MXPA01001021A - Particulate compositions having a plasma-induced, graft polymerized, water-soluble coating and process for making same - Google Patents

Abstract

A composition having a plasma-induced, graft polymerized, water-soluble coating for controlling solubility, chemical stability and physical properties is disclosed. A process for making such a composition is also disclosed which involves subjecting a particulate material to plasma after which a water-soluble organic monomer is graft polymerized onto at least a portion of the particulate material. The compositions are particulate or non-particulate in form and can be used in shampoos, skin care and other cosmetic products, deodorant products, laundry, dishwashing, carwashing or other similar detergent products.

Description

PARTICULAR COMPOSITIONS THAT HAVE A COATING SOLUBLE IN WATER, POLYMERIZED BY GRAFT, INDUCED BY PLASMA AND PROCEDURES TO PREPARE THE SAME FIELD OF THE INVENTION The present invention relates in general to particulate compositions, and more particularly, to particulate compositions having a plasma-induced, water-soluble, graft-polymerized coating. The particulate compositions can be used in shampoos, skin care products and other cosmetic products, deodorant products, in laundry applications, dishwashing, car washing and other similar applications. The water-soluble, plasma-grafted polymer-soluble coating can control solubility, dispersion, flowability, can increase chemical stability or can be a functional additive for the particulate composition. The invention also provides a method for making such particulate compositions with graft polymerized, plasma-induced coating.

BACKGROUND OF THE INVENTION Currently, formulators of various cosmetic, laundry, dishwashing, shampoo, and other compositions containing particulate matter face numerous problems that impede the delivery of the active ingredients and obtain the full benefit of all the ingredients in such compositions. By way of example, recent low-dosage or "compact" detergent products experience dissolution problems, especially in laundry solutions at cold temperatures, (i.e. at temperatures less than about 30 ° C). More specifically, the low dissolution results in the formation of "lumps" which appear as solid masses of white color remaining in the washing machine or in the washed clothes after the conventional washing cycles. These "lumps" prevail in a special way under washing conditions in cold temperature and / or when the order of addition to the washing machine is first the laundry detergent, then the laundry and the last water (commonly known as "Order of Addition"). Inverse "or" ROOA "). In the same way, this phenomenon of lumping can contribute to an incomplete supply of detergent in washing machines equipped with dispenser drawers or in other dispensing devices, such as a granulette. In this case, the undesired result is an undissolved detergent residue in the dispensing device.

Another similar problem with detergent compositions, especially granular laundry and dishwashing detergents, is the degradation of physical properties through the extended storage period. More particularly, spray-dried granules and other particulate detergent ingredients have a tendency to form a "cake" while stored in the detergent box, especially under high humidity conditions. Such "cake formation" is unacceptable to consumers and can lead to difficulties in "spooning" or otherwise removing the detergent from the box in which it is contained. This problem can also result in improper dosing of the laundry solution resulting in reduced cleaning performance. Other problems include chemical instability of the detergent composition and difficulty in dispersing the polymers in the wash solutions. To date, detergent formulators have tried unsuccessfully to solve or minimize all the aforementioned problems, and they continue to seek suitable solutions that do not affect other properties of the detergent composition. Accordingly, despite prior descriptions in the art, there is a need for compositions, and a process for making such compositions, that have improved physical properties, solubility and / or chemical stability.

BRIEF DESCRIPTION OF THE INVENTION The invention meets the needs identified above by providing a composition having a water-soluble coating, induced by plasma, polymerized by grafting to control the properties of solubility, chemical and physical stability. The invention also provides a method for making a composition as such which involves subjecting a particulate material to a luminescent zone of plasma to form free radicals on the surface, after which a hydrophilic organic monomer is introduced in such a way that it finally deposits on the particulate material by graft polymerization to form a water soluble coating. The plasma luminescent zone is contained in a plasma chamber and operates at selected energies and pressures so as not to destroy or otherwise alter the functionality or stability of the coating of the particulate material being coated. In accordance with one aspect of the invention, a composition is provided. The composition comprises a particulate material having at least a portion having a water-soluble, plasma-induced, graft-polymerized coating, in which the water-soluble coating is formed by ionizing gas in a plasma chamber to form radicals Free on the portion of the particulate material after which an organic hydrophilic monomer is deposited on the portion of the particulate material, by graft polymerization, so as to form the water-soluble coating on the portion of the particulate material. In accordance with even another aspect of the invention, a process for producing a water soluble composition is provided. The procedure comprises the steps of: (a) providing a particulate material; (b) subjecting at least a portion of the particulate material to a plasma luminescent zone in which a gas is ionized to form free radicals on the portion of the particulate material, whereby the luminescent areas of plasma are contained in a chamber of plasma operating at a pressure from about 1 mTorr to about 300 Torr and at an energy from about 0.1 Watts to about 500 Watts; (c) introducing a water-soluble hydrophilic organic monomer into the chamber after step (b) in such a way that the organic hydrophilic monomer reacts with the free radicals on the portion of the particulate material so as to form a water-soluble coating on the portion of the particulate material. As the present invention is used, the "plasma luminescent zone" is the space or region in which plasma is generated using electricity, such as the space between two electrodes in a vacuum chamber for plasma. As the present invention is used, the phrase "plasma chamber" or "vacuum chamber for plasma" includes or may be modalized in fluidized beds, rotating drums, vibrating belts and other similar apparatuses. All percentages, ratios and proportions used in the present invention are by weight, unless otherwise indicated. All documents including patents and publications cited in the present invention are incorporated therein for reference. Accordingly, it is an advantage of the invention to provide a composition having improved physical properties, solubility and / or chemical stability. It is also an advantage of the invention to provide a method for producing such compositions in a convenient form. These and other advantages and features of the present invention will become apparent to those skilled in the art from a reading of the following detailed description of the preferred embodiments and the appended claims.

