IE60528B1 - Stable liquid detergent composition containing hydrophobic brightener - Google Patents
Stable liquid detergent composition containing hydrophobic brightenerInfo
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- IE60528B1 IE60528B1 IE61187A IE61187A IE60528B1 IE 60528 B1 IE60528 B1 IE 60528B1 IE 61187 A IE61187 A IE 61187A IE 61187 A IE61187 A IE 61187A IE 60528 B1 IE60528 B1 IE 60528B1
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- 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
- C11D1/60—Sulfonium or phosphonium compounds
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- 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
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- 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)
Abstract
Stable isotropic liquid laundry detergents containing a surfactant and a hydrophobic brightener to reduce brightener staining of fabrics. Suitable species of preferred hydrophobic brighteners include disulfonated tetra-anilino naphthotriazolyl stilbene brighteners.
Description
60528 Technical Field The present invention relates to stable, preferablysingle-phase, isotropic liquid laundry detergents containinga particular hydrophobic disulfonate brightener which 5 reduces or eliminates brightener staining of fabrics while maintaining an excellent level of whitening. Particularlypreferred are disulfonated tetra-anilino naphthotriazolylstilbene brighteners. In some embodiments, the hydrophobicbrighteners herein may be combined with variable levels of -JO .> conventional liquid detergent brighteners to further improve and optimize overall fabric appearance. In the event such mixed brighteners are employed, the hydrophobic brightener herein should represent at least 40% of the total brightener in order to provide the desirable performance 2 benefits .
Optical brighteners, also known as fluorescent whiteningagents, are commonly used in laundry detergents.
Brighteners deposit onto fabrics where they absorbultraviolet radiant energy and reemit it as a blue light.This reduces or eliminates any yellowish cast to fabrics andgives them a brighter appearance, however, undesirablebrightener staining can occur when liquid detergents come indirect contact with cotton-containing fabrics. The presentInvention reduces or eliminates such staining whilemaintaining an acceptable level of fabric whitening.
Background Art To overcome and reduce undesirable brightener stainingsubstantial effort had been directed towards usingasymmetrical monosulfonated naphthotriazolyl stilbenebrighteners (MSB). Representative ©f these art undertakingsare a series of published patents.
British Patent 2,028,365, Gray, published March 5, 1980,' discloses built liquid detergents containing anionic surfactants and one or more brighteners, including MSB. 13.S. Patent 3,812,041, Inamorato, issued Hay 21, 1974,discloses unbuilt liquid detergents containing nonionic surfactants and anionic surfactants in a weight rati© ofnonionic to anionic of at least 1. Optional brightener® caninclude the MSB type. U.S. Patent 3,959,157, Inamorato, issued Hay 25, 1976,discloses liquid detergents containing nonionic surfactants, quaternary ammonium softening agents and optionalbrighteners, equally including MSB. 3 US Patent 4,430,236, Franks, issued February 7, 1984,discloses liquid detergents containing nonionic surfactantsoptional anionic surfactants, hydrogen peroxide, brightenerand preferably quaternary ammonium softening compounds.MSB's are specifically mentioned as being useful.
Japanese Patent Application J74-017004, published April 26,1977, discloses liquid detergents containing MSB said to be stable to light.
German Patent Application 25 43 998, published April 7,1977, discloses clear liquid detergents containing certaindiphenyl distyryl brighteners. Examples 1 and 2 are ofliquid detergents containing mixtures of HS3 anddisulfousted brighteners.
German Patent Application 26 09 752, published September22, 1977, relates to improving the low temperaturestability of brightener-containing detergent compositionsand makes no distinction between brighteners of differinghydrophobicity or solubility.
European Application 85200988.5, filed June 21, 1985, teaches the use of MSB, optionally in combination withconventional di-anilino di-»orpholino distilbene brightenerswith a view to reduce undesirable brightener deposits.
While those prior art attempts can yield considerableimprovements versus conventional brighteners as regardsreducing staining, their washing performance, e.g.,whiteness maintenance, is not better than what is obtained from current disulfonate brightener. 4 FR-A-2 130 105 published 3 November, 1972 teaches a composition and method, of solubilization of water insoluble brighteners. It discloses liquid detergents containing anionic and/or nonionic surfactants, organic builder, 5 hydrotope, optical brightener, ethylene glycol ether and/or dimethyl sulphoxide.
