GB2318361A

GB2318361A - Detergent composition

Info

Publication number: GB2318361A
Application number: GB9621656A
Authority: GB
Inventors: Mario Dubini; Werner Kaufmann; Josiane Kielwasser
Original assignee: Ciba Geigy AG; Ciba Spezialitaetenchemie Holding AG; Ciba SC Holding AG
Current assignee: Novartis AG; BASF Schweiz AG
Priority date: 1996-10-17
Filing date: 1996-10-17
Publication date: 1998-04-22
Also published as: GB9621656D0

Abstract

A solid compact detergent composition comprises: a) 1 to 80%, preferably 5 to 50% by weight of a detersive surfactant; b) 0.01 to 80%, preferably 1 to 50% by weight of a detergent builder; and c) 0.5 to 10%, especially 1 to 5% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising 1 mole of urea and 1.3 to 2, preferably 1.3 to 1.8 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 1 to 20, preferably 2 to 10, especially 3 to 7 microns and having a specific BET surface of 5 to 100, preferably 15 to 60 m 2 /g. The addition to a solid compact detergent of a specific highly dispersed, solid, water-insoluble urea-formaldehyde resin imparts excellent flow properties to the solid compact detergent. In addition, the urea-formaldehyde resin, by virtue of its free methylol groups, provides a vehicle by which other desirable active ingredients, such as colour-care additives and perfumes, can be incorporated, in a more permanent manner, into the solid compact detergent. In this way, for example, the odour permanence of the solid compact detergent can be significantly improved.

Description

Detergent cOmsition The present invention relates to a detergent composition and, in particular, to a compact detergent composition containing, as anti-caking additive, a highly dispersed, solid, water.

insoluble organic polymer.

In the field of detergent manufacture, a trend has developed recently towards the production of so-called compact detergents which contain increased amounts of active substance. In order to minimize energy expenditure during the washing process, the compact detergents are required to operate efficiently at temperatures as low as 40 C., or even at room temperatures, e.g. at 25"C. Such low temperature efficiency can be imparted to compact detergents by increasing their content of peroxide component and by including a peroxide activator in the detergent composition.

Unfortunately, solid compact detergents have a marked tendency to agglomerate. This tendency, which can be caused,e.g., by the presence of high amounts of nonionic detergent at the surface of granules of the detergent, is especially disadvantageous in the context of household storage.

Consequently, there exists a need to find means to overcome the agglomeration tendency of solid compact detergents and thereby improve their flow properties.

Out of the wide range of anti-caking agents which has been recommended for use in powders, it has now been found that the addition to a solid compact detergent of a specific highly dispersed, solid, water-insoluble urea-formaldehyde resin imparts excellent flow properties to the solid compact detergent. In addition, the urea-formaldehyde resin, by virtue of its free methylol groups, provides a vehicle by which other desirable active ingredients, such as colour-care additives and perfumes, can be incorporated, in a more permanent manner, into the solid compact detergent. In this way, for example, the odour permanence of the solid compact detergent can be significantly improved.

While water-insoluble urea-formaldehyde resin has been recommended for use (in US-A4 130 498) as an anti-caking additive for conventional detergents, and as a filler for paper in GB-A-2 284 829, neither of these disclosures suggested that the urea-formaldehyde resin could impart excellent flow properties to a solid compact detergent. Moreover, neither of these disclosures suggested that the urea-formaldehyde resin, by virtue of its free methylol groups, could provide a vehicle by which other desirable detergent active ingredients, such as colour-care additives and perfumes, could be incorporated, in a more permanent manner, into the solid compact detergent.

Accordingly, the present invention provides a solid compact detergent composition comprising: a) 1 to 80%, preferably 5 to 50% by weight of a detersive surfactant; b) 0.01 to 80%, preferably 1 to 50% by weight of a detergent builder; and c) 0.5 to 10%, especially 1 to 5% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising 1 mole of urea and 1.3 to 2, preferably 1.3 to 1.8 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 1 to 20, preferably 2 to 10, especially 3 to 7 microns and having a specific BET surface of 5 to 100, preferably 15 to 60 m2/g.

