EP1119606A1

EP1119606A1 - Detergent and descaling composition tablets and use in dishwasher and washing machine

Info

Publication number: EP1119606A1
Application number: EP99946276A
Authority: EP
Inventors: Patrick Ferlin; Francisco Javier Dupuy Arnau
Original assignee: Rhodia Chimie SAS
Current assignee: Rhodia Chimie SAS
Priority date: 1998-10-09
Filing date: 1999-10-01
Publication date: 2001-08-01
Also published as: RU2213132C2; FR2784392A1; ZA200102369B; CN1323342A; FR2784392B1; AU754500B2; HK1042109A1; AU5869799A; WO2000022090A1

Abstract

The invention concerns detergent and descaling composition tablets comprising compacted sodium tripolyphosphate particles with a high phase I content and water homogeneously distributed in said sodium tripolyphosphate, said tablets being characterised in that said sodium tripolyphosphate present in the tablet or in a region of the tablet contains: 70 % to 100 % wt.%, preferably 80 % to 98 wt.% of phase I relative to all the anhydrous tripolyphosphate phases; 7 % to 16 % of its weight in water, at least 50 %, preferably 70 % to 90 % of said water being in the form of crystallisation water.

Description

TABLETS OF DETERGENT OR ANTICALCAL COMPOSITION AND THEIR IMPLEMENTATION IN DISHWASHER OR WASHING MACHINE

The subject of the present invention is tablets of compacted detergent or anti-scale composition particles; these can be implemented for carrying out washing operations in a washing machine or dishwasher.

It is known to prepare detergent compositions in the form of tablets having a rapid disintegration and dissolution rate in an aqueous medium, by compacting particles comprising sodium tripolyphosphate (NaTPP), said NaTPP consisting of at least 40% of phase. I and containing from 0.5 to 5% by weight of water of hydration distributed in a homogeneous manner (EP-A-839 906).

The Applicant has found that the presence of a higher amount of water in the NaTPP consisting mainly of phase I, makes it possible to avoid the transfer of water present in the tablet to this NaTPP, thus preventing the risks of heating of the tablet with disintegration of sensitive constituents such as enzymes in particular.

In addition, the presence of a greater quantity of water makes it possible to multiply the number of germs of hydrated NaTPP and thus facilitates the disintegration and the dissolution of the tablet.

A first subject of the invention consists of tablets of detergent or anti-limescale composition comprising compacted particles based on sodium tripolyphosphate having a high content in phase I and water distributed homogeneously in said sodium tripolyphosphate, said tablets being characterized in that said sodium tripolyphosphate present in the tablet or in a region of the tablet,

^* contains from 70% to 100%, preferably from 80% to 98% by weight of phase I relative to all the phases of anhydrous sodium tripolyphosphates

^* 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 form of water of crystallization.

Said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, can represent from 5% to 100%, preferably of the order of 10% to 90% by weight ( expressed in sec) relative to the weight of the tablet (in sec) or the region of the tablet in which it is located.

The NaTPP consisting at least mainly of phase I used for the production of the tablets of the invention, can be obtained according to a three-step process stages, spray drying of a sodium orthophosphate liquor, calcination in NaTPP anhydride phase I and hydration.

The spray drying step can be carried out in a known manner, for example using a nozzle or turbine atomizer, using a sodium orthophosphate liquor having a dry extract which may be on the order of 50% to 70%, preferably on the order of 60% by weight, and a pore-forming element, in particular ammonium carbonate, injected into the orthophosphate liquor at the spray head; the content of ammonium carbonate introduced can be of the order of 0.1 to 0.6, by weight (expressed in dry) per 100 parts of orthophosphate (expressed in dry). The inlet temperature of the attack gases depends on the size of the atomizer and the flow rates of the fluids; this can be of the order of 500 to 600 ° C.

The gas outlet temperature can be between 120 and 200 ° C, preferably 140 and 160 ° C. The orthophosphate particles thus obtained generally have a residual humidity of less than 5% by weight; their density is of the order of 0.25 g / cm ³ to 0.45 g / cm ³ , preferably of the order of 0.35 g / cm ³ ; their median diameter is generally between 200 and 400 μm, preferably of the order of 300 μm. The calcination operation can be carried out in a known manner, for example in a rotary furnace with direct co-current flame, the product being directly cooled after calcination.

