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
  • C11D3/40—Dyes ; Pigments
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B31/00—Disazo and polyazo dyes of the type A->B->C, A->B->C->D, or the like, prepared by diazotising and coupling
  • C09B31/02—Disazo dyes
  • C09B31/04—Disazo dyes from a coupling component "C" containing a directive amino group
  • C09B31/053—Amino naphthalenes
  • C09B31/057—Amino naphthalenes containing acid groups, e.g. —CO2H, —SO3H, —PO3H2, —OSO3H, —OPO2H2; Salts thereof
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B33/00—Disazo and polyazo dyes of the types A->K<-B, A->B->K<-C, or the like, prepared by diazotising and coupling
  • C09B33/02—Disazo dyes
  • C09B33/08—Disazo dyes in which the coupling component is a hydroxy-amino compound
  • C09B33/10—Disazo dyes in which the coupling component is a hydroxy-amino compound in which the coupling component is an amino naphthol
• • C—CHEMISTRY; METALLURGY
  • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
  • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
  • C09B45/00—Complex metal compounds of azo dyes
  • C09B45/02—Preparation from dyes containing in o-position a hydroxy group and in o'-position hydroxy, alkoxy, carboxyl, amino or keto groups
  • C09B45/24—Disazo or polyazo compounds
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S8/00—Bleaching and dyeing; fluid treatment and chemical modification of textiles and fibers
  • Y10S8/93—Pretreatment before dyeing
  • Y10S8/931—Washing or bleaching

Definitions

• ABSTRACT The apparent whiteness of fabrics is enhanced by a method of treating the fabrics with an effective amount of an alkali and heat stable water-soluble disazo dyestuff using a sulfonated disazo dyestuff of the diphenyl, dinaphthyl type.
• a fabric softening and laundry detergent composition are disclosed therefor.
• the disazo blue dyestuffs of the invention are alkali FABRICS BY APPLYING AN EFFECTIVE AMOUNT and heat stable and water-soluble and are sulfonated OF AN ALKALI AND HEAT STABLE with at least one and preferably two or more alkali WATER-SOLUBLE DISAZO BLUE DYESTUFF, metal sulfonate radicals.
• the compounds will also pref- FABRIC SOFTENING AND DETERGENT 5 erably contain two naphthyl rings and two phenyl rings.
• Such compounds will prefby treating the fabrics with a disazo dyestuff, and more erably have the following structural formulas:
• y g halogen, y y lower a o y f 1-3 is possible to use these materials either as an after rinse, Carbon atoms and lower alkyl of Carbon atoms, M in a f b i Softener, in a pre soak, or when used in is an alkali or alkaline earth metal, such as sodium, pobination with a liquid or solid detergent composition.
• Naoas gents appear to be even whiter with these color materi- A specific dyestuff material of the phenyl-azo-naphtals than when they are omitted.
• anionic detergents which fall within the scope of the anionic detergent class includethe water-soluble salts, e.g., the sodium, ammonium, and alkylolammonium salts, of higher fatty acids or resin salts containing about 8 to 20 carbon atoms, preferably 10 to 18 carbon atoms.
• Suitable fatty acids can be obtained from oils and waxes of animal or vegetable origin, e.g., tallow, grease, coconut oil, tall oil and inn tures thereof.
• Particularly useful are the sodium and potassium salts of the fatty acid mixtures derived from coconut oil and tallow, e.g., sodium coconut soap and potassium tallow soap. 7
• the anionic class of detergents also includes the water-soluble sulfated and sulfonated synthetic detergents having an alkyl radical of 8 to 26, and preferably about 12 to 22 carbon atoms, in their molecular structure.
• alkyl includes the. alkyl portion of higher acyl radicals.
• sulfonated anionic detergents include higher alkyl aromatic sulfonates such as the higher alkyl benzene sulfonates containing from l'to 16 carbon-atoms in the higher alkyl group in a straight or branched chain, e.g., the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates, higher alkyl phenol sulfonates, and higher naphthalene sulfonates.
• higher alkyl aromatic sulfonates such as the higher alkyl benzene sulfonates containing from l'to 16 carbon-atoms in the higher alkyl group in a straight or branched chain, e.g., the sodium, potassium and ammonium salts of higher alkyl benzene sulfonates, higher alkyl toluene sulfonates, higher alky
• a preferred sulfonate' is linear alkyl benzene sulfonate having a high content of 3 (or higher) phenyl isomers and a correspondingly low content (well below 50 per cent) of 2- (or lower) phenyl isomers, i.e., wherein the benzene ring is preferably attached in large part at the 3 or higher (e.g., 4, S, 6 or 7) position of the alkyl group and the content of isomers in which the benzene ring is attached at the 2 or 1 position is correspondingly low.
• Particularly preferred materials are set forth in U.S.
