Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
  • C11D3/3776—Heterocyclic compounds, e.g. lactam
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0021—Dye-stain or dye-transfer inhibiting compositions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines

Definitions

• Particulate composition comprising dve 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.
• 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.
• dye-fixing polymers 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 household sector, by means of which dye loss and/or dye transfer can be reduced further, and to provide washing formulations suitable for that method.
• 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 0 to 15 % by weight water, the percentages in each case denoting percent by weight, based on the total weight of the composition.
• a particulate composition especially granules
• 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 composition 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 multi-layer 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.
• 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 ® , Alcof ⁇ x ® , such as Alcofix R ® , or Tinof ⁇ x FRD ® , preferably Agefloc WT40 ® , Agefloc WT40 SV ® and Agefloc WT40 SVL ® ; also bischloromethylbiphenylpolyquats, as described in Patent Specifications DE 2 657 582 and EP 225 281; and polyethyleneimines obtainable from BASF under the
• 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 ®
• Levogen FL ® Levogen WSR ®
• Levogen WRD ® Lavaf ⁇ x ®
• Neofix RE ® Neofix E-225 ®
• Neofix E-117 ® Neofix RPA ®
• Neofix F ® Neofix RP-70 ®
• Neofix R-250 ® which are obtainable from Nicca
• Sevofix SR ® Sevofix FFK ®
• Sevofix NOF ® which are obtainable from Textil Color
• Indosol E-50 ® Indosol CRR ®
• Sandofix FFN ® Solidogen FRZR ®
• Sandofix TPS ® Sandofix TPS ®
• Sandofix TPSR ® Sandofix WE56R ® and Sandofix SWE ® , which are obtainable from Clariant.
• 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, bischloromethylbiphenylpoiyquat compounds, the compound polyethyleneimine and basic polycondensation products, preferably those containing imidazolidine units and more preferably Tinofix CL ® .
• a dye fixative selected from the group of the following dye fixatives: polydiallyldimethylammonium compounds, especially polydiallyldimethylammonium salts, bischloromethylbiphenylpoiyquat compounds, the compound polyethyleneimine and basic polycondensation products, preferably those containing imidazolidine units and more preferably Tinofix CL ® .
• textilefibre 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 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,
• Ri, R 2 , R3 and R 4 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.
• a in formula (1) is preferably C 2 -C 20 alkylene uninterrupted or interrupted by -O-, -S-, -NH- or by -N(C C 4 alkyl)- and/or unsubstituted or substituted by hydroxy, preferably C 2 -C 20 alkylene interrupted one or more times by -NH-.
• R 4 are each independently of the others preferably hydrogen or d-C 4 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.
• 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.
• 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.
• 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.
• 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.
• organic acids examples include 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.
• aliphatic carboxylic acids especially those having a total number of from 1 to 12 carbon atoms.
• Preferred acids are aliphatic C ⁇ - 2 -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.
• mixtures of the mentioned acids by way of example, mention may be made of the mixture of maleic acid and propionic acid.
• Suitable carriers b) are, for example, those disclosed in EP-A-133562, for example water- soluble inorganic and organic salts, which may be textile washing component constituents that are customary perse, but preferably without the salt-type surfactants.
• Such carriers are primarily the customary structural substances, or builder substances, of washing compositions, such as e.g. the alkali metal silicates, carbonates, bicarbonates and borates also known as washing alkalis, and the alkali metal polyphosphates.
• 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, mellitic 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 salts of organic polyphosphonic acids, such as e.g. isohydroxyethanediphosphonic acid, aminotri- .
• di- and poly-carboxylic acids such as e.g. adipic acid, glutaric acid, succinic acid, maleic acid, phthalic acid, mellitic acid and cyclohexanehexacarbox
• methylenetriphosphonic acid ethyldiaminotetramethylenetetraphosphonic acid
• 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 cf 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.
• 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.
• 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.
• 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.
• 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.
• 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 2) ZnO, MgO, AI 2 O 3 , AI(OH) 3 and Fe 2 O 3 .
• 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:
• the textile fibre material is treated with a particulate composition
• 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.
• the textile fibre material is treated with a particulate composition
• 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.
• binders c) are, for example, anionic dispersants, non-ionic surfactants and dispersants or water-soluble polymers, which are defined hereinbelow.
• the anionic dispersants used are, for example, commercially available water-soluble anionic dispersants for dyes and pigments.
