MXPA00006501A - Alkaline solid block composition - Google Patents

Abstract

We have found that long standing problems relating to the stability of organic materials in alkaline detergents, including the reversion or hydrolysis of condensed phosphate sequestrants in alkaline solid detergent compositions can be alleviated by the use of an organic composition having vicinal hydroxyls. Such a solid block detergent can be manufactured by a process in which a source of alkalinity, a functional material including a condensed phosphate sequestering agent, an organic compound having two vicinal hydroxyl groups, are combined in a pourable composition or liquid. Such a liquid can be introduced into a plastic capsule and solidified. During manufacture and solidification, we have found that the vicinal hydroxyl compound prevents substantial hydrolysis or reversion of the condensed phosphate maintaining effective hardness ion sequestration during the use of the detergent. The stabilizer can also stabilize color, chlorine content and dispensing properties.

Description

SOLID BLOCK ALKALINE COMPOSITION FIELD OF THE INVENTION This invention relates to inorganic alkaline materials that can be manufactured in the form of a solid block. Functional materials include detergents, pre-soaking materials, enzyme-based cleaners, disinfectants, etc. In the manufacture of solid functional material or detergent, a mixture capable of flowing or liquid is formed into a block or placed in a large container, bottle or capsule for solidification. After solidification, the water soluble or dispersible material or detergent, solid is typically supplied through a spray jet creating an aqueous concentrate used at a target site. The concentrate can be directed to a variety of sites including a dish washing machine, a laundry washing machine, a hard surface cleaning apparatus, etc. The functional material described maintains a high degree of functional capacity due to the nature of stabilization, particularly at elevated temperatures during manufacture, storage or use, of a vicinal hydroxyl compound.

BACKGROUND OF THE INVENTION The use of solid block compositions in institutional and industrial cleaning operations was initiated by the solid or solid detergent block technology Ecolab's SOLID POWER®. This technology was first claimed by Fernholz and others, patents of E. U. A. Reissue Nos. 32,763 and 32,818. In addition, alkaline detergent materials in the form of pellets are shown by Gladfelter et al., U.S. Patent Nos. 5,078,301; 5, 198, 198 and 5,234,615. Extruded alkaline detergent materials are described by Gladfelter et al., U.S. Patent No. 5,316,688. In these pioneering technologies, substantial attention was paid to how alkaline materials, based on a substantial proportion of sodium hydroxide, can be cast and solidified. The first solid block products used substantial proportions of a solidification agent, typically sodium hydroxide hydrate, to solidify the cast material in a freezing process using the low melting point of the sodium hydroxide monohydrate. In the manufacture of the solid block, the particulate components of the detergent were dispersed in a liquid phase comprising aqueous sodium hydroxide and cooled for the purpose of solidifying a functional solid useful with the dispersed compositions. The resulting solid comprised a mixture of hydrous sodium hydroxide with the other detergent ingredients dissolved, dispersed or suspended in the hydrated matrix. In these pioneer products, low-melting sodium hydroxide hydrate is an ideal detergent candidate, since the highly alkaline nature of the caustic material produces excellent cleaning and efficient manufacturing. Another hydration type process for making cast, caustic or carbonate-based detergents is described by Heile et al., U.S. Patent Nos. 4,595,520 and 4,680, 134. During the manufacture of the solid block detergent compositions, it has been found that the condensed phosphate compositions may be hydrolytically unstable or may revert to less active phosphate species. When contacted with a strong base, water and liquid compositions that can be cast, the condensed phosphate compositions can be hydrolyzed and form orthophosphate or pyrophosphate compositions. The strong base and other chemical constituents of solid block detergents can also have harmful effects on color sources, organic materials and uniformity of assortment. Chlorine sources are usually used for spotting. Said sources of active chlorine are generally reactions with compositions in the solid block and are substantially reduced in activity or concentration under severe conditions. Organic materials such as nonionic surfactants or defoaming compositions can react and decolorize the solid in brown form. A variety of enzyme compositions may also be unstable upon contact with the alkaline materials in the functional solid material. The instability may be the result of chemical incompatibility or high temperature deactivation of the enzyme protein structure. Finally, under certain circumstances, the cast solid block material may be dispensed non-uniformly. By being dispensed non-uniformly it is meant that the aqueous spray in a spray jet is brought into contact with the surface of the alkaline material within a capsule, and a worn hemispherical surface is formed. That is, the caustic material is consumed, the hemispherical surface wears through the caustic mass until the spray reaches the bottom of the bottle leaving "rims" of the caustic material at the corners of the bottom of the capsule. As the spray assortment continues, these ridges can usually disintegrate and present a clogged spout and uneven assortment. In the commercial manufacture of caustic solid materials, the hydrolysis of condensed phosphate additives can be controlled using a variety of careful process controls. Chlorine sources encapsulated in solid detergents have been used to avoid instability problems with chlorine. There is an important need to improve the stability of the chlorine source encapsulated in solid block detergents. In addition, the stability of one or more organic materials in the severe caustic solid block environment when contacted with reactive chlorine sources can result in substantial instability. There is a need to increase the stability of organic materials in solid block detergents. Finally, the uniformity, improved for the assortment can improve the economy in the use of solid block detergents. Therefore, there is a need to improve the assortment uniformity. There is a substantial need to improve the quality of the assortment or erosion or wear caused by the action of water spraying on the surface of the solid detergent. In addition, when the capsule is completely lacking in detergent, the uneven dissolution of the material can introduce an excess or minimum amount of solid material cast into the liquid concentrate, which is then directed to the machine for washing dishes. An extrusion technology has been developed in which the hydrolysis of condensed phosphate has been reduced to a minimum during production by reducing the amount of water and the heat history of the composition during manufacture. Said compositions avoid hydrolysis since the materials are not substantially heated and even if heated, they do not come in contact with sufficient water to produce a hydrolytic reaction condition. Said processes are shown by Olson et al., EP0737244B, issued July 15, 1998. In the manufacture of solid detergents, the use of organic solidification agents is also known. Such agents include a wide variety of materials including materials that solidify by cooling and hardening at a temperature below their melting point. An example of such a curing agent is polyalkylene oxide including polyethylene oxide, propylene oxide and its block or heteric copolymers (including random, statistical, alternating and grafting). Typically, said materials have a molecular weight greater than about 800 to 8000 and more, do not contain vicinal hydroxyl and have not been shown in the past to contribute to the hydrolytic stability of condensed phosphate materials. Representative examples of said description are shown by organson, patents of E. U. A. Nos. 4,624,713 and 4,861, 518. Cristóbal, patent of E. U. A. No. 4,320,026 teaches the use of a diol compound to reduce discoloration in solid detergents. Alternating methods to reduce the hydrolytic instability of condensed phosphates are useful in areas where access to known technology is limited. These may include small manufacturers, distant manufacturers or sites with limited processing capacity. Therefore, there is a substantial need to provide an alternative solid detergent manufacturing capacity with a reduced condensed phosphate hydrolytic stability.COMPENDIUM OF THE INVENTION It has been found that combining an organic compound of C or greater, preferably of C4-i6 having at least two vicinal hydroxyl groups in a liquid composition that is cast to form a solid block detergent composition, can (1) suppress or reduce the hydrolysis or reversion of condensed phosphate sequestering agents to less active forms, (2) reduce the loss of compounds that produce available chlorine (Cl2), (3) reduce the color change of organic materials in solid detergents, (4) increase enzyme stability, and (5) improve the erosion quality of the solid during the assortment. The functional solid block composition made in accordance with the invention exhibits a reversion rate of 15% by weight or less of the condensed phosphate sequestering agent originally present. Preferably, less than 10% by weight of the condensed phosphate sequestering agent is reversed, most preferably less than 7% by weight undergoes reversion. Typically, the organic compound is added to the liquid composition capable of flowing or semi-liquid dispersion before the addition of the condensed phosphate sequestering agent. Sufficient organic compound is added to limit the reversion, or otherwise stability or improve the properties of the solid block, so that, after the material is cast and solidified, the composition typically contains a source of alkalinity greater than 80% p / p, preferably greater than 90% w / w of the amount of condensed phosphate sequestering agent added during the preparation. The organic compound reversion inhibitor optionally, in combination with a variety of other useful compositions, provides positive cleaning benefits. Said amounts of stabilizing compound reduce chlorine losses during the mixing and processing of the solid detergent. In addition, the stabilization compound inhibits a color change to coffee in organic ingredients in the solid detergent. The solid block detergent, assorted from a spray nozzle, wears evenly and does not clog during the assortment of an aqueous detergent concentrate in the dishwasher. Finally, the enzyme components retain surprising amounts of activity in the block chemicals. Accordingly, the invention relates to a method for manufacturing a solid block functional composition. This method describes the stabilization of the components of the composition, including the inhibition or reduction of the hydrolytic stability of condensed phosphate sequestering agents. This is achieved by combining an effective amount of an inorganic source of alkalinity, at least 10% by weight of a condensed phosphate sequestering agent, an effective amount of a reversal inhibitor comprising an organic compound of C to C6 having at least two neighborhood hydroxyl groups. The composition is mixed and formed into a solid wherein less than 15% by weight of the phosphate is reverted. The invention also relates to a solid block alkaline detergent composition, which is made in accordance with this method. The detergent composition includes from 10 to 60% by weight of an inorganic source of alkalinity, from 10 to 45% by weight of a condensed phosphate sequestering agent and from 1 to 15% by weight of a reversal inhibitor. In the resulting composition, less than 15% by weight of the phosphate is reversed. For the purpose of this patent description, the term "at least two vicinal hydroxyls" refers to a compound having a structure in the compound that includes the fragment: OH OH I I - c- c- wherein each empty bond can be directed to hydrogen, carbon, oxygen, nitrogen, sulfur, or other atoms common in the molecules of organic materials that can be used in the solid detergent. It has also been found that nearby compounds of the invention are improved through a borate compound. For the purpose of this patent application, the term "reversion" or "revert" or "hydrolytic instability" refers to the tendency of the condensed phosphate sequestering agent, such as sodium tripolyphosphate (STPP), to react with the water at elevated temperature to form a mixture of pyrophosphate and orthophosphate or to form substantially orthophosphate. Since condensed phosphates, such as tripolyphosphate, are typically manufactured by heating phosphate species until they are condensed, lose water and form condensed phosphate, the relatively high energy bonds between the phosphate portions tend to be hydrolytically unstable, particularly in the presence of heat and / or a caustic.

