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EP0006271B2 - Compositions nettoyantes et adoucissantes contenant des azurants non-ioniques - Google Patents

Compositions nettoyantes et adoucissantes contenant des azurants non-ioniques Download PDF

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Publication number
EP0006271B2
EP0006271B2 EP19790200302 EP79200302A EP0006271B2 EP 0006271 B2 EP0006271 B2 EP 0006271B2 EP 19790200302 EP19790200302 EP 19790200302 EP 79200302 A EP79200302 A EP 79200302A EP 0006271 B2 EP0006271 B2 EP 0006271B2
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EP
European Patent Office
Prior art keywords
formula
alkyl
composition according
weight
methyl
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German (de)
English (en)
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EP0006271A1 (fr
EP0006271B1 (fr
Inventor
Richard Geoffrey Harris
Allan Campbell Mcritchie
Alexander David Wilson
Barry Stoddart
Lowell W. Bernardino
Joseph Mcgrady
Frederick Edward Hardy
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Procter and Gamble Co
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Procter and Gamble Co
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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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/835—Mixtures of non-ionic with cationic compounds
    • 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
    • C11D3/001—Softening 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
    • C11D3/40—Dyes ; Pigments
    • C11D3/42—Brightening agents ; Blueing agents
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • 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
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols

Definitions

  • the present invention relates to detergent compositions which have very good cleaning properties and also have textile softening properties.
  • the problem is believed to arise from three causes.
  • the first is the ineffectiveness of most of the usual optical brighteners when applied in the presence of cationic surfactants due to the failure of the brightener to deposit upon fabrics in such surroundings and/or from an actual quenching of the fluorescence of the brightener in the presence of cationic surfactant.
  • the second main cause of yellowing is build-up of the brightener itself, which in some circumstances can act as a dyestuff at visible wavelengths.
  • the third cause is apparently an interaction between the cationic or nonionic-cationic surfactants and colouring matter in the water used to make up the wash baths.
  • Iron content may be one relevant factor but probably organic e. g. peaty colouring matter is more usually the principal cause.
  • a detergent composition which imparts a soft feel to fabrics washed therewith, which comprises :
  • the preferred granular compositions according to this invention are prepared by first making spray dried carrier granules comprising all or some of the detergency builders, a low level of anionic surfactant, and other non-heat sensitive components of the composition. A moving bed of these carrier granules is then sprayed in suitable mixing equipment with a mixture of the nonionic surfactant and cationic softener. Heat sensitive solid components, e. g. bleaching agent, enzymes, are dry mixed with the carrier granules before or after the spray-on process.
  • Heat sensitive solid components e. g. bleaching agent, enzymes
  • the invention comprises three essential components, i. e. a nonionic detergent (A), a cationic textile softener (B), and a nonionic optical brightener (C).
  • a nonionic detergent A
  • B cationic textile softener
  • C nonionic optical brightener
  • Water-soluble nonionic ethoxylates constitue the principal surfactant component of the present composition.
  • Such surfactants can be broadly defined as compounds produced by the condensation of ethylene oxide groups (hydrophilic in nature) with an organic hydrophobic (lipophilic) compound, which may be aliphatic or alkylaromatic in nature. The number of ethylene oxide groups condensed with any particular hydrophobic group is adjusted to yield a water-soluble compound having a hydrophilic- lipophilic balance (HLB) of between 8 and 15.
  • HLB hydrophilic- lipophilic balance
  • Suitable nonionic detergents include :
  • Preferred nonionic detergents are coconut alcohols with 6 ethoxy residues per molecule, and Dobanol 45-7 (C l4 -C l5 primary alcohol containing seven ethoxy groups/mole).
  • the nonionic detergent comprises from 10 % to 30 %, preferably from 10 % to 20 % by weight of the composition.
  • Any cationic softener may be used in the compositions of the invention.
  • Suitable cationic softeners are the conventional substantially water-insoluble quaternary ammonium compounds, and C e - 25 alkyl imidazolinium salts.
  • R 1 and R 2 represent hydrocarbyl groups of from 10 to 22 carbon atoms ;
  • R 3 and R 4 represent hydrocarbyl groups containing from 1 to 4 carbon atoms
  • X is an anion such as halide, a C 2 -C 4 carboxylate, of an alkyl-or arylsulf(on)ate.
  • preferred anions include bromide, chloride, methyl sulfate, toluene-, xylene-, cumene-, and benzene-sulfonate, benzoate, parahydroxybenzoate acetate, and propionate.
