MXPA06004161A - Methods for treating glassware surfaces using corrosion protection agents. - Google Patents

Abstract

Methods for treating glassware surfaces, for example dishes and glasses, using corrosion protection agents, especially corrosion protection agents comprising zinc-containing materials. Methods using corrosion protection agents that form a part of a treatment system and/or are incorporated in a composition of matter are also provided.

Description

METHODS TO TREAT GLASS SURFACES THAT EMPLOY AGENTS OF PROTECTION AGAINST CORROSION FIELD OF THE INVENTION The present invention relates to methods for treating glassware surfaces, for example dishes and glasses, which employ corrosion protection agents, especially corrosion protection agents comprising zinc-containing materials. Methods employing corrosion protection agents that are part of a treatment system and / or incorporated into a composition of matter are also provided.

BACKGROUND OF THE INVENTION Automatic dishwashing detergents constitute a distinct, generally recognized, class of detergent compositions whose purpose may include breaking down and removing food stains; inhibit the formation of foam; promote wetting of wash articles to reduce or eliminate visually perceptible stains and coatings; eliminate stains such as those that can be caused by beverages such as coffee and tea or by vegetable oils such as dirt caused by carotenoids; avoid the accumulation of dirt layers on the surfaces of the items to be washed; and reduce the fogging of cutlery without practically engraving, corroding or in any other way damaging the surface of the glasses or plates. The problem of corrosion on glassware surfaces during the washing cycle in an automatic dishwasher has been known for a long time. The current opinion is that the problem is the result of two different phenomena. On the one hand, the high pH necessary for cleaning causes the hydrolysis of silica. This silica / dissolved silicate deposit (together with the silicates intentionally added to prevent corrosion of dishes and metal) on the surface of the glassware produces an iridescence and opacity. On the other hand, the additives produce corrosion. The additives will chelate metal ions of chelates on glassware surfaces, which produces the leaching of metal ions and makes glass less durable and less resistant to chemical compounds. After several washes in an automatic dishwasher, both phenomena can produce considerable corrosion damage on glassware surfaces, such as opacity, scratches, and scratches that make the consumer feel dissatisfied. Most consumers agree that the corrosion on glassware surfaces caused by the use of automatic dishwashers (ADW) is one of their most serious unmet needs. A methodology for reducing corrosion on glassware surfaces is to provide corrosion protection agents comprising water-soluble metal salts (such as zinc, chloride, sulfate or acetate salts) to provide some measure of protection on glassware surfaces. . Another methodology is to reduce the formation of precipitates, caused by the introduction of soluble zinc salts in an environment with a high pH; this is achieved by spraying a water-soluble zinc salt solution onto granular polyphosphate particles. Another methodology is to combine the soluble zinc with a chelating agent. Another methodology is to use an insoluble zinc salt to control the release of Zn2 + ions in the rinse in order to avoid film formation. Another methodology is to provide an automatic dishwashing composition having a mixture of disilicate and metasilicate. Another methodology is to provide an additive to an automatic dishwashing composition, such as a copolymer of an organomineral siliconate, which is obtained by the polymerization and condensation of an alkali metal disilicate and an alkali metal siliconate. Another methodology is to provide an alkali metal silicate partially substituted with calcium, magnesium, strontium or cerium, as a counter-ion. Another methodology is the use of metal salts, in particular aluminum, wherein the metal salt is sequestered to form a metal salt-sequestering agent complex such as an aluminum (III) -secreting complex. In still another methodology, a fast-dissolving aluminum salt is employed, but this aluminum salt is combined with more than about 10% by weight of silicate in high alkalinity products. Therefore, although many methodologies are available, there is still a need to develop alternative methods to reduce corrosion on glassware surfaces that employ corrosion protection agents, so that the benefits of Glassware care is achieved and also the problem of corrosion on glassware surfaces is reduced.

BRIEF DESCRIPTION OF THE INVENTION The present invention relates to methods at the domestic, institutional, industrial and / or commercial level for employing corrosion protection agents, in particular certain zinc-containing materials such as zinc-containing particulate materials (PZCM, for its acronym in English) and stratified materials containing zinc (ZCLM), to treat surfaces of glassware in automatic dishwashers. The corrosion protection agents described herein can be used alone, in combination with detergent compositions, or as part of a treatment and / or composition system for the purpose of reducing the corrosion of glassware surfaces in processes of automatic dishwashers. According to one aspect, a method is provided for reducing the corrosion of glassware surfaces in automatic dishwashers; the method comprises the step of contacting a glassware surface with a corrosion protection agent. The corrosion protection agent comprises: (a) an effective amount of certain zinc-containing materials such as PZCM and ZCLM; and (b) optionally an auxiliary ingredient.

According to another aspect, a method is provided for reducing the corrosion of glassware surfaces; The method employs a treatment system. A corrosion protection agent comprising an effective amount of certain zinc-containing materials, such as PZCM and ZCLM, can be part of the treatment system to reduce the corrosion of glassware surfaces in an automatic dishwasher. According to another aspect, a method is provided for reducing the corrosion of glassware surfaces; the method employs a composition of matter. The composition of matter comprises a washing solution comprising a corrosion protection agent which in turn comprises zinc-containing materials such as PZCM and ZCLM. According to another aspect, a process for manufacturing a corrosion protection agent is provided. The process comprises the steps of: (a) Providing and (b) combining certain zinc-containing materials such as PZCM and ZCLM; and (c) optionally adding an auxiliary ingredient to form the corrosion protection agent.

BRIEF DESCRIPTION OF THE DRAWINGS Figure 1 depicts the structure of a stratified material containing zinc. Figure 2 represents a comparison of the strength of the glassware surface using a mirror reflex IR.

