MXPA97004132A - Compositions of granular detergent containing deflecular polymers - Google Patents

Abstract

The present invention relates to a process for preparing a concentrated granular detergent composition containing about 15% by weight of water or less comprising: a) forming a crusher solution by mixing at least one organic surfactant, at least a detergent enhancer, water and a deflocculating polymer having a weight average molecular weight of above 3,000 up to and including 10,000 and containing polymer chains of the P-SR structure wherein P represents a polymer chain segment of a polymer hydrophilic and SR represents an end-capped mercapto group, R is an organic hydrophobic radical containing from about 4 to 28 carbon atoms, said crusher solution comprises lamellar droplets of said sufactant dispersed in the aqueous phase and having a viscosity at the range from about 2000 to 500,000 centipoises; and b) subjecting said solution to spray drying conditions for pro ducing a granular detergent composition having a water content of about 15% by weight or less and a deflocculating polymer content in the range of from about 0.01 to about 7.5% by weight, said solution being characterized by a lower viscosity that of an otherwise identical solution which is free of said polymer composition deflocculates

Description

COMPOSITIONS OF GRANULAR DETERGENT CONTAINING DEFROST-ACID POLYMERS BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to granular detergent compositions which contend a hydrophilic end-cap polymer as a deflocculation agent of the support suspension. 2. Description of Related Art Heavy-duty granular detergents useful for washing clothes both in the washing machine and by hand are well-known materials that have been described in a number of patents and literature. Generally, they are prepared by drying in an aqueous-based support suspension containing at least one, or a compatible mixture, of two or more detergent-active surfactants selected from anionic, cationic, nonionic, zwitterionic and amphoteric species. These compositions may also contain detergent-forming components and / or release agents such as, for example, inorganic phosphates or phosphonates, alkali metal carbonates, alkali metal aminopolycarboxylates such as, for example, nitrilotriacetic acid salts and ethylenediamine-tetraacetic acid salts, alkali metal silicates, aluminosilicates, different zeolites and a mixture of one or more thereof. Other components that may be present in the detergents include optical brighteners, enzymes and their stabilizers, perfumes, colorants, anti-foam agents, for example silicone compounds, preservatives and similar known additives.

One of the common methods for preparing powdered detergent is, first, to form a pumpable aqueous suspension or dispersion of the detergent components, generally referred to as a support suspension, and then, to atomize the suspension by pumping it through a spray nozzle, to a pressure of approximately 400 to 2000 psi in a spray-drying tower along with air that is introduced at a temperature of 300-1000 ° F. The air that comes into contact with the suspension provides a hot drying gas for the droplets of the suspension, so that most of the water evaporates. The resulting particles or beds are collected at the bottom of the tower while moisture and hot air come from above.

There is a tendency in the detergent industry to provide powder detergent compositions having higher concentrations of active ingredients (payload), including surfactants. These include highly concentrated, heavy duty powder detergent formulations containing more than about 25% by weight of surfactant. While it may seem simple enough to provide these materials, there is a limiting factor in terms of the maximum amount of surfactants that can be included in the support suspension while still maintaining a suspension with a sufficiently low viscosity so that it can be pumped to the tower. sprayed, for example a viscosity of about 500,000 or less.

Generally, the support suspension can be characterized as the component of laminar dispersed droplets in an electrolyte / aqueous former phase. The layered droplets consist of a configuration of two concentric layers of surfactant molecules between whose layers water or electrolyte solution is trapped. These suspensions may also contain suspended or dissolved solids such as, for example, the suspended or dissolved formers mentioned above. To facilitate spray drying, it is also preferred to have the levels of non-aqueous solids in the support suspension as high as possible, but without increasing the viscosity of the suspension to the point where pumping is not possible. Also, as the level of surfactant in the support suspension increases, the volume fraction of the suspended laminar droplets also increases, resulting in a decrease in the separation between the droplets. The contact of laminar droplets suspended between them, can lead to freezing or to the phenomenon of flocculation, resulting in a marked increase in the viscosity of the suspension. Suspensions containing flocculated maniculate droplets and high levels of solids may be unacceptable due to lack of ability to pump the viscous suspension from the mixing tank to the drying and granulation process. In addition, high levels of surfactants induce the suspension to foam under blending conditions, requiring the addition of foam controlling agents such as, for example, silicones.

Concentrated liquid detergents containing a polymeric additive are presented in the prior art. The polymer serves to stabilize the detergent and control the viscosity.

One approach to improving the stability of these liquid detergent compositions is the inclusion of minor amounts, for example, 0.01 to 5% by weight of a deflocculation polymer in the detergent formulation. For example, U.S. Patent No. 5,147,576 discloses random interpolymers derived from hydrophilic monomers, such as, for example, acrylic acid, and also containing one or more copolymerized monomers, having sloping hydrophobic side chains randomly dispersed throughout. of the polymer chain. The use of these interpolymers in detergent compositions is presented to prevent or prevent flocculation of latent surfactant droplets dispersed in the detergent, and therefore, improves stability. Granular detergent compositions containing similar deflocculation polymers are presented in WO / 91/09932.

Hydrophilic polymeric materials have also been used in liquid detergent compositions as viscosity controlling agents. For example, U.S. Patent No. 4,715,969 and its counterpart, U.S. Patent 2,168,717, disclose that the addition of less than about 0.5% by weight of a polyacrylate polymer, for example sodium polyacrylate, having a molecular weight from about 1,000 to 5,000, to the aqueous detergent compositions containing mainly, anionic surfactants will stabilize the viscosity of the composition and prevent a greater increase in viscosity after a storage period of the formulated composition. Also, EPO 301,883 presents similar compositions containing about 0.1 to 20% by weight of a water soluble, viscosity reducing polymer such as polyethylene glycol, dextran or a dextrone sulfonate.