• Suitable anionic detergents are the olefin sulfo nates, including long-chain alkene sulfonates, longchain hydroxyalkane sulfonates or mixtures of allcenesulfonates and hydroxyalkane-sulfonates.
• sulfate or sulfonate detergents are paraffin sulfonates containing about -20, preferably about -20, carbon atoms, e.g., the primary parafiin sulfonates made by reacting long-chain alpha olefins and bisulfites and paraffin sulfonates havingthe sulfonate groups distributed along the paraffin chain as shown in U.S. Pat. Nos. 2,503,280; 2,507,088; 3,260,741; 3,372,188 and German Pat. No. 735,096;
• sodium and potassium sulfates of higher alcohols containing 8 to 18 carbon atoms such as sodium lauryl sulfate and sodium tallow alcohol sulfate; sodium and potassium salts of a -sulfofatty acid esters containing about 10 to 20 carbon atoms in the acyl group, e.g., methyl 0 -sulfomyristate and methyl or :sulfo-tallowate, ammonium sulfates of monoor diglycerides of higher (C C fatty acids, e.g., stearic monoglyceride monosulfate; sodium and alkylolammonium salts of alkyl polyethenoxy ether sulfates produced by condensing l to 5 moles of ethylene oxide with one mole of higher (C -C alcohol; sodium higher alkyl (C -C glyceryl ether sulfonates; and sodium or potassium alkyl phenol polyethenoxy
• Paraffin sulfonates useful in the present invention are usually mixed secondary alkyl sulfonates having from 10 to 20 carbon atoms per molecule, preferably they willhave at least percent, usually at least percent, of from lO-17 carbon atoms per molecule. Where the major proportion has 14-15 carbon atoms per molecule, optimum foaming performance appears to be obtained at varying concentrations and water hardnesses.
• These sulfonates are preferably prepared by subjecting a cut of paraffin, corresponding to the chain lengths specified above, to the action of sulfur dioxide and oxygen in accordance with the well known sulfoxidation process.
• the product of this reaction is a secondary sulfonic acid which is then neutralized with a suitable base to provide thewater soluble secondary alkyl sulfonate for use in the present invention.
• Similar useful secondary alkyl sulfonate may be obtained by other methods, e.g., by the sulfochlorination method in which chlorine and sulfur dioxide are reacted with paraffins in the presence of actinic light, the resulting sulforyl chlorides being hydrolyzed and neutralized to form the secondary alkyl sulfonates.
• These compounds are particularly useful in heavy duty liquid detergent formulations containing the bluing agents of the invention.
• the suitable anionic detergents include also the C,,-C, acyl sarcosinates (e.g., sodium lauroyl sarcosinate), sodium and potassium salts of the reaction prod uct of higher fatty acids containing 8 to 18 carbon atoms in the molecule esterified with isethionic acid, and sodium and potassium salts of the C -C acyl N- methyl taurides, e.g., sodium cocoyl methyl taurate and potassium stearoyl methyl taurate.
• Anionic phosphate surfactants in which the anionic solubilizing group attached to the hydrophobic group is an oxyacid of phosphorous are also useful in the de-' tergcnt compositions.
• Suitable phosphate surfactants are the sodium potassium and ammonium alkyl phosphate esters such as (R-O) PO,M and ROPO M in which R represents an alkylchain containing from about 8 to about 20 carbon atoms or an alkyl phenyl group having 8 to 20 carbon atoms and M represents a soluble cation.
• R sodium potassium and ammonium alkyl phosphate esters
• R represents an alkylchain containing from about 8 to about 20 carbon atoms or an alkyl phenyl group having 8 to 20 carbon atoms and M represents a soluble cation.
• Particularly desirable salts of this type include the ammonium, triethanolammonium, sodium and potassium salts of the higher alkyl sulfates and the C C acyl sarcosinates.
• the nonionic synthetic organic detergents are generally the condensation product of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophilic alkylene oxide groups.
• any hydrophobic compound having a carboxy, hydroxy, amido, or amino group with a free hydrogen attached to the nitrogen can be condensed with an alkylene oxide such as ethylene oxide or with the polyhydration products thereof, e.g., polyethylene glycol, to form a nonionic detergent.
• the length of the polyalkyleneoxy chain can be adjusted to achieve the desired balance between the hydrophobic and hydrophilic elements.
• nonionic compound types of hydrophobes are higher aliphatic alcohols and alkyl phenols, although others may be used such as carboxylic acids, carboxamides, mercaptans, sulphonamides, etc.
• the ethylene oxide condensates with higher-alkyl phenols represent a preferred class of nonionic compounds.
• the hydrophobic moiety should contain at least about 6 carbon atoms, and preferably at least about 8 carbon atoms, and may contain as many as about 50 carbon atoms or more.
