ZA200404615B

ZA200404615B - Particulate composition comprising dye fixatives.

Info

Publication number: ZA200404615B
Application number: ZA200404615A
Authority: ZA
Inventors: Petr Kvita; Ullrich Menge; Hauke Rohwer; Pierre Dreyer; Elke Haiss; Josiane Kielwasser; Barbara Weber; Katrin Bahn
Original assignee: Ciba Sc Holding Ag
Priority date: 2002-01-07
Filing date: 2004-06-10
Publication date: 2005-08-12
Also published as: AU2002367419A1; US20050039266A1; BR0215478A; CN1612928A; MXPA04006559A; WO2003057815A1; CN100335605C; JP2005514531A; EP1472333A1; KR20040073553A; JP4443929B2; AU2002367419B2

Description

Particulate composition comprising dye fixatives

The present invention relates to a method of reducing dye loss or dye transfer from textile , fibre materials, especially in the household sector, and to the particulate compositions used in that method, especially granules, comprising a dye fixative and a carrier, and to washing and softener compositions comprising such granules.

In customary household washing methods, dye loss when washing coloured textiles is a known problem. A further problem in that context is the transfer of dye when washing coloured textiles together with coloured or white textiles, especially with pale-coloured or white textiles.

The use of dye fixatives in textile care is known from WO 01/72982, which describes textile care products that comprise at least one cellulase and a dye-fixing basic polymer.

EP-A-692 511 discloses a method according to which fibre materials are dyed on an industrial scale and then treated with a dye fixative, the basic polycondensation product mentioned below, wherein the polycondensation product has not, however, been neutralised with an acid.

A problem with dye-fixing polymers is that they are deactivated in washing formulations that comprise anionic surfactants and are therefore no longer available for the intended use, namely the reduction of dye loss or dye transfer from textile materials.

The object of the present invention is to provide an improved method, suitable for the house- hold sector, by means of which dye loss and/or dye transfer can be reduced further, and to provide washing formulations suitable for that method.

It has now been found, surprisingly, that the mentioned objective can be met to a great ’ extent by means of particulate compositions comprising a dye fixative and a carrier.

The present invention accordingly relates to a method of reducing dye loss or dye transfer from textile fibre materials, especially in the household sector, in which method the textile fibre materials are treated with a particulate composition, especially granules, comprising a) from 1 to 90 % by weight of at least one water-soluble dye fixative,

b) from 2 to 80 % by weight of at least one carrier, c) from 0 to 60 % by weight of at least one binder that is soluble/dispersible in water, ) d) from 0 to 20 % by weight of at least one further additive, and e) from O to 15 % by weight water, the percentages in each case denoting percent by weight, based on the total weight of the composition.

The particulate compositions are preferably granules. :

The particulate compositions are not glassy particles.

The particulate compositions can be used especially as a constituent in a washing composi- tion and in washing composition additives or additive concentrates, e.g. pre- and/or after- treatment agents, stain-treatment salt, washing power enhancers, softeners, bleaching agents, UV protection enhancers, etc. in conventional concentrations. Such formulations can be present in all known and customary forms, especially in the form of powders, (super) compact powders, in the form of a single- or multilayer tablet ("tabs"), bars, blocks, sheets, pastes, including in the form of pastes, gels or liquids which are used in capsules or in bags (sachets).

Powders can also be used in suitable sachets or bags.

Suitable dye fixatives a) are anionic, non-ionic or cationic compounds, especially cationic compounds, such as those disclosed, for example, in EP-A-692 511; or dye-fixing polymers, as disclosed, for example, in WO 01/74982. Dye-fixing polymers in the context of the present invention are to be understood as including, in addition to polymers, also oligomers and mixtures of oligomers and polymers. :

Examples of dye fixatives are polydiallyldimethylammonium compounds, especially salts thereof and/or copolymers thereof, for example with polyacrylate, polyacrylamide and ’ polyvinylpyrrolidone. Some of those compounds are obtainable from CIBA SC under the names Agefloc®, such as Agefloc C 505°, Agefloc WT40%, Agefloc WT40 SV® and Agefloc ’ WT40 SVL®, or Agequat®, such as Agequat 3204%, Alcofix®, such as Alcofix R®, or Tinofix

FRD®, preferably Agefloc WT40%, Agefloc WT40 SV® and Agefioc WT40 SVL®;

also bischloromethylbiphenylpolyquats, as described in Patent Specifications DE 2 657 582 and EP 225 281; ) and polyethyleneimines obtainable from BASF under the name Lupasoi®, such as Lupasol

SK?®, Lupasol PS®, Lupasol FC®, Lupasol WF®, Lupasol P®, Lupasol G20%, anhydrous

Lupasol G20°®, Lupasol G 100%, Lupasol HF®, Lupasol PR8515% and Lupasol FG® and preferably Lupasol G 100%, Lupasol HF®, Lupasol PR8515® and Lupasol FG®, and

Cyclanon®; further dye fixatives are, for example, basic polycondensation products containing imidazoline units, as described in WO 01/74982, or

Tinofix CL®, Tinofix ULC®, Tinofix ECO®, Cibafix ECO® and Solfix E®, which are obtainable from CIBA SC; also Levogen FL®, Levogen WSR®, Levogen WRD?® and Lavafix®, which are obtainable from

Bayer;

Gafquat 755N®, Gafquat HS-100%, Copolymer 845%, Copolymer 958%, Copolymer VC-713°,

Chromobond S-100® which is obtainable fromISP; and also Neofix RE®, Neofix E-225%, Neofix E-117®, Neofix RPA®, Neofix F®, Neofix RP-70%® and Neofix R-250%, which are obtainable from Nicca; : also Sevofix SR®, Sevofix FFK® and Sevofix NOF®, which are obtainable from Textil Color; and also Indosol E-50%, Indosol CRR®, Sandofix FFN®, Solidogen FRZR®, Sandofix TPS®,

Sandofix TPSR®, Sandofix WE56R® and Sandofix SWE®, which are obtainable from Clariant.

