AU5869799A - Detergent and descaling composition tablets and use in dishwasher and washing machine - Google Patents

Description

WO 00/22090 1 PCT/FR99/02343 DETERGENT OR DESCALING COMPOSITION TABLETS AND THEIR USE IN DISHWASHERS AND WASHING MACHINES The present invention relates to tablets of 5 compacted particles of a detergent or descaling composition; these tablets can be used for carrying out washing in a washing machine or dishwasher. It is known practice to prepare detergent compositions in the form of tablets which have a fast 10 speed of disintegration and dissolution in an aqueous medium, by compacting particles comprising sodium tripolyphosphate (NaTPP), the said NaTPP consisting of at least 40% phase I and containing from 0.5% to 5% by weight of homogeneously distributed water of hydration 15 (EP-A-839 906). The Applicant has found that the presence of a larger amount of water in NaTPP consisting mainly of phase I makes it possible to avoid the transfer of water present in the tablet to this NaTPP, thus 20 preventing the risks of heating of the tablet with disintegration of the sensitive constituents, in particular such as the enzymes. In addition, the presence of a larger amount of water makes it possible to multiply the number of 25 seeds of hydrated NaTPP and thus helps the tablet to disintegrate and dissolve.

2 A first subject of the invention consists of tablets of a detergent or descaling composition comprising compacted particles based on sodium tripolyphosphate with a high content of phase I and 5 water distributed homogeneously in the said sodium tripolyphosphate, the said tablets being characterized in that the said sodium tripolyphosphate present in the tablet or in the region of the tablet * contains from 70% to 100%, preferably from 10 80% to 98%, by weight of phase I relative to all of the anhydrous sodium tripolyphosphate phases, * contains from 7% to 16%, preferably from 8% to 12%, of its weight of water, at least 50%, preferably from 70% to 90%, of this water being in the 15 form of water of crystallization. The said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water can represent from 5% to 100%, preferably from about 10% to 90%, by weight (expressed as solids) 20 relative to the weight of the tablet (as solids) or of the region of the tablet in which this sodium tripolyphosphate is located. The NaTPP, consisting at least in the majority of phase I used to prepare the tablets of the 25 invention, can be obtained according to a three-step process: spray-drying of a sodium orthophosphate 3 liquor, calcination to NaTPP anhydride phase I and hydration. The spray-drying step can be carried out in a known manner, for example with the aid of a nozzle 5 sprayer or a turbomixer sprayer, using a sodium orthophosphate liquor having a solids content which can be from about 50% to 70%, preferably about 60% by weight, and a gas-generating component, in particular ammonium carbonate, injected into the orthophosphate 10 liquor at the spraying head; the amount of ammonium carbonate introduced may be from about 0.1 to 0.6 by weight (expressed as solids) per 100 parts of orthophosphate (expressed as solids). The inlet temperature of the attacking gases 15 depends on the size of the atomizer and on the fluid flow rates; this temperature can be from about 500 0 C to 600 0 C. The gas outlet temperature can be between 120 0 C and 200 0 C, preferably between 140 0 C and 160 0 C. 20 The orthophosphate particles thus obtained generally have a residual moisture content of less than 5% by weight; their density is from about 0.25 g/cm 3 to 0.45 g/cm 3 , preferably about 0.35 g/cm 3 ; their median diameter is generally between 200 pm and 400 pm; 25 preferably about 300 pm. The calcination operation can be carried out in a known manner, for example in a co-current direct- 4 flame rotating oven, the product being cooled immediately after calcination. The sodium orthophosphate introduced can be calcined over about 30 minutes to one hour, up to a 5 temperature of 4500C to 600 0 C, preferably from 4900C to 530*C. The product thus obtained is an NaTPP powder consisting in the majority of phase I (from about 70% to 100%); it has a particle size of about 250 pm to 10 450 pm, preferably of about 350 pm; its density is from about 0.4 g/cm 3 to 0.65 g/cm 3 , preferably about 0.55 g/cm 3 . The NaTPP powder is then hydrated by spraying with water, for example in a drum, a fast mixer or a 15 fluidized bed, fitted with pulverizers of two-fluid nozzle type generating droplets of about 20 pm to 300 pm, preferably of about 100 pm, until a water content ("water of hydration") of the NaTPP in the particles of about 7% to 16% is obtained. This water 20 content is preferably from about 8% to 12%. The density of the product is less than or equal to 0.8 g/cm 3 , preferably from 0.45 g/cm 3 to 0.65 g/cm 3 . According to a first embodiment, this 25 hydration step is carried out by spraying with an aqueous solution of a base or of a basic salt, such as sodium hydroxide, potassium hydroxide, aqueous 5 solutions