• 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 alkylnaphthalenesulfonic acid, sodium salts of polymerised alkylbenzenesulfonic acids, alkylarylsulfonates, 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 salt
• 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:
• fatty alcohols having from 8 to 22 carbon atoms, especially cetyl alcohol
• alkylene oxide especially ethylene oxide
• substituted epoxides such as styrene oxide and/or propylene oxide
• fatty acids fatty amines or fatty amides having from 8 to 22 carbon atoms
• benzyl alcohols phenylphenols, benzylphenols or alkylphenols, the alkyl radicals thereof having at least 4 carbon atoms
• condensation products of alkylene oxides, especially of propylene oxide (block polymerisation products);
• 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,
• 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
• R 5 is C 8 -C 22 alkyl or C 8 -C 18 alkenyl
• R 6 is hydrogen; C,-C 4 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 R5 and R ⁇ 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.
• R 5 and R 3 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, Cg-Cnoxoalcohol, tridecyl alcohol, isotridecyl alcohol and linear primary alcohols (Alfol ® products) having from 8 to 22 carbon atoms.
• natural alcohols for example lauryl alcohol, myristyl alcohol, cetyl alcohol or stearyl alcohol
• synthetic alcohols for example 2-ethyl- hexanol, 1 ,1,3,3-tetramethylbutanol, octan-2-ol, isononyl alcohol, trimethylhexano
• Alfol ® products examples include 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-O chains are preferably divalent radicals of formula
• cycloaliphatic radical examples include cycloheptyl, cyclooctyl or preferably cyclohexyl.
• Suitable non-ionogenic dispersants are preferably surfactants of formula
• R 7 is C 8 -C 22 alkyl
• R a is hydrogen or C ⁇ C ⁇ Ikyl
• Y v Y 2 , Y 3 and Y 4 are each independently of the others hydrogen, methyl or ethyl; n 2 is a number from 0 to 8; and n 3 is a number from 2 to 40.
• R 9 is C 9 -C 14 alkyl
• R 10 is C 1 -C 4 alkyl
• Y 5 , Y ⁇ , Y 7 and Y 8 are each independently of the others hydrogen, methyl or ethyl, one of the radicals Y 5 and Y 6 and one of the radicals Y 7 and Y 8 always being hydrogen; and n 4 and n 5 are each independently of the other an integer from 4 to 8.
• non-ionogenic dispersants of formulae (2) to (4) can be used in the form of mixtures.
• suitable surfactant mixtures are non-end-group-terminated fatty alcohol ethoxylates of formula (2), that is to say compounds of formula (2) wherein R 5 is C 8 -C 22 alkyl, ⁇ is hydrogen and the alkylene-O chain is the radical -(CH 2 -CH 2 -O)-, and end-group-terminated fatty alcohol ethoxylates of formula (4).
• non-ionogenic dispersants of formulae (2), (3) and (4) examples include reaction products of a C 10 -C 13 fatty alcohol, e.g. of a C 13 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 13 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 1 -C 4 alkyl, preferably methyl or butyl.
• Suitable water-soluble organic polymers are, for example, sugars and sugar derivatives, such as cyclodextrins, polysaccharides (e.g. starch, maltodextrin), carboxymethybellulose, hydroxymethylcellulose, alginates, polyaspartic acid, polyethylene glycols, ethylene oxide/- propylene oxide copolymers, gelatin, polyacrylates, polymethacrylates, polyvinylpyrrolidones, vinylpyrrolidones, vinyl acetates, copolymers of vinylpyrrolidone with long-chained ⁇ -olefins, copolymers of styrene and acrylic acid, polycarboxylic acids, poly(vinyfc>yrrolidone/- dimethylaminoethyl methacrylates), copolymers of vinylpyrrolidone/dimethylamin ⁇ ropyl- methacrylamides, copolymers of vinylpyrrolidone/dimethyl
• 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, polyvinyl 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 are, for example, polymethacrylic acid, polyethylenesulfonic acids, polystyrenesulfonic acids, copolymers of acrylic acid with sulfonated styrenes, gum arabic, hydroxypropylcellulose, hydroxymethylpropylcellulose 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 20 % 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 liquid 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), c) or d), or allowing them to
• 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 until 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.
• processes are suitable for preparing the granules from the aqueous suspension.
• processes involving a continuous procedure and also processes involving a discontinuous procedure are suitable.
• 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.
• 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 ⁇ m) resulting from 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.
• 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.
• 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.
• 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.
• 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.
• 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. ln 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.
• 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.
• 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.
• Preferred particulate compositions according to the invention are granules.
• compositions according to the invention consist of a) from 1 to 90 % by weight of at least one basic polycondensation product of an amine of formula
• R 3 and R 4 each independently of the others being hydrogen or alkyl unsubstituted or substituted by amino, hydroxy, cyano or by 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 0 to 60 % by weight of at least one compound from the group consisting of starch, maltodextrin and carboxymethylcellulose, 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