In a preferred variant of the method according to the invention, the textile fibre material is treated with a particulate composition, which is especially in the form of granules, that comprises a dye fixative selected from the group of the following dye fixatives: polydiallyldimethylammonium compounds, especially polydiallyldimethylammonium salts, bischloromethylbiphenylpolyquat compounds, the compound polyethyleneimine and basic polycondensation products, preferably those containing imidazolidine units and more preferably Tinofix CL®.

Preference is also given to the method according to the invention wherein textilefibre i material is treated with a particulate composition, which is especially in the form of granules, that comprises a dye fixative that is a basic polycondensation product of an amine of formula

AN a

AA (1)

Rs R, and a cyanamide, wherein the mentioned polycondensation products either have not been neutralised with an acid or have been neutralised wholly or partially with an inorganic or organic acid,

Rs, Ry, Ry and R; each independently of the others being hydrogen or alkyl unsubstituted or substituted by amino, hydroxy, cyano or by C,-C alkoxy, and

A being alkylene unsubstituted or substituted or uninterrupted or interrupted by one or more hetero atoms.

Ain formula (1) is preferably C,-Cpalkylene uninterrupted or interrupted by -O-, -S-, -NH- or by -N(C,-C,alkyl)- and/or unsubstituted or substituted by hydroxy, preferably C.-Casalkylene interrupted one or more times by -NH-.

Ri, Rz, Rs and R, are each independently of the others preferably hydrogen or C;-C,alkyl.

Examples of suitable compounds of formula (1) are 1,4-butanediamine, 1,6-hexanediamine, dipropylenetriamine, N-(2-aminoethyl)-1,3-propanediamine, N,N-bis(2-aminopropyl)methyl- © amine, polyethyleneimines or polyethylenepolyamines, such as diethylenetriamine, tri- ethylenetetramine, tetraethylenepentamine and pentamethylenehexamine.

Preferred compounds of formula (1) are polyethylenepolyamines and especially diethylenetriamine. The number of repeating units of the monomers of formula (1) in the basic polycondensation products is, for example, from 4 to 100, especially from 4 to 50.

Suitable cyanamides are, for example, cyanamide, dicyandiamide, guanidine and biguanidine. Dicyandiamide is preferred.

The above-mentioned dye fixatives are known, for example, from EP-A-692 511 or ) WO 01/74982 and can be obtained according to the processes disclosed therein.

For example, an amine of formula (1) is reacted with an ammonium salt in the presence of a non-aqueous solvent and the resulting protonated product is reacted with a cyanamide at ’ elevated temperature. ’ Suitable ammonium salts are, for example, ammonium salts of organic or inorganic acids, for example ammonium chloride, ammonium sulfate, ammonium carbonate, ammonium formate and ammonium acetate, especially ammonium chloride.

Suitable non-aqueous solvents are, for example, hydroxyl-group-containing solvents, such as e.g. ethylene glycol, 1,2- or 1,3-propylene glycol, butylene glycol, di-, tri- or tetra-ethylene glycol and ethers thereof, and polyethylene glycols having a molecular weight of, for example, from 600 to 5000, and mixtures thereof.

The amine of formula (1) and the ammonium salt are used, for example, in a molar ratio of from 1:0.1 to 1:2.5, preferably from 1:0.7 to 1:2. The amount of hydroxyl-group-containing solvent can vary within a wide range and is, for example, from 0.2 to 20 mol, preferably from 0.4 to 5 mol, per mol of compound of formula (1).

The reaction of the amine of formula (1) with the ammonium salt is carried out especially at elevated temperature, such as from 80 to 200°C, especially from 100 to 160°C. For example, the amine of formula (1) is introduced into the hydroxyl-group-containing solvent or solvent mixture and the ammonium compound is metered in; advantageously the reaction step is carried out under inert conditions, such as under a nitrogen atmosphere.

The resulting protonated product is then reacted with, for example, from 0.5 to 2 mol, preferably from 0.8 to 1.5 mol, of cyanamide per mol of starting compound of formula (1).

That reaction is carried out, for example, in the presence of one or more of the above- mentioned hydroxyl-group-containing solvents at elevated temperature, which is, for example, from 80 to 250°C, especially from 140 to 220°C. The reaction products are : generally melts, having basic properties, that are solid at room temperature and yield clear solutions in water.

Neutralisation with an inorganic or organic acid is carried out, for example, in an aqueous medium, the addition of the acid being carried out in such a manner that a pH of, for example, from 2 to 12, especially from 3 to 10 and preferably from 4 to 8, is obtained. Special preference is given to an amount of acid that yields a pH of about 7. :

Suitable inorganic or organic acids are, for example, mono- or poly-carboxylic acids, hydrochloric acid, phosphoric acid, sulfuric acid or a mixture of at least two such acids.

Preference is given to organic acids.

Examples of organic acids that may be mentioned are oxalic acid, tartaric acid, acetic acid, propionic acid, succinic acid, maleic acid, citric acid, formic acid, gluconic acid, p-toluene- sulfonic acid, terephthalic acid, benzoic acid, phthalic acid, acrylic acid and polyacrylic acid.

Of special interest are aliphatic carboxylic acids, especially those having a total number of from 1 to 12 carbon atoms. Preferred acids are aliphatic C4-Ci,-mono- or poly-carboxylic - acids, and in the case of monocarboxylic acids especially those having a total number of at least 3 carbon atoms. Suitable substituents of carboxylic acids are, for example, hydroxy and amino, especially hydroxy. Also of interest are mixtures of the mentioned acids; by way of example, mention may be made of the mixture of maleic acid and propionic acid.

