yo-triacetic nitrilotriacetic acid and polyaminocarboxylic acids AYA ‏

Sub Jie acids ethylenediaminetetraamine pentacetic acid, ethylenediaminetetraamine pentacetic acid, ethylenetriamine pentacetic acid, ethylenediaminetetraacetic acid; And ethylene diamine diglutaric acid and 7- hydroxypropylene diamine disuccinic acid, sl «2-hydroxypropylenediamine disuccinic acid, any salts thereof. Particularly preferred is JBN, No succinic acid (EDDS) ethylenediamine-N,N'-disuccinic acid, salts of the alkali metal, the alkaline earth metal, ammonium, ammonium substituted for this acid, or mixtures thereof. The preferred EDDS compounds are free acids and sodium or magnesium salt, or a complex of these. Crystal growth inhibitor ingredient Cleaning tablets preferably contain a crystal growth inhibitor ingredient; Preferably used organic diphosphonic acid component at a level from 960.01 to 965 and preferably from 960.1 to 967 of the compositions weight. Organic diphosphonic acid here means an organic diphosphonic acid that does not contain nitrogen as part of its chemical composition. This definition thus excludes organo-aminophosphonates which nonetheless can be used in formulations of this invention as components of heavy metal ion separators. The organic diphosphonic acid is (0-0) diphosphonic acid 0 Preferably Cy aes diphosphonic acid Jie cethylene diphosphonic acid ethylene diphosphonic acid or more preferably 1-hydroxy-a-ethane acid; 1-Diphosphonic ethane 1-hydroxy-1, 1-diphosphonic acid (HEDP) can exist in the ionized form Ga or WIS and in particular as a salt or compound 45M

OLA WATER SOLUBLE SULFATE SALT The cleaning tablet optionally contains a water soluble sulphate salt. And if Taga se, then the sulfate salt soluble in water is at a level from 960.1 to 0, and more Sait from 961 to 90700, and more than 965 to 9675 of the weight of the oe formulations is preferred. The water-soluble sulfate salt can be any sulfate salt with any antication. The preferred salts were selected from the sulphates of the alkali metals and the alkali earth metals, particularly sodium sulfate. 1 Alkali metal silicate The alkali metal silicate is one of the preferred ingredients in the tablet of this invention. The preferred alkali metal silicate is sodium silicate which has a ratio of S10; Less than Ye, preferably from Ja 9601 9015, preferably more than 967 up to 96017 of weight d 510. The alkali metal silicate in Vo may be in the form of either an anhydrous salt or a hydrated salt. The Lal alkali metal silicate can be present as a component of an alkaline system. It is preferable that the base system also contains sodium metasilicate present at a SiO level of at least 54 by weight. This sodium metasilicate has a nominal ratio J510 :11820 of 1. The weight ratio of this sodium metasilicate to that of 0 -sodium metasilicate is; Measured as (SiO; preferably from 1 ion up to #: 4 and more Daly from 1 110 up to 7:1 preferably over 1:01 up to Yoo) The term 'colourant' as used herein means any material that absorbs certain wavelengths of light from the visible light spectrum. These pigments, 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 and can 4m

_Vo- Colorants are for example either dyes or pigments. It is preferable that the colored materials be stable in the composition in which they will be used. Therefore, in a formula that has a high pH, and in a formula that has a low pH, it is preferable that the coloring matter be stable, as the coloring matter is acidic.

8 The first phase and/or the second phase and/or the optional subsequent phases may contain a colored substance, a mixture of colored substances, colored particles, or a mixture of colored particles so that the different phases have different visible shapes. It is preferable that one of the first or second phases contains a colored substance. When both the first and second phases and/or subsequent phases contain a pigment it is preferable that the pigments have different visible shapes.