The sodium orthophosphate introduced can be calcined in approximately 30 minutes to one hour, up to a temperature of 450 to 600 ° C, preferably 490 to 530 ° C. The product thus obtained is a NaTPP powder consisting mainly of phase I (of the order of 70 to 100%); it has a particle size of the order of 250 to 450 μm, preferably of the order of 350 μm; its density is of the order of 0.4 g / cm ³ to 0.65 g / cm ³ , preferably of the order of 0.55 g / cm ³ .

The NaTPP powder is then hydrated by spraying water, for example in a drum, a rapid mixer or a fluidized bed, fitted with sprayers of the bi-fluid nozzle type generating droplets of the order of 20 μm to 300 μm, preferably of the order of 100 μm, until a water content ("water of hydration") of the NaTPP in the particles is obtained of the order of 7 to 16%. Preferably, this water content is of the order of 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 hydration step is carried out by spraying an aqueous solution of a base or a basic salt, such as sodium hydroxide, potassium hydroxide, aqueous solutions of alkali metal silicates, of tripolyphosphate sodium ... Mention may in particular be made of the spraying of an aqueous solution of NaTPP preferably containing less than 20 ppm of Ca or Mg, so as to form "nucleis" of NaTPP, 6H ₂ 0.

A second embodiment consists in carrying out the hydration step by spraying with an aqueous solution of a wetting agent such as nonionic surfactants such as polyethoxylated fatty alcohols, or of a sequestering agent such as the salts of polyacetic acids (ethylenediaminetetraacetates ...), polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, methylene salts diphosphonates ...).

According to a variant of the invention, said tablets also comprise at least one other sodium tripolyphosphate, for example a sodium tripolyphosphate having a phase I content of less than 70%, or a tripolyphosphate consisting mainly or completely of phase II.

In particular, said other sodium tripolyphosphate is a sodium tripolyphosphate having a phase II content of at least 70% relative to all of the anhydrous phases of sodium tripolyphosphate, and a water content which can range from 0 to 15 %, preferably of the order of 5 to 10%.

Said other sodium tripolyphosphate may be present in the tablets of the invention in an amount such that the total amount of NaTPP in the tablets is of the order of 5 to 100%, preferably from 10 to 90% depending on the use sought. .

The tablets which are the subject of the invention can be detergent tablets for washing machines or dishwashers, as well as anti-limescale tablets. They can have one or two or even several regions.

In the case of tablets comprising two regions, said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, is preferably located in the two regions of the tablet. In the case of washing machine tablets, the amount of said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, may represent from 5% to 80%, preferably of the order of 10% to 60% by weight (expressed in sec) relative to the weight of the tablet (in dry) or of the region of the tablet in which it is located. Among the other additives that may be present in washing machine tablets, mention may be made of sodium tripolyphosphates having a phase I content of less than 70%, or tripolyphosphates consisting mainly or completely of phase II, in particular tripolyphosphates consisting of at least 70% of phase II relative to all of the anhydrous phases and having a water content of 0 to 15%, preferably of the order of 5 to 10%; these can be present in the tablets in an amount such that the total amount of NaTPP in the tablets is of the order of 5 to 60%, preferably from 10 to 50% other or organic mineral builders, in amounts up to 50% by weight, such as

- hexametaphosphates of alkali metals, ammonium or alkanolamines

- tetraborates or borate precursors - amorphous or crystallized alkali metal silicates

- alkali metal carbonates

- the cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868, for the detergent powder compositions - the aluminosilicates crystalline or amorphous of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, ...