Special preference is given to aliphatic C,-C,polycarboxylic acids, especially aliphatic

C»-Cgpolycarboxylic acids. Very special preference is given to hydroxy-substituted aliphatic

C,-Cspolycarboxylic acids. :

Suitable carriers b) are, for example, those disclosed in EP-A-133 562, for example water- soluble inorganic and organic salts, which may be textile washing component constituents that are customary per se, but preferably without the salt-type surfactants. Such carriers are : primarily the customary structural substances, or builder substances, of washing composi- tions, such as e.g. the alkali metal silicates, carbonates, bicarbonates and borates also known as washing alkalis, and the alkali metal polyphosphates. Also suitable are, however, alkali metal sulfates that are virtually inert in the washing process, such as e.g. sodium sulfate. ’ Organic salts that can be used as carriers include water-soluble salts, especially alkali metal salts, of di- and poly-carboxylic acids, such as e.g. adipic acid, glutaric acid, succinic acid, ) maleic acid, phthalic acid, melltic acid and cyclohexanehexacarboxylic acid; of hydroxy- carboxylic acids, such as e.g. citric acid, tartaric acid and salicylic acid; of aminocarboxylic acids, such as e.g. nitrilotriacetic acid and ethylenediaminetetraacetic acid; the saits of organic polyphosphonic acids, such as e.g. isohydroxyethanediphosphonic acid, aminotri- . methylenetriphosphonic acid, ethyldiaminotetramethylenetetraphosphonic acid, and the salts of polymeric polycarboxylates, such as e.g. homo- and co-polymerisation products of acrylic acid, hydroxyacrylic acid, maleic acid, methylenemalonic acid, and the copolymerisation products of such acids with vinyl methyl ether or methacrylic acid.

A further class of suitable carriers includes finely divided organic solids that are capable swelling in water and/or are partially water-soluble, and absorbent polymeric powders, granules, fibres or fabrics, for example of the types cellulose, starch, especially carboxy- methyl starch, dextrins and appropriate guar and algal derivatives, and also polyester, polyethylene, polyacrylonitrile, lignin, wood flour and sawdust.

Finally, a third class of suitable carriers consists of mixtures of very finely dispersed inorganic compounds that are insoluble in water. These include bentonites, such as sodium - montmorillonite, layered silicates, and kieselguhr, talc, kaolin, mica, fuller's earth, feldspar and cation-exchanging zeolites of type A and X and hydrosodalite that also have a builder action in the washing process and are accordingly also suitable as phosphate exchange substances. Especially suitable carriers are sodium aluminium silicates, and especially silicates having a cavity structure. Also suitable as carriers of that class, however, are non- cation-exchanging finely divided zeolites and zeolites of the above types that are already - present in the calcium form and cation-exchanging and non-cation-exchanging X-ray- amorphous alkali aluminosilicates, and also clay minerals, especially from the group of kaolins and the group of montmorillonites, also known as smectites. The very finely dispersed inorganic carriers that are insoluble in water include also very finely dispersed metal oxides and metal hydroxides and mixed oxides of silicon, aluminium, magnesium, zinc and titanium. These include very finely divided silicic acids that can be prepared by precipitation or pyrogenically, which, also in a form in which they have been reacted with polyorganosiloxanes, can be a main constituent of silicone oils. Typical examples of suitable metal oxides are very finely dispersed magnesium oxide, titanium oxide, zinc oxide and ’ aluminium oxide. Such compounds have excellent carrier properties because of their high specific surface area, with the result that relatively small amounts are sufficient for their use ’ as carrier in the particulate composition according to the invention and thus, when used in the washing process, subsequent loading of the washing liquor therewith is avoided.

A further class of suitable carriers are formaldehyde-containing polymers or oligomers of monomeric units such as melamine and formaldehyde or urea and formaldehyde, or phenol- formaldehyde resins.

Suitable carriers are also aerosils, silicon dioxide, metal oxide or metal hydroxide powders, such as, for example, TiO,, ZnO, MgO, AlQ;, Al(OH); and Fe; Os. :

Further suitable carriers are alkaline earth metal salts, for example a calcium halide, such as calcium chloride, calcium bromide and calcium fluoride, calcium sulfate, calcium acetate, : magnesium chloride, magnesium bromide, magnesium fluoride, magnesium sulfate and magnesium acetate.

The carriers may be used individually or in the form of a mixture of two or more carriers.

The carriers are commercial compounds and, for example, are obtainable commercially - under the following names: :

I cc A i AN a Le ec J

PQ Corp. Co

Ela i aad

Pergopak M” Martinswerk condensation product of

I a er

MCA LR

. Arbocel FDY600~, J. Rettenmaier & Séhne cellulose fibres p= i : sodium chloride, Merck, Riedel ——

In a further preferred variant of the method according to the invention, the textile fibre material is treated with a particulate composition comprising a carrier that comprises at least one of the following components: a) water-soluble inorganic and/or organic salts, which may especially be customary textile washing composition constituents but are preferably not surfactant components, . b) finely divided organic solids that are capable of swelling in water and/or are partially water- soluble, and c) very finely dispersed water-insoluble inorganic carriers.

In an especially preferred variant of the method according to the invention, the textile fibre material is treated with a particulate composition comprising a carrier selected from the group of the following carriers: zeolites, bentonites, kieselguhr, talc, kaolin, mica, fuller's earth, cellulose, feldspar and condensation products of urea and formaldehyde.

In the present invention binders c) are, for example, anionic dispersants, non-ionic surfactants and dispersants or water-soluble polymers, which are defined hereinbelow. a) Anionic dispersants

The anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes and pigments.