Ya Examples of suitable dyes include active dyes, direct dyes, and azo dyes. Preferred dyes include phthalocyanine, anthraquinone, and quinoline; monoisomers, diisobes, and multiple azos. Most popular Shai dyes include anthraquinones; quinoline and mono-azo. Favorite dyes include SANDOLAN E-HRL 976180 pul (5 aul) SANDOLAN MILLING BLUE (trade name) TURQUOISE ACID BLUE Ne (trade name) and SANDOLAN BRILLIANT GREEN (trade name) All available from Clariant UK HEXACOL QUINOLINE YELLOW (tradename) HEXACOL BRILLIANT BLUE (tradename) and both available from Pointe UK (oss aul) ULTRA MARINE BLUE; available from Holiday or Levafix TURQUISE BLUE EBA. (trade name) available from Bayer, USA. The pigment may be introduced into the phases by any suitable means. Appropriate methods include mixing all or some of the cleaning ingredients with the dye in a mill or spraying them all or some of them with the dye in a rotating mill. And when the pigment is present as a component in the first phase, it is present at the Yo level from ...96 to 901.9, preferably from 900.01 to 901; Preferably more than 960.1 up to 4 pm

L". When it is present as a component in the second phase and/or the optional phases, Lad, the pigment is generally present at a level from 960,001 to 960.1 preferably from 58 to 960.06 and preferably from 960.001 to 0.07 96. The corrosion inhibitor compound ° can contain The tablets of the present invention suitable for use in dishwashing methods contain corrosion inhibitors selected from organic silvering agents; in particular paraffin; nitrogen-containing JS inhibitor compounds; Mall compounds) and in particular salts (105011) of organic ligands. Description of organic silver coating agents in the international patent application No. 01 7 and the provisional European patent application EP-A-690122. Nitrogen-containing corrosion retarding compounds were described in the European patent application No. EP-A-634,478. Description of Mn(l) compounds for use in corrosion inhibition in provisional European patent application No. EP-A-672.749 The organic silver coating agent can be introduced at a level from 960.05 to 9600 V0 preferably from 160.1 to 968 V0. The total weight of the composition The functional role of the silver coating agent is to form a protective coating 'during use' or any silver components in the wash load in which the compositions of this invention are placed. The silvering agent must therefore have a high affinity for bonding to the solid silver surfaces; In particular when in the form of a component of the aqueous wash and bleaching solution with which YL Solid Silver surfaces have been treated. Suitable organic silvering agents include the fatty esters of mono or polyhydric alcohols having 1 to Ee carbon in the hydrocarbon chain. The fatty acid fraction of the fatty ester can be obtained from mono or polycarboxylic acids having from 1 to 1 carbon atom in Os Sond ule hydrocarbon Yo 4m

Salha Suitable examples of monocarboxylic fatty acids include behenic acid at the taste; cstearic acid, oleic acid, palmitic acid, myristic acid, dauric acid, acetic acid, propionic acid, butyric acid And isobutyric acid, acid 9010716, Valerie acid, lactic acid, dlactic acid, glycolic acid, PB = P, dihydroxyisobutyric acid, Jains. - Malonic acid, n-butyl-malonic acid, isocitric acid, citric acid, cmaleic acid | 0, malic acid, and succinic acid. The fatty alcohol moiety of the fatty ester can be represented by monoalcohols or polyhydroxyl having from 1 to 56 carbon atoms in the hydrocarbon chain Examples of suitable fatty alcohols include cbehenyl, carachidyl, ccocoyl, vinyl alcohol, ediglycerol and xylitol Ne, sucrose, erythritol, pentaerythritol, cerythritol, sorbitol, sorbitan. Preferably with the fatty acid group and/or fatty alcohol of the fatty ester cofactor from 1 to Y carbon atom in Alkyl series. The fatty esters of choice here are ethylene glycol esters; 0 and glycerol; sorbitan; The fatty acid fraction of the ester usually contains select varieties of behenic acid, stearic acid, oleic acid, palmitic acid, or myristic acid. Cl is glycerol. Highly preferred Lad are the mono, di, or tri esters of glycerol and fatty acids described earlier. Qom

