MXPA96005001A - Detergent compositions containing diaminotetracarboxylic acid or im salts - Google Patents

Abstract

The use of diaminotetracarboxylate chelating agents obtained from ethylendisuccinic acid (EDDS), ethylenediaminediglutaric acid (EDDG) or in 2-hydroxypropylenediamine-disuccinic acid (HPDD5) or mixtures thereof in a detergent composition to reduce enamel loss and corrosion during a Machine washing procedure in which the silicon surfaces of the machine or the articles washed in it are exposed to the detergent solution

Description

DETERGENT COMPOSITIONS CONTAINING DIFLMINOTETRFILCBOXILIC ACID OR SOLES OF THE SAME CPMPO DE Lñ INVENCIÓN The present invention relates to detergent compositions containing diarrhea notet chelating agents a- '< arboxilate More particularly, the present invention relates to the use of diarninoteetcarboxylate chelating agents obtained from ethylene diaminosuccinic acid (EDDS), ethylenediamine-duodenal acid or 2-hydroxypropylenedi-arnmo-disuccimic acid (HPDDS). or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, or mixtures thereof, in a detergent composition to reduce the loss and corrosion of enamel during a machine washed process in which the surfaces of the machines or articles washed therein are exposed to the detergent solution, said surfaces being obtained from enamel surfaces and porcelain surfaces. Finally, the present invention relates to a detergent composition which contains levels of corrosion inhibitors lower than the conventional ones allowed by the unexpected benefit of tetracarboxyl chelators to reduce the loss and corrosion of the emulsifier.

?TO BACKGROUND OF THE INVENTION Laundry detergent compositions which contain the non-phosphorous chelator, ethylene acid, arnino-N, N'-d? Succinic acid (EDD?) Are known in the art. For example, EP-R-0267 653 teaches that the EDDS, when incorporated into such, impositions for clothes, assists in the elimination of food, beverages and other certain organic stains of the fabrics during the laundry procedure. It also teaches that EDD can be used? as a substitute for all or part of the phosphonate chelators that are commonly used in many existing clothing products. In addition, detergent compositions are disclosed in IO 94/0357 ?, UO 94/03554 and UO 94/03553 which teach that EDDS with other components give other enhanced benefits in removing stains, Washing compositions are also known in the art. jars with an oxygen-based bleach system containing EDDS, described, for example, in UO 92/09680. This description teaches that EDDS, when incorporated into the oxygen bleach system, aids in the removal of food and beverage stains from the tsetse. In addition, EDDS analogs such as acid et? Lenod? Am? No-N, N'- < l? glutápco (FDDG) and 2- ludrox i propí -lenod? armnod? ucc? n? co-N, N '-disucci ico (HPDDS) in what is commonly referred to as the D American Application «Je Patent No. 08 / 026,084. This description teaches that fDDG and IIPDDS are useful components in detergent compositions to provide benefit in the removal of dirt. The problem of corrosion of the metal and enamel surfaces of the washing machines is also perceived in the art. Detergent compositions usually contain some corrosion inhibitors such as plains or silicates. Silicates are useful to reduce enamel loss. They are usually added as a dry mix ingredient, or a structural surfactant of the dry granules by spray or agglomerate of surfactant paste that is normally part of the laundry detergent composition. However, when co-ingredient or dry mix ingredient is added, high levels of soluble silicate are detrimental to "Assortment properties of the granular composition When added with a structural surfactant in a spray-dried granule incorporating an aluminosilicate builder, high silicate levels are detrimental to the solubility of the granular composition. What is the partial or total replacement of a phosphonate chelator by a diarrhene tetracarboxylate chelator obtained from CKIO et ileiadia nos? cci meo (EDDS), acid et 11 oondLarní nod? <; jl? - Tápco (EDDG) or 2-h acid? Drox i prop l dia i nodisucci ni co (HPDDS) or alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, or mixtures thereof in a detergent composition, results in a reduction in the level of the loss and corrosion of the enamel. Therefore, the detergent composition has a lower corrosion inhibitor level than the conventional one. This unexpected benefit is provided during the use of diamino-tetracarboxylate chelating agents in a detergent composition in which said inotetracarboxylate dialyzate is obtained from its racemate structure and its isomeric structures. It is an object of the invention to provide a detergent composition that reduces the loss of enamel, provides a lower level of corrosion and entails other advantages.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to the use of diaminotetracarboxylate elastomers obtained from ethylene diamine nosuccinic acid (EDDS, ethylenediane-diglutaric acid (EDDG) or 2-hydroxy acid). ro? ilenod? am? nd succ? -nic (HPDDS), or alkali metal, alkaline earth, ammonium or substituted salts thereof, or mixtures thereof, in a detergent composition to reduce the loss and corrosion of enamel during a washing process <- machine in which the siliceous surfaces of the machine or of the H c the ones washed in it are exposed to the detergent solution.

DETAILED DESCRIPTION OF THE INVENTION The present invention relates to the use of diaminotetracarboxylater q-elastomers obtained from ethylenediamine-cyclic acid (EDDS), ethylenediodanodiglutaric acid (EDDG) or 2-hydroxyprolenylene-cyclinic acid (HPDDS), or alkaline metal, organic earth, ammonium or substituted ammonium salts thereof, or mixtures thereof, in a detergent composition to reduce the loss and corrosion of the enamel during a machine washing process, in which the siliceous surfaces of the machine or articles washed therein to the detergent solution. For the present application, the term "washing machine" includes a laundry washing machine as well as a washing machine. Porcelain enamel or enamel is defined as a substantially vitreous or crystalline inorganic coating bonded to the metal by melting at a temperature above 425 °. The porcelain enamel protects against corrosion and resists the attack of alkalis, acids and other chemical substances. The main use of this material in washing machines and clothes washers is manifested. For the purposes of the invention, the earthenware article includes translucent and vitreous ceramic articles such as bone china, glassware and porcelain, as well as opaque non-vitreous ceramic articles such as stone and clay articles. For the purposes of the present invention, the teimino "siliceous surface" includes an enamel surface and a earthenware surface. Silica is the basic ingredient of enamel and earthenware, and a siliceous or silica surface is defined as a silica-containing surface. Detergent compositions that can be used for diarrheatracarboxylate elastomers include compositions , which are to be used to employ substrates, such as fabrics, fibers, hard surfaces, skin, etc., for example hard surface cleaning compositions (with or without abrasives), laundry detergent compositions, automatic laundry detergent compositions. The laundry detergent compositions useful in the present invention can have essentially any physical form. Preferred applications include granular compositions, especially concentrated granular clothing compositions, and high power liquid compositions. Such detergent compositions also exhibit other advantages. First, the use of the diarrheatetracarboxylate chelators in accordance with the present invention per-mito use of lower levels of the costly inhibited. It is from silane-based corrosion in high potency liquid compositions. Secondly, in the liquid compositions, of great power when silicate is used as inhibitor of \? Instead of corrosion, the use of the chelates of diaminotetracarboxylate makes it easier to stabilize the composition at a low / medium pH. In the high-power granular compositions formulated with zeolite-based spray-dried granules or a zeolite-based agglomerate, the partial or total replacement of the phosphonates by dichlorotetracarboxylate chelators allows silicate reduction and improves the solubility of the product. Where high-potency granular compositions with dry mixed amorphous silicate are formulated, the use of diarninotetracarboxylates allows the reduction of the level of added dry silicate and improves the product's supply. In automatic dishwashing applications, (ADU), the use of dianmotetracarboxylates in detergent compositions in accordance with the present invention offers greater advantages than those described above. The main additional advantage is to provide benefits against the corrosion of the earthenware. Therefore, the level of the corrosion inhibitors in the earthenware such as silicate can be reduced, while still maintaining an excellent care of the earthenware exposed to earthenware. multiple washing cycles in a machine for automatic washing of dishes. In addition, the reduction in the level of conventional ingredients for the care of earthenware such as silicate results in less sedimentation of the silicate on the glass surfaces, providing the additional benefit "It will reduce the damage to the articles of glass. drio. In order to provide the above benefits, the chelator of diarynotetracar box ilato is added to give a material level in the sol ution from 0.05% to 10% by weight of the composition, preferably from 0.05% to 3%, and very preferred. still from 0. 1% to 1.5%. This is usually achieved by the composition of the diarninotetracarboxylate and the JL -imposition of the product used in the washing process, although the direct addition of the diarninotet racarboxylate to the washing solution or the introduction via an additive product to part of the main washing product is also within the purpose of the present invention. Preferred EDDS compounds for inclusion in granular detergent compositions are the free acid form and the sodium or magnesium salt thereof. Examples of such ial is preferred from EDDS sodium include the Mg EDDS and the ED2 g2. Magnesium complexes are highly preferred for inclusion in the granular compositions according to the invention. These complexes can be added to the compositions as such, or they can be formed during the process to produce the composition by the reaction of an inert magnesium salt such as MgCl2 or MgSO4 with an added EDDS compound either the acid, or as salt or complex. Where the EDDS compound is added in the manufacturing process, together with the ine-magnesium salt, it is preferred that the molar ratio of magnesium to EDDS is greater than 1: 1, preferably more than 3: 1, to ensure the formation of the desired magnesium complexes. The structure of the acid form of the EDDS is as follows: H - N - CH 2 - CH 2 N - H CH 2 - CH CH 2 COOH ACOOH CC I < OOH COOH EDDS can be synthesized, for example, from easily obtainable and inexpensive materials such as maleic anhydride and ethylenediamine as follows: A more complete description of methods for synthesizing the EDDS can be found from commonly available materials in US Pat. No. 3,158,635, Kezerian and Rainsay, issued November 24, 1964. The synthesis of EDDS from metal anhydride and ethylenediamine produces a mixture of 3 optical isomers, [R, R3, CS, S], and CS, R], due to two asymmetric carbon atoms. Biodegradation «Jel EDDS is optical and isomer-specific, decomposing the CS, S isomer rapidly and extensively. It is possible to synthesize the C s, S 3 somer of the EDDS to the L-aspartic acid and the 1, 2-dibro-noethane, as follows: CH2-CH-NH2 * Br-CH2-CH2-CH2-r > U s, s] EDDS COOH COOH A more complete description of the reaction of L-aspartic acid with l, 2-d-brornoethane can be found to form the CS, S.3 isomer of EDDS in Neal and Rose, Stereospecific Ligands and Their Complexes of Ethylenedi Disccinic Acid, Inorganic Chemistry, Vol. 7 (1968), pp 2405-2412. Another class of chelator suitable for the present invention is ethyl diaminodiglutaric acid (EDDG), and - ^ ci or 2-hydroxypropylenedi-arninodisuccinic acid. (HPDDS), as described in US Patent Application No. 08 / 026,884, which provides the benefit of soil removal in detergent compositions.