DETAILED DESCRIPTION OF THE INVENTION It has been discovered with great surprise that glassware can be protected in automatic dishwashers using methods to treat glassware surfaces, this is achieved by contacting the glassware with corrosion protection agents containing certain zinc-containing materials such as PZCM. and ZCLM. This is especially true in soft water conditions where the chelating agents and additives can damage the glassware by chelating metal ions in the glass structure itself. Thus, even in the harsh environments of automatic dishwashers, damage to glass by surface corrosion can be reduced with the use of ZCLMs in automatic dishwashing detergent compositions without the negative effects associated with the use of metal salts such as: (a) the high cost of manufacturing; (b) the need for higher salt levels in the formula due to the poor solubility of the insoluble material; (c) the thinning of the gel compositions due to the interaction of the metal ions, for example the Al3 + ions and the Zn2 + ions, with the thickening material; or (d) a reduction in cleaning performance for tea stains due to interference with the bleach during the entire wash cycle. It has also been discovered with great surprise that the benefit of glassware care provided by the ZCLM is greatly enhanced when the ZCLM is dispersed before being added to or during the manufacturing process of the anti-scavenging agent. corrosion. The achievement of a good dispersion of the ZCLM particles in the corrosion protection agent significantly reduces the agglomeration of the ZCLM particles in the wash solution. In the methods described herein, any suitable corrosion protection agent can be employed, alone or in combination with a composition of matter (such as washing solution), and / or as part of a treatment system comprising a kit having an effective amount of certain zinc-containing materials such as PZCM and ZCLM. Here, "effective amount" refers to an amount that is sufficient, under the conditions of comparative tests described herein, to reduce the corrosion damage of the glassware surface on glassware treated with detergent compositions for use throughout the cycle of washing. PARTICULATE MATERIALS CONTAINING ZINC (PZCM) Zinc-containing particulate materials (PZCM) remain largely insoluble in formulated compositions. Examples of PZCM useful in certain non-limiting embodiments may include the following: Inorganic materials: zinc aluminate, zinc carbonate, zinc oxide and zinc oxide-containing materials (ie, calamine), zinc phosphates (ie, orthophosphate) and pyrophosphate), zinc selenide, zinc sulfide, zinc silicates (ie, ortho- and metazinc silicates), silicofluoride of zinc, zinc borate, zinc hydroxide and hydroxysulfate, zinc-containing layered material, and combinations thereof. Materials / natural minerals that contain zinc: sphalerite (zinc blende), wurtzie, smithsonite, frankiinite, zincite, willemite, troostite, hemiforphite, and combinations of these. Organic salts: salts of fatty acids and zinc (ie, caproate, laurate, oleate, stearate, etc.), zinc salts of alkylsulfonic acids, zinc naphthenate, zinc tartrate, zinc tannate, zinc phytate, monoglycerollate zinc, zinc allantoinate, zinc urate, zinc salts and amino acids (ie, methionate, phenylalinate, tryptophanate, cysteine, etc.), and combinations thereof. Polymer salts: polycarboxylates (ie, polyacrylate) zinc, zinc polysulfate, and combinations thereof. Physically adsorbed forms: ion-exchange resins loaded with zinc, zinc adsorbed on the surfaces of the particles, composite particles in which the zinc salts are incorporated (ie, as core / sheath or aggregate morphologies), and combinations of these . Zinc salts: zinc oxalate, zinc tannate, zinc tartrate, zinc citrate, zinc oxide, zinc carbonate, zinc hydroxide, zinc oleate, zinc phosphate, zinc silicate, zinc stearate, zinc sulphate zinc, zinc undecylate, and the like, and combinations of these. Commercially distributed zinc oxide sources include Z-Cote and Z-Cote HPI (BASF) and USP I and USP II (Zinc Corporation of America).

Physical properties of the PZCM particles In the methods described herein, many of the benefits of using PZCM in corrosion protection agents require that the Zn2 + ion be chemically available without being soluble. This is called "zinc lability." Certain physical properties of PZCM have the potential to affect the lability of zinc. We have developed more effective corrosion protection agents based on the optimization of zinc lability in the PZCM. Some physical properties of the PZCM that may affect the lability of zinc may include, but are not limited to: the crystallinity, the surface area, and the morphology of the particles, and combinations thereof. Other physical properties of the PZCM that can also affect the zinc lability of the PZCM include, but are not limited to: the bulk density, the surface charge, the refractive index, the level of purity, and combinations of these. Crystallinity A PZCM that has a less crystalline structure can result in a relatively higher zinc lability. The crystalline imperfections or the crystalline integrity of a particle can be measured by the maximum average total amplitude (FWHM) of the reflections of an X-ray diffraction pattern (XRD, for its acronym in English). Without theoretical limitations of any kind, it is postulated that the larger the value of FWHM, the lower the level of crystallinity in a PZCM. The lability of zinc seems to increase as the crystallinity decreases. It can be used any crystallinity of PZCM. For example, suitable values of crystallinity may vary from about 0.01 to about 1.00, or from about 0.1 to about 1.00, or from about 0.1 to about 0.90, or from about 0.20 to about 0.90, and as an alternative from about 0.40 to about 0.86. FWHM units at a maximum reflection of 200 (~ 3 ° 2T, 6.9 Á). Particle Size The PZCM particles in the corrosion protection agent can have any suitable average particle size. In certain non-limiting embodiments it has been found that a smaller particle size is directly proportional to an increase in relative lability of zinc (%). Suitable average sizes of the particles include, but are not limited to: a range from about 10 nm to about 100 microns, or from about 10 nm to about 50 microns, or from about 10 nm to about 30 microns, or about 10 nm at about 20 microns, or from about 10 nm to about 0 microns, and as an alternative from about 100 nm to about 10 microns. In another non-limiting embodiment, the PZCM may have an average particle size of less than about 15 microns, or less than about 10 microns, and as an alternative less than about 5 microns.