- water-soluble polyphosphonates (ethane 1-hydroxy-1, 1-diphosphonates, methylene salts diphosphonates, ...)

the water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids with a molecular mass of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, acid or maleic anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular mass of the order of 5,000 to 75,000 (EP-A-66,915)

- polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts

- hydroxypolycarboxylate ethers - citric acid and its salts, mellitic acid, succinic acid and their salts

- the salts of polyacetic acids (ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl) -nitrilodiacetates)

- C ₅ -C ₂ o succinic acids and their salts (2-dodecenylsuccinates, lauryl succinates, ...) - polyacetal carboxylic esters

- polyaspartic acid, polyglutamic acid and their salts

- polyimides derived from the polycondensation of aspartic acid and / or glutamic acid

- the polycarboxymethylated derivatives of glutamic acid [such as N, N-bis (carboxymethyl) glutamic acid and its salts, especially of sodium] or other amino acids of anionic or nonionic surfactants in quantity of the from 5 to 40% by weight, agents such as anionic surfactants (in amounts of the order of 0 to 20%) such as. the alkyl esters sulfonates of formula R-CH (SO ₃ M) -COOR ', where R represents an alkyl radical in C ₈ -C ₂₀ , preferably in C ₁₀ -C ₁₆ , R' an alkyl radical in CC ₆ , preferably in CC ₃ and M an alkali cation (sodium, potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...);

. the alkyl sulphates of formula ROSO ₃ M, where R represents a C ₅ -C ₂₄ , preferably C ₁₀ -C ₁₈ , alkyl or hydroxyalkyl radical, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 30 units, preferably from 0.5 to 10 OE and / or OP units;

. the sulfonated alkylamides of formula RCONHR'OSO ₃ M, in which R represents a C ₂ -C ₂₂ , preferably C ₆ -C ₂₀ , alkyl radical, R ′ a C ₂ -C ₃ alkyl radical, M representing a d atom hydrogen or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 OE and / or OP units;

. the salts of C ₈ -C ₂₄ , preferably C ₁₄ -C ₂₀ saturated or unsaturated fatty acids, C ₉ -C ₂₀ alkylbenzenesulfonates, C ₈ -C ₂₂ primary or secondary alkylsulfonates, alkylglycerol sulfonates, sulfonated polycarboxylic acids described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates , alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derivative d '' an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...); . sophorolipids, such as those in acid or lactone form, derived from 17-hydroxyoctadecenic acid; non-ionic surfactants (in amounts of the order of 0 to 30%) such as polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C ₆ -C ₁₂ and containing from 5 to 25 oxyalkyiene units ; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy., the IGEPAL NP2 to NP17 from RHÔNE-POULENC;

. polyoxyalkylenated C ₈ -C ₂₂ aliphatic alcohols containing from 1 to 25 oxyalkyiene units (oxyethylene, oxypropylene); by way of example, mention may be made of TERGITOL 15-S-9, TERGITOL 24-L-6 NMW marketed by Union Carbide Corp., NEODOL 45-9, NEODOL 23-65, NEODOL 45-7, NEODOL 45-4 marketed by Shell Chemical Cy, KYRO EOB marketed by The Procter & Gamble Cy, SYNPERONIC A3 to A9 from ICI, RHODASURF IT, DB and B from RHÔNE-POULENC, PLURAFAC LF 403 marketed by BASF;

. the products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, of molecular weight by weight of the order of 2,000 to 10,000, such as the PLURONIC sold by BASF; . products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as TETRONIC sold by BASF;

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

. amides of C ₈ -C ₂₀ fatty acids containing from 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, very particularly from 2 to 20 oxyalkylene units (preferably oxyethylene;. amine oxides such as C ₁₀ -C ₁₈ alkyl oxides dimethylamines, alkoxy oxides C ₈ -C ₂₂ ethyl dihydroxy ethylamines; alkoxylated terpene hydrocarbons such as ethoxylated and / or propoxylated - or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units;

. alkylpolyglycosides obtainable by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865; US-A-4,565,647; EP-A-132,043; EP-A-132 046 ...) having a C ₂₀ -C ₂₀ , preferably C ₈ -C ₁₈ alkyl group, as well as an average number of glucose units of the order of 0.5 to 3, preferably of the order of 1.1 to 1.8 per mole of alkylpolyglycoside (APG); we can mention in particular those presenting