It is a main object of this invention t© foraulatebrightener containing concentrated heavy-duty liquiddetergent compositions which do not exhibit brightener 1 0 staining negatives during use while delivering, at least equivalent, whiteness maintenance as compared toconventional detergent brighteners- The above and other objects can new be obtained by theincorporation in heavy-duty liquid detergent of disulfonated brightener® which are more hydrophobic than current disulfonated brightener.
Summary of the Invention The present invention relates t® stable isotropic 5 heavy-^uty laundry detergent compositions comprising, byweight. (a) from 3® to 60% of a, surf ace-active agent selected from anionic and nonionic surfactants andmixtures thereof; and TO (b) from 0,01% to 1% of a hydrophobic disulfonated brightener which represents at least 40% ofthe total brightener in the composition, th® hydrophobic brightener having the formula: wherein K, , R_, 8,. and represent, X 2 j tetra-anilino, tetra-piperazino, tetracyclo-hexylamino, dianilino-dipiperazino, and dianilino- dicyclohexylamino; and (c| a solvent selected from lower aliphatic alcoholshaving from 2 to 6 carbon atoms and iron 1 to 3 hydroxyl groups. 20 6 Detailed Description of the Invention The compositions of the present invention comprise from3% to 60% of a surface-active agent, from 0,01% to i 1% of a hydrophobic brightener and a lower aliphatic 5 alcohol solvent™ The essential ingredients of the invention as well as optional components that candesirably be incorporated in the compositions of thisinvention are described hereinafter.
The percent indications, throughout the specification,stand, unless indicated otherwise, for "percent by weight" The hydrophobic brightener herein has the formula: wherein Ri, R2* R3 ®nd a4 ar® selected from the tetra-anil ino» tefcra-piperazino, fcefcra-cyclohexylaraino,dianilino-dipiperazino; and the dianilino-dicyclohexyl-amino species. 0 Highly preferred for reasons of minimizing brightenerstaining are the tetraanilino derivatives, hauling thefollowing formula : 4, 4'-bis (4-anilino~6-anilino-$-triazin-2~yl)amino)~2 , 2' -stilbe5 ne disulfonic acid sodium salt (ft). A preferred brightener system in the context of this invention contain® at least40% (by reference to the total amount ©f the detergentbrightener) of the specific hydrophobic brightener referredto hereinbefore in combination with a conventional detergent 10 brightener, e.g., a di-sulfonated dianilino, dimorpholinostilbene brightener.
Conventional detergent brighteners for use incombination with the hydrophobic species describedhereinabove embrace common detergent brighteners inclusive 15 of: 4-(2H-naphtho(1,2~d)triazol-2-yl)-2-stiIbenesulfonic acid,sodium salt; (i) 4,46-bis ((4-anilino-6(N-2"hydroxyethyl-N-methylamino)-S"fcriazin-2~yl)amino)-2,29-stilbenedisulfonic acid disodium 20 salt; (ii) 4,4’ -bis ( (4-anilino-6-morpholino~s-triazin-2~yl)amino)-2,2 * -stilbenedisulfonic acid, sodium salt; (iii) 2,2-(4,4*-biphenylene divinylene)-dibenzenesulfonic acid,disodium salt; (ivi) 25 A, 4’ -bis (4-phenyl-2H-l, 2,3-triazol-2-yl) disodium salt (vi) 4,4·-bis ((4-anilino-0~morpholino-l,3,5-triazin-2-yl)amino)- 2-stilbene sulfonate sodium salt. (oil) While the hydrophobic brightener shall represent, at 30 least, 40% of the total brightener, it is understood thatthe level can vary depending upon the particular nature ofthe conventional brightener. fls an example, thetetra-anilino hydrophobic brighteners can desirablyrepresent from 55%~8O% of the total brightener in the event 35 the conventional brightener is represented by (i). 8 The surface-active agent can be represented by anionicand nonionic surfactants and mixtures thereof. Thesurfactant usually represents from 3* to 60%, preferablyfrom 10% to 50%. Suitable anionic surfactants are disclosedin U.S. Patent 4,285,841, Barrat et al.„ issued August 25,1981, and in U.S. Patent 3,929,678, Laughlin et al., issuedDecember 30, 1975, both incorporated herein by reference.