• a in formula (1) of the dye fixative is C 2 -C 20 alkylene uninterrupted or interrupted by -O-, -S-, -NH- or by -N(d-C alkyl) and/or unsubstituted or substituted by hydroxy, preferably C 2 -C 20 alkylene 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.
• 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.
• 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.
• 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 5 % by weight, preferably from 0 to 1 % by weight, water, and may be based on a suspension 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).
• washing compositions are preferably in the form of non-aqueous formulations, powders, tabs or granules.
• the present invention accordingly relates also to washing formulations comprising I) 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, II) 5 - 70 % of C) at least one builder substance, based on the total weight of the washing formulation,
• E) 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,
• the present invention accordingly preferably relates also to washing formulations comprising
• E) 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 0 to 20 % by weight of at least one further additive, and e) from 0 to 15 % by weight of water,
• the anionic surfactant A) may be, for example, a sulfate, sulfonate or carboxylate surfactant or a mixture thereof.
• Preferred sulfates are those having from 12 to 22 carbon atoms in the alkyl moiety or alkylethoxy sulfates in which the alkyl moiety has from 10 to 20 carbon atoms and the head group possesses on average 2 or 3 ethoxy units.
• Preferred sulfonates are, for example, alkylbenzenesulfonates having from 9 to 15 carbon atoms in the alkyl moiety and/or alkylnaphthalenesulfonates having from 6 to 16 carbon atoms in the respective alkyl moiety.
• the cation in the case of the anionic surfactants is preferably an alkali metal cation, especially sodium.
• Preferred carboxylates are alkali metal sarcosinates of the formula R ⁇ CO-N(R 12 )-CH 2 COOM 1 , wherein Rn is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl moiety, R
• the non-ionic surfactant B) may be, for example, a condensation product of from 3 to 8mol of ethylene oxide with 1 mol of primary alcohol having from 9 to 15 carbon atoms.
• Suitable builder substances C) are, for example, alkali metal phosphates, especially tripoly- phosphates, carbonates or bicarbonates, especially the sodium salts thereof, silicates, aluminium silicates, polycarboxylates, polycarboxylic acids, organic phosphonates, amino- alkylenepoly-(alkylene phosphonates) or mixtures of those compounds.
• silicates are the sodium salts of crystalline layered silicates of the formula NaHSi t t+ ⁇ .pH 2 O or Na 2 Si t O 2t fi.pH 2 O, wherein t is a number from 1.9 to 4 and p is a number from 0 to 20.
• aluminium silicates preference is given to those which are available commercially under the names Zeolite A, B, X and HS, as well as mixtures containing two or more of those components.
• polycarboxylates preference is given to the polyhydroxy carboxylates, especially citrates, and acrylates and copolymers thereof with maleic anhydride.
• Preferred poly- carboxylic acids are nitrilotriacetic acid, ethylenediaminetetraacetic acid as well as ethylenediamine disuccinate both in racemic form and in the enantiomerically pure S,S form.
• phosphonates or aminoalkylenepoly(alkylene phosphonates) are alkali metal salts of 1-hydroxyethane-1,1-diphosphonic acid, nitrilotris(methylenephosphonic acid), ethylenediamine-tetramethylenephosphonic acid and diethylenetriaminepenta- methylenephosphonic acid.
• Suitable as the peroxide component D) are, for example, the commercially available organic and inorganic peroxides known from the literature, which bleach textile materials at customary washing temperatures, for example from 10 to 95°C.
• the organic peroxides are, for example, mono- or poly-peroxides, especially organic per-acids or salts thereof, such, as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxy- nonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
• organic peroxides for example persulfates, perborates, percarbonates and/or persilicates.
• mixtures of inorganic and/or organic peroxides are, for example, mono- or poly-peroxides, especially organic per-acids or salts thereof, such, as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxy- nonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
• the peroxides may be present in various crystalline forms and may have different water contents and can also be used together with other inorganic or organic compounds in order to improve their storage stability.
• the addition of the peroxides to the washing composition is preferably carried out by mixing the components, for example by means of a screw metering system and/or a fluidised bed mixer.
• the washing compositions can also comprise one or more fluorescent whitening agents, for example from the class bis- triazinylamino-stilbene-disulfonic acid, bis-triazolyl-stilbene-disulfonic acid, bis-styryl- biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative, a coumarin derivative or a pyrazoline derivative.
• fluorescent whitening agents for example from the class bis- triazinylamino-stilbene-disulfonic acid, bis-triazolyl-stilbene-disulfonic acid, bis-styryl- biphenyl or bis-benzofuranylbiphenyl, a bis-benzoxalyl derivative, a bis-benzimidazolyl derivative, a coumarin derivative or a pyrazoline derivative.
• the washing compositions may also comprise suspending agents for dirt, e.g. sodium carboxymethylcellulose, pH regulators, e.g. alkali metal or alkaline earth metal silicates, foam-regulators, e.g. soap, salts for regulating spray-drying and granulating properties, e.g. sodium sulfate, fragrances and, optionally, antistatics and softeners, enzymes, such as amylase, bleaching agents, pigments and/or toning agents.
