CA2266430A1 - Method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation - Google Patents
Method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation Download PDFInfo
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- CA2266430A1 CA2266430A1 CA002266430A CA2266430A CA2266430A1 CA 2266430 A1 CA2266430 A1 CA 2266430A1 CA 002266430 A CA002266430 A CA 002266430A CA 2266430 A CA2266430 A CA 2266430A CA 2266430 A1 CA2266430 A1 CA 2266430A1
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- deposition aid
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/37—Polymers
- C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
- C11D3/3726—Polyurethanes
-
- 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
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N25/00—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests
- A01N25/30—Biocides, pest repellants or attractants, or plant growth regulators, characterised by their forms, or by their non-active ingredients or by their methods of application, e.g. seed treatment or sequential application; Substances for reducing the noxious effect of the active ingredients to organisms other than pests characterised by the surfactants
-
- A—HUMAN NECESSITIES
- A01—AGRICULTURE; FORESTRY; ANIMAL HUSBANDRY; HUNTING; TRAPPING; FISHING
- A01N—PRESERVATION OF BODIES OF HUMANS OR ANIMALS OR PLANTS OR PARTS THEREOF; BIOCIDES, e.g. AS DISINFECTANTS, AS PESTICIDES OR AS HERBICIDES; PEST REPELLANTS OR ATTRACTANTS; PLANT GROWTH REGULATORS
- A01N31/00—Biocides, pest repellants or attractants, or plant growth regulators containing organic oxygen or sulfur compounds
- A01N31/08—Oxygen or sulfur directly attached to an aromatic ring system
- A01N31/16—Oxygen or sulfur directly attached to an aromatic ring system with two or more oxygen or sulfur atoms directly attached to the same aromatic ring system
-
- 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
- A61K8/33—Cosmetics or similar toiletry preparations characterised by the composition containing organic compounds containing oxygen
- A61K8/34—Alcohols
- A61K8/347—Phenols
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/86—Polyethers
-
- 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
- A61K8/72—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds
- A61K8/84—Cosmetics or similar toiletry preparations characterised by the composition containing organic macromolecular compounds obtained by reactions otherwise than those involving only carbon-carbon unsaturated bonds
- A61K8/87—Polyurethanes
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q17/00—Barrier preparations; Preparations brought into direct contact with the skin for affording protection against external influences, e.g. sunlight, X-rays or other harmful rays, corrosive materials, bacteria or insect stings
- A61Q17/005—Antimicrobial preparations
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61Q—SPECIFIC USE OF COSMETICS OR SIMILAR TOILETRY PREPARATIONS
- A61Q19/00—Preparations for care of the skin
- A61Q19/10—Washing or bathing preparations
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- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- General Health & Medical Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Animal Behavior & Ethology (AREA)
- Wood Science & Technology (AREA)
- Veterinary Medicine (AREA)
- Public Health (AREA)
- Engineering & Computer Science (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Birds (AREA)
- Organic Chemistry (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Epidemiology (AREA)
- Zoology (AREA)
- Environmental Sciences (AREA)
- Plant Pathology (AREA)
- Pest Control & Pesticides (AREA)
- Agronomy & Crop Science (AREA)
- Dentistry (AREA)
- Dermatology (AREA)
- Emergency Medicine (AREA)
- Toxicology (AREA)
- Agricultural Chemicals And Associated Chemicals (AREA)
- Detergent Compositions (AREA)
Abstract
A method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation. The method includes the step of blending a polymeric deposition aid composed of a mixture of liquid, hydroxyl-terminated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent and a surfactant such that the liquid cleaning formulation has at least 10 percent greater antimicrobial activity than the same formulation without the polymeric deposition aid.
Description
METHOD OF INCREASING THE ANTIMICROBIAL ACTIVITY OF AN AQUEOUS, ANTIMICROBIAL LIQUID CLEANING FORMULATION
FIELD OF THE INVENTION
The present invention relates to a method of enhal-ci,~g the antimicrobial erre-,tiicness of liquid fommulations for pe, sonal cleaning.
BACKGROUND
It is well known that certain types of sLJIrdcLdnla tend to inhibit desirable dntilll ~,bial 10 activity of some antimicrobial agents derived from phenol. E~er",~lay phenol derivative antimicrobial agents include, for example, ll idosan, phenoxyell ,anol, chloroxylenol, phenylphenol and ~phenylphenate and the like. Nonionic and cationic su, racldl)ls have been idenliried as having a particularly negative influence on antimiuobial activity. Their activity is stated to be highly dependent on the pH of the system. The effect of some of these 15 s~,ral~ta"t, may be so great as to co",F'~t~'y eliminate most measurable antimicrobial activity.
In view of this, many ~queou~, antimicrobial liquid fommulations for personal cleaning contain other su,rd-,tdnls and compounding additives that strive to minimize i"leirering with antimiuobial activity of phenol derivative antimiuobial a9ents. However, even these sulrd~ldl1ls and compounding additives may cause some reduction in the activity of phenol 20 derivative antimiuobial agents.
Accordingly, there is a need for a simple, inexpensive method of increasing the activity of ~queous, antimicrobial liquid cleaning fomlulations that contain phenol derivative antir": obial agents. This need extends to a method of inat:asing the activity of such aqueous, antimiuobial liquid cleaning formulations containing anionic surFactants and cationic 25 su,racld"~a. This need also extends to such fommulations containing predominantly non.o n sulrdc,ldllta and a""~hoteric sulrd~dl)la and/or slJIrdctdnl systems.
SUMMARY OF THE INVENTION
The pl~b'- ~,s des~ibed above are addressed by the present invention which provides 30 a method of incr~asi,)g the anffmiuobial activity of an aqueous, antimicrobial liquid cleaning ~ fommulation containing an phenol derivative antimicrobial agent and a SUI rd.. lant or su, rd~,ldl)l system. The method indudes the step of blending a polymeric deposil;on aid composed of a mixture of liquid, hydroxyi-temlinated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent, and a sul~d~,ldnl or s~lrd~.tdlll system such that the 35 liquid deaning fommulation has at least 10 percent greater antimicrobial activity than the same fommulation without the polymeric depssition aid. For example, the method of the present invention may i"~:ase the antimicrobial activity of an ~queous, antimicrobial liquid deaning W O98/17773 PCTnUS97/17701 fomlulation by at least 20 percent more than the antimicrobial activity than the same formulation without the polymeric derositiQn aid. The formulation may further include one or more conventional formulating co",pol)el1ls including, but not limited to, carriers, preservatives, hu",e~ nl~, emollients and combi.~ations thereof. Generally speaking, greater 5 antimicrobial activity may be ~ ,d~ l~ri~ed as a percent de~ase in Microbial Colony Number values as determined by tecl~ es such as, for example, R.O.D.A.C. (R~Fl'c~t~ O~yan;sn~
ne~ on And Counting) plate testing.
According to the invention, the polymeric depo iticn aid is a hydroxy temminatedurethane compound having the formula:
1 0 formula:
Il l l I
H-- (O-R')m-O-C--N--R--N--C ---n --(O--Rl)m--O--C-N--R--N--C--O--(R'--~)m ~
-- C--N--R--N--C--O--(R'--~)m --H
-n wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cycloalkylene or c~,~ls-";e"ylene radical containing from about 5 15 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, uns~lhstit~ted or s~ ~hst~uted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or dirrerenl alkylene or alkenylene radical, wherein m is an integer sel~d to provide an (~R') moiety having r" ~ ' ac~ r weight of from about 40 to about 6000, and 20 wherein n and n' are the same or dirr~ integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-tell" la~ed urethane compound having a Ill~"9~ -r weight of up to about 200,000.
Desi,dbly, m will have a value of 8 and n and n~ will have a value of 1 to 4 predominately. It is also desi, '2~ that the values of m, n and n' be co"~:hled so as to 25 provide a hydroxy-temlinated urethane compound having a ~~'s~~ weight of about 1,800.
WO 98/17773 PCT/US97/lMOl In an embodiment of the invenUon, the polymeric depo: ;~;on aid may be poly(oxy-1,2-e..,aned;yl),a-hydro~-hydroxy-, polymerv~ith 1,1'-methylene-bis-(4,isocyanatocyclohexane).
The phenol derivaUve anUmicrobial agent may be 5el~ from 2,4,4'-tnchlor~2'-hydroxy diphenyl ether ~also referred to as licbsa"), phenox~,~U,aool, chloroxylenol, 5 pheny'pl1enol and ~phenyl~henale). Desi,dbly, the phenol derivative antimicr~bial agent is 2,4,4'-trichloro-2'-hydroxy diphenyl ether.