Particle size distribution Any suitable particle size distribution of PZCM can be used. Suitable particle size distributions of PZCM include, but are not limited to: a range from about 1 nm to about 150 microns, or from about 1 nm to about 100 microns, or from about 1 nm to about 50 microns, or from about 1 nm to about 30 microns, or from about 1 nm to about 20 microns, or from about 1 nm to about 10 microns, or from about 1 nm to about 1 micron, or from about 1 nm to about 500 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about 50 nm, or from about 1 nm to about 30 nm, or from about 1 nm to about 20 nm, and alternatively, from about 1 nm or less, to about 10 nm. MATERIALS IN LAYERS CONTAINING ZINC (ZCLM) As previously defined, the ZCLM are a subclass of the PZCM. Layered structures are those that have a crystal growth that occurs mainly in two dimensions. Conventionally, layered structures are described as those in which all the atoms are incorporated in well-defined layers, but also as those in which there are ions or molecules between the layers called gallery ions (A.F. Wells "Structural Inorganic Chemistry" (Structural inorganic chemistry) Clarendon Press, 1975). For example, ZCLM can have Zn2 + ions incorporated in the layers and / or as more labile components of gallery ions. Many of the ZCLMs are found in nature as minerals. Common examples include hydrozincite (zinc hydroxycarbonate), basic zinc carbonate, auricalcite (zinc and copper hydroxycarbonate), rosesite (copper and zinc hydroxycarbonate) and many related zinc-containing minerals. Natural ZCLMs can also be found, where anionic species in layers such as clayey minerals (eg, phyllosilicates) contain ions from ion exchange zinc galleries. Other suitable ZCLMs include the following: zinc hydroxyacetate, zinc hydroxychloride, zinc hydroxy lauryl sulfate, zinc hydroxyinitrate, zinc hydroxysulfate, hydroxide double salts, and mixtures thereof. Natural ZCLMs can also be obtained synthetically or they can be formed in place in a composition or during a manufacturing process. The double hydroxide salts can be represented by the general formula: [? 2 ?? 2 + 1 +? (0?) 3 (1.?)? An- (1 = 3y) / n- nH20 wherein the two metal ions may be different; if they are equal and are represented by zinc, the formula is simplified to IZni + x (OH) 2] 2x + 2x A "nH20 (see Morioka, H., Tagaya, H., Karasu, M, Kadokawa, J, Chiba, K Inorg.

Cr? Em.1999 (Inorganic Chemistry), 38, 4211-6). This last formula represents (where x = 0.4) common materials such as zinc hydroxychloride and zinc hydroxynitrate. These are also related to hydrozincite, when a divalent anion replaces the monovalent anion. Commercially available sources of zinc carbonate include basic zinc carbonate (Cater Chemicals: Bensenville, IL, USA), zinc carbonate (Shepherd Chemicals: Norwood, OH, USA), zinc carbonate (CPS Union Corp .: New York , NY, USA), zinc carbonate (Elementis Pigments: Durham, UK), and zinc carbonate AC (Bruggemann Chemical: Newtown Square, PA, USA). The aforementioned ZCLM types represent relatively common examples of the general category and are not intended to limit the broader scope of materials that fit this definition. In the methods described herein, any suitable ZCLM can be employed in any suitable amount. Suitable amounts of a ZCLM include, but are not limited to: a range: from about 0.001% to about 20%, or from about 0.001% to about 10%, or from about 0.01% to about 7%, and as an alternative of about 0.1% to about 5% by weight of the composition. MECHANISM OF STRENGTHENING OF VITREA NETWORK OF ZCLM It is well known that silica glass is a continuous three-dimensional network (3D) of tetrahedra of Si-O shared in the corners and that they lack symmetry and periodicity (see W. H. Zachariasen, J. Am. Chem. Soc. 54, 3841, 1932). Si + ions are network forming ions. At the apex of each tetrahedron, and shared between two tetrahedra, there is an oxygen atom known as a bridge oxygen. The mechanical properties of the glass surface, such as chemical resistance, thermal stability, and durability may depend on the very structure of the surface of the glassware. Without theoretical limitations of any kind, it is believed that when some network-forming positions are occupied by zinc compounds or Zn2 + ions, the mechanical properties of the glassware surface structure improve (see G. Calas et al., CR Chimie 5 2002, 831-843). Figure 1 depicts a layered structure containing zinc with crystal growth occurring primarily in two dimensions. Zn2 + ions are incorporated in the layers and / or as more labile components of gallery ions. For example, ZCLMs such as synthetic zinc hydroxycarbonate (ZCH) or hydrozincite (HZ) found in nature can have the formula: 3Zn (OH) 2.2ZnC03 or Zn5 (OH) 3 (C03) 2, and consists of Zn2 + ions forming brucite-like layers of hydroxide with some octahedral vacancies as shown in Figure 1. Some of the Zn2 + ions are placed just above and below the vacant sites outside the hydroxide layers in tetrahedral coordination (Td). The anions between layers are weakly bound to the Tn Zn2 + ions completing the tetrahedral coordination. In the wash solution, an ADW detergent composition with labile Td Zn2 + ions is stable at the typical alkaline pH. When a ZCLM is present in the wash water, the cationic charge in the brucite-type hydroxide-like layers is the driving force to interact with the negatively charged surface of the glass. This leads to efficient deposition of zinc compounds or Zn2 + ions on the surface of the glass, so that a very low level of ZCLM is needed to provide a benefit. As soon as brucite-type hydroxide layers are placed in contact with the glass, zinc compounds or Zn2 + ions can be easily deposited on the glass and fill the vacancies created by the leaching of metal ions and the hydrolysis of silica that normally occurs with ADW products. In this way, new compounds of zinc or Zn2 + ions are introduced as forming vitreous networks, strengthening the glass and preventing the corrosion of the glass during other washes. CORROSION PROTECTION AGENTS AND MATERIAL COMPOSITIONS The methods described in this document provide at least some protection against corrosion to glassware surfaces when treated with the corrosion protection agent during at least some portion of the wash cycle. .