of alkali metal silicates, of sodium tripolyphosphate, etc. Mention may be made in particular of spraying with an aqueous NaTPP solution preferably containing less than 20 ppm of Ca or Mg, so 5 as to form "nuclei" of NaTPP-6H 2 0. A second embodiment variant consists in carrying out the hydration step by spraying with an aqueous solution of a wetting agent, for instance nonionic surfactants such as polyethoxylated fatty 10 alcohols, or of a sequestering agent such as salts of polyacetic acids (ethylenediaminetetraacetates, etc.) and polyphosphonates (ethane 1-hydroxy-1,1 diphosphonates, methylenediphosphonate salts, etc.). According to one variant of the invention, 15 the said tablets also comprise at least one other sodium tripolyphosphate, for example a sodium tripolyphosphate with a phase I content of less than 70%, or a tripolyphosphate consisting in the majority or totally of phase II. 20 Most particularly, the said other sodium tripolyphosphate is a sodium tripolyphosphate with a phase II content of at least 70% relative to all of the anhydrous sodium tripolyphosphate phases, and a water content which can range from 0% to 15%, preferably from 25 about 5% to 10%. The said other sodium tripolyphosphate may be present in the tablets of the invention in an amount 6 such that the total amount of NaTPP in the tablets is from about 5% to 100%, preferably from 10% to 90%, depending on the desired use. The tablets which form the subject of the 5 invention can be detergent tablets for washing machines or dishwashers, as well as descaling tablets. They can comprise one, two or even more regions. When they are tablets comprising two regions, 10 the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water is preferably located in the two regions of the tablet. When they are washing machine tablets, the amount of the said sodium tripolyphosphate containing 15 from 70% to 100% by weight of phase I and from 7% to 16% water can represent from 5% to 80% by weight, preferably from about 10% to 60% by weight (expressed as solids), relative to the weight of the tablet (as solids) or of the region of the tablet in which this 20 sodium tripolyphosphate is located. Among the other additives which may be present in the washing machine tablets, mention may be made of sodium tripolyphosphates with a phase I content of less 25 than 70%, or tripolyphosphates consisting in the majority or totally of phase II, in particular tripolyphosphates consisting of at least 70% phase II 7 relative to all of the anhydrous phases, and having a water content of from 0 to 15%, preferably from about 5% to 10%; these sodium tripolyphosphates can be present in the tablets in an amount such that the total 5 amount of NaTPP in the tablets is from about 5% to 60%, preferably from 10% to 50% organic or other inorganic detergent adjuvants ("builders"), in an amount which can be up to 50% by weight, these adjuvants being such as 10 - alkanolamine, ammonium or alkali metal hexametaphosphates, - tetraborates or borate precursors - amorphous or crystalline alkali metal silicates 15 - alkali metal carbonates - the cogranulates of alkali metal silicate hydrates and of alkali metal (sodium or potassium) carbonates rich in silicon atoms, in Q2 or Q3 form, described in EP-A-488,868, for detergent compositions 20 in powder form - crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or of ammonium, such as zeolites A, P, X, etc. - water-soluble polyphosphonates (ethane 25 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.) 8 - water-soluble salts of carboxylic polymers or copolymers such as water-soluble salts of polycarboxylic acids with a molecular mass of about 2000 to 100,000, obtained by polymerization or 5 copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid or methylenemalonic acid, and most particularly polyacrylates with a molecular mass of 10 about 2000 to 10,000 (US-A-3,308,067), and copolymers of acrylic acid and of maleic anhydride with a molecular mass of about 5000 to 75,000 (EP-A-66915) - polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its 15 salts, disuccinic acid tartrate and its salts) - hydroxypolycarboxylate ethers - citric acid and its salts, mellitic acid, and succinic acid and their salts - polyacetic acid salts (ethylenediamine 20 tetraacetates, nitrilotriacetates and N-(2 hydroxyethyl) nitrilodiacetates) - Cs-C 2 0-alkyl succinic acids and their salts (2-dodecenyl succinates, lauryl succinates, etc.) - polyacetal carboxylic esters 25 - polyaspartic acid, polyglutamic acid and their salts R4,, 9 - polyimides derived from the polycondensation of aspartic acid and/or glutamic acid - polycarboxymethylated derivatives of glutamic acid [such as N,N-bis(carboxymethyl)glutamic 5 acid and its salts, in particular the sodium salts] or of other amino acids anionic or nonionic surfactants, in an amount from about 5% to 40% by weight, these agents being such as anionic surfactants (in amounts from about 0% to 20%), 10 for instance - alkyl ester sulphonates of formula R-CH(SO 3 M)-COOR', where R represents a C 8