• suspending agents for dirt e.g. sodium carboxymethylcellulose
• pH regulators e.g. alkali metal or alkaline earth metal silicates
• foam-regulators e.g. soap
• salts for regulating spray-drying and granulating properties e.g. sodium sulfate, fragrances and, optionally, antistatics and softeners
• enzymes such as amylase, bleaching agents, pigments and/or toning agents.
• the washing formulation may additionally comprise 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 the washing conditions.
• washing compositions according to the invention may also comprise so-called perborate activators, e.g. TAED orTAGU.
• TAED perborate activators
• the percentages of components I) to VI) in the following washing formulations are always based on the total weight of the washing formulation.
• a preferred washing formulation according to the invention consists of
• At least one anionic surfactant from the group consisting of C ⁇ 2 -C 22 alkylethoxysulfates 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 R 11 -CO-N(R 12 )-CH 2 COOM 1 , wherein Rn is alkyl or alkenyl having from 8 to 18 carbon atoms in the alkyl or alkenyl moiety,
• R 12 is C C 4 alkyl
• M is an alkali metal
• E) 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, 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 0 to 60 % by weight of at least one non-ionic dispersant and/or water-soluble polymer from the group consisting of starch, maltodextrin and
• the present invention relates also to a softener composition for reducing dye loss or dye transfer from textile fibre materials, especially in the household sector, comprising a particulate composition that comprises a carrier and a dye fixative.
• a softener composition comprising a particulate composition consisting of 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.
• Softeners especially hydrocarbon softeners, which can be used herein are selected especially from the following classes of compounds:
• Cationic quaternary ammonium salts (i) Cationic quaternary ammonium salts.
• the counter-ion of such cationic quaternary ammonium salts may be a halide, for example chloride or bromide, dimethyl sulfate or other ions known from the literature.
• the counter-ion is preferably dimethyl sulfate or any desired alkyl sulfate or halide, with dimethyl sulfate being most preferred for the articles of this invention added to the dryer.
• Examples of cationic quaternary ammonium salts include but are not limited to: (1) Acyclic quaternary ammonium salts which contain at least two C 8 -C 30 -, preferably C 12 -C 22 -alkyl or -alkenyl chains, for example: ditallow dimethylammonium dimethyl sulfate, di(hydrogenated tallow) dimethylammonium dimethyl sulfate, di(hydrogenated tallow) dimethylammonium methyl chloride, distearyl- dimethylammonium dimethyl sulfate, dicocodimethylammonium dimethyl sulfate and the like.
• Acyclic quaternary ammonium salts which contain at least two C 8 -C 30 -, preferably C 12 -C 22 -alkyl or -alkenyl chains, for example: ditallow dimethylammonium dimethyl sulfate, di(hydrogenated tallow) dimethylammonium dimethyl
• the textile softener compound is preferably a water-insoluble quaternary ammonium material that contains a compound having two C 12 -C 18 -alkyl- or -alkenyl groups bonded to the molecule by at least one ester bond.
• the presence of two ester bonds in the quaternary ammonium material is especially preferred.
• An especially preferred ester-bonded quaternary ammonium material for use in this invention can be represented by the following formula: wherein each group R 13 is selected independently of the other from d- alkyl, hydroxyalkyl or C 2 -C 4 - alkenyl groups;
• T is either -O-C(O)- or -C(O)-O-, and wherein each group R 1 is selected independently of the other from C a -C. 8 alkyl or C 8 -C 28 alkenyl groups; and e is an integer from 0 to 5.
• a second preferred type of quaternary ammonium can be represented by the formula:
• Cyclic quaternary ammonium salts of the imidazolinium type for example di(hydrogenated tallow) dimethylimidazolinium dimethyl sulfate, 1-ethylene-bis(2-tallow-1- methyl)imidazolinium dimethyl sulfate and the like;
• Diamido quaternary ammonium salts for example: methyl-bis(hydrogenated tallow amidoethyl)-2-hydroxethylammonium dimethyl sulfate, methyl-bis(tallow amidoethyl)-2- hydroxypropylammonium dimethyl sulfate and the like;
• Biodegradable quaternary ammonium salts such as N,N-di(tallow-oyl-oxy-ethyl)-N,N- dimethylammonium dimethyl sulfate and N,N-di(tallow-oyl-oxy-propyl)-N,N-dimethyl- ammonium dimethyl sulfate.
• Biodegradable ammonium salts are described, for example, in U.S. Patent Specifications 4 137 180, 4 767 547 and 4 789 491 and are included herein by virtue of that literature reference.
• Preferred biodegradable quaternary ammonium salts include the biodegradable cationic diester compounds, as are described in U.S. Patent Specification 4 137 180, and are included herein by virtue of that literature reference.
• Tertiary fatty amines containing at least one, preferably two, C ⁇ -Qo-, preferably C ⁇ 2 -C 22 - alkyl chains examples include hydrogenated tallow dimethylamine and cyclic amines such as 1 -(hydrogenated tallow) amidoethyl-2-(hydrogenated tallow) imidazoline. Cyclic amines which can be used for the compositions herein are described in U.S. Patent Specification 4806255 and are included herein by virtue of that literature reference.
• Carboxylic acids having from 8 to 30 carbon atoms and one carboxyl group per molecule.
• the alkyl moiety has from 8 to 30, preferably from 12 to 22, carbon atoms.
• the alkyl moiety may be linear or branched, saturated or unsaturated, with linear saturated alkyl being preferred.