DETAILED DESCRIPTION OF THE PREFERRED MODALITY In essence, the invention is directed to particulate and non-particulate compositions having a water soluble coating, induced by plasma, polymerized by grafting. In the preferred modes of the invention, the particulate material is selected from water insoluble particles such as those used in cosmetic and shampoo compositions, soluble particles such as spray-dried granules, agglomerates and mixtures thereof which are typically used. in detergent compositions. The non-particulate compositions of the present invention can also be used in laundry or dishwashing, for example, as a tablet, block, cylinder, sheet, bucket or other non-particulate configuration for laundry or dishwashing. The graft polymerization of the water soluble coating by exposing the particulate or non-particulate material to an organic hydrophilic monomer after the particulate or non-particulate material is subjected to plasma. It is essential for the step of graft polymerization process that the organic monomer be introduced after the plasma has been generated in the plasma chamber. Preferably, the water-soluble coating is formed from an organic hydrophilic monomer, which is even more preferably selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, maleates, fumarates, vinyl ethers and mixtures thereof. same. More preferably, the organic monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, N, N-dimethylacrylamide, acrylic acid, methacrylic acid and mixtures thereof. Most preferably, the organic monomer is acrylic acid. The water soluble coating is on at least a portion of the compositions described in the present invention. "At least one portion" means that at least 1%, preferably 90% to 100% of the particulate or non-particulate composition has a water-soluble coating. It should be understood that not all of the composition needs to be coated to be within the scope of the invention. For that purpose, a plasma coating process is used to place the water soluble coating on the composition. As detailed later in the present invention, this is achieved by ionizing a gas, such as argon, using high frequency electricity in a plasma vacuum chamber. Suitable gases can be selected from the group consisting of argon, helium, oxygen, nitrogen and mixtures thereof. As used in the present invention, the phrase "plasma-induced, graft-polymerized" means that which has been deposited, coated or otherwise stratified using one or more of the plasma graft deposition techniques in which the material to be deposited reacts, grafts, adheres, binds or in some other way binds to the free radicals formed on the surface of the material during the generation of plasma in a plasma chamber. Typical plasma cameras will have a "plasma luminescent zone" which can be the region between the two electrodes used to generate the high frequency electricity, and therefore the plasma between them. The pressure inside the plasma chamber is typically maintained at a pressure of about 5 mTorr to about 300 Torr, preferably from about 10 mTorr to about 1 Torr, and more preferably from about 50 mTorr to about 250 mTorr. The power used in the plasma chamber is selected to be from about 0.1 Watts to about 500 Watts, more preferred from about 0.5 Watts to about 100 Watts, and most preferably from about 1 Watt to about 10 Watts. This application of a high frequency electric field to a gas to form a plasma of gas ions is a known technique which is used in the polymerization of monomers such as organic hydrophilic monomers which are suitable for use in the present invention to form the water soluble coating on the detergent composition. This technique has been described, for example, in Luster, patent E.U.A. No. 2,257,177. In general, this involves the continuous contact of the polymerizing monomer in the vapor phase with the gas plasma until the graft polymerization is substantially completed on the substrate. This technique tends to form an interlaced product as suggested by the patent E.U.A. No. 3,287,242. Due to the high entanglement associated with plasma polymerization, said technique is generally employed for the purpose of forming thin films or water insoluble coatings instead of the water soluble coating currently contemplated by the present invention. The activation is confined to a region near the surface of the substrate in which the bonds and interlacing are formed. A modification of the film / coating formation techniques in which the monomer is directly polymerized from the gaseous state is described in Knox et al, U.S. Pat. No. 3,475,307. In that document, the substrate is cooled so that a thin layer of liquid monomer condenses on the substrate in order to increase the polymerization rate. However, in this technique, the person skilled in the art should avoid the "excessive" condensation of the monomer on the surface, since otherwise incoming activated molecules from the gas phase will not reach the monomer removed from the gaseous liquid interface. which has been established causes a coating of poor adherence (col.10, lines 54-60). It is indicated that the order of magnitude of the monomer condensed before the polymerization is a few molecules in thickness (col 4, lines 1-4). Another plasma coating technique is to initiate polymerization using an ionized gas plasma that is not in equilibrium and to complete most of the polymerization in the absence of the plasma. In this way, a high molecular weight polymer is formed. The formation of the ionized gas plasma can be achieved in any of the known techniques for producing said plasmas. For example, see J.R. Hollahan and A.T. Bells, eds., "Techniques of Applications of Plasma Chemistry", Wíley, New York, 1974 and M Shen, ed. "Plasma Chemistry of Polymers", Marcel Dekker, New York, 1976. In one technique, a gas that can be ionized is contained under vacuum between parallel plate electrodes connected to a radio frequency generator sold by International Plasma Corporation under the designation " Model 3001". Plasma can be created with such parallel plates whether they are outside or inside the plasma chamber. In another technique, an external induction coil creates an electric field that produces the ionized gas plasma. In yet another technique, the electrode points with opposite charges are placed directly in the plasma vacuum chamber in separate relation to create the plasma. Any plasma formed by these techniques or any other in which an electric field generates an electric conduction path entirely within the gas phase is suitable for use in the invention. As used herein, the term "plasma" should be distinguished from any liquid or solid environment in which an electric field is applied to create ions in a path through the solid or liquid. This does not exclude the possibility that an electric field could also be applied through the non-vaporized monomer. However, if so, it is believed that it would not have any beneficial function; rather, it would be strange for plasma in the vapor phase. The operating parameters for the plasma vary from monomer to monomer. In general, it is preferable to use reduced gas pressures to form a luminescent discharge by releasing electrons which causes gas phase ionization. When a plasma is created in a chamber at a pressure below atmospheric pressure, plasma is formed when the potential between electrodes exceeds a threshold value that is sufficient to ionize or "disintegrate" the gas. This is a function of the composition of the gas, its pressure and the distance between the electrodes. After disintegration, the gas has conductivity and a stable plasma can be maintained through a wide range of currents. Although the exact composition of the plasma is unknown, it is believed to include electrons, ions, free radicals, and other reactive species. In a related procedure, the creation of active sites on the substrate or on the particulate material can be facilitated by direct activation of the ionized gas. For this purpose, the presence of any gas that can be ionized under the conditions prevailing in the plasma can be used. For example, water vapor can be ionized to create active polymerization sites for some monomers. Other gases that could be ionized by such plasmas include hydrogen chloride, carbon tetrachloride and inert gases such as helium or argon. Those gases that can be ionized in the plasma are well known to those skilled in the art. The monomer to be deposited can be in an essentially pure monomeric state or in solution. In the latter case, organic or inorganic solvents can be used that can complete the dissolution of the monomer. Typical organic solvents for some monomers include benzene and acetone. For any given plasma deposition technique such as those described in the present invention, the method may involve the use of high frequency microwaves to ionize the gas in the plasma chamber. Alternatively, high frequency radio waves or direct current electricity can be used to ionise, for example, the gas between two electrode points with opposite charges used to define the plasma luminescent zone in a plasma vacuum chamber. Another option is to pulse or in some other way intermittently ionize the gas in the plasma luminescent zone in the plasma chamber so that the plasma-induced deposition of the monomer on the particulate detergent material can be controlled. In the process of the present invention, additional control of plasma induced deposition can be achieved by placing the particulate detergent material which will be coated with the hydrophilic monomer outside the plasma luminescent zone. Alternatively or additionally, the water-soluble hydrophilic monomer can likewise be introduced outside the plasma luminescent zone to provide additional control of the deposition. The particulate or non-particulate material that will subsequently be subjected to the plasma is then exposed (ie, after the plasma has been generated in the plasma chamber) to a hydrophilic organic monomer that will eventually be polymerized by grafting onto at least a portion of the surface of the particulate or non-particulate material. The so-called "graft polymerization" is known and has been used in the art with many graft copolymers such as ABS resins (acrylonitrile-butanedi-styrene) which have achieved considerable commercial success. It is also known in the art that various vinyl monomers can be polymerized onto polymeric substrates that have been first treated with ionizing radiation in the presence of oxygen or ozone to form peroxy groups on the surface of said substrates. The E.U.A. Nos. 3, 008,920 and 3,070,573 teach how to graft selected monomers onto surfaces containing ozone. However, problems have arisen when such polymerization is performed by grafting. For example, a serious complication involves the graft polymerization of the vinyl monomer on the substrate as desired, but with the simultaneous and unwanted homopolymerization or crosslinking of the vinyl monomer, which leads to a water insoluble coating. In contrast, the present invention relates to a composition and method for modifying the surface characteristics of a particulate substrate with minimum crosslinking to obtain a water soluble coating. In that sense, it is important to operate the plasma chamber at the selected power and pressure levels described previously. Typically, graft polymerization of the organic monomer will take from about 1 minute to about 40 minutes, preferably from 10 minutes to about 30 minutes. The organic monomer may be in the form of a liquid, a solid, or a solid / liquid mixture. For the liquid monomer, the monomer vapor is supplied by evaporating the monomer in the plasma which is facilitated by the application of vacuum. Similarly, for the solid monomer, such free radicals and / or ions are supplied by sublimated monomer vapor. To make the description simpler, the non-vaporized monomer to be activated will be described in the present invention as being in the liquid state unless otherwise specified.

