MXPA99005077A - - Google Patents

Description

GRANULATED COMPOSITIONS OF N-ALKYLAMONIO ACETONITRILE PE COMPOUNDS FIELD OF THE INVENTION The present invention generally relates to n-alkylammonium acetonitrile compounds useful in applications such as bleaching and cleaning, and particularly in the form of granules useful for oxidative applications when dissolved in the presence of an active oxygen source. This application is a continuation in part of serial number 08 / 475,292, filed on June 7, 1995, entitled "N-alkyl ammonium acetonitrile bleach activators," inventors Arbogast et al .; of common allocation in the present.

BACKGROUND OF THE INVENTION Peroxy compounds are effective bleaching agents, and compositions that include mono- or diperoxy acid compounds are useful for the operations of industrial or domestic laundries. For example, the Patent of E.U.A. 3,996,152, issued December 7, 1976, Edwards et al., Describe bleaching compositions including peroxygen compounds such as diperazelaic acid and diperisophthalic acid.

Peroxyacids (also known as "perished") have typically been prepared by the reaction of carboxylic acids with hydrogen peroxide in the presence of sulfuric acid. For example, the patent of E.U.A. 4,337,213, inventors Marynowski et al., Issued June 29, 1982, describe a method for making diperoxy acids in which high solids yield can be achieved. However, granulated bleach products containing peroxyacid compounds tend to lose bleaching activity during storage, due to the decomposition of the peroxyacid. The relative instability of the peroxyacid may present a problem of storage stability to the compositions consisting or including peroxyacids. One approach to the problem of the reduced bleaching activity of the peroxyacid compositions has been to include activators of hydrogen peroxide or an active oxygen source. The patent of E.U.A. No. 4,283,301, inventor Diehl, issued August 11, 1981, discloses bleaching compositions including peroxygen bleaching compounds, such as sodium perborate monohydrate or sodium perborate tetrahydrate, and activating compounds such as isopropenyl hexanoate and hexanoylmalonic acid diethyl ester. Other examples of activators include tetraacetylethylenediamine (TAED), nonanoyloxybenzenesulfonate (NOBS), and nonanoylglycolate phenolsulfonate (NOGPS). NOBS and TAED are described, for example, in the U.S. Patent. 4,417,934, Chung et al., And NOGPS is described, for example, in the U.S. Patent. 4,778,618, Fong et al., The descriptions of which are incorporated herein by reference. In this way, the patent of E.U.A. 4,778, 618, Fong and others; issued on October 18, 1988, provides new bleaching compositions comprising perishing precursors with the general structure GOLD II I II R-C-O-C-C- L I Fí¬ wherein R is branched linear alkyl of C 1-20, alkylethyloxy, cycloalkyl, aryl, substituted aryl; R 'and R "are independently H, C1-20 alkyl, aryl, C1-20 alkylaryl, substituted aryl, and N + R3, wherein Ra is C1-30 alkyl, and wherein L is a leaving group which can be displaced in peroxygen bleach solution by the peroxide anion US Patents 5,182,045 issued January 26, 1993, and 5,391,812, issued February 21, 1995, inventors Rowland et al. similar, but are polyglycolates of the precursors, or activators of Fong monoglycolate and others US Patent 4,915,963, issued April 10, 1990, Aoyagi et al., discloses that said compounds are peracid precursors having nitrile moieties. U.S. Patent 5,236,616, issued August 17, 1993, inventors Oakes et al., describes that said compounds are cationic peroxyacid precursors having nitrile portions. Such nitrile-containing activators do not contain a leaving group, such as the Fong and other leaving groups, but instead include a quaternary ammonium group suggested to activate the nitrile and, under the reaction or perhydrolysis in the presence of hydrogen peroxide , generate a peroxyimidic acid as bleaching species. Activators of Aoyagi and others include an aromatic ring, which tends to cause yellowing of the fabric. The German patent application P4431212.1, published on March 7, 1996 describes the production of quaternized glycinonitriles in the form of stable aqueous solutions. New peroxygen activators that provide excellent bleaching and that can be formulated for liquid or solid compositions are still desirable for applications such as laundry and household bleaching and cleaning.

BRIEF DESCRIPTION OF THE INVENTION In one aspect of the present invention nitriles are provided in substantially solid form, having the structure of formula I.

FORMULA I N '? 1- "CR2R3oC = N. Y ° .ZH O where A is a saturated ring consisting of 5 atoms in addition to the NL atom the five saturated ring atoms being four carbon atoms and one heterogeneous atom, the Ri bond replaces the Ni atom of the structure of formula I including (a ) an alkyl or alkoxylated alkyl of C1-2 wherein the alkoxy is C2-4, (b) a cycloalkyl of C4-2, (c) an alkaryl of C7-24, (d) an alkoxy of • repeating or not- repeating or alkoxylated alcohol, wherein the alkoxy unit is C2-, or (e) -CR2R3C = N wherein R2 and R3 are each H, a C1-24 alkyl, cycloalkyl, or alkaryl, or alkoxy or alkoxylated alcohol of repetition or non-repetition, where the alkoxy units are C2-4. The compounds of the formula I have a quaternary nitrogen atom (Ni), requiring the presence of at least one counterion (Y) to be associated therewith, which is illustrated in formula I "Y9", but as already understood , it can be monovalent or multivalent. And it includes counterions, or organic and inorganic anions such as chlorine, bromine, nitrate, alkylsulfate, disulfate, sulfate, tosylate, and mesylate. Especially preferred are methylisulfate, sulfate, bisulfate, tosylate and mixtures thereof. Z will be on a scale from 0 to 10. Said compounds or salts are particularly suitable for granular bleaching and cleaning compositions. Nitriles with the structure of formula I are particularly useful when formulated as compositions that include an active oxygen source, and said compositions provide excellent bleaches in alkaline solutions. Preferred embodiments include lower alkyl substituted in Ni, ie, N-methylmorpholinium acetonitrile, N-ethylmorpholinium acetonitrile, N-butylmorpholinium acetonitrile, which is also illustrated by formula II (with "n" preferably being 0 to 24, where "Y" is one of the counterions described above).

FORMULA II A particularly preferred embodiment is an acetonitrile salt of N-methylmorpholinium wherein "n" of formula II is 0. Preferred embodiments are in granular form so that nitriles are stabilized and protected even when formulated or mixed with other components . Compositions including such nitriles are useful, for example, in laundry products such as bleaching additives, detergents, detergency builders, detergents with bleach, bleaches, bleaching aids, stain removers, and stain treatment products such as removers. of stain, auxiliary for laundry of prewash and preenjabonamiento. Among the advantages derived from said compositions are the improved cleaning, removal of stain, removal of dirt, whitening and polishing of treated articles.

