Classifications

• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q11/00—Preparations for care of the teeth, of the oral cavity or of dentures; Dentifrices, e.g. toothpastes; Mouth rinses
  • A61Q11/02—Preparations for deodorising, bleaching or disinfecting dentures
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/19—Cosmetics or similar toiletry preparations characterised by the composition containing inorganic ingredients
  • A61K8/22—Peroxides; Oxygen; Ozone
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
  • A61K8/00—Cosmetics or similar toiletry preparations
  • A61K8/18—Cosmetics or similar toiletry preparations characterised by the composition
  • A61K8/30—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds
  • A61K8/40—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing nitrogen
  • A61K8/41—Amines
  • A61K8/416—Quaternary ammonium compounds
• • A—HUMAN NECESSITIES
  • A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
  • A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
  • A61Q5/00—Preparations for care of the hair
  • A61Q5/08—Preparations for bleaching the hair
• • 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
  • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3945—Organic per-compounds

Definitions

• Chlorine-free as used herein means free of chlorine atoms which yield an active chlorine species in aqueous solution.
• An active chlorine species is either chloride or hypochlorite ion.
• chlorine substituents such as those on an aromatic ring which do not yield chloride or hypochlorite ions in aqueous solution may be present.
• compositions may also be used for cleaning sinks or dentures and .for restoring natural coloring to hair after use of artificial hair coloring.
• these compositions are in the form of a concentrated product which can be added to water for actual use at both high and low bleaching temperatures.
• the invention employs a combination of a peroxygen bleaching compound; a quaternary ammonium salt as a micelle catalyst and fabric softener and a buffering compound to maintain the bleaching solution at a proper pH. While acting as micelle catalysts for the bleaching reaction, the quaternary ammonium salts retain their fabric softening capabilities.
• a commonly encountered household bleach is in the form of a liquid solution employing a hypochlorite species as the bleaching active.
• hypochlorite species as the bleaching active.
• Such compounds are effective stain-removing bleaches when used in relatively high concentrations, but these hypochlorite or active chlorine bleaches also cause rather severe damage to fabric colors and can, in addition, damage textile fibers with repeated use.
• Liquid bleaches of this type also present handling and packaging problems.
• Potassium dichloroisocyanurate for example, is a dry bleach but that compound again yields an active chlorine species in bleaching solution. As with other chlorine bleaches, higher concentrations of this substance will cause undesirable color damage.
• Chlorine-free bleaches reduce color damage but have additional shortcomings.
• a common solid peroxygen bleach, potassium monopersulfate is relatively safe for colored fabrics but is not comparable to active chlorine bleaches in stain removal.
• Solid quaternary ammonium peroxysulfate bleaches such as those disclosed in Diamond of al., U.S. 3,475,493, Oct. 28, 1969, while slightly more effective than potassium monopersulfate, have solubility limitations.
• compositions consist essentially of:
• peroxy bleaching agent selected from the group consisting of sodium or potassium monopersulfate; organic peroxy acids (or watersoluble salts thereof) of the general formula 0 HO-O-(l-R-YN wherein R is a substitutedor unsubstituted alkylene or arylene group and Y is or any other group which in water yields an anionic group and mixtures thereof;
• R is an alkyl group containing from about 12 to 20 carbon atoms
• R is selected from the group con sisting of alkyl groups containing about 1 to 14 carbon atoms, cycloalkyl groups containing about to 8 carbon atoms, carboxymethyl groups, aryl groups containing from 6 to 8 carbon atoms, alkaryl groups containing from 7 to carbon atoms, pyridyl and groups of the general formula (C H O) (C H O) H wherein a and b are integers and a-l-b is l to 50; R R and R are each selected from the group consisting of alkyl groups containing about I to 3 carbon atoms, cycloalkyl groups containing about 5 to 8 carbon atoms, carboxymethyl groups, aryl groups containing from 6 to 8 carbon atoms, a karyl groups containing from about 7 to 10 carbon atoms, pyridyl
• compositions are dissolved in water to provide fabric softening and catalyzed bleaching of both colored and white fabrics.