Useful anionic surfactants Include the water-solublesalts, particularly the alkali metal, aeonium andalkylolammonium (e.g., monoethanolammonium ortriethanolammonlum) salts, of organic sulfuric reactionproducts having in their molecular structure an alkyl groupcontaining· from _ SO to . 20 carbon atoms and asulfonic acid or sulfuric acid ester group. (Included inthe term ‘•alkyl* is the alkyl portion of aryl groups.)Examples ©f this group of synthetic surfactants are thealkyl sulfates, especially those obtained by sulfating thehigher alcohols (Cg-C^g carbon atoms) such as thoseproduced by reducing the glycerides of tallow or coconutoil; and the alkylbenzene sulfonates in which the alkylgroup contains from $ to 15 carbon atoms, instraight chain or branched chain configuration, e.g., thoseof the type described in U.S. Patents 2,220,099 and2,477,383. Especially valuable are linear straight chainalkylbenzene sulfonates in which the average number ofcarbon atoms in the alkyl group is from about Si to 14.
Other anionic surfactants herein are the water-solublesalts of: paraffin sulfontes containing from· 8 to24 (preferably 12 to 18) carbon atoms; alkyl glyceryl ether glyceryl ether sulfonates, especially thoseethers of C„ ,a alcohols (e.g., those derived from tallowand coconut oil); alkyl phenol ethylene oxide ether sulfatescontaining from 1 to . 4 units of ethylene oxide par molecule and from Ϊ0 to 20 carbon atoms in the alkyl group. 9 Other useful anionic surfactants herein include the water-soluble salts of esters ©f alpha-sulfonated fatty acids containing from 6 to 20 carbon atoms in th® fatty acid group and from about 1 to 10 carbion atoms in 5 the ester group; water-soluble salts of 2-acyloxyalkane-l-sulfonic acids containing' from 2 to9 carbon atoms in the acyl group and from 9 to 23 carbon atoms in the alkane moiety; water-soluble salts ofolefin sulfonates containing from 12 to 24 carbon 10 atoms; and beta-alkyloxy alkane sulfonates containing from1 to 3 carbon atoms in the alkyl group and from, 8 to 20 carbon atoms in the alkane moiety.
Preferred anionic surfactants are the alkyl 10 18 sulfates containing an average of from 0 to 4 ethylene 15 oxide unit® per mole of alkyl sulfate. C^-C^, linearalkylbenzene sulfonates, and mixtures thereof. 20 25 The nonionic surface-active agent can be represented byknown species which are eminently well-known in thetechnical community and many of which have found widespreadcommercial acceptance. Suitable ethoxylated nonionicsurfactants for use herein have th® formulaR^COCgHp^OH, wherein Rl is a C^-C^ alkylgroup or a Cg-C,^ alkyl phenyl group, n is from. 3t© , .. 9, said nonionic surfactant hawing an hLB (hydrophile-lipophile balance) of from ' 10 to· 13. These surfactants ar® more fully described in U.S.Patent 4,285,841, Barrat et al., issued August 25, 1981; and4,284,532, Leikhim et al., issued August 18, 1981, bothincorporated herein by reference. Particularly preferredare condensation products of C12-C15 alcohols with from3 to 8 moles of ethylene oxide per mol® of alcohol, e.g., C19-C13 alcohol" condensed with 6.5moles of ethylene oxide p@r mole of alcohol. 30 15 Ο ft well-known non-ionic for use herein can be representedby amine oxide surfactants such as the alkyl dimethyl amine oxides. ftfimime oxide surfactants are frequently used in levels of5 from 0.5% to 4% in combination with conventional ethoxylated nordomies.