• the amount of alkylene oxide will vary considerably depending upon the hydrophobe, but as a general guide and rule, at least about 5 moles of alkylene oxide per mole of hydrophobe should be used.
• alkylene oxide will vary, also, but no particular criticality can be ascribed thereto. As much as 200 or more moles of alkylene oxide per mole of hydrophobe may be employed. While ethylene oxide is the preferred and predominating oxyalkylating reagent, other lower alkylene oxides such as propylene oxide, butylene oxide, and the like may also be used or substituted in part for the ethylene oxide.
• nonionic compounds which are suitable are the polyoxyalkylene esters of the organic acids such as the higher fatty acids, the rosin acids, tall oil acids, acids from petroleum oxidation products, etc. These esters will usually contain from about 10 to about 22 carbon atoms in the acid moiety and from about 12 to about 30 moles of ethylene oxide or its equivalent.
• nonionic surfactants are the alkylene oxide condensates with the higher fatty acid amides.
• the fatty acid group will generally contain from about 8 to about 22 carbon atoms and this will be condensed with about 10 to about 50 moles of ethylene oxide.
• the corresponding carboxamides and sulphonamides may also be used as substantial equivalents.
• Still another class of nonionic products are the oxyalkylated higher aliphatic alcohols.
• the fatty alcohols should contain at least 6 carbon atoms, and preferably at least about 8 carbon atoms.
• the most preferred alcohols are lauryl, myristyl, cetyl, stearyl and oleyl alcohols and the said alcohols should be condensed with at least about 6 moles of ethylene oxide and, preferably, about 10 to 30 moles of ethylene oxide.
• a typical nonionic product is oleyl alcohol condensed with 15 moles of ethylene oxide.
• the corresponding alkyl mercaptans when condensed with ethylene oxide are also admirably suitable in the compositions of the present invention.
• nonionics are the polyoxyethylene polyoxypropylene adducts of l-butanol.
• the hydrophobe of these nonionics has a minimum molecular weight of 1,000 and consists of an aliphatic monohydric alcohol containing from 1 to 8 carbon atoms to which is attached a heteric chain of oxyethylene and oxypropylene.
• the weight ratio of oxypropylene to oxyethylene covers the range of 95:5 to 85:15. Attached to this is the hydrophilic polyoxyethylene chain which is from 44.4 to 54.6 per cent of the total molecular weight of 1,400 to 4,000.
• a particularly useful group of nonionics is marketed under the trade name Pluronics.
• the compounds are formed by condensing ethylene oxide with a hydrophobic base formed by the condensation of propylene oxide with propylene glycol.
• the molecular weight of the hydrophobic portion of the molecule is of the order of 950 to 4,000 preferably 1,200 to 2,500.
• the addition of polyoxyethylene radicals to the hydrophobic portion tends to increase the solubility of the molecule as a whole.
• the molecular weight of the block copolymers varies from 1,100 to 15,000 and the polyethylene oxide content may comprise 20 to per cent by weight.
• Suitable nonionics may be derived by the condensation of ethylene oxide with the product resulting from the reaction of propylene oxide and ethylene diamine.
• the molecular weight varies from 500 to 4,500.
• nonionic detergents include the ethylene oxide addends of monoesters of hexahydric alcohols and inner ethers thereof with higher fatty acids containing about 10 to 20 carbon atoms, e.g., sorbitan monolaurate, sorbitan mono-oleate, and mannitan monopalmitate.
• amphoteric detergents which can be used in the compositions of this invention are generally watersoluble salts of derivatives of aliphatic amines which contain at least one cationic group, e.g., nonquaternary nitrogen, quaternary ammonium, or quaternary phosphonium group, at least one alkyl group of about 8 to 18 carbon atoms and an anionic watersolubilizing carboxyl, sulfo, sulfato, phosphato or phophono group in their molecular structure.
• the alkyl group may be straight chain or branched and the specific cationic atom may be part of a heterocyclic ring.
• ampholytic detergents include the alkyl beta-aminopropionates, RN(H)C H,COOM; the alkyl betaiminodiproprionates, RN(C H.,COOM) the alkyl and hydroxy alkyl taurinates, RN(CH )C H SO M; and the long-chain imidazole derivatives having the following formulas:
• R is an acyclic group of about 7 to 17 carbon atoms
• W is selected from the group of R OH, R COOM, and R OR COOM
• Y is selected from the group consisting of 01-1
• R OSO R is an alkylene or hydroxyalkylene group containing 1 to 4 carbon atoms
• R is selected from the group consisting of alkyl, alkyl aryl and fatty acyl glyceride groups having 6 to 18 carbon atoms in the alkyl or an acyl group
• M is a water-soluble cation, e.g., sodium potassium, ammonium or alkylolammonium.