^* a C ₈ -C ₁₄ alkyl group and on average 1, 4 glucose unit per mole

* a Cι ₂ -C ₁₄ alkyl group and on average 1, 4 glucose unit per mole

* a C ₈ -C ₁₄ alkyl group and on average 1, 5 glucose unit per mole * a C ₈ -C ₁₀ alkyl group and on average 1, 6 glucose unit per mole sold respectively under the names GLUCOPON 600 EC ^® , GLUCOPON 600 CSUP ^® , GLUCOPON 650 EC ^® , GLUCOPON 225 CSUP ^® , by HENKEL anti-fouling agents, in quantities of the order of 0.01-10%, preferably of the order of 0.1 to 5% , and very particularly of the order of 0.2-3% by weight, agents such as cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048) polyvinyl alcohols polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units, with a molar ratio ( number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene terephthalate of the order of 1/10 to 10/1, the polyoxyethylene terephthalate units having polyoxyethylene units having a molecular weight of the order of 300 at

10,000, with a molecular weight of the copolyester of the order of 1,000 to 100,000 - polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene and / or polyoxypropylene units, with a molar ratio

(number of units) ethylene terephthalate and / or propylene terephthalate / (number of units) polyoxyethylene and / or polyoxypropylene of the order of 1/10 to 10/1, the polyoxyethylene and / or polyoxypropylene units having a molecular weight of in the range of 250 to 10,000, with a molecular weight of the copolyester in the range of 1,000 to 100,000

(US-A-3 959 230, US-A-3 962 152, US-A-3 893 929, US-A-4 116 896, US-A-4702 857,

US-A-4,770,666, EP-A-253,567, EP-A-201,124)

- ethylene or propylene terephthalate / polyoxyethylene terephthalate copolymers comprising sulfoisophthaloyl units in their chain (US-A-4,711,730; US-A-4,702,857; US-A-4,713 194)

- terephthalic copolyester oligomers with a sulfonated, sulfoaroyl polyalkyleneoxyalkyl ending and optionally containing sulfoisophthaloyl units in their chain (US-A-4,721,580; US-A-5,415,807; 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) - sulfonated terephthalic copolyesters of molecular weight less than 20,000, obtained for example from a diester of terephthalic acid, isophthalic acid, a diester of sulfoisophthalic acid and a diol, ethylene glycol in particular (WO 95/32997)

- the polyesters-polyurethanes obtained by reaction of a polyester with a molecular weight of 300-4,000 obtained from a diester of terephthalic acid, optionally a diester of sulfoisophthalic acid and a diol, onto a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4,000 and a diisocyanate (US-A-4,201,824)

- the sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxyl allyl alcohol, dimethyl terephthalate and 1, 2 propylene diol, having from 1 to 4 sulfonated groups (US-A-4,968,451). anti-redeposition agents, in amounts of about 0.01-10% by weight for a powdered detergent composition, agents such as - ethoxylated monoamines or polyamines, polymers of ethoxylated amines (US-A-4,597,898, EP-A-11,984)

- carboxymethylcellulose

- the sulfonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulfosuccinate and of diethylene glycol (FR-A-2 236 926)

- the polyvinylpyrrolidones of bleaching agents, in an amount of about 0.1-20%, preferably 1-10% of the weight of said detergent powder composition, such as

- perborates such as sodium perborate monohydrate or tetrahydrate - peroxygen compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhyd failed, sodium peroxide, sodium persulfate

- percarboxylic acids and their salts (called "percarbonates") such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonyiamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide of peroxysuccinic acid, decyldiperoxysuccinic acid, preferably combined with a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose, ... fluorescent agents, in quantity of about 0.05-1.2% by weight, agents such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, azoles, methinecyanins, thiophenes, ... foam suppressants, in amounts up to '' at 5% by weight, agents such as

- C ₁₀ -C ₂₄ monocarboxylic fatty acids or their alkali, ammonium or alkanolamine salts, fatty acid triglycerides

- aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons, such as paraffins, waxes

- N-alkylaminotriazines

- monostearylphosphates, monostearyl alcohol phosphates

- polyorganosiloxane oils or resins optionally combined with silica particles, softening agents, in amounts of about 0.5-10% by weight, agents such as clays of enzymes in amounts up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3553139, US-A-4101457, US-A-4 507 219, US-A-4 261 868) and other additives such as

- alcohols (methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin)

- buffering agents or fillers such as sodium sulphate, carbonates or bicarbonates of alkaline earth metals.