-

2 0 , preferably C 1 o-C 1 , alkyl radical, R' represents a C 1

-C

6 , preferably C 1

-C

3 , alkyl radical and M represents an alkali-metal (sodium, 15 potassium, lithium) cation, an ammonium cation which is substituted or unsubstituted (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium, etc.) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.); 20 - alkyl sulphates of formula ROSO 3 M, in which R represents a C 5

-C

2 4 , preferably Cio-C 18 , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as the ethoxylenated (EO) and/or propoxylenated (PO) 25 derivatives thereof, having on average from 0.5 to 30, preferably from 0.5 to 10, EO and/or PO units; 10 - alkylamide sulphates of formula RCONHR'OSO 3 M in which R represents a C 2

-C

2 2 , preferably C6-C 2 0, alkyl radical, R' represents a C 2

-C

3 alkyl radical, M representing a hydrogen atom or a cation of the same definition as 5 above, as well as the ethoxylenated (EO) and/or propoxylenated (PO) derivatives thereof, having on average from 0.5 to 60 EO and/or PO units; - saturated or unsaturated C 8

-C

2 4 , preferably C 1 4

-C

2 0, fatty acid salts, C 9

-C

2 0 alkylbenzene sulphonates, 10 primary or secondary C 8

-C

2 2 alkyl sulphonates, alkylglycerol sulphonates, the sulphonated polycarboxylic acids described in GB-A-1,082,179, paraffin sulphonates, N-acyl-N-alkyl taurates, alkyl phosphates, isethionates, alkyl succinamates, alkyl 15 sulphosuccinates, sulphosuccinate monoesters or diesters, N-acylsarcosinates, alkylglycoside sulphates and polyethoxycarboxylates; the cation being an alkali metal (sodium, potassium, lithium), an ammonium residue which is substituted or 20 unsubstituted (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium, etc.) or an alkanolamine derivative (monoethanolamine, diethanolamine, triethanolamine, etc.); - sophorolipids, such as those in acid or lactone form, 25 derived from 17-hydroxyoctadecenoic acid; nonionic surfactants, (in amounts from about 0% to 30%), for instance 11 - polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C 6

-C

12 and containing from 5 to 25 oxyalkylene units; by way of example, 5 mention may be made of Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Co. and Igepal NP2 to NP17 from Rh8ne-Poulenc; - polyoxyalkylenated C 8

-C

22 aliphatic alcohols containing from 1 to 25 oxyalkylene (oxyethylene, 10 oxypropylene) units; by way of example, mention may be made of Tergitol 15-S-9, Tergitol 24-L-6 NMW sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7, Neodol 45-4 sold by Shell Chemical Co., Kyro EOB sold by The Procter & Gamble Co., Synperonic A3 to A9 15 from ICI, Rhodasurf IT, DB and B from Rh8ne-Poulenc and Plurafac LF 403 sold by BASF; - products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol or ethylene glycol, with a weight-average molecular mass 20 of about 2000 to 10,000, such as the Pluronic products sold by BASF; - products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as the Tetronic products sold by BASF; 25 - ethoxylated and/or propoxylated C 8

-C

18 fatty acids containing from 5 to 25 ethoxylated and/or propoxylated units; 12 - CB-C 2 0 fatty acid amides containing from 5 to 30 ethoxylated units; - ethoxylated amines containing from 5 to 30 ethoxylated units; 5 - alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, and most particularly from 2 to 20, oxyalkylene (preferably oxyethylene) units; - amine oxides such as C 10

-C

18 alkyl dimethylamine oxides, C 8

-C

22 alkoxy ethyldihydroxyethylamine oxides; 10 - alkoxylated terpenic hydrocarbons such as ethoxylated and/or propoxylated a- or @-pinenes, containing from 1 to 30 oxyethylene and/or oxypropylene units; - alkylpolyglycosides which can be obtained by condensation (for example by acid catalysis) of glucose 15 with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-132,043; EP-A-132,046, etc.) having a C 4