Specific examples of fatty alcohol esters used herein include: c-palmityl di-Jactate, oly cocoyl isobutyrate, coleyl maleate, coleyl dimaleate, and ctallowyl propionate. Proprionate Esters of the fatty acid used herein include: xylitol monopalmitate, pentaerythritol monostearate, sucrose monostearate 110101051637316, glycerol monostearate, ethylene glycol monostearate and sorbitan esters. Suitable sorbitan esters include sorbitan monostearate 0 ounces e; als sorbitan palmitate sorbitan monolaurate and sorbitan monolaurate 10001017115316 G5 sorbitan mono-oleate sorbitan dilaurate sorbitan distearate - sorbitan dibehenate | 0 01016816 Lady “sorbitan” sorbitan mono- and di-oleate mixed tri-alkyl esters. old glycerol; Favorite . Here are glycerol monostearate, glycerol mono-oleate, glycerol monopalmitate, and glycerol monobehenate | 0-glycerol distearate and including suitable organic silver coating agents; triglycerides and mono or diglycerides; and their hydrogenated derivatives (GIS) or partially, and any mixtures thereof. Suitable sources of fatty acid esters include vegetable oils, fish oils, and animal fats. Suitable vegetable oils include soybean oil and cottonseed oil; castor oil; olive oil; and oil m

4 l

Sudanese Jl; yellow oil and sunflower oil; rapeseed oil; grapeseed oil; palm oil; and corn oil. The waxy materials are; Including fine-crystalline waxy materials, organic silvering agents are suitable here. The preferred waxy gas of gall has a melting point in the range 2770 to

5101 m and usually contain from 11 to 11 carbon atoms, preferably waxy petroleum materials of the type

Paraffin and microcrystalline, which consist of long-chain saturated hydrocarbons.

Alginate and gelatin are suitable organic silvering agents here.

Diakylamine oxides such as Mo2-0,© methylamine oxide and quaternary alkylammonium compounds and its salts such as Cpp-Cop methylammonium halides are also suitable here.

1 Other suitable organic silvering agents include some polymeric materials. did als Polyvinylpyrrolidones having an average molecular weight of 0 to 700001 and polyethylene glycols (PEG) polyethylene glycols having an average molecular weight of 09 to Nad gg 00.0086 polyamine oxide N-oxide 658 +; And the conjugated polymers (-N) copolymers (N-vinylpyrrolidone)

Ns 0 vinylimidazole <N-vinylimidazole and cellulose derivatives Jia cellulose Methyl cellulose Jie (oS Shy) cellulose. P0108L00<70060716. 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.

7 Lid polymeric dirt-removing agents can be used as silver-coating agents

membership.

dele The preferred organic silver coating is opi ll oil, and it is actually a branched aliphatic hydrocarbon with a number of carbon atoms in the range from 0 to 00, and the preferred paraffin oil was chosen from the Cosas species. branching shape

:1 to 7:1; Preferably from 1:00 of Ala - permanent which has a cyclic hydrocarbon ratio to the Yo

5 m

Am, and paraffin oil, in which these qualities are found.” Which has a hydrocarbon ratio of 1:1 to © Salzburg Wintershall Sold by Wintershall GA FY Ada to La Ads

WINOGT0 under the trade name (Lila) (Salzbergen) Nitrogen-containing corrosion inhibitor compounds Suitable nitrogen-containing corrosion inhibitor compounds include imidazole and its derivatives such as ° and imidazole derivatives 2-heptadecyl imidazole benzimidazole and 7- heptadecyl imidazole Those described in Czech Patent No. 139, 279 and imidazole patent application which also describes a method for preparing imidazole compounds GB-A-1, 137,741 uk imidazole. Also suitable are nitrogen compounds and nitrogen-containing corrosion inhibitor compounds Ya pyrazole 056 and its derivatives, especially those in which pyrazole is substituted in any of 11 or Ry where Rs Ras Res Ry is * or ; or © with substituents 1 in any of the positions or JS C-Cyp is any of Rsy Ry and can be COCHs or CONH3 or CH,OH