In such nonionic systems, the weight ratio ©f amineoxide:nonionic ethoxylate is frequently in the range from1:8 to 1:50. 10 While the compositions herein can fee based on an-all anionic or all-nonionic surfactant combination, it isfrequently desirable to use anionic and nonionic surfactantsin a, weight rati© of frcifmi· I: l to 3:1. In this weight rati©expression, the nonionic surfactant can be represented by a 15 mixture of a nonionic ethoxylate and amine oxide surfactant.
The compositions herein can in addition to the essentialsurfactants described hereinbefore, also contain as optionalingredients other synthetic surfactants known in the artsuch as the cationic, zwitterionic and ampholytic 2q surfactants. These optional surfactants can be used at additive levels and should normally represent less than 40%of the total surfactant in the formula. Suitable examplesof these optional surfactants are disclosed in t’S Patents4.285.841 and 3.929.678. 25 The compositions herein are aqueous compositions and contain, depending upon the relative levels of essentialingredients and the possible levels of optional ingredients,a level of water to make the balance to 100%. In somepreferred heavy duty liquid executions herein, the waterlevel can b© in the range from e.g. 60% to 20%. 30 » Si The compositions of this invention frequently have a pH, measured at a i% aqueous solution, at 20®C, in the neutral to mildly alkaline range, i.e., from 6,5 to 9.
In addition to the essential ingredients describedhereinbefore, the compositions herein frequently contain aseries of optional ingredients which are used for theirknown functionality in conventional quantities. Theseoptional Ingredients augment and enhance, generally, thedetergent performance of the claimed compositions. Examplesof the like optional ingredients include: perfumes, dyes,«specifiers, germicides, antioxidants, suds regulantsinclusive of silicones and hydrogenated fatty acids,builders inclusive of tartrate monosuccinic acid, sodiumtripolyphosphate and sodium pyrophosphate, citric acid,completely hydrated zeolite having a particle diameter inthe range of from !~SO pm ; . and alkenylsuccinates having from 10 to 16 carbon atoms in the alkenyl moiety. Furtheroptional components include soil release agents such aspolyethylene glycol terephthalate, performance boosters e.g.tetraethylene pentamine with 15-19 EO, corrosion inhibitorssuch as aminosilanes, enzymes, cationic surfactants, textilesoftening agents such as quaternary ammonium salts andbentonite clays, ethylene diaminetetra-acetiC acid,diethylenetriamine pentaacetic acid, fatty acids, alkylenepolyaminopolyalkylenephosphonic acids, enzyme stabilizingsystems, as well as liquid matrix ingredients inclusive ofwater and suitable solvents.
Suitable fatty acids, saturated or unsaturated, havefrom 10 to 18 carbon atoms in the alkyl chain. Preferredare unsaturated species having from 12 to 18 carbon atoms inthe alkyl chain, most preferably oleic acid. The ·corresponding soaps can equally be used. The optional fattyacid/soaps are used in levels up to 20%, frequently from 5%to 15%.
Detergent enzymes generally aid and augment the removalof specific stains. Suitable enzymes can be represented byproteases, amylases, lipases, glucose-oxidases, cellulase, .. or mixtures thereof. Proteases and amylases are preferred in the claimed liquid concentrated compositions. They arefrequently employed in a level from 0.01% to 2%.
All generally known enzyme stabilizing systems can beused in the compositions herein in the art establishedlevel. Examples of suitable stabilizing systems includeshort C? chain carboxylic acid, particularly formicacid, in combination with low level of calcium, boric acidand the water-soluble salts thereof possibly in combinationwith polyols.
Suitable alfcylene-polyaminopolyalfeylene phosphonic acidsfor use herein include ethylene diamine tetramethylenephosphonic acid, diethylene triamine pentamethylenephosphonic acid, or the ©alts thereof. Thesepolyphosphonates are advantageously utilized in an amountfrom O.i%-3%, preferably Q.4%-1.2%; the preferred tetra- andpentamethylene phosphorate species can also be used incombination e.g. in a weight ratio of tetra to penta of from3:1 to 1:3. / Acceptable detergent suds regulants herein includehydrogenated fatty acids having from 16 to 22 carbon atomsin the alkyl chain and alkylated polysiloxanes such asdimethylpolysiloxane©. The fatty acids suds regulant isfrequently used in a level from O.5 to 5% whereas thesilicone can b® effectively used in levels in the range from0.05 to 0.5%. The suds regulant can also to© represented bya combination of hydrogenated fatty acid and silicone.