Water Soluble Coating As previously mentioned, the water soluble coating is formed from an organic hydrophilic monomer, some of which were mentioned above. The compositions preferably comprise an effective amount of said monomer to achieve the desired solubility, flowability and / or chemical stability of the particulate or non-particulate composition. In typical formulations, the coating that is formed from the grafted monomer in the particulate or non-particulate composition will have a thickness in the range of about 0.01 microns to about 1000 microns, more preferred of about 0.05 microns to about 50 microns and yet most preferred from about 0.1 microns to about 10 microns. Suitable organic hydrophilic monomers generally include conventional water-soluble vinyl monomers such as: acrylates and methacrylates of the general structure. wherein R 2 is hydrogen or methyl and R 3 βs is hydrogen or an aliphatic hydrocarbon group of up to 10 carbon atoms substituted with one or more water solubilizing groups such as carboxy, hydroxy, amino, lower alkylamine, lower dialkylamino, an oxide group, polyethylene having from two to about 100 repeating units, or substituted with one or more sulfate, phosphate, sulfonate phosphonate, carboxamido, sulfonamido or phosphonamido groups, or mixtures thereof; acrylamides and methylacrylamides of the formula: in which R2 and R3 are as previously defined; acrylamides and methylacrylamides of the formula.

H2C = C-CON (R4) 2 wherein R is lower alkyl of 1 to 3 carbon atoms and R 2 is as defined above; maleates and fumarates of the formula. in which R3 is as previously defined; vinyl ethers of the formula.

H ^ CH-O-F ^ in which R3 is as previously defined; vinyl aliphatic compounds of the formula R2CH-CHR3 in which R2 is as defined above and R3 is as defined above with the proviso that R3 is different from hydrogen; and vinyl substituted heterocycles, such as vinylpyridines piperidines and imidazoles and N-vinylactams such as N-vinyl-2-pyrrolidone. Included among the useful water soluble monomers are: 2-hydroxyethyl-, 2-hydroxypropyl- and 3-hydroxypropyl-, 2,3-dihydroxypropyl-, polyethoxyethyl-, and polyethoxypropyl acrylates, methacrylates, acrylamides and methacrylamides; acrylamide, methacrylamide, N-methylacrylamide, N-methylmethacrylamide, N, N-dimethylacrylamide, N, N-dimethylmethacrylamide; N, N-dimethyl- and N, N-diethyl-aminoethyl acrylate and methacrylate and the corresponding acrylamides and methacrylamides; 2-vinylpyridine and 4-vinoilpridine; 4-methyl-5-vinylpyridine and 2-methyl-5-vinylpyridine; N-methyl-4-vinylpiperidine; 2-methyl-1-vinylimidazole; N, N-dimethylalylamine; dimethylaminoethyl vinyl ether, N-vinylpyrrolidone; acrylic and methacrylic acid; itaconic, crotonic, fumaric and maleic acids and the lower hydroxyalkyl monoesters and diesters thereof, such as fumarate and 2-hydroxyethyl maleate, sodium acrylate and methacrylate; maleic anhydride; 2-methacryloyloxyethyl sulfonic acid and alisulfonic acid. Preferred water soluble monomers include 2-hydroxyethyl methacrylate; N, N-dimethyl acrylamide; acrylic acid and methacrylic acid; and more preferred 2-hydroxyethyl methacrylate.

DETERGENT COMPONENTS The particulate and non-particulate compositions described in the present invention may be in the form of detergent compositions which preferably comprise a detersive surfactant and a builder, and optionally, a variety of common detergent ingredients. The surfactant system of the detergent composition can include surfactants of the anionic, nonionic, zwitterionic, ampholytic and cationic types and compatible mixtures thereof. The detergent surfactants are described in the patent E.U.A. 3, 664,961, Norris, issued May 23, 1972, and in the patent E.U.A. 3,919,678, Laughiin et al., Issued December 30, 1975, both incorporated herein by reference. Cationic surfactants include those described in the U.S.A. 4,222,905, Cockrell, issued September 16, 1980, and in the patent E.U.A. 4,239,659, Murphy, issued December 16, 1980, both incorporated in the present invention for reference. Non-limiting examples of surfactant systems include the conventional CnC-β8 alkylbenzenesulfonates ("LAS") and Ci6-C or, branched chain randomized primary alkyl sulfates ("AS"), the secondary alkyl sulfates (2,3) C? 0-C? 8 of the formula CH3 (CH2) x (CHOS03"M +) CH3 and CH3 (CH2) and (CHOSO3" M +) CH2CH3 where x and (y +1) are integers of at least 7, preferably at least about 9, and M is a cation soluble in water, especially sodium, unsaturated sulfates such as oleyl sulfate, the alkylalkoxy sulfates of C-io-C-is ("AEXS"; especially ethoxysulfates EO 1-7), alkylalkoxycarboxylates of C 10 -C 8 (especially ethoxycarboxylates, EO 1 -5), glycerol ethers of C 0 -C 8, alkyl polyglucosides of Cío-Cía and their corresponding sulphated polyglycosides, and esters of alpha-sulfonated fatty acid of C? 2-C? 8. If desired, conventional non-ionic and amphoteric surfactants such as alkylethoxylated ("AE") of C? -C? 8 including the so-called narrow-spiked alkylkylated and C6-C- alkylphenylatedkoxylated | (especially ethoxylates and ethoxy / mixed propoxy), C-betaines? -C18 and sulfobetaines ("sultaines"), amine oxides of C-? O-C? 8 and the like, can also be included in the surfactant system. The C10-C18 N-alkyl polyhydroxyl fatty acid amides may also be included. Typical examples include the N-methylglucamides of C? .2-C-? 8. See WO 9,206,154. Other surfactants derived from sugar include the N-alkoxy polyhydric acid fatty acid amides, such as N- (3-methoxypropyl) glucamide of C-? Or-C-? 8. The N-propyl to N-hexylglucamides of C? 2-C? 8 can be used for low foaming. Conventional C? O-C20 soaps can also be used. If high foaming is desired, branched-chain C-10-C16 soaps can be used. Mixtures of anionic and nonionic surfactants are especially useful. Other useful conventional surfactants are listed in standard texts. The detergent composition can, and preferably includes a builder. The detergency builders are generally selected from the various water soluble, alkali metal, ammonium or substituted ammonium phosphates, polyphosphates, phosphonates, polyphosphonates, carbonates, silicates, borates, polyhydroxysulfonates, polyacetates, carboxylates and polycarboxylates. The salts, especially sodium, of alkali metal of the above are preferred. Preferred for use in the present invention are phosphates, carbonates, silicates, fatty acids of C-? Or-C-? 8, polycarboxylates and mixtures thereof. More preferred are sodium tri-phosphate, tetrasodium pyrophosphate, citrate, tartrate mono- and di-succinates, sodium silicate and mixtures thereof (see below). Specific examples of inorganic phosphate builders are tripolyphosphate, pyrophosphate, sodium and potassium polymeric metaphosphate having a degree of polymerization of about 6 to 21 and orthophosphates. Examples of polyphosphonate builders are the sodium and potassium salts of ethylene diphosphonic acid, the sodium and potassium salts of 1-hydroxy-1,1-diphosphonic acid and the sodium and potassium salts of ethane, , 1, 2-triphosphonic. Other phosphorus detergency builders are described in U.S. Patents 3,159,581; 3,213,030; 3,422,021; 3,422,137; 3,400,176 and 3,400,148, all incorporated by reference in the present invention. Examples of inorganic builders that do not contain phosphorus are carbonate, bicarbonate, sesquicarbonate, tetraborate decahydrate of sodium and potassium, and silicates having a weight ratio of SiO2 to alkali metal oxide of about 0.5 to about 4.0, preferably around 1.0 to about 2.4. The water-soluble, non-phosphorus-containing organic builders useful in the present invention include the various alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates and polyhydroxy sulphonates. Examples of polyacetate and polycarboxylate builders are the sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylene diamine tetraacetic acid, triacetic nitrile acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids and citric acid.