-C

2 0 , preferably C 8

-C

18 , alkyl group, as well as an average number of glucose units of about 0.5 to 3, preferably of about 1.1 to 1.8, per mole of 20 alkylpolyglycoside (APG); mention may be made in particular of those having * a C 8

-C

14 alkyl group and on average 1.4 glucose units per mole * a C 1 2

-C

1 4 alkyl group and on average 1.4 glucose 25 units per mole * a C 8

-C

14 alkyl group and on average 1.5 glucose units per mole 13 * a Ca-Cio alkyl group and on average 1.6 glucose units per mole sold respectively under the names Glucopon 600 EC7, Glucopon 600 CSUP7, Glucopon 650 EC7 and Glucopon 225 5 CSUP7 by Henkel; antisoiling agents, in amounts of about 0.01-10%, preferably of about 0.1-5% and most particularly of about 0.2-3%, by weight, these agents being such as - cellulose derivatives such as cellulose hydroxy 10 ethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose and hydroxybutyl methylcellulose, - polyvinyl esters grafted onto polyalkylene trunks, such as polyvinyl acetates grafted onto polyoxyethylene trunks (EP-A-219,048) 15 - polyvinyl alcohols - polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and polyoxyethylene terephthalate units, with an ethylene terephthalate and/or propylene terephthalate (number of 20 units)/polyoxyethylene terephthalate (number of units) molar ratio from about 1/10 to 10/1, the polyoxyethylene terephthalate units having polyoxyethylene units with a molecular weight from about 300 to 10,000, with a molecular mass of the 25 copolyester from about 1000 to 100,000 - polyester copolymers based on ethylene terephthalate and/or propylene terephthalate and 14 polyoxyethylene and/or polyoxypropylene units, with an ethylene terephthalate and/or propylene terephthalate (number of units)/polyoxyethylene and/or polyoxypropylene (number of units) molar ratio from 5 about 1/10 to 10/1, the polyoxyethylene and/or polyoxypropylene units having a molecular weight from about 250 to 10,000, with a molecular mass of the copolyester from about 1000 to 100,000 (US-A-3 959 230, US-A-3 962 152, US-A-3 893 929, US-A-4 116 896, 10 US-A-4 702 857, US-A-4 770 666, EP-A-253 567, EP-A-201 124) - ethylene or propylene terephthalate/polyoxyethylene terephthalate copolymers comprising sulphoisophthaloyl units in their chain 15 (US-A-4 711 730; US-A-4 702 857; US-A-4 713 194) - terephthalic copolyester oligomers with sulphonated polyalkenoxyalkyl and sulphoaroyl end groups and optionally containing sulphoisophthaloyl units in their chain (US-A-4 721 580; US-A-5 415 807; 20 US-A-4 877 896; US-A-5 182 043; US-A-5 599 782; US-A-4 764 289; EP-A-311 342; WO 92/04433; WO 97/42293) - sulphonated terephthalic copolyesters with a molecular mass of less than 20,000, for example obtained from a diester of terephthalic acid or of 25 isophthalic acid or from a diester of sulphoisophthalic acid and of a diol, in particular ethylene glycol (WO 95/32997) 15 - polyester-polyurethanes obtained by reaction of a polyester with a number-average molecular mass of 300-4000 obtained from a terephthalic acid diester, optionally from a diester of sulphoisophthalic acid and 5 of a diol, with a prepolymer containing isocyanate end groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and from a diisocyanate (US-A-4 201 824) - sulphonated polyester oligomers obtained by 10 sulphonation of an oligomer derived from ethoxylated allyl alcohol, from dimethyl terephthalate and from 1,2-propylene diol, containing from 1 to 4 sulphonated groups (US-A-4 968 451); anti-redeposition agents, in amounts of about 0.01-10% 15 by weight for a detergent composition in powder form, these agents being such as - ethoxylated monoamines or polyamines and ethoxylated amine polymers (US-A-4 597 898, EP-A-11 984) 20 - carboxymethylcellulose - sulphonated polyester oligomers obtained by condensation of isophthalic acid, dimethyl sulphosuccinate and diethylene glycol (FR-A-2 236 926) - polyvinylpyrrolidones 25 bleaching agents, in an amount of about 0.1-20%, preferably 1-10%, of the weight of said detergent composition in powder form, such as I-I57 7 N47 ,x 16 - perborates such as sodium perborate monohydrate or tetrahydrate - peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, 5 urea peroxyhydrate, sodium peroxide and sodium persulphate - percarboxylic acids and their salts (known as percarbonates") such as magnesium monoperoxyphthalate hexahydrate, magnesium meta 10 chloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, peroxysuccinic acid nonylamide and decyldiperoxysuccinic acid, preferably combined with a bleaching activator 15 generated in situ in the washing medium, a peroxycarboxylic acid; among these activators, mention may be made of tetraacetylethylenediamine, tetraacetylmethylenediamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulphonate, pentaacetyl 20 glucose, octaacetyl lactose, etc. fluorescence agents, in an amount of about 0.05-1.2% by weight, these agents being such as derivatives of stilbene, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes, etc. 25 foam suppressants, in amounts which can be up to 5% by weight, these agents being such as 17 - C 10