• Formula 1 detergents are disclosed in Volume 11 of Surface Active Agents and Detergents" and in French Pat. No. 1,412,921 and Formula 11 detergents are de- Zwitterionic detergents such as the betaines and sulfobetaines having the following formula are also useful:
• R is an alkyl group containing about 10 to 18 carbon atoms
• R and R are each C,-C alkyl
• R is an alkylene or hydroxyalkylene group containing about 1 to 4 carbon atoms
• X is C or 8:0.
• the alkyl group can contain one or more intermediate linkages such as amido, either or polyether linkages or non-functional substituents such as hydroxyl or halogen which do not substantially affect the hydrophobic character of the group.
• the detergent is called a betaine
• X is S10
• the detergent is called a sulfobetaine or sultaine.
• Preferred betaine and sulfobetaine detergents are l-(lauryl dimethylammonio) acetate, l-(myristyl dimethylammonio) propane-3- sulfonate, and l-(myristyl dimethylammonio)-2- hydroxy-propane-3-sulfonate.
• the polar nonionic detergents are those in which the hydrophilic group contains a semi-polar bond directly between two atoms, for example, N O; P As 0; and S 0. There is charge separation between the two directly bonded atoms, but the detergent molecule bears no net charge and does not dissociate into ions.
• the polar nonionic detergents of this invention include open-chain aliphatic amine oxides of the general formula R,R,R -,N 0.
• R is an alkyl, alkenyl, or monohydroxy'alkyl radical having about l0 to 20 carbon atoms.
• R and R are each selected from the group consisting of methyl, ethyl, propyl, ethanol, and propanol radicals.
• operable polar nonionic detergents are the open-chain aliphatic phosphine oxides having the general formula R,R,R;,P 0 wherein R, is an alkyl, alkenyl, or monohydroxyalkyl radical ranging in chain length from 10 to 18 carbon atoms, and R and R are each alkyl and monohydroxyalkyl radicals containing from 1 to 3 carbon atoms.
• Cationic surface active agents may also be employed. Such agents are those surface active detergent compounds which contain an organic hydrophobic group and a cationic solubilizing group. Typical cationic solubilizing groups are amine and quaternary groups.
• Suitable synthetic cationic detergents are normal primary amines RNH, wherein R is C,,-C,,,; the diamines such as those of the type RNHC, l-l,l-ll-l wherein R is an alkyl group of about 12 to 22 carbon atoms, such as N-Z-arninoethyl stearyl amine and N-2- aminoethyl myristyl amine; amide-linked amines such as those of the type R,CONHC,H,NH wherein R, is an alkyl group of about 8 to 20 carbon atoms, such as N-2- amino ethyl-stearyl amide and N-amino ethylmyristyl amide; quaternary ammonium compounds wherein typically one of the groups linked to the nitrogen atom is an alkyl group of about 8 to 22 carbon atoms and three of the groups linked to the nitrogen atom are alkyl groups which contain 1 to 3 carbon atoms, including alkyl groups bearing
• the alkyl group may contain intermediate linkages such as amido which do not substantially affect the hydrophobic character of the group, e.g., stearyl amido propyl quaternary ammonium chloride.
• Typical quaternary ammonium detergents are ethyl-dimethyl-stearyl ammonium chloride, benzyldimethyl-stearyl ammonium chloride, trimethylstearyl ammonium chloride, trimethyl-cetyl ammonium bromide, dimethyl-ethyl-lauryl ammonium chloride, dimethyl-propyl-myristyl ammonium chloride, and the corresponding methosulfates and acetates.
• the concentration of water-soluble organic detergent in the detergent compositions of the invention varies with the nature and form of the product, that is, usually from about 5 to per cent by weight of detergent can be used. Preferably 8 to 35 per cent by weight is used in solid products, such as spray-dried powders; soap based products will normally contain 30-95 and preferably 50-90 per cent of soap, and from 5 to 30 per cent, preferably 8 to 20 per cent, by weight of detergent is used in liquid products.
• Builder salts useful in the detergent formulations of the invention may be of any type well known in the detergent art generally and may be any suitable watersoluble, organic or inorganic builder salt.
• Useful builder salts include salts of alkali metal, alkaline earth metal, or heavy metals or combinations thereof. Ammonium or an ethanolammonium salt in a suitable amount may be added also, but generally, the sodium, potassium, or similar salts are preferred.
• Preferred inorganic hydratable builder salts are the alkali metal polyphosphate salts which have the property of inhibiting precipitation of calcium and magnesium material in aqueous solution and of contributing to the heavy-duty performance of the detergent product. They may be considered as derived from orthophosphoric acid or the like by the removal of molecularly-bound water, though any suitable means of manufacture may be employed if desired. Such complex or molecularly dehydrated polyphosphate salts may be used in the form of the normal or completely neutralized salt, e.g., pentapotassium tripolyphosphate, pentasodium tripolyphosphate, and potassium acid tripolyphosphate. The alkali metal salts of tetraphosphoric acid may be used also. The alkali metal polyphosphate salts may be used in either anhydrous form or partially hydrated form.