BRIEF DESCRIPTION OF THE DRAWINGS FIGS. 1 to 8 demonstrate the unique value of the invention wherein the vicinal hydroxyl compounds protect inorganic fused phosphate hardness sequestering agents from hydrolytic instability or reversion under a variety of conditions and formulations. Figure 9 is a bar graph showing surprisingly improved soil removal properties (particularly lipstick spots).

DETAILED DESCRIPTION The stabilized block functional materials of the invention contain a reversal inhibitor of a nearby hydroxide compound or chemical stabilizer. It has been found that a class of organic hydroxy compounds that seems to interact with alkali sources, inorganic fused phosphate water and other components such as organics, chlorine sources, enzymes, in such a way that they reduce the hydrolysis of condensed phosphate during manufacture and storage and increase the stability and dispersion capacity.

It has been found that functional materials include alkaline detergent, enzyme-based cleaners, disinfectants, rinsing agents, etc. In the manufacture of said materials, the active functional material such as an enzyme, surfactant, disinfectant, etc. , it is formed in a solid matrix of an alkaline material. As the alkaline material is stocked, the included functional material is dissolved or suspended in the aqueous concentrate for use at a site of use. In the solid functional material, it has been found that the near hydroxy compound stabilizes a condensed phosphate, an enzyme, an organic surfactant such as a nonionic surfactant or other material and improves the assortment properties. The reversion stabilizer compositions of the invention include a C4 compound with at least one hydroxide group nearby which corresponds to the following formula: OH OH I I - c- c- I I where the empty bonds correspond to carbon, oxygen, hydrogen, sulfur, nitrogen or other atoms common in available stabilizing compounds. The simplest examples are glycerin derivatives such as lower alkyl monoesters of glycerin and ethers including glyceryl monostearate, glyceryl monooleate, glyceryl-monoethyl ether, diethyl glyceryl ether, 2,3-dihydroxybutyraldehyde and other organic compounds of C4 having hydroxyls neighborhoods A class of preferred reversal inhibitors are the monosaccharides including aldotetrose, aldopentose, aldohexose, aldopetose, aldooctose, ketotetrosa, ketopentose, ketohexose, etc. Such compounds include erythrose, ribose, fructose, glucose, mannose, galactose, and isomers and derivatives thereof and other similar monosaccharides. In addition, disaccharide compounds that include sucrose, lactose, cellobiose, maltose, are useful. Trisaccharides, oligosaccharides and polysaccharides of large molecular weight can also be selectively used, but appear to have reduced activity. Cellulose and oxidized cellulosic materials, although considered a polysaccharide, seem to have reduced utility in this application. Compounds that are structurally similar to such carbohydrates can also be used, these compounds include 1,1-dihydroxy-cyclohexane, 1,2,3-trihydroxy-clohexane, sorbitol, and derivatives thereof, which are frequently used.