DETAILED DESCRIPTION OF THE PREFERRED MODALITIES The application with serial number 08 / 475,291, filed on June 7, 1995, entitled "N-Alkyl Ammonium Acetonitrile Bleach Activators," describes nitriles, typically quaternized, for which a preferred embodiment was acetonitrile methylisulfate of N- methylammonium, with which this request is related. There are several aspects of the present invention. One aspect is where quaternized novel nitriles are provided having certain counterions that result in substantially reduced hygroscopicity (with respect to acetonitrile methanesulfate of amorphous N-methylammonium, or MMAMS). Another aspect is where the novel nitriles are supplied as granules when transported, coated, or mixed with a suitable particular material. Said granules have improved the stability and / or reduced hygroscopic characteristics with respect to the amorphous MMAMS. Yet another aspect of the invention is for an improved method of manufacturing quaternized novel nitriles to have reduced amounts of the unwanted byproduct. Said inventive aspects have a common element of certain novel nitriles with the structure generally illustrated by the formula I The Ni atom of the compound of the formula I is part of a saturated ring, illustrated by "A" in the formula I.

FORMULA I This saturated ring, of which N-i is a part that has a plurality of atoms. The saturated ring screened by the "A" ring in the formula I preferably has at least one heterogeneous atom in the saturated ring in the N al addition most preferably wherein the ring includes an oxygen atom, a sulfur atom, one or two additional nitrogen atoms. At least one nitrogen in the saturated ring (Ni) shown in formula I is N-acetonitrile substituted and also quaternized. Without being limited by theory, the attraction nature of the quaternary hydrogen electron can be increased by being part of a saturated, heterocyclic ring and can also function to improve the hydrophilic character of the oxidant.

A substituent RT will bind to the Ni atom of the structure of formula I and additionally a portion of nitrile (-CR2R3C = N) is linked to the Ni atom, wherein R2 and R3 are H, a C? -24 alkyl, cycloalkyl , or alkaryl, or a repeating or non-repeating alkoxy or alkoxy alcohol wherein the alkoxy unit is C2-4. The R 1 substituent may be a C 24 alkyl or alkoxylated alkyl wherein C 2 -4 alkoxy, C 4-24 cycloalkyl, C 7-24 alkaryl, a non-repeating or non-repeating alkoxy or alkoxylated alcohol, wherein the alkoxy unit is C2-, and illustrative of said groups are, for example, OH) where j = 1 to 24. It is substituent Ri can also be another and again R2 and R3 are H, a C1-24 alkyl, cycloalkyl, or alkaryl, or a repeating or non-repeating alkoxy or alkoxylated alcohol wherein the alkoxy unit is C2-4, and illustrative of said groups are: (C where j = 1 to 24.

Particularly preferred are the saturated rings which form the cyclic configuration A of the formula I which contains 6 atoms including the Ni atom, but the number of atoms forming the cyclic configuration can vary from 3 to 9. When two heterogeneous atoms are present with the cyclic configuration A of formula I, then a ring of three members is unusual; but, for the cyclic configuration B of formula III shown below, where only Ni can be Ni as the only heterogeneous atom, then the rings of three members are very similar. As mentioned above, the particularly preferred saturated ring, of which Ni is a part, has 5 atoms in addition to Ni, with at least one heterogeneous atom being found in the saturated ring in addition to Ni, preferably wherein the heterogeneous atom of the ring is an oxygen atom or a sulfur atom, most preferably wherein the heterogeneous atom is oxygen. Particularly preferred activator modalities are illustrated by formula II (wherein "Y" and "Z" will be described later, "n" is from 0 to 24).

FORMULA Y ° - ZH 2 O Derivatives of the nitriles of the formulas I and II include peroxymetric intermediates which are formed from the nitriles in the presence of an active oxygen source. Already formed, the peroxypic derivatives will typically be short-lived intermediates formed in situ when the nitriles of the invention interact with a source of hydrogen peroxide and wherein the reactive nitrile portion forms a peroxydic acid. However, said peroxydic derivatives can also be prepared in situ by analogy to the synthesis known in the art.

Counterions Although the new nitrile compounds are normally quaternized, they will include at least one counterion (called "Y"). Suitable counterions are monovalent or multivalent and include tosylates, lower alkyltosylate (i.e., methyltosylate and ethyltosylate) and mesylates. Further, in the copending application mentioned above with serial number 08 / 475,292, issued June 17, 1995, N-alkylammonium acetonitrile compounds are described as typically including a wide variety of counterions, such as chlorine, bromine, nitrate , alkyl sulfate and the like, and wherein a preferred embodiment was described therein as the acetonitrile methylisulfate of N-methylammonium. When the granule appearance is selected in the present invention then such a wide variety of counterions remains available by selecting which counterion can be desired, including the methylisulfate as a counter ion. The above is due to the fact that most granule modalities protect the stability of the nitrile (for example, against moisture during storage). However, the new nitrile compounds do not need to be in granulated form to be suitable for various applications and to provide stabilized compounds against moisture collection. A particularly preferred embodiment of the present is wherein the counterions are sulfate, bisulfate, or mixtures thereof. Said sulfate or bisulfate salt (or mixtures thereof) can be produced from a heated and acidified N-methylmorpholinium methylsulfate methylisulfate, or MMAMS (wherein the counterion before conversion to bisulfate or sulfate is methylisulfate). The two particularly preferred salts are illustrated by the formulas IIIA and IIIB. A third particularly preferred salt, N-methylmorpholinium acetonitrile tosylate ("MMATS"), is illustrated by the formula NIC.

FORMULA III IIIA IIIB SO '4 I MMAB MMATS The modalities of MMABS, MMAS and MMATS are particularly useful where a substantially solid composition is desired to have reduced hydroscopicity with respect to MMAMS. Although the modalities of MMABS, MMAS; and MMATS can also be in granular form, they do not need to be in such form, and they are useful in crystalline or amorphous forms. The sulfate and disulfate counterions are in equilibrium with each other in solution, and the predominant species are independent of the pH solution. Above pH 2, the sulphate group predominates, while below the pH 2, the disulfate form predominates. In this way, the particular desired form can be obtained by controlling the pH solution, although a mixture is obtained at an intermediate pH. However, the particularly preferred embodiment is where the granules are provided when the nitrile salt is bisulfate, which has crystallized, the crystals have been redissolved and the solution is granulated (thus having impurities removed).

Water content of nitrile The novel nitriles can exist as anhydrous salts (essentially free of water) or as stable hydrates having discrete amounts of water of hydration. Thus, in formulas I and II, Z is on a scale from 0 to 10, preferably from 0 to 6, and most preferably from 0 to 1. Said "Z" can be seen as an average number of moles. of hydration. Because mixtures of the compounds of formulas I and II may be with integer mole numbers of hydration, the actual value for Z may be a non-integer value. The value for Z can be reduced when a novel crystalline or amorphous form of nitrile is converted to a granular form.