Optional detergent ingredients The detergent compositions can also contain in general terms those ingredients commonly found in detergent products which may include organic IVOS surfactants, detergency builders, anti-sedimentation and dirt-suspending agents, foam suppressants, enzymes, polished It is optical, bleach-it is photoactivated, perfumes, filler salts, anticorrosion agents and dyes. Laundry detergent compositions may also contain softening and anti-static agents of the fabrics.

Detergent surfactants A wide range of surfactants can be used in the detergent compositions. A typical listing of ammonium, non-ionic, ampholytic and zwitterionic classes, and species of tensio-active agents are given in American Patent 3,929,678 published for Laughlin and Heupng on December 30, 1975. A list of cationic surfactants is given. suitable in the American Patent 4,259,217 issued to Murphy on March 31, 1981.

A-anionic surfactants.

Mixtures of anionic surfactants, particularly mixtures of sulfate, sulfonate and / or carboxyl t surfactants, are suitable herein. Normally, mixtures of sulphonate and sulfate surfactants are used at a sulfonate to sulphate weight ratio of 5: 1 to 1: 2, preferably 3: 1 to 2: 3, most preferably 3: 1 to 1. :1. Preferred sulfates include the alkylene Ibenisulfonates having from 9 to 15, especially from 11 to 13 carbon atoms of the alkyl radical, and the methyl esters of fatty acid alphasulfonated in which the fatty acid is derived from the fat source C12-C18 , preferably from a Ciß-Ciß fatty source- In each example the cation is an alkali metal, preferably sodium. The preferred sulfate surfactants in such sulphonate and sulfate mixtures are alkydyl phosphates having 12 to 22, preferably 16 to 18 carbon atoms in the alkyl radical. Another useful system of surfactants consists of a mixture of two alkali metal materials whose respective average chain lengths differ from one another. Such a system consists of a mixture of C14-C15 alkyl sulfate and Ciß-Ciß alkyl sulfate in a weight ratio of C14-C15: Ciß-Ciß of 3: 1 to 1: 1 - Alkyl-phosphates can also be combined with alkylethoxy Lyses having from 10 to 20, preferably from 10 to 16 carbon atoms in the alkyl radical and an average degree of ethoxylation from 1 to 6. The cation of each example is again an alkali metal, preferably sodium. Another highly preferred system of ammonium surfactant-IVOS agents consists of a mixture of C12-C20 alkylphosphate salt with a water-soluble salt of Cn-Ciß alkylethylsulfate containing an average of 1 to 7 ethoxy groups per ol in which the ratio The weight of the alkylsulfate to the ethyletoxysulfate salt is in the range from 2: 1 to 19: 1, most preferably from 3: 1 to 12: 1 and most preferably even from 3.5: 1 to 10: 1. The alkylsullate salts can be derived from natural or synthetic hydrocarbon sources. Preferred examples of such salts include the branched C 14 -C 15 alkyl sulfate salts, which is where the degree of branching of the C 14 -C 15 alkyl chain is about 20% higher. Such substantially unified C 1 -C 8 alkyl sulfate salts are generally derived from synthetic sources. Also preferred are C16-C20 alkyl sulfate salts which are generally derived from natural sources such as tallow grease and marine oils. The Cn-Ciß isylphosphate alkali salt consists of a primary alkoxy-sulphate which is derived from the condensation of the condensed Cn-Ciß alcohol product with an average of 1 to 7 ethylene oxide groups per mole. Preferred are C12-C15 alkylethylsulfate atoms with an average of 1-5 ethoxy groups per mole, and most preferably by an average of 1 to 3 ethoxy groups per mole. The Cn-Ciß alcohol itself can be obtained from natural or synthetic sources. In this way, the Cn-Ciß alcohols. Natural fat derivatives, or Ziegler ole ina formations, or 0X0 synthesis can form convenient sources for the alkyl group. Examples of synthetically derived materials include Dobanol 25 (RTM) sold by Shell Chemicals (UK) Ltd. which is a mixture of C12 -C15 alcohols, Ethyl 24 sold by Ethyl Corporat ion, a mixture of Ci3-C alcohols. ? s in the ratio 67% of C13, 33% of C15 sold under the trade name L? tensol by BASF GrnbH and Symperonic (RTM) by ICI Ltd., and Lial 125 sold by Liquichirnica Italiana.

Examples of materials found in nature and from which alcohols can be derived are coconut oil and palm oil, and the corresponding fatty acids. The level of alkylcytosis? Cn-Ciß is preferably from 0.5% to 10%, rn? And preferably 0.05% a % and still preferably from 1% to 3% by weight of the composition. Other anionic surfactants for the purposes of the invention are the alkali metal sarcosinates with the formula R-CON (RI) CH2COOM wherein R is a linear or branched alkyl or alkenyl group C5-0i7, R1 is an alkyl Ci group -C ¿> and M is an alkali metal ion. Preferred examples are the sarcosinates of lauroyl, C12-C14 cocoyl, myristyl and oleol in the form of their sodium salts.

B-NON-IONIC TENSIOACTIVE AGENTS A class of nonionic surfactants useful in the present invention consists of condensates of oxides of ethylene with a hydrophobic portion, which provides surfactants having an average hydrophilic-lipophilic balance (HL.B) on the scale of 8 to 17, preferably 9.5 to 13.5, rn? And preferably 10 to 12.5. The hydrophobic- (lipophilic) portion can be aliphatic or aromatic in nature and the length of the polyoxyethylene group that can be condensed by any particular hydrophobic group can easily be adjusted to produce a water-soluble compound which has the desired degree of balance between the hydrophilic elements and H ~, Idro óbico. Especially preferred nonionic surfactants of this type are the primary ethoxylates of C9-C15 alcohol which contain an average of 3-8 moles of ethylene oxide per mole of alcohol, particularly the primary alcohols C14-C15 which contain An average of Ce moles of ethylene oxide per mole of alcohol and the primary alcohols Ci2 ~ Ci5 containing an average of 3-5 moles of ethylene oxide per mole of alcohol. Another class of nonionic surfactants consists of the alkyl polyglycoside compounds with the general formula RO (CnH2n0) tZ "in which Z is a portion derived from glucose; R is a saturated hydrophobic alkyl group containing from 6 to 1.8 carbon atoms; t is from 0 to 10 and n is 2 or 3; x is from 1.1 to 4, including the lesser compounds of 10% fatty alcohol without reaction and less than 50% of short chain Ipolyglycoxylated alkyls. Compounds of this 1 po and their use in detergent compositions are described in FP-B 0070074, 0070077, 0075996 and 0074110. Another preferred nonionic surfactant is a surfactant based on polyhydroxy fatty acid amides having the structural formula : Rl II I (i) R2-C-N-Z wherein R is hydrogen, hydrocarbyl C? ~ C ?, 2-hydroxyl, or 2-hydroxypropyl, or a mixture thereof, preferably alkyl C1-C4, most preferably Ci or C2 alkyl, preferably even Ci alkyl (ie, methyl); and R2 is a C5-C31 hydrocarbyl, preferably a C7-C19 straight-chain alkyl or alkenyl, most preferably an straight-chain C9-C17 alkyl or alkyl, most preferably still a C11-alkyl or alkylalkyl. C17 straight chain, or a mixture of the same; and Z is a polyhydroxyhydrocarbyl having a straight chain of hydrocarbyl with at least 3 hydroxyls directly connected to the chain, or a derivative to the cox 1 side (preferably ethoxylated or propoxylated) thereof. Z preferably will be derived from a reducing sugar in a reductive union reaction; rnuy preferably Z is a glycityl. Suitable reducing sugars include glucose, fructose, maltose, lactose, galactose, mannose and silose. As raw materials, high dextrose corn syrup, high fructose corn syrup, and high maltose corn syrup, as well as the individual sugars listed above, can be used. These maize jar-abes can produce a mixture of sugar components for Z. It should be understood that it is not intended in any way to exclude other suitable raw materials. Z will preferably be selected from the group consisting of -CH2- (CH0H) "-CH2OH, -CH (CH2OH) - (CHOH)" -? -CH2OH, -CH2-r * "t CH0H) 2 ~ (CH0R ') (CHOHY-CH? OH, in which n is an integer from 3 to 5, inclusive, and R' is H or a cyclic or aliphatic onosacaride and alkoxylated derivatives of the same.Highly preferred still are the glycityls in which n is 4, particularly -CH 2 - (CHOH -CH 2 OH.In the formula (I), R 1 can be, for example, N-ethyl, N- ethanol, N-propyl, N-isopropyl, N-butyl, N-2-hydroxyethyl, or N-2-hydroxyl pro.R2-C0 ~ N < may be, for example, cocarni, stearamide, oleamide , lauramida, mipstamida, capricarnida, palrnitarnida sebarnida, etc. Z can be l-deox? gluc? t? io, 2-deox? fructit? lo, 1- deoxi alititiio, 1-deoxilactit? io, 1-deoxigalact? t? io, 1-deoxy-amyl, 1-deoxy-maltoyl, etc. The preferred compounds are the C-Ciß fatty acid amides of N-methyl-N-ldeoxy-lucityl, or a class of suitable surfactants for The purposes of the invention are the twin hydroxyl acid amides described in more detail in the American Application. Patent Code 08/187251.