Polymeric polycarboxylate builders are indicated in U.S. Patent 3,308,067, Diehl, issued March 7, 1967, the disclosure of which is incorporated herein by reference. Such materials include the water-soluble salts of homo- and co-polymers of aliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconic acid, fumaric acid, aconitic acid, citronconic acid and methylenemalonic acid. Some of their materials are useful as the water-soluble anionic polymer as described hereinafter in the present invention, but only if it is in an intimate mixture with the non-soap anionic surfactant. Other polycarboxylates suitable for use in the present invention are the polyacetal carboxylates described in US Patent 4,144,226, issued March 13, 1979 to Crutchfield et al., And US Patent 4,246,495, issued March 27, 1979 to Crutchfield. et al., both incorporated in the present invention as reference. These polyacetal carboxylates can be prepared by putting together a glyoxylic acid ester and a polymerization initiator under the polymerization conditions. The resulting polyacetal carboxylate ester is attached to groups of chemically stable ends to stabilize the polyacetal carboxylate against rapid depolymerization in alkaline solution, converted to the corresponding salt, and added to a detergent composition. Particularly preferred polycarboxylate builders are ether carboxylate builders comprising a combination of tartrate monosuccinate and tartrate disuccinate described in US Pat. No. 4,663,071, Bush et al., Issued May 5, 1987, the description of which is incorporated by reference. it is incorporated in the present invention as a reference. The water-soluble silicate solids represented by the formula SiO2 »M20, M being an alkali metal and having a weight ratio of SiO2: M20 of about 0.5 to about 4.0, are useful salts in the detergent granules of the invention at surrounding levels from 2% to about 15% on an anhydrous basis, preferably from about 3% to about 8%. Anhydrous or hydrated particulate silicate can also be used. Any number of additional ingredients can also be included as components in the granular detergent composition. These include other detergency builders, bleaches, bleach activators, foam enhancers or foam suppressors, anti-rust and anti-corrosion agents, soil suspending agents, soil release agents, germicides, setting agents of pH, alkalinity sources not detergent builders, chelating agents, smectite clays, enzyme stabilizing agents and perfumes. See the patent of E.U.A. 3,936,537, issued February 3, 1976 to Baskerville, Jr. et al, incorporated herein by reference. Bleach agents and activators are described in the US patent. 4,412,934, Chung et al, issued November 1, 1983, and in the U.S. patent. 4,483,781, Hartman, issued November 20, 1984, which are incorporated by reference in the present invention. Chelating agents are also described in the patent of E.U.A. 4,663,071, Bush et al, from column 17, line 54, to column 18, line 68, incorporated herein by reference. Foam modifiers are also optional ingredients, and are described in the U.S. Patents. 3,933,672, issued January 20, 1976 to Bartoletta et al, and 4,136,045, issued January 23, 1979 to Gault et al., Both incorporated herein by reference. Smectite clays suitable for use in the present invention are described in the U.S.A. 4,762,645, Tucker et al., Issued August 9, 1988, column 6, line 3, column 7, line 24, incorporated herein by reference. Other detergency builders suitable for use in the present invention are listed in the Baskerville patent, column 13, line 54, column 16, line 16, and in the U.S. patent. 4,663,071, Bush et al., Issued May 5, 1987, both incorporated herein by reference.

Cosmetic components The compositions of the present invention may also be in the form of cosmetic compositions, or components thereof. Typically, said compositions contain insoluble particles at levels of from about 0.1% to about 20%, more preferably from about 0.25% to about 15%, and more preferably from about 0.5% to about 10%, based on the weight of the total composition. Said insoluble particles are useful for increasing the cleaning effect, when the compositions of the present invention are in the form of a cleaning composition. The term "insoluble", as used in the present invention, means that the particles are essentially insoluble in the compositions of the present invention. In particular, the insoluble particles must have a solubility of less than about 1 gram per 100 grams of the composition at 25 ° C, preferably less than about 0.5 grams per 100 grams of the composition at 25 ° C, and more preferably less than approximately 0.1 grams per 100 grams of the composition at 25 ° C. Useful in the present invention are micronized insoluble particles of conventional size. The micronized particles, for the most part, are of a size that is smaller than the tactile threshold, and are essentially non-abrasive to the skin. The particles of conventional size are tactilely perceptible, and are added by the scrubbing and abrasive effect they provide.