  • quaternary softeners include ditallow dimethyl ammonium chloride ; ditallow dimethyl ammonium methyl sulfate ; dihexadecyl dimethyl, ammonium chloride ; di(hydrogenated tallow) dimethyl ammonium chloride ; dioctadecyl dimethyl ammonium chloride ; dieicosyl dimethyl ammonium chloride ; dieicosyl methyl ethyl ammonium chloride ; didocosyl ammonium chloride ; di(hydrogenated tallow) dimethyl ammonium methyl sulphate ; dihexadecyl diethyl ammonium chloride ; dihexadecyl dihydroxyethyl ammonium methyl sulphate ; di(coconutalkyl) dimet ammonium chloride.
  • Ditallow dimethyl ammonium chloride, di(dihydrogenated tallow alkyl) dimethyl ammonium chloride and di(coconutalkyl) dimethyl ammonium chloride are preferred.
  • the single long chained quaternary ammonium compounds of the above formula wherein R 1 is C 10 to C 22 alkyl or alkenyl, preferably C 16 to C 20 alkyl, and R 2 , R 3 and R 4 are lower alkyl groups, that is C, to C 4 alkyl groups especially methyl, or aryl groups, and X is as defined above.
  • R 2 , R 3 and R 4 may together represent a heterocyclic ring.
  • Some representative examples of such compounds are behenyl trimethyl ammonium bromide, oleyl dimethyl benzyl ammonium chloride, myristyl dimethyl ethyl ammonium bromide, cetyl trimethyl ammonium bromide, behenyl trimethyl ammonium methosulfate, oleyl methyl diethyl ammonium chloride, cetyl, stearyl or oleyl pyridinium chloride, behenyl pyridinium bromide, stearyl methyl morpholinium chloride, stearyl or oleyl ethyl or propyl morpholinium chloride.
  • quaternary ammonium cationic surfactants which may be mentioned have the formula : wherein R 1 and R 2 are as defined above or R 2 may be hydrogen and x and y are at least 1 and (x+y) is from 2 to 25. Examples are :
  • C S - 25 alkylimidazolinium salts can be represented by C S - 25 alkylimidazolinium salts.
  • Preferred salts are those conforming to the formula ; wherein R 6 is a C 1 -C 4 alkyl radical, R 5 is hydrogen or a C 1 -C 4 alkyl radical, R 5 is hydrogen or a C l -C 4 alkyl radical, R 5 is hydrogen or a C 1 -C 4 alkyl radical, R 8 is a C 8 -C 25 alkyl radical and R 7 is hydrogen or a C 8 -C 25 alkyl radical.
  • X is a charge balancing ion which has the same meaning as X defined in the quaternary ammonium surfactant above.
  • a preferred member of this class believed to have R 6 methyl, R 7 and R B tallow alkyl, R 5 hydrogen, in sold under the Trade Name Varisoft 455 or 475 (Ashland Chemical Company), or Steinaquat M5040/H (Chemische Werke Rewo).
  • R 10 is an alkyl or alkenyl group having from about 10 to 24, preferably 12 to 20, especially from 16 to 18 carbon atoms, the groups Rg which may be the same or different, each represent hydrogen, a (C 2 H 4 O) p H, or a (C 3 H 6 O) q H, or a C 1-3 alkyl group where p and q may each be 0 or a number such that (p + q) does not exceed 25, n is an integer from 2 to 6, preferably 3, m is from about 1 to 9, preferably from 1 to 4, most preferably 1 or 2, and X ( - ) represents one or more anions having total charge balancing that of the nitrogen atoms.
  • Preferred compounds of this class are, most preferred, N-tallow-N,N',N'-trimethyl-1,3-propylene diamine dichloride or di-methosulphate, commercially available under the Trade Names Lilamin 540 EO-3 (Lilachem), Dinoramox SH3, Inopol ODX3 (Pierrefitte-Auby), and N-tallow-N,N,N',N',N'-pentamethyl-1, 3-propylene diamine dichloride, commercially available under the Trade Names Stabiran MS-3 (Pierrefitte-Auby) ; Duoquad (Armour Hess) ; Adogen 477 (Ashland Company). Also suitable is the substance sold as Dinormac (Pierrefitte-Auby) or Duomac (Armour Hess) believed to have the formula :
  • Rg in these components is hydrogen
  • the pH of the formulation be such that one or more of the nitrogen atoms is protonated.
  • Other suitable cationic surfactants are disclosed in our copending European Patent Application Nos. 0000234 and 0000235 published January 10th, 1979 and incorporated herein by reference.
  • Preferred cationic softeners are ditallowyl dimethyl ammonium halides or methosulphate, and imidazolinium salts e. g. Varisoft 455 or 475.
  • compositions of the invention contain from 1 % to 15 %, preferable from 3 to 10 %, by weight, of cationic softening agent. It is preferred that the weight ratio of nonionic detergent to cationic softening agent to be in the range from 10 : 1 to 0.5 : 1, especially from 3 : 1 to 1 : 1.