SEMIPOLAR TENSIOFlCTIVE CLOGGERS Another class of surfactants are the polar surfactants such as the amine oxides. Suitable amine oxides of the C6-Q20 monoamine are selected, preferably amine oxides of N-alkyloyl or C10-C14 alkylate and of propylene-1, 3-dianamine dioxides in which the N-positions are replaced by methyl, hydroxyethyl or hydroxypropyl groups.

DIFFERENT CULTURAL DENSITIZERS Cationic surfactants can also be used in the detergent compositions herein and the appropriate quaternary ammonium surfactants are obtained from the N-alkylene or alkylane or mono Cß-Ciß, preferably C 10 -C 14, surfactants. , in which the remaining N positions are replaced by methyl, hydroxyethyl and hydroxypropyl groups. The laundry detergent compositions of the present invention comprise from 3% to 30% of the present surfactant, but commonly they consist of 5% 20%, preferably from 7% to 15% of surfactant by weight of the compositions .

The laundry detergent compositions of the present invention comprise from 0% to 10% by weight, preferably from 0.5 to 10% by weight, most preferably still from 1% to 5% of the surfactant by weight of the compositions The surfactants of anionic, cationic, nonionic, amphoteric or zwitterionic surfactants can be selected. Most preferably the surfactants are of low foaming A typical listing of surfactants is given for inclusion in the detergent compositions for automatic dishwashing in EP-A-0414549. Combinations of the types of agents are preferred. surfactants, more especially anionic-nonionic and also anionic-ionic-cationic mixtures Particularly preferred combinations are described in GB-A-2040987 and EP-A-0087914. Although the surfactants can be incorporated into the compositions as mixtures, it is preferable to control the point of addition of each surfactant in order to improve the physical characteristics of the composition and avoid problems in the process.

DETERGENCIfl IMPROVERS Another highly preferred component of the detergent compositions of the invention is a builder system consisting of one or more additional non-phosphate builders. These may include, but are not restricted to, alkali metal alkanmosilicates, monomepic polycarboxylates, homo- or copolymeric polycarboxylic acids or their salts in which the polycarboxylic acid consists of at least two carboxylic radicals separated from each other by no more than 2 carbon atoms. , sodium silicates with a crystalline layer, borates, rhenates, bicarbonates, silicates and mixtures of any of the foregoing. While a series of materials can be used with aluminosilicate ion exchange, the preferred sodium aminosilicate zeolites, such as those described in British Patent 1429143, have the unit cell formula. NazC (Al? 2) z (Si02)) -] xH20) where z and y are at least 6; the molar ratio of zay is 1.0 to 0.5 and x is at least 5, preferably from 7.5 to 276, more preferably from 10 to 264. The aluminosilica materials are in hydrated form and are preferably crystalline, containing from 10% to 28% , most preferably from 18% to 22% in water in bound form. Alkalymethyl ion exchange materials useful in the practice of this invention are commercially available and may be materials that are found in nature, but preferably are derived synthetically. A method for producing materials with alkylosilicate ion exchange in American Patent No. 3,985,669. Preferred synthetic crystalline materials with ion exchange of alurninosilicate useful herein are available under the designations Zeolite A, Zeolite B, Zeolite P, Zeolite X, Zeolite HS, Zeolite MAP and mixtures thereof. In a particularly preferred embodiment, the crystalline material with ionic change of alurnmosilicate is Zeolite A and has the formula Nai2C (A102) 12 (Sl? 2) l23. XH20 in which x is from 20 to 30, especially 27. The Zeolite X of the formula Naßß C (A102) εe (S1O2) εβ -1. 276 H2O is also suitable, as well as Zeolite HS of the formula Naß C (AIO2) ß (S1O2) ß 17.5 H2O). Suitable detergency builders based on water-soluble monomeric or oligomeric carboxylate can be selected from a wide range of compounds, but such compounds preferably have a first logarithmic carboxy acidity constant (pKi) of less than 9, preferably from 2. and 8.5, and most preferably between 4 and 7.5. The carboxylate or polycarboxylate builder, as described in UO 94/03554, may be monomeric or oligornepic in type although preferred polymers are preferred for reasons of cost and performance. You can select nejoradoree detorgoncia inonomepcos and olí gornépcos from c a rbox 1 latos acidices, 00 alicyclic, heterocyclic and aromatic. Suitable carboxylates which contain a carboxy group include water-soluble salts of lactic acid, glycolic acid and ether derivatives thereof as described in Belgian Patents Nos. 831,368, 821,369 and 821,370.

Polyols containing two carboxy groups include water-soluble salts of succinic acid, rhenalonic acid, "Acid (et? oxod? ox?) acetic acid, alelic acid, diglycolic acid, tartaric acid, tartronic acid and fumaric acid, as well as the ethereal carboxylates described in German Patent 2,446,686, and 2,446,687 and the American Patent No. 3,935,257, and the sulfyl carboxylates described in Belgian Patent No. 840,623. Polycarboxylates containing 3 carboxy groups include, in particular, water-soluble citrates, aconids and citraconates as well as succinate derivatives ^ "- such co or carboxymethyloxysuccinates described in the patent British Patent No. 1,379,241, the lactoxysuccinates described in British Patent no. 1,389,732, and the ammosuccinates described in Dutch Patent No. 1,389,732, and oxypolycarboxymate materials such as the 2-oxa-1, 1,3-propane tncarboxylates described in British Patent No. 1,387,447. The polycarboxylates containing four carboxy groups include those or idisuccinates described in British Patent No. 1,261,829, the tetracarboxylates of 1,1,2,2-ethane, the tet racarboxylates of l, l, 3- and 3-H and the tet acarboxi lates of 1, 1,2,3 -propane. Polycarboxylates containing sulfo constituents include the sulfosuccinate derivatives described in British Patent Nos. 1,398,421 and 1,398,422 and American Patent No. 3,936,440, and the sulfonated pyrolysed citrates described in the patent.

British No. 1,439,000 The acyclic and heterocyclic polycarboxylates ncl? Y in the cyclopentane-c? S, c? S, c? S-tetracarboxylates, the cyclopentadiemdopentaca rbox i latos, the 2,3,4,5-tetrah? rofura ~ no-c? s, c? s, c? s-tetracarboxylates, the 2,5-tetrah? drofurano-cis-dicarboxiltos, the 2,2,5,5-tetrahydrofurano-tetracarbox? lato, the 1, 2 , 3,4,5,6-hexanohexacarboxylates and the carboxymethio derivatives of polyhydric alcohols, such as sorbitol, rhamtol and xylitol. Aromatic polycarboxylates include rhnelitic acid, pyromellitic acid and phthalic acid derivatives described in British Patent No. 1,425,343. Of the foregoing, preferred polycarboxylates are hydroxycarboxylates containing up to 3 carboxy groups per molecule, particularly citrates. Acid generators of chelating agents based on monomeric or oligomeric polycarboxylates, or mixtures thereof with their salts, for example citric acid or mixtures of citric acid and citric acid, as well as components of the organic acid systems, have also been contemplated. ? nejoradore < The detergency in the detergent compositions is in accordance with the present invention.