Micronized particles have a diameter of average particle size and particle size distribution, so that they are below the tactile perception of most users, and yet they are not too small to be ineffective in facilitating the removal of oil, dust and waste (for example, makeup). It is found in the present invention that particles having an average particle size diameter greater than about 75 microns are tactilely perceived during the cleaning process, and it is important to minimize the amount of these larger particles if it is desired that the particles are not perceived by the user. Conversely, it is found that particles having a diameter of average particle size of less than about 1 to about 5 microns are generally less effective in providing a cleaning benefit. Without being limited by theory, it is thought that the micronized cleaning particles should be of a size that is in order of the thickness of the powder, oil or layer of waste to be cleaned. In most cases, it is thought that this layer will be in the order of a few microns. Therefore, it is found in the present invention that micronized particles should have an average particle size diameter of from about 1 to about 75 microns, more preferably from about 15 to about 60 microns, and most preferred from about 20 to about 50 microns, to provide effective cleaning without being tactilely perceptible. Particles having a wide scale of shapes, surface characteristics and hardness characteristics can be used in the present invention, as long as the particle size requirements are met. The micronized particles of the present invention can be derived from a wide variety of materials, including those derived from inorganic, organic, natural and synthetic sources. Non-limiting examples of these materials include those selected from the group consisting of almond flour, alumina, aluminum oxide, aluminum silicate, apricot kernel powder, atapulguite, barley flour, bismuth oxychloride, boron nitride, carbonate calcium, calcium phosphate, calcium pyrophosphate, calcium sulfate, cellulose, clay, chitin, clay, corn cob meal, corn cob powder, corn flour, corn starch, diatomaceous earth, dicalcium phosphate, dicalcium phosphate dihydrate, fuller's earth, hydrated silica, hydroxyapatite, iron oxide, jojoba seed powder, kaolin, scouring pad, magnesium trisilicate, mica, microcrystalline cellulose, montmorilonite, oat bran, oatmeal, peach bone powder, walnut shell powder, polybutylene, polyethylene, polyisobutylene, polymethylstyrene, polypropylene, polystyrene, polyurethane, nylon, Teflon (ie, polytetrafluoroethylene), polyhalogenated olefins, pumice, rice bran, rye flour, sericite, silica, silk, sodium bicarbonate, sodium silicoaluminate, soy flour, synthetic hectorite, talc, tin oxide, titanium dioxide, tricalcium phosphate, walnut shell powder, wheat bran, wheat flour, starch wheat, zirconium silicate, and mixtures thereof. Also useful are the micronized particles obtained from mixed polymers (e.g., copolymers, terpolymers, etc.), such as polyethylene / polypropylene copolymer, polyethylene / propylene / isobutylene copolymer polyethylene / styrene copolymer, and the like. Typically, polymeric particles and mixed polymeric particles are treated by an oxidation process to destroy impurities, and the like. The polymeric particles and the mixed polymeric particles can also be optionally entangled with a variety of common entanglement agents, non-limiting examples of which include butadiene, divinylbenzene, methylenebisacrylamide, allyl sucrose ethers, allyl pentaerythritol ethers, and mixtures thereof . Other examples of useful mechronized particles include waxes and resins such as paraffins, carnauba wax, ozokerite wax, candelilla wax, urea-formaldehyde resins, and the like. When such waxes and resins are used in the present invention, it is important that these materials be solids at room temperature and skin temperature. Among the preferred micronized and water insoluble particulate materials useful in the present invention are the synthetic polymer particles selected from the group consisting of polybutylene, polyethylene, polyisobutylene, polymethylstyrene, polypropylene, polystyrene, polyurethane, nylon, Teflon, and mixtures thereof. . More preferred are the mechronized polyethylene and polypropylene particles, with the oxidized versions of these materials being especially preferred. Examples of commercially available particles useful in the present invention include the micronized polyethylene waxes ACumist.TM. available from Allied Signal (Morristown, N.J.), available as the A, B, C and D series in a variety of average particle sizes ranging from 5 microns to 60 microns. Preferred are the oxidized polyethylene particles ACumist. TM. A-25, A-30 and A-45 that have an average particle size of 25, 30 and 45 microns, respectively. Examples of commercially available polypropylene particles include the Propyltex series, available from Micro Powders (Dartek). Insoluble particles of conventional size are well known to chemists of formulations in the art. These particles typically have larger particle sizes than the micronized particles described in the present invention. These particles generally have an average particle size diameter that is about 75 microns or greater, which is approximately the tactile threshold described above. These conventional sized particles typically have average particle sizes of up to about 400 microns and greater. These particles can be made from the same materials that are used for the micronized particles just described. Among the preferred conventional sized particulate materials useful in the present invention are the synthetic, polymeric particles from the group consisting of polybutylene, polyethylene, polyisobutylene, polymethylstyrene, polypropylene, polystyrene, polyurethane, nylon, Teflon and mixtures thereof. More preferred are micronized polyethylene and polypropylene particles, with the oxidized versions of these materials being especially preferred. An example of a conventional commercially available particle size is Acuscrub.TM.51, available from Allied Signal (Morristown, NJ.) Having an average particle size of about 125 microns. Other forms of product containing particles coated with plasma according to the invention are also contemplated. As an example, McAtee et al, patent E.U.A. No. 5,665,364, and La Fleur et al, patent E.U.A. No. 5,683,706, describe cosmetic compositions and a variety of particulate ingredients suitable for plasma coating with a water soluble coating according to the invention. The following examples are presented for purposes of illustration only and are not intended to limit the scope of the appended claims in any way.