Physical form of the nitriles The amorphous forms of the nitriles of the formulas I and II can be obtained by rapid evaporation or precipitation of the solutions (such as spray drying, column drying and the like). Alternatively, the crystalline salts can be obtained by crystallization or careful evaporation, the crystalline forms of which tend to be less hygroscopic than the amorphous forms. It is believed that said reduced hygroscopicity of the crystalline salts, without being limited by theory, due to the tight packing of the molecules within the crystal, prevents the penetration of water volume and the reduced total surface area of a crystalline solid compared to a amorphous of the same solid. The granule modalities can also be prepared from the nitriles in the crystallized or amorphous forms.

Amazing Properties of Nitrile Granules Granulated forms have the advantage of being stable on the shelf (ie, they remain able to flow without clumping, forming cakes or otherwise agglomerating) and maintaining their bleaching effectiveness until they are use, even when the granules are formulated or mixed with other components, such as sources of alkalinity and active oxygen. In addition, the granule protection allows the use of a smaller amount of nitriles in granulated formulations used in bleaching and laundry preparations which reduces possible damage to the dye. Dye damage can be caused by dissolving the formulations when they are inadvertently placed in direct contact with textiles that have particularly sensitive pigments.

Bleaching and cleaning compositions The bleaching and cleaning compositions of the invention include the nitrile salts of the formula I as activator, together with an active oxygen source. The peroxide or active oxygen source for the compositions of the invention can be selected from the alkaline earth metal salts of percabonate, perborate, persilicate and adducts of hydrogen peroxide and hydrogen peroxide. Most preferred are sodium percarbonate, perborate, sodium mono- and tetrahydrate, and hydrogen peroxide. Other sources of peroxygen may also be possible, such as monopersulfates and monoperphosphates, or their equivalent aqueous forms, such as monopersulfuric acid, known in the market as Caro or Caroat acid, a product of BASF AG, Germany.

The activating peroxide scale is preferably determined as a molar ratio of peroxide to activator. In this way, the peroxide scale for each activator is a molar ratio of from about 0.1: 1 to 100: 1, most preferably from about 1: 1 to 10: 1 and most preferably from about 2: 1 to 8: 1. Said per activating peroxide / peroxide composition should provide approximately 0.5 to 100 ppm O.A .; most preferably about 1 to 50 ppm of O.A peracid (active oxygen), and most preferably about 1 to 20 ppm of O.A. of peracid in an aqueous medium for typical applications for laundry. The formulations intended for hard surface cleaning will typically have more peracid activator / peroxide, providing about 0.5 to 1,000 ppm O.A., most preferably about 1 to 500 ppm O.A. of peracid, and most preferably from about 1 to 200 ppm O.A. of peracid. It has been found that the compositions of the invention provide superior bleaching benefits (cleaning and removal of dirt) in common laundry soils.

Granulated modes and supply systems. The substantially solid salt activators can be used directly in a crystalline or amorphous form, for example by incorporation into a solid matrix in solid detergent bleaches. As will be described, more fully below, the preparation of the novel nitriles in the form of bisulfate or sulfate will typically be done by the conversion of another counter ion (eg, methylisulfate). The conversion can be complete or partial. In this way, a salt composition of the formula I or II can include about 1% by weight to about 99% by weight of another compound related to the compound of the formula I, but differing therefrom in counterion. The degree of conversion to bisulfate or sulfate will be directly related to the amount of hygroscopicity reduction of said salt composition. Depending on whether or not they are converted to bisulfate or sulfate, the incorporation of the novel nitrile salts into dry, or granulated, formulations can be achieved by several different embodiments. Granulated formulations have several advantages in liquid formations, such as, for example, reduced shipping costs. Other advantages are an increased stability of the nitrile activator against moisture, alkalinity (for example carbonate), against premature activation and reduction in possible damage to the dye. Typically, the precursor composition prior to granulation is of a spreadable consistency, i.e., in the form of a liquid, suspension or solution. A suitable process for the granulation can be carried out in a fluid bed or rotating cylinder agglomerator, such as described in the document US 08554,672, issued on November 8, 1995, entitled "Agglomerated Colorant Specke Exhibiting Reduced Colorant Spotting, "incorporated herein by reference.

In the granulated embodiments the nitrile salts can be coated, coated or mixed with a solid particulate, such as an inert, porous material. Said granules can also have a coating that is sufficient to retard dissolution in aqueous solution. For example, such suitable coatings include surfactants, waxes, polymers, or mixtures thereof, and powders or flow agents such as silicas and silicates. The coatings can encapsulate the nitrile-containing core. The granules preferably have an average particle size of about 3 nm to about 2 mm. For example, the activators of the invention can be dispersed in a solid or granular carrier such as silica gel, silicic acid, silicate, aluminum oxide, kaolin, aluminum silicate, mixtures or other vehicles such as clay, zeolite., organic polymers including starch and ion exchange material. Additional solids useful for vehicles include alkali metal and alkaline earth metal salts of carbonate, bicarbonate, sesquicarbonate, phosphate, chlorine, sulfate, bisulfate and borate. A high internal surface area of the vehicle materials for said granular mode is preferred. The total surface area of preference is in the range of 10 to 500 m2 / g or, especially 100 to 460 m2 / g or especially, 250 to 450 m2 / g. Although most conventional types of the chemically inert and porous materials can be used as carrier materials, silicas, silicates, precipitated silicas, aluminum oxides, various varieties of aluminum clays or silicates or mixtures thereof are preferred. Silica gels (silica gels, silicic acid gels, wax) are colloidal, formed or unformed silicic acids, of elastic to solid consistency, with a freedom to compact the pore structure and a high adsorption capacity. The silica gel surfaces usually show acidic properties. Silica gel is usually made of water-glass by reaction with mineral acids. The precipitated silicas are powders obtained by coagulation of silica particles of an aqueous medium under the influence of coagulants. Among the silicic acids, thermally generated silicic acids, ie highly dispersing Sio2 (pyrogenic) qualities (ie Aerosils® or Cab-oSils®) which are usually prepared by SiCI flame hydrolysis, can be used in particular advantageous in addition to the silicic acids which are obtained according to the wet process. In an especially preferred form of the embodiment of the present invention, use is made of silicic acid with an average particle size (agglomerate) of 100 nm or 30 mm or, especially 100 to 1.5 mm and a SiO2 content of 95 to 100. % by weight or, preferably, 98 to 100% by weight. In addition, the precipitated silicone, such as the SIPERNAT® silica material, can be used advantageously. Aluminum oxides occur in nature in, for example, the shape of clay or corundum. In this regard, aluminum oxide is present in the modification a. Industrially, a-AI O3 is obtained from bauxite, using the Bayer procedure. Suitable "active" aluminum oxides with a high specific surface area are prepared in the form of adsorbents, by precipitation processes of the aluminum salt solutions or by calcination of aluminum hydroxide. Clays are crystalline and hydrated amorphous aluminum, iron, magnesium, calcium, potassium and sodium silicates that occur naturally.