The compact detergent composition according to the present invention has a higher density, namely a density of from 550 to 950 g/l, relative to conventional solid detergents.

Moreover, the compact detergent composition according to the present invention contains a lower amount, namely a maximum of 10% by weight of inorganic filler salt. Typical filler salts are alkali metal chlorides or sulfates, such as sodium sulfate.

The detersive surfactant component may be of the anionic, nonionic, zwitterionic, ampholytic or cationic type, or can comprise any compatible mixture of such types. Of these surfactants, anionics and nonionics are preferred.

The anionic surfactant component may be, e.g., a sulfate, sulfonate or carboxylate surfactant, or a mixture of these.

Preferred sulfates are alkyl sulfates having 12-22 carbon atoms in the alkyl radical, optionally in combination with alkyl ethoxy sulfates having 10-20 carbon atoms in the alkyl radical.

Preferred sulfonates include alkyl benzene sulfonates having 9-15 carbon atoms in the alkyl radical.

In each case, the cation is preferably an alkali metal, especially sodium.

Preferred carboxylates are alkali metal sarcosinates of formula R-CO(Rt)CH2COOMl in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is Ci- C4 alkyl and M' is alkali metal.

The nonionic surfactant component may be, e.g., a condensate of ethylene oxide with a Og- 015 primary alcohol having 34 moles of ethylene oxide per mole.

The builder component of the detergent composition according to the present invention may be an alkali metal phosphate, especially a tripolyphosphate; a carbonate or bicarbonate, especially the sodium salts thereof; a silicate or disilicate; an aluminosilicate; a polycarboxylate; a polycarboxylic acid; an organic phosphonate; or an aminoalkylene poly (alkylene phosphonate); or a mixture of these.

Preferred silicates are crystalline layered sodium silicates of the formula NaHSirnOm+1.pH2O or Na2Si,Ozm,l.pHz0 in which m is a number from 1.9 to 4 and p is 0 to 20.

Preferred aluminosilicates are the commerdally-available synthetic materials designated as Zeolites A, B, X, and HS, or mixtures of these. Zeolite A is preferred.

Preferred polycarboxylates include hydroxypolycarboxylates, in particular citrates, polyacrylates and their copolymers with maleic anhydride.

Preferred polycarboxylic acids include nitrilotriacetic acid and ethylene diamine tetra-acetic acid.

Preferred organic phosphonates or aminoalkylene poly (alkylene phosphonates) are alkali metal ethane 1-hydroxy diphosphonates, nitrilo trimethylene phosphonates, ethylene diamine tetra methylene phosphonates and diethylene triamine penta methylene phosphonates.

With respect to component c) of the detergent composition according to the present invention, the water-insoluble urea-formaldehyde resin component and its production are known and have been described, e.g., by A.Renner: Makromolekulare Chemie 149 1-27 (1971).

The specific BET surface of the water-insoluble urea-formaldehyde resin is determined according to the method of Brunauer, Emmett and Teller [c.f.

J.Am.Chem.Soc. 60, 309-319 (1938), Chemie-lng.Techn. 32 349-354 (1960) and 35, 568-589 (1963)].

The urea-formaldehyde resin component is readily produced by reacting formaldehyde with urea in aqueous solution in the above-mentioned ratios. The reaction is preferably conducted in two stages. In the first step, the urea and formaldehyde may be reacted normally, according to the conventional condensation mechanism, to form a low molecular, water-soluble precondensate. In the second stage, an acidic crosslinking catalyst may be introduced, to accelerate the reaction and the crosslinking, and produce an insoluble, finely-divided solid.

The amount of water in the reaction solution should never be substantially lower than the total weight of the organic reactants present in it, and should be present in substantial excess over the total weight of all other components of the reaction mixture during the actual formation and precipitation of the insoluble polymer particles.

The reaction temperature in the first step is generally in the range of from 20 to 100"C., preferably from 40 to 85"C, and especially from 60 to 800C. The pH value may be adjusted to 6 to 9, preferably to 6.5 to 7.5, by adding an aqueous inorganic strong base, e.g. a sodium hydroxide solution.