- pigments

- disintegrating agents - compacting agents such as polyethylene glycols.

When it comes to dishwasher tablets, the amount of said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, can represent from 10% to 90% in weight (expressed in sec) relative to the weight of the tablet (in sec) or of the region of the tablet in which it is located. Among the other additives which may be present in the dishwasher tablets, one can mention

- sodium tripolyphosphates having a phase I content of less than 70%, or tripolyphosphates consisting mainly or totally of phase II, in particular tripolyphosphates consisting of at least 70% phase II compared to all of the anhydrous phases and having a water content of 0 to 15%, preferably of the order of 5 to 10%; these can be present in the tablets in an amount such that the total amount of NaTPP in the tablets is of the order of 20 to 80%.

- other alkalizing additives or sequestering agents which are soluble in the washing medium such as. hexametaphosphates of alkali metals, ammonium or alkanolamines

. tetraborates or borate precursors. alkali metal silicates (0 to 30% by weight). alkali metal carbonates (0 to 30% by weight)

. cogranules of hydrated alkali metal silicates and alkali metal carbonates (sodium or potassium) rich in silicon atoms in Q2 or Q3 form, described in EP-A-488 868, for powdered detergent compositions

. crystalline or amorphous aluminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X, ...

. water-soluble polyphosphonates (1-hydroxy-1-ethane, 1-diphosphonates, methylene salts diphosphonates, ...)

. the water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids with a molecular weight of about 2,000 to 100,000, obtained by polymerization or copolymerization of carboxylic acids ethylenically unsaturated such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates with a molecular mass of the order of 2,000 to 10,000 (US-A- 3,308,067), the copolymers of acrylic acid and maleic anhydride with a molecular mass of the order of 5,000 to 75,000 (EP-A-66,915)

. polycarboxylate ethers (oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts

. hydroxypolycarboxylate ethers

. citric acid and its salts, mellitic acid, succinic acid and their salts. polyacetic acid salts (ethylenediaminetetraacetates, nitrilotriacetates,

N- (2 hydroxyethyl) -nitrilodiacetates)

. succinic C ₅ -C ₂₀ alkyl acids and their salts (2-dodecenylsuccinates, lauryl succinates, ...)

. polyacetal carboxylic esters. polyaspartic acid, polyglutamic acid and their salts

. 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, especially of sodium] or other amino acids

- bicarbonates and sesquicarbonates of alkali metals

- bleaching agents such as perborates and percarbonates of alkali metals (0 to 20%) associated with a bleaching activator (tetraacetylethylene diamine) (up to 10%) and possibly associated with a bleaching catalyst (organometallic manganese complexes, cobalt ...) (0 to 1%)

- non-ionic surfactants (0.2 to 5%) such as

. polyoxyalkylenated (polyethoxyethylenated, polyoxypropylenated, polyoxybutylenated) alkylphenols in which the alkyl substituent is C ₆ -C ₁₂ and containing from 5 to 25 oxyalkyiene units; by way of example, mention may be made of the TRITON X-45, X-114, X-100 or X-102 sold by Rohm & Haas Cy, the IGEPAL NP2 to NP17 from RHÔNE-POULENC;

. polyoxyalkylenated C ₈ -C ₂₂ aliphatic alcohols containing from 1 to 25 oxyalkyiene units (oxyethylene, oxypropylene); 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 marketed by Shell Chemical Cy, KYRO EOB marketed by The Procter & Gamble Cy, SYNPERONIC A3 to A9 from ICI, RHODASURF IT, DB and B from RHONE-POULENC, PLURAFAC LF 403 marketed by BASF; . the products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, of molecular weight by weight of the order of 2,000 to 10,000, such as the PLURONIC sold by BASF;

. products resulting from the condensation of ethylene oxide or propylene oxide with ethylenediamine, such as TETRONIC sold by BASF;

. ethoxylated amines containing from 5 to 30 ethoxylated units; . alkoxylated amidoamines containing from 1 to 50, preferably from 1 to 25, very particularly from 2 to 20 oxyalkylene units (preferably oxyethylene;

. amine oxides such as C ₁₀ -C ₁₈ alkyl oxides dimethylamines, C ₈ -C ₂₂ alkoxy oxides ethyl dihydroxy ethyiamines;

. alkoxylated terpene hydrocarbons such as ethoxylated and / or propoxylated α- or β-pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units;

- anionic surfactants (0 to 5%)

- enzymes (0 to 4%)

- dyes, perfumes

- agents helping with compaction, such as polyethylene glycols, or with the disintegration of tablets.