• aqueous solutions may also be used as hard surface or denture cleaners and as agents for restoring natural color to artificially colored hair.
• R is again an alkylene or arylene group.
• a micelle is a highly charged colloidal aggregate. It is believed that such positively charged aggregates serve as rallying points for the S0 and HSO anions and their organic peroxyacid counterparts, thereby facilitating formation of the indispensible transition complex of r the bleaching reaction.
• Quaternary ammonium salts are (1) Bleaching agents.-The principal bleaching actives in the instant compositions are sodium or potassium monopersulfate (NaHSO and KHSO and the organic monoand diperoxyacids (or water-soluble salts thereof) having respectively the following formulas:
• Monoperoxy acid and a Ho-o-h-rt-h-O-mn- Diperoxy acid wherein R can be alkylene or arylene and Y can be any group which yields an anionic moiety in solution such as H II Potassium monopersulfate is available commercially from the E. I. Du Pont de Nemours and Company under the trade name Oxone. It contains approximately 42.8% by weight KHSO the balance being KHSO and K in about equal proportions.
• the organic peroxyacids or salts thereof of the invenvention can contain either one or two peroxy groups and can be either aliphatic or aromatic.
• the alkylene linkage between the anionic groups can contain halogen or other non-interferring groups.
• the unsubstituted acid has the general formula for example.
• YH groupings can be in any relative posit'on around the aromatic ring.
• the ring can contain any non-interferring substituent such as halogen groups.
• suitable aromatic peroxy acids include monoperoxyphthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid and the monosodium salt of diperoxyterephthalic acid.
• the preferred aromatic pe oxyacids are the monoand diperoxyisophthalic acids.
• the bleaching compositions can contain from about 8% to about 60% by weight of the bleaching agent.
• the preferred monopersulfate weight range is from about 25% to about 30% by weight.
• a preferred organic peroxyacid weight range is from about 16% to about 35% by weight. Mixtures of the monopersulfate compounds and the peroxyacids can be employed in the instant invention.
• bleaching compositions are, of course, dissolved in aqueous solutions for actual use on fabrics, sinks, dentures or hair.
• the bleaching composition is added in quantities suflicient to yield from about to 80 ppm. available oxygen in solution from either the persulfate or organic peroxyacid bleach actives.
• the above bleaching actives when employed in the catalyzed compositions of the present invention provide effective bleaching at all practical bleaching solution temperatures and bleach effectively after a very short contact time with the material to be bleached. As noted, color and fabric damage is minimal.
• Quaternary ammonium compounds-Quaternary ammonium compounds useful herein have the general formulas wherein R is an alkyl group containing from about 12 to 20 carbon atoms, R is an alkyl group of about 1 to 14 carbon atoms, a cycloalkyl group of about 5 to 8 carbon atoms, a carboxymethyl group, a 6 to 8 carbon aryl group, an alkaryl group of 7 to carbon atoms, a pyridyl group, or a group of the general formula wherein a and b are integers and a+b is 1 to 50; R R and R are either alkyl groups of about 1 to 3 carbon atoms, cycloalkyl groups of about 5 to 8 carbon atoms, carboxymethyl groups, 6 to 8 carbon aryl groups, alkaryl 1 groups of 7 to 10 carbon atoms, pyridyl groups, or
• R falls within the definition of the R R or R groups or is H;
• R- is either a 1 to 3 carbon atom alkylene group, a 5 to 8 carbon arylene group or a group of the formula -CH CH --OCH -CH X is any noninterfering, water-soluble salt forming anion such as fluoride, nitrate, sulfate, methylsulfate, hydrogen phosphate, dihydrogen phosphate, carbonate, chlorate or hydroxide and n is 1 when X is a monovalent anion and 2 when X is a divalent anion.
• a noninterfering anion is one which does not render the quaternary ammonium compound insoluble or does not yield species in solution which interfere with the bleaching, softening, color-damage, or catalysis properties of the dissolved compositions.