In a non-limiting embodiment, a corrosion protection agent comprises an effective amount of a ZCLM, so that when the ZCLM is brought into contact with the surface of the glassware, a quantity of zinc compounds or Zn2 + ions are deposited on it. and / or in the imperfections or empty spaces on the surface of the glassware. For example, the treated glassware surface may have zinc compounds or Zn2 + ions present from about 1 nm to about 1 miera, or from about 1 nm to about 500 nm, or from about 1 nm to about 100 nm, or from about 1 nm to about 50 nm, or from about 1 nm to about 20 nm, and alternatively from about 1 nm to about 10 nm above or below the treated surface of the glassware. In another non-limiting embodiment, a composition of matter comprises a washing solution, which comprises a corrosion protection agent which in turn comprises an effective amount of a ZCLM, in an automatic dishwasher during at least a part of the cycle of washing, from about 0.0001 ppm to about 100 ppm, or from about 0.001 ppm to about 50 ppm, or from about 0.01 ppm to about 30 ppm, and as an alternative from about 0.1 ppm to about 10 ppm of a ZCLM may be present in the washing solution. In the methods described herein, any suitable pH can be employed in an aqueous corrosion protection agent. 7 that contains a ZCLM. In certain embodiments, a suitable pH can have any value in the range of about 6.5 to about 14. For example, certain embodiments of the corrosion protection agent have a pH greater than or equal to about 6.5, or greater than or equal to to about 7, or greater than or equal to about 9, and alternatively, greater than or equal to about 10.0. AUXILIARY INGREDIENTS Any suitable auxiliary ingredient can be used in any quantity or form. As an example, a detergent active and / or rinsing aid active, adjuvant and / or an additive may be used in combination with a ZCLM to form a composite corrosion protection agent. Auxiliary ingredients include, but are not limited to, cleaning agents, surfactants (eg anionic, cationic, nonionic, amphoteric, zwitterionic and mixtures thereof), chelating agent / sequestering agent, bleaching systems (eg bleach) of chlorine, oxygen bleach, bleach activator, bleach catalyst and mixtures thereof), enzymes (for example a protease, lipase, amylase and mixtures thereof), source of alkalinity, water softening agents, secondary modifiers of solubility, thickeners, acids, stain-release polymers, dispersant polymers, thickeners, hydrotropes, binders, carrier media, antibacterial actives, detergent fillers, abrasives, foam suppressants, defoamers, antiredeposit agents, agents and systems threshold, intensifying agents of aesthetic characteristics (ie dye, colorants, perfume, etc.), oil, solvent, and mixtures thereof. Dispersing polymer Any suitable dispersing polymer can be used in any suitable amount. Unsaturated monomeric acids which can be polymerized to form suitable dispersing polymers (eg, homopolymers, copolymers, or terpolymers) include acrylic acid, maleic acid (or maleic anhydride), fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid and methylenemalonic acid. The presence of monomeric segments that do not contain carboxylate radicals such as methylvinyl ether, styrene, ethylene, etc., may be suitable as long as these segments do not constitute more than about 50% by weight of the dispersant polymer. Suitable dispersant polymers include, but are not limited to, those described in U.S. Pat. num. 3,308,067; 3,308,067; and 4,379,080. It is also possible to use substantially neutralized polymer forms in corrosion protection agents. The molecular weight of the polymer can vary over a wide range, for example from about 1000 to about 500,000, as an alternative of about 1000 to about 250,000. Acrylamide and acrylate copolymers having a molecular weight of from about 3000 to about 100,000, or from about 4000 to about 20,000, and a content of less than about 50%, and as an alternative less than about 20%, by weight of the dispersing polymer. The dispersant polymer can have a molecular weight of about 4000 to about 20,000 and an acrylamide content of about 0% to about 5%, by weight of the polymer. Suitable modified polyacrylate copolymers include, but are not limited to, the low molecular weight copolymers of unsaturated aliphatic carboxylic acids described in U.S. Pat. num. 4,530,766, and 5,084,535; and European patent no. 0.066.915. Other suitable dispersing polymers include polyethylene glycols and polypropylene glycols having a molecular weight of about 950 to about 30,000, which can be obtained from the Dow Chemical Company of Midland, Michigan. For example, these compounds with a melting point within a range of about 30 ° C to about 100 ° C can be obtained with a molecular weight of 1450, 3400, 4500, 6000, 7400, 9500 and 20000. These compounds are formed by polymerization of ethylene glycol or propylene glycol with the number of moles of ethylene or propylene oxide required to obtain the respective desired molecular weight and melting point and propylene glycol. Reference is made to polyethylene, polypropylene and mixtures of glycols by the following formula: HO (CH2CH2O) m (CH2CH (CH3) O) n (CH (CH3) CH20) OH where m, n, and o are integers that satisfy the molecular weight and temperature requirements mentioned above. Suitable dispersing polymers also include polyaspartate, carboxylated polysaccharides, in particular starches, celluloses and alginates, described in U.S. Pat. no. 3,723,322; the dextrin esters of polycarboxylic acids described in U.S. Pat. no. 3,929,107; the starchy hydroxyalkyl ethers, the starch esters, oxidized starches, dextrins, starch hydrolysates described in U.S. Pat. no. 3,803,285; the carboxylated starches described in U.S. Pat. no. 3,629,121; and the dextrin starches described in U.S. Pat. no. 4,141, 841. The dispersant cellulose polymers described above include, but are not limited to: cellulose sulfate esters (e.g. cellulose acetate sulfate, cellulose sulfate, hydroxyethyl cellulose sulfate, methyl cellulose sulfate, hydroxypropyl cellulose sulfate, and mixtures of these), sodium cellulose sulfate, carboxymethyl cellulose, and mixtures thereof. In certain embodiments, a dispersant polymer may be present in an amount in the range of from about 0.01% to about 25%, or from about 0.1% to about 20%, and as an alternative from about 0.1% to about 7% by weight of the composition. Carrier Medium Any suitable carrier media can be used in any suitable amount. Suitable carrier media include both liquids as well as the solids, depending on the desired form of the corrosion protection agent. A solid carrier medium can be used in dry powders, granules, tablets, encapsulated products, and combinations thereof. Suitable solid carrier media include, but are not limited to, carrier media that are non-active solids at room temperature. For example, any organic polymer, such as polyethylene glycol (PEG), can be used. In certain embodiments, the solid carrier medium may be present in an amount in the range of from about 0.01% to about 20%, or from about 0.01% to about 10%, and as an alternative from about 0.01% to about 5% by weight of the composition. Suitable liquid carrier media include, but are not limited to: water (distilled, deionized or tap water), solvents, and mixtures thereof. The liquid carrier medium may be present in an amount in the range of about 1% to about 90%, or from about 20% to about 80%, and alternatively, from about 30% to about 70% by weight of the aqueous composition. However, the liquid carrier medium can also contain other materials which are liquid, or which dissolve in the liquid carrier medium at room temperature, and which can also serve other functions in addition to that of a carrier. These materials include, but are not limited to: dispersants, hydrotropes, and mixtures thereof. The corrosion protection agent can be provided in a "concentrated" system. For example, a liquid composition The concentrate can contain a smaller amount of a suitable carrier medium, compared to conventional liquid compositions. A suitable content of the carrier medium of the concentrate system may be present in the amount of from about 30% to about 99.99% by weight of the concentrated composition. The dispersant content of the concentrated system may be present in the amount of about 0.001% to about 10% by weight of the concentrated composition. FORM OF THE PRODUCT Any suitable form of the product can be used. Suitable forms of the product include, but are not limited to: solids, granules, powders, liquids, gels, pastes, semi-solids, tablets, water-soluble pouches, and combinations thereof. The corrosion protection agent may also be packaged in any suitable form, for example as part of a treatment system comprising a case, which may comprise (a) a package; (b) an effective amount of a stratified material containing zinc; (c) optionally an auxiliary ingredient; and (d) instructions for use of the corrosion protection agent to reduce corrosion of glassware surfaces. The corrosion protection agent, as part of the treatment system, can be formulated in a single-compartment or multi-compartment water-soluble bag, so as to reduce negative interactions with other components.