The polymeric additives in powder detergents have also been used. For example, Canadian Patent No. 1,174,934 discloses granular detergents containing surfactant, aluminum silicate and alkali salt formers and from about 0.1 to 10% by weight of a forming film, water soluble acidic polymer such as acrylic or functional polymers of sulfate. The polymers provide dry granules having superior free-flowing characteristics and good water solubility. Also, U.S. Patent No. 3,308,067 discloses granular detergents containing a water soluble salt of a homopolymer of an aliphatic polycarboxylic acid as a polyelectrolytic forming material.

U.S. Patents 3,668,239; 3,839,405; 3,772,382 and 3,776,874 issued to Uniroyal, Inc., present alkyl sulfide, alkyl sulfoxide and alkyl sulfone terminated in oligomers for use in polymerization emulsion. Oligomers have been widely shown to be useful as surface active agents, emulsifiers and thinners.

EP 623670A discloses the use of stabilizers in an aqueous surfactant composition to reduce flocculation of systems containing a flocculation surfactant. The stabilizers are described as surfactants having a hydrophobic portion and a hydrophilic portion. The hydrophilic portion is typically a polymer bonded at one end to the hydrophobic portion.

SYNTHESIS OF THE INVENTION The present invention provides concentrated granular detergent compositions comprising a mixture of: a) from about 15 to about 50% by weight of a surfactant; b) at least one detergent former, and c) from about 0.01 to about 7.5% by weight of a deflocculation polymer composition containing polymer chains of structure P-QR, wherein P represents a segment of the polymer chain of a hydrophilic polymer, and QR represents a hydrophobic cap end group wherein R is an organic hydrophobic radical containing from about 4 to about 28 carbon atoms, and Q is select from a group consisting of O, C02, S, SO, S02, NRP P04RP P03RP SiOR'R ", SiR'R", CR'OH, CR'R "and CR'OR" where R'R "are each hydrogen, an alkyl group containing from about 1 to 4 carbon atoms or an aryl group; Y d) water The granular detergent was prepared by drying the support suspension comprising an aqueous dispersion of an organic surfactant, detergent builder, deflocculation polymer and other ingredients that may be present in the composition. The presence of the deflocculation polymer in the suspension retards the propensity of the laminar droplets dispersed in the aqueous electrolytic phase of the suspension to flocculation, particularly where the droplets occupy a higher volume portion as the result of high concentrations of surfactant present in the The detergent. The resulting suspension has a much lower viscosity than the similar suspension that does not contain the deflocculation polymer, and therefore, is more fluid and easier to pump to and through the drying stage of the manufacturing process.

DETAILED DESCRIPTION OF THE INVENTION The granular compositions of the invention contain one or more compatible mixtures of two or more detergent-active surfactants that can be selected from anionic, cationic nonionic, zwitterionic and amphoteric species.

Desirable anionic detergents include water-soluble alkali metal salts having alkali radicals containing from about 8 to about 22 carbon atoms, the term "alkaline" being used to include the alkaline portion of the higher acyl radicals. Examples of the desirable synthetic anionic detergent compounds are sodium and potassium alkali sulfate, especially those which are obtained by sulfatating higher alcohols (C8-C18) produced, for example, from tallow or coconut oil; benzene sulfonates (C9-C20) alkaline sodium and potassium, particularly benzene sulphonates (C10-C15) secondary linear sodium alkaline; alkaline sodium glycerol ether sulfonates, especially those ethers of higher alcohols derived from tallow or coconut oil and synthetic oils derived from petroleum; sulphates and sulphonates monoglycerides fatty sodium coconut oil; higher potassium and sodium salts of higher alcohol (C8-C18) alkoxy alkylene esters, particularly products of the ethylene oxide reaction; products of the reaction of fatty acids, for example coconut fatty acids, esterified with isethionic acid and neutralized with sodium hydroxide; salts of potassium and sodium of fatty acid amides of taurine methyl; alkali monosulfonates, for example, the derivatives of alpha-olefins (C5-C20) with sodium bisulfite and those derived from the reaction of paraffins with S02 and CL2 and then hydrolyzed with a base to produce a random sulfonate; and olefin sulfonates, which term is used to describe the material made by reacting olefins, particularly, C10-C20 alpha-olefins, S03 and then neutralizing and hydrolyzing the product of the reaction; Preferred anionic detergents are linear alkaline benzene sulphonates (C10-C16), polyethoxyalkali sulfates (C10-C13) and a mixture thereof.

The most preferred anionic detergent is one or a mixture of higher linear (linear or branched) alkylbenzene sulfonate and polyethoxyalkylene. While other higher linear, water soluble alkylbenzene sulfonates may be present in the formulas of the invention, these potassium salts and, in other cases, ammonium and / or alkanolammonium salts, where appropriate, it has been found that sodium salts are highly preferred, which is also the case with respect to the components of polyethoxyalkali sulfate detergents. The alkylalbenzene sulfonate is that in which the higher alkali group has 10 to 16 carbon atoms, preferably 12 to 15, and more preferably 12 to 13 carbon atoms. The polyethoxyalkali sulfate, which is also referred to as a higher sulphonated polyethoxylated linear alcohol, or the product of the sulfated condensation of a high fatty alcohol and ethylene oxide or glycol polyethylene, is that in which the alkali group is 10. to 18 carbon atoms, preferably 12 to 15 carbon atoms, and which includes from 2 to 11 ethylene oxide groups, preferably 2 to 7, preferably 3 to 5 and even more preferably approximately 3 groups of ethylene oxide .