According to the invenUon, at least one su,rat,Lanl or su,racLdnl system is combined with the other co- "ponenl5. The su, ra~ldl ll or su, ~d~,Ldnl system may be co" ,,,~osed of one or more anionic su,rdl~lanls, cationic su,ra.,~nla, non ~ n ~ sLIlrd-,Ldl~t~ and/or ar"~,hoteric 10 su,rdcla,)ls. At least one other conv~ntional fommulaffng cor",uol)enl may be combined with the polymeric deposiLion aid, phenol derivative antimiuobial agent and su,ra~,La,)L. One or more conventional formulating components may be selected from carriers, preservaUves, h--",e~;lanls, emollients and corn~:.,aLons thereof.
The present invention which provides a method of i"c;,c:asi,-y the antimicrobial activity of an aqueous, antimicrobial liquid cleaning fommulation containing an phenol derivative anUmicrobial agent and a su, rd~lanl or su, rac.lanl system.
The method of the present invention includes the step of blending a polymeric 20 dero~iL;on aid cor"posed of a mixture of liquid, hydroxyl-temlinated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent, a sulrdl,ldlll or su, rd~.ldnl system, and at least one other fommulating cor"pone, ll such that the liquid cleaning fommulation has at least 10 percent greater antimicrobial activity than the same fommulation without the polymeric deposition aid.
The polymeric deposition aid is a hydroxy temminated urethane compound having the general formula:
__ ................................................................... ..
W O 98117773 PCTrUS97/17701 ~I-- (~--~)m--O--C--N--R--N--C ---n ~(~--R~)m--O--C--N--R--N--C--O--(R~~~)m---- C--N--R--N--C--O--(R'--O) --H
wherein R is sele~t~d from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cydoalkylene or cyc'~ nylene radical containing from about 5 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 5 6 to about 10 carbon atoms, unsllhstitllt~d or s~hstitJ~ted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or difrerenl alkylene or alkenylene radical, wherein m is an integer selectad to provide an (aR') moiety having ", - 'e ~ r weight of from about 40 to about 6000, and wherein n and n~ are the same or different integers of from 0 to about 30 inclusive, cO~eld~d 10 v.~ith m so as to provide a hydroxy-terminated urethane compound having a n~'2 ~ ~r weight of up to about 200,000. Exe",,~lary polymeric depo~ilicn aids of this type are generally described in U.S. Patent No. 5,051,260, issued Se,utenlLer 24, 1991, to Chess et al.; U.S.
Patent No. 5,045,317, issued Sepler"ber 3, 1991,to Chess et al.; and U.S. Patent No.
4,97,080, issued November 20, 1990, to Chess et al.; all of which are i"c~",-,-dled herein by 15 .~:fe,~nce.
Desirably, m will have a value of 8 and n and n' will have a value of 1 to 4 predominately. It is also desirable that the values of m, n and n' be correlated so as to provide a hydroxy-terminated ~"etl,al-e compound having a n~ ~rweight of about 1,800.
An eA~..,plary polymeric deposiliQn aid is Topicare(~ Delivery Compound PP-15 20 (Polyolprepolymer-15) made by Penede m, Inc., Foster City, California. Polyolprepolymer-15 is a mixture of liquid, hydroxyl-terminated polymers in polyethylene glycol. The CAS name is POIY(OAY-1~2 Lll,anediyl),a-hydro~-hydroAy-, polymer with 1,1'-methylene-bis-(4,isocyanatocycloheAd.1e). The CTFA name is PEG-8/SMDI Copolymer.
The polymeric deposition aid should be misdble or soluble in water. Although the25 inventors should not be held to any particular theory of oper~lion, misdbility of the polymeric , 3 PCT/US97tl7701 depo~:t;on aid in water is i",po, lanl for the agueous, antimiuobial liquid cleaning fommulaUons of the present invention to function properly.
Solubility i"f~""dtion for Polyolprepolymer-15 (PP-15) provided by Penede"" Inc., is listed in Table 1.
l~tK~;tr~lT
SOLVENT SOL( BILIl Y ~% whN) Water soluble Alcohol (95%SDA 40-2) 50 Isopropyl Alcohol 50 Propylene Glycol 50 Polysorbate 20 50 Miglyol 812 insoluble Silicone (Di."ell, xne) insoluble Mineral Oil insoluble Ethoxydiglycol 50 Glycerine di~pe, aible2 1 - PP-15 shows i"~t:asing ~queQllC solubility as lel,lperalure decreases.
2 - Vvhen a level of 1.0% or less of PP-15 was added to Glycerine, tiny dl.,c'e'- were observed underthe mi~uscope.
The phenol derivative antimicrobial agent may be selected from 2,4,4'-trichloro-2'-15 hydroxy diphenyl ether (also referred to as ~,.,losan), 3,4,4'-bi~ .ocd,banilide (also referred to as llicloca,ban), phenoxyethanol, chloroxylenol, ~phenylphenol and o-phenyl\,henate).
The method of the present invention has been found to work well when the phenol derivative antimicrobial agent is 2,4,4'-trichloro-2'-hydroxy diphenyl ether. The phenol derivative antimicrobial agent is generally present in an amount ranging from about 0.1% to about 10%, 20 by weight. Desi,dbly, the phenol derivative antimicrobial agent is present in an amount ranging from about 0.1% to about 3%, by weight. More dea;,dbly, the phenol derivative antimicrobial agent is present in an amount ranging from about 0.1% to about 1%, by weight.
According to the invention, at least one su,~d-,~ant or sulrd.,l~"l system is C'411 bined with the other cor.lponents. The s~" racldl ,I may be an anionic SUI rc~ldl ll, cationic su, rd~.ldnt, 25 nonir n ~ sulrd~ and/or a",phcte.ric sl,lrdclct"l.
E~F~"~.,la~y anionic sulrdclant~ include, but are not limited to ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, alkyl sulfosu~ndl~s, alpha-sulfonated fatty acids, their salts andlor their esters, alkyl ethoxy carboxylates and mixtures thereof.
E3t~ plary a".~v~,ulenc sL"~aclanb include, but are not limited to, cowll~pllOcdlLù,~ty~ r--F ~ ~dle~ cocdlllphocdltJu,~y Pl~r~ acid, cocd"l~,ho~c~ , and cocd""~ho~ c~late. Generally speaking, cGr"")e~ally available a",~holeric slJIrduldn~ of this type are made and sold in the foml of ele~,t,uneutral complexes with, for example, hydroxide cou"terions or with anionic sulfate or sulfonate sulrdcld,~ts. Suitable ~"""e~al 10 products include, but are not limited to, produds sold under the trade names of Empigen (Albright & Wilson); Miranol (Rhone-Poulenc); Alkateric (Alkaril Chemicals); Amphole,ye (Lonza, Inc.); 1~1cndleric (Mona Industries); Rewoteric (Rewo Chemical Group); and Scher~Lc (Scher Chemicals).
The surfactant systems may be composed of a combination of s-"ra-,Lanb. For 15 e,~d",,~'s, the s~ d~,lanl systems may be composed of a mixture of one or more anionic su,rd~,lallta with nol1:on~, al"pholeric and/or betaine su,ra..tdnta. Various convenLional su, rduldl 11 systems are co" ""er~ally available and are knov,/n to those of skill in the art.
For e)~dl l Ir 'B, in an embodiment of the invention, at least one non- ., n c su, rd~_lanl andlor a",pho~ric slJIrd~,ldlll may be co",b ~ed with the other ~r",~)one,lta. Of course, a non.on;c 20 and/or a" ,photeric su, rdulanl system may be used. The SUI rd~,ldnVsul rdc.ldl ll system is desirably a non~n:~ su,raclant and/or amphoteric su,rat,ld"l that is mild to the skin and induces significantly less redness and dryness and is less disruptive to the statum comeum.
Of course, anionic and/or cationic sulrd~,ldnls may be t'snded withthe non~.1- andlor amphoteric su, rd-,ldl ,ts.
Suitable sl" rd~,lar,l systems include Miracare M~1 (available from Rhone-Poulenc) and Standd",-)x CAW (available from Henkel Corp.). Miracare MS-1 includes PEG 80 sorbitan laurate, sodium ~ide~UI sulfate, PEG 150 distearate and lau,ud,,,l)hoc!i3ce~ in a water base. SLa,-da",ox CAW includes cocd".:~Frupylamine oxide in a water base. It is contemplated that other individual sulrdc,Ld"la and/or surfactant systems noted for their 30 mildness may be used.
Other suitable s~"rauLd"l systems may include con"~onenta such as, for example, sodium cocoyl isuU,:Dnale, sodium laureth sulfate, an""onum sulfate, cocd".:iaF upyl betaine, an""on um lauryl sulfate, PEG 80 sollJitdl~ laurate, and/or sodium llideceU, sulfate.
One or more other conventional formulating c~",,oonent or co",pone"la may be 35 combined with the polymeric deposition aid, phenol derivative antimicrobial agent and s~"rd.,lant or sulta~ nl system. For example, carriers, preservatives, hulne~,ld,lts, solvents and the like may be combined with the conventional formulating co,..ponen~s.
