CA1087955A - Cleansing-sanitizing composition - Google Patents
Cleansing-sanitizing compositionInfo
- Publication number
- CA1087955A CA1087955A CA266,834A CA266834A CA1087955A CA 1087955 A CA1087955 A CA 1087955A CA 266834 A CA266834 A CA 266834A CA 1087955 A CA1087955 A CA 1087955A
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- composition
- cleansing
- weight
- inorganic salt
- hypochlorite
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Abstract
ABSTRACT OF THE DISCLOSURE
Cleansing and sanitizing compositions containing conventional cleansing surface active agents along with an inorganic hypochlorite salt and an inorganic salt of a hydroxycarboxylic acid. The invention is useful in the formulation of domestic, industrial, and personal care cleansing and sanitizing compositions.
Cleansing and sanitizing compositions containing conventional cleansing surface active agents along with an inorganic hypochlorite salt and an inorganic salt of a hydroxycarboxylic acid. The invention is useful in the formulation of domestic, industrial, and personal care cleansing and sanitizing compositions.
Description
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l FIELD OF TH~ INVEN1ION
,, This invention relates to cleansing and sanitizing compositions ¦l containing conven~ional cleansing surface ac~ive agents along with an !l I
'I inoTganic hypochlorite salt and an inorganic salt of a hydroxycarboxylic , acid. The invention is useful in the formulation o~ domestic, industrial, I a~d personal care cleansing and sanitizin~ co~positions.
il BACKGROUND OF THE INVENTI~)N
It has been common practice in the past to combine the func~ions of various types of cleansing products with germidically or germistatically , .
active materials for the purpose of achieving an effective cleanser-sanitizer.
-~ While it has been possible to formulate the desired cleansing characteristics , into such comblned products, their utllity as sanitizers has often been less than optimum. Many such compositions have relied upon high use temperatures or the presence of detrimentally high concentrations of sanitizing compounds to control bacterial populations. Others have employed sanitizing compounds capable of producing dermal irritation or have relied upon long residual contact times, either o which can limit usefulness of such composition5 in applications where intentional or unintentional contact of the skin of the user can be foreseen. Among such compounds are hypochlorite solutions ~hich
l FIELD OF TH~ INVEN1ION
,, This invention relates to cleansing and sanitizing compositions ¦l containing conven~ional cleansing surface ac~ive agents along with an !l I
'I inoTganic hypochlorite salt and an inorganic salt of a hydroxycarboxylic , acid. The invention is useful in the formulation o~ domestic, industrial, I a~d personal care cleansing and sanitizin~ co~positions.
il BACKGROUND OF THE INVENTI~)N
It has been common practice in the past to combine the func~ions of various types of cleansing products with germidically or germistatically , .
active materials for the purpose of achieving an effective cleanser-sanitizer.
-~ While it has been possible to formulate the desired cleansing characteristics , into such comblned products, their utllity as sanitizers has often been less than optimum. Many such compositions have relied upon high use temperatures or the presence of detrimentally high concentrations of sanitizing compounds to control bacterial populations. Others have employed sanitizing compounds capable of producing dermal irritation or have relied upon long residual contact times, either o which can limit usefulness of such composition5 in applications where intentional or unintentional contact of the skin of the user can be foreseen. Among such compounds are hypochlorite solutions ~hich
2~ ha~e been used or many years in a variety of sanitizing applications where hypochlorite~corrosivity is not a problem and rspeated dermal contact can be avoided.
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~ I It has recently been found that aqu~ous hypochlorite solutions can ~, . ..
bo used for routine sanitizing of sensitive ma~erials includlng human skin if 25 such solutions contain an inorganic salt of a hy1roxycarboxyiic acid and `~ sufficient added acid to adjust the pH to a value of 5.0 to 8.0, preferably ~ . , , .
