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
  • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/835—Mixtures of non-ionic with cationic compounds

Definitions

• compositions comprising quaternary ammonium germicides and nonionic detergents wherein unique compatibility with respect to performance of the quaternary ammonium germicides is achieved in the presence of amounts of detergent which are at least twice the amount of germicide, by employing a nonionic detergent in which the major portion of the molecule is made up of block polymeric C to C alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and -45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks containing ethylene oxides and 045% of C to C alkylene oxide providing a significant hydrophilic function.
• compositions are detergent sanitizers con taining quaternary ammonium germicides in combination with 5 to times as much detergent.
• enhanced and extended germicidal action can be provided by employing as the nonionic detergent component a detergent-iodine complex, or by adding a PVP- iodine complex.
• Quat manufactures who acutally participated in the development of this method through industry-regulatory agency cooperation, quickly put a ceiling on the amount (ratio) of nonionic which could be used with quats.
• This ceiling universally adopted by the trade for the past ten years, places a limit of from 1.5 to 2.0 parts of nonionic to one part of quat in a detergent-sanitizer formulation.
• a minimum of 200 p.p.m. quat was, and is now, generally accepted as being the least amount of quat which can be safely recommended in a detergentsanitizer use dilution based on a conventional nonionic and germicidal (even hard water) quat.
• the present invention resides in the discovery that the expected interference of nonionic detergent with germicidal quats can be avoided, paving the way for the formulating of compositions containing both germicidal quats and nonionic detergents without the traditional limitation on the proportions of components, by selecting the detergent from a limited class of nonionic detergents in which the major portion of the molecule is made up of block polymeric C C' alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and 0-45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks containing ethylene oxide and 0-45 of C to C alkylene oxide providing a significant hydrophilic function.
• Such detergents while preferably built up from an alkylene oxide chain starting group, can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, and secondary alcohols.
• Typical detergents falling within Formula B above which may be employed in the new compositions include the following, identified in terms of the stated values for the difierent variables in the formula:
• Other examples of detergents of the general type embraced by Formula B include: Tergitol XD, Tergitol XH, and Tergitol X60 which are butoxy derivatives of propylene oxide, ethylene oxide block polymers having molecular weights within the range of about 2000-5000.
• Cationic germicide Composition Hyamine 2389 Methyl dodecylbenzyl trimethyl ammonium chloride, and methyl dodecyl xylylene bis (trimethyl) ammonium chloride.
• Emcol E607 N(lauroyl colaminoformylmethyl) pyridinium chloride.
• Hyamine 1622 Diisobutyl phenoxy ethoxy ethyl dimethylbenzyl ammonium chloride.
• Igepal CO-710 Nonyl phenol-ethylene oxide condensate with 10-11 moles of ethylene oxide.
• Igepal CO-880 Nonyl phenol-ethylene oxide condensate with about 30 moles of ethylene oxide.
• Igepal AR660 Polyoxyethylene* fatty alkyl ether 60-65% ethylene oxide Cm-Cm (3V. C14) Octyl phenol-ethylene oxide condensate with about 10 moles of ethylene oxide.
• Triton X100 from coco fatty acids x+y 5.
• Ethomid HTlS As above In the examples germicidal activity is measured by one of the following test procedures:
• Procedure B The following procedure, which involves slight modification of Procedure A:
• the test solution is prepared by appropriate dilution of a sample in water of specific hardness (page 88).
• a sterile 250 ml. erlenmeyer flask containing 99 ml. of the test solution is placed in a 20 C. constant temperature water bath, and the solution is brought to temperature.
• a 24- hour culture of S. choleraesuis ATCC No. 10708 grown in AOAC broth (page 80) is used as the test culture.
• This culture meets the AOAC requirements for phenol resistance, i.e., it is killed by a 1:90 dilution of phenol in minutes, but not in .5 minutes, and it resists a 1:100 dilution of phenol for minutes.