Said clays may also contain amounts of aluminum oxide and silica. Useful clays may include kaolins, serpentines, talcs, pyrophyllites, attapulgites, sepiolites, morinoiites and bauxitic clays. Said clays may undergo several procedures before use. For example, clays can be floated in air, washed with water, calcined, delaminated, activated by acid or treated with dispersants. A preferred process for providing an aluminum silicate vehicle particle is described by the document with serial No. 08 / 554,672, mentioned above, which method can also be used to provide a vehicle for a pigment or other colorant. Aluminum silicates are compounds with different proportions of AI2O3 and SiO2. The aluminum silicate minerals in which the Al occupies the lattice positions in the crystal lattice instead of Si are the aluminosilicates (ie the different varieties of aluminosilicates). ultramarine, zeolite and feldspar). The freshly precipitated aluminum silicates are finally dispersed and have a large surface area and a high adsorption capacity. Among the useful aluminosilicates are the synthetic zeolites commonly used as builders. The ratio of nitrile salt and carrier materials in a solid composition according to the invention may vary within certain limits, depending on the method of manufacturing the solid composition and the properties of the vehicle, and the end use. A preferred ratio is from 10 to 95 parts by weight of the nitrile at 5 to 90 parts by weight of the vehicle, especially 10 to 70 parts by weight of the nitrile at 10 to 70 parts by weight of the vehicle. The ratio of 50 to 90 parts by weight of formula I, to 10 to 50 parts by weight of the vehicle is especially preferred where it is desired to maximize the concentration of active formula I. A ratio of 50 to 10 parts by weight of formula I a to 90 parts by weight of the vehicle is especially preferred where it is desired to disperse active formula I, for example to reduce localized bleaching. The parts indicated by weight are based on the anhydrous solid. For example, the granules of the invention may include a surfactant or a mixture of surfactants to constitute an amount of preferably from about 0.5 to about 50 parts by weight.

Supply System Surfactants As mentioned above, the compositions of the invention often desirably contain various amounts of surfactants, which can act as an active cleaning agent, as well as to help disperse sparingly soluble materials in liquid phase when the compositions are started to be used. The surfactants with which activators and active oxygen compositions can be combined or mixed include linear ethoxylated alcohols, such as those sold by Shell Chemical Company under the tradename Neodol. Other suitable nonionic surfactants may include other linear ethoxylated alcohols with an average length of 6 to 16 carbon atoms and averaging about 2 to 20 moles of ethylene oxide per mole of alcohol; ethoxylated, linear and branched, primary and secondary alcohols, propoxylated, with an average length of about 6 to 16 carbon atoms and averaging 0-10 moles of ethylene oxide of about 1 to 10 moles of propylene oxide per mole of alcohol; linear and branched alcohols of alkyphenoxy (polyethoxy), otherwise known as alkylphenols and ethoxylates, with an average chain length of 8 to 16 carbon atoms and averaging 1.5 to 30 moles of ethylene oxide per mole of alcohol; and mixtures thereof. Other suitable nonionic surfactants may include esters of polyoxyethylene carboxylic acid, esters of fatty acid glycerol, fatty acid and ethoxylated fatty acid alkalonamides, certain blocking copolymers of propylene oxide and ethylene oxide, and blocking polymers or propylene oxide and ethylene oxide with propoxylated ethylenediamine. Also included are said semi-polar nonionic surfactants such as amine oxides, phosphine oxides, sulfoxides and their ethoxylated derivatives. Anionic surfactants may also be suitable. Examples of such anionic surfactants may include ammonium, substituted ammonium (i.e., mono-di-, and triethanolammonium) alkali metal and alkaline earth metal salts of C6-C20 fatty acids and spray acids, linear and branched alkylbenzene sulphonates, ether sulphates, alkyl ethoxylates, ether sulfates, alkylethoxylated or propoxylated, alkylsulfates, alkyl ether sulphates, alkane sulphonates, a-colein sulphonates, hydroxyalkane sulphonates, fatty acid monoglyceride sulphates, alkyl glycerol, ether sulfates, acyl sarcosinates and acyl N-methyl taurides. Suitable cationic surfactants may include quaternary ammonium compounds in which typically one of the groups bonded to the nitrogen atom is a C12-C1S alkyl group and the other three groups are short chain alkyl groups which may bear substituents and inerts such as phenyl groups. Suitable amphoteric and zwitterionic surfactants contain an anionic water-solubilizing group, a cationic group or an hydrophobic organic group including aminocarboxylic acids and their salts, aminodicarboxylic acids and their salts, alkylbetaines, alkylaminopropylbetaines, sulphobetaines, alkylimidazolinium derivatives, certain compounds of quaternary ammonium, certain quaternary phosphonium compounds and certain tertiary sulfonium compounds.

Other common detergent adjuvants can be added if a bleaching or detergent bleach product is desired. Table 1 illustrates modalities of dry bleaching composition, incorporating the salts of formula I.

TABLE 1 COMPONENT COMPONENT SCALES (% BY WEIGHT) Surfactant: Linear alkyl benzene sulfonate (LAS) 0-15 Alkylsulfonate (AS) 0-15 Ethoxysulfate alcohol (AEOS) 0-15 Ethoxylate alcohol (AE) 0-15 Detergency detergent: Sodium carbonate 20-70 Zeolite 0-50 Polyacrylate Polymer 0-5 Sodium Silicate 0-8 Filler: Sodium Chloride 0-30 Sodium Sulfate 0-30 Water 0-5 TABLE 1 (CONTINUED) Blanching system: Sodium perborate monohydrate 4-40 MMA1 1-10 activator Other: Enzyme (s) 2 0-3 Brightener 0-2 Coloring / pigment as necessary Perfume as necessary 1. - Nitrile, inventive, preferably MMAMS, MMAS, MMABS, or MMATS. 2. Examples that include but are not limited to protease, amylase, lipase, cellulase (alone or in combinations).

Acid / base sources The compositions of the invention, when combined with an active oxygen source, preferably function to better whiten at an alkaline pH, but become more shelf stable at an acidic pH, particularly a pH of 0- 5, most preferably 0-2, most preferably 0-1. In this way, the compositions of the invention preferably include a source of protons as an "acid rinse". The above can be achieved, for example, by adding acid, preferably at levels of about 0-50% by weight of the final solid weight to the liquid containing the nitriles before any other granulation process (mixing or drying). Preferred acids include citric acids, sulfuric acid, succinic acid, hydrochloric acid, sulfuric acid, arylsulfonic acids and alkylarylsulfonic acids, as well as polyalbrilic acid, maleic acid, nitric acid, and sulfamic acid. Most preferred are sulfuric acid and sulfurous acid. When the composition is ready for use, it is especially advantageous to have an amount of alkaline pH regulator sufficiently present to maintain a pH greater than about 8, most preferably in the range of about 8.5 to about 10.5 for the most effective bleaching, when the granules dissolve, they are dispersed in an aqueous washing system. If used as a hard surface cleaner, on the other hand it may be useful to distribute the alkaline pH regulator in a separate composition, preferably liquid. Such alkaline pH regulators include, but are not limited to, the hydroxides of alkali metal (sodium, lithium, potassium), ammonium hydroxide, alkali metal carbonate and ammonium, alkali metal and ammonium carbamates, alkali metal and ammonium polyacrylates, and alkali metal and ammonium succinates, alkali metal and ammonium alkali and additional conjugate bases of weak organic acids, such as those mentioned above. In addition, organic bases are included, such as, without limitation, ethanolamine, diethanolamine, triethanolamine, hydroxylamine, methylamine, dimethylamine and trimethylamine.