NO, or NH, any of the 11 or Ry hydroxyls Other suitable nitrogen-containing corrosion inhibitor compounds are benzotriazole Jal Veo ~o~lié -1 and “2-mercaptobenzothiazole” — Y cbenzotriazole azole and thionalide <1-phenyl-S-mercapto-1,2,34-tetrazole —€ FF —€ 0-etapacrim melamine and morpholine morpholin cthionalide cyanuric acid stearoyl stearamide cdistearylamine aminotetrazole cdistearylamine aminotetrazole caminotriazole amino triazole cyanuric base 0 indazole and andazole as amines Jie Nitrogen amines and compounds containing Nitrogen chloride Jie ammonium and ammonium compounds cdistearylamine especially stearylamine or cammonium bromide sulfate or ammonium bromide cammonium chloride ammonium

Ammonium sulphate or diammonium hydrogen citrate is suitable for use here. Corrosion Inhibitor Compounds (110)011 The cleaning tablets may contain a corrosion inhibitor compound (20001. © Compound Mn) can be used preferably at level from 960,006 to 965 wt; Preferably from 0601 to 961 and preferably from 960.07 to 960.4 of the fittings weight. Preferably the M(Il) compound is used at a level of 1 ppm to You ppm; Preferably from 1.9 ppm to 50 ppm and preferably more than 1 ppm to 01 ppm by weight for MID ions) in any bleaching solution. Ve compound (100) can be an inorganic salt in anhydrous or hydrated forms. The suitable salts include dmanganese sulphate, manganese carbonate, ananganese phosphate, and manganese nitrate. Manganese acetate and manganese chloride. MID compound can be a salt or complex of organic fatty acid BaVo. Manganese acetate or manganese stearate. Manganese stearate can be A MID compound is a salt or complex of an organic binding molecule. In one preferred embodiment the organic binding molecule is a heavy metal ion separator. In another preferred embodiment, the organic binding molecule is a crystal growth inhibitor. Other Corrosion Inhibitor Compounds for Jedi Corrosion Inhibitor Compounds Other suitable additive .mercaptans and diols and in particular mercaptans with .; to Te a carbon atom including led mercaptan lauryl mercaptan cthiophenol thionapthol thionalide thionthranol 1080:8001 suitable Lal is 0o0-m,© saturated or unsaturated fatty acids Saturated or its salts, especially aluminum tri-stearate, aluminum Yo, when reconstituted. Cip-Coo are hydroxy fatty acids or their salts

Ag 0 is also suitable and octadecane to which phosphanates are added and other antioxidants such as gall hydroxytoluene (BHT) betahydroxytoluene are also suitable here. Butadiene and maleic cacid copolymers, particularly those obtained under reference name 17787 by © Poly106 Polysciences, have been found to be particularly useful as corrosion inhibitors. Hydrocarbon oils Another preferred cleaning-ingredient to use in this invention is chydrocarbon oil, actually permanently chain aliphatic hydrocarbons Lh having a number of carbon atoms in the range 0*0 to Wo 0 and the preferred hydrocarbons are saturated and/or branched. Cy was selected as the preferred hydrocarbon from the fully branched Cosas species having a cyclic to acyclic hydrocarbon ratio of 1:01 up to ?:1 and preferably from: 1 #5 to 1:1 and the preferred hydrocarbon oil is paraffin. And paraffin oil that meets the previous characteristics and that has a ratio of cyclic to acyclic hydrocarbons TA 7” is that sold by “Wintershall 0 AA: © 5120 Germany under the name WINOGT70 NO Bismuth compounds that are soluble in water can be That the Chal tablets in this invention used in dishwashing liquids contain a water-soluble bismuth compound and it is preferable that it be present at a level from 760.005 to 9670 and preferably from 960.01 to 900 and preferably more than 960.1 to 561 The compound of bismuth that is completely soluble in water can be any salt or a complex compound of bismuth with any inorganic or organic counter anion, and the preferred inorganic bismuth salts were chosen from bismuth trihalides and nitrate Bismuth nitrate, bismuth phosphate, and Bismuth acetate and citrate are the preferred salts with an organic anti-anion.