Generally speaking, the carrier used for the formulations of the present invention is water. The carrier may indude, v;s~ity modifiers, thickeners, colorants, rldy,d"ces and/or 5 buffers and/or pH control agents. For example, an e,~L."~lary additive to the carrier is Ucare JR 400 which provides a smooth after-use feel to the skin.
Useful hurnecldnls include, for example, glycerine. H~""ecl~nb are added so the fommulation retains moisture in the skin to prevent erythema. Useful preservatives and preservative enhal-ce~ indude, for example, DMDM Hydantoin and Tetrasodium ETDA.Wlth respect to the method of the present invention, it is il"pG,lanl to be aware of the dis'i. ,~,tion between aqueo~ls, antimicrobial liquid deaning formulations used for washing and emulsion CGI ~ lposilions used to deanse, treat or condition skin.
Generally speaking, ~queous, antimicrobial liquid deaning fommulations refer to de~,yenl-based~ a~l~iba~lerial "liquid soaps" used for washing skin (e.g., hand-washing, 15 bathing, showering, or the like). The formulations are typically applied to the skin (with or without water), worked into a lather, and then rinsed off the skin with water. Ex~."plary det~.yenl-based liquid soaps of this type include Lever 2000(~) antiba~lendl liquid soap (Lever l~uU,er:,) and Dial~ a"til,aclerial liquid soap (Dial Corporation). Frequent, repe~t~d use of these fl~ueous, antimicrobial liquid deaning form~ ~'c' -ns have a tendency to cause erythema 20 and skin irritation.
In con~ dsl, emulsion co" ,positions are generally used to cleanse, treat and/or condition the skin. Such emulsion co",positions are oil-in-water emulsions used to deposit certain ingredients on the skin from the oil phase of the oil-in-water emulsion. These oil-in-water emulsions are usually in the fomm of a cream, lotion or the like. It is generally thought that 25 such oil-in-water emulsions have little or no lenclen~ to cause erythema and skin irritation and, in some cases, are actually used to treat skin irritation.
An exe,n~lary fommulation useful in prd~,ti~ng the method of the present invention may originate as a water phase, a su,rd.,lanl phase, a preservative phase and an active phase that are b'~nded together utilizing con\,enlional mixing t~-,hn:,ues to produce the fl~ueous, 30 antimicrobial liquid deaning formulation.
The water phase may be cor"posed of sterile, de;oni~ed water and may include additives such as for example Ucare JR 400.
The sulrd-,lalll phase contains one or more non:cn- or an"~h:t~Fic sulrdcldnls or slJIrd~ldnl systems. It is conte" ,plaled that the 5UI ra~tanl phase may include minor amounts of cationic or anionic sulrd~ldnb. The sultd~,tdlll phase may also contain the poly."eric depo- :~;on aid. Deai,aLly, the su,ra~.ldnl phase may contain sulra~,ldnl sysbms such as, for example, Mir~are MS-1, Stdlldalllux CAW, and the like.
The preservative phase may contain glycerine and preservatives and preservative 5 enl ,ance,a sudh as, for example, DMDM Hydantoin, Tetrasodium EDTA, and the like.
The active phase contains the phenol derivative antimicr~bial agent and may alsoindude addi ional non ~n ~ su,rd-,lanl and a r,ag,dnce. Desi~dLly, the active phase contains l,i-,bsan as the antimicrobial agent. The non ~n~ su,rd~.lanl may be Pol~sGIL.dle 40, NF, available under the trade desiynalion Tween 40 from ICI Specialty Chelll:-~ls~ Wllmington, 10 Delaware. An exen~pldry rldgl~nce is Elias Fragrance #16783 available from the Elias F~dylclnce Company.
Generally speaking, the water phase is heated to about 65~C and the su,racld,)l phase is blended into the water phase with stirring. Next, the preservative phase is blended into the mixture with sUrring and then the active phase is added last. The pH is usually adjusted to 15 between 6.5 and 7 using citric acid and the mixture is stirred thol~ughly. E~e""~la,y fommulations of an embodiment of the invention are given in Table 2.
E~e. "pla~y FormulaUons ., INGREDIENTPe.~enl CGI-~I'O~;I';GI~ rer~ CCr.~r~KjOn (Broad Range) (N- .,o.~ rRange) WATER PHASE
Deioni~ed water 20.0 to 75.0 25.0 to 35.0 Ucare JR 400 0.05 to 0.5 0.1 to 0.25 SURFACTANT
PHASE
Miracare MS~1 20.0 to 50.0 40.0 to 50.0 Standa",o~ CAW 2.0 to 10.0 4.0 to 6.0 Topicare PP-15 0.5 to 5.0 1.0 to 3.0 Amercil 357 0.0 to 1.0 0.0 to 1.0 ~tSt~VATlVF
PHASE
Glycerine 1.0to 10.0 5.0 to 10.0 DMDM Hydantoin 0.4 or as "eeded 0.4 or as neeJ~d Tetrasodium EDTA 0.1 oras .,eeJ~J 0.1 oras ne~dtJ
ACTIVE PHASE
Tridosan 0.1 to 1.0 0.5 to 1.0 Tween 40 1.0 to 5.0 1.0 to 3.0 Fldyldllce O.Oto 0.3 0.0 to 0.1 According to the invention, these aqueous, antimicrobial liquid cleaning formulations provides at least about 10 percent greater (e.g., 20 percent greater or more) antimicrobial activity than the same fomlulation without the polymeric depo~itiQn aid.
W O 98/17773 PCTrUS97/17701 EXAMPLES
Formulation The fc"~i)g t~",,~'es desuil~e ~ueous, antimiaobial liquid cleaning formulations.
Generally speaWng, the ingredients are identified by their cher.li~~' name, CFTA name, or in 5 some cases, by their trade names. The ingredients were combined by conventional mixing and/or soap formulating lechn:; es The specific amounts of ingredients for Examples 1-5 are identified in Table 3.
Percent Composiffon Example 1 Example2 Example3 Example4 Example 5 WATERPHASE
Deionized water 30.2 29.2 2~.2 27.2 25.2 Ucare JR 400 0.2 0.2 0.2 0.2 0.2 SURFACTANT
PHASE
Miracare M~1 50.0 50.0 50.0 ~0.0 50.0 Std,~dal-,ox CAW 5.0 5.0 5.0 5.0 5.0 Topicare PP-15 0.0 0.0 1.0 3.0 5.0 Amercil357 0.0 1.0 0.0 0.0 o.o l~tStK\~ATlVE
PHASE
Glycerine 10.0 10.0 10.0 10.0 10.0 DMDM Hydantoin 0.4 0.4 0.4 0.4 0.4 Tetrasodium EDTA 0.1 0.1 0.1 0.1 0.1 ACTIVEPHASE
Triclosan 1.0 1.0 1.0 1.0 1.0 Tween 40 3.0 3.0 3.0 3.0 3.0 Fl~y,dnce 0.1 0.1 0.1 0.1 0.1 The general procedure for combining the ingredients utilized convenlional tec.l~n ~LIes.
A water phase was prepared by adding polymer Ucare JR 400 to deioni~ad water at room len~perdture. Generally speaking, sufficient time was allowed for dispersion of polymer Ucare 15 JR 400 (e.g., about 10 minutes). The water phase was then heated to 65~C.
, .. ..
W O 98/17773 rCT~US97/17701 In three seps,dl- vessels the slJIrduldlll phase the preservative phase and the active phase were each pre-mixed. The su,rd.tdnl phase was pr~pa~ad by mixing Miracare MS-1 with Standd",ox CAW and Topicare PP-15. Other o~tiondl ingredients such as for example Amercil 357 were added to the sulrdcldllt phase at this point. Thus the su~ra~ t phase 5 contained the polymeric delivery aid and the su, rdulal~t.
The preservative phase was pr~pa~d by combining glycerine with DMDM Hydantoin and Tetrasodium EDTA.
The active phase was p~dl~d by combining bi~;losan with Tween 40 and a rldgldnce.
After the water phase reached a ter"per;~lure of 65~C the Sul ~dC~ phase was added 10 to the water phase with slow stirring.
The combined water phase and sulrduldllL phase was maintained at a te",perdture of 50~C while the preservative phase was added with stirring.
Next the combined water phase su,rd- Idnl phase and preservabve phase was maintained at a l~mperdlure of 40~C while the active phase with stirring.
The pH of the mixture was checked and adjusted to a pH between 6.5 and 7 with addition of small amounts of a 5% solution of citric acid. The mixture was stirred at a high stirring speed ovemight during which time it cooled to room l~:""~e,dt~lre.
Antimicrobial Activitv Aqueous antin,:~ ~bial liquid cleaning fomm~ 1S were tested to measure their antim: ~bial effeds. These anli",: ubial effects were co",,ua,~d to control formulations and conventional liquid soaps both with and without anlim ubial ingredients.