Other suitable water-soluble organic salts are the polycarboxylic acid or copolymeric acids and their salts in which the polycarboxylic acid comprises at least two carboxyl radicals separated from one another by no more than 2 carbon atoms. Polymers of this type are described in GB-A-1,596,756. Examples of such salts are polyacrylates of molecular weight 2000-5000 and their copolymers with anhydride The copolymers have a molecular weight of 20,000 to 70,000, especially about 40,000.These materials are normally used at levels of 0.5% to 10% by weight, more preferably 0.75% to 8%, most preferably still 1% to 6% by weight of the composition. Preferred salts of non-phosphate detergent builders are sodium silicates with a crystalline layer of the general formula NaMSl * 02x + 1"and H 2? wherein M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20. Sodium silicates with such a crystalline layer are described in EP-A-0164514 and in the British Patent Application. No. 9,216,409.4, and the methods for this preparation are described in DE-A-3417649 and US-A-3742043. The incorporation of other additional ingredients to the crystalline silicate and the water soluble ionizable compound can be advantageous particularly in the elaboration of the rnacropartic material and also in enhancing the stability of the detergent compositions in which they are included. macropartic materials. In particular, certain types of agglomerates may require the addition of one or more linking agents in order to assist the binding of the silicate and the soluble water soluble material to produce the particulate materials with acceptable physical characteristics. The linkers can be present at a level of 0% to 20% by weight of the composition. Preferably,. The linking agents will be in an intimate mixture with the silicate and the water soluble ionizable material. Preferred linking agents have a melting point between 30 ° C and 70 ° C. The linking agents are preferably present in amounts of 1-10% by weight of the composition and most preferably 2-5% by weight of the composition. Preferred linking agents include the C 1 -C 20 alcohol ethoxylates which contain 5-100 moles of ethylene oxide per mole of alcohol and most preferably the primary alcohol ethoxylates C 15 -C 20 containing 20-100 moles of ethylene oxide per mole. of alcohol. Other preferred linking agents include certain polymeric materials. Polyvinylpyrrolids with an average molecular weight of 12,000 to 700,000 and polyethylene glycols with an average weight of 600 to 10,000 are examples of such poly meric materials. The copolymers of the aleic anhydride with ethylene, ether-methylammonium or tetrahydric acid, the molar anhydride constituting at least 20% by molecular weight of the polymer are other examples of polymeric materials useful as linkers. These polymer materials can be used as such or in combination with solvents such as water, propylene glycol and the C10-C20 alcohol ethoxylates mentioned above containing from 5 to 100 moles of ethylene oxide per mole. Other examples of linking agents according to the invention include C10-C20 mono- and diglycerol ethers and also C10-C20 fatty acids. Solutions of certain inorganic salts including sodium silicate are also useful for this purpose. Cellulose derivatives such as methylo-lulose, carboxymethylcellulose and hydroxyethylcellulose, and polycarboxylic acid homopolymer or copolymer or their salts are other examples of linking agents according to the invention. The particulate materials can adopt a variety of physical forms such as extrudates, sea urns, agglomerates, flakes or compressed granules. A preferred process has been described for preparing compressed granules consisting of crystalline silicate and water curable material in the commonly-assigned document EP-581895. The detergent compositions useful in carrying out the present invention will consist of enhancer compounds. of non-phosphate detergent at a level of 1% to 80% by weight of the compositions, most preferably from 10% to 60% by weight and most preferably even from 20% to 50% by weight.

Within the preferred detergent compositions, a sodium lurnmosilicate such as zeolite A consists of % to 80% by weight of the total amount of the detergent builder, a monomeric or non-monomeric carboxylate will consist of 5% to 30% by weight of the total amount of the builder, and a silicate with a crystalline layer will consist of 10% by weight. 65% by weight of the total amount of the detergency builder.

. In such compositions, the builder system preferably also incorporates a combination of inorganic and auxiliary organic builders, such as sodium carbonate and the copolymers of aleic anhydride and acrylic acid in amounts up to 35% by weight of the total builder. detergency Bleaching agents as detergents The solid detergent compositions of the present invention will generally include inorganic pein bleach, usually in the form of the sodium salt. Generally, the period is added at a level of 3% to 40% by weight, preferably 5% to 30% by weight and most preferably even 5% to 15% by weight of the composition. The perhydrate can be any of the inorganic salts such as the salts perborate, percarbonate, per-phosphate and persilicate, but conventionally it is an alkali metal, usually perborate or sodium percarbonate. The sodium perbor ate can be in the form of a nonohydrate of the nominal formula aE? 2H2? 2 or tetrahydrate? 2H2? 2.3H20.

/ - Sodium percarbonate, which is the preferred perhydrate, is an addition compound having the formula corresponding to 2 a2C? 3.3H2O2, and is commercially available as crystalline solid. Although percarbonate can be incorporated into detergent compositions without additional protection, preferred applications of such compositions utilize a coating coated with the material. The preferred cladding cladding consists of a mixture of sulfate salts and carbonate of alkali metals. Such coatings have been described together with the coating processes previously in GB-1, 66, 799, granted to Interox on March 9, 1977. The weight ratio of the mixed coating material based on salts to the percarbonates is on the scale from 1: 200 to 1: 4, most preferably from 1:99 to 1: 1, and rn? and preferably still from 1:49 to 1:19. Preferably, the mixed salt is sodium sulfate and sodium carbonate which has the general formula N 2 S0. n.N 2 CO3 where n is from 0.1 to 3, preferably n is from 0.3 to 1.0 and rnuy preferably still n is from 0.2 to 0.5. Another suitable coating material is sodium silicate with the ratio S 2: 2? from 1.6: 1 to 3.4: 1, preferably 2.8: 1, applied as an aqueous solution to give a level of 2% to 10% (usually 3% to 5%) of silicate solids by weight of the carbonate. Boron silicate (described in US Pat. No. 4,526,698) or magnesium silicate can also be included in the coating.

The bleach systems incorporated into the detergent compositions of the present invention preferably include the precursors of solid peroxyacid-based bleaches (bleach activators). Solid peroxyacid bleach precursors are usually incorporated at a level of from 1% to 20%, preferably from 1% to 15%, most preferably still from 1% to -3% by weight of the composition. These precursors probably contain one or more acyl groups N or 0, pressurizers that can be selected from a wide range of classes. Suitable classes include anhydrides, esters, imides and acylated derivatives of imidazoles and oximes, and examples of these materials useful within these classes are described in GB-A-1586789. Preferred classes are esters such as those described in GB-A-835988, 364,798, 1147871 and 2143231 and the imides as described in GB-A-855735 and 1246338. Particularly preferred precursor compounds are N-compounds. , N, N, N tetraacetylated formula where x can be 0 or an integer number between and 6. Examples include tet raacetylrnetylenedi amine (TAMD) in which x = l, tetraacetylethylene diamine (TAED) in which x = 2 and tetraacetylhexylendiarnine (TAHD) in which x = 6. These and other analogous compounds are described in GB-A-907356. The preferred precursor of peroxyacid bleach is TAED. Another preferred class of peroxyacid bleach Os activator compounds are compounds with amide substitution with the following formulas: R1-C-N-R2-C-LO R1-N-C-R2-C-L wherein R is an aryl or alkaryl group with from about 1 to about 14 carbon atoms, R 2 is an alkylene, arylene and alkarylene group that approximately contains 1 to 14 carbon atoms, and R5 ee H or an alkyl group, aplo, to the car-yl containing 1 to 10 carbon atoms and L may be any residual group. R preferably contains from about 6 to 12 carbon atoms. R2 preferably contains from about 4 to 8 carbon atoms. R may be a straight or branched chain alkyl, a substituted rile or alkylamino containing branching, substitution or both, and obtainable from synthetic or natural sources, including for example tallow fat. Other analogous structural variations are permissible for R2. The substitution may include alkyl, aryl, halogen, nitrogen, sulfur and other substituent groups or organic compounds. Rs Jl it is preferably H or methyl. Rl and R5 should not contain more than 18 carbon atoms in total. Bleaching activator compounds substituted by amide of this type are described in EP-A-0170386. Other peroxyacid bleach precursor compounds include the Nonanoyloxybenzenesulfonate (NOBS, described in US 4,412,934), the 3,5-trirnethexanoloxyl? benzene, fonate (IONOBS, described in EP 120,591), acetoxybenzenesulphonate, benzoyloxybenzenesulphonate as described, for example, in EP-A-0341947, Benzoylcaprolactarn and the phenolsulfonate ester of acylamidocaproic acid. of the invention can also contain organic peroxyacids at a level of from 1% to 15% by weight, rn? and preferably from 1% to 10% of the composition.A particularly preferred class are the peroxyacids substituted by amide with the general formulas: R1-C-N-R2-C-00H or R1-N-C-R2-C-00H wherein R1, R2 and R5 are as defined above for the corresponding peroxy-substituted bleach activating compounds substituted by amine Other organic peroxyacids They include diperoxy dodecanediococid, diperoxy tetradecanediococid, diperoxyhexadecanediococid, mono- and dihydric acid, mono- and diperbrassilic acid, monoperoxy phthalic acid, per- benzoic acid, and its salts as described in EP-A-0341 947.