  • optical brighteners suitable for compositions of the invention are nonionic in character and are selected from the following groups ;
  • Nonionic benzoxazole brighteners useful in the invention have the following structural formulae :
  • Suitable coumarin derivatives have the formula wherein R 1 represent H, a C 1-4 alkyl or an aralkyl group, R 2 represents H, an aryl or ⁇ COOR 4 , R 3 represents ⁇ OR 4 , -N(R 4 ) 2 or NHCOCH 3 , and each R 4 independently represents a C 1-4 alkyl group.
  • Some compounds of this class are 4-methyl-7-dimethyl amino coumarin, 4-ethyl-7-dimethylamino coumarin, 4-methyl-7-diethylamino coumarin, 4-isopropyl-7-dimethylamino coumarin, 4-isobutyl-7-di- methylamino coumarin, 4-propyl-7-diethylamino coumarin, 3,4-di-methyl-7-dimethylamino coumarin, 4-methyl-7-ethoxy coumarin, 4-ethyl-7-methoxy coumarin, 4-methyl-7-carboxymethylamino coumarin, 4-benzyl-7-dimethyl amino coumarin, 4-benzyl-7-benzyl amino coumarin, 3-phenyl-7-diethylamino coumarin, 3-carboxymethoxy-4-methyl-7-dimethylamino coumarin.
  • each A is selected from the group consisting of hydrogen, C 1 -C 8 alkyl, C 1 -C 8 hydroxyalkyl, C 1 -C 8 alkenyl, ⁇ (CH 2 ) n OCH 3 , wherein n is from 1 to 8, ⁇ (CH 2 ) n N(CH 3 ) 2 , wherein n is from 1 to 8, wherein x is from 2 to 12, ⁇ (CH 2 CH 2 CH 2 O) ⁇ H, wherein x is from 1 to 12, and wherein x is from 1 to 12, wherein m is from 1 to 12 and y is from 1 to 12.
  • each A is a C 1 -C S alkyl group, preferably a C l -C 4 alkyl group, and most preferably a methyl group.
  • the A groups may be both the same (for ease in synthesizing the molecule) or may be chosen so as to be different (to make the molecule substantive to both cotton and synthetic fabrics).
  • A is selected from the group defined under (c) above or where (A) 2 forms an oxazine ring containing the N atom.
  • compositions may contain from about 0.001 % to about 3 %, preferably from about 0.01 to about 0.5 %, and most preferably from about 0.02 to about 0.1 by weight of the specific nonionic optical brighteners described above.
  • Suitable detergent builder salts useful in the preferred granular compositions herein can be of the polyvalent inorganic and polyvalent organic types, or mixtures thereof.
  • suitable water-soluble, inorganic alkaline detergent builder salts include the alkali metal carbonates, borates, phosphates, polyphosphates, tripolyphosphates, bicarbonates, silicates, and sulfates.
  • Specific examples of such salts include the sodium and potassium tetraborates, bicarbonates, carbonates, tripolyphosphates, pyrophosphates, pentapolyphosphates and hexametaphosphates.
  • Mixtures of organic and/or inorganic builders can be used herein.
  • One such mixture of builders is disclosed in Canadian Patent No. 755,038, e. g. a ternary mixture of sodium tripolyphosphate, trisodium nitrilotriacetate, and trisodium ethane-1-hydroxy-1,1-diphosphonate.
  • Such « seeded builder compositions are fully disclosed in British Patent Specification No. 1,424,406.
  • Preferred water soluble builders are sodium tripolyphosphate and sodium silicate, and usually both are present.
  • a substantial proportion, for instance from 3 to 15 % by weight of the composition of sodium silicate (solids) of ratio (weight ratio Si0 2 : Na 2 0) from 1 : 1 to 3.5 : 1 be employed.
  • a further class of detergency builder materials useful in the present invention are insoluble sodium aluminosilicates, particularly those described in Belgian Patent 814,874, issued November 12, 1974 incorporated herein by reference.
  • This patent discloses and claims detergent compositions containing sodium aluminosilicates of the formula : wherein Z and Y are integers equal to at least 6, the molar ratio of Z to Y is in the range of from 1 : 0 : 1 to about 0.5 : 1 and X is an integer from about 15 to about 264, said aluminosilicates having a calcium ion exchange capacity of at least 200 mg.eq./gram and a calcium ion exchange rate of at least about 2 grain/minute/gram.
  • a preferred material is Na I2 (Si0 2 AI0 2 ) 12 27H 2 0.