• Typical examples of hydratable organic builder salts which may be employed alone or in the aforementioned admixtures include the water-soluble aminopolycarboxylates such as the trisodium salt of nitrilotriacetic acid and the di-, tri-, and tetrasodium salts of ethylene-diamine tetraacetic acid.
• hydratable alkaline builder salts may be employed also, such as the soluble alkali metal borates, sulfates, carbonates, bicarbonates and silicates.
• Suitable silicates are sodium silicates having an Na,0 to SiO ratio of 12.35, 12.5, 1:32 and so forth.
• suitable materials include citrates, diglycolates, nitrates chlorides, perborates and percarbonates.
• mixtures of two or more inorganic or organic salts can be used, as can mixtures of inorganic salts with inorganic salts.
• the proportion of builder salts is preferably, for example, in the range of about I to 20 parts per part of the active detergent.
• Various other materials may be added in suitable amounts.
• Materials such as the higher fatty acids amides may be added to improve detergency and modify the foaming properties in a desirable manner.
• Examples thereof are the higher fatty acid alkanolamides, preferably having 2-3 carbons in each alkanol group and a fatty acyl radical within the range of l-l8 carbons, preferably I0-l4 carbons, such as lauric or myristic monoethanolamides, diethanolamides and isopropanolamides.
• Tertiary higher alkyl amine oxides such as having about -18 carbons in one alkyl group, e.g., lauryl or myristyl dimethylamine oxide, may be added also.
• Fatty alcohols of 10-18 carbons such as lauryl or coconut fatty alcohols, or cetyl alcohol are suitable additives also.
• a hydrotropic material such as the lower alkyl aryl sulfonates, e.g., sodium tolueneor xylene-sulfonates, also can assist processing. In general, these materials are added in minor amounts, usually from about is to 10 percent, preferably 1 to 6 percent based on the total solids.
• the mixtures may also contain optical brightening agents or fluorescent dyes (e.g., in amounts in the range of about l/ to 3 percent); germicidal ingredients such as halogenated carbanilides, e.g., trichlorocarbanilide, halogenated salicylanilide, e.g., tribromosalicylanilide, halogenated bis-phenols, e.g., hexachlorophene; halogenated trifluoromethyldiphenyl urea; the zinc salt of l-hydroxy-2-pyridinethione and the like (e.g., in amounts in the range of about 1/50 to 2 percent).
• germicidal ingredients such as halogenated carbanilides, e.g., trichlorocarbanilide, halogenated salicylanilide, e.g., tribromosalicylanilide, halogenated bis-phenols, e.g., hexachlorophene;
• Soil-suspending agents can also be included. These are generally water-soluble or hydrophilic polymeric substances such as the lower alkyl cellulose ethers, e.g., methyl cellulose and ethyl cellulose, hydroxyalkyl cellulose ethers, e.g., hydroxyethyl cellulose, cellulose ethane sulphonic acid, cellulose glycollic acid, carboxy lower alkyl cellulose compounds, e.g., sodium carboxy methyl cellulose, potassium carboxy methyl cellulose, sodium carboxy ethyl cellulose, sodium carboxy propyl cellulose, and the like, water-soluble or dispersible synthetic polymeric materials which may be homopolymers, copolymers, graft copolymers, terpolymers, interpolymers, and the like and are illustrated by polyvinyl pyrrolidone, polyvinyl alcohol, hydrolyzed polyvinyl acetate, polyacrylic acid, polyacrylamide, maleic anhydride copoly
• antioxidants such as 2,6-ditertbutylphenol, or other phenolic antioxidant material (e.g., in amounts in the range of about 0.001 to 0.1 percent); bleaching agents; corrosion inhibitors; sequestrants, e.g., ethylene diamine tetraacetic acid, sodium gluconate, and the like; alcohols to improve the compatibility of the various components such as ethanol, propanol and isopropanol; tarnish inhibitors such as ethylene thiourea; perfumes; and thickening agents.
• antioxidants such as 2,6-ditertbutylphenol, or other phenolic antioxidant material (e.g., in amounts in the range of about 0.001 to 0.1 percent); bleaching agents; corrosion inhibitors; sequestrants, e.g., ethylene diamine tetraacetic acid, sodium gluconate, and the like; alcohols to improve the compatibility of the various components such as ethanol, propanol and isopropanol; tarn
• the bluing agents are useful when applied from presoak products as well as from regular laundry detergent compositions.
• Presoak products are similar to the laundry detergent compositions and generally contain a surface active agent and a builder salt such as those described above.
• the presoak product also often will contain an enzyme of the proteoiytic type (e.g., pepsin, subtilisin, trypsin, papain, bromelin, and the like).