It can be advantageous to perform the production of the pre-condensate in the presence of a surfactant, e.g. a cationic quaternary ammonium base, an anionic fatty alcohol sulphonate, a nonionic polyethylene ether, preferably a salt of a sulphosuccinic acid ester, in particular sodium dodecylbenzene sulphonate. The amount of surfactant used may range, e.g., from 0.5 to 5% by weight, based on the total weight of the urea and formaldehyde. Ionic surfactants effect an increase in the specific surface of the urea-formaldehyde polymer product, whereas non-ionic surfactants have the reverse effect.

The presence of a macromolecular, water-soluble protective colloid having polyelectrolyte characteristics during the first reaction step may also prove useful.

Examples of such colloids include gelatine, tragacanth, agar and polyvinyl pyrrolidone, especially homo- or copolymers of acrylic- or methacrylic acids, in particular polymethacrylic acid. The amount of colloid used may range, e.g., from 0.5 to 5% by weight, based on the total weight of the urea and formaldehyde.

Neither polyvinyl pyrrolidone nor polymethacrylic acid effects an increase in the specific surface of the water-insoluble urea-formaldehyde resin.

One of the most important conditions for the successful production of infusible, insoluble and finely-divided urea-formaldehyde polymers of adequate quality for use in the present invention is the use, in the second step of the reaction, of a suitable gelation catalyst. Suitable catalysts include, e.g., the relatively strong inorganic and'or organic acids such as sulphuric acid, sulphurous acid, sulphamic acid, phosphoric acid, hydrochloric acid, chloracetic acid, maleic acid or its anhydride. Generally, these gelation catalysts should have an ionisation constant of more than 1 0t'. Sulphuric acid and its acidic ammonium- or amine salts such as ammonium-, methylamine- or ethanolamine-hydrogen sulphate, are preferred.

The acids are usually employed as 1 to 15% by weight aqueous solutions.

As a rule, 20 to 100 millimoles of cross-linking catalyst are used per mole of added urea. This effects a lowering of the pH value of the reaction mixture to 1.5 to 3.0 in the second step, i.e. during the formation of the polymer.

If sulphamic acid is used, generally water-insoluble urea-formaldehyde resins of relatively high specific surface are obtained, whereas the other acids mentioned above, in particular sulfuric acid and its ammonium- or amine salts have the opposite effect.

The reaction temperatures used in the second, resin formation reaction1 generally range from 20 to 1000C., preferably from 40 C. to 850C., especially from 40 to 65"C. Large temperature fluctuations in the reaction mixture should be avoided while adding the catalyst. It is therefore desirable, prior to adding the aqueous catalyst solution, to pre-heat it to the temperature of the reaction mixture.

Generally, a white gel is obtained after only 15 to 30 seconds. The cross-linking reaction is usually complete after a time ranging from 30 minutes to 3 hours.

The insoluble polymer, obtained as a white gel, may be mechanically comminuted, treated with an approximately equal amount of water, adjusted to pH 6 to 9, preferably to pH 6.5 with alkali or ammonia, in particular with sodium hydroxide solution, and then separated from the aqueous liquid, e.g., by filtration, centrifuging or evaporation. Drying can be conducted, e.g., by spray drying or by convection drying. Although the final product basically comprises fine particles, it is nevertheless desirable to submit the solid product to comminution or deagglomeration, to reduce the mean agglomerate size and to increase the absorption value for inks and other liquids.