Antimicrobial effects were measured utilizing R.O.D.A.C. (Replicate O,~a";s", Detection and Counting) plates. These plates are 65 x 15 mm dishes specially desig"ed to allow a 25 raised convex surface of culture medium. Ledthin and Poly~o,bz~ 80 are inco",o,dlad in the culture medium to inactivate residual chemicals on the hands that would il"e,rar~ with growth of mi~uu,yan;_ "s in the culture dish.
The three types of culture media are: Trypticase Soy Agar (TSA) MacConkey Agar (MAC) and Sabouraud Dextrose Agar (SDA). Each media contained al,p,u,~i,,,agely 0.7 g.L
30 of ledthin and 5.0 g/L of Polysorbate 80.
The TSA media was used to grow gram positive bacteria that may be present on thethumb The MAC media was used to grow gram negative bacteria that may be present on the middle finger. The SDA media was used to grow yeast and molds that may be present on the palm of the hand.
W O 98/17773 rCTAUSg7117701 The procedure was: 1) contact the target area with the specific R.O.D.A.C. media to develop an initial count of the mi~volyan;_.,l, 2) wet and wash hands for 1 minute followed by drying with a paper towel; and 3) contact the target area with the specific R.O.D.A.C.
media to develop an after-washing count of the mi~uo.yalis,,,. The p6~nt~ge de~:ase 5 was calculated by subUacL,)g the count of step 3 from the count of step 1 and dividing that value by the count of step 1. This procedure was l~pea~d for several test pa~ ti~,a"ts and an average value was calculated.
The liquid cleaning fommulations of Example 1 and Example 3 were tested along with the f~'hJ.;ng co"""er~dlly available liquid soaps: Dial~ Antibaul~rial Soap, Lever 2000~), 10 Ope,dL"g Room Scrub, Sanifresh Soap v~ith 1.25% parachloru,,,et~l~nol (PCMX). Three non-antibacterial soaps were also tested. They were as follovus: S.~t~oap~, Sanifresh Premium, and EulubaUI~. The results are It:polled in Table 4.
r~n,enl Dec~ase in M;c.~)Lial Colony Number rer~.el~l Dec. e:ase in (gram negative l~act~.. ia Material Mic,vbial Colony Number only) Tested (all) Example 3 60 55 Example 1 0 0 Dial~Soap 40 38 Lever 2000~ 28 20 O-R Scrub 45 50 Sani-Fresh 1.25%PCMX 50 62 Sorboap~3) 0 o Sani-Fresh Premium 0 0 E~,lu~,dUI~ 0 0 The R.O.D.A.C. (Replicate O~yan;s~ll Dete_tion and Counting) plates test descliLed above (with the same data r~porLi"g procedure) was used to study the effect of adding a polymeric delivery aid to a conv~"lional liquid antiL,ac,te,ial soap fommulation. Dial~ Liquid Antibacterial soap was used as the control. The test fomlulation was Dial~ Liquid 20 A"til,a~,le,idl soap with 3%, by weight, Topicare~ Delivery Compound PP-15. The results are IY~pGI l~d in Table 5.
Material Tesbd % Kill (Bacteria) % Kill (YeasVMold) Dial~9 Soap 55 33 Dial~ Soap + 3% PP-1565 53 The R.O.D.A.C. (R~rli~-'P O,yan,~", Det~lion and Counting) plates test des~ibed above (but with a different data It:pGI ling procedure) was used to study the effect of adding a polymeric delivery aid to a aqtleo~ ~c antimicrobial liquid deaning formulation that includes mild sulrdcldllb which may decrease antimicrobial activity. The fommulation of Example 1 was used as the control. The fommulation of Example 3 containing 1.0% by weight Topicare@) 10 Delivery Compound PP-15 was used as the test. The results are ,t:po,led in Table 6. The Percent Decrease in Microbial Colony Number values ~pOI led in Table 6 were calculated as descnbed above except that negative numbers were zeroed for averaging. This gene,dl~s a greater pe~enlage de~ase for poorer perfomming fommulations that are likely to have microbial growth instead of a decrease. Average values calculated in this manner provide a 15 more conservative co"",arison of products that perfomm well (i.e. provide large de~ases in microbial growth).
Example 1 Example 3 Oly~n;~ % Dec,.~ee % D~cn,Ese gram (+) bacteria 38 50 gram (-) bacteria 18 39 yeas~l"~ ~ 16 39 The R.O.D.A.C. (ReFl[- t~ O~ganism Det~ on and Counting) plates test des~il,ed v~/as compa,-: the antimicrobial activity of ~,-" "e,~ally Lever 2000(9) Liquid Antibacterial soap with the formulation of Example 3. The results are ,epo,l~d in Table 7. The Percent De~:ase 25 in Microbial Colony Number values l~po~led in Table 7 were calculated as des~iL,ed above with the negative numbers included for averaging.
WO 98tlM73 PCT/US97/17701 Lever 2000~ Example 3 Organism % Dec.~as~ % D~C~ K
gram (~) ba-,~ria 35 50 gram (-)bacl~na 30 39 yea ,Um~'~ 34 39 As can be seen from data l~pol led in Tables 5 and 7, the present invention provides a method of inue:asillg the antimicrobial activity of conventional arltil,acl~rial soap fommulations such as, for example, Dial~ A"tiba, lerial liquid soap and Lever 2000(~ liquid soap. The improvement in the Percent De~t:ase in Microbial Colony Number by the practice of the method of the present invention may be 10% or more. For example, the improvement may be 20%. In some cases, the improvement may be 40% or even 60% or more.
The data in Tables 4 and 6 indicate the present invention provides a mild, liquid deaning fommulation that also has acce~'~hle levels of antimicrobial activity. Without the addition of the polymeric delivery aid, the mild, liquid cleaning fommulation had lower levels of antimicrobial activity. In fact, the data in Table 4 show essentially no measurable antimicrobial 15 activity for the fommulation without the polymeric delivery compound.
While the present invention has been des~ibed in connection with certain embodiments, it is to be ~"de,~lood that the subject matter encc",passed by way of the present invention is not to be limited to those specific embodiments. On the contrary, it is il,t~nded for the subject matter of the invention to include all altemaUves, modificaUons an 20 equivalents as can be included within the spirit and scope of the r~ 9 daims.
FIELD OF THE INVENTION
The present invention relates to a method of enhal-ci,~g the antimicrobial erre-,tiicness of liquid fommulations for pe, sonal cleaning.
BACKGROUND
It is well known that certain types of sLJIrdcLdnla tend to inhibit desirable dntilll ~,bial 10 activity of some antimicrobial agents derived from phenol. E~er",~lay phenol derivative antimicrobial agents include, for example, ll idosan, phenoxyell ,anol, chloroxylenol, phenylphenol and ~phenylphenate and the like. Nonionic and cationic su, racldl)ls have been idenliried as having a particularly negative influence on antimiuobial activity. Their activity is stated to be highly dependent on the pH of the system. The effect of some of these 15 s~,ral~ta"t, may be so great as to co",F'~t~'y eliminate most measurable antimicrobial activity.
In view of this, many ~queou~, antimicrobial liquid fommulations for personal cleaning contain other su,rd-,tdnls and compounding additives that strive to minimize i"leirering with antimiuobial activity of phenol derivative antimiuobial a9ents. However, even these sulrd~ldl1ls and compounding additives may cause some reduction in the activity of phenol 20 derivative antimiuobial agents.
Accordingly, there is a need for a simple, inexpensive method of increasing the activity of ~queous, antimicrobial liquid cleaning fomlulations that contain phenol derivative antir": obial agents. This need extends to a method of inat:asing the activity of such aqueous, antimiuobial liquid cleaning formulations containing anionic surFactants and cationic 25 su,racld"~a. This need also extends to such fommulations containing predominantly non.o n sulrdc,ldllta and a""~hoteric sulrd~dl)la and/or slJIrdctdnl systems.
SUMMARY OF THE INVENTION
The pl~b'- ~,s des~ibed above are addressed by the present invention which provides 30 a method of incr~asi,)g the anffmiuobial activity of an aqueous, antimicrobial liquid cleaning ~ fommulation containing an phenol derivative antimicrobial agent and a SUI rd.. lant or su, rd~,ldl)l system. The method indudes the step of blending a polymeric deposil;on aid composed of a mixture of liquid, hydroxyi-temlinated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent, and a sul~d~,ldnl or s~lrd~.tdlll system such that the 35 liquid deaning fommulation has at least 10 percent greater antimicrobial activity than the same fommulation without the polymeric depssition aid. For example, the method of the present invention may i"~:ase the antimicrobial activity of an ~queous, antimicrobial liquid deaning W O98/17773 PCTnUS97/17701 fomlulation by at least 20 percent more than the antimicrobial activity than the same formulation without the polymeric derositiQn aid. The formulation may further include one or more conventional formulating co",pol)el1ls including, but not limited to, carriers, preservatives, hu",e~ nl~, emollients and combi.~ations thereof. Generally speaking, greater 5 antimicrobial activity may be ~ ,d~ l~ri~ed as a percent de~ase in Microbial Colony Number values as determined by tecl~ es such as, for example, R.O.D.A.C. (R~Fl'c~t~ O~yan;sn~
ne~ on And Counting) plate testing.