• the surface active agent is typically present in an amount of 3-95 percent by weight of the presoak composition, preferably about 5-25 percent by weight.
• the builder salt when present is employed in the amount of 30-90 percent by weight, and, W6 EEHHEG, the enzyme is present in amounts of 0.001 to 4.0 per cent preferably 0.05 to 2.0 per cent by weight.
• various other additives can be included to alter or enhance the effectiveness and the esthetics of the composition.
• the bluing agents can also be applied to fabrics when incorporated into a fabric softener composition.
• Fabric softeners are of any suitable type known to have the de sired conditioning effects.
• cationic, amphoteric, nonionic and anionic surface active agents are useful. Included in this group are the quaternary ammonium halides such as the mixed higher and lower alkyl ammonium chlorides and bromides wherein there are present one or two higher alkyls of 8 to 20 carbon atoms, preferably l2 to 18 carbon atoms, and two or three lower alkyls of 1 to 4 carbon atoms, preferably of l or 2 carbon atoms.
• an aryl alkyl radical such as benzyl may be used.
• Exemplary of useful cationic compounds are distearyl dimethyl ammonium chloride, lauryl trimethyl ammonium bromide and stearyl dimethyl benzyl ammonium chloride.
• various other cationics such as alkyl pyridine salts, alkyl imidazolines, higher alkyl amines, of the primary, secondary, or tertiary types and higher alkyl guanidine salts, e.g., l-methyl-lstearyl aminoethyl-Z-stearyl imidazolinium methosulfate, Z-heptadecyl-l-methyl-l(2-stearoylamido)ethyl imidazolinium methyl sulfate, stearyl pyridinium ha lides, cetyl isoquinolinium bromide and alkyl morpholinium chlorides.
• lower alkyl is of l to 5 carbon atoms, preferably 1 or 2, and higher
• amphoteric materials those sold as Soromines, Deriphats, Miranols, etc., are good conditioners.
• the Soromines, AL and AT are complex fatty amido softeners which have been found to be excellent for the intended purpose.
• nonionics the preferred products are polyoxyethylene (4) lauryl ether, sold as Brij 30; myristyl dimethyl amine oxide, sold as Textamine Oxide TA; nonylphenoxy polyethoxy ethanol, sold as Igepal CO-880; and polyoxyethylene sorbitan monostearate, sold as Tween 61.
• the soaps include the alkali metal, amine, ammonium, and alkanolamine soaps.
• the higher fatty acids are of 8 to 20 carbon atoms, preferably mostly of 12 to 18 carbon atoms and are those that occur naturally in vegetable and animal oils and fats, usually in mixtures in triglycerides.
• the amines and alkanolamines are of lower alkyls and alkanols such as those of I to 4 carbon atoms, preferably of 2 to 3 carbon atoms.
• the sulfuric reaction products are balanced compounds having lipophilic and hydrophilic groups, with the lipophile portion usually being a higher alkyl or alkyl aryl, e.g., alkyl phenyl wherein the alkyl is of 12 to 15 carbon atoms.
• the higher alkyls may be of 8 to 20 carbon atoms, preferably of 12 to 18.
• the lipophile portion may be made of polymerization of lower alkylene oxide(s) to a suitable chain length, usually of 10 to 40 oxyalkylene groups of 2 to 4 carbon atoms each.
• the lipophile balancing group the hydrophilic moiety, will usually be a water-soluble sulfate or sulfonate of an alkali metal, an alkaline earth metal, ammonium, amine or alkanolamine of the type previously described in conjunction with the nonionic softener exposition.
• softeners Lengthy descriptions of the softeners are not given herein because all such compounds are generally applicable to the present invention and are known to those of skill in the art. For example, descriptions of softeners can be found in the reference work Detergents and Emulsifiers 1969 Annual, by John W. McCutcheon, wherein those surface active agents that are especially useful as softeners are so characterized. Also, see the text SYNTHETIC DETERGENTS, by Schwartz, Perry and Berch, published in 1958 by lnterscience Publishers.
• Fabric softener compositions may also contain various adjuvants to impart desirable properties in addition to softening and bluing to the fabrics treated.
• they may contain bactericides, fungicides, fluorescent or optical brighteners, e.g., aminostilbenes, triazines, ozazoles, pyrazolines, etc., perfumes, deodorants and lubricants.
• Still another method for applying the bluing agents of this invention to fabrics simply involves the addition of a premeasured amount of bluing agent in an aqueous medium to a given quantity of fabric to be blued.
• the disazo dye will nor mally be used in an amount by weight of the disazo blue dyestyff of not greater than 1.5 parts per million parts by weight of the fabric to be treated, and preferably will be less than 1.0 part per million.
• the lower limit on the amount of disazo blue dye to be added is that amount necessary to effectively whiten the fabrics. Generally at least about 0.03 part per million will be used, and preferably at least about 0.1 part per million is used.