The corrosion protection agent suitable for use herein can be dispensed from any suitable device, including, but not limited to: baskets or dispensing vessels, bottles (bottles assisted by pumps, squeeze bottles, etc.). ), mechanical pumps, multi-compartment bottles, capsules, multi-compartment capsules, pulp dispensers, and single-compartment and multi-compartment water soluble bags, and combinations thereof. For example, a multi-stage tablet, a water-soluble or water-dispersible bag, and combinations thereof, may be employed to supply the detergent composition for the entire automatic dishwashing cycle in any suitable solution or substrate. Suitable solutions or substrates include, but are not limited to: hot and / or cold water, washing and / or rinsing solution, hard surfaces, and combinations thereof. The multiphase product can be contained in a single-compartment or multi-compartment water soluble bag. In certain embodiments, a corrosion protection agent may comprise a unit dose permitting controlled release (e.g., delayed, prolonged, trickle, or slow release). The unit dose may be delivered in any suitable form including, but not limited to: tablets, single compartment and multi-compartment water soluble bag, and combinations thereof. For example, the corrosion protection agent can be supplied as a unit dose in the form of a multiphase product comprising a solid (such as granules or tablets) and a liquid and / or gel can be separately provided in a multi-compartment water soluble bag. MANUFACTURING PROCESS Any suitable process having any number of suitable process steps can be employed in order to manufacture the corrosion protection agents in any suitable form (for example solids, liquids, gels). The corrosion protection agent can be formulated with any suitable amount of the ZCLM in any suitable form either alone or in combination with an auxiliary ingredient. The ZCLM can be non-brittle, water-soluble or water-dispersible and / or can be dissolved, dispersed and / or melted in a temperature range from about 20 ° C to about 70 ° C. The corrosion protection agent can be manufactured in the form of a powder, granule, crystal, core particle, aggregate of core particles, agglomerate, particle, flake, extruded product, nuggets or as a composite material (e.g., in the form of a composite particle, composite flake, compound extruded product, compound nuggets) , and combinations of these. A corrosion protection agent composed in the form of a composite particle, nugget, flake and / or extrudate can be made separately by mixing particles of the raw material ZCLM in powder form with the desired auxiliary ingredient (such as surfactant). , dispersant polymer and / or carrier medium) in any order. The use of the composite corrosion protection agent tends to reduce the segregation. Therefore, the tendency of the corrosion protection agent to decant or agglomerate in the final product is reduced. Even more, once the composite corrosion protection agent has been supplied during the wash cycle, an improvement in the dispersion of the ZCLM particles in the wash solution is observed. It has also been observed that by supplying an increased dispersion of the ZCLM particles in the wash solution, a considerable improvement in the performance of the action of protection against corrosion of the glassware surface occurs in comparison with the action of using the agent of protection against corrosion that comprises ZCML particles of raw material, in equal levels, without the action of incorporating an auxiliary ingredient. When the aforementioned composite corrosion protection agent comprises one or more carrier components, the carrier component (s) can be heated above their melting points before adding the desired components (such as a ZCLM, and / or an ingredient). assistant). Suitable carrier components for preparing a solidified melt product are usually non-active components that can be heated above their melting temperature to form a liquid, and cooled to form a thermo-molecular matrix that can effectively trap the desired components. The corrosion protection agent can also be incorporated into a powder, granule, tablets and / or solids placed in water-soluble pouch formations by spraying a liquid agent of protection against corrosion (such as a mixture of ZCLM and a liquid carrier) on the desired components, for example solid base detergent granules. The liquid carrier can be, for example, water, solvent, surfactant and / or any other suitable liquid, by means of which the corrosion protection agent can be dispersed. The aforementioned dew step can happen at any time during the manufacturing process of the corrosion protection agent. In certain embodiments, by mixing and / or directly dispersing ZCLM particles of raw material in a liquid carrier or liquid composition, a liquid corrosion protection agent can be made. The ZCLM can be dispersed in water (and / or solvent) before the addition of other desired components. When a liquid corrosion protection agent is placed in a dispenser such as a water soluble bottle or bag, sufficient dispersion of the ZCLM in the liquid can be achieved by stabilizing the corrosion protection agent in the composition, alone or in combination with a suitable auxiliary ingredient, without the need to elaborate the particle, pip, flake and / or compound extruded product mentioned above. Another non-limiting embodiment comprises the process steps of forming a molten corrosion protection agent by mixing an effective amount of the ZCLM in a molten carrier medium (such as polyethylene glycol). This molten corrosion protection agent can then be sprayed, for example, on granules, powders and / or tablets, if desired.