Alkaline Sources To provide an alkaline pH, the functional solid composition comprises a source of alkalinity. In general, the source of alkalinity elevates the pH of the composition to at least 10.0 in aqueous solutions to 15 by weight and preferably the pH is in the range of 10.5 to 14. This pH value is sufficient for the removal of dirt and particle breakdown when the chemical is placed in use and also facilitates the rapid dispersion of spots. The general character of the alkalinity source is limited only to those chemical compositions that have a substantial aqueous solubility. Illustrative alkalinity sources include an alkali metal carbonate, silicate, hydroxide, or mixtures thereof. The source of alkalinity can be increased through conventional improvers, which improve the detergent activity forming complexes of hardness ions. The composition produced according to the invention can include effective amounts of one or more alkaline sources to improve the cleaning of a substrate and improve the stain removal performance of the composition. The composition comprises 10-80% by weight, preferably 15-70% by weight of an alkaline source, most preferably 20-60% by weight. The total alkalinity source may comprise an alkali metal hydroxide, carbonate or silicate. The metal carbonate, such as carbonate, bicarbonate, sodium or potassium sesquicarbonate, and mixtures thereof may be used. Suitable alkali metal hydroxides include, for example, sodium or potassium hydroxide. An alkali metal hydroxide may be added to the composition in the form of solid beads, dissolved in an aqueous solution, or a combination thereof. The alkali metal hydroxides are commercially available as a solid in the form of solids in the form of pellets or beads having a mixture of particle sizes varying from about 12-100 mesh US, or as an aqueous solution, such as for example 50 % by weight and a solution of 73% by weight. Examples of useful alkaline sources include a metal silicate such as sodium or potassium silicate (with an M 2 O: SiO 2 ratio of 1: 2.4 to 5: 1 M representing an alkali metal) or metasilicate; a metal borate such as sodium or potassium borate, and the like; organic bases such as methanolamines and amines; and other similar alkaline sources can also be used. The source of alkalinity may include an alkali metal hydroxide including sodium hydroxide, potassium hydroxide and lithium hydroxide, mixtures of these hydroxides may also be used. Also the alkali metal silicates can act as a source of alkalinity for the detergents of the invention. The useful alkali metal silicates correspond to the general formula (M 2 O: SiO 2), wherein for each mole M 2 O there is less than one mole of S 2 O 2. Preferably, for each mole SiO2, there is about 1 to about 100 mole 2O, wherein M preferably comprises sodium or potassium. In preferred silicate, the ratio of Na 2 O: SiO 2 is from about 1: 2 to 20: 1. The preferred alkalinity sources are alkali metal hydroxides, alkali metal orthosilicate, alkali metal metasilicate, and other well-known detergent silicate materials. . Kidnapping agents.

Sequestering Agents In order to soften or treat water, to prevent the formation of precipitates or other salts, the composition of the present invention generally comprises components known as chelating agents, builders or chelating agents. Generally, sequestering agents are those molecules capable of complexing or coordinating the metal ions commonly found in tap water and thus preventing the metal ions from interfering with the function of the detersive components within the composition. Any number of sequestering agents can be used according to the invention. Representative sequestering agents include salts of amino carboxylic acids, salts of phosphonic acid, water-soluble acrylic polymers, among others. The molecular weight (Mn) of these polymeric materials is 200-8000, preferably 4000-6000. An essential ingredient of a stabilized cast solid detergent material of the invention is a condensed phosphate sequestering agent. The term "condensed phosphate" indicates a material having at least one group according to the formula: OH OH OH I I i -O- P- o- P- o- P- o- II II II O O O wherein the empty bonds are directed to other phosphate groups, cations which may be part of a linear, condensed or cyclic phosphate composition. Compounds with phosphate moieties useful as sequestering agents are condensed alkali metal phosphates, cyclic phosphates, organophosphonic acids and salts of organophosphonic acid. Useful fused phosphates include alkali metal pyrophosphate, an alkali metal polyphosphate such as sodium tripolyphosphate (STPP) available in a variety of particle sizes. Useful organophosphonic acids include mono, di, tri and tetraphosphonic acids, which may also contain groups capable of forming anions under alkaline conditions such as carboxy, hydroxy and thio. The tendency of the condensed phosphate materials to reverse can be controlled using a condensed phosphate that reduces the impact of caustic and water on the sequestering material. Said effects can be reduced by using an effective particle size sequestering agent and using barrier technologies. The inorganic fused phosphate can also be combined with an organic carboxylate, phosphate, phosphonic acid or phosphonic acid salt. Organic materials can help to sequester hardness ions in cleaning processes. Suitable amino carboxylic acid chelating agents include N-hydroxyethyliminodiacetic acid, nitrilotriacetic acid (NTA), ethylenediaminetetraacetic acid (EDTA), N-hydroxyethyl-ethylenediamine triacetic acid (HEDTA), and diethylenetriamine pentacetic acid (DTPA). When used, these amino carboxylic acids are generally present in concentrations ranging from 1% by weight to 50% by weight, preferably from 2% by weight to 45% by weight and most preferably from 3% by weight to 40% by weight. weight. Other suitable sequestering agents include water-soluble acrylic polymers having -CO 2"1 pendant groups, used to condition wash solutions under end use conditions, Such polymers include polyacrylic acid, polymethacrylic acid, copolymers of acrylic acid-methacrylic acid, copolymers of acrylic acid-itaconic acid, hydrolyzed polyacrylamide, hydrolyzed methacrylamide, hydrolyzed acrylamide-methacrylamide copolymers, hydrolyzed polyacrylonitrile, hydrolyzed polymethacrylonitrile, hydrolyzed acrylonitrile-acrylonitrile copolymers, and mixtures thereof Water-soluble salts or partial salts thereof Polymers such as their respective alkali metal (eg, sodium or potassium) or ammonium salts may also be used.The number average molecular weight of the polymers is from about 4000 to about 12,000.The preferred polymers include polyacrylic acid, the partial sodium salts of polyacrylic acid or sodium polyacrylate having an average molecular weight within the range of 4000 to 8000. These acrylic polymers are generally useful in concentrations ranging from 0.5% by weight to 20% by weight, preferably from 1 to 10, and most preferably from 1 to 5.