  • Built granular detergent compositions in accordance with the invention contain from 10-80 % of builder, preferably from 20 % to 70 % of builder.
  • compositions of the present invention also contain from 0.3 % to 5 % of a discolouration inhibitor selected from
  • Highly preferred materials of this type are ethoxylated tallow alcohols with 25 or 80 ethoxy groups, (conveniently abbreviated as TAE 25 , TAE eo ).
  • polyethylene glycols of molecular weight from about 1,000 to 30,000, especially from 6,000 to 20,000, and polyvinyl alcohols of molecular weight from 10,000 to 20,000, preferably about 14,000, and polyoxyethylene sorbitan C, 2 -C, e fatty acid esters having 17 or more ethylene oxide residues in their constitution.
  • Soil suspending agents such as sodium carboxymethyl cellulose are useful for this purpose, and it is preferred that these should be present at a level from about 0.5 % to 1.5 % by weight of the composition.
  • methyl vinyl ether - maleic anhydride copolymers or the corresponding acids and their salts e. g. sodium salts, such as, for instance, Gantrez AN-119, Gantrez S95 (Trade Name - GAF) and the corresponding acids or salts.
  • this component is used at from about 0.5 % to 1.5 % by weight of the composition.
  • Sequestering agents effective for chelating especially ferric iron such as sodium ethylene diamine tetraacetate, diethylene triamine penta acetate, ethylene diamine tetra methylene phosphonate, diethylene triamine pentaphosphonate, and hydroxyethane-1,1,-di-phosphonate are also useful and may function both as bleach stabilisers and as agents to inhibit yellowing caused by iron in tap water.
  • Preferred agents are ethylene diamine tetra acetates, ethylene diamine tetra methylene phosphonates or both together, especially in the form of the sodium salts.
  • Suds controlling agents such as mono or diethanolamides of fatty acids as suds stabilisers, and C '6 . 24 soaps or fatty acids, silicones, microcrystalline waxes and mixtures thereof as suds depressants.
  • proteolytic amylolytic or lipolytic enzymes, especially proteolytic.
  • potassium lithium or ammonium or amine salts may be used instead if their extra cost etc. are justified for special reasons.
  • compositions of the present invention may be produced in a variety of forms, including liquid, solid, granular, paste, powder or substrate compositions.
  • Substrate articles may be formulated according to U.S. Patent Application Serial No. 781,378, Flesher et al, filed March 25, 1977, incorporated herein by reference.
  • the compositions of the present invention are formulated as liquids and contain up to abouat 20 % of a lower alkyl (C, to C 4 ) alcohol, particularly ethanol. Liquid compositions containing lower levels of such alcohols (i.e., about 7 to 12 %) tend to exhibit less phase separation than compositions containing higher alcohol levels.
  • the cationic softener be finely and intimately dispersed.
  • the cationic softener may be mixed in the form of fine solid particles with the rest of the composition, or in the case of spray dried granular products it may be included in the crutcher mix.
  • the nonionic detergent (and optionally the discolouration inhibitor) may also be included in the crutcher mix.
  • spray dried granular products it is much preferred to make carrier granules by spray drying a crutcher mix containing at least part, and usually substantially all of the detergency builders, and the other non-heat sensitive components.
  • anionic surfactant especially sodium C 9 ., 6 alkyl benzen sulphonate
  • Other anionic surfactants such as sodium C 10-20 alkyl sulphates, and the corresponding alkyl ether sulphates with from 1 to 5 ethoxy groups per molecule, C 10-20 alkane sulphonates and C lo . 20 olefin sulphonates, and C 10-20 soaps may be employed.
  • the amount of anionic surfactant should be less than the amount of nonionic surfactant and less than the stoichiometric equivalent of the cationic softener in the compositions, and it is usually from 0.1 % to 5.0 % by weight of the composition, especially about 0.2 % to 1.5 %. Larger amounts of anionic are undesirable because they impair the cleaning and the softening properties of the compositions.
  • a moving bed of carrier granules in any suitable mixing equipment such as a pan granulator, a rotating drum of a fluidised bed, is sprayed with a fluid mixture comprising the nonionic detergent and the cationic softener, usually melted together, and generally having dissolved or dispersed therein, for instance, the optical brightener, the discolouration inhibitor and the methyl vinyl ether-maleic acid copolymer, and other components if convenient. It has been found to be advantageous to maintain the carrier granules, while they are being sprayed and/or afterwards at a temperature of above 35 °C especially about 40 °C to 75 °C for a period of about 1/2 to 5 minutes, whereby the free flowing properties of the composition are improved.
  • Heat sensitive solid, granular or powdery, components are dry mixed with the carrier granules either before or after spray on of the nonionic detergent-cationic softener mixture.
