Classifications

• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/75—Amino oxides
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3723—Polyamines or polyalkyleneimines

Definitions

• This invention relates to isotropic liquid laundry detergents containing polymeric quaternary ammonium salts in combination with one or more nonionic surfactants.
• U.S. Patent 3,771,989 discloses poly­meric polyelectrolytes, useful as algicides, having the formula: where n is an integer from 4 to 40, with molecular weights ranging from 1,000 to 10,000, which are chemically desig­nated poly[oxyethylene(dimethyliminio)ethylene(dimethyl­iminio)ethylene dichloride]. As far as is presently known, compounds of this class are not known to have useful bactericidal properties nor are they known to be useful for incorporation in laundry detergents.
• U.S. Patents 3,931,319; 4,001, 432 and 4,012,446 disclose so-called "capped” polymers useful as "microbiocidal” agents, which have linear polymeric quaternary chains terminated by quaternary ammonium moieties, having the formula: where X ⁇ is halide and "n is an integer from about 2 to about 30; where R′ and R ⁇ may be either (1) a primary or secondary alkyl radical having from 1 to 20 carbon atoms, (2) hydroxy or dihydroxy derivatives of R′ and R ⁇ , (3) benzyl, or (4) benzyl containing at least one alkyl group...; where Z consists of from one to three aliphatic divalent radicals, each of which has 2 to 10 carbon atoms, each aliphatic radical containing 0 to 2 double bonds and 0 to 2 hydroxy substituents" and where "R III , R IV and R V may be either (1) primary or secondary alkyl containing from 1 to 20 carbon atoms, or (2) hydroxy­
• the compounds are said to be effective against bacteria and algae and to a lesser extend against fungi. They are also stated to be non-foaming, a property which is said to be important in anti-microbial agents used in products and processes where the generation of foam is undesirable.
• U.S. Patent 4,091,113 discloses "ran­domly terminated” capped linear quaternary ammonium poly­mers prepared in the same manner as described in U.S. Patent 4,027,020 supra .
• the quaternaries are said to be "uniquely excellent hair conditioning agents" which are "compatible in binary or tertiary systems with most of the lathering and cleansing surfactants used in hair conditioning consumer products".
• the patentee states that 40% aqueous solutions are non-irritating to the skin and that 4% aqueous solutions are non-irritating to the eyes.
• the quaternaries are described as being compatible with surfactants and emulsi­fiers of the cationic, nonionic, amine oxide, alkylol­amide, amphoteric, aminoacetic or ⁇ -aminopropionic acid and betaine or betaine salt classes.
• the compositions are exemplified in Examples 28, 29 and 30 by formulations containing the polymeric quaternary which is produced by reaction of 1,4-bis-dimethylamino-2-butene, triethan­olamine and 1,4-dichloro-2-butene in water in combination with surfactants of the cationic (AMMONYX®4, i.e.
• stearal­konium chloride -Example 30 nonionic (TERGITOL® 15-S-12, i.e. pareth-15-12 - Example 29), alkylolamide (ONYXOL® 42, i.e. stearyl diethanolamide - Example 30 and SUPER AMIDE® GR, i.e. cocoyldiethanolamide - Example 28), ampho­teric (MIRANOL® C-2M-SF, i.e. cocoamphocarboxypropionate and SANDOPAN® TFL, i.e. oleoamphopropylsulfonate - both Example 28) and anionic (MAPROFIX® 60S, i.e.
• U.S. Patent 4,333,862 discloses, as one possible cationic surfactant in liquid detergent compositions containing an anionic, a cationic and a nonionic surfactant, polyammonium salts of the formula: where R3 is C8-C20 alkyl, alkenyl or aralkyl; each R4 is C1-C4 alkyl or hydroxyalkyl; n is from 1 to 6; and m is from 1 to 3.
• polymeric linear quaternary ammonium salts of the structural types represented by those dis­closed in U.S. Patents 3,771,989; 3,931,319; 4,001,432; 4,012,446; 4,027,020 and 4,091,113 are not known to have been incorporated in laundry detergents.
• polymeric quaternary ammonium salts of those classes when formulated in an aqueous medium with one or more nonionic surfactants, provide stable, isotropic liquid laundry detergents and sanitizer compositions having good detergency and bactericidal properties, which, in addition, are moderately irritating to the eyes and practically non-irritating to the skin.