The detergent composition according to the present invention preferably also contains an organic or inorganic peroxide compound. Suitable peroxides are those described in the literature or available on the market, which bleach textiles at conventional washing temperatures, e.g. temperatures in the range of from 5"C. to 90"C. In particular, the organic peroxides are, for example, monoperoxides or polyperoxides having alkyl chains of at least 3, preferably 6 to 20, carbon atoms; in particular diperoxydicarboxylates having 6 to 12 C atoms, such as diperoxyperazelates, diperoxypersebacates, diperoxyphthalates and/or diperoxydodecanedioates, especially their corresponding free acids, are of interest. It is preferred, however, to employ very active inorganic peroxides, such as persulfate, perborate and/or percarbonate. It is, of course, also possible to employ mixtures of organic and/or inorganic peroxides. The peroxides, especially the inorganic peroxides, are preferably activated by the inclusion of an activator such as tetraacetyl ethylenediamine or nonoyloxybenzene sulfonate. Bleaching catalysts which may be added include, e.g., enzymatic peroxide precursors and/or metal complexes. Preferred metal complexes are manganese or iron complexes such as manganese or iron phthalocyanines or the complexes described in EP-A-0509787.

The detergent composition according to the present invention preferably also contains a photobleaching agent. Preferred photobleaching agents are phthalocyanines containing water-solubilising groups such as sulfo groups. As water-soluble phthalocyanines, it is possible to use metal-free phthalocyanines or metal complexes of phthalocyanines. Metal complexes of phthalocyanines are preferably those of aluminium, zinc, magnesium, calcium, iron, sodium or potassium. . Particularly preferred photobleaching agents are sulfonated zinc or aluminium phthalocyanines. Mixtures of photobleaching agents may be used such as mixtures of water-soluble zinc and aluminium phthalocyanines.

The detergent composition according to the present invention will usually contain one or more auxiliaries such as a fluorescent whitening agent; a colour-care additive, in particular a dye transfer inhibitor, a soil suspending agent, for example sodium carboxymethylcellulose; a salt for adjusting the pH, for example alkali or alkaline earth metal silicates; a foam regulator, for example soap; a salt for adjusting the spray drying and granulating properties, for example sodium sulfate; a perfume; and also, if appropriate, antistatic and softening agents such as smectite clays; enzymes, such as amylases and proteases; pigments; and/or shading agents. These constituents should, of course, be stable to any bleaching system employed.

The fluorescent whitening agent may be, e.g., a bis-triazinylamino-stilbene-disulfonic acid, a bis-triazolyl-stilbene-disulfonic acid, a bis-styryl-biphenyl-disulfonic acid, a bisbenzofuranylbiphenyl, a bis-benzoxazolyl derivative, a bis-benzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative.

If a fluorescent whitening agent is used which has no affinity (substantivity) for fabrics to be washed with the detergent composition of the present invention, the appearance of such detergent composition is greatly improved, relative to the analogous detergent composition containing no fluorescent whitening agent, without the risk of the occurrence of any consequent shade changes in coloured fabrics so washed. An example of a nonsubstantive fluorescent whitening agent which may be used in this way to improve the appearance of a detergent powder is a bis-benzoxazolyl derivative having the formula:

in which R1 is C1-C8alkyl, preferably t-butyl.

On the other hand, if a fluorescent whitening agent is used which has high affinity (substantivity) for fabrics to be washed with the detergent composition of the present invention, the addition of such a highly substantive fluorescent whitening agent can be effected at the conclusion of the detergent production process, which technique is of considerable techical advantage to the detergent producer.

Examples of highly substantive fluorescent whitening agents which may be used in this way are bis-triazinylamino-stilbene-disulfonic acids or salts having the formula:

in which R2 and R3, independently, are OH, NH2, O-Ci-C4-alkyl, 0-aryl, NH-C,-C4-alkyl, N(C,-C4-alkyl)2, N(C,-C4-alkyl)(C,-C4-hydroxyalkyl), N(C 1-04-hydroxyalkyl)2, NH-aryl, morpholino, S-C,-C4-alkyl(aryl), Cl or OH; R4 is H, SO3M, O-C1-Cralkyl, CN, Cl, COO-C1-C4- alkyl, or CON(C,-C4-alkyl)2; M is H, Li, Na, K, Ca, Mg, ammonium, mono-, di-, tri- or tetra-C1 C4-alkylammonium, mono-, di- or tri-C,-C4-hydroxyalkylammonium or ammonium that is dior tri-substituted with a mixture of C,-C4-alkyl and C,-C4-hydroxyalkyl groups; and p is 0 or 1.