Another non-limiting mode is directed to a process for forming a solid corrosion protection agent. This process is used for granules, powders, tablets and / or solids placed in water soluble bags. The process allows the fused corrosion protection agent described above to cool in a solid before it is crushed into a desired shape and particle size (ie, a composite particle, nugget, or flake). Optionally, one or more auxiliary ingredients may be added in any amount, form or order to the molten carrier medium before the cooling step. The molten mixture can also be extruded to form an extruded compound, and then cooled and crushed to a desired shape and particle size. These ground mixtures form the desired corrosion protection agent, and can be supplied in a wide range of applications (i.e., alone or in combination with automatic dishwashing detergent compositions) in one or more of the above-mentioned ways to promote optimal corrosion protection performance on treated glassware surfaces . RESULTS OF THE TEST The results of several tests on corrosion protection agents are presented in Tables I-IX and Figure 2. Luminescence and etching tests were carried out under the same conditions using the same or similar substrates. (for example, glass, sliding glass and / or dishes) unless otherwise indicated. In each test, the substrate was washed for 50 to 100 cycles in a General Electric washing machine Model GE2000, under the following washing conditions: water of 0 gpg - 54 ° C (130 ° F), regular wash cycle, with the hot drying cycle being on. The following substrates are placed on the upper shelf of the GE 2000 dishwashing machine: four (4) Collins glassware Libbey 53, not heat treated, of 300 mL (10 oz); three (3) white wine glasses brand Libbey 8564SR Bristol Valley 250 mL (8 ½ oz); three (3) glass glasses for Hi Bail English brand Libbey 39, 380 mL (3 oz); three (3) glass cups for drinks brand Luminarc Metro type Cooler, 470 mL (16 oz) or 350 mL, (12 oz) (use only one size per test); one (1) glass of wine brand Longchamp Cristal d'Arques of 170 mL (5¾ oz); and one (1) glass of Anchor Hocking Pooh brand juice (CZ84730B) of 240 mL (8 oz) (when there is one or more designs per box, use only one design per test). On the bottom shelf of the GE 2000 dishwashing machine, the following substrate is placed: two plates (2) of table Libbey Sunray brand no. 15532 of 23.5 cm (9 ¼ inch); and two (2) black ceramic stoneware tableware, Gibson brand no. 3568DP (optionally, if not used, replace with 2 concrete table plates). All vessels and / or dishes are visually classified by iridescence after washing and drying using a rating scale of 1 to 5 (described in general terms below). All glasses and / or plates are also visually classified by engraving signals using the same grading scale from 1 to 5 used in the iridescence test. The values of the Classification scale are as follows: "1" indicates very severe damage to the substrate; "2" indicates severe damage to the substrate; "3" indicates some damage to the substrate; "4" indicates very light damage to the substrate; and "5" indicates no damage to the substrate. The results of the luminescence test are shown in Tables I-III and represent a comparison of the iridescence of the substrate. The results of the engraving test are shown in Tables IV-VII represent a comparison of engraving degrees. The results of the X-ray photoelectron spectroscopy (XPS, x-ray photoelectron spectroscopy) are shown in Table VII and represent a comparison of the deposition of the zinc compound or Zn2 + ion on substrates using hydrozincite.

Table 1 Iridescence of glassware substrates washed 100 cycles with liquid products: Substrate Liquid gel without HZ Liquid gel with 0.1% HZ Libbey 53 glass (4 glasses in 5 average) 1 Glass for B. Valley wine (3 glasses in 5 average) 1 Luminarc glass (3 glasses in 5 average) 1 LC Wine ( 1 glass) 1 5 Sunray dish (2 dishes on average) 1 5 Table l Iridescence of glassware substrates washed 50 cycles with powder products: Table III Iridescence of glassware substrates washed 50 cycles with powder products: Substrate Liquid gel with liquid gel with 0.1% zinc hydroxysulfate zinc hydroxysulfate Hi-Ball English (3 glasses in 3 5 average) Luminarc glass (3 glasses in 3 5 average) Sunray dish (2 dishes in 3 5 average) Table IV Etching glassware substrates washed 100 cycles with liquid gel products: Table V Etching glassware substrate washed 50 cycles with powder products: Substrate Powder with HZ Powder with 0.1% HZ English Hi-Ball (3 glasses on average) 2.5 3.5 B. B. Valley Wine Glass (3 glasses 4.3 4.8 on average) Luminarc Glass (3 glasses in 2.3 3.8 average) Glass for deep juice (1 glass) 2.5 3.5 Table VI Etching glassware substrate washed 50 cycles with liquid gel: Table VII Engraving grades of the addition of different amounts of hydrozincites It is noted that even a small amount of ZCLM (for example 0.1% ZCH and / or 0.1% zinc hydroxysulfate) is sufficient to help maintain the iridescence and also makes possible the considerable benefits of antigraving on the surfaces of glassware treated. The addition of 0.1% HZ in the liquid gel detergent provides approximately 7 ppm active Zn2 + ions in the wash solution.