• Stearic acid is a preferred fatty acid for use in the composition of this invention. Examples of such carboxylic acids are commercial grade stearic acid and palmitic acid and mixtures thereof, which may contain small amounts of other acids.
• Esters of polyhydric alcohols for example sorbitan esters or glycerin stearate.
• Sorbitan esters are the condensation products of sorbitol or isosorbitol with fatty acids, for example stearic acid.
• Preferred sorbitan esters are monoalkyl.
• SPAN ® 60 SPAN ® 60 (ICI), a mixture of sorbitan and isosorbitol stearates.
• softeners are described in greater detail in U.S. Patent Specification 4 134 838, the disclosure of which is included herein by virtue of that literature reference.
• Preferred softeners for use in this invention are acyclic quaternary ammonium salts. It is also possible to use mixtures of the above-mentioned softeners.
• the softener composition used in this invention preferably comprises from about 0.1 to about 95 % by weight of the T softener component, based on the total weight of the softener composition. Preference is given to an amount of from 0.5 to 50 % by weight, especially an amount of from 2 to 50 % by weight and most especially an amount of from 2 to 30 % by weight.
• the amount of cationic polymer in the softener composition is preferably from 0.005 to 15 % by weight, based on the total weight of the softener composition. Preference is given to an amount of from 0.01 to 10 % by weight, especially an amount of from 0.05 to 5 % by weight and most especially an amount of from 0.1 to 5 % by weight.
• the softener composition may also comprise additives conventional for commercial softener compositions, for example alcohols, such as ethanol, n-propanol, isopropanol, pdyhydric alcohols, for example glycerol and propylene glycol; amphoteric and non-ionic surfactants, for example carboxyl derivatives of imidazole, oxyethylated fatty alcohols, hydrogenated and ethoxylated castor oil, alkyl polyglycosides, for example decylpolyglucose and dodecylpoly- glucose, fatty alcohols, fatty acid esters, fatty acids, ethoxylated fatty acid glycerides or fatty acid partial glycerides; also inorganic or organic salts, for example water-soluble potassium, sodium or magnesium salts, non-aqueous solvents, pH buffers, fragrances, dyes, hydrdropic agents, antifoams, greying inhibitors, enzymes, fluorescent whitening
• Such additives are preferably used in an amount of from 0 to 30 % by weight, based on the total weight of the softener composition. Preference is given to the use of an amount of from 0 to 20 % by weight, especially an amount of from 0 to 10 % by weight, and most especially an amount of from 0 to 5 % by weight.
• the softener compositions are preferably in liquid aqueous form.
• the softener compositions preferably have a water content of from 25 to 90 % by weight, based on the total weight of the composition.
• the water content is especially from 50 to 90 % by weight, more especially from 60 to 90 % by weight.
• the softener compositions preferably have a pH of from 2.0 to 9.0, especially a pH of from 2.0 to 5.0.
• the softener compositions can be prepared, for example, as follows: An aqueous formula t ion of the cationic polymer is first prepared as described above.
• the softener composition according to the invention is usually, but not exclusively, prepared by first stirring the active ingredient, i.e. the hydrocarbon-based softener component, in molten form into water, following which further desired additives are added, if necessary, and lastly the formulation of the cationic polymer is added.
• the softener composition can also be prepared, for example, by mixing a pre-formulated softener with the cationic polymer.
• Such softener compositions are conventionally prepared in the form of dispersions comprising, for example, up to 30 % by weight of active component in water. They usually have a cloudy appearance. It is, however, also possible to prepare alternative formulations, which normally comprise active ingredients in amounts of from 5 to 40 % by weight together with solvents, in the form of microemulsions which have a clear appearance (with regard to solvents and formulations see, for example, US-A 5543067 and WO-A 98/17757).
• a very preferred softener composition according to the invention is in liquid form and comprises:
• the softener compositions can also be used in the form of a sheet for use in a dryer. In such forms of application, the compositions are usually incorporated in impregnating agents on nonwoven sheets. However, other forms of application are also known.
• the particulate composition is a constituent of a washing or softener composition
• the content of dye fixative is, for example, in the range of from 0.1 to 70 % by weight, especially from 0.2 to 50 % by weight and preferably from 0.3 to 40 % by weight, based on the total weight of the washing or softener composition. For that purpose, preference is given to liquid washing and softener compositions.
• the fixative is used together with a bleaching agent.
• Suitable bleaching agents are solid bleaching agents.
• peroxide component for example, the commercially available organic and inorganic peroxides known from the literature, which bleach textile materials at customary washing temperatures, for example from 10 to 95°C.
• the organic peroxides are, for example, mono- or poly-peroxides, especially organic per- acids or salts thereof, such as phthalimidoperoxycaproic acid, peroxybenzoic acid, diperoxydodecanedioic acid, diperoxynonanedioic acid, diperoxydecanedioic acid, diperoxyphthalic acid or salts thereof.
• inorganic peroxides for example persulfates, perborates, percarbonates and/or persilicates.
• persulfates for example persulfates, perborates, percarbonates and/or persilicates.