In the compounds of formulae (2), C1-C4-alkyl groups are, e.g., methyl, ethyl, n-propyl, isopropyl and n-butyl, especially methyl. Aryl groups are, e.g., naphthyl or, especially, phenyl.

Preferred compounds of formula (2) are those in which R2 and R3, independently, are methoxy, phenoxy, NH2, NH-methyl, N(methyl)2, N(methyl)(hydroxyethyl), NH-ethyl, N(hydroxyethyl)2, NH-phenyl, morpholino, S-methyl(phenyl), Cl or OH.

Specific examples of preferred compounds of formula (2) are those having one of the formulae:

Any fluorescent whitening agent used is preferably present in an amount of from 0.005 to 5% by weight, based on the total weight of the detergent composition.

Preferred dye transfer inhibitors include polyamine Oxide polymers, copolymers of Nvinylpyrrolidone and N-vinylimidazole and the manganese complexes described in US-A 5462564 or GA-2 296015.

The present invention also provides a process for the production of a detergent composition comprising mixing together a) 1 to 80%, preferably 5 to 50% by weight of a detersive surfactant; b) 0.01 to 80%, preferably 1 to 50% by weight of a detergent builder; and c) 0.5 to 1 0,.. especially 1 to 5% by weight of a highly dispersed, solid, water-insoluble urea formaidehyde resin comprising 1 mole of urea and 1.3 to 2, preferably 1.3 to 1.8 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 1 to 20, preferably 2 to 10, especially 3 to 7 microns and having a specific BET surface of 5 to 100, preferably 15 to 60 m2/g.

Preferably, the ingredients a), b) and c) are so mixed that a solid, compact detergent, in granular form having a specific weight above 500 g/l, is obtained.

In a particularly preferred embodiment, the process is conducted in three steps. In a first step, a premix is formed comprising anionic detersive surfactant (and optionally a minor proportion of the nonionic detersive surfactant component) and detergent builder; in a second step, this premix is sprayed with a major proportion of the nonionic detersive surfactant component; and, in a third step, there are added sensitive components such as bleaching systems and/or enzymes, as well as the highly dispersed, solid, water-insoluble urea-formaldehyde resin. The process is conveniently conducted in a fluidised bed.

In a further preferred embodiment, the individual stages are not conducted entirely separately, so that a certain overlap occurs between the stages. This process is conveniently conducted in an extruder to produce granules in the form of megaperls.

As a further aspect, the present invention provides a method of washing soiled fabrics, comprising contacting said fabrics with a wash solution which contains an effective amount of a detergent composition according to the present invention.

The following Examples further illustrate the present invention. Parts and percentages shown therein are by weight unless otherwise stated.

Examples 1 to 4 A standard solid compact detergent is produced in the following manner using a conventional fluidised bed drier having a rotating plate. Firstly, a base powder is prepared having the composition: 8.7 parts of a linear alkylbenzene sulfonate (Marlon A 375) 3.1 parts of sodium lauryl sulfate (Texapon K 12) 12.3 parts of sodium aluminium silicate (Wessalith P) 5.1 parts of a maleicJacrylic copolymer (Sokalan CP 5) 17.5 parts of sodium carbonate 3.1 parts of sodium sulfate and 0.31 part of magnesium silicate.

The whole of an agglomeration fluid, consisting of 9 parts of an ethoxylated C,2873fatty alcohol containing 6.5 moles of ethylene oxide (Dobanol 23-6.5) and 1 part of deionised water, is sprayed on to the base powder and finally 10 parts of sodium perborate monohydrate, 5 parts of TAED and 1 part of urea-formaldehyde resin are added and the whole is tumbled until dry. The urea-formaldehyde resin used has a diameter of the primary particles of 0.1 micron; a diameter of the agglomerates of the primary particles of about 6 microns; a specific surface area of the primary particles of 20 m2!g (BET); and a specific weight of 1.45 gloom3.