| Preferred enzyme stabilization system Preferred enzyme-containing formulations can contain 960.009 to 01096; preferably 960.005 to TA and preferably 960.00 to 967 by weight for an enzyme stabilization system. The enzyme stabilization system can be any stabilization system that is compatible with the enzyme cleaner. © These stabilized systems may contain calcium ion, boric acid, propylene glycol, and short-chain carboxylic acid; cboronic acid and chlorine bleach; and mixtures thereof. These liad anchoring systems can contain reverse-Jie (reverse protease inhibitors) inhibitors. 0 - Lime soap dispersant The tablets of this invention may contain lime soap dispersant preferably at a level from 960.1 to 9640 by weight; more preferably from 961 to 90,710 by weight; Preferably over 967 to 9600 of the weight of the fittings. Calcium soap dispenser is a substance that prevents precipitation of alkali metal salts, ammonium VO, or amines of fatty acids by calcium or magnesium ions. The preferred lime soap dispersing compounds are described in International Patent Application No. 08877/177093. The foam inhibition system preferably contains the cleaning tablets of the present invention; when configured for use in machine-washing formulations; On foam inhibition system located at level from 960.01 to Ye 9015; Preferably from 960.05 to 9600 and preferably more than 96.1 to 965 of the formula weight. Suitable anti-foaming systems for use herein may include any well-known anti-foaming compound “ded La” eg silicone anti-foaming compounds; and Y=2-alkyl and alcanol anti-foaming compounds. Preferred foam inhibiting systems and anti-foaming compounds are described in Adel gd may patent application No. WO93/08876 Yo and EP-A-705 324 74m

A

Polymeric dye transfer inhibitors preferably from 95600 from 960.01 up to Lad. The cleaning tablets here can contain up to 960.9 by weight of polymeric dye transfer agents. 8 Polymeric dye transfer inhibitors are chosen preferably Polyamine N-oxide polymers Polyamine N-oxide polymers No imidazole id and [A2-N-vinylpyrrolidone Jud -N) copolymers polyvinylpyrrolidonepolymers Polyvinylpyrrolidone & ped gy «N -vinylimidazole or combinations thereof. Other optional active ingredients Other optional active ingredients suitable for use in formulations of this invention include aromatics and filler salts with sodium sulfate being a filler salt. For formulations pH pH It is not preferable that the cleaning tablets in this invention be composed so that they have an excessively high pH of 9761, but it is preferable that they have a pH measured as a solution of 4.0 of AST and preferably 11.48 and so Most preferred from 9 to 107.5 (WA) in distillate of NO

Ave to the method of washing dishes in a machine Any suitable methods for washing or cleaning dirty cutlery in a machine have been conceived. knives and mixtures finished by means of an aqueous Ye liquid having an effective quantity dissolved or atomized therein from the cleaning tablet of this invention. It means an effective amount of ¥ g of product dissolved or dispersed in a wash solution of a volume of 01 cleaning tablets / g to or wash solution volumes normally used in Glad methods liters in the form of doses produced from 10 to g to 560 g Vo Dishwashing in the usual machine. It is preferable that the cleaning tablets be from gm in weight. Vo gm to 01 gm in weight, preferably from Yo

AY4

—Ao— Examples Abbreviations used in examples: In cleaning formulations, abbreviated ingredient definitions have the following meanings: 0000 tri polyphosphate STPP Up SSodium hydrogen carbonate SuBicarbon Citric Anhydrous mesAnhydrous Citric acid Usa SAAnhydrous sodium carbonate <li go SCarbonate Sodium Amorphous GSluAmorphous Sodium Silicate 1110816