• the actual number of organisms (the challenge) originally subjected to the action of the test solution is determined at the same time as follows: One ml. of the test culture is added to 99 ml. of phosphate buflFer (pH 7.2) dilution water (page 87) held at 20 C. At the end of 30 seconds, 1 ml. of the culture-buffer mixture is transferred serially to 3 bottles containing 100 ml. each of phosphate buffer dilution water. The final dilution is plated in duplicute in 1 ml. and 0.1 ml. amounts in Tryptone Glucose Extract Agar, and the resultant colonies counted. The average counts per ml.
• Igepal CO-990 which shows what might be considered borderline performance at the 5/1 detergent/ quaternary ratio should be disregarded because this material contains so much ethylene oxide that it is no longer useful as a detergent.
• EXAMPLE IV Detergent-germicide solutions were prepared in 500 p.p.m. hard water using as germicide 200 p.p.m. of Tetrosan 3,4 D and varying amounts of different detergents as indicated. The resulting solutions were tested for germicidal activity by Procedure A above described using E. coli as the test organism. The comparative results, at 30 sec. and 1 min., expressed in plate count and percent, reduction in the number of organisms, for the germicide alone and the germicide plus detergent under the varied conditions are as follows:
• EXAMPLE VI A number of solutions were prepared in water of different hardness, as indicated, containing 200 p.p.m. of Hyamine 3500 and detergents in the proportions indicated; and these solutions were tested according to Procedure A above using E. coli as the test organism with the following results expressed in percent reduction in the number of organisms:
• EXAMPLE VII A number of solutions were prepared in 200 p.p.m. hard water containing 200 p.p.m. of Hyamine 3500 and 400 p.p.m. (2/1 detergent/quat ratio) of various conventional detergents and block polymer detergents, and
• Block polymer A a compound of the formula HO(C H O) (C H O) (C H O) H having a molecular weight of approximately 4000 with equal parts by weight of ethylene oxide and propylene oxide.
• Block polymer B a compound similar to the Pluronics of Formula A in which the hydrophobe y contains about 90% PO and E0 and has a molecular weight of about 2500 and the hydrophile x+x contains about 90% E0 and 10% PO and has a molecular weight of about 1700.
• Block polymer C a compound similar to Block polymer B in which both hydrophobe and hydrophile have molecular weights of about 2500.
• EXAMPLE VIII A number of solutions were prepared in water of different hardness, as indicated, containing 200 p.p.m. of Tetrosan 3, 4 D and difierent detergents of the conventional type and the block polymer type in the proportions indicated. These solutions were tested according to Procedure A above using E. coli as the test organism with the following results:
• Example IIX The procedure of Example VIII was repeated using a different quaternary ammonium compound, BTC 471, at the 200 p.p.m. level, and a number of conventional type detergents and block polymer detergents in the amounts indicated. Testing of the solutions according to Procedure A gave the following results:
• Block Polymer D is a nonionic detergent identified by Formula B(a) and Block Polymer E is identified by Formula B(g).
• block polymeric material Pluronic P65 in the foregoing examples are characteristic of block polymer detergents generally as embraced by Formulas A to E above. While there may be some variation in organism kill obtained when switching from one block polymer to another as indicated in Example II or when switching from one cationic material to another as indicated in Example III, the use of block polymer detergents permits extensive variation of the detergent/ quat ratio and of the water hardness without the severe restriction in the functioning of the germicide which is characteristic of ordinary nonionic detergents.
• quaternary ammonium compounds are characterized as having at least one long chain alkyl or aryl group of 8 to 22 carbon atoms joined to the quaternary nitrogen. Furthermore, germicidal activity which is of practical significance requires that the quaternary ammonium compound have a phenol coeflicient of at least 50, and preferably at 11 least 100, with respect to S. aureus and S. typhosa at 20 C.
• the minimum amount of the most active quaternary ammonium compound accepted as passing this test is 400 p.p.m.