Also useful are the phosphonic acids and are 1-hydroxy-1-1,1-diphosphonic acid; aminotri (methylene phosphonic acid); aminotri- (methylenephosphonate), sodium salt of 2-hydroxyethyl-iminobis (methylene phosphonic acid); diethylenetriaminepenta- (methylene phosphonic acid); sodium salt of diethylenetriamine penta (methylenephosphonate); (tetramethylenephosphonate) of hexamethylenediamine, potassium salt; bis (hexamethylene) triamine (pentamethylene phosphonic), (HO2) POCH2N [(CH2) 6N [CH2PO (OH) 2J2] 2; and phosphorous acid H3PO3. The preferred phosphonate is aminotrimethylene phosphonic acid or salts thereof, optionally combined with diethylene diaminepenta (methylene phosphonic acid) when used as a sequestering agent in the invention, the phosphonic acids or salts are present in a concentration ranging from 0.25 to 25% by weight , preferably from 1 to 20% by weight and most preferably from 1 to 18% by weight based on the solid detergent.

Solidification Agent The invention may also comprise a solidifying agent for creating a solid detergent mass from a mixture of chemical components. In general, any agent or combination of agents that provide a degree of solidification and aqueous solubility requirement can be used with the invention. A solidifying agent can be selected from an organic or inorganic compound, which imparts a solid character and / or controls the soluble character of the composition present when placed in an aqueous environment. A preferred agent is one that forms a hydrate of a metal hydroxide or carbonate. The solidification agent can provide the controlled assortment using solidification agents having an increased aqueous solubility. For systems requiring less aqueous solubility or a lower rate of dissolution, an organic non-ionic or amide hardening agent may be appropriate. For a higher degree of aqueous solubility, an inorganic solidification agent or a more soluble organic agent, such as urea, may be used. The compositions which can be used with the present invention to vary the hardness and solubility include amides such as stearic monoethanolamide, lauric diethanolamide, and stearic diethanolamide. It has also been found that nonionic surfactants impart varying degrees of hardness and solubility when combined with a coupler such as propylene glycol or polyethylene glycol. The color stability of the nonionic agents is improved through the presence of the stabilization compounds of the invention. Nonionic agents useful in this invention include nonylphenol ethoxylates, linear alkyl alcohol ethoxylates, ethylene oxide / propylene oxide block copolymers, such as Pluronic® surfactants, commercially available from BASF Wyandotte. Particularly desirable nonionic surfactants as hardeners are those which are solid at room temperature and have an inherently low aqueous solubility as a result of the combination with the coupling agent. Other surfactants that can be used as solidifying agents include anionic surfactants having high melting points to provide a solid at the application temperature. Anionic surfactants which have been found to be very useful include linear aiquilbenzene sulphonate surfactants, alcoholic acid sulfates, alcohol ether sulfates and alpha olefin sulphonates. In general, two linear alkylsulfonates are preferred for reasons of cost and efficiency. Other compositions that can be used as curing agents in the solid compositions of the invention include urea, also known as carbamide, and other organic solidifying agents including PEGs, nonionic surfactants, etc. The solidification agents can be used in concentrations that promote the solubility and structural integrity required for the given application. In general, the concentration of the solidifying agent ranges from 0 wt% to 50 wt%, preferably from 10 wt% to 25 wt% and most preferably from 15 wt% to 20 wt%.

Enzyme The composition of the invention may also comprise from 0.01 to 10% by weight of an enzyme, preferably from 0.5 to 5% by weight for reasons of removal of dirt, and most preferably 1% by weight of an enzyme for removal reasons. of dirt. Suitable enzymes include but are not limited to the following: protease, waxy, amylase, lipase and combinations thereof. The esperase and protease serve to break down the protein, while the amylase breaks the starch and the lipase breaks down fats. If three enzymes are used, the broad scale for each enzyme can vary from 0.1 to 5.0% by weight. In this way, the pre-soak can comprise up to 15% by weight of enzyme if three different enzymes are used. It has been found that detergents containing a solid enzyme stabilized through the stabilization compounds of the present invention can also be improved using a borate stabilization material. The combination of an alkali metal borate with the near hydrocarbon stabilizer compositions of the invention produces improved stability. The chemistry of boric acid as well as many other chemistries, is complex and contains many simple and complex compounds. The major anion in a kind of alkali metal borate is an alkali metal borate (1: 1) such as Na2-O-B2O3-4H2O. Mixtures of B (OH) 3 and B (OH) "1 also appear in conventional pH buffer systems depending on the pH, sodium borate, potassium borate, disodium tetraborate, etc. can be used in the stabilized materials of the invention. disodium tetraborate pentahydrate, disodium tetraborate tetraborate, etc.

Bleach Source The detergent composition of the invention may also comprise an encapsulated chlorine or bleach source, preferably chloroisocyanurates, sodium salt that liberates OCI "under conditions normally found in typical cleaning processes." Preferred species include sodium dichloroisocyanurate, dichloroisocyanurate potassium, pentaisocyanurate and hydrates thereof A preferred source of chlorine comprises an encapsulated chlorine source.These sources of encapsulated chlorine are shown by Olson et al., U.S. Patent Nos. 4,681, 914 and 5,358,635. Suitable chlorine releasing substances as the core material of the encapsulated active chlorine compound include chlorine components capable of releasing active chlorine species such as HOCI, under conditions commonly used in fret washing and laundry processes. comprise from 0 to 10% by weight of a source of bleaching, or bleach preferably encapsulated from 2 to 6% by weight for reasons of economy, and most preferably 5% by weight for reasons of cost effectiveness. Suitable sources of bleach include, but are not limited to the following: calcium hypochlorite, lithium hypochlorite, chlorinated trisodium phosphate, sodium dichloroisocyanurate dihydrate, potassium dichloroisocyanurate dihydrate, sodium dichloroisocyanurate, the source of bleaching comprising dihydrate sodium dichloroisocyanurate for reasons of availability and economy.