Optional chelating ingredients The detergent compositions can be optionally chelated ingredients. Such chelators may include organic phosphonates, including arninoalkylene-poly (alkylenephosphonate), alkali metal ethan-1-hydroxydiophosphonates, nitrile tri-etiienphosphonates, ethylene diarylene ether phosphonates and diethylene glycerin-pentaethylene phosphonates. The phosphonate compounds may be present in either their acid form or as a complex of an ion, either alkali or alkali metal, the molar ratio of said metal ion being to said phosphonate compound of at least 1: 1. Such complexes are described in US-A-4,259,200. Preferably, the organic phosphonate compounds where they are present are in the form of their magnesium salt, but in the HDEP example preferably they will be in their acid form. The level of phosphorus-containing chelators in the compositions of the invention are in the range from 0% to 20%, preferably from 0% to 10%, most preferably from 0% to 6% by weight of the compositions. Silicates are useful components of detergent compositions for automatic dishwashing and laundry detergent compositions. Suitable silicates include water-soluble sodium silicates with a S 2: a 2? Ratio. from 1.0 to 3.2. The silicates may be in the form of either anhydride salt or hydrated salt. Sodium silicate with a ratio of a? of 2: 0 is very preferred. The silicates are present in the detergent compositions for the machine washing of dishes at a level of 5% to 40% by weight of the composition, most preferably from 10% to 25% by weight of the composition. While soluble silicates are useful for In a variety of purposes in conventional laundry detergent formulations, its essence may be unnecessary in detergent compositions incorporating silicate material with a crystalline layer. However, since the crystalline silicate, which forms part of the detergent builder system of a detergent composition, should be added as a dry mixed ingredient, the soluble silicates may still be useful as structural surfactants in the detergent compositions. spray-dried granules that are normally part of the laundry detergent composition. This is particularly desirable if the spray-dried granules do not incorporate a builder detergent and, on the contrary, consist of only organic materials. Suitable silicates are those that have a ratio of Si? 2: N 2? in the range of 1.6 to 3.4, ratios of 2.0 to 2.8 being preferred. The silicates are present in the granular laundry detergent solutions at a level of from 1% to 20% by weight of the composition, preferably from 1% to 10% by weight, most preferably from 1% to 5% by weight of the composition. the composition. The detergent compositions in which peroxy bleach and solid precursors are protected through an acidic coating to minimize damage to tissue color are described in EP-A-571524. Suitable antiredeposition and soil suspending agents herein include the cellulose derivatives such as ethyl cellulose, carboxymethyl cellulose and hydroxyethyl cellulose, polycarboxylic acid or polymers or their salts and polyamino compounds. Polymers of this type include the polyacrylates and copolymers of rnalene anhydride with ethylene, dimethylvinyl ether or methacrylic acid, the maleic anhydride constituting at least 20% by molecular weight of the copolymer q? E being described in detail in EP-A-137669 The amino compounds such as the derivatives of a-tartaric acid are disclosed in EP-A-305282, EP-A-305283 and EP-A-351629. Normally these materials are used at levels of 0.5% to 10% by weight, most preferably from 0.75% to 8%, most preferably still from 1% to 6% by weight of the composition. Other useful polymeric materials are polyethylene glycols, particularly loe of molecular weight-1000-10000, very particularly from 2000 to 8000 and most preferably of about 4000. These are used at levels of 0.20% to 5%, preferably not 0.25. % to 2.5% by weight. These polymers and the abovementioned homo or opolymeric polycarboxylate salts are valuable for improving the preservation of whiteness, the sedimentation of ash from the tissues, and the cleaning performance on the * * * *, protein and oxidizable soils in presence of transition metal impurities. The preferred optical brighteners are anionic in character, examples of which are the disodium 4,4i-b? S (2-d? Ethanolammo-4-aniiino-s-triazm-d-? Lamino) st? Lbeno-2: 21 The sulphonate, the disodium 4,41 -bis ~ (2-rnorfol? No-4-anilino-2-tr? Az? N-6-ylam?) St? lbeno-2: 2-disulfonate, the disodium 4,41-b? s- (2-morpholino-4-aml? no-2-tr? azin-6-ylamino) t-lbene-2: 21-disulfonate, the monosodium 41, 411 -bis- (2,4-dian? lino-s-tpaz? n-6? larn? no) stilbene-2-sulfonate, disodium 4,4 -bis- (2-anilino-4-) (N-methyl-N-2-hydrox? Eti lamino) -2-t riazin-6- i lamino) st? lbeno-2, 2i-d? s? fonate, the disodium 4,4 -bis- (4 ~ phen? l-2, l, 3-tpazol-2-l) stilbene-2, 21-disulfonate, the disodium 4,41 -bis- (2-anilino-4- (l-rnet? l-2-hydrox-letila-ino) -s-triazin-6-? lamino) stilbene-2, 21-disulfonate and sodium 2 (st ? lb? l-4H - (naphthano-li, 21: 4, 5) -l, 2, 3-tpazol-2i-sulfoanto, the disodium 4,4'-bis- (2-sulfost r? l) -biphenyl These are used at levels of 0.05% to 1.2% by weight of the composition.Dirt release agents useful in the detergent compositions are conventionally copolymers or terephthalic acid terpolymers with ethylene glycol and / or propylene glycol units in various arrangements. They are also referred to as "polymers" in which US Pat. Nos. 4116885 and 4711730 and Patent Application / - published in Europe No. 0272033 are commonly designated. A particular polymer has the formula.

Certain polymeric materials such as polyvinylpyrrolidones, typically of molecular weight of 5000-20000, preferably 10000-15000, also form useful agents to prevent the transfer of labile pigments between the tends during the washing process. Dirt release agents are present in the detergent composition at a level of from 0.01% to 10% by weight of the composition, preferably from 0.1 to 5% by weight of the composition, most preferably from 0.2% to 3% by weight of the composition. Another optional ingredient of the detergent composition is a foam suppressor, exemplified by silicones and silica-silicone blends. Silicones are generally represanted by alkylated polysiloxane materials while silica is commonly used in finely-diluted forms, exemplified by silica archaelites and xelogels and hydrophobic silicas of various types. These materials can be incorporated as particulates in which the foam suppressor is advantageously incorporated in an illiberable manner in a waterproof carrier in the detergent, substantially non-active on the surface, soluble in water or dispersible in water. Alternatively, the foam suppressant may be dissolved or dispersed in a liquid carrier and applied by spraying to one or more of the other components. As mentioned above, the silicone useful agents that control the foam can cost a mixture of an alkylated siloxane, of the type mentioned hereinabove, and solid silica. Such mixtures are prepared by adding the silicone to the surface of the solid silica. A preferred silicone agent for controlling the foam is represented by a hydrophobic silanated silica (most preferably ethyl silane tp) having a particle size in the range of 10 nanometers to 20 nanometers and a specific surface area above 50 rn2 / g, intimately mixed with dirnetyl silicone fluid having a molecular weight in the range from about 500 to about 200,000 at a weight ratio of silicone to silica silanated from about 1: 1 to about 1: 2. A preferred silicone agent is described to control the foam in the American Patent Bartollota and other H- 3,933,672. Other particularly useful foam suppressors are the silicone-based foam suppressors, described in the German Patent DTOS 2,646,126. Other examples of such a compound is DC0544, commerically available from Dow Corning, which is a copolymer of siloxane and glycol. A highly preferred particulate foam controlling agent is disclosed in EP-A-0210731 and consists of JTn silicate anti-foam compound and an organic carrier material having a melting point in the range of 50 ° C to 85 ° C. , in which the carrier-organic material consists of a monoester- of glycerol and a fatty acid which has a carbon chain containing 12 to 20 carbon atoms. EP-A-0210721 discloses other particulate foam controlling agents which are preferred in that the organic carrier material is a fatty acid or an alcohol having a carbon chain containing from 12 to 20 carbon atoms, or a mixture thereof. same, with a melting point of 45 ° C to 80 ° C. Other highly preferred particulate foam controlling agents are described in co-pending European Application 91870007.1 to Probre and Gamble Company, in which the agents consist of a silicone anti-pore compound, a carrier material, an organic spreader material and glycerol in the weight ratio of glycerol to the antispurna compound of sil con from 1: 2 to 3: 1. European Co-pending Application 91201342.0 also discloses highly preferred macroparticle foam controlling agents consisting of silicone antifoam compound, a carrier material, an organic coater material and crystalline or amorphous alkylinosilicate in a weight ratio of the aluminosilicate. to the antispurna silicone compound «le 1: 3 to 3: 1. The preferred carrier material of the two highly preferred granular foam controlling agents described above is starch. An exemplary particulate foam controller-agent for use in accordance with this document is an agglomerated component of microparticles., made by an agglomeration process, which comprises in combination: (i) from 5% to 30%, preferably from 8% to 15% by weight of the component of the silicate antispun compound, preferably consisting of a combination of polydirnethylsiloxane and silica; (n) from 50% to 90%, preferably from 60% to 80% by weight of the component, of the carrier material, preferably starch; (m) from 5% to 30%, preferably from 10% to 20% by weight of the agglomerated linker component, in which as the present document is composed may be any compound, or mixtures thereof typically employed as linkers for algorithms, most preferably said agglomerated linker compound consists of an ethoxylated alcohol Ci6 ~ C? ß with an ethoxylation degree of 50 to 100; and (iv) from 2% to 15%, preferably from 3% to 10%, by weight of fatty acid hi ogenated C 12 -C 2 The foam suppressors described above &nt; -, e - ~ they normally employ at levels of 0.01% to 15% by weight of the composition, preferably from 0.05% to 10% by weight, most preferably still from 0.1% to 5% by weight of the composition. An optional ingredient useful in the present invention is one or more enzymes. Preferred enzymatic materials include the commonly available amylases, proteases, iipasae, esterases, and cellulases, neutral or alkaline, conventionally incorporated into detergent compositions. Suitable enzymes are discussed in U.S. Patents 3,519,570 and 3,533,139. The commercially available protease preferred enzymes include the media under the trade names Alcalase and Savmase by Novo Industries 0 / S (Denmark) and Maxatase by International Bio-Synthetics, Inc. (The Netherlands). The preferred alasics include, for example, the alasics w obtained by a special class of liche forms B, described in more detail in GB-1,269,839 (Novo). Commercially available amylases which are preferred include, for example, Rapidase, sold by International Bio-Synthetics Inc. and Ter amyl, sold by Novo Industries A / S. A specially prepared enzyme is manufactured and sold by Novo Tnd? Ers A / S (Dinamai ca) under the trade name Lipolase (Biotechnology Newswatch, 7 May 1988, page 6) and mentioned together with other lipases convenient in EP-A-0258068 (Novo).