-C

24 monocarboxylic fatty acids or their alkali-metal, ammonium or alkanolamine salts, and fatty acid triglycerides - saturated or unsaturated aliphatic, 5 alicyclic, aromatic or heterocyclic hydrocarbons, such as paraffins or waxes, - N-alkylaminotriazines - monostearyl phosphates and monostearyl alcohol phosphates 10 - polyorganosiloxane oils or resins optionally combined with silica particles softeners, in amounts of about 0.5-10% by weight, these agents being such as clays enzymes in an amount which can be up to 5 mg by weight, 15 preferably about 0.05-3 mg, of active enzyme/g of detergent composition, these enzymes being such as proteases, amylases, lipases, cellulases and peroxidases (US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4 261 868) 20 and other additives such as - alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol and glycerol) - buffers or fillers such as sodium sulphate, alkaline earth metal carbonates or bicarbonates 25 - pigments - disintegrating agents - compacting agents such as polyethylene glycols. < 7-~ hiyN-/" 18 When they are dishwasher tablets, the amount of the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water can represent from 10% to 90% by weight (expressed as 5 solids) relative to the weight of the tablet (as solids) or of the region of the tablet in which this sodium tripolyphosphate is located. Among the other additives which may be present in the dishwasher tablets, mention may be made 10 of - sodium tripolyphosphates with a phase I content of less than 70%, or tripolyphosphates consisting in the majority or totally of phase II, in particular tripolyphosphates consisting of at least 70% phase II 15 relative to all of the anhydrous phases, and having a water content of from 0% to 15%, preferably from about 5% to 10%; these sodium tripolyphosphates can be present in the tablets in an amount such that the total amount of NaTPP in the tablets is from about 20% to 20 80%; - other basifying additives or sequestering additives that are soluble in the washing medium, for instance - alkanolamine, ammonium or alkali metal hexametaphosphates 25 tetraborates or borate precursors alkali metal silicates (0% to 30% by weight) 19 - alkali metal carbonates (0% to 30% by weight) - the cogranulates of alkali metal silicate hydrates and of alkali metal (sodium or potassium) 5 carbonates rich in silicon atoms, in Q2 or Q3 form, described in EP-A-488,868, for detergent compositions in powder form - crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or of ammonium, 10 such as zeolites A, P, X, etc. - water-soluble polyphosphonates (ethane 1-hydroxy-1,1-diphosphonates, methylene diphosphonate salts, etc.) - water-soluble salts of carboxylic polymers 15 or copolymers such as water-soluble salts of polycarboxylic acids with a molecular mass of about 2000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or 20 anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid or methylenemalonic acid, and most particularly polyacrylates with a molecular mass of about 2000 to 10,000 (US-A-3,308,067), copolymers of acrylic acid and of maleic anhydride with a molecular 25 mass of about 5000 to 75,000 (EP-A-66915) 20 - polycarboxylate ethers (oxydisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts) - hydroxypolycarboxylate ethers 5 - citric acid and its salts, mellitic acid, succinic acid and their salts - polyacetic acid salts (ethylenediamine tetraacetates, nitrilotriacetates and N-(2 hydroxyethyl) nitrilodiacetates) 10 - Cs-C 2 0 -alkyl succinic acids and their salts (2-dodecenyl succinates, lauryl succinates, etc.) - polyacetal carboxylic esters - polyaspartic acid, polyglutamic acid and their salts 15 - polyimides derived from the polycondensation of aspartic acid and/or glutamic acid - polycarboxymethylated derivatives of glutamic acid [such as N,N-bis(carboxymethyl)glutamic acid and its salts, in particular the sodium salts] or 20 of other amino acids - alkali metal bicarbonates and sesquicarbonates - bleaching agents such as alkali metal perborates and percarbonates (0% to 20%) combined with a bleaching activator (tetraacetylethylenediamine) (up to 10%) and 25 optionally combined with a bleaching catalyst (organometallic complexes of manganese, cobalt, etc.) (0% to 1%) 21 - nonionic surfactants (0.2% to 5%), for instance - polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated or polyoxybutylenated) alkylphenols in which the alkyl substituent is C6-C 12 and containing 5 from 5 to 25 oxyalkylene units; by way of example, mention may be made of Triton X-45, X-114, X-100 or X-102 sold by Rohm & Haas Co. and Igepal NP2 to NP17 from Rh6ne-Poulenc; - polyoxyalkylenated C 8