The following products in particular come into consideration: condensation products of aromatic sulfonic acids and formaldehyde, condensation products of aromatic sulfonic acids with optionally chlorinated diphenylene or diphenyl oxides and optionally formaldehyde, (mono-/di-)alkylnaphthalenesulfonates, sodium salts of polymerised organic sulfonic acids, sodium salts of polymerised alkylnaphthalenesuifonic acid, sodium salts of polymerised alkylbenzenesuifonic acids, alkylarylsuifonates, sodium salts of alkylpolyglycol ether sulfates, polyalkylated polynuclear arylsulfonates, methylene-linked condensation products of aryl- sulfonic acids and hydroxyarylsulfonic acids, sodium salts of dialkylsulfosuccinic acids, sodium salts of alkyldiglycol ether sulfates, sodium salts of polynaphthalenemethane- sulfonates, lignin sulfonates or oxylignin sulfonates or heterocyclic polysulfonic acids.

b) Non-ionic surfactants and dispersants

Suitable non-ionic dispersants are especially compounds that are emulsifiable, dispersible or : soluble in water, preferably having a melting point of at least 35°C. They are, for example, the following compounds: 1. fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol; 2. addition products of preferably from 2 to 80 mol of alkylene oxide, especially ethylene oxide, it being possible for individual ethylene oxide units to have been replaced by substituted epoxides, such as styrene oxide and/or propylene oxide, with higher unsaturated or saturated monoalcohols, fatty acids, fatty amines or fatty amides having from 8 to 22 carbon atoms, or with benzyl alcohols, phenylphenols, benzylphenols or alkylphenols, the alkyl radicals thereof having at least 4 carbon atoms; 3. condensation products of alkylene oxides, especially of propylene oxide (block polymeri- sation products), 4. ethylene oxide/propylene oxide adducts with diamines, especially ethylenediamine; 5. reaction products of a fatty acid having from 8 to 22 carbon atoms and a primary or secondary amine having at least one hydroxy-lower alkyl or lower alkoxy-lower alkyl group or alkylene oxide addition products of such hydroxyalkyl-group-containing reaction products; 6. sorbitan esters, preferably having long-chained ester groups, or ethoxylated sorbitan esters, such as e.g. polyoxyethylene sorbitan monolaurate having from 4 to 10 ethylene oxide units or polyoxyethylene sorbitan trioleate having from 4 to 20 ethylene oxide units, 7. addition products of propylene oxide with a tri- to hexa-hydric aliphatic alcohol having from 3 to 6 carbon atoms, e.g. glycerol or pentaerythritol; and 8. fatty alcohol polyglycol mixed ethers, especially addition products of from 3 to 30mol of ethylene oxide and from 3 to 30 mol of propylene oxide with aliphatic monoalcohols having from 8 to 22 carbon atoms.

Especially suitable non-ionogenic dispersants are surfactants of formula ’ Rs-O-(alkylene-0)n-Rs (2) wherein

Rs is C4-C,,alkyl or C4-C, alkenyl;

Re is hydrogen; C,-C alkyl; a cycloaliphatic radical having at least 6 carbon atoms; or benzyl; “alkylene” is an alkylene radical having from 2 to 4 carbon atoms, and n is a number from 1 to 60. : The substituents Rs and Rg in formula (2) are advantageously the hydrocarbon radical of an unsaturated or preferably saturated aliphatic monoalcohol having from 8 to 22 carbon atoms.

The hydrocarbon radical can be straight-chained or branched. Preferably Rsand Rs are each independently of the other an alkyl radical having from 9 to 14 carbon atoms.

Suitable aliphatic saturated monoalcohols are natural alcohols, for example lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol, and synthetic alcohols, for example 2-ethyl- hexanol, 1,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexanol, trimethyl- nonyl alcohol, decanol, Cq-C;10x0alcohol, tridecyl alcohol, isotridecyl alcohol and linear primary alcohols (Alfol® products) having from 8 to 22 carbon atoms. Examples of such Alfol® products are Alfol® (8-10), Alfol® (9-11), Alfol® (10-14), Alfol® (12-13) and Alfol® (16-18).

Unsaturated aliphatic monoalcohols are, for example, dodecenyl alcohol, hexadecenyl alcohol or oleyl alcohol.

The alcohol radicals can be present individually or in the form of mixtures of two or more components, for example mixtures of alkyl and/or alkenyl groups derived from soybean fatty acids, palm kernel fatty acids or tallow oils. : . (Alkylene-0) chains are preferably divalent radicals of formula

CHg CHa -(CHp-CHy-0)-, -(CH-CH,-0)- or -(CH,-CH-0)-

Examples of a cycloaliphatic radical are cycloheptyl, cyclooctyl or preferably cyclohexyl.

Suitable non-ionogenic dispersants are preferably surfactants of formula rer 15 3)

Ry-O-(CH-CH-O)7{CH-CH-0)=R, wherein : R; is C4-C, alkyl;

R, is hydrogen or C.-C alkyl;

Y,. Y, Y; and Y, are each independently of the others hydrogen, methyl or ethyl; n, is a number from O to 8; and n, is a number from 2 to 40.

Further important non-ionogenic dispersants correspond to formula

Ys Ye Y, Ys bol I

Ry-0-(CH-CH-0) —tCH-CH-0) ~R +o “@ wherein

Ry is C4-C, alkyl;

Rio is C,-C alkyl;

YY, Y and Y, are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y, and Y, and one of the radicals Y; and Yg always being hydrogen; and n, and n, are each independently of the other an integer from 4 to 8.

The non-ionogenic dispersants of formulae (2) to (4) can be used in the form of mixtures. For example, suitable surfactant mixtures are non-end-group-terminated fatty alcohol ethoxylates of formula (2), that is to say compounds of formula (2) wherein

Ry; is Cg-Cpalkyl,

Rs is hydrogen and the alkylene-O chain is the radical -(CH,-CHz-O)-, and end-group-terminated fatty alcohol ethoxylates of formula (4).

Examples of the non-ionogenic dispersants of formulae (2), (3) and (4) that may be mentioned include reaction products of a C,,-C,, fatty alcohol, e.g. of a C,;oxoalcohol, with from 3 to 10 mol of ethylene oxide, propylene oxide and/or butylene oxide or the reaction product of 1 mol of a C,, fatty alcohol with 6 mol of ethylene oxide and 1 mol of butylene oxide, it being possible for the addition products each to be end-group-terminated by

C,-C,alkyl, preferably methyl or butyl. ¢) Water-soluble polymers

Suitable water-soluble organic polymers are, for example, sugars and sugar derivatives, : such as cyclodextrins, polysaccharides (e.g. starch, maltodextrin), carboxymethytellulose, hydroxymethylcellulose, alginates, polyaspartic acid, polyethylene glycols, ethylene oxide/- propylene oxide copolymers, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-chained a-olefins,

copolymers of styrene and acrylic acid, polycarboxylic acids, poly(vinybyrrolidone/- dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylamincpropyl- methacrylamides, copolymers of vinylpyrrolidone/dimethylaminopropylacrylamides, quaternised copolymers of vinylpyrrolidones and dimethylaminoethyl methacrylates, terpolymers of vinylcaprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, copolymers of vinylpyrrolidone and methacrylamidopropyltrimethylammonium chloride, terpolymers of caprolactam/vinylpyrrolidone/dimethylaminoethyl methacrylates, polyacryl- amides, polyvinyl alcohols, optionally hydrolysed polyvinyl acetate, copolymers of ethyl acrylate with methacrylate and methacrylic acid, copolymers of maleic acid with unsaturated hydrocarbons and mixed polymerisation products of the mentioned polymers.