• Bromide for example, is an interfering anion since bromide in solution with some peroxygen bleaches can cause severe color damage to fabrics.
• quaternary ammonium compounds employable in the compositions include tetradecyltrirnethylammonium methylsulfate; tetradecyltrimethylammonium nitrate; [C H N( (CH CO cetyltrimethylammonium chlorate; cetyltrimethylammonium hydroxide; octadecyltrimethylammonium dihydrogzn phosphate; octadecyltrimethylammonium fluoride; octadecyltrimethylammonium nitrate;
• Preferred quaternary ammonium compounds are C 6, C and C alkyltrimethylammonium nitrates.
• the compositions contain from about 10% to about 60% by weight of the quaternary ammonium component.
• the quaternary ammonium constituent serves two purposes in the instant compositions. These surface active compounds form the micelles for catalysis of the peroxygen bleaching, and in addition they impart fabric softening characteristics to the bleaching solutiozs. In solutions prepared from the compositions of this invention, the quaternary ammonium salt concentration should range from about 100 ppm. to about 500 ppm.
• quaternary ammonium compounds of the type herein employed function as fabric softeners. They have heretofore been utilized alone in laundry rinse water since they are incompatible with anionic detergents. It has been discovered, however, that these compounds are compatible with the bianionic, complex-forming bleach agents of the present invention and, in fact, act as micelle catalysts while retaining their fabric softening properties.
• a preferred embodiment of the invention is a dry composition which contains about 2% to about 30% by weight of an 18 to 20 carbon chain quaternary ammonium salt and about 8% to 30% by weight of 14 to 18 carbon chain quaternary ammonium salts.
• aqueous solution prepared from this preferred composition there should be from about 20 ppm. to about ppm. of the C1g 2g quaternary ammonium salt to provide softening capability.
• a preferred bleaching process employing these compositions utilizes both C alkyl trimethylammonium and C or C trimethylammonium compounds in a C /C weight ratio of 1:4 in solution.
• Buffering agent.--It has been discovered that micelle catalysis and formation of the bianionic complexes discussed above are greatly facilitated by maintenance of the bleaching solution at a carefully controlled pH.
• the pH of the solution at which the concentration of the SO and H80; anions are equal (the pK,,) occurs at a pH of 9.2.
• the pK of the organic peroxyacid system is from a pH of 7 to 8. Consequently the best belaching performance occurs when the pH of the bleaching solution is 7 8 maintained between about 7 and about 10. Outside this dischloroisocyanurate.
• Composition No. 13 contains pH range, bleaching performance diminishes markedly. monopersulfate with a chloride salt as suggested by To maintain this controlled pH in solution, any non- Lake, US. 3,098,546, Aug. 7, 1962.
• composition number 1 2 3 4 5 6 7 8 9 10 11 12 13 Com onent, weight percent:
• compositions 2, 3, 4, 6 and 9 the bufferin a sodium hydrogen phosphate and sodium hydrogen phosphate in a Nag-HPO. to NaI'IQPO-I ratio of a proximately 5.1.
• g gent is a mixture of (11 interfering compound which can alter and maintain pH 20
• Some of these compositions are employed in a Bleaching such as any standard buffering agent or combination is Performance Test.
• the Bleaching Performan T employed. For example, phosphates, carbonates or bicaranalyzes bleaching performance of the various com osibonates which buffer within the 7-10 range are useful. tions of Table I.
• a Tergotometer (United States T ti Examples of suitable buffering agents include sodium Company) operated at a constant agitation rate f 5 bicarbonate, sodium carbonate, disodium hydrogen phos- 25 c.p.m. is used for all experiments. Unless otherwise Stated phate and sodium dihydrogen phosphate. Sodium carbonruns are made at 120 F. for 10 minute Swatches ate is the preferred buffering agent for monopersulfate graded before and after bleaching on a Hunter color difsystems. Disodium hydrogen phosphate and sodium dihyferenc meter. An initial and final whiteness grade was drogen phosphate are preferred for peroxy acid systems.