Fabric softening agents can also be incorporated in the detergent compositions according to the present invention. These agents may be of inorganic or organic type. The inorganic softening agents are exemplified by smectite slimes described in GB-A-1,400,898. Organic fabric softening agents include tertiary amines insoluble in water as described in GB-A-1514276 and EP-B-0011340. Its combination with C12-C14 quaternary ammonium salts in EP-B-0026527 and 528 is described. Other organic tissue softening agents that are useful are the dilonga chain amides as described in EP-B-0242919. Other organic ingredients of fabric softening systems include high molecular weight polyethylene oxide materials as described in EP-A-0299575 and 0313146. Smectite silt levels are normally in the range of 5% to 15%, more preferably from 8% to 12% by weight, the material being added as a dry mixed component to the rest of the formulation. Organic fabric softening agents such as tertiary and water soluble amines or dilonga chain amide materials are incorporated at levels of 0.5% to 5% by weight, normally from IC% to 3% by weight, while High molecular weight polyethylene oxide materials and water-soluble cationic materials are added at levels of 0.1% to 2%, usually 0.15% to 1.5% by weight. Where it is spray dried, a portion of the composition, se ~ they can add these materials to the aqueous slurry fed to the spray dryer tower, although in some cases it may be more convenient to add them to a dry mixed acropar ticulture, or sprinkle them as a molten liquid to the other solid components in the composition. DETERGENT FORMULATION Laundry detergent compositions useful in carrying out the present invention may be pasty, liquid or granular forms. In liquid compositions of potency, phosphonates such as diethylene ethene (methylene phosphonic acid) (DTPMP), diethylene glycemic acid (methylene phosphonic) acid (DDTMP), ethane-l-hydroxyl acid? Phosphonic (HEDP) and its alkali metal and alkaline earth metal salts provide the main contribution to the elimination of beverage stains including tea, coffee, wine and blackberry. However, these high-power liquid compositions tend to cause enamel pria and thus require enamel corrosion inhibitors that are either cost (eg, xylans) but are difficult to stabilize and formulate at a low / medium scale) (6-9.5) of pH (for example silicates) the partial or total substitution of phosphonates by EDDS improves the compatibility of the enamel of the formation and allows the use of lower levels of plains (<0.5%) or silicate (0% -3%).

Thus, the present invention relates to a detergent composition adapted to reduce the loss and corrosion of enamel in which said detergent composition has a high potency liquid composition formulated with conventional detersive surfactants, optional detergency builders and detersive additives which consist of: a) from 0% to 0.6% of phosphonate chelators obtained from diethylenetrinose (methyienphosphinic acid) (DTPMP), diethylenetriamine phosphine acid (DDTMP), ethan-1-hydroxydiphosphinic acid ( HEDP) of alkali metal and alkaline earth metal; b) at least 0.15% by weight of the composition of the dianyltracarboxylate chelating agents obtained from ethylenediamine disuccinic acid, ethylenediamine diluthalic acid or 2-hydroxy? -dolenediaminedisuccinic acid, or alkali metal, alkaline earth, ammonium or substituted ammonium salts of the same or mixtures thereof in which the weight ratio of said phosphonate to said dianintetracarboxylate has a value of minus 2.0; c) less than 0.5% of xylan corrosion inhibitors by weight of the composition. Also, the present invention relates to the detergent composition adapted to reduce the loss and corrosion of enamel in which said detergent composition is a high potency liquid composition formulated for conventional detersive surfactants, optional builders and detersive additives. consist of der. (a) from 0% to 0.6% of phosphonate chelating agents obtained from diethylene-acid obtained from ethylenediaminesuccinic acid, ethylenediandronic acid, or 2-hydroxypropionic acid and its salts of alkali metal or alkaline earth metal; b) at 0.15% by weight of the composition the phosphonated chelators obtained from diethylene acid obtained from ethylenediaminsuccinic acid, ethylenediaminedigluthacic acid or r-, L-acid 2-hydroxypyridinic disuccinic diarrhea, or either alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, or mixtures thereof in which the weight ratio of said phosphonate to said diamotetracarboxylate has a value of minus 2.0; c) less than 3% silicate corrosion inhibitors by weight of the composition. In general, granular detergent compositions can be made by a variety of methods including dry mixing, spray drying, agglomeration and granulation, and preferred methods involve combinations of these techniques. The bulk density of the granular detergent compositions of the present invention may be in the range of about 450 to 600 g sobr-e liter as is typical for conventional laundry detergent compositions. Alternatively, the granular detergent compositions may be concentrated granular detergent compositions which are characterized by a relatively high density as compared to conventional detergent compositions. Such high density compositions have a bulk density of at least 650 g / liter more usually at the rates of 700 g / liter and preferably, from 800 g / liter to 1100 g / liter. Concentrated detergent co-workers for clothing also usually incorporate a component •, "Multi-ingredient", ie, they do not consist of compositions formed merely by individual ingredients of dry mix. Compositions in which each individual ingredient is mixed dry are generally powdery, slow to dissolve and also tend to alternate and develop poor characteristics in the flow of particles in storage. In the compositions of high-power granules formulated with spray-dried granules based on zeolite or In a zeolite-based agglomerate, silicate adhesion is necessary to provide enamel compatibility. The joint addition of silicate and zeolite in a spray-dried granule or granule agglomerate causes the formation of insoluble substances that cause residues in the fabric during washing. The replacement of phosphonates by EDDS provides the new effect of reducing the loss and corrosion of enamel, which therefore allows the use of lower amounts of silicate, ie a ratio of silicate to zeolite below 1: 2. In this way, the present invention relates to a detergent composition adapted to reduce the loss and corrosion of the enamel in which said detergent composition is a high-power granule formulated with conventional detersive surfactants, optional detergency, detersive additives and spray-dried granules based on zeolite or zeolite agglomerate consisting of: a) from 0% to 0.6% of phosphonate queiatants obtained from the diethylene acid obtained from ethylenediamine acid, the acid etiienodiarninodiglutápco or the acid 2-h? drox? prop? len diammo disuccinic and its salts of alkali metal or alkaline earth metal; b) at 0.15% by weight of the composition loe phosphonated milling agents obtained from diethylene acid obtained from ethylenediaminsuccinic acid, ethylenediaminemodiglutaric acid or 2-hydroxypropylene diacidine disuccinic acid, or alkali metal, alkaline earth , ammonium or substituted ammonium salts thereof, or mixtures thereof in which the weight ratio of said phosphonate to said diarninotetracarboxylate has a value of less than 2.0; c) Amorphous silicate based on less than 4% by weight of the composition in which the weight ratio of said silicate to said spray-dried granule based on zeolite or agglomerated null agglomerate of zeolite is less than 1: 2. In high power granule compositions formulated with dry mixed amorphous silicate, the high silicate levels necessary for enamel protection cause the loss of supply due to the gelling of the product. The substitution of phosphonate by EDDS would allow a reduction to the level of dry aggregate silicate, thus improving the product supply, providing protection to the enamel, and giving the same performance in the elimination of stains. In this way, the present invention relates to a detergent composition adapted to reduce the loss and corrosion of enamel in which said detergent composition is a high-power granule formulated with conventional detersive surfactants, builders and builders. optional detergency, detersive additives and amorphous dry-mixed silicate consisting of: a) at 0.6% phosphonate chelators obtained from diethi lentriaminpenta (methylenephosphine? co) acid (DTPMP), diethylene diamine acid (rnetylene phosphine? co) (DDTMP), the alkali metal and alkaline earth metal ethan-1-hydrox? difoefimic acid (HEDP); b) at least 0.15% by weight of the composition of the dianyltracarboxylate chelating agents obtained from etiiendiaryindisuccinic acid, lendianunderthaaric acid or 2-hydroxypropylenecarboxylate succimic acid, or metal alkaline, alkaline earth, ammonium or substituted ammonium salts thereof or rnezclae thereof in which the ratio of weight of said phosphonate to said day inotet r carboxylate has a value of minus 2.0; c) amorphous silicate and in a dry aggregate material at a level of 4% by weight of the composition.