The anionic detergent may be present in a granular detergent, at a level of about 15 and about 50% by weight, more preferably from 20 to 45% by weight. When the mixture of two or more different anionic detergents is used, such as, for example, sulfate and sulfonate mixtures, as described above, they can be mixed in relative proportions in a portion from about 5 to 95% by weight of each type.

The composition of the present invention may also contain, in a supplementary manner, anionic and amphoteric surfactants. The desired anionic surfactants include, in particular, the products of the reaction of the compounds having a hydrophobic group and a hydrogen reactive atom, for example, aliphatic alcohols, acids, amides and alkali phenols with alkylene oxides, commercially ethylene oxide, both only or with propylene oxide. The specific nonionic detergent compounds are branched or linear primary or secondary alcohols (C6-C18) alkyl with ethylene oxide, and products made by the condensation of ethylene oxide with the products of the reaction of propylene oxide and ethylenediamine. Other non-anionic detergent compounds include long chain tertiary amine oxides, long chain phosphinothermal oxides, alkyl sulfoxides, glycerol (8-C18) fatty esters, sorbitan and the like, alkali polyglycosides, glycerol ethoxylates, sorbitans ethoxylate and esters ethoxylated phosphate.

The preferred nonionic detergent compounds are those of the mixed ethoxylate and fatty alcohol (C6-C18) ethoxylate-propyloxylates type. Nonionic surfactants may be present in the composition at a preferred level of from about 1 to 15% by weight.

It is also possible to include alkali metal soap of a mono or dicarboxylic acid, especially a soap of an acid having from 12 to 18 carbon atoms, for example, oleic acid, ricinoleic acid, (non) yl succinate, for example dodecenyl succinate , fatty acids derived from castor oil, colsa oil, peanut oil, coconut oil, palm oil or a mixture thereof. You can also use sodium or potassium soaps of these acids. When used, the level of soap in the composition of the invention is from about 0.5 to 15% by weight of the composition.

Particularly preferred combinations of the surfactant include: 1. A mixture comprising from 15 to 30% by weight of linear alkyl benzene sulfonate, wherein the alkyl group contains from about 10 to 16 carbon atoms and about 1 to 10% by weight of polyethoxyalkyl sulfate, wherein the alkyl is to 18 carbon atoms and the polyethoxy is from 2 to 7 ethylene oxide groups. 2. A mixture comprising 1 or both surfactants mentioned in item 1 above and a non-ionic ethoxylated fatty alcohol, wherein the fatty alcohol is 8 to 18 carbon atoms, and the polyethoxy is 2 to 7 oxide groups. The average of anionic to nonionic surfactant is from about 1: 4 to 10: 1.

A more detailed illustration of the different detergents and types of detergents mentioned can be found in the text Surface Active Aaents- Vol. II, by Schwartz, Perry and Berch (Interscience Publishers, 1958), in a series of annual publications entitled McCutcheon's Detersénts and Emulsifiers, issued in 1969, or in Tensid-Taschenbuch, H. Stache, 2 *. Carl Hanser Verlag Edition, Munich and Vienna, 1981.

The composition of this invention also includes at least one detergent former. Suitable formers include phosphorus-containing inorganic salts, organic formers and formers that do not contain phosphorus. The main function of the former is to make a complex with hard water cations that form insoluble salts in water, for example, calcium and magnesium cations, through the mechanism of segregation or cation exchange.

Examples of phosphorus-containing inorganic detergent formers include water-soluble salts, especially alkali metal pyrophosphates, orophosphates, polyphosphates and phosphonates. Specific examples of inorganic phosphate formers include sodium and potassium tripolyphosphates, phosphates and hexametaphosphates. Segregant phosphonate formators can also be used. Examples of organic detergent formers, which can be used, include the alkali metal, ammonium and substituted ammonium polyacetates, carboxylates, polycarboxylates, po 1 i a c e t i 1 or c a box and polyhydroxysulfonates. Specific examples include sodium, potassium, lithium, ammonium and substituted ammonium salts of ethylenediaminetetraethytic acid, nitrolotriacetic acid, oxydisuccinic acid, mellitic acid, benzene polycarboxylic acids, monatotarate succinate, succinate ditartrate, alken (not) yl succinates and citric acid. The organic detergent formers include water-soluble alkali metal carbonates and bicarbonates, as well as the mixture thereof with phosphates, for example, a mixture of sodium carbonate and sodium tripolyphosphate.

Trainers other than phosphorus-containing compounds can also be used. Preferred formers for use in the phosphorus-free compositions include alkali or amorphous aluminosilicates of cation exchange of natural or synthetic origin. The desired aluminosilicate zeolites include "Zeolite A", "Zeolite B", "Zeolite X", "Zeolite Y" and "Zeolite HS". The most preferred zeolite is zeolite A crystalline sodium silicoaluminate. Preferably, the zeolite should be in a finely divided state with a final particle diameter of about 20 microns, eg, from 0.05 to 20 microns, preferably from 0.01 to 15 microns, and more preferably from 0.01 to 8 microns as the size of average particle, for example 3 to 7 microns, if it is in crystalline form, and 0.01 to 0.1 microns if it is in amorphous form. Although the final particle sizes are much lower, usually the zeolite particles will have a size ranging from 100 to 400 mesh, preferably 140 to 325 mesh. The zeolites of a smaller size will turn to powder, and those of a larger size will not be suspended satisfactorily and sufficiently in the support suspension.

In another embodiment of the invention in which phosphorus-free formers are used, the former can comprise compounds which do not contain water-soluble phosphors, which are dissolved in an aqueous phase of the support suspension, forming an electrolyte solution. Examples of the formers include alkali metal carboxylates mentioned above, for example, sodium citrate, used alone or in a mixture with a water-soluble alkali metal carbonate or bicarbonate, for example, sodium or potassium carbonate.