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~ -2--~L~8~9S5 ." ',`i, ' , , ,, , 6.5 to 7.5. The preparation and use o such compositions in disinfecting ,I human skin and clo~hing contaminatcd with Bacillis subtillis var. niger is il described in Echols et al. ~,S. Pa~ent No. 3,717,580. l i l~ Since hypochlorous acid is believed to be the active ~ermicidal component in aqueous hypochlorite solutions~ the purpose of lowering the ,, ! pH o commercially available solutionsJ which have a pH of 10.5 to 11, is to jl snift the equilibrium OCl- ~ H = HOCl - ;I to the right. Whereas the ratio of HOCl/OCl- in aqueous solution at 25 is ~ 0.00026 at a pH of 11, i~ increases to 2.7 at a pH o 7, consistent with the vast difference in sanitizing capability between the two solutions. For example, a 0.2% aqueous calcium hypochlorite solution acidified to a pH of 7.0 has been found capable of a disinfection efficiency better than 99.9% in ~ ~ive seconds against Bacillis subtillis var niger deposited on a cottont nylon fabric.
Advantage is taken of the rapidity of actlon of such compositions " by incorporating an inorganic salt of a hydroxycarboxylic acid such as citric i1 . . .
'~ or malic acid to bring about the rapid and spontaneous conversion of hypo-Il chlorite ion to innocuous products, presumably Cl-, HC03 and H20. The rate ~f this reaction between the hypochlorite and hydroxycarboxylate ions is controlled by the concentrations and proportions of the two species.
I,', We have ~ound that a wide variety of surfaces and materials can be l; efectively cleaned and sanitized by the short term application of a Il suitably packaged aqueous composition containing conventional cleansing surface active agents along with an inorganic hypochlorite salt and an ,~
" ; i inorganic salt of a hydroxycarboxylic acid, the composition having a pH of .. ..
5.0 to 8.0, preferably 6.5 to 7.5 at the time of application.
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, - 1~)8'7~S5 Although U.S. Patent No. 3,717,580 discloses that small quantities of anionic or nonionic detergents may be incorporated in hypochlorite disinfecting solutions as wetting agents, there is no suggestion that such solutions might be used in preparing cleansing compositions in which the quantity of surfactant employed is many fold greater than ~he quantity of disinfectant composition.
SUMMARY OF THE INVENTION
In one particular aspect the present invention provides a cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing a water soluble inorganic salt of a hydroxycarboxylic acid, the other part of said composition comprising an aqueous solution containing a water soluble inorganic salt of hypochlorous acid, at least one of said parts containing, in addition, a cleansing surface active agent, the two parts of the composition, when mixed together, having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weight of the water soluble inorganic salt of hydrochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxycarboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having 1 to 20 percent by weight of the cleansing surface active agent.
' 1 In another particular aspect the present invention provides a cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing sodium citrate and cleansing surface active agent, the other part of said composition comprising an aqueous solution containing sodium hypochlorite, the two parts of the composition, when mixed together, having a pH of 6.5 to 7.5, containing 0.05 to 2.0 percent by weight sodium citrate, having a molar ratio of citrate ion to hypochlorite ion of 2/1 to 13.5/1, and having 1 to 20 percent by weight of cleansing surface ,:
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In a further particular aspect the present invention provides a method for cleansing and saniti~ing a ~acterially contaminated surface comprising the application of an aqueous composition containing a water soluble inorganic salt of a hydroxycarboxylic acid, a water soluble inorganic salt of hypochlorous acid and a cleansing surface active agent, the composition having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weigh~ of the water soluble inorganic salt of hypochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxycarboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having l to 20 percent by weight of the cleansing surface active agent.
DETAILED DESCRIPTION OF THE INVE~TIO~
In its broadest form our invention comprises conducting a simultaneous cleansing-disinfecting operation by the application of a conventional cleansing composition containing a water soluble salt of hypochlorous acid, the pH of the composition being adjusted to 5.0 to 8.0, preferably 6.5 to 7.5, to increase bactericidal activity, and also containing a quantity of a water soluble inorganic salt of a hydroxy-carboxylic acid to provide for rapid and spontaneous conversion of the hypochlorite ion to innocuous products.
The invention is broadly applicable to all types of cleansing products based upon anionic or nonionic or ampholytic ,~
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1(~8~955 ~-~urface active agen~s, both syn~hetlc and naturally derived.