Additional functional / aesthetic adjuvants Other adjuvants (useful in cleaning and laundry applications) are optionally included in the inventive compositions. The dyes include anthraquinone and similar blue dyes. The pigments can also be used, and they can have a bluing effect by deposition on fabrics washed with a detergent bleach containing UMB.

Monoastral dyes are also possible for inclusion. Brighteners or bleaches may be included, such as stilbene, styrene and styrynaphthalene brighteners (fluorescent whitening agents), fragrances used for aesthetic purposes are commercially available from Norda, International Flavors and Fragrances, and Givaudon. The stabilizers include hydrated salts, such as magnesium sulfate and boric acid. In some of the compositions herein, the adjuvants include (and are especially preferred) a chelating or sequestering agent, and preferably a non-phosphate containing sequestrant, and most preferably, an aminopolyphosphonate. Such chelating agents help to maintain the stability of the solution of the salt activators and the active oxygen source to achieve optimum performance. In this way, the heavy metal ions act to chelate, which cause the catalyzed decomposition of the active oxygen source and (it is believed) of the peroxyidic acids formed in situ, although the above is a non-binding theory of its action and not limiting. The chelating agent is selected from a number of known agents that are effective in chelating heavy metal ions. The chelating agent must be resistant to hydrolysis and rapid oxidation by oxidants. Preferably, it must have a constant acid dissociation (pka) of about 1-9 indicating that it dissociates at lower pHs to drive the bond to the metal cations. Acceptable amounts of the chelating agent (optional) vary from 0-1000, most preferably 5-500, most preferably 10-100 ppm chelating agent, in the wash liquor. The most preferred chelating agent is an aminopolyphosphonate, which is commercially available under the trade name Dequest of Monsanto Company. Examples thereof are Dequest 2000, 2041, and 2060. (see also Bossu, U.S. Patent 4,473,507, column 12, line 63 to column 13, line 22 to column 13, line 22, incorporated herein by reference). A polyphosphonate, such as Dequest 2010, is also suitable for use. Other preferred chelating agents that do not contain phosphate, such as ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA) may also be suitable for use even new ones, the preferred chelating agents being novel propylene diamine tetra acetates, such as Hampshire 1 , 3 PDTA, from WR Grace, and Chel DTPA 100 # F, from Ciba Geigy A.G. Mixtures of the above may be adequate. Additional desirable adjuvants are enzymes (augh it may also be preferred to include an enzyme stabilizer). Proteases are an especially preferred class of enzymes. Preferably they are selected from the alkaline proteases. The term "alkaline" is preferred for the pH at which the activity of the enzymes is optimal. Alkaline proteases are available from a wide variety of sources, and are typically produced from several microorganisms (ie, Bacillus subtilisis). Typical examples of alkaline proteases include Maxatasa and Maxacal from International BioSyntlhetics, Alcalasa, Savinasa, and Esperasa, all available from Novo Industri A / S. See also Stanislowski and others; Patent of E.U.A. 4,511, 490, incorporated herein by reference. In addition, suitable enzymes are amylases, which are carbohydrate-hydrolyzing enzymes. It is also preferred to include mixtures of amylases and proteases. Suitable amylases include Rapidase, from Societe Rapidase, Milezima from Miles Laboratory, and Maxamil from International BioSynthetics. Still other suitable enzymes are cellulases, such as those described in Tai, U.S. Pat. 4,479,881, Murata et al., U.S. Patent. 4,443,355, Barbesgaard et al., U.S. Patent. 4,435,307, and Ohya et al., U.S. Patent. 3,983,082, incorporated herein by reference. Still other suitable enzymes are lipases, such as those described in Silver, U.S. Pat. 3,950,277, and Thom et al., U.S. Patent. 4,707,291, incorporated herein by reference. The hydrolytic enzyme should be present in an amount of about 0.1-5%, most preferably about 0.01-3%, and most preferably about 0.01-2% by weight of the composition. Mixtures of any of the above hydrolases are desirable, especially protease / amylase mixtures.

Antiredeposition agents, such as carboxymethylcellulose, are potentially desirable. Foam impellers, such as suitable anionic surfactants, may be suitable for inclusion herein. Similarly, in the case of excess foaming resulting from the use of certain surfactants, antifoaming agents, such as alkylated polysiloxanes, ie, dimethyl polysiloxane, would be desirable.

Size, density and shape of the preferred granule Granule particle sizes can vary from about 100 μm to about 1200 μm, most preferably 150-850 μm. The density of the granule will normally vary from about 0.5 g / c3 to about 1.0 g / c3, most preferably 0.75 g / c3 about 0.80 g / c3. A wide variety of granule shapes can be used, including spheres, hearts, moons, stars, shamrocks, cylindrical sections, and cubic sections.

Applications The compositions of the invention are useful as or in laundry products, such as bleach additives, detergents, detergency builders, bleach detergents, bleaches, bleach aids and soil removers. Among the advantages derived from the compositions of the invention is the improvement of cleaning, removal of dirt, removal of stain, whitening, and polishing of treated articles. Other product applications include household cleaning products, such as hard surface cleaners that moisten or dissolve in water before use. Exemplary surface cleaners are tile and cement cleaners, bathroom (floor, toilet and vanity) and kitchen cleaners (floor, sink and cupboard). Additionally, kitchen products such as dishwashing detergents with bleach or cleaning pads and whitening scrubbing are contemplated. Among the benefits derived from the use of the inventive compositions in such applications is the improved removal of dirt and stain and the general cleaning of the treated surfaces to remove food, rust, grime, mildew, mold and other typical soils found on said surfaces. Additionally, applications of the non-domestic product are contemplated where an effective level of general active oxygen in situ to treat water is useful. The pond and spring additives are illustrative of such applications, as well as cleaners to remove dirt on the surfaces of external concrete, stucco, lining, wood and plastic.

Preparation of Nitriles In general, N-quaternary acetonitrile compounds can be easily prepared from N-acetonitrile precursors by using selected alkyl halide and using well-known synthetic approaches, such as those described by Menschutkin, Z. Physik. Chem., 5, 589 (1890), and Z. Physik. Chem., 6, 41 (1890); Abraham, Progr. Phys. Org. Chem., 11, 1 (1974); Arnett, J. Am. Chem. Soc, 102, 5892 (1980); German Application of 05 44 312 212. All of the above are incorporated by reference. Compounds having the structure of formula I have a saturated ring formed by a plurality of atoms, which vary widely from 3 to 9, although preferably they contain six atoms including the N-i atom.