Mixtures containing two or more of the detergent formers described above can also be used. The former or the mixture thereof may be present in the granular detergent at an average of from about 15 to about 60% by weight of the composition, more preferably from 20 to 50% by weight. When the former is a zeolite material, it is normally present at an average of about 5 to 30% by weight of the composition, and is preferably used in combination with other compatible forming materials.

Preferably, the granular detergent also contains one or a mixture of metalalkaline silicates which function to form a rigid glass film, capable of strengthening the granular walls and imparting better flow characteristics to dry detergent granules. Preferred silicates are those having an average alkali metal oxide and Si02 of 1.5 to 2.0 since these tend to be more soluble in water. Sodium silicate is the preferred silicate. The silicate may be present in the detergent granules at a level of from about 3 to about 40% by weight, more preferably from about 5 to about 35% by weight. The key ingredient in the composition of the present invention is the hydrophobically modified deflocculation polymer which stabilizes the support suspension and lowers its viscosity. The hydrophobic end groups present in the hydrophilic polymer are likewise wrapped in the layered droplets formed by the surfactant phase of the suspension, therefore, both sterically and electrostatically inhibit the flocculation of these droplets, even in relatively high concentrations. This results in a stable, low viscosity, and pumpable suspension.

Useful deflocculation polymers, according to this invention, are characterized in that they comprise a chain segment of the hydrophilic polymer (P) having a hydrophobic part (QR) covalently attached to the terminal carbon atom, present in at least some of the segments of the hydrophilic chain. These polymers are generally characterized, because they contain the P-QR structure, where P represents the hydrofolic polymer and R is an organic hydrophobic radical, containing from 4 to about 28 carbon atoms, more preferably it contains an alkyl radical from about 6 to 18 carbon atoms.

Q represents a group or molecule, which is capable of binding the hydrophilic polymer P to the organic hydrophobic radical R and therefore acts as the terminator of the polymer chain (or initiator). In general, Q is selected from a group consisting of of O, C02, S, SO, S02, NRP P04RP P03RP SiOR'R ", SiR'R", CR'OH, CR'R ", and CR'OR" S, SO, S02 NRP P04RP P03R ', SiOR' R ", CR'OH, CR'R", and CR'OR "wherein R 'and R" are each a hydrogen, the alkyl group contains from 1 to 4 carbon atoms or an aryl group. R is an alkyl of 4 to 28 carbon atoms, or an alkenyl or aralkyl group, preferably an alkyl or aralkyl group, containing from 6 to 18 carbon atoms. Preferred polymers of the invention end with an end group in alkali sulphide, alkaline sulfoxide or sulfonal alkali cap.

Monomers that can be polymerized to form hydrophilic polymer segments include 1 or a mixture of water-soluble monomers or a combination of water-soluble and relatively water-insoluble monomers, such that the resulting polymer is soluble in water at a room temperature to a point greater than about 10 g per liter. Examples of these monomers include ethylenically unsaturated amides, such as, for example, acrylamides, methacrylamides and furamides and their N-substituted derivatives, such as, for example, sulfonic acid 2-acrylamido-2-methylpropane, N- (dimethylaminomethyl) acrylamide, as well as chloride of N- (dimethylaminomethyl) acrylamide and N- (trimethylammoniopropyl) methacrylamide chloride; ethylenically unsaturated carboxylic acids or dicarboxylic acids, such as, for example, acrylic acids, maleic acid, itaconic acid, fumaric acid, crotonic acid, aconitic acid and citraconic acid and other ethylenically unsaturated quaternary ammonium compounds, for example, trimethylbenyl ammonium chloride -benzyl; sulfoalkyl esters of unsaturated carboxylic acids, such as, for example, 2-sulfoethyl methacrylate; aminoalkyl esters of unsaturated carboxylic acids, such as, for example, 2-aminoethyl methacrylate, dimethylaminoethyl (metha) acrylate, diethylaminoethyl (metha) acrylate, dimethylaminomethyl (meth) acrylate, diethyl aminomethyl (meth) acrylate, and their quaternary ammonium salts, vinyl or allyl amines, such as, for example, pyridinovinyl and morpholinovinyl or allylamine; diallylamines and ammoniodialyl compounds, such as, for example, ammonium dimethyldiallyl chloride; heterocyclic vinyl amides, such as for example vinyl pyrrolidone; arylovinyl sulfonates, such as, for example, vinylbenzyl sulfonate; vinyl alcohol, which is obtained by the hydrolysis of a vinyl acetate; acrolein; allyl alcohols, vinyl acetic acid, sodium vinyl sulfonate; allyl sodium sulfonate, as well as the salts of the above monomers. These monomers can be used alone or in a mixture thereof.

Optionally, the polymeric hydrophilic segment may contain small amounts of relative hydrophobic units, for example, those derived from polymers having a solubility of less than 1 g / 1 in water, provided that the total solubility of the hydrophilic polymer still satisfies the solubility requirements. specified above. Examples of relatively soluble polymers in water, polyvinyl acetate, methacrylate polyolethyl, polyethyl acrylate, polyethylene, polypropylene, polystyrene, polybutylene oxide, polypropylene oxide and polyhydroxypropyl acrylate.

A particular class of sulfonated alkyl-terminated polymers according to the invention are presented according to the following structural form: wherein R is a branched or branched primary or secondary tertiary alkyl group having from 5 to 20 carbon atoms; Rx and R3 are each a hydrogen, methyl, ethyl, or -COOH; R2 and R4 are each hydrogen, methyl, ethyl, -COOH, -CH2COOH; Y is selected from a group consisting of -COOH, -CONH2, -OCH3, -_DC2H5, and -CH2OH; X is selected from the group consisting of -COCC2H4OH, -COOC3H6OH, -CONHCH2OH, -CONHCH3, -CONHC2H5, -CONHC3H7, -COOCH3, -COOC2H5, -CN, -OOCCH3, -OOCC2H5, and -COOCH3CHOCH2.