  • the compostions of the present invention are used in the laundering process by forming an aqueous solution containing from about 0.01 % (100 parts per million) to about 1.0 % (10,000 parts per million), preferably from about 0.02 % to about 0.75 %, and most preferably from about 0.2 % to about 0.75 %, of the detergent compositions defined herein, and agitating the soiled fabrics in that solution.
  • the fabrics are then rinsed and dried.
  • the compostions of the present invention yield outstanding brightening performance, without discolouring the fabrics upon repeated washing, as well as exceptionally good particulate and greasy/oily soil removal, together with fabric solftening, static control, colour fidelity, and dye transfer inhibition benefits, without requiring the use of a conventional fabric softening additive product.
  • Granular detergent compositions of the following compositions were prepared.
  • compositions were prepared by making spray dried granules comprising components (a) with some moisture, spraying these granules with a dispersion in water of components (b), and then spraying them with a molten mixture comprising components (c). If necessary, some improvements in flow properties of the product can be obtained by heating the granules after the two spray-on steps to from 37-47 °C in a fluidised bed, fluidised by hot air, for from 1 to 5 minutes. After cooling (if necessary) the granules are dry mixed with components (d) to form the finished product.
  • compositions I, II, and III cleaned fabrics as well as a typical commercial heavy duty anionic detergent composition, and the washed fabrics were as soft as those washed with this detergent composition and treated in the final rinse with a 0.1 % dispersion of a typical rinse-added textile solftener.
  • Fabrics washed in Composition I were less yellow than fabric washed in the same compositions except containing 0.04 % of brighteners :
  • Tallow alcohol-E so is replaced by Tallow alcohol-E 25 , polyethylene glycol (M.Wt. 6.000) or polyvinyl alcohol (M.Wt. 14,000).
  • An effective textile washing and solftening composition has the formula, in parts per cent by weight ;
  • a detergent composition with pronounced textile softening properties has the formula, in parts per cent by weight : Similar results are obtained when the brightener is replaced by 4-methyl-7-diethylamino coumarin.
  • a textile softening heavy duty detergent has the following formula, in parts per cent by weight:
  • a granular detergent composition was prepared having the following formula ;
  • Fabrics repeatedly washed in each to the products of Examples IV through VII above are notably whiter than fabrics washed in similar compositions employing conventional anionic or nonionic brighteners.
  • a granular detergent composition of the following formula is prepared.
  • composition is prepared by making spray dried granules comprising components (a) with some moisture, spraying these granules with a molten mixture comprising components (b). After cooling (if necessary) the granules are dry mixed with components (c) to form the finished product.
  • This composition cleans fabrics as well as a typical commercial heavy duty anionic detergent composition and the washed fabrics are as soft as fabrics so washed and thereafter treated in a final rinse with a 0.1 % dispersion of a typical rinse added textile softener composition.
  • a typical anionic optical brightener namely 1-(4-amino sulphonylphenyl)-3-(4-chlorophenyl)-2-pyrazoline instead of the 0.04 % of coumarin-type brightener.
  • Tinopal SWN is replaced by an equivalent weight of 4-methyl-7-dimethylamino coumarin, 4-ethyl-7-dimethylamino coumarin, 4-isopropyl-7-dimethylamino coumarin, 4-isopropyl-7-dimethylamino coumarin, 4-propyl-7-diethylamino coumarin, 3.4-di-methyl-7-dimethylamino coumarin, 4-methyl-7-ethoxy coumarin, 4-ethyl-7-methoxy coumarin, 4-methyl-7-carbox- ymethylamino coumarin, 4-benzyl-7-dimethylamino coumarin, 3-phenyl-7-diethyl-amino coumarin, or 3-carbomethoxy-4-methyl-7-dimethylamino coumarin.
  • a liquid composition of the present invention was as follows :
  • This composition exhibited excellent removal of particulate and greasy/oily soils and outstanding brightening performance without discolouration problems. It also delivered fabric softening, static control, color fidelity and dye transfer inhibition benefits.
  • nonionic surfactant in Composition A is replaced, in whole or in part, by the condensation product of C 14-15 alcohol with 2.25 moles of ethylen oxide ; the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide ; the condensation product of C 12-15 alcohol with 9 moles of ethylene oxide ; the condensation product of C 12-13 alcohol with 6.5 moles of ethylene oxide, which is stripped so as to remove lower ethoxylate and nonethoxylated fractions ; the condensation product of coconut alcohol with 5 moles of ethylene oxide ; the condensation product of coconut alcohol with 6 moles of ethylene oxide ; the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide ; the condensation product of tallow alcohol with 9 moles of ethylene oxide ; a 1 : 1 by weight mixture of the condensation product of C 12-15 alcohol with 7 moles of ethylene oxide and the condensation product of C 14-15 alcohol with 7 moles of ethylene oxide ; and other mixtures of those surfactants.