HIV picture Deposit of zinc on glassware surfaces in the presence of hydrozincite It has also been observed that the addition of a small amount of ZCLM (eg 0.25% HZ) in the formulation produces a deposit of the zinc compound or the Zn2 + ion on glassware surfaces. In this test, it is also observed that the amount of zinc compounds or Zn2 + ions deposited on the glassware surface is not correlated with the number of wash cycles. While not wishing to be bound by any theory, the fact that zinc compounds or Zn2 + ions do not appear to accumulate on glassware surfaces would indicate that a portion of the zinc or Zn2 + ions initially deposited are washed and subsequently removed. replenish with the subsequent washing. The results of XPS resolved at an angle (not shown) indicate that zinc compounds or Zn2 + ions are stratified or incorporated into the treated glassware surface. It also appears that the compounds of Zn2 + ions are practically homogeneous within the first 10 nm of the glassware surface after the wash cycle. Crystal integrity test The crystal integrity test is an indirect measure of the particle crystallinity of the ZCLM. The maximum average total amplitude (FWHM) of the X-ray diffraction pattern reflections (XRD) is a measure of crystallinity imperfections and is a combination of instrumental and physical factors . With similar resolution instruments, crystal imperfections or crystal integrity can be related to the FWHM of the maximums that are sensitive to paracrystalline property. Following this method, crystalline distortion / perfection is assigned to different ZCLM samples. It is found that three maxima (200, -13 ° 2T, 6.9 Á, 111, -22 ° 2T, 4. 0 Á; 510, 36 ° 2T, 2.5 A) are sensitive to distortions in the network, reflection 200 is selected for the analysis. The maximums are individually adjusted by profile using normal algorithms Pearsori VII and Pseudo-Volgt in Jade software 6. 1 per MDI. Each maximum is adjusted by profile 0 times in the definition of the fund and algorithm to obtain the average FWHM with standard deviations. The results of the test are summarized in Table IX.

Table IX Crystallinity The crystallinity seems to be related to the FWHM of its source. Without theoretical limitations of any kind, it is postulated that a lower crystallinity can help to maximize the lability of zinc. Strengthening test results Figure 2 represents a comparison of the strength of the glassware surface using a mirror reflex IR (spectroscopy by specular reflection absorption (IRRAS).) The substrate, a microscopic microscope slide. glass, washed with commonly used detergent compositions using the same washing conditions as those described above in the etch test.The spectra of the microscopic slide were collected as% transmittance spectra in a Digilab Instrument (Bio-Rad) with a precedent harvested from the alignment mirror provided with the SpIitPea accessory (Harrick Scientific Instruments), using a low angle of the incidence of its specular reflectance. Accordingly, the resulting spectra are reflectance spectra. The strengthening of the structure of the glassware surface is correlated with the IR spectral changes in the Si-O stretch vibration region. While not wishing to be bound by any theory, it is considered that the reduction in the stretching vibration of Si-0 by 1050 cm-1 and above in the spectrum of glass treated with a liquid gel detergent composition containing a small amount of a ZCLM (for example 0.1% -1% of HZ) can be attributed to the increase in roughness which is indicative of the strength of the glassware surface, and to a decrease in the number of Si-O bridge links in the raw glass which is indicative of damage to the glassware surface. Very little or no damage (ie, superior strength) was observed on glassware surfaces treated with a liquid gel detergent composition having a small amount of a ZCLM (eg 0.1% -1% HZ) compared to a liquid gel detergent composition without a ZCLM after 50 cycles. Since the addition of a ZCLM to the liquid gel detergent composition results in IRRAS invariable results from the treated glassware surface (i.e. the glassware surface is not damaged), an increase in the strength of the surface of the glass is postulated. glassware. Referring to the polymers described herein, the term weight average molecular weight is the weighted average molecular weight as determined using permeation chromatography in gel in accordance with the protocol found in Colloids and Surfaces A. Physico Chemical & Engineering Aspects, Vol. 162, 2000, pages 107-121. The units are Daltons. The description of all patents, patent applications (and any patents granted thereon, as well as any corresponding applications for published foreign patents) and the publications mentioned throughout this description are considered part of the present reference. . However, it is expressly denied that any of the documents incorporated herein by reference teach or describe the present invention. Any numerical range given in this specification shall include any narrower range falling within the broader numerical range, as if all those more closed numerical intervals had been explicitly annotated in the present. All minimum numerical limits cited in this specification shall include all major numerical limits as if such numerical major limits had been explicitly quoted herein. All numerical ranges cited in this specification shall include all minor intervals that fall within the larger numerical ranges as if all minor numerical intervals had been explicitly quoted in the present. Although particular embodiments of the present invention have been described, it will be obvious to persons with experience in the industry that they can make various changes and modifications to the present invention without deviating from the spirit and scope thereof. It is clear to those skilled in the industry that various changes and modifications can be made without departing from the scope of the invention and that it should not be considered limited to the embodiments and examples described in the specification.