• the invention resides in stable, isotropic liquid laundry detergent and sanitizer composi­tions comprising: (A) a polymeric linear quaternary ammo­nium salt selected from the group consisting of a poly[oxy­ethylene)di-lower-alkyliminio)ethylene(di-lower-alkyliminio)-­ethylene dihalide] and a polymeric quaternary ammonium halide corresponding to formula IB hereinbelow; (B) one or more nonionic surfactants selected from the group consisting of the polyethylene glycol long chain alkyl ether, polyethylene glycol alkylphenyl ether, N-alkyl-­N,N-di-lower-alkylamine-N-oxide and alkyl polyglycoside classes; and (C) water.
• A a polymeric linear quaternary ammo­nium salt selected from the group consisting of a poly[oxy­ethylene)di-lower-alkyli
• the isotropic liquid laundry detergent and sanitizer compositions of the invention comprise: (A) a polymeric linear quaternary ammonium salt selected from the group consisting of a poly[oxy­ethylene)di-lower-alkyliminio)ethylene(di-lower-alkyl­iminio)ethylene dihalide] having the formula: where R1 is lower-alkyl having from one to four carbon atoms, a is an integer from 4 to 40, with an average value of 19, and X ⁇ is halide, and a polymeric quaternary ammonium halide having the formula: where R2 is hydroxy-lower-alkyl having from two to four carbon atoms, b is an integer from 27 to 57 and R1 and X ⁇ have the meanings given above; (B) one or more nonionic surfactants selected from the group consisting of a polyethylene glycol long chain alkyl ether having the formula: R4 OCH2CH2) c OH IIA where R4 is C
• the polymeric quaternary ammonium salts of for­mulas IA and IB used to prepare the compositions of the invention are well known classes of compounds.
• the poly­[oxyethylene)di-lower-alkyliminio)ethylene(di-lower-alkyl­iminio)ethylene dihalide] quaternaries of formula IA include, for example, poly[oxyethylene(dimethyliminio)­ethylene(dimethyliminio)ethylene dichloride] sold under the trade name BUSAN® 77 by Buckman Laboratories, Memphis, Tennessee as a 60% actives solution in water which is identified as WSCP (water soluble cationic polymer).
• the polymeric quaternary ammonium halides of for­mula IB include, for example, poly(dimethylbutenyl ammo­nium chloride) - ⁇ , ⁇ -bis triethanolammonium chloride (as named by the manufacturer) sold under the trade names ONYXSPERSE® 12S and ONAMER® M by the Onyx Chemical Company, Jersey City, New Jersey, now owned by The Stepan Company, Northfield, Illinois.
• ONYXSPERSE® and ONAMER® are aqueous solutions of the salt each containing, respec­tively, 28.5% and 29.5% actives and 12% and 1% sodium chloride respectively.
• nonionic surfactants of formulas IIA, IIB and IIC and the nonionic alkyl polyglycoside surfactants used in the practice of the present invention are well known in commerce.
• examples of the polyethylene glycol long chain alkyl ethers of formula IIA are sold under the Union Carbide (Danbury, Connecticut) trade name TERGITOL® or the Shell Chemical Company (Houston, Texas) trade name NEODOL® and are identified by the CTFA adopted name, pareth.
• Suitable members of the group for the practice of the present invention are pareth-15-5, pareth-15-7, pareth-15-9, pareth-15-12, pareth-23-7, pareth-25-5, pareth-25-7, pareth-25-9, pareth-25-12, pareth-45-7, pareth-45-11 and pareth-45-13, where the first given numbers 15, 23, 25 and 45 indicate R4 alkyl chain lengths from 11 to 15, 12 to 13, 12 to 15 and 14 to 15 carbon atoms, respectively, and the second given numbers 5, 7, 9, 11, 12 and 13 indicate the average number (c) of ethyleneoxy groups.
• polyethylene glycol alkyl phenyl ethers of formula IIB are available, for example, under the Rohm and Haas (Philadelphia, Pennsylvania) trade names TRITON® X and TRITON® N or the GAF Corporation (Wayne, New Jersey) trade names IGEPAL® CA and IGEPAL® CO and are identified by the CTFA adopted names of octoxynols and nonoxynols.
• octoxynol-7 octoxynol-10 and octoxynol-13
• R5 in formula IIB is C8 alkyl and d has an average value of 7, 10 and 13, respectively
• R5 in formula IIB is C9 alkyl, and d has an average value of 7, 8, 9 and 13, respectively.
• alkylamine oxides of formula IIC are sold under the trade name AMMONYX® by the Onyx Chemical Com­pany (Jersey City, New Jersey) and include, for example, lauramine oxide, myristylamine oxide, palmitamine oxide and stearamine oxide which are the CTFA adopted names for the compounds of formula IIC and R1 in each in­stance is methyl and the alkyl group has 12, 14, 16 and 18 carbon atoms respectively.