Na, O: SiO(Y = crystalline stratified silicate of formula SKS-6

Crystalline layered silicate of formula 5-Na,Si,Os sodium perborate monohydrate PB1

Anhydrous sodium perborate monohydrate

Ci3-Crs ethoxylated / isd mixed fatty alcohol No Jun 32 3 propoxylated 2,8 has a mean ethoxylated grade and a mean propoxylated grade ©,4 sold under the trade name plurafac by BASF Alii Tetraacetyl ethylene diamine TAED

Fthane 1-hydroxy-1,1-diphosphonicacid [11]pentamine cobalt acetate PAAC

Pentaamine acetate cobalt (III) salt sold under the trade name od Cu Winog 0 by Caper Avene

Wintershall. Proteolytic a iY 1Proteolytic enzyme 016856

aya

CAT— Amylose hydrolysate a 33Y!Amylolytic enzyme Amylase 3benzotriazole 6020182016 BTA Sodium Anhydrous Cl SAAnhydrous sodium sulphate As Sulfate 106 Ethylene Glycol JsPolyethylene Glycol Approximate Molecular Weight 55 PEG3000 Available From Hoechst 001 11061 Ethylene Glycol J sPolyethylene Glycol Approximately Juda Weight PEG6000 Available from Hoechst 001 +

Yo as a solution of 961 in distilled water at (elie, pH) and all levels were estimated in the following examples as parts by weight. 1-17 Examples The following shows examples of cleaning tablets in this invention suitable for use in dishwashers. ,

VI 7 1 111 II 1 1 PHASE q,0V q,0V 016 7 47 STPP ML You 1,0. YY 84 silicate m f or m SKS-6 °,Yeo £0) Y,04 v,0 carbonate 7 ara Ca +, TA +, YA SYA YA SYA HEDP

Y,TA YA YA 6 Y,to Y,t0 PB1

Covet Coen CY Coen Coan PAAC

CATY AY “YoY 0 AY YEA amylase fed ‘ed (04 Ce Vat et protease) 0 ARA GA CA ER non-ionic YA LY +71 on é PEG6000

AY 4

Sala oo 'ot NY ot Lk BTA Yo 8 “Vo oY) oe Ye Cdl Aromatic A CNY GY VY oY VY L-7 sulfate” YAEY Total aa) A,00 Vvy,Yo And ajm jm jm jm al-Tur? Amylase ‘Yo Yo VY’ Yo Yo GY Protease M OY YY L 17” L Citric acid L ne oY OY sulfamic acid L a bicarbonate fo io qa fo to carbonate 0 2 silicate RE 15" NY CaCl, Va oa vo NA va oe PEG3000 Total 0, ?g 0.1g 7.1g 1.1 date diate g Polyphasic tablet formulations prepared As follows, the effective cleaning composition of phase 1 was prepared by mixing the granular and liquid components and then passing them into the mold in a regular rotary press. The press includes a hammer shaped to form a die and the section of the die is LE 2720 mm. The composition was then subjected to a compressive strength of 1460 kg/You and then the tamper was lifted to reveal the ©_first phase in the disc containing a mold on its upper surface. The active cleaning composition in the “phase” was prepared in a similar manner and passed into the mould. Then the active particulate composition was subjected to a compressive strength of VY kg/cm; Then the batter was raised; and eject the multiphase disc from the disc press. The resulting tablet is dissolved or crumbled in a washing machine as described by Gil through VY AY 4.

—AA— When does the phase dissolve? to tablets within 0 minutes. The tablets are given JARED melting properties and excellent cleaning in addition to good cohesion and tablet strength. 4m

Claims (1)