Compositions Disinfectants The disinfectant compositions, the solid functional material in block form of the invention may contain the disinfecting agent. Disinfecting agents may comprise bleaching agents (discussed above) or a variety of other materials. Useful disinfecting agents include hydrogen peroxide, peroxycarboxylic acids, glutaraldehyde, quaternary ammonium compounds and a variety of other materials. A preferred disinfectant composition comprises a peroxycarboxylic acid disinfectant. Such materials are typically made by oxidizing a monocarboxylic acid using hydrogen peroxide. In general, useful concentrations of peroxycarboxylic acid disinfectant typically range from 0.1 to 40% by weight, preferably from 3 to 30% by weight.

Non-ionic Surfactants and Rinse Aids The nonionic surfactants useful in the context of this invention are generally polyether compounds (also known as polyalkylene oxide, polyoxyalkylene glycol or polyalkylene glycol). More particularly, the polyether compounds in general are polyoxypropylene or polyoxyethylene glycol compounds. Typically, the surfactants useful in the context of this invention are polyoxypropylene (PO) -poyioxyethylene (EO) organic block copolymers. These surfactants comprise a diblock polymer comprising an EO block and a PO block, a center block of polyoxypropylene (PO) units, and having polyoxyethylene blocks grafted onto the polyoxypropylene unit or an EO center block with PO blocks attached. In addition, this surfactant may have additional blocks of either polyoxyethylene or polyoxypropylene in the molecule. The average molecular weight of useful surfactants varies from 1000 to 40,000 and the content by weight percent of ethylene oxide ranges from 10-80% by weight. The composition of the invention may also comprise a defoaming surfactant or rinsing auxiliary surfactant useful in dishwashing compositions. A defoamer is a chemical compound with a hydrophobic-hydrophilic balance suitable for reducing the stability of protein foam. The hydrophobic character can be provided by an oleophilic portion of the molecule. For example, an aromatic alkyl, or alkyl, an oxypropylene or an oxypropylene chain, or other oxyalkylene functional groups other than oxyethylene provide this hydrophobic character. The hydrophilic character can be provided by oxyethylene units, chains, blocks and / or ester groups. For example, organophosphate esters, salt-like groups or salt-forming groups all provide hydrophilicity within a foaming agent. Typically, defoamers are non-ionic organic surface active polymers having hydrophobic groups, blocks or chains and hydrophilic ester groups, blocks, units or chains. However, anionic, cationic and amphoteric defoamers are also known. The phosphate esters are also suitable for use as defoaming agents. For example, the esters of the formula RO- (P? 3M) nR where n is a number ranging from 1 to 60, typically less than 10 for cyclic phosphates, M is an alkali metal and R is an organic group or M , with at least 1 of R being an organic group such as an oxyalkylene chain. Suitable defoaming surfactants include nonionic surfactants blocked from ethylene oxide / propylene oxide, fluorocarbons and alkylated phosphate esters. When defoaming agents are present, these may be present in a concentration ranging from 0.1% by weight to 10% by weight, preferably from 0.5% by weight to 6% by weight, and most preferably from 1% by weight to 4% by weight. weight of the composition. Rinsing aids are selected for the action of rolling and surface energy. Also useful in the context of this invention are the surfactants comprising alcohol alkoxylates having EO, PO and BO blocks. The straight aliphatic primary alcohol alkoxylates may be particularly useful as rolling agents. Said alkoxylates are also available from various sources including BASF Wyandotte, where they are known as surfactants 'Plac'. A particular group of alcohol alkoxylates that is useful are those having the general formula R- (EO) m- (PO) n wherein m is an integer of 2-10 and n is an integer of 2-20. R can be any suitable radical such as a straight chain alkyl group having 6-20 carbon atoms. Other useful nonionic surfactants of the invention comprise aliphatic alcohol alkoxylates blocked at their terminus. These blockages at its end include, but are not limited to, methyl, ethyl, propyl, butyl, benzyl and chlorine. Preferably, said surfactants have a molecular weight of 400 to 10,000. The blocking at the end improves the compatibility between the nonionic agent and the oxidants hydrogen peroxide and percarboxylic acid, when formulated to an individual composition. Another useful nonionic surfactant of the invention comprises a fatty acid alkoxylate, wherein the surfactant comprises a fatty acid moiety with an ester group comprising an EO block, a PO block or a mixed block or heteric group. The molecular weights of said surfactants vary from 400 to 1,000,000, a preferred surfactant comprises an EO content of 30-50% by weight, and wherein the fatty portion contains from 8 to about 18 carbon atoms. Similarly, alkylphenol alkoxylates have also been found useful in the manufacture of rinse agents of the invention. Said surfactants can be made from a portion of alkylphenol having an alkyl group with 4 to 18 carbon atoms, it can contain an ethylene oxide block, a propylene oxide block or a block of ethylene oxide, propylene oxide mixed, or a portion of heteric polymer. Preferably, said surfactants have a molecular weight of 100 to 10,000 and have from 5 to 20 units of ethylene oxide, propylene oxide or mixtures thereof. The functional composition may contain the formulation of the following general composition: Composition Table The processes used to make the solid block material of the invention typically involve preparing a liquid or pourable material containing the ingredients of the invention, which is then placed in a container for cooling and solidification. The liquid portion of the castable material typically contains components of a matrix that can be solidified. The solidified form of the solid block detergent comprises a solid matrix having particulate ingredients for washing dishes dispersed through the solid matrix. This process technology that can be used to make the detergents of the invention is described by Fernholz et al., U.S.A. Reissue Patents Nos. 32,763 and 32,818. In addition, the processing of alkaline detergent materials in pellet form is shown by Gladfelter et al., U.S. Patent Nos. 5,078,301; 5, 198, 198 and 5,234,615. The processing of extruded alkaline detergent materials is described by Gladfelter et al., U.S. Patent No. 5,316,688. Another hydration type process for making cast detergent based on caustic or carbonate is described by Heile et al., U.S. Patents. A. Nos. 4,595,529 and 4,680, 134, These conventionally cast solid detergent materials are assorted using water dispersion jets which dissolve the solid block material from the plastic bottle or capsule for use in a dish washing machine. The above discussion provides a basis for understanding the invention. The following methods and examples of mixing and data provide an understanding for the end-use manufacture of the invention.