In a preferred embodiment of the composition according to the invention, non-ionic dispersants and/or water-soluble polymers are used as binders. Special preference is given to starch, maltodextrin and carboxymethylcellulose, hydroxymethylcellulose, polyethylene glycols, ethylene oxide/propylene oxide copolymers, polyviny! alcohols and gelatin.

The particulate compositions according to the invention may comprise further additives, for example wetting agents, water-insoluble or water-soluble dyes, fillers, pigments, perfume oils, foam-regulators, thickeners, microbicides, complexing agents, dissolution accelerators and fluorescent whitening agents, UV absorbers, antioxidants or anti-dust agents.

The particulate compositions, which are especially granules, can also be prepared in such a manner that they are in the form of coated particles or granules. Suitable coating materials, - in addition to the conventional substances mentioned in connection with the binders, are, for example, polymethacrylic acid, polyethylenesulfonic acids, polystyrenesulfonic acids, copolymers of acrylic acid with sulfonated styrenes, gum arabic, hydroxypropylicellulose, hydroxymethylpropylicellulose or the phthalate thereof, and waxy substances, such as e.g. glyceryl monostearate, glyceryl distearate, beeswax, waxy paraffins, stearic acid or the magnesium or calcium salts thereof. Such additives are present in an amount of from 0 to % by weight, based on the total weight of the particulate compositions. ’ The particulate compositions according to the invention, which are especially granules, may also be uncoated and have a substantially homogeneous distribution of their constituents.

The particulate compositions according to the invention also comprise from 0 to 15 % by weight water.

The particulate compositions according to the invention, especially granules, are prepared in various ways starting from fiquid or solid dye fixative, by a) dissolving a dye fixative or a dye fixative and a binder, and then bringing a solid carrier into contact with the solution, preferably forming a suspension therein, or b) dissolving a dye fixative or a dye fixative and a binder, and then applying the solution to the solid carrier or granulating it therewith, or c) extruding a paste comprising a dye fixative, a carrier and a binder, or d) granulating a mixture consisting of a dye fixative, a carrier and possibly a binder, by spray application of a solvent or a melt in which further binders may have been dissolved, and drying the compositions obtained according to methods a), b), ¢) or d), or allowing them to solidify by cooling. Coating of the resulting granules can also be carried out, for example, by, in a subsequent step, spraying the granules with a solution of a coating material and drying them or coating them with a melt. in respect of method a): : First the active ingredient, the binder and optionally further additives are dissolved in water and the mixture is stirred, optionally with heating, until a homogeneous solution is obtained.

The carrier material is then suspended in that aqueous solution. The mixture is stirred untit a homogeneous suspension is obtained. The solids content of the suspension should preferably be at least 30 % by weight, especially from 40 to 50 % by weight, based on the total weight of the solution. The viscosity of the solution is preferably less than 1500 mPas.

In a drying step all the water except for a residual amount is then removed from the aqueous suspension prepared in that manner, solid particles, for example granules, being formed at the same time.

Generally known processes are suitable for preparing the granules from the aqueous suspension. In principle, processes involving a continuous procedure and-also processes ’ involving a discontinuous procedure are suitable. Preference is given to the use of continuous processes, especially spray-drying and fluidised bed granulating processes.

Especially suitable are spray-drying processes in which the active ingredient solution is sprayed into a chamber with circulating hot air. Atomisation of the solution is effected by means of unitary or binary nozzles or by the spin effect of a rapidly rotating disk. In order to increase the size of the particles, the spray-drying process can be combined with additional agglomeration of the liquid particles with solid seeds in a fluidised bed incorporated into the chamber (so-called fluid spray). The fine particles (< 100 ym) resulting fran a conventional spray-drying process can be fed, optionally after being separated out from the discharge gas stream, as seed, without further treatment directly into the spray cone of the atomiser of the spray-dryer to achieve agglomeration with the liquid drops of the active ingredient.

During the granulation step, water can be removed rapidly from the suspensions comprising the carrier and the dye fixative, and agglomeration of the drops forming in the spray cone or of drops with solids particles is expressly intended.

If required, the granules formed in the spray-dryer are separated out in a continuous process, for example by a screening procedure. In that process, the fines and oversize material are either recycled directly (without intermediate dissolution) or suspended in the liquid active ingredient formulation and then granulated again.

In respect of method b):

First a solution consisting of dissolved dye fixative and optionally further binders and additives is prepared. The solution is then applied to the carrier in a granulator by means of a spray device, granules being formed by agglomeration. The granulation is effected either in a batch process or in a continuous procedure. Suitable granulators are fluidised bed granulators or horizontally or vertically rotating mixers. When the granulation process is complete, the water is removed from the granules with the exception of the desired residual amount. This is effected either in the same apparatus or in a separate after-dryer.

In respect of method c):

A paste consisting of a dye fixative, carrier and optionally a binder is prepared in a kneading apparatus. The components are made into a paste either by the addition of a suitable amount of water or by melting one or more of the formulation components. The paste is then : fed into an extruder and shaped into cylindrical particles (diameter 0.5 - 2 mm, length 1 - 3 mm; ratio of diameter/length from 1:1 to 1:4). The extruded material is dried/solidified in a : further step. If desired, the extruded material can be rounded off in a separate step. Any fines produced are recycled in the process.