• mixtures of inorganic and/or organic peroxides may be present in various crystalline forms and may have different water contents and can also be used together with other inorganic or organic compounds in order to improve their storage stability.
• bleach-activating substances are known transition metal salts or complexes and/or conventional bleach activators; that is to say compounds that, under perhydrolysis conditions, yield unsubstituted or substituted perbenzo- and/or peroxo-carboxylic acids having from 1 to 10 carbon atoms, especially from 2 to 4 carbon atoms.
• customary bleach activators mentioned earlier that carry O- and/or N-acyl groups having the mentioned number of carbon atoms and/or unsubstituted or substituted benzoyl groups.
• polyacylated alkylenediamines especially tetraacetylethylenediamine (TAED), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N,N-diacetyl-N,N- dimethylurea (DDU), acylated triazine derivatives, especially 1 ,5-diacetyl-2,4-dioxohexa- hydro-1,3,5-triazine (DADHT), and compounds of formula (7)
• R 15 is a sulfonate group, a carboxylic acid group or a carboxylate group
• R 16 is linear or branched (C 7 -C 15 )alkyl.
• activators known under the names SNOBS, SLOBS and DOBA
• acylated polyhydric alcohols especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5- dihydrofuran and acetylated sorbitol and mannitol and acylated sugar derivatives, especially pentaacetylglucose (PAG), sucrose polyacetate (SUPA), pentaacetylfructose, tetra- acetylxylose and octaacetyllactose and acetylated, optionally N-alkylated glucamine and gluconolactone.
• PAG pentaacetylglucose
• SUPA sucrose polyacetate
• pentaacetylfructose tetra- acetylxylose and octaacetyllactose and acetylated
• bleach activators nitrile compounds that form periminic acids with peroxides. Mention may also be made of sodium hypochlorite, Javelle water and hydrogen peroxide.
• the bleaching agents are preferably used as a further constituent of the liquid, aqueous dye fixative formulations given above.
• the definitions and preferred meanings given above apply also to those aqueous, liquid formulations.
• the definitions and preferred meanings given above apply also to the dye fixatives.
• dye fixatives of formula(1) that have been neutralised wholly or partially with acetic acid.
• the concentration of the bleaching agents can vary within a wide range and is preferably from 0.1 to 25 % by weight, especially from 0.5 to 20 % by weight and preferably from 0.5 to 10 % by weight, based on the total weight of the formulation. Preference is given to a lower limit of 1 % by weight, especially 2 % by weight.
• the bleach-containing dye fixative is preferably not a constituent of a washing or softener composition.
• Textile fibre materials that come into consideration are, for example, hydroxy-group containing and amino-group-containing fibre materials. Examples that may be mentioned are polyamide, wool and especially natural or regenerated cellulose.
• the materials treated according to the method of the invention exhibit markedly reduced dye transfer to other materials, for example materials that are undyed or are dyed in different or pale shades, that effect being almost entirely retained without renewed treatment even after several washes.
• the colour shade of the dyed materials is also retained to a great extent even after several washes.
• the particulate compositions can be formulated with the addition of surfactants without reducing the activity profile of the dye fixatives; especially for treatment before or after washing.
• the particulate compositions can also be combined surprisingly well with bleaching agents, thereby enabling them to be applied together with bleaching agents.
• the dye fixatives can also be combined very well with commercially available washing compositions.
• the following Examples illustrate the invention. Parts denote parts by weight, unless otherwise indicated. The temperature is in degrees Celsius, unless otherwise indicated.
• the suspension having a solids content of 30.7% is then filtered through a 50 ⁇ m screen and then granulated in a bench-scale fluidized spray dryer (FSD).
• FSD bench-scale fluidized spray dryer
• the exhaust air temperature is lowered in order to initiate the granulation process.
• Granulation of the entire suspension is carried out at an exhaust air temperature of 62°C and a fluidised bed temperature of 65°C.
• the product at the outlet of the granulator contains about 11 % by weight residual moisture and is then dried to the desired value of 5 % by weight in a vacuum cabinet at 90°C and 200 mbar.
• the finished granules contain 31.2 % of the dye-fixing active ingredient and are from 50 to 310 ⁇ m in size, having a bulk density of 650 g/litre.
• the granules can be incorporated directly into a solid washing composition.
• An aqueous suspension having the same composition as in Example 1 is prepared and is spray-granulated in a laboratory spray tower instead of in the FSD.
• Flowable granules having a mean particle size of 65 ⁇ m, a bulk weight of 380 g/litre and a residual water content of 6.0 % are obtained.
• the granules prepared in that manner contain 30.9 % of the dye fixative.
• Example 3 dye fixative: 25 % by weight of active ingredient analogous to Example 1 , carrier: 49 % by weight of zeolite (Na-AI silicate) (Advera 401 P* PQ Corp.), binders: 2 % by weight of the sodium salt of polymerised alkylnaphthalene sulfonic acid, 12 % by weight of maltodextrin (Glucidex 15D ® , Roquette, France), 5 % by weight of carboxymethylcellulose (Blanose 7ULC ® , Aqualon,
• Example 4 dye fixative: 30 % by weight of active ingredient analogous to Example 1 , carrier: 58 % by weight of cellulose fibres (Arbocel FDY600 ® , J.