-C

22 aliphatic alcohols 10 containing from 1 to 25 oxyalkylene (oxyethylene or oxypropylene) units; by way of example, mention may be made of Tergitol 15-S-9 and Tergitol 24-L-6 NMW sold by Union Carbide Corp., Neodol 45-9, Neodol 23-65, Neodol 45-7 and Neodol 45-4 sold by Shell Chemical Co., Kyro 15 EOB sold by The Procter & Gamble Co., Synperonic A3 to A9 from ICI, Rhodasurf IT, DB and B from Rh6ne-Poulenc, and Plurafac LF 403 sold by BASF; - products resulting from the condensation of ethylene oxide or of propylene oxide with propylene 20 glycol or ethylene glycol, with a weight-average molecular mass of about 2000 to 10,000, such as the Pluronic products sold by BASF; - products resulting from the condensation of ethylene oxide or of propylene oxide with 25 ethylenediamine, such as the Tetronic products sold by

BASF;

22 - ethoxylated and/or propoxylated C 8

-C

18 fatty acids containing from 5 to 25 ethoxylated and/or propoxylated units; - C 8

-C

20 fatty acid amides containing from 5 5 to 30 ethoxylated units; - ethoxylated amines containing from 5 to 30 ethoxylated units; - alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25 and most particularly 10 from 2 to 25, oxyalkylene units (preferably oxyethylene units); - amine oxides such as (Cio-C 18 ) alkyldimethylamine oxides and (C 8

-C

2 2 ) alkoxyethyldihydroxyethylamine oxides; 15 - alkoxylated terpenic hydrocarbons such as ethoxylated and/or propoxylated a- or P-pinenes, containing from 1 to 30 oxyethylene and/or oxypropylene units; - anionic surfactants (0% to 5%) 20 - enzymes (0% to 4%) - dyes, fragrances - tablet-compacting agents, such as polyethylene glycols, or tablet-disintegrating agents. When they are descaling tablets, the amount 25 of the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water can represent from 10% to 100% by weight, preferably 23 from 20% to 90% by weight (expressed as solids), relative to the weight of the tablet (as solids) or of the region of the tablet in which this sodium tripolyphosphate is located. 5 Among the other additives which may be present in the descaling tablets, mention may be made of - sodium tripolyphosphates with a phase I content of less than 70%, or tripolyphosphates consisting in the 10 majority or totally of phase II, in particular tripolyphosphates consisting of at least 70% phase II relative to all of the anhydrous phases, and having a water content of from 0% to 15%, preferably from about 5% to 10%; these sodium tripolyphosphates can be 15 present in the tablets in an amount such that the total amount of NaTPP in the tablets is from about 30% to 99%, preferably from 50% to 90%. - sodium hexametaphosphate (0% to 10%) - amorphous or crystalline alkali metal silicates (0% 20 to 30%) - alkali metal carbonates (0% to 30%) - amorphous or crystalline ammonium or alkali metal aluminosilicates (0% to 30%) - water-soluble polyphosphonates (ethane-l-hydroxy-1,1 25 diphosphonates, methylenediphosphonate salts, etc.) (0% to 5%) 37T RR' 7_ 24 - water-soluble salts of carboxylic polymers or copolymers (0% to 20%), such as water-soluble salts of polycarboxylic acids with a molecular mass of about 2000 to 100,000, obtained by polymerization or 5 copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid, maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid or methylenemalonic acid, and most particularly polyacrylates and 10 copolymers of acrylic acid and of maleic anhydride - surfactants (0% to 10%). The tablets forming the subject of the invention can be obtained in a conventional manner by pressing the desired amount of a particulate 15 composition in a mould, this composition containing the various constituents of the said tablets. The density of the tablets may be from about 0.9 g/cm 3 to 2 g/cm 3 , depending on the desired use. The examples which follow are given as a 20 guide. Examples 1-10 The following are introduced into an industrial Niro atomizer equipped with a turbomixer * 3 m 3 /h of sodium orthophosphate liquor with 25 a solids content of 61% by weight, at a temperature of 90 0