Analogous solid compact detergents were prepared containing, respectively, 0, 3, 5 and 10 parts of the urea-formaldehyde resin.

The flow property of the respective solid compact detergents is then determined in the following manner. A weighed portion (5 g.) of the detergent powder under test is poured through a funnel on to a cardboard channel and the length of the resulting strip of poured detergent (maximum strip length is 63 cm.) is measured. Eight determinations are conducted for each detergent and the mean value is determined. The remaining test parameters are as follows: height of drop 5 cm. (end of funnel to cardboard channel); inclination of cardboard channel 27 ; upper end of cardboard channel 30 cm. above table edge; and lower end of cardboard channel 0 cm. above table edge.

The results obtained are set out in the following Table.

Table

Example Parts of resin Strip length (cm) 0 22.9 1 1 31.5 2 3 36.8 3 5 37.3 4 10 39.0 The results in the Table clearly demonstrate the improved flow property of detergent compositions according to the present invention.

Claims

1. A solid compact detergent composition comprising: a) 1 to 80% by weight of a detersive surfactant; b) 0.01 to 80% by weight of a detergent builder; and c) 0.5 to 10% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising 1 mole of urea and 1.3 to 2 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 1 to 20 microns and having a specific BET surface of 5 to 100 m2/g.

2. A composition according to claim 1 comprising: a) 5 to 50% by weight of a detersive surfactant; b) 1 to 50% by weight of a detergent builder; and c) 1 to 5% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising 1 mole of urea and 1.3 to 1.8 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 2 to 10 and having a specific BET surface of 15 to 60 m2/g.

3. A composition according to claim 2 comprising: a) 5 to 50% by weight of a detersive surfactant; b) 1 to 50% by weight of a detergent builder; and c) 1 to 5% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising I mole of urea and 1.3 to 1.8 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 3 to 7 microns and having a specific BET surface of 15 to 60 m2Jg.

4. A composition according to any of the preceding claims having a density of from 550 to 950 g/l.

5. A composition according to any of the preceding claims in which detersive surfactant component is an anionic surfactant, a nonionic surfactant or a mixture thereof.

6. A composition according to claim 5 in which the anionic surfactant is a sulfate, sulfonate or carboxylate surfactant, or a mixture of these.

7. A composition according to claim 6 in which the sulfate is an alkyl sulfate having 12-22 carbon atoms in the alkyl radical.

8. A composition according to claim 7 in which the alkyl sulfate is used in combination with an alkyl ethoxy sulfate having 10-20 carbon atoms in the alkyl radical.

9. A composition according to claim 6 in which the sulfonate is an alkyl benzene sulfonate having 9-15 carbon atoms in the alkyl radical.

10. A composition according to claim 6 in which the carboxylate is an alkali metal sarcosinate of formula R-CO(R')CH2COOM1 in which R is alkyl or alkenyl having 9-17 carbon atoms in the alkyl or alkenyl radical, R1 is C1-C4 alkyl and M1 is an alkali metal.

11. A composition according to claim 6 in which the nonionic surfactant component is a condensate of ethylene oxide with a Cg-CXs primary alcohol having 3-8 moles of ethylene oxide per mole.

12. A composition according to claim 1 in which the builder component is an alkali metal phosphate, a carbonate or bicarbonate, a silicate or disilicate, an aluminosilicate, a polycarboxylate, a polycarboxylic acid, an organic phosphonate or an aminoalkylene poly (alkylene phosphonate), or a mixture of these.

13. A composition according to claim 12 in which the alkali metal phosphate is a tripolyphosphate.

14. A composition according to claim 12 in which the carbonate or bicarbonate is the sodium salt thereof.

15. A composition according to claim 12 in which the silicate is a crystalline layered sodium silicate of the formula NaHSirnOm+1.pH2O or Na2SimO2",+1.pH2O in which m is a number from 1.9 to 4 and p is 0 to 20.

16. A composition according to claim 12 in which the aluminosilicate is a commerciallyavailable synthetic material designated as Zeolite A, B, X, and HS, or a mixture of these.