• the quat level may actually have to be increased, so that as much as 500 p.p.m. of quat are necessary.
• the amount of iodine present is preferably about 1 to 2 times the amount of germicidal quat, with the optimum amount in each instance being dependent upon the relative activity 12 of the germicidal quat and the physical stability of the inherently complex formulation.
• the following example illustrates a typical detergentsanitizer composition of the present invention containing both germicidal quat and iodine.
• the HI-I is first mixed with the Pluronic.
• the other components are then added in the order listed and mixed until a uniform clear dark-brown colored solution is obtained, the entire mixing being effected at room temperature.
• This composition is a multipurpose detergent-sanitizer currently being readied for commercial distribution.
• the composition provides a good general purpose detergent-sanitizer, which passes the Use Dilution Confirmation Test AOAC. (1965 pages 82-84.
• the major germicidal activity is the rapid activity which is provided by the iodine.
• the germicidal quat fills an important role. It provides a continuing germicidal action on surfaces coated with the composition.
• a detergent sanitizer is prepared containing:
• the order of mixing is not critical.
• the HII can be first mixed with the Pluronic and the other components added, or the HII can be mixed with the PVP aqueous solution and the other components added. Either procedure leads to a similar distribution of complexed iodine between the Pluronic and the PVP.
• block polymer nonionic detergents with as few as 2 or 3 and as many as 8 blocks per molecule.
• the number of blocks appears to be immaterial, and detergents with intermediate numbers of blocks or higher numbers, as well as a greater number of alternating blocks are within the scope of the invention provided these blocks provide the essential hydrophobic and hydrophilic functions previously described.
• a germicidal detergent composition consisting essentially of a germicidal quaternary ammonium compound and a nonionic detergent in which the major portion of the molecule is made up of block polymeric C to C alkylene oxides, with alkylene oxide blocks containing C to C alkylene oxides and -45 ethylene oxide providing a significant hydrophobic function, and alkylene oxide blocks consisting of ethylene oxide and 0-45 of C to C alkylene oxide providing a significant hydrophilic function, the nonionic detergent being a member selected from the group consisting of the following formulae:
• EO and PO represent ethylene oxide and proylene oxide, respectively, y equals at least 15, (E0) equals 20-90% of the total weight of said compound and the molecular weight is within the range of about 2,000 to 15,000;
• the alkoxy group contains 1-20 carbon atoms
• EO and PO represent ethylene oxide and propylene oxide, respectively
• the weight percent of E0 is within the range of 0 to 45% in one of the blocks a, b and within the range of 60 to 100% in the other of the blocks a, b
• the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and to 100 moles in the E0 rich block;
• EO and P0 are ethylene oxide and propylene oxide, respectively, the group (PO,EO) contains 90% PO and has a molecular weight of about 2500, and the groups (EO,PO) contain about 90% E0 and have a molecular weight of about 1700, the minimum ratio of nonionic detergent to quaternary ammonium compound in said composition being not less than 2:1, and in which composition said germicidal quaternary ammonium compound has a phenol coeflicient of at least 50 with respect to S. aureus and S. typhosa at 20 C., and is further characterized by having at least one 8-22 carbon atom containing substituent selected from the group consisting of alkyl and aryl radicals which substituent is joined to the quaternary nitrogen.

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Citations (5)

• 1967
  • 1967-07-12 US US652685A patent/US3539520A/en not_active Expired - Lifetime
• 1968
  • 1968-06-28 GB GB1226985D patent/GB1226985A/en not_active Expired
  • 1968-07-08 DE DE19681767976 patent/DE1767976A1/de active Pending
  • 1968-07-10 CH CH1025468A patent/CH516639A/de not_active IP Right Cessation
  • 1968-07-12 FR FR1576016D patent/FR1576016A/fr not_active Expired
  • 1968-07-12 NL NL6809889A patent/NL6809889A/xx not_active Application Discontinuation

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