C

25 * 0.3 part by weight (as solids) of ammonium carbonate per 100 parts by weight (as solids) of sodium orthophosphate. The gas inlet temperature is 500*C; the 5 outlet temperature is 150 0 C. The product obtained, with a density of 0.35 g/cm 3 , is then calcined up to 520 0 C in a co-current direct-flame rotating oven. The NaTPP obtained has the following characteristics: 10 * a phase I content of 87% relative to all of the anhydrous phases * a density of 0.55 g/cm 3 . A portion of the product is hydrated in an industrial drum by spraying it with water, so as to 15 obtain an NaTPP having different degrees of "hydration": * 3.3% water, 54% of this water being in the form of water of crystallization * 4.4% water, 62% of this water being in the 20 form of water of crystallization * 8% water, 74% of this water being in the form of water of crystallization Examples 1, 2 and 3, respectively. Another portion is not hydrated (Example 4). 25 A third portion is hydrated batchwise in a Lbdige high-speed blender, by spraying it with water, 26 so as to obtain an NaTPP with different degrees of "hydration": * 4% water, 63% of this water being in the form of water of crystallization 5 * 8% water, 75% of this water being in the form of water of crystallization * 10% water, 78% of this water being in the form of water of crystallization Examples 5, 6 and 7, respectively. 10 A fourth portion is hydrated by spraying it with water continuously in a Comessa fluidized bed (from Comessa), for which the flow rate of powder is from 50 kg/h to 100 kg/h, so as to obtain an NaTPP with different degrees of "hydration": 15 * 4% water, * 8% water, * 10% water, Examples 8, 9 and 10, respectively. Test 1 20 31.5 g of non-hydrated or hydrated NaTPP of Examples 4 to 7 are compacted without further modification, using a Zwick 14 78 00/01 press, the force applied being 2.4 knewtons, to form cylindrical tablets 41 mm in diameter. 25 Each tablet is placed on a screen (mesh size of 2 mm) immersed in 9 litres of demineralized water at 22*C, with stirring (200 rpm).

27 The dissolution speed (DS) of each tablet is determined by monitoring the conductivity of the water. The time required for 90% of the tablet to dissolve is thus determined. 5 The results are given in Table 1. Test 2 30 parts of NaTPP of Examples 1 to 3, 5-6 and 8 to 10 are mixed with 70 parts of a washing base containing: 10 * 11% alkylbenzene sulphonate * 5% nonionic surfactant * 30% phase (I) NaTPP of Examples 1-3, 5-6 and 8-10 * 10% NaTPP of LV brand sold by Europhos * 7% atomized and granulated silicate of ratio R2 15 * 6% sodium carbonate * 15% sodium percarbonate * 4% TAED * 2% of an antifoaming agent (granulated) * 2% Sokalan CP5 from BASF 20 * 4% enzymes and fragrance 31.5 g of each mixture are compacted, the force applied being 1.6 knewtons or 2.4 knewtons, to form cylindrical tablets 41 mm in diameter. The dissolution speed and the longitudinal 25 breaking tension t in pascals are measured for each tablet. '7A 28 The longitudinal breaking tension t is given by the equation t = 2F/nDe, in which * F is the force applied, in newtons * D is the diameter of the tablet, in metres 5 * e is the thickness of the tablet, in metres. The results are given in Table 2. TABLE 1 NaTPP of Degree of Force applied DS90 in Example "hydration" in kN minutes in % 4 -0 2.4 16 5 4 2.4 4 6 8 2.4 2 7 10 2.4 0.6 29 TABLE 2 NaTPP Degree of Force DS90 t of Example "hydration" applied in minutes in kPa in % in kN 1 3.3 1.6 6.7 9.9 2.4 9.3 15.2 2 4.4 1.6 4 9.9 2.4 5.2 15.3 3 8 1.6 2.6 10.3 2.4 4.2 23 5 4 1.6 3.7 19.0 2.4 5.6 32.4 6 8 1.6 2.7 19.2 2.4 3.9 33.1 8 4 2.4 4.4 25.7 9 8 2.4 3 25.5 10 10 2.4 3.2 27.3 ST /'

Claims (15)

1. Tablets of a detergent or descaling composition comprising compacted particles based on 5 sodium tripolyphosphate with a high content of phase I and water distributed homogeneously in the said sodium tripolyphosphate, the said tablets being characterized in that the said sodium tripolyphosphate present in the tablet or in the region of the tablet 10 * contains from 70% to 100%, preferably from 80% to 98%, by weight of phase I relative to all of the anhydrous sodium tripolyphosphate phases, * contains from 7% to 16% of its weight of water, at least 50%, preferably from 70% to 90%, of 15 this water being in the form of water of crystallization.