Mixing Procedure 1 Low Temperature Processing Procedure 1.- Add the caustic surfactant, liquid aqueous, defoamer of phosphonate ester and water.

Heat to 48.8 ° C. 2_- Add polyacrylate, add sucrose. 3.- Add NaOH. Add sodium carbonate. Take it to the temperature of 57.2 to 60 ° C. 4.- Add sodium tripolyphosphate and the source of encapsulated chlorine. Pack when the viscosity exceeds 4000 cps (4 Pa's) Mixing Process 2 High Temperature Processing Procedure 1- Add the liquid caustic. Add sodium chlorite. Add the water. Add the surfactant and defoamer. 2- Heat from 71 to 82 ° C 3 - Add polyacrylic acid. Mix 15 minutes. Add sucrose Mix until dissolved. Dissolve the dye in 20 ml of water and add. 4- Add the caustic pearl. 5 - Add the sodium carbonate. 6 - Bring the temperature from 68 to 74 ° C. 7- Add the STPP. 8 - Mix and pack.

Mixing procedure 3 High temperature processing with pre-coated sequestering agent Procedure 1.- Add tripoli to batten mixer 2 - Add surfactant and mix for 15 minutes.

Formula rub m in o 1.- Add the liquid caustic. 2.- Add sodium chlorite. 3.- Add water. 4.- Heat from 71 to 82 ° C. 5.- Add the polyacrylic acid. Mix 15 minutes. Add sucrose Mix until dissolved. 6.- Dissolve the dye in 20 ml of water and add. 7.- Add caustic pearl. 8.- Add dense ash. 9.- Bring the temperature from 68 to 74 ° C 10.- Add STPP. 11.- Mix and pack.

When using the mixing procedures 1 and 3, a large volume of experimental work was performed to demonstrate the improved stability of the reversion reduction or hydrolysis control by STPP using the vicinal hydroxyl compounds of the invention. A large number of compounds were tested for the reversion control at variable temperatures, water content and particle sizes of STPP, both with coated and uncoated sodium tripolyphosphate. It was found that under all these variable conditions, the reversal inhibitor provided some degree of control over the polyphosphate hydrolysis. The following summary table presents the results of the experimental program. In the frame, a reversion percentage of sodium tripolyphosphate is shown. This number represents the percentage of the aggregated tripolyphosphate that was hydrolyzed. In developing these data, experiments similar to those shown in the 1 -4 mixing procedures were conducted using proportions of the reversal inhibitor ranging from 2 to 8% by weight. It was found that the concentration of the reversal inhibitor generally increased its control of proportionally increased reversion. However, the summary table demonstrates the experience to control the reversion with the compounds of the invention. The following table shows the ability to control the reversal of STPP. A low reversion of pre-coated STPP (6.25% by weight of coating, see mixing procedure 3) was achieved during production even under conditions difficult to control, including a formula with a high water content (18.5 to 20% by weight) of water), using small particles of STPP and with extended mixing times. The results presented are based on a 6.0% by weight addition of the reversal inhibitor, except where indicated.

Table 1 of Results Summary of the Results of the Inhibitors of the Invention and Comparative Materials Not the same conditions, but similar.

The summary table shows that the best inhibitory compounds are the carbohydrate compounds that are monosaccharide or disaccharide compounds. Preferably, the compound allows reversion control of less than 10% by weight (based on the weight percentage of STPP). It was also found that the stabilization compounds of the invention reduce the loss of chlorine activity from encapsulated chlorine compounds. The solid detergents of the invention have improved stability during manufacture when made with stabilization compounds. Without the stabilization compounds of the invention, the solid detergent can lose 50-85% of the added chlorine activity from the encapsulate after packing (based on a mixing time of 2-4 hours). With the stabilizer, the loss of chlorine activity at 6-12% can be eliminated under the same conditions. The ability of the stabilization compounds of the invention to prevent color change due to the color instability of the organic materials in the solid detergents of the invention during the manufacture and storage of alkaline dishwashing detergents and washing detergents has also been discovered. laundry containing surfactant mixtures. In Example I w the addition of an effective amount of sucrose (typically 3 to 6% by weight) prevents a color change to coffee in the cast solid detergent. The original whitish white color does not change. Example I When made with an organic surfactant and a brightening agent (Example II), the cast product is a bright yellow solid product. Without the stabilizer, the product is made a yellow / brown color. A stability test was carried out on the solid material for more than 4 months without any change or discoloration of the original color.

Example II It has also been found that the stabilization compounds of the invention stabilize assortment characteristics of the solid detergent composition. Cast solid detergents based on sodium hydroxide (similar to those made in blending procedures 1-4) were prepared containing 6 wt% sucrose based on the solid which also contains 12-16 wt% water. It was found that the addition of sucrose stabilizes the physical integrity of the solid block during spray assortment. The surface of the solid block wears linearly on the surface of the block and prevents cracking or rupture of the cast solid material. The physical integrity resulting from the solid block provides a consistent assortment until the block is completely consumed by the spraying jet. No part of the solid crumbles or disintegrates from the solid mass and blocks the spout. It has also been found that nearby compounds of the invention stabilize enzymes in an alkaline solid enzyme cleaning material. It has also been observed that natural materials containing materials such as carbohydrate, disaccharide, trisaccharide or polysaccharide are equally useful for stabilizing the compositions of the invention as the relatively pure reagent chemicals. It has been found that milk solids containing a substantial proportion of lactose in combination with proteins such as casein can increase the stabilization of sucrose or provide a stabilizing effect. It has also been found that borate compounds are also useful in combinations with vicinal hydroxyl compounds of the invention to stabilize organic materials and particularly enzymes. The use of general methods to form solid block materials, the materials set forth in Table 2, were prepared using varying proportions of dry milk or sucrose or combinations thereof, as a source of lactose or sucrose as the neighborhood hydroxyl stabilizing compound. The use of sucrose and milk stabilizes the alkaline protease in a solid block detergent to a certain degree. The solids of sucrose plus borate or sucrose plus borate plus milk provided surprising levels of stability when compared to the solid enzyme-containing material without sucrose borate or milk solids.