According to the invention, the polymeric depo iticn aid is a hydroxy temminatedurethane compound having the formula:
1 0 formula:
Il l l I
H-- (O-R')m-O-C--N--R--N--C ---n --(O--Rl)m--O--C-N--R--N--C--O--(R'--~)m ~
-- C--N--R--N--C--O--(R'--~)m --H
-n wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cycloalkylene or c~,~ls-";e"ylene radical containing from about 5 15 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, uns~lhstit~ted or s~ ~hst~uted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or dirrerenl alkylene or alkenylene radical, wherein m is an integer sel~d to provide an (~R') moiety having r" ~ ' ac~ r weight of from about 40 to about 6000, and 20 wherein n and n' are the same or dirr~ integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-tell" la~ed urethane compound having a Ill~"9~ -r weight of up to about 200,000.
Desi,dbly, m will have a value of 8 and n and n~ will have a value of 1 to 4 predominately. It is also desi, '2~ that the values of m, n and n' be co"~:hled so as to 25 provide a hydroxy-temlinated urethane compound having a ~~'s~~ weight of about 1,800.
WO 98/17773 PCT/US97/lMOl In an embodiment of the invenUon, the polymeric depo: ;~;on aid may be poly(oxy-1,2-e..,aned;yl),a-hydro~-hydroxy-, polymerv~ith 1,1'-methylene-bis-(4,isocyanatocyclohexane).
The phenol derivaUve anUmicrobial agent may be 5el~ from 2,4,4'-tnchlor~2'-hydroxy diphenyl ether ~also referred to as licbsa"), phenox~,~U,aool, chloroxylenol, 5 pheny'pl1enol and ~phenyl~henale). Desi,dbly, the phenol derivative antimicr~bial agent is 2,4,4'-trichloro-2'-hydroxy diphenyl ether.
According to the invenUon, at least one su,rat,Lanl or su,racLdnl system is combined with the other co- "ponenl5. The su, ra~ldl ll or su, ~d~,Ldnl system may be co" ,,,~osed of one or more anionic su,rdl~lanls, cationic su,ra.,~nla, non ~ n ~ sLIlrd-,Ldl~t~ and/or ar"~,hoteric 10 su,rdcla,)ls. At least one other conv~ntional fommulaffng cor",uol)enl may be combined with the polymeric deposiLion aid, phenol derivative antimiuobial agent and su,ra~,La,)L. One or more conventional formulating components may be selected from carriers, preservaUves, h--",e~;lanls, emollients and corn~:.,aLons thereof.
The present invention which provides a method of i"c;,c:asi,-y the antimicrobial activity of an aqueous, antimicrobial liquid cleaning fommulation containing an phenol derivative anUmicrobial agent and a su, rd~lanl or su, rac.lanl system.
The method of the present invention includes the step of blending a polymeric 20 dero~iL;on aid cor"posed of a mixture of liquid, hydroxyl-temlinated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent, a sulrdl,ldlll or su, rd~.ldnl system, and at least one other fommulating cor"pone, ll such that the liquid cleaning fommulation has at least 10 percent greater antimicrobial activity than the same fommulation without the polymeric deposition aid.
The polymeric deposition aid is a hydroxy temminated urethane compound having the general formula:
__ ................................................................... ..
W O 98117773 PCTrUS97/17701 ~I-- (~--~)m--O--C--N--R--N--C ---n ~(~--R~)m--O--C--N--R--N--C--O--(R~~~)m---- C--N--R--N--C--O--(R'--O) --H
wherein R is sele~t~d from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cydoalkylene or cyc'~ nylene radical containing from about 5 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 5 6 to about 10 carbon atoms, unsllhstitllt~d or s~hstitJ~ted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or difrerenl alkylene or alkenylene radical, wherein m is an integer selectad to provide an (aR') moiety having ", - 'e ~ r weight of from about 40 to about 6000, and wherein n and n~ are the same or different integers of from 0 to about 30 inclusive, cO~eld~d 10 v.~ith m so as to provide a hydroxy-terminated urethane compound having a n~'2 ~ ~r weight of up to about 200,000. Exe",,~lary polymeric depo~ilicn aids of this type are generally described in U.S. Patent No. 5,051,260, issued Se,utenlLer 24, 1991, to Chess et al.; U.S.
Patent No. 5,045,317, issued Sepler"ber 3, 1991,to Chess et al.; and U.S. Patent No.
4,97,080, issued November 20, 1990, to Chess et al.; all of which are i"c~",-,-dled herein by 15 .~:fe,~nce.
Desirably, m will have a value of 8 and n and n' will have a value of 1 to 4 predominately. It is also desirable that the values of m, n and n' be correlated so as to provide a hydroxy-terminated ~"etl,al-e compound having a n~ ~rweight of about 1,800.
An eA~..,plary polymeric deposiliQn aid is Topicare(~ Delivery Compound PP-15 20 (Polyolprepolymer-15) made by Penede m, Inc., Foster City, California. Polyolprepolymer-15 is a mixture of liquid, hydroxyl-terminated polymers in polyethylene glycol. The CAS name is POIY(OAY-1~2 Lll,anediyl),a-hydro~-hydroAy-, polymer with 1,1'-methylene-bis-(4,isocyanatocycloheAd.1e). The CTFA name is PEG-8/SMDI Copolymer.
The polymeric deposition aid should be misdble or soluble in water. Although the25 inventors should not be held to any particular theory of oper~lion, misdbility of the polymeric , 3 PCT/US97tl7701 depo~:t;on aid in water is i",po, lanl for the agueous, antimiuobial liquid cleaning fommulaUons of the present invention to function properly.
Solubility i"f~""dtion for Polyolprepolymer-15 (PP-15) provided by Penede"" Inc., is listed in Table 1.
l~tK~;tr~lT
SOLVENT SOL( BILIl Y ~% whN) Water soluble Alcohol (95%SDA 40-2) 50 Isopropyl Alcohol 50 Propylene Glycol 50 Polysorbate 20 50 Miglyol 812 insoluble Silicone (Di."ell, xne) insoluble Mineral Oil insoluble Ethoxydiglycol 50 Glycerine di~pe, aible2 1 - PP-15 shows i"~t:asing ~queQllC solubility as lel,lperalure decreases.
2 - Vvhen a level of 1.0% or less of PP-15 was added to Glycerine, tiny dl.,c'e'- were observed underthe mi~uscope.
The phenol derivative antimicrobial agent may be selected from 2,4,4'-trichloro-2'-15 hydroxy diphenyl ether (also referred to as ~,.,losan), 3,4,4'-bi~ .ocd,banilide (also referred to as llicloca,ban), phenoxyethanol, chloroxylenol, ~phenylphenol and o-phenyl\,henate).
The method of the present invention has been found to work well when the phenol derivative antimicrobial agent is 2,4,4'-trichloro-2'-hydroxy diphenyl ether. The phenol derivative antimicrobial agent is generally present in an amount ranging from about 0.1% to about 10%, 20 by weight. Desi,dbly, the phenol derivative antimicrobial agent is present in an amount ranging from about 0.1% to about 3%, by weight. More dea;,dbly, the phenol derivative antimicrobial agent is present in an amount ranging from about 0.1% to about 1%, by weight.
According to the invention, at least one su,~d-,~ant or sulrd.,l~"l system is C'411 bined with the other cor.lponents. The s~" racldl ,I may be an anionic SUI rc~ldl ll, cationic su, rd~.ldnt, 25 nonir n ~ sulrd~ and/or a",phcte.ric sl,lrdclct"l.
E~F~"~.,la~y anionic sulrdclant~ include, but are not limited to ethoxylated alkyl sulfates, alkyl glyceryl ether sulfonates, methyl acyl taurates, fatty acyl glycinates, alkyl sulfosu~ndl~s, alpha-sulfonated fatty acids, their salts andlor their esters, alkyl ethoxy carboxylates and mixtures thereof.
E3t~ plary a".~v~,ulenc sL"~aclanb include, but are not limited to, cowll~pllOcdlLù,~ty~ r--F ~ ~dle~ cocdlllphocdltJu,~y Pl~r~ acid, cocd"l~,ho~c~ , and cocd""~ho~ c~late. Generally speaking, cGr"")e~ally available a",~holeric slJIrduldn~ of this type are made and sold in the foml of ele~,t,uneutral complexes with, for example, hydroxide cou"terions or with anionic sulfate or sulfonate sulrdcld,~ts. Suitable ~"""e~al 10 products include, but are not limited to, produds sold under the trade names of Empigen (Albright & Wilson); Miranol (Rhone-Poulenc); Alkateric (Alkaril Chemicals); Amphole,ye (Lonza, Inc.); 1~1cndleric (Mona Industries); Rewoteric (Rewo Chemical Group); and Scher~Lc (Scher Chemicals).