• detergent compositions containing the disazo blue dyestuffs of the invention may be added in the crutcher before spray drying of a spraydried particulate detergent, or they may be mixed into the composition after spray drying or added at any other time during the formulation of the liquid detergents. They may also be post-added to the detergent composition either alone or on a suitable carrier.
• the compounds of the invention are both alkali and heat stable and therefore lend themselves to widely varied formulating techniques.
• a fabric softener composition When used in a liquid detergent, a presoak, or a fabric softener composition the per cent of disazo dye used will be approximately twice the amount described above for use in a granular or spray-dried composition. This is because an amount by weight of roughly half of these compositions is used for a normal load of wash compared to the amount of granular detergent used.
• a fabric softener composition may contain the disazo blue dye in an amount up to about 0.01% by weight.
• nonionic surface active agent which is a polyethoxylated long chain alkanol, specifically the reaction product of l 1 mols of ethylene oxide with one mol of a blend of 14 and 15 carbon atoms primary alltanols described hereinabove
• the spray-dried product had a white color, a cup weight of about grams and a density of about 0.35.
• a plurality of swatches of cotton, Dacron, Arnel, Orlon, Creslan, nylon and blends of these fabrics together with cleaned cotton towels to form a full load (8 pounds) is washed in an automatic washing machine in ordinary tap water (New Brunswick, New Jersey hardness of about PPM), containing approximately 100 grams of the spray-dried detergent composition equivalent to approximately 0.15 percent of detergent.
• the wash water temperature is F. and has a pH of approximately 9.5. The washing is continued for 10 minutes after which the load is thoroughly rinsed in the same tap water at a temperature about 90l00 F.
• the resulting cleaned and whitened fabrics were evaluated against a similarly constituted batch of fabrics washed with a detergent composition that was the same except that it did not contain the Sirius Supra Violet BL.
• the evaluation was made by ten panelists under both incandescent light and north daylight. The panelists showed a strong preference for the fabrics that were washed in the composition containing Sirius Supra Violet BL.
• the detergent composition itself was considerably whiter looking than a control without the bluing agent. Readings were taken of the detergent and the control on a Hunter D-25 Color Difference Meter and the detergent with the dyestuff was considerably less yellow. The results of the Difference Meter Readings are shown in the chart below wherein Rd is the Reflectance value, -a is the greenness indication, and +b is the yellowness indication.
• EXAMPLE 2 A spray-dried composition similar to that described above was formulated using 0.002 percent of C.I. Acid Blue 113 instead of the Sirius Supra Violet BL (i.e., C.I. Direct Violet 48).
• a spray-dried granular laundry detergent composition can be prepared from the following components:
• Neodol 45-11 10.0 Sodium Carbonate 45.0 Sodium Silicate (1:2.35. Na,O:SiO,) 18.4 Carboxymethyl cellulose 0.5 Brighteners 0.84 Water 10.0 C.1. Direct Violet 48 0.002 Sodium Sulfate 15.258
• the spray-dried product had an 80 gram cup weight and a density of about 0.35.
• the fabrics treated with the control composition were considerably less white than those treated in accordance with the invention.
• EXAMPLE 5 A spray-dried composition similar to that described in Example 4 was formulated using 0.001 percent of C.I. Direct Violet 48 instead of C.I. Acid Blue 113. A substantially white detergent product was obtained. The product clearly enhanced the apparent whiteness of the fabrics treated therewith.
• EXAMPLE 6 A composition similar to that described in Examples 4 and 5 above was formulated with the exception that the bluing agent constituted a mixture of 60 percent C.I. Direct Violet 48 and 40 percent C.I. Acid Blue 1 13. The total amount of blue dyestufi' was 0.001 percent.
• a spray-dried laundry composition was formed having the following composition:
• EXAMPLE 8 A product similar to that described in Example 7 above was formulated except that an equivalent amount of C.I. Direct Violet 48 was substituted for the C.I. Acid Blue 113. The resulting product was equally efficacious in enhancing the visual whiteness of test towels.
• EXAMPLE 9 A composition similar to that described in Example 7 above was formulated using a detergent having the same composition described therein but wherein the cup weight was grams rather than 80 grams and the amount of C.I. Acid Blue 113 used was sufficient to form a laundry detergent composition containing 0.0013 percent of the dyestuff. A visual examination following a five wash bundle test showed that the composition containing the dye-stuff was again preferred over the control.
• the above formulation was spray-dried with the C.I. Direct Violet 48 having been added in the crutcher prior to the spray-drying operation.
• the product powder had enhanced whiteness when visually compared to a control without the bluing agent.
• composition was used to wash test fabrics in a similar manner similar to that described in Example 1 above with the result that panelists judged the fabrics treated with the detergent containing the blue dye to be preferred to a significant degree over a control composition not containing blue dyestuff.