In the case of anti-lime tablets, the amount of said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, can represent from 10% to 100%, from preferably from 20 to 90% by weight (expressed in sec) relative to the weight of the tablet (in dry) or of the region of the tablet in which it is located.

Among the other additives which may be present in the anti-scale tablets, there may be mentioned

- sodium tripolyphosphates having a phase I content of less than 70%, or tripolyphosphates consisting mainly or totally of phase II, in particular tripolyphosphates consisting of at least 70% phase II compared to all of the anhydrous phases and having a water content of 0 to 15%, preferably of the order of 5 to 10%; these can be present in the tablets in an amount such that the total amount of NaTPP in the tablets is of the order of 30 to 99%, preferably from 50 to 90%. - sodium hexametaphosphate (0 to 10%)

- amorphous or crystallized alkali metal silicates (0 to 30%)

- alkali metal carbonates (0 to 30%) - crystalline or amorphous aluminosilicates of alkali metals or ammonium (0 to 30%)

- water-soluble polyphosphonates (1-hydroxy-1, 1-ethane-diphosphonates, methylene diphosphonate salts, etc.) (0 to 5%) - water-soluble salts of carboxylic polymers or copolymers (0 to 20%) such as the salts water-soluble polycarboxylic acids of molecular weight of the order of 2,000 to 100,000, obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, mesaconic acid, acid citraconic, methylenemalonic acid, and especially polyacrylates, copolymers of acrylic acid and maleic anhydride

- surfactants (0 to 10%)

The tablets which are the subject of the invention can be obtained in a conventional manner by pressing in a mold the desired quantity of a particulate composition containing the various constituents of said tablets. The density of the tablets can be of the order of 0.9 to 2 g / cm ³ , depending on the use sought.

The following examples are given as an indication.

Examples 1 -10

Introduced into a NIRO industrial atomizer fitted with a turbine

^* 3 m ³ / h of sodium orthophosphate liquor having a dry extract of 61% by weight, at a temperature of 90 ° C.

* 0.3 part by weight (dry) of ammonium carbonate per 100 parts by weight (dry) of sodium orthophosphate

The gas inlet temperature is 500 ° C; the outlet temperature is 150 ° C. The product obtained, with a density of 0.35 g / cm ³ , is then calcined up to 520 ° C. in a co-current rotary oven with direct flame. The NaTPP obtained has the following characteristics: * a rate of phase I of 87% relative to all of the anhydrous phases

* a density of 0.55 g / cm ³ Part of the product is hydrated in an industrial drum by spraying water, so as to obtain an NaTPP having different "hydration" rates:

* 3.3% of water, 54% of this water being in the form of water of crystallization

* 4.4% of water, 62% of this water being in the form of water of crystallization ^* 8% of water, 74% of this water being in the form of water of crystallization respectively examples 1, 2 and 3.

Another part is not hydrated (example 4).

A third part is hydrated in a fast Lôdige mixer batchwise by spraying with water, so as to obtain an NaTPP having different "hydration" rates:

^* 4% water, 63% of this water being in the form of water of crystallization

* 8% of water, 75% of this water being in the form of water of crystallization * 10% of water, 78% of this water being in the form of water of crystallization respectively examples 5, 6 and 7.

A fourth part is hydrated by spraying water continuously in a COMESSA fluidized bed (from COMESSA), the powder flow rate is 50 to 100 kg / h, so as to obtain an NaTPP having different "hydration" rates:

^* 4% water,

^* 8% water,

^* 10% water, examples 8, 9 and 10 respectively.