In the presence of oxidizable materials, thecompositions herein can also contain known antioxidants inthe art established levels, i.e., 0.01% to 0.25% (by reference to total composition). These antioxidants arefrequently introduced in conjunction with unsaturatedorganic acids. While many suitable antioxidants are readilyknown and available for that purpose, especially preferredfor use in the compositions herein are: 2,6 ditertiarybutyl-p-cresol, more commonly known as butylatedhydroxytoluene, BHT, and 2-tertiaryteutyl-4~hydroxyanisole.Other suitable antioxidants are 4,4’thiobis(S-ter-butyl-m-cresol) and 2~methyl"4,6~dinonylphenol Builders such as sodium tripolyphosphate, sodiumpyrophosphate, tartrate monosuccinie acid, citric acid, Chelants such as alkylene polyamino-polyalkylenepolycarboxylic and/or polyphosphonie are frequently used atlevels fromO.l to 3%.
Known textile softening agents inclusive ofditallowdimethylammonium salts and imidazolinium salts aswell bentonite clays such as known from DE-PS 23 34 899 canalso be used depending upon the envisaged functionality ofthe composition. If the softening agents are present theynormally can represent from 2% to 8%.
The liquid matrix ingredients should also comprise asolvent selected from the lower aliphatic alcohols havingfrom 2 to 6 carbon atoms and from X to 3 hydroxyl groups,,for example ethanol; n-propanol; iso propanol; butanol; 1,2~propansdiol; 1-3-propane diol» 1 4 Other liquid matrix ingredients are further optionalcomponents in the compositions herein. This componenttogether with water and the lower aliphatic alcohols canconstitute the solvent matrix for e.g. the concentratedliquid executions. Suitable ingredient classes includeethers of diethyleneglvcol and lower aliphaticmonoaIcohoIs having from 1 to & carbon atoms. Specific examples of phaseregulants are : monomethyl-, ethyl-, propyl-, and monobutyl ethers of di-ethylene glycol. Theliquid matrix ingredients can be used at varying levels,depending upon e.g. the total leuel of ingredients in thecomposition. In the concentrated HOL executions herein, theliquid solvent can represent from 5% to 30". Theconcentrated heavy duty liquid compositions hereinconstitute a preferred execution of the claimed technology.These compositions can have the following formula.
Component General by weight Preferred Surface-active agent anionicSurface-active agent nonionicBuilder Chelant Enzyme - protease(1.5 ftU/g.) - amylase(7000 TAU/g.) Brightener - hydrophobic- conventional Mater Solvent(liquid matrix) UO - 502 - 25 0.1 - 30.1 - 1.50.05- 0.80.01- 1 0-0.570 - 20 3-30 10 - 305-205-22 0.4 - 1.20.4 - 1.20.1 - 0.50.07- 0.30.05- 0.300 - 30 5-14 EXAMPLE I The fabric staining tendency of various brighteners is evaluated in the following composition.