—A4- Claims of protection in g to Ve polyphase for a dish washer machine having a weight of detergent tablet 1 1 g consisting of 56 7 a) first phase in the form of a molded body at least one in it; And a second phase in the form of a sticky compact body located inside the aforementioned template, which (=) ¢ Enzym is made of a solid particle, which has a weight of less than ; g; And in it the second phase includes enzyme 0 and in it the dissolution times are 1 multiphase according to the element detergent tablet - “1 The first phase and the second phase in the dishwashing machine are not synchronized with each other.” Multiphase according to the element 7 In which the detergent tablet is pressed or compressed -* 1 Now kg/You second phase at a pressure less than XY multiphase according to any of the previous elements; Cleaning 1 and Yau kg / Tou is compressed or pressed. The formed body is prepared at a compressive pressure of at least “Now kg / You.” The second phase is at a pressure less than Y for any of the previous elements, in which the second phase dissolves ls detergent tablet aati —o 1 tablet more quickly than the first phase. Y of any of the above elements in which it dissolves Gig multiphasic detergent tablet —1 —1 washing dishes in less than © minutes AT second phase at Y 99 AD —q,— For any of the previous elements and in which Ga, multi-phase detergent tablet is formed - 17 1 NY The compressive stresses of the layer on the first and second phases are in a ratio of at least "to any of the previous elements; and in it the compressive stresses of the layer are made Multiphase detergent tablet Eg A YT 9680 preferably at least 96100; most preferred (JY on 9600+) Disk configuration 8 minutes; 0 minutes preferred; 01 Released to wash through the enzyme at least 0 of the enzyme wt and more preferably within ?1 minutes of any of the foregoing items; and in which includes a, multiphase detergent tablet 1-4 Enzyme 1202700 is permanently concentrated in the second phase. Y is polyphase according to any of the previous elements and contains detergent tablet - 1 bond. sala The second phase includes the Y of the element \ in which you choose the binder ad Polyphasic detergent tablet Detergent tablet 1-1 Organic polymer starch derivatives Li of the group containing sugar ¢ Sugar derivatives Y and inorganic. Detergent tablet -1 ¢ Agia The second phase includes a fumigating agent selected from effervescent agents and mixtures o according to any of the preceding items additionally including a detergent tablet —VF 1 . A separator layer between the first and second phases, in which the multi-phase VY layer includes, according to the element, detergent tablet. mouth ga BVO 1 cleaning the multiphase detergent tablet according to any of the previous elements so that the enzyme was selected from the protease cAmylase lipase peroxidase V 08868 no «0© t; Cutinase and cellulose. Cellulase -11 1 multi-phase detergent tablet Gy for any of the above elements and in which the weight of the first and second phases is Y in a ratio of at least 7: 0 and preferably at least 1. 01: ya AVY) multiphase detergent tablet a, of any of the above items and in which VA is AL process dishwashing including charge AT dishwashing with one or more multi-tablets Y “PHASE” Each disc has a weight of 0 to 15 pounds and includes: 1 second phase in the form of a compact, contiguous body J contained within said mold which is a solid particle aE which has less than ; g; In which the second phase includes Enzyme-11 Enzyme 1 Gig process of element YA so that the multi-phase cleaning tablet dissolves or disintegrates in less than 101 Y minutes in the dishwasher. -01-1 Gg process of element 18 or element 14 so that the differential melting of the existing phases takes place. 1 1?- method according to any of the elements VA to 010 so that the second shall dissolves more quickly than the first “phase. mouth — 7 8 _ —YY 1 Process according to any of the elements 18 to 1? So that the second phase dissolves in the dishwasher in less than * minutes. -YY 1 Gay method for any of the 18 elements to TY so that the first phase dissolves in the dishwasher within 10 to 115 minutes. -Y¢ 1 process according to any of the elements YA to yy so that delivery lasts + at least 96086 ' and preferably at least 9600 + and more preferably at least %A of the enzyme weight for washing within 01 YT minutes; Preferably within 0 minutes. and more Sain by (BEY Ades -7*© 1) according to any of the 18 items to TE and in which the process of washing soiled items Y selected from crockery; glass; silver; metal tools and cutlery and mixtures thereof.-71 1 Gi process of any of the elements 18 to yo in which the disk has any of the additional ¥ characteristics mentioned in the elements Y & 7 5 and 1 to AY AY 4