The surfactant systems may be composed of a combination of s-"ra-,Lanb. For 15 e,~d",,~'s, the s~ d~,lanl systems may be composed of a mixture of one or more anionic su,rd~,lallta with nol1:on~, al"pholeric and/or betaine su,ra..tdnta. Various convenLional su, rduldl 11 systems are co" ""er~ally available and are knov,/n to those of skill in the art.
For e)~dl l Ir 'B, in an embodiment of the invention, at least one non- ., n c su, rd~_lanl andlor a",pho~ric slJIrd~,ldlll may be co",b ~ed with the other ~r",~)one,lta. Of course, a non.on;c 20 and/or a" ,photeric su, rdulanl system may be used. The SUI rd~,ldnVsul rdc.ldl ll system is desirably a non~n:~ su,raclant and/or amphoteric su,rat,ld"l that is mild to the skin and induces significantly less redness and dryness and is less disruptive to the statum comeum.
Of course, anionic and/or cationic sulrd~,ldnls may be t'snded withthe non~.1- andlor amphoteric su, rd-,ldl ,ts.
Suitable sl" rd~,lar,l systems include Miracare M~1 (available from Rhone-Poulenc) and Standd",-)x CAW (available from Henkel Corp.). Miracare MS-1 includes PEG 80 sorbitan laurate, sodium ~ide~UI sulfate, PEG 150 distearate and lau,ud,,,l)hoc!i3ce~ in a water base. SLa,-da",ox CAW includes cocd".:~Frupylamine oxide in a water base. It is contemplated that other individual sulrdc,Ld"la and/or surfactant systems noted for their 30 mildness may be used.
Other suitable s~"rauLd"l systems may include con"~onenta such as, for example, sodium cocoyl isuU,:Dnale, sodium laureth sulfate, an""onum sulfate, cocd".:iaF upyl betaine, an""on um lauryl sulfate, PEG 80 sollJitdl~ laurate, and/or sodium llideceU, sulfate.
One or more other conventional formulating c~",,oonent or co",pone"la may be 35 combined with the polymeric deposition aid, phenol derivative antimicrobial agent and s~"rd.,lant or sulta~ nl system. For example, carriers, preservatives, hulne~,ld,lts, solvents and the like may be combined with the conventional formulating co,..ponen~s.
Generally speaking, the carrier used for the formulations of the present invention is water. The carrier may indude, v;s~ity modifiers, thickeners, colorants, rldy,d"ces and/or 5 buffers and/or pH control agents. For example, an e,~L."~lary additive to the carrier is Ucare JR 400 which provides a smooth after-use feel to the skin.
Useful hurnecldnls include, for example, glycerine. H~""ecl~nb are added so the fommulation retains moisture in the skin to prevent erythema. Useful preservatives and preservative enhal-ce~ indude, for example, DMDM Hydantoin and Tetrasodium ETDA.Wlth respect to the method of the present invention, it is il"pG,lanl to be aware of the dis'i. ,~,tion between aqueo~ls, antimicrobial liquid deaning formulations used for washing and emulsion CGI ~ lposilions used to deanse, treat or condition skin.
Generally speaking, ~queous, antimicrobial liquid deaning fommulations refer to de~,yenl-based~ a~l~iba~lerial "liquid soaps" used for washing skin (e.g., hand-washing, 15 bathing, showering, or the like). The formulations are typically applied to the skin (with or without water), worked into a lather, and then rinsed off the skin with water. Ex~."plary det~.yenl-based liquid soaps of this type include Lever 2000(~) antiba~lendl liquid soap (Lever l~uU,er:,) and Dial~ a"til,aclerial liquid soap (Dial Corporation). Frequent, repe~t~d use of these fl~ueous, antimicrobial liquid deaning form~ ~'c' -ns have a tendency to cause erythema 20 and skin irritation.
In con~ dsl, emulsion co" ,positions are generally used to cleanse, treat and/or condition the skin. Such emulsion co",positions are oil-in-water emulsions used to deposit certain ingredients on the skin from the oil phase of the oil-in-water emulsion. These oil-in-water emulsions are usually in the fomm of a cream, lotion or the like. It is generally thought that 25 such oil-in-water emulsions have little or no lenclen~ to cause erythema and skin irritation and, in some cases, are actually used to treat skin irritation.
An exe,n~lary fommulation useful in prd~,ti~ng the method of the present invention may originate as a water phase, a su,rd.,lanl phase, a preservative phase and an active phase that are b'~nded together utilizing con\,enlional mixing t~-,hn:,ues to produce the fl~ueous, 30 antimicrobial liquid deaning formulation.
The water phase may be cor"posed of sterile, de;oni~ed water and may include additives such as for example Ucare JR 400.
The sulrd-,lalll phase contains one or more non:cn- or an"~h:t~Fic sulrdcldnls or slJIrd~ldnl systems. It is conte" ,plaled that the 5UI ra~tanl phase may include minor amounts of cationic or anionic sulrd~ldnb. The sultd~,tdlll phase may also contain the poly."eric depo- :~;on aid. Deai,aLly, the su,ra~.ldnl phase may contain sulra~,ldnl sysbms such as, for example, Mir~are MS-1, Stdlldalllux CAW, and the like.
The preservative phase may contain glycerine and preservatives and preservative 5 enl ,ance,a sudh as, for example, DMDM Hydantoin, Tetrasodium EDTA, and the like.
The active phase contains the phenol derivative antimicr~bial agent and may alsoindude addi ional non ~n ~ su,rd-,lanl and a r,ag,dnce. Desi~dLly, the active phase contains l,i-,bsan as the antimicrobial agent. The non ~n~ su,rd~.lanl may be Pol~sGIL.dle 40, NF, available under the trade desiynalion Tween 40 from ICI Specialty Chelll:-~ls~ Wllmington, 10 Delaware. An exen~pldry rldgl~nce is Elias Fragrance #16783 available from the Elias F~dylclnce Company.
Generally speaking, the water phase is heated to about 65~C and the su,racld,)l phase is blended into the water phase with stirring. Next, the preservative phase is blended into the mixture with sUrring and then the active phase is added last. The pH is usually adjusted to 15 between 6.5 and 7 using citric acid and the mixture is stirred thol~ughly. E~e""~la,y fommulations of an embodiment of the invention are given in Table 2.
E~e. "pla~y FormulaUons ., INGREDIENTPe.~enl CGI-~I'O~;I';GI~ rer~ CCr.~r~KjOn (Broad Range) (N- .,o.~ rRange) WATER PHASE
Deioni~ed water 20.0 to 75.0 25.0 to 35.0 Ucare JR 400 0.05 to 0.5 0.1 to 0.25 SURFACTANT
PHASE
Miracare MS~1 20.0 to 50.0 40.0 to 50.0 Standa",o~ CAW 2.0 to 10.0 4.0 to 6.0 Topicare PP-15 0.5 to 5.0 1.0 to 3.0 Amercil 357 0.0 to 1.0 0.0 to 1.0 ~tSt~VATlVF
PHASE
Glycerine 1.0to 10.0 5.0 to 10.0 DMDM Hydantoin 0.4 or as "eeded 0.4 or as neeJ~d Tetrasodium EDTA 0.1 oras .,eeJ~J 0.1 oras ne~dtJ
ACTIVE PHASE
Tridosan 0.1 to 1.0 0.5 to 1.0 Tween 40 1.0 to 5.0 1.0 to 3.0 Fldyldllce O.Oto 0.3 0.0 to 0.1 According to the invention, these aqueous, antimicrobial liquid cleaning formulations provides at least about 10 percent greater (e.g., 20 percent greater or more) antimicrobial activity than the same fomlulation without the polymeric depo~itiQn aid.
W O 98/17773 PCTrUS97/17701 EXAMPLES
Formulation The fc"~i)g t~",,~'es desuil~e ~ueous, antimiaobial liquid cleaning formulations.
Generally speaWng, the ingredients are identified by their cher.li~~' name, CFTA name, or in 5 some cases, by their trade names. The ingredients were combined by conventional mixing and/or soap formulating lechn:; es The specific amounts of ingredients for Examples 1-5 are identified in Table 3.
Percent Composiffon Example 1 Example2 Example3 Example4 Example 5 WATERPHASE
Deionized water 30.2 29.2 2~.2 27.2 25.2 Ucare JR 400 0.2 0.2 0.2 0.2 0.2 SURFACTANT
PHASE
Miracare M~1 50.0 50.0 50.0 ~0.0 50.0 Std,~dal-,ox CAW 5.0 5.0 5.0 5.0 5.0 Topicare PP-15 0.0 0.0 1.0 3.0 5.0 Amercil357 0.0 1.0 0.0 0.0 o.o l~tStK\~ATlVE
PHASE
Glycerine 10.0 10.0 10.0 10.0 10.0 DMDM Hydantoin 0.4 0.4 0.4 0.4 0.4 Tetrasodium EDTA 0.1 0.1 0.1 0.1 0.1 ACTIVEPHASE
Triclosan 1.0 1.0 1.0 1.0 1.0 Tween 40 3.0 3.0 3.0 3.0 3.0 Fl~y,dnce 0.1 0.1 0.1 0.1 0.1 The general procedure for combining the ingredients utilized convenlional tec.l~n ~LIes.