The preparation of said compounds will begin more conveniently with a compound that already have the ring formed. For example, a number of inventive nitrile preparations described below will begin with morpholine (see, for example, the structure of formula II). An example of rings with three members is aziridine, that is, N-methylacetonitrile aziridinium; as an example of four-membered rings is azetidine, ie, azetidinium of N-ethyl-acetonitrile; as an example of five-membered rings is pyrrolidine, ie N-butylacetonitrile pyrrolidinium; as an example of six-membered rings, in addition to the morpholine, piperidine is found, ie piperidinium of N-methylacetonitrile; as an example of seven-member rings is the homopiperidinium, as an example of eight-membered rings is the tropane, that is, N-methylacetonitrile-8-azabicyclo [3.2.1] octane; and, as an example of nine-membered rings is octahydroindole, that is, octahydrorindolinium of N-methylacetonitrile.

More particularly, in the preferred method of preparation, a suitable mine is reacted with a monoaldehyde or a dialdehyde and with HCN or an alkali metal cyanide in an aqueous medium (step A) followed by subsequent quatemization (step B) with an renting In step A, the preferred reaction is on the pH scale of 8 to 14, and the pH value is maintained at not less than 2 in step B. In this way, an amine with the formula it is reacted as in step A with a monoaldehyde or a dialdehyde R8 CHO or OHC R5 CHO, wherein R5 is a chemical bond or an alkylene bridge of Ci to C6 or an oxyethylene bridge, and R6 refers to H or C 1 to C 2 alkyl, and to hydrogen cyanide or an alkali metal cyanide in an aqueous medium. Step B is quaternization with an R 1 X alkylating agent in an aqueous medium without isolating the intermediate product from step A. Preferred alkylation agents are dimethyl sulfate, diethylsulfate, a methyl halide, an ethyl halide, dimethylcarbonate, diethylcarbonate , methyl methylate, ethyltosylate, methyl mesylate, methyl mesylate, or a benzyl halide. In step A, cyanohydrins, ie, formaldehyde cyanohydrin, can be formed as side products of the aldehyde, which is used, and a hydrogen cyanide. Said cyanohydrin does not further react with alkylating agent in step B, so that the renewed cleavage of the cyanohydrins of the aldehyde and the hydrogen cyanide in the final product is possible. Without the process according to the invention, step B usually proceeds in such a way that, as a result of the hydrolysis of the added alkylating agent, the pH value of the reaction mixture is separated from the alkaline or neutral region in the region strongly acidic with reaction time that increases. The protonation of the amine nitrogen atom of the glycinonitrile, which has not yet been quaternized, established in -, competing with alkylation - starting from a certain pH value so that, at the end of the addition of the alkylating agent, it is not carried out any other reaction of the glycinonitrile. The non-quaternized glycinonitrile in the final product may also represent an unwanted source of hydrogen cyanide. Step A generates especially good results if a pH scale of 9 to 13 or, especially, 10 to 12 is used. On that pH scale, the cyanohydrin that is formed is present in equilibrium with the aldehyde and the hydrogen cyanide for that the reformed adducts can react upon completion with the amine to give the glycinonitrile. If an excess of amine having from about 2 to 20% by mole or, especially, from about 3 to 10% by mole or, more particularly, from about 4 to 75 by mole is also used, based on the amount of cyanide of hydrogen or alkali metal cyanide that is used, then a more extensive suppression of hydrogen cyanide and auxiliary components is achieved, which releases the hydrogen cyanide in the final product. Step B generates especially good results if the pH values are not reduced below 2.5 and, especially, below 3. An optimal pH scale for the quaternization of step B is 2.5 to 5 or, especially, 3 to 4. An excess of alkylating agent containing from 10 to 40% by mole or, especially, from 15 to 25% by mole is also used based on the amount of amine that is used in step A, then a even more extensive suppression of hydrogen cyanide and secondary components, which release hydrogen cyanide, into the final product. Once the nitriles are prepared in quaternized form, the formation of the preferred bisulfate or sulfate form is preferably by heating an alkyl sulfate form in an aqueous acidic solution. For example, a suitable elevated temperature is from about 40 ° C to about 150 ° C, most preferably about 70 ° C to about 110 ° C. The aqueous acidic solution may have a pH in the range of about -1 to 6, most preferably about 0 to 3, with heating for a period of 1 to 50 hours. The aspects of the invention are now illustrated by the following examples. It will be understood that said examples are intended to illustrate, and not limit, the invention.

EXAMPLE 1 527. 2 g (6.05 moles) of morpholine were introduced into the reaction vessel and cooled to 10 ° C. In a period of one hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were then measured. The addition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25 wt.%) Was initiated half an hour after the addition of formaldehyde was initiated. The time of addition was one hour. During the addition, the temperature could be raised to 35 ° C and the stirring then took place for another hour at 35 ° C. Then cooling took place at 30 ° C and 927.8 g (7.35 moles) of dimethisulfate (DMS) were added for two hours at 30 ° C. During the addition of DMS, the pH value fell to the acidic region starting from 8. At pH 3.5, the regulated pH addition of the aqueous caustic soda (25% by weight) was controlled by counter so that the remaining constant pH 3.5 during the remaining addition time and the following post-reaction time of 3 hours at 30 ° C. The mixture was then heated to 50 ° C and the pH value was allowed to fall into said connection. After one hour at 50 ° C, the excess DMS was completely destroyed. The pH value was then l. Analytical results: HCN 0 ppm formaldehyde cyanohydrin 74 ppm Morpholinoacetonitrile 55 ppm (Molar ratio HCN: CH: morpholine = 1: 1.01: 1.02; morpholine molar ratio: dimethylsulphate = 1: 1.21) EXAMPLE 2 527. 2 g (6.05 moles) of morpholine were introduced into the reaction vessel and cooled to 10 ° C. 6.6 g aqueous caustic soda (20% by weight) were added to raise the pH value. In a period of one hour, 600 g (6.0 moles) of formaldehyde (30% by weight) were then measured. The adition of 161. 6 g (5.94 moles) of hydrogen cyanide (99.25% by weight) was started a half hour after initiating the addition of formaldehyde. The time of addition was one hour. During the addition, the temperature could be raised to 35 ° C and the stirring then took place for an additional hour at 35 ° C. The pH value was 11.4 at the end of said part of the synthesis. The pH was then adjusted to 8-8.2 with sulfuric acid. Then cooling took place at 30 ° C and 932.4 g (7.4 moles) of dimethisulfate (DMS) were added for two hours at 30 ° C. During the addition of DMS, the pH value fell in the acidic region starting from 8. In pH 3.5 the regulated addition of aqueous caustic soda pH (25% by weight) was controlled by counter so that the pH remained constant at 3.5 during the remaining addition time and the following post-reaction time of three hours at 30 ° C. The mixture was then heated to 50 ° C and the pH value was allowed to fall into said connection. After one hour at 50 ° C, the excess DMS was completely destroyed. The pH value was then 1. Analytical results: HCN 0 ppm formaldehyde cyanohydrin 10 ppm Morpholinoacetonitrile 20 ppm (molar ratio HCN: CH20: morpholine = 1: 1.01: 1.02, molar ratio morpholine: dimethisulfate = 1: 1.22) EXAMPLE 3 537. 2 g (6.17 moles) of morpholine were introduced into the reaction vessel and cooled to 10 ° C. 6.6 g aqueous caustic soda (20% by weight) were added to raise the pH value. In a period of one hour, then 600 g (6.0 moles) of formadehyde (30% by weight) was measured. The addition of 161.6 g (5.94 moles) of hydrogen cyanide (99.25 wt.%) Was initiated half an hour after the addition of formaldehyde was initiated. The time of addition was one hour. During the addition, the temperature could be raised to 35 ° C and the stirring then took place for an additional hour at 35 ° C. The pH value was 11.8 at the end of said part of the synthesis. The pH was then adjusted to 8-8.2 with sulfuric acid. Then cooling took place at 30 ° C and 940 g (7.46 moles) of dimethisulfate (DMS) were added at 30 ° C. for two hours. During the addition of DMS, the pH value fell in the acidic region starting from 8. At pH 3.5, the regulated addition of aqueous caustic soda pH (25% by weight) was controlled by counter so that the pH remained constant at 3.5 during the remaining addition time and the following three-hour post-reaction time at 30 ° C. The addition of caustic soda took place with good mixing (stirring conditions of 800 revolutions / minute). The mixture was then heated to 50 ° C and the pH value could fall in said connection. After one hour at 50 ° C, the excess DMS was completely destroyed. The pH value was then 1. Analytical results: HCN 0 ppm formaldehyde cyanohydrin 0 ppm Morpholinoacetonitrile 20 ppm N-methylmorpholinium acetonitrile methylisulfate 58.0% by weight N-methylmorpholium acetamide methaulfate 3.0% by weight (Molar ratio of HCN: CH2O: morpholine = 1: 1.01: 1.04, molar ratio of morpholine: dimethisulfate = 1: 1.21) Example 4 illustrates another aspect of the invention, which is the preparation of substantially solid bisulfate salts, as prepared by MMABS .