Component Wt.% linear alkylbenzene sulfonic acid 10.0 a~kyl sulfuric acid 3.0 Cia-*J5 alcohol polyethoxylate (7EO) 12.0 C12-ia acid 11.0 Oleic acid 4.0 Citric acid (anhydrous) 1.0 Diethylenetriamine pentamethylene phiosphonic acid 0.8 Triethanolamine 6.0 Sodium hydroxide to pH 7.7 3.4 Propylene glycol 1.6 Ethanol 6.0 Alkaline protease (1.5 AU/g) 0.® Formic acid 0.66 Alpha-amylase (300 KftU/g) 0. 1 Brightener 0.175 Minors and water balance to 100 Won-diluted (as is) detergent samples containing theabove detergent brlghteners are applied to unbrightened 100%cotton siwatches and left for 10 minutes. The swatches ar®thereafter washed with the same detergent solution ¢1%product concentration, 30®C, mild agitation) and tumbledried. The swatches are then graded under U.v. light forbrightener staining, using the following seal®. O no visible staining T trace of stain 1.0 very light stain 1.5 light stain 2.0 medium light stain 2.5 medium stain 3.0 heavy stain The results are as follows: Briqhtener Blue Nightdress Pink Undershirt Green shorts Slue Undershirt Pink Nightdress Blue Pillow case leige muslin(technical swatch) ieig® knitted cotton(technical swatch) Indian cotton(technical swatch) Pink Jogging Stain!ma Grad© *7| Hi *i 3.0' A S . 0 uii 1.0 ii 3.0 A 1. S wii 1.5 iii 3.0 ft 1.5 uii 1.5 iii 3.0 A 1.0 uii 1.0 Τ ·ϊ 4 2.8 A 1.0 uii 1.0 ΐ τ i 2.5 ft 0.5 uii 0.5 "s *a "i ΑΛΑ 3.0 ft 1 .0 uii 1.0 iii 3.0 ft 1.0 wii 1.0 •i -a *£ 3.0 ft 1 .0 uii 1.0 Til 2.9 ft 1 .0 uii 1.0 i the reduced brightener of fabric, of the fcetra- hrightener (A) in accordance with the invention.
The brightener deposition superiority during the laundryoperation is, in a complementary manner, demonstrated with the aid of brightener build-up measurements.
Srightener build-up means the speed with which abrightener deposits onto swatches, brightened andnon-brightened. The build-up measurement is carried out asfollows : Test conditions : Miele^!765, 60®C short cycle, 180 mi product usage (i% product concentration)ballast load = 2 kg 100% cotton bleached(90®*C wash'with perborate Sodium tripolyphosphate),unbrightened,, Tracers : terry unbrightened » unbleached unbrightened terry bleached by 1 wash at SO’C with perborate. Sodium tripoly-phosphate ; terry brightened = bleached brightened terry washed5 times with a heavy duty detergent at 90°C.
Measurement : reemission 44Qnm terry unbrightened start: 83.86 reemission 440nm terry brightened start 149.13 Results : reemission 440nm n of washes I a 8 Swatch unbrightened (A) 120.52 130.68 136.59 (uii) 111.68 119.23 124.84 Swatch brightened (ft) 150.27 149.73 150.33 (uii) 140.64 140.78 141.20 EXAMPLE ZI Additional liquid compositions in accordance with theinvention contain the following ingredients: 10 15 C^-Linear altylbenzene sulfonic acid C13""~1S Oxoalcohol condensed with"? moles of ethylene oxide el2"cl4 fattty diethanolamideSodiumtripolyphosphat® Carbox ymethyIcelluloseHydrogenated fatty acid (C^g-C22)Polydimethylsiloxane' Brightener (see below) Proteolytic enzyme (1.5 AU-basis)Glycerine Sodium tetraborate Sodium hydroxide (3% solution) Optional ingredients inclusive of7perfume, whitener The brightener is represented by:- A % by weight <5 3 2 23 . 3 1 0.2 0.15 - 0.20 . 5 5 2 to 9.0 1. - a mixture of (1:1 - a mixture ©f (9:1 by weight) ft and uii; andby weight) A and iii. 20 1 9 DedecySbenzene sulfonic acid III IV EXAMPLES ΊΓ" VI 8.3 VII Ώ «! 4 lilt VIII 7 Cj2-i1 ky»triethoxy so 1 fate-Ma π 12
Claims (4)