The degree of polymerization, a + b, as it is generally between 2 to 50, and the mole fraction of the monomer has the functional group X, a / (a + b), can range from 0 to 0.6, and preferably is less than 0.5 and more preferably it is 0.2 to 0.5. The presence of the monomer having a functional group X is optional, since the value of "a" will be zero for polymers containing only monomers having a functional group Y. The comprehensive description of these terminated alkyl sulfide polymers and their method of preparation , are presented in US Pat. No. 3,839,405, in a full description of which is incorporated herein by reference.

The polymers particularly for use herein, comprise a hydrophilic polymer terminated by a mercaptohydrophobic capped end group of a mercaptan of an RSH structure, wherein R is an alkyl or aralkyl radical having from 4 to 28 carbon atoms. R must be a sufficiently long chain, so that it has oleophilic characteristics, for example, it is miscible with an oily laminar droplet or a micelle phase of the detergent composition. Preferably, the mercaptans are alkyl mercaptans or aralkyls, containing from 6 to 18 carbon atoms, such as, for example, hexyl mercaptan, decyl mercaptan, dodecylbenzyl mercaptan, dodecyl mercaptan and octadecyl mercaptan.

The backbone of the hydrophilic polymer can also advantageously be a finished chain with a sulphoxide or sulfone group. The class of preferred polymers for use herein may be represented by the following structural formula: wherein R, R1 # R2, R3, R4, X, Y, the degree of polymerization a + b, and the mole fraction a / (a + b) are as defined above; Z is oxygen or may be present. When Z is oxygen the capped end group is a sulphonyl, when Z is not present, the cap end group is a sulphoxidealkyl. For the comprehensive description of this type of polymers terminated in alkyl sulfoxide and sulfonyl and their method of preparation, they are presented in U.S. Patent Nos. 3,772,382; 3,776,874; and 3,668, 230, in a full description which is incorporated herein by reference.

For example, the mercapto-terminated polymers can be prepared by free-radical polymerization of a hydrophilic monomer or a mixture of monomers in an aqueous medium or of water on alcohol, in the presence of a free radical initiator soluble in water and in the presence of a mercaptan SRH. The molar average of the monomer with the mercaptan can generally vary from about 10: 1 to about 150: 1 respectively, more preferably from 25: 1 to about 100: 1 respectively. Under the conditions of free radical polymerization, a number of free radicals RS will be generated, which can serve to initiate the polymerization of the additional monomer or these radicals can be coupled with an increasing polymer chain, resulting in a mixed polymer product, where at least some of the chains have the P-QR structure described above. The number of P and P-QR chains present in the mixed polymer product will vary depending on the polymerization conditions, the average molecular weight of the polymer and the amount of mercaptan present in the polymerization mixture. Preferably from 25 to about 95% of the polymer chains are endcapped by the hydrophobic mercaptan SR.

The polymerization can be carried out by the general procedures described in U.S. Patent 5,021,525, in a full description which is incorporated herein by reference. The preferred aqueous polymerization medium comprises a mixture of at least 50% by weight of water and a soluble co-solvent, such as for example alcohol of 1 to 4 carbon atoms, for example, osopropane, which tends to retard the Precipitation of the cap-shaped polymer that develops from the solution Polymerization initiators that can be used include water-soluble initiators such as hydrogen peroxide, persulfates, perborates and permanganates, present in the solution at generally varying levels from about 0.1 Up to 5% by weight Polymerization can be carried out, initially, by charging an initiator, for example, sodium persulfate, in an aqueous polymerization medium, followed by the gradual introduction of a mixture comprising monomer and mercaptan , at a level ranging from approximately 10 to 55% by weight of the total reactants, the mixture is heated to a temperature ranging from about 70 to 99 ° C for a period of time sufficient to form the polymer of a desired molecular weight, generally from about 3 to 6 hours. Preferably, only a portion of the monomer and initiator are added to the initial medium, followed by viewing the remaining monomer and finally the initiator during the polymerization. Then, the polymer can be recovered by stripping the cosolvent, such as, for example, isopropanol and at least part of the water, followed by neutralization of the polymer with caustic, for example, sodium hydroxide.

The preferred deflocculation polymers used for the purpose of this invention have an average molecular weight, as measured by gel permeation chromatography, using standard polyacrylates, on average from about 200 to 50,000, more preferably from about 200. up to 25,000 and more preferably for polymers based on polymethacrylic acid, from about 3,000 to 10,000. The most preferred polymers are hydrophilic homopolymers, such as, for example, polyacrylic or polymethacrylic acid and copolymers of acrylic or methacrylic acid with less than 50% by weight of maleic acid. (anhydride), wherein the volume of the polymer chains are endcapped, with a simple hydrophobic segment derived from a dodecyl mercaptan.

The deflocculation polymer is generally added to the formula at levels at which the polymer content in granular product dried by final spray, varies from 0.01 to about 7.5% by weight, more preferably from about 0.5 to 5% by weight, and more preferably from about 1 to about 3% by weight.

These polymers and their methods of preparation are further presented in the co-pending U.S. patent application serial number 08 / 212,611, filed March 14, 1994, and the entire disclosure of which is incorporated herein by reference.

The aqueous phase of the support suspension is electrolytic, and therefore contains a water soluble salt. When the former present in the detergent is itself a water-soluble salt, as for example, when the former is an alkali metal carbonate or citrate phosphate, there is no need to add an additional electrolyte. When the former is not soluble in water, such as for example a zeolite, then alkali metal alkates or sulfates may be included as necessary to form the aqueous electrolyte solution.