• Formulation therefore, of dry compositions is simply acre outlined m the followmg summary complished by thoroughly mixing the granular or pow- Grass stain dered components together in the appropriate weight percentage concentrations. It would be possible to provide a 200 of freshly Cut untreated g ss i mixed with 1000 bleaching solution containing the components of this presof 5 gn/gadhardness Water in a Waring blender unent invention by adding such components to the bleaching a Inform Slurry 15 produced s Slurry is strained solution in liquid form.
• tions of the present invention do not cause running of teX- The Solutlon filtered through cotton Cloth and liquor tile colors or undesirable color transfer.
• the fast-acting 6 made up to gallon f hot Water- Q Square yards low temperature bleaching acitvity of the dissolved corn- 0 of cotton. are.lmmersed.
• the Cloth hfted out of the q and tra sferred to The following test serves to illustrate the bleaching per- 3 P gr-/galwatef (PI-1 at F.
• compositions of the instant to rmset is done t Atlas electric padder. invention.
• Table 1 provides 13 concentrated bleaching The cloth trotted, to fix the Stall! and allowed o age for compositions by component weight percentages.
• Composithree days at tion Nos. 1, 2, 3, 4, 5, 6 and 7 are representative examples of compositions of the instant invention.
• Composition No. 8 contains potassium monopersulfate with no bleach- Gravy A one ounce package of Durkees brown gravy mix is ing catalyst.
• Composition No. 9 contains monoperoxymixed with 1 cup of water and brought to a boil with phthalic acid with no bleaching catalyst. Composition stirring. The mixture is removed from the heat and stirred No.
• Composition 10 is a dihydrogenated tallow ammonium monoperwith a high-shear homogenizer for 5 minutes.
• Composition No. 11 is a typical gravy solution is then placed in a container and the cloth liquid household hypochlorite formulation.
• Composition No. 12 is a typical dry, active-chlorine bleach, potassium is run through the solution and padded. The stained cloth 75 is then dried in an oven. Two applications are given.
• bleaching agent selected from the group consisting of (1) sodium monopersulfate,
• Potassium monopersulfate (p.8.m. av. 0g) Diperazelaie acid (p.p.m. av. 2) Monoperoxyphthalie acid (p.p.m. av. 0
• compositions of the instant invention provide stain removal superior to the other prior art compositions at comparable strength in solution and superior to compositions not containing all of the essential components of the instant invention.
• Preferred composition No. l performs at a very low strength about as well as a comparably concentrated NaOCl bleaching solution (#11).
• Compositions of the instant invention provide their stain removal results with significantly less color damage than the active chlorine bleaches. 7
• compositions of Table I not appearing in Table II are dissolved in water at comparable concentrations, they provide stain removal substantially equivalent to Compositions l, 2, 3 and 4.
• the potassium monopersulfate of Composition 1 is replaced with sodium monopersulfate in equivalent concentration and substantially similar stain removal results are secured.
• diperazelaic acid of Composition 2 is replaced with an equivalent concentration of monoperazelaic acid to provide substantially similar stain removal performance.
• diperoxyisophthalic acid of Composition 3 is replaced with an equivalent concentration of diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt of diperoxyterephthalic acid or a monoeroxy compound of the general formula RCH-( )OOX QsY I wherein R is an alkyl group of from about 8 to about 18 carbon atoms and wherein X and Y are each se ected from the group of cations consisting of hydrogen, sodium, potassium, ammonium and substituted ammonium cations; and substantially similar stain removal results are secured.
• composition 1 When the quaternary ammonium component of Composition 1 is replaced with a mixture containing 3% by weight of the total composition of an eicosyltrimethylammonium compound and 11% of a cetyltrimethylammonium compound, the resulting composition provides substantially similar stain removal performance and is an especially useful fabric softening composition.