In respect of method d):

A homogeneous dry mixture consisting of a dye fixative, carrier and binder is prepared in a mixer. The mixture is then granulated in a granulator with spray application of a molten ) binder, an aqueous binder solution or, where appropriate, water alone. The granulation is effected either in a batch process or continuously. Suitable granulators are both fluidised bed granulators and horizontally or vertically rotating mixers. When the granulation process is . complete, water is removed from the granules with the exception of the desired residual amount, or in the case of molten binder, the granules solidify.

The granules according to the invention are resistant to abrasion, low in dust, free-flowing and easily meterable. They are distinguished by a rate of dissolution in water that can be controlled by means of the composition of the formulation.

The dye fixative content of the granules is from 1 to 90 % by weight, preferably from 5 to 88 % by weight, especially from 10 to 78 % by weight. The size of the granules can be matched to suit the target product and is from 0.05 mm to 4 mm, preferably from 0.1 mm to 2 mm.

Accordingly, the present invention relates also to the above-defined particulate compositions, especially granules, comprising - a) from 1 to 90 % by weight of at least one water-soluble dye fixative, b) from 2 to 80 % by weight of at least one carrier, c) from 0 to 60 % by weight of at least one binder that is soluble/dispersible in water, d) from 0 to 20 % by weight of at least one further additive, and e) from 0 to 15 % by weight water, the percentages in each case denoting percent by weight, based on the total weight of the composition.

All the definitions and preferred meanings mentioned above for the method according to the invention apply also to the particulate compositions according to the invention.

Preferred particulate compositions according to the invention are granules.

Further preferred particulate compositions according to the invention, especially granules, consist of a) from 1 to 90 % by weight of at least one basic polycondensation product of an amine of formula

AN / : N——A—N mm re” e, and a cyanamide, wherein the mentioned polycondensation product either has not been : neutralised or has been neutralised wholly or partially with an inorganic or organic acid, -

R., Rs, Rs and R, each independently of the others being hydrogen or alkyl unsubstituted or substituted by amino, hydroxy, cyano or by C;-Calkoxy, and

A being alkylene unsubstituted or substituted or uninterrupted or interrupted by one or more hetero atoms, b) from 2 to 80 % by weight of at least one carrier from the group consisting of zeolites, bentonites, kieselguhr, talc, kaolin, mica, fuller's earth, cellulose, feldspar and/or : condensation products of urea and formaldehyde, c) from O to 60 % by weight of at least one compound from the group consisting of starch, maltodextrin and carboxymethylceliulose, hydroxymethylcellulose, polyethylene glycols, : ethylene oxide/propylene oxide copolymers, polyvinyl alcohols and/or gelatin, d) from 0 to 20 % by weight of at least one further additive from the group consisting of wetting agents, water-insoluble or water-soluble dyes, fillers, pigments, perfume oils, foam- regulators, thickeners, microbicides, complexing agents, dissolution accelerators, fluorescent whitening agents, UV absorbers, antioxidants and/or anti-dust agents, and e) from 0 to 15 % by weight water, : the percentages in each case denoting percent by weight, based on the total weight of the composition.

Still greater preference is given to particulate compositions according to the invention wherein A in formula (1) of the dye fixative is C2Cxalkylene uninterrupted or interrupted by -O-, -S-, -NH- or by -N(C4-C,alkyl) and/or unsubstituted or substituted by hydroxy, preferably

C,-Caoalkylene interrupted one or more times by -NH-.

Especially preferred particulate compositions according to the invention are those wherein the compound of formula (1) is a polyethylenepolyamine, especially diethylenetriamine.

Especially preferred particulate compositions according to the invention are also those wherein the cyanamide is dicyandiamide.

Especially preferred particulate compositions according to the invention are also those wherein the inorganic or organic acid is a mono- or poly-carboxylic acid, hydrochloric acid, phosphoric acid, sulfuric acid or a mixture of at least two such acids.

Depending on the composition of the granules according to the invention, the formulations according to the invention may also be used as an additive in other formulations or in combination with another formulation. The preferred use of the formulations according to the invention is use in a washing composition or in a washing composition additive, for example in pre- and/or after-treatment agents, in stain-treatment salts, in washing power enhancers, in softeners, in bleaching agents or in UV protection enhancers.

The formulations according to the invention are used especially as an additive in a washing formulation. Such a washing formulation may be in solid, liquid, gel-like or pasty form, for example in the form of a liquid, non-aqueous washing composition comprising not more than % by weight, preferably from 0 to 1 % by weight, water, and may be based on a suspen- sion of a builder substance in a non-ionic surfactant, for example as described in GB-A-2 158 454.

The formulation according to the invention may also be in the form of a powder, a (super) compact powder, a single- or multi-layer tablet (tabs), in the form of washing composition bars, washing composition blocks, washing composition sheets, washing composition pastes, washing composition gels, also in the form of powders, pastes, gels or liquids which are used in capsules or in bags (sachets).

However, the washing compositions are preferably in the form of non-aqueous formula- tions, powders, tabs or granules. ‘ The present invention accordingly relates also to washing formulations comprising

N5-90% of A) at least one anionic surfactant and/or B) at least one : non-ionic surfactant, based on the total weight of the washing formulation,

15-70% of C) at least one builder substance, based on the total weight of the washing formulation, iNyo-30% of D) at least one peroxide and optionally at least one activator, based on the total weight of the washing formulation,

IV)0.1-70% of E) at least one particulate composition comprising a) from 1 to 90 % by weight of at least one water-soluble dye fixative, b) from 2 to 80 % by weight of at least one carrier, c) from 0 to 60 % by weight of at least one binder that is soluble/dispersible in water, d) from 0 to 20 % by weight of at least one further additive, and ~ e) from 0 to 15 % by weight of water, :

V)0-60% of F) at least one further additive, and

VI)0-12% of G) water.