The granular detergent compositions are prepared by drying the support suspension comprising an aqueous dispersion of the above components. Generally, the suspension contains from about 25 to 65% by weight of water, more preferably from 35 to 50% by weight of water, in some cases, it is present as a diluent in some of the components of the formulation, such as, for example, surfactans, and some of which are added later when the suspension is prepared. After drying, the detergent granules contain 15% by weight of water or less, generally from 2 to 15% by weight of water and preferably from 2 to 10% by weight.

Various adjuvants, both aesthetic and functional, may be present in the detergent compositions of the present invention, such as fluorescent brighteners, perfumes and dyes. Fluorescent brighteners include the well-known stilbene derivatives, including cotton and nylon brighteners, such as those sold under the trademark Tínopal ®, for example 5BM. The perfumes used generally include oily essences, esters, aldehydes and / or alcohols, all well known in the perfumery art. The colorants may include dyes and water dispersible pigments of various types, including ultramarine blue. Titanium dioxide can be used to ignite the color of the product or to lighten it. Inorganic filter salts, for example, sodium sulfate, sodium chloride may be present, as anti-redeposition agents, such as sodium carboxymethyl cellulose, enzymes such as for example protease, amylase and lipase, whiteners such as for example sodium perborate or percarbonate or materials that contain chloride. Bactericides, fungicides; antifoam agent, such as silicone; anti-stain agents, such as, for example, copolyesters; condoms, such as for example formalin; foam stabilizers, such as, for example, lauric myristic diethanolamine; and auxiliary solvents, such as, for example, ethanol. Normally the individual proportions of the adjuvants will be less than 3%, frequently less than 1% and sometimes even less than 0.5%, except for any filters and solvents, and additional to detergents and formers, for which the proportions, sometimes, They can be as high as 10%. The total of the proportion of adjuvants, including non-designated synthetic detergents and formers, will normally not be greater than 20% of the product and desirably less than 10% thereof, more desirable less than 5% thereof. Of course, the adjuvants used will not interfere with the washing and softening actions of the detergent and will not promote the instability of the product at rest. Also, these will not cause the production of objectionable deposits on clothing.

More preferably, these adjuvants are mixed with the finished granular detergent after the drying operation.

The viscosity of the support suspension composition immediately upon completion of the suspension mixing process will vary depending on the solids content of the suspension and the amount of deflocculation polymer present in the suspension. For suspensions containing a relatively low solids level, for example 35 to 50% by weight solids, the viscosity will vary from about 2,000 to 100,000 cps. For suspensions containing higher solids levels, for example 50-65% by weight, the viscosity will vary from about 100,000 to 500,000 cps, as measured using a Brookfield Viscometer Model LVT-II at an angular speed of 12 rpm and a temperature of 25 degrees centigrade. A No. 3 needle is used to measure viscosities below 10,000 cps and a NO 4 needle for viscosities above 10,000 cps. The most preferable viscosity will vary from about 100,000 to 500,000 cps, more preferably in the range from about 200,000 to 400,000 cps. The pH of the suspension will generally range from about 7 to about 12, preferably from 10 to 12, and the pH can be adjusted if necessary by adding appropriate amounts of a base solution such as 50% KOH to the suspension. %.

The components of the support suspension can be mixed in any desirable order which leads to the uniform development of the dispersion. In a preferred process, water and all liquids (silicates, surfactants and polymers) are first mixed with a high shear mixer in the support; there is a delay step while the phosphate is hydrated. Then, subsequently the solids that include soda ash, zeolite (if not phosphate), sodium sulfate, brighteners and salt are added. The silicone for foam control is finally added to dearate the suspension together before dropping the support into a drop tank, from where it is pumped into the drying tower. Generally, the support suspension will have a final solids content of about 40-75% by weight, more preferably from about 50 to 70% by weight.

The suspension can then be dried using any of the drying procedures well known in the art, such as spray drying, fluid bed drying, flash drying, microwave drying and the like. The preferred method is the spray drying process. In the typical spray-drying process, the support suspension is atomized by pumping this er-a spray nozzle of a spray-drying tower at a pressure which may vary from about 400 to 2.00: psi. The typical dimensions of the spray-drying tower vary from 35-100 feet in height and 12-30 feet in diameter. At the base of the tower, air is introduced at a temperature of approximately 300 ° -1000 ° F, which comes in contact with the atomized suspension to provide a hot drying gas for the suspension droplets, thus evaporating most of the of the water. The resulting dry granules are collected at the base of the tower and cooled. Water-sensitive or heat-sensitive ingredients such as perfumes can then be added to the tower of granules in a subsequent mix or mixing operation.

The following examples illustrate the invention.

EXAMPLE 1 The following ingredients were mixed in parts by weight (grams) in the order shown in the laboratory bowl using a high speed propeller mixer to form a support suspension that can be pumped: Water 11.5 Anionic Surfactant (LDBS) * 60.0 Deflocculation Polymer ** 5.4 Potassium Tripolyphosphate 39.0 Sodium Silicate Solution 17.0 * Linear alkylbenzene sulfonate detergent containing 10-14 carbon atoms.

** Copolymer of acrylic and maleic end-cap acids with dodecyl mercaptan and having an average molecular weight of about 10,000 and about 50: 1 molar average of hydrophilic to dodecyl hydrophobe.

The mixing time was approximately 30 minutes. The resulting suspension had a viscosity of 8,000 ± 1,000 cps measured using a Brookfield No. 3 needle at 12 rpm, and was easily flowed and pumped as required to subsequently dry it by spraying to produce a granular detergent.