  • the brightener herein has the formula :
  • Substantially similar brightening results are obtained when the methyl groups in the above structure are replaced, with C 2 , C 4 , or C 8 alkyl groups ; with hydrogen ; with C 2 or C 8 hydroxyalkyl ; with C 4 alkenyl ; with ⁇ (CH 2 ) 2 OCH 3 ; with ⁇ (CH 2 ) 2 N(CH 3 ) 2 ; with ⁇ (CH 2 CH 2 O) 2 H, ⁇ (CH 2 CH 2 O) 6 H, or ⁇ (CH 2 CH 2 ) 12 H ; with or with ⁇ (CH 2 CH 2 O) 6 (CH 2 CH 2 CH 2 O) 2 H.
  • Substantially similar brightening results are obtained when the methyl groups in the above structure are replaced, with C 2 , C 4 , or C 8 alkyl groups ; with hydrogen ; with C 2 or C 8 hydroxyalkyl ; with C 4 alkenyl ; with ⁇ (CH 2 ) 2 OCH 3 ; with ⁇ (CH 2 ) 2 N(CH 3 ) 2 ; with ⁇ (CH 2 CH 2 O) 6 H, or ⁇ (CH 2 CH 20 ) 12 H ; with or with ⁇ (CH 2 CH 2 O) 6 (CH 2 CH 2 CH 2 O) 2 H.
  • Substantially similar brightening results are obtained when the methyl groups in the above structure are replaced, with C 2 , C 4 or C 8 hydroxyalkyl ; with C 4 alkenyl ; with ⁇ (CH 2 ) 2 OCH 3 ; with ⁇ (CH 2 ) 2 N(CH 3 ) 2 ; with ⁇ (CH 2 CH 2 O) 2 H, ⁇ (CH 2 CH 2 0) 6 H, or ⁇ (CH 2 CH 2 O) 12 H ; with or with ⁇ (CH 2 CH 2 O) 6 (CH 2 CH 2 CH 2 O) 2 H.
  • the substituted groups may be both the same (for ease in synthesizing the molecule) or may be chosen so as to be different (to make the molecule substantive to both cotton and synthetic fabrics).

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
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  • Detergent Compositions (AREA)

Claims (14)

1. Composition détergente qui confère un toucher doux aux tissus lavés avec cette composition, caractérisée en ce qu'elle comprend :
(A) de 10 à 30 % en poids d'un ou de plusieurs détergents polyéthoxylés non ioniques ayant un équilibre hydrophile/lipophile de l'ordre de 8 à 15 et n'ayant pas plus qu'une moyenne de 16 unités éthoxy par molécule à condition que, si le détergent non ionique comprend un éthoxylate d'alcool de suif dans lequel la portion alkyle de suif contient de 16 à 20 atomes de carbone, cet éthoxylate d'alcool de suif contienne en moyenne entre 7 et 12 moles d'oxyde d'éthylène par mole d'alcool ;
(B) de 1 à 15 % en poids d'un ou de plusieurs adoucissants cationiques pour textiles ;
(C) de 0,001 à 3 % en poids d'un agent de blanchiment optique non ionique des types suivants :
(a) benzoxazoles
(b) coumarines
(c) 2,5-bis(benzimidazolyl)furannes
(d) 4,4'-bis(2-sulfonamide styryl)biphényles
(D) de 0 à 80 % en poids d'un adjuvant de détergence ;
(E) de 0 à 5 % en poids d'un inhibiteur de décoloration ;
(F) de 0 à 5,0 % en poids d'un agent tensio-actif anionique

dans laquelle le rapport pondéral de l'agent tensio-actif anionique à l'agent tensio-actif non ionique est inférieur à 1 : 1 et le rapport molaire de l'agent tensio-actif anionique à l'adoucissant cationique est inférieur à 1 : 1.
2. Composition selon la revendication 1, caractérisée en ce qu'elle comprend : de 10 à 20 % en poids du constituant (A), de 3 à 10 % en poids du constituant (B), de 0,01 à 0,5 % en poids du constituant (C), et de 20 à 70 % en poids du constituant (D).
3. Composition selon l'une des revendications 1 et 2, caractérisée en ce que le détergent non ionique est choisi parmi les produits de condensation de monoalcools primaires ou secondaires ramifiés ou non ramifiés ayant de 8 à 20 atomes de carbone et les produits de condensation d'alkyl-phénois ayant de 6 à 16 atomes de carbone dans la chaîne alkyle, chacun contenant de 4 à 16 moles d'oxyde d'éthylène par molécule, et des mélanges de ces produits de condensation.