• nonionic alkyl polyglycoside surfactants are sold by Staley Industrial Products of the A. E. Staley Manufacturing Company (Decatur, Illinois) and include, for example, APG-23-3 which is a surfactant of the alkyl polyglycoside class having an alkyl chain derived from a C12-C13 straight chain alcohol and an average of 3 glucose units in the polyglycoside moiety.
• compositions of the invention contain from about 5.5 to about 20 weight percent of the polymeric quat­ernary ammonium salt of formulas IA and IB and from about 5 to about 50 weight percent of the nonionic surfactant, all amounts being based on total weight of the composi­tion.
• Preferred ranges are from about 5 to about 10 weight percent of the polymeric quaternary salt and from about 5 to about 17 weight percent of the nonionic surfactant, and particularly preferred amounts are about 5.5 to about 6.5 weight percent of the polymeric quaternary salt and from about 7 to about 12 weight percent of the nonionic surfactant.
• compositions may, in order to provide addi­tional benefits, optionally contain nonessential ingred­ients such as fragrances, dyes, pH adjusters such as triethylamine, brighteners, solvents such as eth­anol, and thickners.
• nonessential ingred­ients such as fragrances, dyes, pH adjusters such as triethylamine, brighteners, solvents such as eth­anol, and thickners.
• fragrances may be used in amounts up to about 0.7 weight percent
• dyes in amounts up to about 0.02 weight percent
• pH adjusters in amounts up to about 4 weight percent
• brighteners in amounts up to about 0.5 weight percent
• ethanol in amounts up to about 7 weight percent
• thickners in amounts up to about 2.0 weight percent.
• compositions are prepared by addition to water, with stirring and heating as necessary, of the nonionic surfactants(s), followed by alcohol if desired, followed by the polymeric quaternary ammonium salt, followed by the dyes, fragrances, brightners, pH adjusters or thickeners, stirring being continued at each stage to effect complete solution or homogeneous dispersion.
• compositions of the invention possess very good detergency and bactericidal properties and further­more have very low eye and skin irritancy. They are therefore particularly valuable in household sanitizing and cleaning operations where such properties are desir­able, such as in laundry detergents and hard surface cleaners.
• a number of formulations, composed as indicated in Table 1, each containing a quaternary ammonium salt and at least one nonionic surfactant were prepared using the procedure described above.
• Formulations A-K each containing a polymeric quaternary of formulas IA or IB and one or more nonionic surfactants of formulas IIA, IIB or IIC or an alkyl poly­glycoside, are formulated in accordance with the inven­tion as described above and are within the ambit of the invention, whereas formulations L-O, each containing a monomeric quaternary halide, i.e. CYNCAL® 80, and a nonionic surfactant, were prepared for comparative pur­poses and are outside the scope of the invention.
• Skin irritation scores are expressed in terms of Primary Irritation Index (P.I.I.) also in accordance with the standard FIFRA method. The lower the score thus obtained, the less irritating is the formulation.
• P.I.I. Primary Irritation Index
• formulations A, C and D prepared in accordance with the invention are markedly superior in detergency properties, as determined in both EMPA and Krefeld detergency test, to any of comparative formulations L, M and N.
• Formulations A, B and C are also shown to be equally or more effective in antimicro­bial activity to comparative formulations L, M, N and O, and Formulation A is shown to have lower eye and skin irritancy than comparative formulation N.
• the liquid laundry detergent formulations of the invention are formulated as concentrates. In use the concentrate is added to the wash water in such amounts as to provide good cleaning and sanitization. It has been found that about 1/2 cup (about 4 ounces) of concen­trate per wash load (or about 4 ounces per 16 gallons), which provides a use dilution of around 1:500, is ade­quate to achieve such purposes.

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Citations (7)

• 1988
  • 1988-04-29 EP EP19880106946 patent/EP0339120A1/de not_active Withdrawn

Patent Citations (7)

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