EXAMPLE CONTROL 2 Example 1 was repeated as stated above except that the deflocculation polymer of the formula was omitted and replaced with an equal amount of a sodium polyacrylate polymer having a molecular weight of about 4500. It was found that the resulting formula had a viscosity in excess of 0.000 cps, which could not be poured from the bowl and therefore could not be pumped into or through the spray-drying tower.

EXAMPLE 3 The ingredients mentioned below (in grams) as in Example 1 were mixed for a period of about 15 minutes to form support suspensions having a nonaqueous solids content of about 56%. - EJ3 CONTROL Water 119 119 LDBS 408 408 Sodium silicate 112 112 Deflocculation polymer * 2 Control polymer ** - 2 Sodium hydroxide 50 50 Potassium tripolyphosphate 256 256 Sodium sulphate 14 14 Viscosity 235,000 900,000 * Copolymer of acrylic and maleic acid end cap with dodecyl mercaptan and having an average molecular weight of about 4000 and about 25: 1 molar average of hydrophilic to dodecyl hydrophobic.

** Acrylic homopolymer having an average molecular weight of about 4500.

The viscosity of the suspension resulting from Example 3 was measured as 235,000 cps using a Brookfield DV-11 viscometer equipped with a rest in the blade path; the control of the suspension had a viscosity of 900,000 cps and was too thin to be pumped in a spray drying process.

EXAMPLES 4-6 Example 3 was repeated, with the exception that the water content of the suspension formula was reduced to provide solid contents of 61, 63 and 65% by weight respectively. The viscosity information for each suspension was obtained as in Example 3 with the following results:% SOLIDS VISCOSITY (CPS.

Example 4 61 220,000 Example 5 63 518,000 Example 6 65 1,500,000 The above information demonstrates that formulas containing 2% by weight of deflocculating polymer and a solids level up to or greater than about 63% by weight have lower viscosities than the control formula at a solids level of only 59% by weight .

EXAMPLE 7 The suspensions were prepared as set forth in Example 3, using the same deflocculation polymer and a control polymer as described in Example 3. Then, the suspensions were dried under the conditions described above. The support suspension and the finished product compositions dried after spraying are set forth in Table 1.

TABLE 1 EXAMPLE 7 Example Control Ingredients% Support Product% Support Finished product finished The spray conditions are the following: cfm (international abbreviation) = cubic feet per minute psi (international abbreviation) = pounds per square inch PROPERTIES Eim 7 Control Density of the finished product 0.32 0.52 Powder% Solids in the suspension sop. 66.5% 58% Viscosity of suspension 239,900 361,000 The formula of Example 7 has a considerably lower viscosity than the control despite the fact that the solids level in the suspension is higher than 8%, higher than the Control.

Also, the density of the spray-dried product of Example 7 was considerably less than that of Control.

Claims (35)