1. A liquid aqueous heavy duty detergent composition comprising (a) from 3% to 50% by weight of a surface-active agent.selected from anionic and nonionic surfactants and mixtures 5 thereof; and (bi frosa 0»01% to 1% by weight of a hydrophobicdisulfonated brightener which represents at least 40% byweight of the total brightener in the composition, thehydrophobic brightener having the formula: < img-format="tif" img-content="drawing" /> < img-format="tif" img-content="drawing" /> < img-format="tif" img-content="drawing" /> wherein the R 1-4 moieties are selected fro® the group of :tetra-anilino» tetra-piperazin©,, tetra-cyclohexylamino,dianilino-dipiperazino, and dianilino-dicyclohexylaaino;and 15 (c) a solvent selected from lower aliphatic alcohols havingfrom 2 to 6 carbon atoms and from i to 3 hydroxyl groups-
2. The composition in accordance with claim 1 wherein the surface'active agent represents from 10% to 50% by weight. 2 5
3. The composition in accordance with the hydrophobic brightener is representedtetra-anilino derivative which is present0.07% to 0.3% by weight. Claim . 2 thereinby the in a level from The composition in accordance with the sorface-actanionic and non of anionic: nonionic ©t ive agent is represented byionic surface-active agents r©e 1:1 t© 3:1. Claim 1 whereina mixture ofin a weight rati© 10 5.ω The composition in accordance wit«hereiR the ncini©nic surface-active agenta combination ©f n©nionic efchoxylates and«eight rati© of ethoxylafce to araine oxide8:1. I Claims 1 and 4is represented byaein© oxides in aof free 50:1 to S, The ceepesition in accordance with Glaisa 1 wherein15 the brightener is represented by a mixture of the hydrophobic brightener and a conventicunal detergentbrightener «hereby the hydrophobic brightener represents, atleast, 40% by weight of the total brightener · 20
4. 7,., The composition in accordance with Claims 1 and«herein the conventional brightener is 4,4’ -bi s C C 4—aniline—G-aaor pholi ο©·stilbene sulfonate sodium salt. a 4- a 2’ in-2-yl)aHin0i)-2- 8. kclaim liquid aqueous heavy ..1 t substantially as duty detergent compositio:iereinbe£ore described and , according toexemplified» \ X < img-format="tif" img-content="drawing" /> < img-format="tif" img-content="drawing" /> P. H. KELLY & CO., AGENTS FOR THE APPLICANTS.
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
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GB8605966A GB2187749B (en) | 1986-03-11 | 1986-03-11 | Stable liquid detergent composition hydrophobic brightener |
Publications (2)
Publication Number | Publication Date |
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IE870611L IE870611L (en) | 1987-09-11 |
IE60528B1 true IE60528B1 (en) | 1994-07-27 |
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IE61187A IE60528B1 (en) | 1986-03-11 | 1987-03-10 | Stable liquid detergent composition containing hydrophobic brightener |
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EP (1) | EP0237119B2 (en) |
JP (1) | JP2859263B2 (en) |
KR (1) | KR950004931B1 (en) |
AT (1) | ATE97159T1 (en) |
AU (1) | AU588979B2 (en) |
DE (1) | DE3788075T3 (en) |
GB (1) | GB2187749B (en) |
GR (1) | GR3022619T3 (en) |
IE (1) | IE60528B1 (en) |
NZ (1) | NZ219558A (en) |
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DE3726266A1 (en) * | 1987-08-07 | 1989-02-23 | Bayer Ag | FLUESSIGWASCHMITTEL |
EP0314630A3 (en) * | 1987-10-30 | 1989-10-25 | Sandoz Ag | Detergent compositions |
US4946619A (en) * | 1988-07-19 | 1990-08-07 | The Clorox Company | Solubilization of brighter in liquid hypochlorite |
IT1237754B (en) * | 1989-11-08 | 1993-06-17 | Sigma Prodotti Chimici Srl | OPTICAL BLEACH LIQUID COMPOSITION. |
JP2855281B2 (en) * | 1990-03-19 | 1999-02-10 | ライオン株式会社 | High bulk density granular detergent composition |