EXAMPLE 1 A dishwashing tablet having the formula indicated in the following Table 1 was placed on the lower electrode of a plasma discharge unit vacuum chamber (available commercially from APS Inc., Model D). The plasma chamber is depressurized up to 20 mTorr. A mixture of carrier gas (Argon / Oxygen at 1/1 ratio) is continuously introduced into the chamber at a constant velocity (10 ccsm), so that the pressure inside the chamber is maintained at 63 mTorr by equilibrium of continuous evacuation and introduction of the carrier gas. While the above conditions are maintained, low temperature plasma is generated within the chamber for a period of 5 minutes by supplying high frequency power (200 Watts) at a frequency of 40 kHz so as to expose the surface of the tablet to the low temperature plasma. After this, a hydrophilic organic monomer (acrylic acid) is introduced into the chamber at a constant rate to maintain the constant pressure in the chamber at 200 mTorr for 10 minutes during which no plasma is generated and deposited on the tablet. The chamber is evacuated (30 mTorr) and flooded with atmospheric air. The resulting tablet has a water soluble coating formed from the deposited monomer. The solubility in water of the tablet is, unexpectedly, equal to that of the uncoated tablets and superior to that of the coated tablets by means other than plasma deposition.

TABLE 1 (% by weight) EXAMPLES ll-IV Several detergent compositions made according to the invention were coated and in a specific form for washing machines which are loaded on the top with an acrylic monomer. Specifically, a prototype apparatus was configured using a modified rotary evaporator, with a quartz tube of 30.5 cm for the treatment chamber and an external coil electrode wound through a length of 15.25 cm. A 50 gram sample of detergent composition was placed in the plasma luminescent zone, and argon gas was introduced into the plasma chamber which was maintained at 200 m Torr for 15 minutes, at an output of 100 Watts by the inductive coupler system using a radio frequency energy system of 13.6 mHz while at the same time rotating the reactor cylinder at 10 rpm. The detergent compositions are then treated with plasma with oxygen for 15 minutes at the output of 100 Watts by the inductive coupling system using a radiofrequency energy system of 13.6 mHz while rotating the reactor cylinder at 10 rpm. After the plasma treatment, acrylic acid vapor is introduced into the chamber, which is maintained at 500 mTorr and the graft polymerization on the detergent compositions is presented for 20 minutes. The resulting compositions are exemplified below. The base granule is prepared by a conventional spray drying process in which the starting ingredients are formed as a suspension and are passed through a spray-drying tower having a counterflow of hot air (200). 300 ° C) which results in the formation of porous granules. The mixed agglomerates are formed from 2 feed streams of various starting detergent ingredients which are fed continuously, at a rate of 1400 kg / hr, into a Lódige CB-30 mixer / densifier, one of which comprises one surfactant paste containing surfactant and water and the other stream contains dry starting detergent material containing aluminosilicate and sodium carbonate. The speed of rotation of the arrow in the mixer / densificator Lódige CB-30 is approximately 1400 rpm. The contents of the mixer / dilutor Lódige CB-30 are continuously fed to a mixer / densifier Lódige KM-600 for additional agglomeration. The resulting detergent agglomerates are then fed to a fluid bed dryer and to a bed cooler fluid before being mixed with spray-dried granules. The remnants auxiliary detergent ingredients are sprinkled on or dry add to the combination of agglomerates and granules.

IV Base Granule Aluminosilicate 18.0 18.0 22.0 Sodium sulphate 10.0 10.0 19.0 Sodium Polyacrylate Polymer 3.0 3.0 2.0 Polyethylene Glycol (P.M. = 4000) 2.0 2.0 1.0 C12-13 Sodium Alkylbenzenesulfonate linear 6.0 6.0 7.0 Sodium alkyl sulphate of C-? -16 Secondary 3.0 3.0 3.0 Ethoxylated Sodium Alkyl Sulfate of C? 4-? 5 3.0 3.0 9.0 Sodium Silicate 1.0 1.0 2.0 Brightener 246 0.3 0.3 0.3 Sodium Carbonate 7.0 7.0 25.7 DTPA1 0.5 0.5 - Mixed Agglomerates Sodium Alkylsulphate of C14.15 5.0 5.0 Sodium Alkylbenzenesulfonate of linear C12-13 2.0 2.0 - Sodium Carbonate 4.0 4.0 - Polyethylene glycol (P.M. = 4000) 1.0 1.0 - Mix C13-15 alkyl ethoxylate (EO = 7) 2.0 2.0 0.5 Perfume 0.3 0.3 1.0 Polyvinylpyrrolidone 0.5 0.5 - Polyvinylpyridine N-oxide 0.5 0.5 - Polyvinylpyrrolidone-polyvinyllimidazole 0.5 0.5 - Distearylamine and cumenesulfonic acid 2.0 2.0 - Dirt-free polymer2 0.5 0.5 - Lipolase Lipozase (100,000 LU / I) 4 Termamyl amylase (60 KNU / g) 4 0.3 0.3 - CAREZYME® Cellulase (1000 CEVU / g) 4 0.3 0.3 - Protease (40 mg / g) 5 0.5 0.5 0.5 NOBS3 5.0 5.0 - Sodium percarbonate 12.0 12.0 - Polydimethylsiloxane 0.3 0.3 - Various ingredients (water, etc.) The rest The rest The rest Total 100 100 100 1 Diethylenetriaminepentaacetic acid 2 Manufactured in accordance with the patent of E.U.A. 5,415,807, issued May 16, 1995 to Gosselink et al 3 Nonanoiloxybenzenesulfonate Acquired from Novo Nordisk A / S 5 Acquired from Genencor 6 Acquired from Ciba-Geígy The resulting detergent compositions unexpectedly have improved chemical stability and flowability.