4. Composition selon l'une quelconque des revendications 1 à 3, caractérisée en ce que l'adoucissant cationique est choisi parmi :
(a) les sels d'ammonium quaternaire, non cycliques ayant au moins une chaîne alkyle en C12-30 dans la molécule
(b) les sels d'alkyl-imidazolinium dans lesquels le groupe alkyle est en C8-25
(c) les sels d'alkyl-pyridinium dans lesquels le groupe alkyle est en C12-20
(d) les sels d'alkyl-morpholinium dans lesquels le groupe alkyle est en C12-20
(e) les sels de polyamines substituées de formule générale :
Figure imgb0068
dans laquelle Rlo est un groupe alkyle ou alcényle ayant de 10 à 24 atomes de carbone, les groupes Rg qui peuvent être identiques ou différents, représentent chacun l'hydrogène, un groupe ―(C2H4O)pH, ou ―(C3H6O)qH, où p et q peuvent être zéro ou un nombre tel que (p + q) ne dépasse pas 25, n est un nombre entier compris entre 2 et 6, m est compris entre 1 et 9 et X(-) représente un ou plusieurs anions dont la charge totale équilibre celle des atomes d'azote, et
(f) leurs mélanges.
5. Composition selon la revendication 4, caractérisée en ce que l'adoucissant cationique est choisi parmi le chlorure de disuif-diméthyl-ammonium, le méthosulfate de 2-suif-1-méthyl-1-(suif-amidoé- thyl)imidazoline, ou leurs mélanges.
6. Composition selon l'une quelconque des revendications 1 à 5, caractérisée en ce que l'adjuvant de détergence est choisi parmi les carbonates, bicarbonates, borates, phosphates, polyphosphates, silicates, sulfates, amino polycarboxylates, phosphonates, de métaux alcalins, solubles dans l'eau, et les mélanges de ces sels.
7. Composition selon l'une quelconque des revendications 1 à 6, caractérisée en ce que l'agent de blanchîment optique, non ionique, est choisi parmi :
(i) les bis(benzoxazol-2-yl)thiophènes de formule :
Figure imgb0069
dans laquelle R est H, un groupe 5-méthyle, 5-diméthylbenzyle ou 5-butyle tertiaire ;
(ii) les 1,2-bis(benzoxazol-2-yl)éthylènes de formule
Figure imgb0070
dans laquelle R1 et R2 sont H, ou R1 est H et R2 est un groupe 5-méthyle,
(iii) les 1,4-bis(benzoxazol-2-yl)naphtalènes de formule
Figure imgb0071
dans laquelle R3 est H ou un groupe 5-carboxyméthyle ;
(iv) les 4,4'-bis-(benzoxazol-2-yl)stilbènes de formule
Figure imgb0072
dans laquelle R4 est H ou un groupe 5-carboxybutyle ou 5-méthyle ;
(v) les 2-(styryl)benzoxazoles de formule
Figure imgb0073
dans laquelle R5 est H ou un groupe carboxyméthyle ;
(vi) le 2-(styryl)naphtoxazole de formule
Figure imgb0074
(vii) le 2-(4-phényl stilbène-4-yl)-5-tert-butyl benzoxazole de formule
Figure imgb0075
et (viii) leurs mélanges.
8. Composition selon la revendication 7, caractérisé en ce que l'agent de blanchiment optique est le composé de formule
Figure imgb0076
dans laquelle R est CH3.
9. Composition selon l'une quelconque des revendications 1 à 8, caractérisée en ce que l'agent de blanchiment optique a la formule
Figure imgb0077
dans laquelle R1 représente H, un groupe alkyle en C1-4 ou un groupe aralkyle, R2 représente H, un groupe aryle ou ―COOR4, R3 représente ―OR4, -N(R4)2 ou -NHCOCH3 et chaque substituant R4 représente indépendamment un groupe alkyle en C1-4.
10. Composition selon la revendication 9, caractérisée en ce que R, est CH3, R2 est H, R3 est N(CH3)2 ou N(C2H5)2.
11. Composition selon l'une quelconque des revendications 1 à 10, caractérisée en ce que l'agent de blanchiment optique a la formule
Figure imgb0078
dans laquelle chaque A est choisi parmi l'hydrogène, un groupe alkyle en Ci-Ce, hydroxyalkyle en C1-C8, alcényle en C1-C8,
―(CH2)nOCH3 où n est compris entre 1 et 8,
―(CH2)nN(CH3)2, où n est compris entre 1 et 8,
―(CH2CH2O)×H, où x est compris entre 2 et 12,
Figure imgb0079
où x est compris entre 1 et 12 et
Figure imgb0080
où x est compris entre 1 et 12,
Figure imgb0081
où m est compris entre 1 et 12 et y est compris entre 1 et 12.