2. Tablets according to Claim 1, characterized in that the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and 20 from 7% to 16% of water represents from 5% to 100%, preferably from about 10% to 90%, by weight (expressed as solids) relative to the weight of the tablet (as solids) or of the region of the tablet in which this sodium tripolyphosphate is located. 25

3. Tablets according to Claim 1 or 2, characterized in that the said sodium tripolyphosphate 31 containing from 70% to 100% by weight of phase I contains from about 8% to 12% water.

4. Tablets according to any one of Claims 1 to 3, characterized in that the said sodium 5 tripolyphosphate containing from 70% to 100% by weight of phase I has a density of less than or equal to 0.8 g/cm 3 , preferably from 0.45 g/cm 3 to 0.65 g/cm 3 .

5. Tablets according to any one of Claims 1 to 4, characterized in that they also comprise at least 10 one other sodium tripolyphosphate, preferably a sodium tripolyphosphate with a phase I content of less than 70% and/or a tripolyphosphate consisting in the majority or totally of phase II.

6. Tablets according to Claim 5, 15 characterized in that the said other sodium tripolyphosphate is a sodium tripolyphosphate with a phase II content of at least 70% relative to all of the anhydrous sodium tripolyphosphate phases, and a water content which can range from 0% to 15%, preferably from 20 about 5% to 10%.

7. Tablets according to Claim 6, characterized in that the said other sodium tripolyphosphate is present in the tablets in an amount such that the total amount of NaTPP in the tablets is 25 from about 5% to 100%, preferably from 10% to 90%.

8. Tablets according to any one of Claims 1 to 7, characterized in that they are detergent tablets 32 for washing machines or dishwashers, or descaling tablets.

9. Tablets according to any one of Claims 1 to 8, characterized in that they are washing machine 5 tablets, in which the amount of the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water represents from 5% to 80%, preferably from about 10% to 60% (expressed as solids), relative to the weight of the tablet (as 10 solids) or of the region of the tablet in which this sodium tripolyphosphate is located.

10. Tablets according to Claim 9, characterized in that they also contain a sodium tripolyphosphate consisting of at least 70% of phase II 15 relative to all of the anhydrous phases and having a water content of from 0% to 15%, preferably from about 5% to 10%, in an amount such that the total amount of NaTPP in the tablets is from about 5% to 60%, preferably from 10% to 50%. 20

11. Tablets according to any one of Claims 1 to 8, characterized in that they are dishwasher detergent tablets, in which the amount of the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water represents 25 from 10% to 90% by weight (expressed as solids) relative to the weight of the tablet (as solids) or of 33 the region of the tablet in which this sodium tripolyphosphate is located.

12. Tablets according to Claim 11, characterized in that they also contain a sodium 5 tripolyphosphate consisting of at least 70% phase II relative to all of the anhydrous phases and having a water content of from 0% to 15%, preferably from about 5% to 10%, in an amount such that the total amount of NaTPP in the tablets is from about 20% to 80%. 10

13. Tablets according to any one of Claims 1 to 8, characterized in that they are dishwasher detergent tablets, in which the amount of the said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7% to 16% water represents 15 from 10% to 100%, preferably from 20% to 90% by weight (expressed as solids), relative to the weight of the tablet (as solids) or of the region of the tablet in which this sodium tripolyphosphate is located.

14. Tablets according to Claim 13, 20 characterized in that they also contain a sodium tripolyphosphate consisting of at least 70% phase II relative to all of the anhydrous phases and having a water content of from 0% to 15%, preferably from about 5% to 10%, in an amount such that the total amount of 25 NaTPP in the tablets is from about 30% to 99%, preferably from 50% to 90%. 34

15. Process for preparing the tablets forming the subject of any one of the preceding claims, by pressing the desired amount of a particulate composition in a mould, this composition containing the 5 various constituents of the said tablets.