Test Table 2 Milk solids typically comprise a mixture of lactose and casein proteins.

It has also been found that the compositions have improved dirt removal properties. The formulas used and test conditions are presented below. The formula used for comparison is a conventional alkaline solid carbonate solid detergent against the same formula with 6% sucrose. The test concentration is 800 ppm of the total detergent in the wash. The lipstick is only read in redepositing glasses. Lipstick results are based on an average of three separate glass readings used in the test. The classification system used in this test is the following: Without lipstick 1 20% remaining 2 40% remaining 3 80% remaining 4 100% remaining 5 The removal of lipstick was reported based on I to removal after one cycle and removal after 2-10 cycles. At least 3 additional but separate tests were operated after this discovery and the results could be duplicated (within experimental error). Solid of Solid Test Conditions Ingredients Control Test with 6% sucrose Running water (approx 4-5 g) 1. Caustic (gram) 8.4 8.4 2000 ppm of three food stains 2 2 .. AAgguuaa 5.6 5.6 Hobart C-44; 10 cycles 3. Premix of agent 0.9 0.9 surfactant Redeposition = 3 glasses of redeposition 4. Surface active agent 3.7 3.7 Nonionic Coated = 5 glasses 5. Polyacrylic acid (50% 2.0 2.0 submerged in whole milk and dried aqueous active) for 8 minutes in a humidity chamber (38 ° C / 65% RH) 6. Coloring traces footprints 7. Caustic pearl 33.1 33.1 8. Sucrose 6.0 9. Anhydrous sodium carbonate 2.5 9. Sodium tripolyphosphate 35.0 35.0 pre-coated 10. Chlorine source 8.8 7.4 encapsulation Table 3 of Results of Solid Test with 6% Sucrose * Averaged glasses Control Solid A comparison of these results shows that the sucrose-containing solid exhibited surprisingly improved soil removal. In particular, the removal of lipstick is substantially better than expected compared to caustic solid detergents made without a carbohydrate stabilizer.

The test glasses were washed in an institutional dish washing machine with a predetermined concentration of test or control detergent and 2000 ppm food stains. Some of the test glasses were completely soaked in whole milk and dried before each cycle. Other vessels were left untreated and examined for redeposition of dirt.

Apparatus and Materials 1. A dish washing machine connected to the appropriate water supply. 2. A Rabum cup holder. 3. Libbey heat-resistant cup dryers, 283.5 g. 4. Stain of stew. 5. Warm spot. 6. Sprouts of potato. 7. Whole milk 8. Rest 9. Sufficient detergent to complete the test. 10. Titrant and reagents to title the alkalinity. eleven . Water hardness test equipment. 12. Coomassie blue dye: 50% methanol in deionized water 454 ml Glacial acetic acid 46 ml Coomassie brilliant blue (50%) 2.50 g Preparation 1 .- Clean 8 glasses. 2.- Prepare a mixture of food dirt. Prepare stewed dirt and hot spot dirt and mix in an equal weight of each dirt to make a 50/50 mix. A 2000 ppm concentration of food dirt was maintained in the wash tank through the test with both 50/50 stew, hot spot dirt or a 2/3 mixture of 50/50 stew, hot spot along with 1/3 of potato shoots. 3. - Fill the dishwasher to wash dishes with the appropriate water. Test the water for hardness. Record the value. Turn on the tank heaters. 4.- The washing cycle temperatures and the rinse cycle temperatures must match the field conditions. For these purposes, the temperature is 71 -77 ° C for the wash tank and 79-88 ° C for the rinse water. 5.- Turn on the dishwasher and let the detergent be distributed or weigh an appropriate amount and add it to the machine at the proper concentration. Most of the tests were run at 1 000 ppm detergent. Use a titrant and 0. 10 N of HCL to titrate the wash water samples to ensure that an appropriate level of detergent is maintained throughout the test. Make adjustments as necessary for the washing machine and spouts to maintain the proper level of detergent. 6.- Add enough food dirt to the machine to achieve the food dirt concentration of 2000 ppm. To calculate this multiply the capacity of the washing tank in liters by 2. 7.- Immerse 5 of the glasses completely in whole milk and let dry for 8 minutes in a humidity chamber at 38 ° C / 65% RH. (These glasses will be soaked in whole milk and dried before each cycle of the test). Place the glasses in the Rabum cup holder after they have been dried. 8.- Place the other 3 clean glasses in the Rabum holder.

Keep them separate from glasses treated with milk. In one of these glasses, make a strip with lipstick each cycle with the red lipstick Cover Girl Really. 9.- Determine how much water is replaced after each wash cycle. This will effect that so much food and detergent dirt, if added by hand, is added after each wash cycle to the machine to maintain the constant level of food soil. 10.- On the Hobart C-44 machine, 7 liters of water are exchanged after each wash cycle. Fourteen grams of food dirt are added to the dishwashing machine each cycle to maintain a level of 2000 ppm. 1 1.- Take 5 glasses of the rest and weigh 14 grams of food dirt and the appropriate amount of detergent, if added by hand, in each glass. Working with 5 glasses at a time helps maintain a better trajectory that so many cycles have been run. Add one of the glasses face down, in the holder during each cycle through the washing machine.

Procedure 1.- Begin the test. Run the support through the washing machine for one wash cycle. Re-stain and dry the glasses treated with milk. Leave the redeposition cups in the holder. Remember to add food and detergent dirt in each cycle. 2. - Repeat step 1 until 5 cycles have been run. Retest the alkalinity wash water to maintain the proper level of detergent. Adjust the detergent level if necessary. 3.- Repeat steps 1 and 2 until 10 cycles have been run. 4.- Let the glasses dry overnight. Classify all glasses for stain and film accumulation using a strong light source. Stains Film 1 No stains 1 No film 2 Random spots 2 Film footprint 3 V surface 3 Light film 4 A surface 4 Medium film 5 100% surface 5 Heavy film . - Submerge one or two glasses treated with milk in the Coomassie blue dye for 20 seconds and then rinse well under running water. The amount of blue dye retained on the vessel is proportional to the amount of protein on the vessel. 1 No blue color No protein 1.5 Blue fingerprints Protein fingerprints 2 Light blue Few proteins 3 Medium blue Medium protein 4 Dark blue Heavy protein 5 Very dark blue Very heavy protein Interpretation of the Results The glasses treated with milk presented the best results when very few spots, film or protein accumulated in them. A standard detergent should be tested and the glasses maintained so that the test formulas can be compared to the standard.