A water phase was prepared by adding polymer Ucare JR 400 to deioni~ad water at room len~perdture. Generally speaking, sufficient time was allowed for dispersion of polymer Ucare 15 JR 400 (e.g., about 10 minutes). The water phase was then heated to 65~C.
, .. ..
W O 98/17773 rCT~US97/17701 In three seps,dl- vessels the slJIrduldlll phase the preservative phase and the active phase were each pre-mixed. The su,rd.tdnl phase was pr~pa~ad by mixing Miracare MS-1 with Standd",ox CAW and Topicare PP-15. Other o~tiondl ingredients such as for example Amercil 357 were added to the sulrdcldllt phase at this point. Thus the su~ra~ t phase 5 contained the polymeric delivery aid and the su, rdulal~t.
The preservative phase was pr~pa~d by combining glycerine with DMDM Hydantoin and Tetrasodium EDTA.
The active phase was p~dl~d by combining bi~;losan with Tween 40 and a rldgldnce.
After the water phase reached a ter"per;~lure of 65~C the Sul ~dC~ phase was added 10 to the water phase with slow stirring.
The combined water phase and sulrduldllL phase was maintained at a te",perdture of 50~C while the preservative phase was added with stirring.
Next the combined water phase su,rd- Idnl phase and preservabve phase was maintained at a l~mperdlure of 40~C while the active phase with stirring.
The pH of the mixture was checked and adjusted to a pH between 6.5 and 7 with addition of small amounts of a 5% solution of citric acid. The mixture was stirred at a high stirring speed ovemight during which time it cooled to room l~:""~e,dt~lre.
Antimicrobial Activitv Aqueous antin,:~ ~bial liquid cleaning fomm~ 1S were tested to measure their antim: ~bial effeds. These anli",: ubial effects were co",,ua,~d to control formulations and conventional liquid soaps both with and without anlim ubial ingredients.
Antimicrobial effects were measured utilizing R.O.D.A.C. (Replicate O,~a";s", Detection and Counting) plates. These plates are 65 x 15 mm dishes specially desig"ed to allow a 25 raised convex surface of culture medium. Ledthin and Poly~o,bz~ 80 are inco",o,dlad in the culture medium to inactivate residual chemicals on the hands that would il"e,rar~ with growth of mi~uu,yan;_ "s in the culture dish.
The three types of culture media are: Trypticase Soy Agar (TSA) MacConkey Agar (MAC) and Sabouraud Dextrose Agar (SDA). Each media contained al,p,u,~i,,,agely 0.7 g.L
30 of ledthin and 5.0 g/L of Polysorbate 80.
The TSA media was used to grow gram positive bacteria that may be present on thethumb The MAC media was used to grow gram negative bacteria that may be present on the middle finger. The SDA media was used to grow yeast and molds that may be present on the palm of the hand.
W O 98/17773 rCTAUSg7117701 The procedure was: 1) contact the target area with the specific R.O.D.A.C. media to develop an initial count of the mi~volyan;_.,l, 2) wet and wash hands for 1 minute followed by drying with a paper towel; and 3) contact the target area with the specific R.O.D.A.C.
media to develop an after-washing count of the mi~uo.yalis,,,. The p6~nt~ge de~:ase 5 was calculated by subUacL,)g the count of step 3 from the count of step 1 and dividing that value by the count of step 1. This procedure was l~pea~d for several test pa~ ti~,a"ts and an average value was calculated.
The liquid cleaning fommulations of Example 1 and Example 3 were tested along with the f~'hJ.;ng co"""er~dlly available liquid soaps: Dial~ Antibaul~rial Soap, Lever 2000~), 10 Ope,dL"g Room Scrub, Sanifresh Soap v~ith 1.25% parachloru,,,et~l~nol (PCMX). Three non-antibacterial soaps were also tested. They were as follovus: S.~t~oap~, Sanifresh Premium, and EulubaUI~. The results are It:polled in Table 4.
r~n,enl Dec~ase in M;c.~)Lial Colony Number rer~.el~l Dec. e:ase in (gram negative l~act~.. ia Material Mic,vbial Colony Number only) Tested (all) Example 3 60 55 Example 1 0 0 Dial~Soap 40 38 Lever 2000~ 28 20 O-R Scrub 45 50 Sani-Fresh 1.25%PCMX 50 62 Sorboap~3) 0 o Sani-Fresh Premium 0 0 E~,lu~,dUI~ 0 0 The R.O.D.A.C. (Replicate O~yan;s~ll Dete_tion and Counting) plates test descliLed above (with the same data r~porLi"g procedure) was used to study the effect of adding a polymeric delivery aid to a conv~"lional liquid antiL,ac,te,ial soap fommulation. Dial~ Liquid Antibacterial soap was used as the control. The test fomlulation was Dial~ Liquid 20 A"til,a~,le,idl soap with 3%, by weight, Topicare~ Delivery Compound PP-15. The results are IY~pGI l~d in Table 5.
Material Tesbd % Kill (Bacteria) % Kill (YeasVMold) Dial~9 Soap 55 33 Dial~ Soap + 3% PP-1565 53 The R.O.D.A.C. (R~rli~-'P O,yan,~", Det~lion and Counting) plates test des~ibed above (but with a different data It:pGI ling procedure) was used to study the effect of adding a polymeric delivery aid to a aqtleo~ ~c antimicrobial liquid deaning formulation that includes mild sulrdcldllb which may decrease antimicrobial activity. The fommulation of Example 1 was used as the control. The fommulation of Example 3 containing 1.0% by weight Topicare@) 10 Delivery Compound PP-15 was used as the test. The results are ,t:po,led in Table 6. The Percent Decrease in Microbial Colony Number values ~pOI led in Table 6 were calculated as descnbed above except that negative numbers were zeroed for averaging. This gene,dl~s a greater pe~enlage de~ase for poorer perfomming fommulations that are likely to have microbial growth instead of a decrease. Average values calculated in this manner provide a 15 more conservative co"",arison of products that perfomm well (i.e. provide large de~ases in microbial growth).
Example 1 Example 3 Oly~n;~ % Dec,.~ee % D~cn,Ese gram (+) bacteria 38 50 gram (-) bacteria 18 39 yeas~l"~ ~ 16 39 The R.O.D.A.C. (ReFl[- t~ O~ganism Det~ on and Counting) plates test des~il,ed v~/as compa,-: the antimicrobial activity of ~,-" "e,~ally Lever 2000(9) Liquid Antibacterial soap with the formulation of Example 3. The results are ,epo,l~d in Table 7. The Percent De~:ase 25 in Microbial Colony Number values l~po~led in Table 7 were calculated as des~iL,ed above with the negative numbers included for averaging.
WO 98tlM73 PCT/US97/17701 Lever 2000~ Example 3 Organism % Dec.~as~ % D~C~ K
gram (~) ba-,~ria 35 50 gram (-)bacl~na 30 39 yea ,Um~'~ 34 39 As can be seen from data l~pol led in Tables 5 and 7, the present invention provides a method of inue:asillg the antimicrobial activity of conventional arltil,acl~rial soap fommulations such as, for example, Dial~ A"tiba, lerial liquid soap and Lever 2000(~ liquid soap. The improvement in the Percent De~t:ase in Microbial Colony Number by the practice of the method of the present invention may be 10% or more. For example, the improvement may be 20%. In some cases, the improvement may be 40% or even 60% or more.
The data in Tables 4 and 6 indicate the present invention provides a mild, liquid deaning fommulation that also has acce~'~hle levels of antimicrobial activity. Without the addition of the polymeric delivery aid, the mild, liquid cleaning fommulation had lower levels of antimicrobial activity. In fact, the data in Table 4 show essentially no measurable antimicrobial 15 activity for the fommulation without the polymeric delivery compound.
While the present invention has been des~ibed in connection with certain embodiments, it is to be ~"de,~lood that the subject matter encc",passed by way of the present invention is not to be limited to those specific embodiments. On the contrary, it is il,t~nded for the subject matter of the invention to include all altemaUves, modificaUons an 20 equivalents as can be included within the spirit and scope of the r~ 9 daims.
Claims (17)
1. A method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation, the method comprising the step of blending a polymeric deposition aid comprising a mixture of liquid, hydroxyl-terminated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent and at least one surfactant such that the liquid cleaning formulation has at least 10 percent greater antimicrobial activity than the same formulation without the polymeric deposition aid.