For spray dried powders, the volumetric density of the particles of the spray-drying tower is conventionally in the range of 540 to 600 g / liter and is then enhanced by subsequent process steps such as size reduction in a cutter. / high speed mixer followed by compression. Alternatively, different spraying methods can be used to directly form a high density particulate. In preferred concentrated detergent products incorporating the alkali metal precarbonate as the perhydrate salt it has been found necessary to control various aspects of the product such as the heavy metal ion content and s? equilibrium relative humidity. Compositions containing sodium percarbonate of this type having enhanced stability are described in what is commonly referred to as PCT US 91/07205. In the products for automatic dishwashing, the detergent compositions useful for carrying out the present invention consist of: a) from 0% to 0.3% of phosphonate chelators obtained from diethylenetrinamine acid (rnet) ? lenfosfóm co (DTPMP), diethylene diaminetetra acid (methylene phosphate DDTMP), acid ethane-1-hydroxyphosphine (HEDP) and its salts of alkali metal and metal to the heat transfer, preferably the acid - l-hydr-oxi cii phosphonic and its salts of alkali metal and metal * - alkaline earthquake, b) at least 0.09% by weight of the composition of the chelating agents diarnmatetracarboxylate obtained from ethylenediarninodisuccinic acid acid or ethylene diamine glutamate or acid 2-h? Drox? Prop? Lend? Am? Nod? Suc? Co, or else alkali metal, alkaline earth, ammonium or substituted ammonium salts thereof, in which the ratio of the weight of said phosphonates to diammotetracarboxylate has a value of less than 2.0; c), (about 25% sodium silicate by weight of the composition) The present invention also relates to the detergent composition adapted to reduce the loss and corrosion of the enamel in which said detergent composition is a liquid composition for Automatic dish washing formulated with conventional detersive surfactants, optional detergency builders and detersive additives consisting of: a) from 0% to 5% phosphonate chelators obtained from diethylene potassium ina penta (methylene phos fonico) (DTPMP), diethylene diamine (ethylene-phophonic) acid (DDTMP), ethane-1-hydroxid acid? phosphonic (phonic ring) (DDTMP), the acid ethan-l-hi droxidi f phosphonic (HEDP) and its alkali metal salts or alkaline earth metal, preferably the acid ethane-1-hydrox? di phosphonic and its alkali metal and alkaline earth metal salts; at least 0.09% by weight of the composition of the dianinatetracarboxylactant chelators or obtained from acid etiienodiarninosuccini acid paitii and the oligodicinodiglottic acid and 2-h? droxipropylendiaminodisuccímeo, or metal-alkaline, alkaline earth, ammonium or substituted ammonium salts thereof, or mixtures thereof, in which the weight ratio of said phosphonate to said diaminotetracaryoxylate will have a value of less than 2.0.; c) less than 25% sodium silicate by weight of the composition. The invention is illustrated in the following non-limiting examples, in which all percentages are based on weight unless otherwise specified.

^ In detergent compositions, the abbreviated component identifications have the following meanings: : Linear sodium C12 alkylbenzene sulfonate: Sodium tallow alkyl sodium TAE: Ethoxylated tallow alcohol with n moles of ethylene oxide per mole of alcohol 45EY: A predominantly linear primary alcohol of C14-15 conched with an average of Y moles of oxide of ethylene Zeol ita A Alumino hydrated sodium silicate of formula i2 (AIO2S1O2) i2 - 2 H20 having a primary particle size on a scale of 1 to 10 microns Citrate: tpsodium citrate dihydrate MA / AA: Copolymer of aleic acid / acrylate acid, sodium salt sold by BASF under the tradename So alanR CP 5 with a molecular weight of 90,000 carbonate. Sodium carbonate anhydrous PBl Sodium perborate bleach anhydrous rnono-hydrated, empirical formula Na? 2-H2? 2 PB4: Sodium perborate anhydrous tet rahydrate TAED: Tetraaceti letilendiainma Phosphonate; Dietary acid and lentparninopent.amet 1 lenphosphonic acid (DETPMP) EDDS Ethylenediamine-N, N'-disuccid acid, (S, S isomer) CMC Carboxi sodium etiicellulose Bleach: Photoactivated zin tetrasulfonated phthalocyanine Lipase Lipolytic enzyme sold by Novo Industries A / S under the trade name Lipolase, _. / - 'roteaea Proteolytic enzyme sold by Novo Industries A / S under the trade name Savinase A ilaea Amylolitic enzyme sold by Novo Industries A / S under the trade name Termarnyl Silicate Amorphous sodium silicate ( ratio of Si? 2: a2? follows normally) Sulfate Magnesium sulfate anhydrous. Silicon Antifoam Sil.icon STPP Sodium tripolyphosphate (NasP3 ??) / "- Example 1 i) - detergent formulation The following high potency granule compositions were prepared with amorphous silicate mixed dry (part by weight). A washing process employing product A constitutes a prior art practice in? ie the product B is a form of the invention. - I Innggrreeddiieennttee AAB LAS 7.0 7.0 TAS 2.4 2.4 TAE11 1.1 1.1 45E7 4.0 4.0 Z Zeeoolliittaa AA 2 200..55 20.5 Citrate 7.5 7.5 MA / AA 4.0 4.0 Carbonate 15.0 15.0 PBl 16.0 16.0 T TAAEEDD 5 5..00 5.0 Phosphonate 0.38 EDDS - 0.22 CMS 0.3 0.3 bleach / photo-activated 0.02 0.02? ? aavviinnaassaa 1 1..44 1.4 1 ipolase 0.4 0.4 Silicate 3.5 3.5 MgS04 0.4 0.4 Silicone 0.4 0.4 Perfumes 0.4 0.4 The rest being water, minor and diverse components n) The results of the loss of the glaze of the two compositions were compared in the washing tests with cycles 40, 60, 100. Procedure for enamel samples The enamel samples are carefully cut in half, washed in a detergent solution , using a manual operation to remove the grease, rinse it completely in water and give it a final rinse in the IMS before careful drying. The samples are placed in a par-a desiccator to be dried from one day to the next, and then each is weighed, wrapped in tissue paper marked with an indication number and put back in the dryer until the weight remains stable 3. When the samples are ready to be used, each of the numbers of the samples are confronted with an identification mark on the plastic cage and each sample is secured inside the cage using a plastic wire tag. Procedures for the work of lava (Jor.

A minimum of 60 wash cycles is required, with interruptions after every 20 cycles, and later on. The loads of clean white linen (2.72 g) are placed in each of the machines and the three cages containing the prepared samples are added to each machine. The machines follow a temperature alteration of 40 ° C with 60 ° C, 40 ° C and * J ° C. The products are also altered between the machines. Each time interval prolonged between wash cycles (eg overnight) the samples are removed, each of its identification tissue is wrapped and allowed to dry. After completing 20 washing cycles, the samples are removed from the cage and immersed for 2 points in a solution of 0.02N EDTA previously heated to 80 ° C, then rinsed with cold running water, followed by a rinse with IMS and it dries overnight in the dryer. Each sample is weighed until it remains stable in its weight and is thickened also in terms of loss of brightness. 6.- Steps 2 to 5 are repeated for as many cycles as required. The results were recorded as weight loss in centrifugation ing in each pause of 20 washing cycles.

H Washing cycles% of enamel loss reduction (B / A) 40 2.3 1.6 30.43 60 3.2 2.1 34.37 100 3.5 2.7 22.86 Conclusion: The reduction of the level of enamel loss in machines that have enamel surfaces exposed to the detergent solution is achieved by the presence of EDDS in the detergent composition.

Example 2 The following detergent compositions were prepared for machine washing (pieces in peeo). The washing process given by the product a) is a practice according to the prior art, while the products B and C are embodiments of the invention.

A B citrate 29.0 20.0 TPP 25.0 MA / AA 3.7 6.0 Silicate (2 rays) 25.5 15.0 7.5 metasilicate - 2.5 Carbonate 20.0 30.0 PBl 1.9 1.9 0.98 PB4 8.6 8.6 4.3 TAED 3.8 3.8 2.4 phosphonate 0.13 EDD? 0.10 0.05 Avinasa 4.0 4.0 2.0 Terrnam.il 1.5 1.0 0.7 AAggeennttee tteennssiiooaaccttiivvoo 1.5 1.5 0.7 nnoo iióónniiccoo? Iendo the rest eulfato, humidity and cornponentee diverse.