Explanation of the Stain, Film and Protein Classification System DETAILED DISCUSSION OF THE DRAWINGS The data shown in Figures 1-8 correspond to a large body of experimental procedures conducted to demonstrate the value of the reversal inhibitor compounds of the invention. These experimental data were derived from preparations similar to those shown in mixing procedures 1-4, using the conditions shown in the drawings. The percentages of tripolyphosphate reversed and in the figures refer to the percent reversion based on the total weight of the solid detergent.

Figure 1 shows the inhibition of reversal of sodium tripolyphosphate in a solid detergent using sucrose as a reversal inhibitor. In Figure 1, solid detergents cast with STPP having a size of 20-30 US mesh (screen opening of 0.55 to 0.84 mm), without barrier coating, were made at 52 ° C in a castable material having 18.5 % of water. The drawing shows 4 experiments with varying proportions of sucrose. As the sucrose concentration increases, the cast detergent obtains an increased reversion protection. Figure 2 shows that the surprising chlorine stability also increases with increasing amounts of sucrose in a solid block made similar to that shown in Figure 1, except that the solid block made at 66 ° C with 1 1% by weight of water. As the concentration of sucrose increases, the stability of chlorine substantially increases. Figure 2 shows percentages based on the detergent block originally containing 3.8% by weight of available chlorine. Figure 3 shows the results of a series of experiments similar to those shown in Figure 1, except that the solid blocks were made at 66 ° C with 12.6% water. The sodium tripolyphosphate used was made with and without a barrier coating with either 0% sucrose or 6% sucrose. The best cast block was made with 6% sucrose and an EOPO block copolymer placed as pre-coating on the tripolyphosphate.

Figure 4 shows the results of a series of experiments similar to those shown in Figure 3, except that the particle size of STPP is approximately 60-80 U.S. mesh (a size of 0.17 to 0.25 mm). Although the smaller particle size resulted in increased reversion, the tripolyphosphate coated in the cast solid using 6% sucrose showed less than 2% by weight of reversion. Figure 5 shows the results of a series of experiments performed under the same conditions as Figure 1 with STPP coated and uncoated in 6% sucrose. The larger particle size at lower temperatures with a pre-coating and 6% sucrose showed a substantial reversion inhibition. Figure 6 shows the results of a series of experiments similar to those shown in Figure 4. Except that the solid blocks were made at 52 ° C and 18.5% water. A similar reversal inhibition was shown. Figures 7 and 8 show the ability to inhibit reversion of a variety of proposed reversal inhibitor compounds at varying concentrations. These solid block detergents were made using conditions similar to those shown in the 1-4 mixing procedures. These experiments show that the preferred inhibitors are mono and disaccharides.

Figure 9 shows that the stabilized solid detergent of the invention made using 6 wt% sucrose had a surprisingly improved cleaning performance. In control tests operating using a solid alkaline detergent and an identical solid alkaline detergent made using sucrose, the stain and film cleaning performances were markedly improved. In particular, the lipstick removal properties of a single cycle and multiple cycles of detergent were markedly superior to a solid detergent made without sucrose.

Claims (10)

1. - A method for manufacturing a solid block functional composition, said method stabilizes the components of the composition and inhibits or reduces the hydrolytic instability of condensed phosphate sequestering agents, the method comprising: (i) combining: (a) an effective amount from an inorganic source of alkalinity; (b) at least 10% by weight of a condensed phosphate sequestering agent; (c) an amount of stabilization and reversion inhibitor of a reversal inhibitor, the inhibitor comprising a monosaccharide of C4 to C6 or a disaccharide comprising sucrose, maltose, lactose or mixtures thereof, to form a mixed mass; and (ii) forming a mass mixed with a solid; wherein less than about 15% by weight of the condensed phosphate sequestering agent is reversed.

2. The method according to claim 1, wherein the tripolyphosphate comprises a particulate material having a particle size of about 200 to 900 microns having a barrier coating.

3. The method according to claim 1, wherein the reversion inhibitor comprises a compound with three or more adjacent vicinal hydroxyl compounds.

4. The method according to claim 1, wherein the solid block functional composition comprises from about 1 to 15% by weight of a carbohydrate composition.

5. The method according to claim 4, wherein the carbohydrate comprises a C4.6 carbohydrate compound or mixtures thereof.

6. The method according to claim 5, wherein the reversal inhibitor comprises glucose, galactose, fructose or mixtures thereof.

7. The method according to claim 4, wherein the reversal inhibitor comprises a disaccharide.

8. The method according to claim 7, wherein the disaccharide comprises sucrose, maltose, lactose or mixtures thereof.

9. The method according to claim 1, wherein less than about 7% by weight of the hardness sequestering agent is reversed.

10. The method according to claim 1, wherein less than about 15% by weight of the condensed phosphate sequestering agent is reverted during processing and packing. The method according to claim 1, wherein the solid detergent does not discolour substantially after forming the mixed mass to a solid. 12. The method according to claim 1, wherein the mixed mass is formed into a solid in a plastic container. 13. A solid block alkaline detergent composition containing an effective amount of a condensed phosphate sequestering agent, the stabilized composition comprising: a) from 10 to 60% by weight of an inorganic source of alkalinity; b) from 10 to 45% by weight of a condensed phosphate sequestering agent; and c) from 1 to 15% by weight of an amount of stabilization and inhibition of effective reversion of a reversal inhibitor, the inhibitor comprising a monosaccharide of C4 to C6, or a disaccharide comprising sucrose, lactose, maltose or mixtures thereof; wherein the solid block is packed within a container and wherein less than 15% by weight of the condensed phosphate sequestering agent is coated. 14. The composition according to claim 13, wherein the reversion inhibitor comprises a compound with three or more adjacent vicinal hydroxyl compounds. 15. The composition according to claim 13, wherein less than about 10% of the condensed phosphate hardness sequestering agent is coated.