2. The method of claim 1, wherein the polymeric deposition aid is a hydroxy terminated urethane compound having the formula:
wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cycloalkylene or cycloalkenylene radical containing from about 5 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or different alkylene or alkenylene radical, wherein m is an integer selected to provide an (O-R') moiety having molecular weight of from about 40 to about 6000, and wherein n and n' are the same or different integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-terminated urethane compound having a molecular weight of up to about 200,000.
is an integer having a value ranging from about 1 to about 8.
wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cycloalkylene or cycloalkenylene radical containing from about 5 to about 10 carbon atoms, a mononuclear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein ~ is the same or different alkylene or alkenylene radical, wherein m is an integer selected to provide an (O-R') moiety having molecular weight of from about 40 to about 6000, and wherein n and n' are the same or different integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-terminated urethane compound having a molecular weight of up to about 200,000.
is an integer having a value ranging from about 1 to about 8.
3. The method of claim 1, wherein the polymeric deposition aid is poly(oxy-1,2-ethanediyl), .alpha.-hydro-.omega.-hydroxy-, polymer with 1,1'-methylene-bis-(4,isocyanato-cyclohexane).
4. The method of claim 1, wherein the polymeric deposition aid is a mixture of liquid, hydroxyl-terminated urethane polymers in polyethylene glycol, said mixture of polymers having an average molecular weight of approximately 1800 and includes 1,1'methylene-bis-(4,isocyanatocyclohexane) moieties.
5. The method of claim 1, wherein the phenol derivative antimicrobial agent is 2,4,4'-trichloro-2-hydroxy diphenyl ether.
6. The method of claim 1, wherein at least one surfactant is selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and combinations thereof.
7. The method of claim 1, wherein the method further includes the step of adding at least one conventional formulating component.
8. The method of claim 7, wherein the at least one conventional formulating component is selected from carriers, preservatives, humectants, emollients and combinations thereof.
9. The method of claim 1, wherein the liquid cleaning formulation has at least 20 percent greater antimicrobal activity than the same formulation without the polymeric deposition aid.
10. A method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation, the method comprising the step of blending a polymeric deposition aid cormprising a mixture of liquid, hydroxyl-terminated urethane polymers in polyethylene glycol together with a phenol derivative antimicrobial agent and at least one surfactant such that the liquid cleaning formulation has at least 20 percent greater antimicrobial activity than the same formulation without the polymeric deposition aid.
11. The method of claim 10, wherein the polymeric deposition aid is a hydroxy terminated urethane compound having the formula:
wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cydoalkylene or cydoalkenylene radical containing from about 5 to about 10 carbon atoms, a mononudear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein R is the same or different alkylene or alkenylene radical, wherein m is an integer selected to provide an (O-R') moiety having weight of from about 40 to about 6000, and wherein n and n1 are the same or different integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-terminated urethane compound having a molecular weight of up to about 200,000.
is an integer having a value ranging from about 1 to about 8.
wherein R is selected from an alkylene or alkenylene radical containing from oneto about 20 carbon atoms, a cydoalkylene or cydoalkenylene radical containing from about 5 to about 10 carbon atoms, a mononudear or fused ring arylene radical containing from about 6 to about 10 carbon atoms, unsubstituted or substituted with one or more lower alkyl, lower alkoxy, nitro or amino groups or halogen atoms, wherein R is the same or different alkylene or alkenylene radical, wherein m is an integer selected to provide an (O-R') moiety having weight of from about 40 to about 6000, and wherein n and n1 are the same or different integers of from 0 to about 30 inclusive, correlated with m so as to provide a hydroxy-terminated urethane compound having a molecular weight of up to about 200,000.
is an integer having a value ranging from about 1 to about 8.
12. The method of claim 10, wherein the polymeric deposition aid is poly(oxy-1,2-ethanediyl),.alpha.-hydro-.omega.-hydroxy-, polymer with 1,1'-methylene-bis-(4,isocyanato-cyclohexane).
13. The method of claim 10,wherein the polymeric deposition aid is a mixture of liquid, hydroxyl-terminated urethane polymers in polyethylene glycol, said mixture of polymers having an average molecular weight of approximately 1800 and includes 1,1'methylene-bis-(4,isocyanatocyclohexane) moieties.
14. The method of claim 10, wherein the phenol derivative antimicrobial agent is2,4,4'-trichloro-2'-hydroxy diphenyl ether.
15. The method of claim 10, wherein at least one surfactant is selected from anionic surfactants, cationic surfactants, nonionic surfactants, amphoteric surfactants and combinations thereof.
16. The method of claim 10, wherein the method includes the step of adding at least one conventional formulating component.
17. The method of claim 16, wherein the at least one conventional formulating component is selected from carriers, preservatives, humectants, emollients and combinations thereof.
Applications Claiming Priority (3)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US73542596A | 1996-10-22 | 1996-10-22 | |
| US08/735,425 | 1996-10-22 | ||
| PCT/US1997/017701 WO1998017773A1 (en) | 1996-10-22 | 1997-09-30 | Method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA2266430A1 true CA2266430A1 (en) | 1998-04-30 |
Family
ID=24955746
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002266430A Abandoned CA2266430A1 (en) | 1996-10-22 | 1997-09-30 | Method of increasing the antimicrobial activity of an aqueous, antimicrobial liquid cleaning formulation |
Country Status (11)
| Country | Link |
|---|---|
| EP (1) | EP0937130A1 (en) |
| JP (1) | JP2001502739A (en) |
| KR (1) | KR20000052686A (en) |
| CN (1) | CN1234068A (en) |
| AU (1) | AU727075B2 (en) |
| BR (1) | BR9712718A (en) |
| CA (1) | CA2266430A1 (en) |
| ID (1) | ID24496A (en) |
| IN (1) | IN184143B (en) |
| WO (1) | WO1998017773A1 (en) |
| ZA (1) | ZA979410B (en) |
Families Citing this family (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US6248343B1 (en) | 1998-01-20 | 2001-06-19 | Ethicon, Inc. | Therapeutic antimicrobial compositions |
| DE19859136A1 (en) * | 1998-12-21 | 2000-06-29 | Pluss Stauffer Ag | Deep freezing formulation containing phenol and / or phenol derivatives |
| AU2001265907B2 (en) | 2000-05-12 | 2006-08-17 | Omya International Ag | Phenolate-containing formulation with low freezing point |
| CN104039306B (en) | 2011-12-15 | 2016-09-21 | 高露洁-棕榄公司 | Cleasing compositions containing polyurethane-34 |
| EP3116986B1 (en) * | 2014-03-14 | 2023-07-05 | GOJO Industries, Inc. | Hand sanitizers with improved aesthetics and skin-conditioning to encourage compliance with hand hygiene guidelines |
Family Cites Families (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4157977A (en) * | 1970-02-13 | 1979-06-12 | Chemed Corporation | Detergent-germicide compositions |
| US4312855A (en) * | 1970-11-16 | 1982-01-26 | Colgate-Palmolive Company | Compositions containing aminopolyureylene resin |
| DE3723994A1 (en) * | 1986-07-23 | 1988-02-04 | Ciba Geigy Ag | Microbicidal preparation |
| GB2211093A (en) * | 1987-10-21 | 1989-06-28 | Unilever Plc | Disinfectant compositions |
| ATE179883T1 (en) * | 1993-07-03 | 1999-05-15 | Procter & Gamble | PERSONAL CLEANING PRODUCT |
-
1997
- 1997-09-30 CA CA002266430A patent/CA2266430A1/en not_active Abandoned
- 1997-09-30 AU AU48932/97A patent/AU727075B2/en not_active Ceased
- 1997-09-30 JP JP10519384A patent/JP2001502739A/en active Pending
- 1997-09-30 BR BR9712718-3A patent/BR9712718A/en not_active Application Discontinuation
- 1997-09-30 WO PCT/US1997/017701 patent/WO1998017773A1/en not_active Application Discontinuation
- 1997-09-30 EP EP97911607A patent/EP0937130A1/en not_active Withdrawn
- 1997-09-30 KR KR1019990703472A patent/KR20000052686A/en not_active Application Discontinuation
- 1997-09-30 CN CN97198958A patent/CN1234068A/en active Pending
- 1997-10-20 IN IN2351MA1997 patent/IN184143B/en unknown
- 1997-10-21 ZA ZA9709410A patent/ZA979410B/en unknown
- 1997-10-30 ID IDW990136D patent/ID24496A/en unknown
Also Published As
| Publication number | Publication date |
|---|---|
| BR9712718A (en) | 1999-10-19 |
| ID24496A (en) | 2000-07-20 |
| KR20000052686A (en) | 2000-08-25 |
| CN1234068A (en) | 1999-11-03 |
| IN184143B (en) | 2000-06-17 |
| JP2001502739A (en) | 2001-02-27 |
| ZA979410B (en) | 1998-05-12 |
| WO1998017773A1 (en) | 1998-04-30 |
| AU4893297A (en) | 1998-05-15 |
| EP0937130A1 (en) | 1999-08-25 |
| AU727075B2 (en) | 2000-11-30 |
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