• a laundry soap powder composition was formed having the following composition:
• a load of fabrics of varying composition was washed in 100 grams of the above composition together with 17 gallons of tap water, and control fabric was treated with the identical composition without the blue dye.
• a visual test showed that the fabrics that were treated in the compositionwith the blue dye were visually whiter than the control fabrics.
• Neodol 25-38 (60% A.l.; 14% ethyl alcohol; remainder water) 25.0 Sodium Citrate 20.0 Sodium Xylene Sulfonate (40% A.l.) 10.0 Brighteners 3.3 Perfume 0.25 C.l. Direct Violet 48 0.0025 Water 41.4475
• the Neodol 25-38 is an anionic surfactant comprising the reaction product of three mols of ethylene oxide with one mol of a blend of 12 to 15 carbon atoms primary alkanols subsequently sulfated and non-- tralized to form'the sodium salt.
• the liquid product had a density of about 1.14 and was designed to be used in an amount of about onethird of a cup in a normal laundry wash load.
• EXAMPLE 14 A composition similar to that described in Examples 12 and 13 above was formulated with the exception that the bluing agent constituted a mixture of 50 percent C.l. Direct Violet 48 and 50 percent C.l. Acid Blue 1 13. The total amount of blue dyestuff was 0.0025 percent. Fabrics treated with this composition also had improved apparent whiteness.
• a fabric softener composition was formed having the following composition:
• a laundry pre-soak composition was formuiated from:
• a laundry detergent composition comprising an organic surface active compound selected from the group consisting of a water-soluble alkali metal soap, anionic, nonionic, amphoteric, zwitterionic, polar nonionic and cationic detergents and an effective amount of an alkali and heat stable water-soluble disazo blue dyestuff containing at least one alkali metal sulfonate radical, said composition being adapted to be applied to substantially all commonly used fabrics whereby enhanced apparent whiteness thereof is obtained said dyestuff being selected from the group consisting of compounds having the formula and those having the formula and the metal complexes thereof, and wherein each of R, R R R R R and R is selected from the group consisting of hydrogen, halogen, hydroxyl, lower alkoxy and lower alkyl groups; M is alkali or alkaline metal and A is NH, NH'CO'NH or NHarylNH.
• an organic surface active compound selected from the group consisting of a water-soluble alkali metal soap, anionic, nonionic,
• a laundry detergent composition in accordance with claim 4 wherein said disazo blue dyestuff comprises a mixture of C.I. Acid Blue 113 (CI. 26360) and CI. Direct Violet 48 (C.l. 29125).
• a laundry detergent composition in accordance with claim 4 wherein said composition is a granular solid and said disazo dyestuff is present in an amount of up to about 0.005 per cent by weight based upon the weight of the total laundry detergent composition.
• a laundry detergent composition in accordance with claim 4 wherein said composition is a granular solid and said disazo dyestuff is present in an amount of up to about 0.003 per cent by weight based upon the weight of the total laundry detergent composition.
• a laundry detergent in accordance with claim 4, comprising from an effective amount up to 0.005 percent by weight of disazo dyestuff, from about 5 to 95 percent by weight of organic surface active compound and from about 1 to 20 parts of builder per part of organic surface active compound said dyestuff being selected from the group consisting of compounds having the formula sO S and the metal complexes thereof, and wherein each of R, R,, R,, R R and R is selected from the group consisting of hydrogen, halogen, hydroxyl, lower alkoxy and lower alkyl groups; M is alkali or alkaline earth metal and A is NH, NH-CO'NH or NH-aryl-NH.

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
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• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Detergent Compositions (AREA)

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Cited By (23)

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• 1971
  • 1971-03-15 US US00124510A patent/US3762859A/en not_active Expired - Lifetime
• 1972
  • 1972-03-01 ZA ZA721375A patent/ZA721375B/xx unknown
  • 1972-03-02 CA CA136,085A patent/CA1002259A/en not_active Expired
  • 1972-03-03 AU AU39597/72A patent/AU464839B2/en not_active Expired
  • 1972-03-07 DE DE19722210811 patent/DE2210811A1/de active Pending
  • 1972-03-08 GB GB1083272A patent/GB1384907A/en not_active Expired
  • 1972-03-09 SE SE7202972-1A patent/SE396780B/xx unknown
  • 1972-03-10 CH CH359872A patent/CH610608A5/xx not_active IP Right Cessation
  • 1972-03-10 FR FR7208370A patent/FR2130149B1/fr not_active Expired
  • 1972-03-13 AT AT207972A patent/AT318781B/de not_active IP Right Cessation
  • 1972-03-13 IT IT48950/72A patent/IT952228B/it active
  • 1972-03-14 BE BE780639A patent/BE780639A/fr unknown
  • 1972-03-15 NL NL7203456A patent/NL7203456A/xx unknown

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