Claims (14)

NOVELTY OF THE INVENTION CLAIMS

1. - The use of diarninotetracarboxylate chelating agents obtained from the group consisting of acid ^ ethylenediarinodisuccinic acid (EDD?), ethylenediarninodiglutápco acid (EDDG) or 2-hydroxyprolenediaminodieuccinic acid (HPDDS) or alkali metal, alkaline earth metal, ammonium or substituted ammonium thereof, or mixtures thereof, in a detergent composition for reduce the loss of enamel and corrosion during a washing process in a washing machine in which the silicious surfaces of the machine or of the articles washed therein are exposed to the detergent solution.

2. The use of diaryl chelating agents notet racarboxylate in a detergent composition according to claim 1, further characterized in that said diarinotetracarboxylate elastiners are selected from the group consisting of their racemate structure and isomeric structures.

3. A detergent composition adapted to reduce the loss of enamel and corrosion, characterized in that said detergent composition is a heavy duty liquid composition formulated with conventional detersive surfactants, optional detergency builders and detersive adjuvants comprising: a) about 0% to about 0.6% of phosphonate chelators obtained from the group consisting of diethylenetriaminepentametylenephosphoric acid (DTPMP), diethylenediaminetetramethienphosphoric acid (DDTMP), ethane-1-hydroxydi-phosphonic acid (HEDP) and its alkali metal salts, or alkaline earth metal; At least about 0.15% by weight of the inotetracarboxylate chelating agent composition obtained from the group consisting of ethylenediarinodieuccinic acid, ethylenediaminedigluthacic acid, or 2-hydroxypropylenediarinodisuccinic acid or alkali metal, alkaline earth metal, ammonium or substituted ammonium salts thereof. same, or mixture of the mis oe, wherein the weight ratio of said phosphonate to said diarninotetracarboxylate has a value less than about 2.0; c) about 0.5% inhibitors of silane corrosion by weight of the composition.

4. A detergent composition adapted to reduce the loss of enamel and corrosion in accordance with claim 3, further characterized in that said diaminotetracarboxylate chelating agents are selected from the group consisting of their structure of racernate and structural structures. 5.- A detergent composition adapted for the loss of enamel and corrosion, fell due to the fact that said detergent composition is a heavy-duty liquid composition formulated with conventional detersive surfactants, optional detergency builders and detersive adjuvants. They comprise: a) from about 0% to about 0.6% of foefonate chelators obtained from the group consisting of diethylenetriarum nopentamethylenephosphoric acid (DTPMP), Jietilendiaminotetrame iienphosphoric acid (DDTMP), ethane-1-hydroxydi-osphonic acid (HEDP) and its alkali metal saltse, or alkaline earth metal; b) at least about 0.15% by weight of the composition of diarrotetracarboxylate elastomers obtained from the group consisting of ethylenedia modisuccinic acid, etiiendiaminodiglutaric acid or 2-hydroxypropylenediamine disuccinic acid or alkali metal, alkaline earth metal, ammonium or ammonium salts substituted thereof, or mixtures thereof, wherein the weight ratio of said phosphonate to said diaminotetracarboxylate has a value less than about 2.0; c) about 3% inhibitors of silane corrosion by weight of the composition. 6. A detergent composition adapted to reduce enamel loss and corrosion in accordance with claim 5, further characterized in that said di minot and racarboxylate chelates are selected from the group consisting of its racernate structure and isomeric structures. . 7.- A detergent composition adapted to reduce the loss of enamel and corrosion, characterized in that said detergent composition is a heavy-duty granule formulated with conventional detersive surfactants, optional builders, detersive adjuvants and zeolite spray-dried granule or zeolite agglomerate. -which comprise: a) of about 0 % to about 0.6% of phosphonate chelators obtained from the group consisting of diethylenetriaminepentamethienphosphoric acid (DTPMP), diethylene diaminetetramethylenephosphatic acid (DDTMP), ethane-1-hydroxydiphosphonic acid (HEDP) and its alkali metal salts, or alkali metal l motérreo; b) at least about 0.15% by weight of the composition and inotetracarboxylate day chelators obtained from the group consisting of etiiendiarninodisuccinic acid, ethylenediaminediglutaric acid or 2-hydroxypropylenediamine epizoic acid or alkali metal, alkalimetal, ammonium or ammonium salts substituted thereof, or mixtures thereof, wherein the weight ratio of said phosphonate to said dianinotetracarboxylate has a value less than about 2.0; c) amorphous silicate at a level of less than 4% by weight of the composition, wherein the weight ratio of said silicate to said spray-dried granule of zeolite or zeolite agglomerate is less than 1: 2. 8. A detergent composition adapted to reduce enamel and corrosion loss according to claim 7, further characterized in that said diarninotetracarboxylate chelating agents are selected from the group consisting of their racemate structure and isomeric structures. 9. A detergent composition adapted to reduce the loss of enamel and corrosion, characterized in that said detergent composition is a heavy-duty granule fornula < -the one with conventional detersive surfactants, optional detergency builders, detersive adjuvants and dry mixed amorphous silicate comprising: a) from about 0% to about 0.6% "chelators" The foefonate obtained from the group consisting of dietary acid ientriaminopentametiienfosfórico (DTPMP), acid dietiiendiammotetrametiienfosfónco (DDTMP), ethan-l-hidroxidifoefónico acid (HEDP) and its salts of alkaline metal, or alkaline earth metal; b) at least about 0.15% by weight of the inotetracarboxylate chelating agent composition obtained from the group consisting of ethylenediarinodisuccinic acid, ethylendiarynineodiglyceride acid or 2-hydroxypropyl-diaminodisuccinic acid or alkali metal salts, alkali metal motor, ammonium or substituted ammonium thereof, or mixtures thereof, wherein the weight ratio S- of said phosphonate to said diamotetracarboxylate has a lower value < - Approximately 2.0; c) amorphous silicate in a dry added material at a minor level of 4% by weight of the composition 10. A detergent composition adapted to reduce the loss of enamel and corrosion in accordance with claim 9, further characterized in that said Relatators « The diarynotetracarboxylate is selected from the group consisting of its structure of scavenger and isomeric structures. 11. A detergent composition adapted to reduce the loss of enamel and corrosion, characterized in that said detergent composition is a granulated composition for automatic dishwashing formulated with conventional detersive surfactants, enhancers of "Optional substances and detersive adjuvants comprising: a) from about 0% to approximately 0.3% of phosphonate chelators obtained from the group consisting of diethylenetriamine pentanethylenephosphatic acid (DTPMP), diethylene diaminetetramethylene phosphatic acid (DDTMP), acid-1-hydroxydiphosphomatic acid (HEDP) and its alkali metal salts, or alkaline earth metal, preferably ethan-i-hydroxydi-phosphonic acid and its alkali metal salts, or alkali metal salts; noterreo; b) at least about 0.09% by weight of the chelating composition "Je diarninotet raca boxil to obtained from the group consisting of tiiendiammodisuccinico acid, ethylendiaminodiglutapco acid or 2-hydroxypropylenediamineodisuccinic acid or salts of alkali metal, alkaline earth metal, ammonium or substituted ammonium thereof, or mixtures thereof, wherein the weight ratio of said phosphonate to said inotetracarboxylate day has a value less than about 2.0; ) less than about 25% sodium silicate by weight of the composition. 12. A detergent composition adapted to reduce enamel loss and corrosion in accordance with claim 11, further characterized in that said diaminotetracarboxylate chelating agents are selected from the group consisting of their racemate structure and isomeric structures. 13. A detergent co-modification adapted to reduce the loss of enamel and corrosion, characterized in that said detergent composition is a granular automatic dishwashing composition formulated with conventional detersive surfactants, optional builders and detersive adjuvants < They comprise, a) from about 0% to about 0.3% of chelated, "Phosphonate obtained from the group consisting of diethylenetriamine-pentanephthalic acid (DTPMP), diethylene diamine-phosphonic acid (DDTMP), etan-1-hydroxydiphosphomatic acid (HFDP) and its alkali metal salts, or alkaline earth metal, preferably with the addition of alkaline metal salts, or alloy metal; b) at least about 0.09% by weight of the chelator composition of the diamotetracarboxylate obtained from the group consisting of etiiendiarninodis acid, cyclic acid, etherendiammodigl urtric acid or 2-, -? idrox? prop? lend? ammod? succimic acid or alkali metal, metal-earth metal, ammonium or substituted ammonium salts thereof, or mixtures thereof, wherein the weight ratio of said phosphonate to said diamotetracarboxylate has a value less than about 2.0; c) less than about 25% sodium silicate by weight of the composition. 14. A detergent composition adapted to reduce enamel loss and corrosion in accordance with claim 13, further characterized in that said diamotetracarboxylate chelating agents are selected from the group consisting of their racemate structure and isomeric structures.