The present invention accordingly preferably relates also to washing formulations comprising

N)5-70% of A) at least one anionic surfactant and/or B) at leastone . : non-ionic surfactant, based on the total weight of the washing formulation,

I) 5 - 50 %, preferably 5-40 % by weight, of C) at least one builder substance, . : based on the total weight of the washing formulation, mo-12% of D) at least one peroxide and optionally at least preferably from 5 to 40 % by weight of an activator, based on the total weight of the washing formulation, and

IV) 0.2 - 50 %, preferably from 0.3 ~40 % by weight, of E) at least one particulate composition comprising a) from 1 to 90 % by weight of at least one water-soluble dye fixative, b) from 2 to 80 % by weight of at least one carrier, c) from 0 to 60 % by weight of at least one binder that is soluble/dispersible in water, d) from O to 20 % by weight of at least one further additive, and e) from 0 to 15 % by weight of water,

V)0-60% of F) at least one further additive, and

V)0-12% of G) water.

The sum of the percent by weight of components I) to VI) in a formulation isalways 100 %.

Claims

What is claimed is:

1. A method of reducing dye loss or dye transfer from textile fibre materials, in which method the textile fibre materials are treated with a particulate composition comprising ’ a) from 1 to 90 % by weight of a water-soluble dye fixative, b) from 2 to 80 % by weight of a carrier, c) from 0 to 60 % by weight of a binder that is soluble/dispersible in water, d) from 0 to 20 % by weight of a further additive, and e) from 0 to 15 % by weight water, the percentages in each case denoting percent by weight, based on the total weight of the composition.

2. A method according to claim 1, wherein the particulate composition is in the form of granules.

3. A method according to either claim 1 or claim 2, wherein treatment is effected with a particulate composition comprising, as the water-soluble dye fixative a), a basic polyconden- sation product of an amine of formula Rin ya N—A—N (1) dg Se and a cyanamide, wherein the mentioned polycondensation product either has not been neutralised or has been neutralised wholly or partially with an inorganic or organic acid, R1, Ry, Ra and Ry each independently of the others being hydrogen or alkyl unsubstituted or substituted by amino, hydroxy, cyano or by C,-Calkoxy, and A being alkylene unsubstituted or substituted or uninterrupted or interrupted by one or more hetero atoms.

: 4. A method according to claim 3, wherein A is C,Cyalkylene uninterrupted or interrupted by ~O-, -8-, -NH- or by -N(C,-Calkyl)- and/or unsubstituted or substituted by hydroxy, preferably : C,-Caoalkylene interrupted one or more times by -NH-.

5. A method according to either claim 3 or claim 4, wherein the compound of formula (1) isa polyethylenepolyamine, especially diethylenetriamine.

6. A method according to any one of claims 3 to 5, wherein the cyanamide is dicyandiamide.

7. A method according to any one of claims 3 to 6, wherein the inorganic or organic acid is a mono- or poly-carboxylic acid, hydrochloric acid, phosphoric acid, sulfuric acid or a mixture of at least two such acids. :

8. A method according to any one of claims 1 to7, wherein treatment is effected with a particulate composition comprising a carrier that comprises at least one of the following components: a) water-soluble inorganic and/or organic salts, which may especially be customary textile washing composition constituents but are preferably not surfactant components, b) finely divided organic solids that are capable of swelling in water and/or are water-soluble, and c) very finely dispersed water-insoluble inorganic carriers.

9. A method according to any one of claims 1 to 8, wherein the carrier b) consists of at least one compound from the group consisting of zeolites, bentonites, kieselguhr, talc, kaolin, mica, fuller's earth, cellulose, feldspar and/or condensation products of urea and formaldehyde.

10. A method according to any one of claims 1 to 9, wherein the binder c) consists of at least one compound from the group consisting of starch, maltodextrin and carboxymethytellulose, hydroxymethylicellulose, polyethylene glycols, ethylene oxide/propylene oxde copolymers, polyvinyl alcohols and/or gelatin.

11. A method according to any one of claims 1 to 10, wherein the particulate compositions comprise wetting agents, water-insoluble or water-soluble dyes, fillers, pigments, perfume oils, foam-regulators, thickeners, microbicides, complexing agents, dissolution accelerators, fluorescent whitening agents, UV absorbers, antioxidants and/or anti-dust agents as further additives d).

12. A method according to any one of claims 1 to 11, wherein the particulate compositions are coated.

13. A method according to any one of claims 1 to 11, wherein the particulate compositions : are uncoated and have a substantially homogeneous distribution of their constituents.

14. A particulate composition comprising a) from 1 to 90 % by weight of a water-soluble dye fixative, b) from 2 to 80 % by weight of a carrier, c) from O to 60 % by weight of a binder that is soluble/dispersible in water, d) from 0 to 20 % by weight of a further additive, and e) from 0 to 15 % by weight water, the percentages in each case denoting percent by weight, based on the total weight of the composition, and the constituents a), b), c), d) and e) being defined according to claims 1to

13.

15. A method for the preparation of the particulate composifon, which comprises a) dissolving a dye fixative or a dye fixative and a binder, and then bringing a solid carrier into contact with the solution, preferably forming a suspension therein, or b) dissolving a dye fixative or a dye fixative and a binder, and then applying the solution to the solid carrier or granulating it therewith, or c) extruding a paste comprising a dye fixative, a carrier and a binder, or d) granulating a mixture consisting of a dye fixative, a carrier and possibly also a binder, by - spray application of a solvent or a melt in which further binders may have been dissolved, and drying the compositions obtained according to methods a), b), ¢) or d), or allowing them to solidify by cooling.

16. A method according to claim 15, wherein, in a subsequent step, the particulate : composition is sprayed with a solution of a coating material and is dried or is coated with a melt.