EXAMPLE 4 The liquid metisulfate, as in any of Examples 1-3, was acidified to a pH of 0.1-1, followed by heating the resulting liquid under a slight vacuum (700-1000 mbar) in a ventilated container at temperatures of 90 -110 ° C for 3-5 hours. The resulting converted bisulfate liquid could then be crystallized and purified for the recovery of the crystalline nitrile salt, it can be dried directly on a carrier / vehicle to produce an amorphous salt, or it can be redissolved after crystallization and then prepared in granule form. A preferred approach to promote crystallization or precipitation may be by the addition of a "seed crystal", which serves as a growth site for crystal formation. Said seed crystal may be, but is not limited to, a precipitated or smoked silica, or a sample of bisulfate crystal salt. Another preferred approach is to allow the salt solution to precipitate by reducing the solubility of the crystal by cooling with time.

EXAMPLE 5 96 kg of liquid MMAMS (48.5% active) were acidified with 6.7 kg of sulfuric acid (50%) at 20 ° C and subsequently heated to 110 ° C for four and a half hours after which the solution was cooled to 30 ° C. C in a period of 18 hours. The resulting mixture was then washed with water and filtered to yield the resulting bisulfate crystal (61.7 kg). When it is desired to prepare the nitrile salts in granule form, one may make use of various methods known in the art, such as fluid bed, agglomeration, spray coating, or smelting mixing approaches, preferably at levels of about 5-40 by weight of the starting particulate weight. Said granules may have the nitrile salts carried in the solid particulate or may have the nitrile salt coated or mixed with solid particulate. Preferred coating conditions are those in which the temperature during coating is less than about 50 ° C, while the coating material is sprayed as a mixture or dispersion on the salt surface by coating or encapsulating the salt core. Example 6 illustrates different shapes of the salt core and a variety of preferred coating materials. Advance coating materials include film forming polymers, fatty acids, soaps, and other solid surfactants having a melting point above 40 ° C.

EXAMPLE 6 Nitrile salt core Preferred coating materials Purified glass salt PLURONIC 68001 Amorphous compacted salt PLURONIC 105001 Amorphous agglomerated salt PLURIOL E 60001 Amorphous acidified salt SOKALAN CP51 LUWAX V1 Polyvinyl alcohol Palmitic acid Paraffin Calcium alginate EXAMPLE 6 (CONTINUED) POLIGEN WE31 DIOFAN 193D1 1 Commercially available from BASF AG, Germany.

Particularly preferred coating materials are PLURIOL E6000 and LUWAX V. (PLURONIC is a trademark for a series of poly (oxyethylene-co-oxypropylene) block copolymers.

EXAMPLE 7 Preparation of a MMAMS / solid acid / solid surfactant composition using a stirring method 3. 4 kg of a highly dispersed silicic acid with a total surface area of approximately 450 m2 / g and an average particle size of approximately 8 mm (SIPERNAT® 50 S from Degussa) and, additionally, 2.3 kg of a fatty alcohol with tallow base reacted with 25 moles of ethylene oxide (Lutensol® AT 25 from BASF) were stirred in 24.3 kg of a 70% by weight aqueous solution of N-methylmorpholinium acetonitrile methylisulfate (MMAMS). The liquid mixture was concentrated by evaporation in a paddle type vacuum dryer at about 10 mbar and at a ca. 80 ° C until a solid formed that was able to flow (residual water content <1% by weight). After cooling, 20 kg of the solid composition was removed. The powder was compacted by a conventional compactor to give flakes and the flakes were then broken in a conventional sieve granulator and sieved to give a usable fraction of average size of 400 to 1200 mm.

EXAMPLE 8 Manufacture of a MMAMS / silicic acid / solid surfactant composition by a spraying process 24. 3 kg of 70% by weight in MMAMS solution was sprayed on 31.6 kg of the highly dispersed silicic acid described in Example 7. The crumbly mixture was dried in a paddle type vacuum dryer at approximately 10 mbar and a wall temperature of approximately 80 ° C until a fine solid is formed which is capable of flowing (residual water content <1% by weight). The product was then agglomerated in a mixture with a 2.3 kg melt of the surfactant which was mentioned in Example 7. The final procedure to give a useful fraction of 400 to 1200 mm was carried out analogously to Example 7.

EXAMPLE 9 Effect of vehicle surfactant materials and agents on the hygroscopic characteristics or, if necessary, the flow characteristics of MMAMS To achieve the effect of auxiliary substances on the hygroscopic characteristics or, if necessary, the flow characteristics of MMAMS, three different samples were prepared in the paddle type dryer and then stored in a dryer at room temperature and atmospheric humidity relative of 76%.

Sample 1: 2100 g MMAMS (solid) Sample 2: 3100 g MMAMS (solid) 400 g SIPERNAT 50 S Sample 3 3100 g MMAMS (solid) 400 g SIPERNAT 50 S 233 g Lutensol AT 25 All samples were prepared from a 70% by weight aqueous solution of MMAMS analogously to Example 7 and dried at 80 ° C and 10 mbar in a paddle type vacuum dryer with a volume of 5 liters until it was not generated more condensed.