12. Composition selon la revendication 11, caractérisée en ce que chacun des groupes substituants A est un groupe méthyle.
13. Composition selon l'une quelconque des revendications 1 à 12, caractérisée en ce que l'agent de blanchiment optique a la formule (2)
Figure imgb0082
dans laquelle chaque A est choisi parmi les groupes définis dans la revendication 11, ou dans laquelle (A)2 est un noyau d'oxazine contenant l'atome d'azote.
14. Composition selon l'une quelconque des revendications 1 à 13, caractérisée en ce que l'inhibiteur de décoloration (E) représente de 0,3 à 5 % d'un matériau choisi parmi :
(a) les produits de condensation d'alcool de suif avec de 20 à 100 en proportions molaires d'oxyde d'éthylène,
(b) les polyéthylène glycols ayant une masse moléculaire comprise entre 1 000 et 30 000 ; et
(c) les alcools polyvinyliques ayant une masse moléculaire comprise entre 10000 et 20 000.
EP19790200302 1978-06-20 1979-06-13 Compositions nettoyantes et adoucissantes contenant des azurants non-ioniques Expired EP0006271B2 (fr)

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Application Number Priority Date Filing Date Title
GB7827378 1978-06-20
GB2737878 1978-06-20
GB3490978 1978-08-29
GB7834909 1978-08-29
US356779A 1979-01-15 1979-01-15
US3567 1995-09-11

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EP0006271A1 EP0006271A1 (fr) 1980-01-09
EP0006271B1 EP0006271B1 (fr) 1982-03-31
EP0006271B2 true EP0006271B2 (fr) 1986-01-22

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US4233167A (en) * 1979-06-14 1980-11-11 S. C. Johnson & Son, Inc. Liquid detergent softening and brightening composition
ATE4600T1 (de) * 1979-09-21 1983-09-15 The Procter & Gamble Company Wasch- und weichmittelzusammensetzungen und verfahren zu ihrer herstellung.
DE3027479A1 (de) * 1980-07-19 1982-03-04 Hoechst Ag, 6000 Frankfurt Mischungen von optischen aufhellern und deren verwendung
JPS598795A (ja) * 1982-07-05 1984-01-18 ライオン株式会社 粒状洗剤用添加剤
US4460485A (en) * 1983-07-15 1984-07-17 Lever Brothers Company Polyester fabric conditioning and whitening composition
GB2217340A (en) * 1988-04-14 1989-10-25 Unilever Plc Preparation of a granular detergent composition
US5122304A (en) * 1991-01-31 1992-06-16 Basf Corporation Stable aqueous dispersions of fluorescent brightening agents of the coumarine type and method of preparing same
IT1295039B1 (it) * 1997-09-19 1999-04-27 3V Sigma Spa Composizioni ammorbidenti contenenti sbiancanti ottici
US20080177089A1 (en) 2007-01-19 2008-07-24 Eugene Steven Sadlowski Novel whitening agents for cellulosic substrates
CN101583704B (zh) * 2007-01-19 2013-05-15 宝洁公司 包含用于纤维质基底的增白剂的衣物洗涤护理组合物
US8715368B2 (en) 2010-11-12 2014-05-06 The Procter & Gamble Company Thiophene azo dyes and laundry care compositions containing the same
EP3097173B1 (fr) * 2014-01-22 2020-12-23 The Procter and Gamble Company Composition de traitement de tissu
EP3097174A1 (fr) * 2014-01-22 2016-11-30 The Procter & Gamble Company Procédé de traitement de surfaces textiles
WO2015112341A1 (fr) * 2014-01-22 2015-07-30 The Procter & Gamble Company Composition de traitement de textile

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USB367524I5 (fr) * 1967-09-20
US3660286A (en) * 1969-01-03 1972-05-02 Lever Brothers Ltd Liquid wash cycle softener
BE745814A (fr) * 1969-04-30 1970-08-11 Henkel & Cie Gmbh Detergent contenant des assouplissants pour textiles
DE1922047C3 (de) * 1969-04-30 1978-03-30 Henkel Kgaa, 4000 Duesseldorf Nachspülmittel für gewaschene Wäsche
DE2021678A1 (de) * 1970-05-02 1971-11-25 Henkel & Cie Gmbh Optische Aufheller enthaltende Waschmittel
DE2308072A1 (de) * 1973-02-19 1974-08-22 Henkel & Cie Gmbh Verfahren und mittel zum waschen und weichmachen von textilien

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EP0006271A1 (fr) 1980-01-09
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