• Example 5 dye fixative: 40 % by weight of active ingredient analogous to Example 1 , carrier: 52 % by weight of Wessalith XD ® , residual moisture: 8 % by weight.
• Granulation continues until all the granulating solution has been sprayed in.
• the granules are then dried in the bed for 1 hour at 63°C and subsequently cooled in the fluidised bed in a cold air stream (20°C).
• the granules have a mean particle size of 480 ⁇ m, a residual moisture content of 5.1% and a bulk weight of 720 g/litre.
• the granules contain 35 % dye- fixing active ingredient.
• the wet granules are discharged from the mixer into a laboratory fluidised bed and then dried in an air stream at a temperature of 80°C until the residual water content is 6.5 %, yielding granules containing 20 % dye fixative and having a particle size of 380 ⁇ m and a bulk weight of 630 g/litre.
• the extruded material has a diameter of 0.8 mm and is 1.5 mm long and is solidified on a cooling belt.
• the extruded material so produced contains 35.5 % of the dye fixative and has a bulk weight of 810 g/litre.
• a mixture of 750 g of the zeolite Wessalith XD ® and 2143 g of liquid Tinofix CL ® (dry material content 35 %) is dried and ground as described in Example 9.
• the dry mixture is introduced into a laboratory fluidised bed granulator (STREA-1 ® ; Aeromatic AG, Bubendorf, Switzerland) and then granulated with a separately prepared granulating solution at a bed temperature of 80°C.
• the granulating solution is composed of 26.4 g of gelatine and 158.2g of dextrin dissolved in 734 g of deionised water.
• the granules are dried to a residual moisture content of 4.2 % in the same fluidised bed.
• the dye fixative content in the finished granules is 42.6 %.
• the granules are on average 500 ⁇ m in size and have a bulk weight of 780 g/litre.
• the melt is then metered into the ploughshare mixer through a unitary nozzle, the speed of the mixer being set at 330 rpm.
• the temperature of the mixer is lowered gradually to 40°C.
• the solidified granules are removed from the mixer.
• the granules contain 32 % of the dye fixative and are on average 520 ⁇ m in size.
• cellulose granules Arbocel G350 ®
• 58 g of calcium carbonate are introduced into 630 g of an aqueous solution of the active ingredient in the form of the dye fixative Tinofix CL ® having a dry material content of 33.2 %.
• the mixture is dried in vacuo in a laboratory paddle dryer as described in Example 9, and the residue is ground.
• the resulting material is then granulated in a laboratory fluidised bed granulator (STREA-1 ® ; Aeromatic AG, Bubendorf) together with 450 g of a 20 % aqueous maltodextrin solution (Glucidex 12D ® ) as granulating solution at a fluidised bed temperature of 75°C.
• STREA-1 ® Aeromatic AG, Bubendorf
• the resulting product is then dried at that temperature to a residual moisture content of 6 % and then cooled to room temperature in a stream of cold air.
• the resulting granules have a mean particle size of 660 ⁇ m with a bulk weight of 610 g/litre and contain 25 % fixative.
• Example 14 Following up the process described in Example 7, the granules, during drying, are sprayed in a second step with a 20 % aqueous solution of a polyethylene oxide/polypropylene oxide block copolymer having 80 % polyethylene in the molecule, until a content of 5 % of the coating material on the core granules is reached.
• the coated granules are dried in the fluidised bed to a residual moisture content of 7 % and have a fixative content of 19 % with a mean particle size of 420 ⁇ m.
• Example 14 Example 14:
• Example 13 After-treatment is carried out analogously to Example 13 by spraying with a heated 10 % aqueous solution of a partially hydrolysed polyvinyl alcohol having a molecular weight of about 15000 g/mol, until the amount of coating material on the resulting granules is 5 %. Drying to a residual moisture content of 8 % yields free-flowing granules having a dye fixative content of 19 % and a mean particle size of 450 ⁇ .
• the granules from the fluidised bed are discharged at 75°C into a L ⁇ dige ploughshare mixer.
• a L ⁇ dige ploughshare mixer At the rated speed of rotation of the mixer, there is metered in, in the course of 60 seconds, sufficient PEG 8000 melt, preheated to 80 to 90°C, to provide 5 % of the coating material on the granules.
• Stirring is then carried out for about 3 to 4 minutes in order to achieve homogeneous distribution of the melt in the mixture, and the mixture is discharged into a fluidised bed for cooling.
• the resulting granules contain 19 % of the dye fixative and have a mean particle size of 410 ⁇ m.
• This Example illustrates the use of the dye fixative formulations in washing compositions and in the washing of textile materials:
• washing formulations are prepared:
• Washing composition no. 1 ECE 98 standard washing composition containing 4 % TINOFIX
• Example 9 5 g of cotton fabric dyed with D Blue (2.09 %) (bleeder fabric) are washed with 5 g of bleached undyed cotton fabric (accompanying fabric) under the following conditions, washing composition concentration : 2.5 g/litre liquor ratio : 1:10 temperature : 40°C duration : 15 minutes
• the fabrics are then rinsed for 30 seconds under running tap water, spun and dried.
• the undyed cloth is removed and replaced by a fresh piece of accompanying fabric, and the wash is repeated, as described above, a further 4 times with the same dyed fabric but in each case a new accompanying fabric.
• the extinction of the wash bath was determined at 600 nm (af er centrifugation to remove the zeolite).
• the washing composition now used for all the pieces of fabric is ECE 77 without any additives. Any possible fixative effect would emerge here most clearly, and can only be caused by the product already present on the textile.
• the extinction of the wash bath was determined at 600 nm.