• a dry bleach composition consisting essentially of:
• R is an alkyl group containing from about 12 to about 20 carbon atoms
• R is selected from the group consisting of alkyl groups containing from about 1 to 14 carbon atoms, cycloalkyl groups containing from about 5 to 8 carbon atoms, carboxymethyl groups, aryl groups containing from about 6 to 8 carbon atoms, alkaryl groups containing from about 7 to 10 carbon atoms, pyridyl, and groups of the general formula -(C H O),,(C H O) H wherein a and b are integers and a+b is l to 50; R R and R are each selected from the group consisting of alkyl groups containing from about 1 to 3 carbon atoms, aryl groups containing from about 6 to
• (C) from 10% to about 75% by weight of a buffering agent effective to maintain a solution pH of from about 7 to about 10 when said composition is dissolved in water for bleaching; said composition being free of any compound which yields an active chlorine species in aqueous solution.
• a composition in accordance with claim 1 wherein the bleaching agent is potassium monopersulfate.
• composition in accordance with claim 1 wherein the bleaching agent is selected from the group consisting of monoperazelaic acid and diperazelaic acid.
• a composition in accordance with claim 1 wherein the quaternary ammonium compound is a mixture containing from about 2% to about 10% by weight of the total composition of an eicosyltrimethylammonium compound and about 8% to about 30% by weight of the total composition of a cetyltrimethylammonium compound.
• a composition in accordance with claim 4 wherein the bleaching agent is selected from the group consisting of diperazelaic acid, diperoxyisophthalic acid, diperoxyterephthalic acid, 4-chlorodiperoxyphthalic acid, the monosodium salt of diperoxyterephthalic acid and a monoperoxy compound of the general formula RCH( -OO-X SOQYI wherein R is an alkyl group of from about 8 to about 18 carbon atoms and wherein X and Y are each selected from the group of cations consisting of hydrogen, sodium, potassium, ammonium and substituted ammonium cations.
• a method for bleaching fabrics comprising contactn ing said fabrics with an aqueous solution consisting essentially of:
• a peroxygen bleach selected from the group consisting of (1) sodium monopersulfate,
• an organic peroxyacid or water-soluble salt thereof said peroxyacid having the general formula wherein R is selected from the group consisting of alkylene groups containing from 1 to about 16 carbon atoms and arylene groups containing from 6 to about 8 carbon atoms and Y is a group providing an anionic moiety in aqueous solution, and
• R is an alkyl group containing from 12 to about 20 carbon atoms
• R is selected from the group consisting of alkyl groups containing from about 1 to 14 carbon atoms, cycloalkyl groups containing from about 5 to 8 carbon atoms, carboxymethyl groups, aryl groups containing from about 6 to 8 carbon atoms, alkaryl groups containing from about 7 to 10 carbon atoms, pyridyl and groups of the general forinula (C H O) (C H O) H wherein a and b are integers and a+b is 1 to 50; R R and R are each selected from the group consisting of alkyl groups containing from about 1 to 3 carbon atoms, cycloalkyl groups containing from about 5 to 8
• the peroxygen bleaching agent is potassium monopersulfate.
• the quaternary ammonium compound is a mixture containing an eicosyltrimethylammonium compound and a cetylor octadecyltrimethylammonium compound in a respective weight ratio in said solution of 1:4.

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Cited By (16)

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• 1971
  • 1971-02-22 US US00117814A patent/US3749674A/en not_active Expired - Lifetime
• 1972
  • 1972-02-14 ES ES399764A patent/ES399764A1/es not_active Expired
  • 1972-02-17 AU AU39100/72A patent/AU456769B2/en not_active Expired
  • 1972-02-17 CA CA134,921A patent/CA972506A/en not_active Expired
  • 1972-02-21 DE DE2207979A patent/DE2207979C2/de not_active Expired
  • 1972-02-21 GB GB796372A patent/GB1378671A/en not_active Expired
  • 1972-02-21 IT IT20829/72A patent/IT959547B/it active
  • 1972-02-21 BE BE779599A patent/BE779599A/fr not_active IP Right Cessation
  • 1972-02-21 FR FR7205796A patent/FR2126256B1/fr not_active Expired
  • 1972-02-22 NL NLAANVRAGE7202293,A patent/NL177427C/xx not_active IP Right Cessation

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