GB2247030B (en) * | 1990-07-03 | 1994-01-12 | Grace W R & Co | The enhancement of fluorescent whitening agents |
US5174927A (en) * | 1990-09-28 | 1992-12-29 | The Procter & Gamble Company | Process for preparing brightener-containing liquid detergent compositions with polyhydroxy fatty acid amines |
US5041048A (en) * | 1990-10-19 | 1991-08-20 | Lehmann Roger W | Multiple graphics selection toy |
US6090372A (en) * | 1997-07-15 | 2000-07-18 | Lever Brothers Company, Division Of Conopco, Inc. | Liquid detergent compositions and process for their preparation |
HUP0104854A2 (en) * | 1998-12-16 | 2002-04-29 | Unilever Nv. | Transparent/translucent liquid enzyme compositions in clear bottles comprising fluorscent dye or uv absorber |
GB0418071D0 (en) * | 2004-08-05 | 2004-09-15 | Unilever Plc | Fabric conditioning compositions |
JP4994869B2 (en) * | 2007-02-02 | 2012-08-08 | 花王株式会社 | Liquid detergent composition |
US20220220420A1 (en) * | 2019-05-16 | 2022-07-14 | Conopco, lnc., d/b/a UNILEVER | Laundry composition |
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DE1098485B (en) * | 1957-06-05 | 1961-02-02 | Bayer Ag | Whitening agents |
NL130816C (en) * | 1964-02-24 | |||
US3726814A (en) * | 1971-03-15 | 1973-04-10 | Colgate Palmolive Co | Liquid laundry detergents and a process for preparing same |
DE2609752A1 (en) * | 1976-03-09 | 1977-09-22 | Henkel & Cie Gmbh | Liquid low temp. detergent concentrate - contg. potassium fatty acid salts, ethoxylated alcohol, alkylbenzene sulphonate, brightener and solubiliser |
DE2847438A1 (en) * | 1978-11-02 | 1980-05-22 | Henkel Kgaa | LIQUID, REFRIGERABLE DETERGENT CONCENTRATE |
JPS58132099A (en) * | 1981-09-28 | 1983-08-06 | ザ・プロクタ−・エンド・ギヤンブル・カンパニ− | Detergent composition |
DD220325A1 (en) * | 1983-09-05 | 1985-03-27 | Bitterfeld Chemie | WASHING TOOLS |
EP0167205B1 (en) * | 1984-07-03 | 1992-03-11 | The Procter & Gamble Company | Stable liquid detergents containing anionic surfactant and monosulfonated brightener |
-
1986
- 1986-03-11 GB GB8605966A patent/GB2187749B/en not_active Expired - Fee Related
-
1987
- 1987-03-03 AT AT87200386T patent/ATE97159T1/en not_active IP Right Cessation
- 1987-03-03 DE DE3788075T patent/DE3788075T3/en not_active Expired - Fee Related
- 1987-03-03 EP EP87200386A patent/EP0237119B2/en not_active Expired - Lifetime
- 1987-03-10 IE IE61187A patent/IE60528B1/en not_active IP Right Cessation
- 1987-03-10 NZ NZ219558A patent/NZ219558A/en unknown
- 1987-03-10 AU AU69856/87A patent/AU588979B2/en not_active Ceased
- 1987-03-10 JP JP62055115A patent/JP2859263B2/en not_active Expired - Lifetime
- 1987-03-11 KR KR1019870002147A patent/KR950004931B1/en not_active IP Right Cessation
-
1997
- 1997-02-20 GR GR970400147T patent/GR3022619T3/en unknown
Also Published As
Publication number | Publication date |
---|---|
EP0237119B2 (en) | 1997-02-19 |
JP2859263B2 (en) | 1999-02-17 |
JPS62275200A (en) | 1987-11-30 |
IE870611L (en) | 1987-09-11 |
EP0237119A3 (en) | 1990-05-16 |
EP0237119B1 (en) | 1993-11-10 |
ATE97159T1 (en) | 1993-11-15 |
DE3788075D1 (en) | 1993-12-16 |
GB2187749B (en) | 1990-08-08 |
KR950004931B1 (en) | 1995-05-16 |
DE3788075T3 (en) | 1997-06-19 |
GR3022619T3 (en) | 1997-05-31 |
DE3788075T2 (en) | 1994-05-11 |
GB2187749A (en) | 1987-09-16 |
GB8605966D0 (en) | 1986-04-16 |
EP0237119A2 (en) | 1987-09-16 |
AU588979B2 (en) | 1989-09-28 |
KR870009008A (en) | 1987-10-22 |
AU6985687A (en) | 1987-09-17 |
NZ219558A (en) | 1989-11-28 |
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Legal Events
Date | Code | Title | Description |
---|---|---|---|
MM4A | Patent lapsed |