Landscapes

• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Coloring (AREA)
• Chemical Or Physical Treatment Of Fibers (AREA)
• Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Priority Applications (1)

Applications Claiming Priority (4)

Publications (1)

Family

ID=8185780

Family Applications (1)

Country Status (10)

Families Citing this family (21)

Family Cites Families (17)

• 2002
  • 2002-12-27 MX MXPA04006559A patent/MXPA04006559A/es active IP Right Grant
  • 2002-12-27 WO PCT/EP2002/014785 patent/WO2003057815A1/en active Application Filing
  • 2002-12-27 EP EP02806027A patent/EP1472333A1/en not_active Withdrawn
  • 2002-12-27 US US10/500,778 patent/US20050039266A1/en not_active Abandoned
  • 2002-12-27 AU AU2002367419A patent/AU2002367419B2/en not_active Ceased
  • 2002-12-27 CN CNB028268237A patent/CN100335605C/zh not_active Expired - Fee Related
  • 2002-12-27 KR KR10-2004-7010627A patent/KR20040073553A/ko active IP Right Grant
  • 2002-12-27 JP JP2003558117A patent/JP4443929B2/ja not_active Expired - Fee Related
  • 2002-12-27 BR BR0215478-1A patent/BR0215478A/pt not_active IP Right Cessation
• 2004
  • 2004-06-10 ZA ZA200404615A patent/ZA200404615B/en unknown

Non-Patent Citations (1)

Also Published As

Similar Documents

Legal Events