1. CLAIMS 1. A concentrated granular detergent composition comprising the mixture of: a) from about 15 to about 50% by weight of a surfactant; b) at least one detergent former, and c) from about 0.01 to about 7. 5% by weight of a deflocculation polymer composition containing polymer chains of structure P-QR, where P represents a segment of the polymer chain of a hydrophilic polymer, and QR represents a hydrophobic cap end group in which R is an organic hydrophobic radical containing from about 4 to about 28 carbon atoms, and Q is selected from a group consisting of O, C02, S, SO, S02, NR ', P04R', P03R ', SiOR'R ", SiR'R", CR'OH, CR'R "and CR'OR" wherein R 'and R "are each hydrogen, an alkyl group containing from about 1 to 4 carbon atoms or an aryl group; Y d) water.
2. 2. The composition, as claimed in clause 1, characterized in that the surfactant comprises at least one anionic detergent selected from an anionic sulfate. 0 sulfonate.
3. 3. The composition, as claimed in clause 2, characterized in that it contains from about 15 to about 30% by weight of an anionic sulfonate benzene detergent having from about 10 to 16 alkaline carbon atoms.
4. 4. The composition, as claimed in clause 2, characterized in that it contains from about 1 to about 10% by weight of an anionic sulfated polyethoxy alkyl potassium or sodium detergent wherein the alkyl group contains from about 10 to 18 carbon atoms and the polyethoxy is from 2 to 7 ethylene oxide groups.
5. 5. The composition, as claimed in clause 3, characterized in that the ionic detergent comprises a mixture of alkyl benzene sulfonate and from about 1 to about 10% by weight of polyethoxy alkyl potassium or sodium sulfate wherein the alkyl group contains from about 10 to about 18 carbon atoms and the polyethoxy is 2 to 7 ethylene oxide groups.
6. 6. The composition, as claimed in clause 3 or 5, characterized in that it also contains from about 1 to 15% by weight of a nonionic ethoxylated fatty alcohol wherein the fatty alcohol contains about 6 to 18 carbon atoms.
7. 7. The composition, as claimed in clause 1, characterized in that the segment P of the hydrophilic polymer chain is polyacrylic or polymethacrylic acid.
8. 8. The composition, as claimed in clause 1, characterized in that the segment P of the hydrophilic polymer chain is a copolymer containing at least 50% by weight of polymerized methacrylic or acrylic acid and less than 50% by weight of polymerized maleic acid or maleic anhydride.
9. 9. The composition, as claimed in clause 1, characterized in that the polymer has an average molecular weight in a proportion from about 2,000 to 25,000.
10. 10. The composition, as claimed in clause 9, characterized in that the polymer has an average molecular weight ranging from about 3,000 to 10,000.
11. 11. The composition, as claimed in clause 1, characterized in that R is an alkyl group containing from about 6 to 18 carbon atoms.
12. 12. The composition, as claimed in clause 11, characterized in that R is dodecyl.
13. 13. The composition, as claimed in clause 1, characterized in that from approximately 25 to 95% by weight of the hydrophilic polymer chains present in the deflocculation polymer composition have the P-QR structure.
14. 14. The composition, as claimed in clause 1, characterized in that the composition of the deflocculation polymer contains a finished sulfido alkyl polymer represented by the following structural formula: wherein R is a straight or branched chain primary, secondary or tertiary alkyl group having from 5 to 20 carbon atoms; R1 and R3 are each hydrogen, methyl, ethyl or -COOH; R2 and R4 are each hydrogen, methyl, ethyl, -COOH or -CH2COOH; Y is selected from a group consisting of -COOOH, -CONH2, -OCH3, -OC2H5, and -CH20H; X is selected from a group consisting of -COOC2H40H, -COOC3H60H, -C0NHCH20H, -C0NHCH3, -CONC2H5, -C0NHC3H7, -C00CH3, -COOC2H5, -CN, -00CCH3, -OOCC2H5 and -COOCH3CHOCH2; the degree of polymerization, a + b, is from 2 to 50 and the mole fraction of the monomer having the functional group X, a / (a + b) is from 0 to 0.6.
15. 15. The composition, as claimed in clause 1, characterized in that the composition of the deflocculation polymer contains a sulfone-terminated alkyl or sulfoxide alkyl polymer represented by the following structural formula: wherein R is a straight or branched chain primary, secondary or tertiary alkyl group having from 5 to 20 carbon atoms; R1 and R3 are each hydrogen, methyl, ethyl or -COOH; R2 and R4 are each hydrogen, methyl, ethyl, -COOH or -CH2COOH; Y is selected from a group consisting of -COOOH, -CONH2, -OCH3, -OC2H5, and -CH20H; X is selected from a group consisting of -COOC2H40H, -COOC3H60H, -CONHCH20H, -CONHCH3, -CONC2H5, -CONHC3H7, -COOCH3, -COOC2H5, -CN, -OOCCH3, -OOCC2H5 and -COOCH3CHOCH2; the degree of polymerization, a + b, is from 2 to 50 and the mole fraction of the monomer having the functional group X, a / (a + b) is from 0 to 0.6, and Z is oxygen or may not be present, such that when Z is oxygen the end-in-cap group is an alkyl sulfone and when Z is not present in the cap-end group it is an alkyl sulfoxide.
16. 16. The composition, as claimed in clause 1, characterized in that the detergent former is present in the composition at levels of from about 15 to about 60% by weight of the composition.
17. 17. The composition, as claimed in clause 16, characterized in that the detergent former comprises one or more phosphates.
18. 18. The composition, as claimed in clause 16, characterized in that the detergent former comprises a zeolite.
19. 19. The composition, as claimed in clause 16, characterized in that the detergent former comprises an alkali metal citrate.
20. 20. The composition, as claimed in clause 16, characterized in that the detergent formed comprises an alkali metal carbonate.
21. 21. The composition, as claimed in clause 16, characterized in that the detergent former is an alkali metal silicate.
22. 22. The composition, as claimed in clause 1, characterized in that it contains 15% by weight of water or less.
23. 23. A process for preparing a concentrated granular detergent composition comprising: a) forming a support suspension by mixing at least one organic surfactant, at least one detergent former, water and a deflocculation polymer composition containing polymer chains of structure P-QR, wherein P represents a segment of the chain of the polymer of a hydrophilic polymer, and QR represents a hydrophobic cap end group wherein R is an organic hydrophobic radical containing from about 4 to about 28 carbon atoms, and Q is selected from a group consisting of O, C02, S, SO, S02, NR ', P04R', P03R ', SiOR'R ", SiR'R", CR'OH, CR'R "and CR'OR" wherein R' YR "are each hydrogen, alkyl group containing from about 1 to 4 carbon atoms or an aryl group: the support suspension comprises layered droplets of a surfactant dispersed in an aqueous phase and having a viscosity ranging from about 2,000 to 5,000 cps, and b) subjecting the suspension to conditions spray drying to produce a granular detergent having a water content of about 15% by weight or less and a deflocculation polymer content ranging from about 0.01 to about 7.5% by weight.
24. 24. The process, as claimed in clause 23, characterized in that the suspension contains from about 15 to 50% by weight of surfactant.
25. 25. The process, as claimed in clause 23, characterized in that the suspension has a viscosity ranging from about 100,000 to 500,000 cps.
26. 26. The process, as claimed in clause 25, characterized in that the viscosity is in the range from about 200,000 to 400,000 cps.
27. 27. The process, as claimed in clause 23, characterized in that the suspension has a solids content ranging from about 35 to 65% by weight.
28. 28. The process, as claimed in clause 27, characterized in that the solids content is in the range from 50 to 65% by weight.
29. 29. The process, as claimed in clause 23, characterized in that the segment P of the hydrophilic polymer chain is polyacrylic or polymethacrylic acid.
30. 30. The process, as claimed in clause 23, characterized in that the segment P is a copolymer containing at least 50% by weight of a polymerized methacrylic or acrylic acid and less than 50% by weight of polymerized maleic acid or maleic anhydride .
31. 31. The process, as claimed in clause 23, characterized in that the polymer has an average molecular weight in a ratio from about 2,000 to 25,000.
32. 32. The process, as claimed in clause 31, characterized in that the polymer has an average molecular weight ranging from about 3,000 to 10,000.
33. 33. The process, as claimed in clause 23, characterized in that from approximately 25 to 95% by weight of the hydrophilic polymer chains present in the deflocculation polymer composition has a P-SR structure.
34. 34. The process, as claimed in clause 33, characterized in that R is an alkyl group containing from about 6 to 18 carbon atoms.
35. 35. The process, as claimed in clause 34, characterized in that R is dodecyl.