17. A composition according to claim 16 in which the Zeolite is Zeolite A.

18. A composition according to claim 12 in which the polycarboxylate is a hydroxypolycarboxylate, a polyacrylate or a copolymer thereof with maleic anhydride.

19. A composition according to claim 18 in which the hydroxypolycarboxylate is a citrate.

20. A composition according to claim 12 in which the polycarboxylic acid is nitrilotriacetic acid or ethylene diamine tetra-acetic acid.

21. A composition according to claim 12 in which the organic phosphonate or aminoalkylene poly (alkylene phosphonate) is an alkali metal ethane 1 -hydroxy diphosphonate, nitrilo trimethylene phosphonate, ethylene diamine tetra methylene phosphonate or diethylene triamine penta methylene phosphonate.

22. A composition according to any of the preceding claims in which an organic or inorganic peroxide compound is also present.

23. A composition according to claim 22 in which the organic peroxide is a monoperoxide or polyperoxide having alkyl chains of at least 3 carbon atoms.

24. A composition according to claim 22 in which the inorganic peroxide is a persulfate, perborate or percarbonate.

25. A composition according to claim 24 in which an activator is also present.

26. A composition according to claim 25 in which the activator is tetraacetyl ethylenediamine or nonoyloxybenzene sulfonate.

27. A composition according to any of the preceding claims in which a photobleaching agent is also present.

28. A composition according to claim 27 in which the photobleaching agent is a phthalocyanine containing water-solubilising groups.

29. A composition according to claim 28 in which the phthalocyanine is sulfonated zinc or aluminium phthalocyanine or a mixture thereof.

30. A composition according to any of the preceding claims which also contains one or more auxiliaries selected from a fluorescent whitening agent, a dye transfer inhibitor, a soil suspending agent, a salt for adjusting the pH, a foam regulator, a salt for adjusting the spray drying and granulating properties, a perfume, an antistatic and softening agent, an enzyme, a pigment and a shading agent.

31. A composition according to claim 30 in which the fluorescent whitening agent is a bis triazinylamino-stilbene-disulfonic acid, a bis-triazolyl-stilbeneRisulfonic acid, a bis-styrylbiphenyl-disulfonic acid, a bis-benzofuranylbiphenyl, a bis-benzoxazolyl derivative, a bisbenzimidazolyl derivative, a coumarine derivative or a pyrazoline derivative.

32. A composition according to claim 30 or 31 in which the amount of fluorescent whitening agent present ranges from 0.005 to 5% by weight, based on the total weight of the detergent composition.

33. A process for the production of a detergent composition comprising mixing together a) 1 to 80% by weight of a detersive surfactant; b) 0.01 to 80% by weight of a detergent builder; and c) 0.5 to 10% by weight of a highly dispersed, solid, water-insoluble urea-formaldehyde resin comprising 1 mole of urea and 1.3 to 2 moles of formaldehyde, which is present in highly disperse form, having a mean particle diameter of 1 to 20 microns and having a specific BET surface of 5 to 100.

34. A process according to claim 33 in which the ingredients a), b) and c) are so mixed that a solid, compact detergent, in granular form having a specific weight above 500 girl, is obtained.

35. A process according to claim 34 in which, in a first step, a premix is formed comprising anionic detersive surfactant (and optionally a minor proportion of the nonionic detersive surfactant component) and detergent builder; in a second step, this premix is sprayed with a major proportion of the nonionic detersive surfactant component; and, in a third step, there are added any sensitive bleaching system and/or enzyme components, as well as the highly dispersed, solid, water-insoluble urea-formaldehyde resin.

36. A process according to claim 35 in which the individual stages are not conducted entirely separately, so that a certain overlap occurs between the stages.

37. A process according to any of claims 33 to 36 in which the process is conducted in a fluidised bed.

38. A process according to claim 36 in which the process is conducted in an extruder to produce granules in the form of megaperls.

39. A method of washing soiled fabrics comprising contacting said fabrics with a wash solution which contains an effective amount of a detergent composition according to claim 1.