17. A washing formulation for reducing dye loss or dye transfer from textile fibre materials, comprising

)5-90% of A) at least one anionic surfactant and/or B) at least one non-ionic surfactant, based on the total weight of the washing formulation, N5-70% of C) at least one builder substance, based on the total . weight of the washing formulation, l0-30% of D) at least one peroxide and optionally at least one : activator, based on the total weight of the washing formulation, IV)0.1-70% of E) at least one particulate composition comprising a) from 1 to 90 % by weight of at least one water-soluble dye fixative, b) from 2 to 80 % by weight of at least one carrier, c) from 0 to 60 % by weight of at least one binder that is soluble/dispersible in water, d) from 0 to 20 % by weight of at least one further additive, and e) from 0 to 15 % by weight water, V)0-60% of F) at least one further additive, and VI)0-12% of G) water.

18. A washing formulation according to claim 17, comprising )5-90% of A) at least one anionic surfactant from the group consisting of C,4,-Cysalkylethoxysulfates in which the alkyl moiety has from 10 to 20 carbon atoms and the head group contains on average 2 or 3 ethoxy units; alkylbenzene- sulfonates having from-9 to 15 carbon atoms in the alkyl moiety; alkylnaphthalenesulfonates having from 6 to 16 carbon atoms in the respective alkyl moiety; or alkali metal sarcosinates of the formula R44~-CO-N(R+,)-CH,COOM;, wherein R,4 is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl moiety, Riz is C4-Caalkyl and } M, is an alkali metal, and/or of B) at least one non-ionic surfactant from the group . consisting of a condensation product of from 3 to 8 mol of ethylene oxide with 1 mol of primary alcohol having from 9 to carbon atoms,

N5-70% of C) a builder substance from the group consisting of alkali metal phosphates; carbonates; bicarbonates; silicates; aluminium silicates; polycarboxylates; polycarboxylic acids; organic phosphonates or aminoalkylenepoly-(alkylene : phosphonates), i) 00-30% of D) a peroxide from the group consisting of organic mono- or poly-peroxides; organic per-acids or salts thereof; persulfates; perborates; percarbonates; persilicates,

V)0.1-70% of E) granules comprising a) from 1 to 90 % by weight, preferably from 5 to 88 % by weight, especially from 10 to 78 % by weight, of polydiallyldimethylammonium compounds, especially polydiallyldimethylammonium salts, bis- chloromethylbiphenylpolyquat compounds, the compound polyethyleneimine and basic polycondensation products, preferably those containing imidazolidine units and especially Tinofix CL®, b) from 2 to 80 % by weight of at least one carrier from the group consisting of zeolites, bentonites, kieselguhr, talc, kaolin, mica, fuller's earth, cellulose, feldspar and condensation products of urea and formaldehyde, PB) from O to 60 % by weight of at least one non-ionic dispersant and/or water-soluble polymer from the group consisting of starch, maltodextrin and carboxymethylcellulose, hydroxymethylcellulose, polyethylene glycols, ethylene oxide/propylene oxide copolymers, polyvinyl alcohols and gelatin, _ d) from 0 to 20 % by weight of at least one further additive from the group consisting of wetting agents; disintegrators; fillers, water-insoluble or water-soluble dyes or pigments; dissolution accelerators; fluorescent whitening agents; aluminium silicates; powdered : cellulose; fibrous cellulose; microcrystalline cellulose; talc; kaolin; TiO,; SiO, and magnesium trisilicate, and

. e) from 0 to 15 % by weight water, in each case based on the total weight of the granules,

V)0-60% of F) further additives from the group consisting of fluorescent whitening agents; suspending agents for dirt; pH regulators; foam- regulators; salts for regulating spray-drying and granulating properties; fragrances; antistatics; softeners; enzymes; bleaching agents; pigments; toning agents; further polymers which during the washing of textiles prevent staining by dyes found in the washing liquor which have dissolved out of the textiles under washing conditions; and bleaching agent activators, and VI) 0-12% of G) water.

19. A softener formulation for reducing dye loss or dye transfer from textile fibre materials, comprising A) from 0.5 to 50 % by weight, based on the total weight of the composition, of at least one softener component; B) from 0.005 to 15 % by weight, based on the total weight of the composition, of at least one thickener, especially a polymeric thickener; Cc) from 0.1 to 70 % by weight, based on the total weight of the composition, of granules comprising : a) from 1 to 90 % by weight, preferably from 5 to 88 % by weight, more a preferably from 10 to 78 % by weight, of polydiallyldimethyl- 3 ammonium compounds, especially polydiallyldimethyl- ammonium salts, bischloromethylbiphenylpolyquat compounds, the compound polyethyleneimine and basic polycondensation products, preferably those containing imidazolidine units and especially Tinofix CL®, b) from 2 to 80 % by weight of at least one carrier from the group consisting of zeolites, bentonites, kieselguhr, talc, kaolin, mica, fuller's earth, cellulose, feldspar and condensation products of urea and formaldehyde, c) from O to 60 % by weight of at least one non-ionic dispersant and/or water- soluble polymer from the group consisting of starch, - maltodextrin and carboxymethyicellulose, hydroxymethyi- cellulose, polyethylene glycols, ethylene oxide/propylene oxide copolymers, polyvinyl alcohols and gelatin, and d) from 0 to 20 % by weight of at least one further additive from the group consisting of wetting agents; disintegrators; fillers, water- insoluble or water-soluble dyes or pigments; dissolution accelerators; fluorescent whitening agents; aluminium silicates; powdered cellulose; fibrous cellulose; microcrystalline cellulose; talc; kaolin; TiO,; SiO, and magnesium trisilicate, and e) from 0 to 15 % by weight water, in each case based on the total weight of the granules, D) from 0 to 20 % by weight, based on the total weight of the composition, of at least one further customary auxiliary substance, and E) waterto 100 % by weight.

20. A method according to claim 1, substantially as herein described and exemplified and/or described with reference to the examples.

21. A particulate composition according to claim 14, substantially as herein described and exemplified and/or described with reference to the examples.

22. A method according to claim 15, substantially as herein described and exemplified and/or described with reference to the examples.

23. A washing formulation according to claim 17, substantially as herein described and exemplified and/or described with reference to the examples.

24. A softener formulation according to claim 19, substantially as herein described and exemplified and/or described with reference to the examples. AMENDED SHEE!