Claims (20)

1. NOVELTY PE THE INVENTION CLAIMS 1. A domestic, institutional, industrial and / or commercial method for reducing corrosion on glassware surfaces in an automatic dishwasher, characterized in that it comprises the step of contacting a glassware surface with a corrosion protection agent comprising: a) an effective amount of a stratified material containing zinc; and b) optionally an auxiliary ingredient. The method according to claim 1, further characterized in that the layered zinc-containing material comprises a component selected from the group comprising basic zinc carbonate, zinc and copper hydroxycarbonate, hydroxy double salts wherein the metal is only zinc, phyllosilicate containing Zn2 + ions, zinc hydroxyacetate, zinc hydroxycarbonate, zinc hydroxychloride, zinc and copper hydroxycarbonate, zinc hydroxy lauryl sulfate, zinc hydroxynitrate, zinc hydroxysulfate, and mixtures thereof. 3. The method according to claim 2, further characterized in that the stratified material containing zinc is zinc hydroxycarbonate having the formula: 3Zn (OH) 2.2ZnC03 or Zn5 (OH) 6 (C03) 2. 4. The method according to claim 2, further characterized in that the stratified material containing zinc is zinc and copper hydroxycarbonate. The method according to claim 2, further characterized in that the layered zinc-containing material is basic zinc carbonate having the formula: [ZnC03] 2. [Zn (OH2] 3. 6. The method according to claim 2, further characterized in that the stratified material containing zinc is zinc hydrochloride 7. The method according to claim 2, further characterized in that the stratified material containing zinc is zinc hydroxyinitrate 8. The method according to claim 2, further characterized in that the stratified zinc-containing material is zinc hydroxysulfate 9. The method according to claim 2, further characterized in that when an auxiliary ingredient is combined to form a compound corrosion protection agent, the layered zinc containing is present from about 0.001% to about 10% by weight of the composition. 10. The method according to claim 1, further characterized in that the stratified material containing zinc has a range of average particle size from about 10 nm to about 100 microns. 11. The method according to claim 1, further characterized in that the zinc compounds or Zn2 + ions are present on the surface of the glassware surfaces treated in a range of about 1 nm to about 1 miera after the wash cycle. 12. The method according to claim 1, further characterized in that the zinc compounds or Zn2 + ions are present on the surface of the glassware surfaces treated in a range of about 1 nm to about 100 microns after the wash cycle. 13. A method at the domestic, institutional, industrial and / or commercial level to employ a treatment system to reduce the corrosion of glassware surfaces in automatic dishwashers; The method is characterized in that it comprises the step of contacting a glassware surface with a corrosion protection agent; wherein the treatment system comprises a case which in turn comprises: (a) a package; (b) a corrosion protection agent for treating glassware surfaces; the corrosion protection agent comprises an effective amount of a stratified material containing zinc; (c) optionally an added ingredient; e (d) instructions for use of the corrosion protection agent. 14. The method according to claim 13, further characterized in that the stratified material containing zinc comprises a component selected from the group comprising basic zinc carbonate, zinc and copper hydroxycarbonate, hydroxy double salts wherein the metal is only zinc, phyllosilicate containing Zn 2+ ions, zinc hydroxyacetate, zinc hydroxycarbonate, zinc hydroxychloride, zinc and copper hydroxycarbonate, zinc hydroxy lauryl sulfate, zinc hydroxy nitrate, zinc hydroxysulfate, and mixtures thereof. The method according to claim 13, further characterized by one or more of the following: a) when the corrosion protection agent combines an auxiliary ingredient to form a composite corrosion protection agent, the laminated material containing zinc is present from about 0.001% to about 10% by weight of the composition; b) the stratified material containing zinc has a range of average particle size from about 10 nm to about 100 microns; c) Zinc compounds or Zn2 + ions are present on the surface of the glassware surfaces treated in a range of about 1 nm to about 1 miera after the wash cycle; or d) zinc compounds or Zn 2+ ions are present on the surface of the glassware surfaces treated in a range of about 1 nm to about 100 nm after the wash cycle. 16. A method at the domestic, institutional, industrial and / or commercial level to use a composition of matter in an automatic dishwasher to reduce the corrosion of glassware surfaces; the method is characterized in that it comprises the step of contacting a glassware surface with a washing solution; wherein the wash solution comprises a corrosion protection agent comprising from about 0.0001 ppm to about 100 ppm of the zinc-containing stratified material, and optionally an auxiliary ingredient, in the wash solution during at least some part of the cycle washing in the automatic dishwasher. 17. The method according to claim 16, further characterized in that the washing solution comprises an auxiliary ingredient; and wherein the wash solution comprises from about 0.001 ppm to about 50 ppm of a layered material containing zinc in the wash solution. 18. The method according to claim 17, further characterized in that the stratified material containing zinc is zinc hydroxycarbonate having the formula: 3Zn (OH) 2.2ZnC03 or Zn5 (OH) 6 (C03) 2. 19. A process for manufacturing a protective agent against domestic, institutional, industrial and / or commercial corrosion; The process is characterized in that it comprises one of the following steps: a) provide, combining and mixing an effective amount of a stratified material containing zinc, and optionally an auxiliary ingredient; b) forming a liquid premix comprising an effective amount of a layered zinc-containing material, and optionally an auxiliary ingredient, by mixing the stratified material containing zinc in a liquid carrier, and spraying the liquid premix onto one or more of the liquid premixes. following components: an active detergent or an auxiliary ingredient, in any order; c) mixing an effective amount of a stratified material containing zinc, and optionally, an auxiliary ingredient, in a molten carrier medium, and spraying the molten mixture onto one or more of the following components: an active detergent or an auxiliary ingredient, in any order; d) mixing an effective amount of a stratified material containing zinc, and optionally an auxiliary ingredient in a molten carrier medium, allowing the molten mixture to cool in a solid compound, grinding the solid into particulate, flake and / or compound nuggets, and dispersing the compounds in one or more of the following components: an active detergent or an auxiliary ingredient, in any order; oe) mixing an effective amount of a stratified material containing zinc, and optionally, an auxiliary ingredient, in a molten carrier medium, extruding the molten mixture to form an extruded compound, cooling and grinding the extruded product into particles, flakes and / or compound nuggets, and disperse the compounds in one or more of the following components: an active detergent or an auxiliary ingredient, in any order. 20. The process according to claim 19, further characterized in that the composition comprises a particle, flake, nugget and / or composite extruded product which in turn comprises a layered material containing zinc and an auxiliary ingredient.