Test l

31.5 g of non hydrated or hydrated NaTPP from Examples 4 to 7 are compacted as such using a ZWICK 14 78 00/01 press, the force applied being 2.4 kNewton, to form cylindrical tablets of 41 mm in diameter. Each tablet is placed on a sieve (2 mm mesh) immersed in 9 liters of demineralized water at 22 ° C, with stirring (200 revolutions / minute).

The dissolution rate (VD) of each tablet is carried out by monitoring the conductivity of the water. This determines the time required for the dissolution of 90% of the tablet. The results are shown in Table 1. Test 2

30 parts of NaTPP from Examples 1 to 3, 5-6 and 8 to 10 are mixed with 70 parts of a detergent base containing:

* 11% alkylbenzene sulfonate

* 5% non-ionic surfactant

^* 30% NaTPP phase (I) from examples 1-3, 5-6, 8-10

^* 10% NaTPP brand LV marketed by EUROPHOS

^* 7% atomized and granulated R2 ratio silicate

* 6% sodium carbonate

* 15% sodium percarbonate

^* 4% of TAED

^* 2% of a defoaming agent (granulated)

* 2% of SOKALAN CP5 from BASF

* 4% of enzymes and perfume

31.5 g of each mixture are compacted, the applied force being 1.6 kNewton or

2.4 kNewton, to form cylindrical tablets 41 mm in diameter.

The dissolution rate and the longitudinal tensile strength t in Pascal of each tablet are measured.

The longitudinal breaking tension t is given by the equation t = 2F / πDe, where

* F is the force applied in Newton

^* D the diameter of the tablet in meters

* e the thickness of the shelf in meters The results are shown in Table 2.

TABLE 1

TABLE 2

Claims

1) Tablets of detergent or anti-limescale composition comprising compacted particles based on sodium tripolyphosphate having a high content in phase I and water distributed in a homogeneous manner in said sodium tripolyphosphate, said tablets being characterized in that said sodium tripolyphosphate present in the tablet or in a region of the tablet,

^* contains from 7% to 16% of its weight of water, at least 50%, preferably from 70% to 90% of this water being in the form of water of crystallization.

2) Tablets according to claim 1), characterized in that said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to

16% water represents from 5% to 100%, preferably of the order of 10% to 90% by weight

(expressed in sec) relative to the weight of the tablet (in sec) or the region of the tablet in which it is located.

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

4) Tablets according to any one of claims 1) to 3), characterized in that said sodium tripolyphosphate containing from 70% to 100% by weight of phase I has a density 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 one other sodium tripolyphosphate, preferably a sodium tripolyphosphate having a phase I content of less than 70% and / or a tripolyphosphate consisting mainly or totally of phase II.

6) Tablets according to claim 5), characterized in that said other sodium tripolyphosphate is a sodium tripolyphosphate having a phase II content of at least 70% relative to all of the anhydrous phases of sodium tripolyphosphate, and a water content which can range from 0 to 15%, preferably of the order of 5 to 10%. 7) Tablets according to claim 6), characterized in that said other sodium tripolyphosphate is present in the tablets in an amount such that the total amount of NaTPP in the tablets is of the order of 5 to 100%, preferably 10 90%.

8) Tablets according to any one of claims 1) to 7), characterized in that they are detergent tablets for washing machine or dishwasher, or anti-limescale tablets.

9) Tablets according to any one of claims 1) to 8), characterized in that they are detergent tablets for washing machines, in which the amount of said sodium tripolyphosphate containing from 70% to 100% by weight of phase I and from 7 to 16% of water, represents from 5% to 80%, preferably of the order of 10% to 60% by weight (expressed in dry) relative to the weight of the tablet (in dry) or the region of the tablet in which it 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 relative to all of the anhydrous phases and having a water content of 0 to 15%, preferably of the order of 5 to 10%, in an amount such that the total amount of NaTPP in the tablets is of the order of 5 to 60%, preferably of 10 to 50%.

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

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

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

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

15) Process for preparing the tablets which are the subject of any one of the preceding claims by pressing in a mold the desired amount of a particulate composition containing the various constituents of said tablets.