In the case of examples 8 and 9, a solid of powder type obtained, which was able to flow after drying, with water contents of 0. 74% or 0.45% by weight, respectively; MMAMS without the auxiliary substances (sample 1) led to a crumbly, crumbly solid with a water content of 0.63% by weight. These solids were then ground to the same average particle size and stored in the dryer. The results are presented in the following table 2. It is clearly observed that the solid MMAMS is obtained in a high concentration and is stable in storage over a long period in a relatively atmospheric humidity of 76% only as a result of the addition of the substances designated assistants.

TABLE 2 EXAMPLE 10 Effect of vehicle materials on storage stability and dye damage characteristics The MMAMS samples in various vehicles were prepared and placed in a bleaching composition to determine any benefit in storage stability or damage to the colorant.

Storage stability MMA methylisulfate has a higher storage stability in an inert support, such as zeolite or clay. The presence of an acid rinse, such as HLAS (alkylbenzenesulfonic acid), also boosts stability. The aqueous solution of MMA methylisulfate (3.6 of 45%) was added to 38.5 g of sodium carbonate containing 5.0 g of sodium perborate monohydrate and the dried solid. The above was compared by first adding the MMA metisulfate to 6 parts of zeolite 4A (Valfour 100 from PQ Corp.) and then adding to the sodium carbonate / perborate mixture. MMA metisulfate can also be mixed with 6 parts of clay (Attapulgite L96117 from Oil-Dry Corp.) and then added to the sodium carbonate / perborate mixture. The MMA metisulfate was also mixed with 2 parts of the same clay.

The following results in Table 3 show the surprisingly driven stability when the MMA metisulfate is incorporated into the inventive supports.

TABLE 3 Substrate of MMMA% active MMA after in carbonated / Perborate one week storage at 26.6 ° C / 80% HR MMAMS 0% MMAMS / Zeolite = 1/6 98% MMAMS / HLAS / Zeolite = 1/2/6 100% MMAMS / Clay = 1/6 100% MMAMS / Clay = 1/2 100% Dye damage test The amount of MMAMS representing 5% of the base (sodium carbonate / perborate mixture) was placed on a diagnostic cloth (100% cotton coffee dried with Fast Orange RD, Direct Brown 5R and Rapideger Red LT ). The MMAMS was covered with the base and then 10 ml of deionized water was applied. After 10 minutes, the fabric was rinsed and dried. Dye damage was assessed visually on a scale of 0 to 10, where 0 represents non-visible damage. The same samples that were previously prepared for the stability test were used. The results again show the benefit of adding MMAMS to an inert support, with or without an acidic coagent.

Nitrile substrate Dye damage Aqueous MMA metisulfate 10 MMAMS / Zeolite = 1/6 3 MMAMS / HLAS / Zeolite = 1/2/6 1 Mmams / Clay = 1/6 1 It should be understood that while the invention has been described in conjunction with the preferred specific embodiments, the description and examples are intended to illustrate and not limit the scope of the invention, which is defined by the scope of the appended claims.

Claims (22)

NOVELTY OF THE INVENTION CLAIMS

1. - A process for the preparation of a compound having the structure of formula I

FORMULA 1 wherein A is a saturated ring formed by a plurality of atoms in addition to the Ni atom, the saturated ring atoms include at least one carbon atom and at least one of the O, S and N atoms, the substituent Ri bond at atom Ni of the structure of formula I includes any (a) an alkyl or alkoxylated of C? -24 wherein the alkoxy is C2-4, (b) a cycloalkyl of C4-24, (c) an alkaryl of C7- 24 (d) a repeating or non-repeating alkoxy or alkoxy alcohol, wherein the alkoxy unit is C2-4 or (e) -CR2R3C = N wherein R2 and R3 are H, a C-24 alkyl, cycloalkyl or alkaryl, or alkoxy or repeating or non-repeating alkoxylated alcohol wherein the alkoxy unit is C2-4, the substituents R2 and R3 are H, a d-4 alkyl, cycloalkyl or alkaryl, or repeating alkoxy or alkoxylated alcohol or non-repetition where the alkoxy unit is C2-4, Z is a value on the scale from 0 to 10, and where Y is a counter ion; a solid particulate material with which the salt is carried or with which the salt is coated or mixed. 2. The granules according to claim 1, further characterized in that A of the formula I is a saturated ring formed by four carbon atoms and an oxygen atom in addition to the Ni atom.

3. The granules according to claim 1, further characterized in that A of the formula I is a saturated ring formed by four carbon atoms and an N2 atom in addition to the Ni atom, N2 being a secondary amine, a tertiary amine which has the substituent -CR5R6CN or a quaternary amine having the substituents -R5 and CR5R6CN, and R5, further characterized in that R5 and Rβ can each be an H or C-? -6 alkyl.

4. Granules according to claim 1, further characterized in that the particulate material is in an amount of 2 to about 95 parts by weight of the granules and has a total surface area of 10 to 500 m2 / g.

5. The granules according to claim 1, further characterized in that the particulate material is silica gel, silicic acid, silicate, aluminum oxide, clay, aluminum silicate or mixtures thereof.

6. The granules according to claim 1, further characterized in that they comprise a coating sufficient to delay the dissolution in aqueous solution.

7. - The granules according to claim 1, further characterized in that they comprise an acidic agent.

8. The granules according to claim 1, having a water content, including the water of hydration, of less than about 20% by weight.

9. The granules according to claim 1, further characterized in that Ri is a lower alkyl.

10. The granules according to claim 1, further characterized in that Ri is methyl.

11. The granules according to claim 10, further characterized in that R2 and R3 are both hydrogen.

12. The granules according to claim 1, further characterized in that the counterion is sulfate, bisulfate, methylisulfate or tosylate.

13. The granules according to claim 1, further characterized in that Z of the salt is 0 to 6.

14. The granules according to claim 1, which have from 1 to 45% by weight of the salt of the Formula I within itself.

15. The granules according to claim 1, which have an average particle size of about 3 to nm 2 mm.

16. The granules according to claim 1, which include a surfactant or a mixture of surfactants in an amount of about 0.5 to about 50 parts by weight.

17. - A bleaching composition, comprising: the granules according to claim 1; and a source of active oxygen.

18. The bleaching composition according to claim 17, characterized in that it also includes an alkaline regulator.

19. The bleaching composition according to claim 17, further characterized in that it includes a chelating agent.

20. The bleaching composition according to claim 17, further characterized in that it includes one or more brightening agents and a bleaching agent.

21. The bleaching composition according to claim 17, further characterized in that it includes an enzyme.

22. The bleaching composition according to claim 17, further characterized in that from 1 to about 70% of peroxy active acid derivative is supplied based on the weight of the bleaching composition when dissolved in an alkaline solution.