EXAMPLES V-XVI The following detergent compositions according to the invention are especially suitable for front loading washing machines, and are coated with an acrylic acid monomer as described in example II. The compositions are obtained as in examples ll-IV. (% by weight) V VI Vil Granules based Aluminosilicate 24.0 24.0 24.0 Sodium Sulfate 6.0 6.0 6.0 Acrylic acid / maleic acid copolymer 4.0 4.0 4.0 Sodium linear alkylbenzenesulfonate of C12.13 8.0 8.0 8.0 Sodium silicate 3.0 3.0 3.0 Carboxymethylcellulose 1.0 1.0 1.0 Rinse aid 47 0.3 0.3 0.3 Silicone antifoams 1.0 1.0 1.0 DTPMPA1 0.5 0.5 0.5 Alkylated C12.15 alkyl ethoxylate (EO = 7) 2.0 2.0 2.0 C12.15 alkyl ethoxylate (EO = 3) 2.0 2.0 2.0 Perfume 0.3 0.3 0.3 Sodium carbonate 13.0 13.0 13.0 Sodium perborate 18.0 18.0 18.0 Sodium Perborate 4.0 4.0 4.0 TAED2 3.0 3.0 3.0 Savinase Protease (4.0 KNPU / g) 3 1.0 1.0 1.0 Lipoza Lipolase (100,000 LU / I) 3 0.5 0.5 0.5 Amylase Termamyl (60 KNU / g) 0.3 0.3 0.3 Sodium Sulfate 3.0 3.0 5.0 Various ingredients (water, etc.) The rest The rest The rest Total 100.0 100.0 100.0 1 Dethylenetriaminepentamethylenephosphonic acid 2 Tetraacetylethylenediamine 3 Acquired from Novo Nordisk A / S The resulting detergent compositions have unexpectedly improved chemical stability and fluidity, and characteristics of excellent dissolution.

Accordingly, having thus described the invention in detail, it will be obvious to those skilled in the art that they can be made several changes without departing from the scope of the invention, and that it should not be consider that the invention is limited to what is described in the specification.

Claims (20)

1. NOVELTY OF THE INVENTION CLAIMS 1.
2. A composition comprising: a particulate material having at least a portion having a plasma-induced, water-soluble, graft-polymerized coating, characterized in that said water-soluble coating is formed by ionizing gas in a plasma chamber to form free radicals on said portion of said particulate material after which a hydrophilic organic monomer is deposited on said portion of said particulate material by graft polymerization so that said water-soluble coating is formed on said portion of said particulate material. according to claim 1, further characterized in that said organic monomer is selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, maleates, fumarates, vinyl ethers, and mixtures thereof.
3. 3. The composition according to claim 2, further characterized in that said organic monomer is selected from the group consisting of 2-hydroxyethyl methacrylate, N, N-dimethylacrylamide, acrylic acid, methacrylic acid, and mixtures thereof. the same.
4. 4. The composition according to claim 2, further characterized in that said organic monomer is acrylic acid.
5. 5. - The composition according to claim 2, further characterized in that said particulate material is selected from spray-dried granules, agglomerates, and mixtures thereof.
6. 6. The composition according to claim 1, further characterized in that said particulate material includes detersive surfactants which are selected from the group consisting of anionic surfactants, nonionic surfactants, cationic surfactants, and mixtures thereof.
7. 7. A detergent composition for laundry according to claim 1.
8. 8. A detergent composition for dishwashing according to claim 1.
9. 9. A cosmetic composition according to claim 1.
10. 10. A process for producing a composition, comprising the steps of: (a) providing a particulate material; (b) subjecting at least a portion of said particulate material to a plasma luminescent zone, in which a gas is ionized to form free radicals on said portion of said particulate material, characterized in that said plasma luminescent zone is contained in a plasma chamber operating at a pressure of about 1 mTorr to about 300 Torr and an energy of about 0.1 Watts to about 500 Watts; c) introducing a water-soluble organic hydrophilic monomer in said chamber after said step b), so that said organic hydrophilic monomer reacts with said free radicals on said portion of said particulate material to form a water-soluble coating on said portion of said particulate material.
11. 11. The process according to claim 10, further characterized in that said organic monomer is selected from the group consisting of acrylates, methacrylates, acrylamides, methacrylamides, maleates, fumarates, vinyl ethers, and mixtures thereof.
12. 12. The process according to claim 10, further characterized in that said gas is selected from the group consisting of argon, helium, oxygen, nitrogen, and mixtures thereof.
13. 13. The method according to claim 10, further characterized in that said organic monomer is introduced in a form that is selected from the group consisting of vapor, liquid or mixtures thereof.
14. 14. The method according to claim 10, further characterized in that said organic monomer is atomized in said chamber using acoustic nozzles.
15. 15. The method according to claim 10, further characterized in that said gas is ionized using high frequency microwave.
16. 16. The method according to claim 10, further characterized in that said gas is ionized using high frequency radio waves.
17. 17. The method according to claim 10, further characterized in that said gas is ionized using direct current electricity.
18. 18. The method according to claim 10, further characterized in that said gas is ionized by pulsation.
19. 19. The method according to claim 10, further characterized in that said detergent material is placed outside said plasma luminescent zone.
20. 20. The method according to claim 10, further characterized in that said organic monomer is introduced outside said plasma luminescent zone.