Included are domestic and industrial products for dishwashing, ~ carpet and upholstery cleansers, laundry products, floor and wall cleansers, and products for the cosmetic or medical treatment of human or animal skin or hair. The formulation of such products is well within the purview of those skilled in the art and involves the combina~ion of suitable ampholytic, nonionic and/or anionic surface active agents with adjuvants chosen to fit the requirements of the particular product type involved. Useful s~rface ~ctive a8ents iDcl~de the following:
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_ Anionic Surfactants Nonionic Surfactants fatty taurat~s fatty alkanolamides isethionates alkoxylated amides sarcosinates amine oxides alkyl and aryl sulfonates sorbitan esters alkyl-aryl sulfonates phosphate esters napthalene sulfonates fatty esters sulfosuccinates glycerol fatty esters fatty ester sulfates fatty alcohols fatty acid sulfates alkoxylated alcohols alcohol sulfates alkoxylated fatty acids ethoxylated alcohol sulfates and sulfonates i ethoxylated alkyl-arylphenol sulfates ethoxylated fatty sulfates ether sulfates alkyl and aryl phosphates salts of fatty acids ' Ampholytic Surfactants betaines sulfobetaines carboxyimidazoles ., .
Just as the species of surface active agent used is 1 ~ dictated by the type of cleànsing product involved, so is the .j quantity to be employed. Where an aggresive and thorough cleansing result is desired, a higher proportion of surface active agent will be required than when a more gentle .! .
cleansing result is sufficient. In general, the amount of surface active agent in the compositions of this invention may range from 1 to 20%.
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The sanitiæing capabilities of the compositions of this invention are derived from the inclusion of a mixture .
, of an inorganic hypochlorite salt and an inorganic salt of ; a hydroxycarboxylic acid. Although any inorganic ~ hypochlorite salt may be used without affecting the sanitizing ., .
capabilities of the compositions, the preferred salts are sodium, calcium, potassium, and lithium.
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79~5 The inorganic salt of the hydroxycarboxyl:ic acld is the eomponent in the compositions of this invention which reacts with the aetive germicidal species, the hypochlorite, to bring about spontaneous conversion of hypochlorite ion to innocuous produets, the ra~e of conversion being controlled by the concentration and proportions of the two species. Although any inorganic salt of any hydroxy-eontaining earboxylie aeid is effeetive, the water soluble salts of eitric and malic acid are preferred, especially the sodium, potassium, lithium, and calcium salts.
As alluded to above, aqueous hypochlorite compositions when aeidified to a pH of 5.0 to 8.0 are eapable of aehieving essentially total disinfection efficiency in very short contact times and . .
~ relatively low concentrations. While we have found that as little as ;~ 0.01% by weight hypochlorite salt in the mixed compositions of this invention is eapable of useful disinfection, we prefer to employ 0.05 to 2.0~. While even higher concentrations may be employed, up to 5.5~, there is usually little need to employ more than 2.0~.
The rate at which the hypochlorite species is converted by the hydroxyearboxylate to innoeuous produets is a funetion of ~he 20 eoncentrations of the two species, their relative proportions, and the ~, nature of the other components in any given formulation.
~` When all variables are held constant except the eoncentration of hydroxyearboxylate ion, it is found that an increase in its eoneentration will yield a corresponding reduction in the half life of the hypochlorite.
` For example, a eomposition having a molar ratio of citrate ion/hypochlorite ion of 0.5~1.0 has a hypoehlorite eoneentration half liEe of about 10 minutes whereas a similar eomposition having a eitrate ion/hypoehlorite ioA ratio of 7.0/1.0 has a half life of 0.8 minutes.
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When the proportions of hypochlorite/hydroxycar~oxylate are held constant, but the concentrations of the two species varled, it is foùnd that an increase in concentrations will yield a corresponding reduction in the half life of the hypochlorite. For example a composition having a molar ratio of citrate ion/hypochlorite ion of 2/1 and a hypochlorite concentration of 0.05% has a half life of 8.0 minutes. Doubling the concentrations of the two species reduces the half life to 2,25 minutes. Doubling the concentrations again further reduces the half life to 0.9 minutes.
Where the compositions of this invention are to be used for personal care or where hypochlorite corrosivity may be a problem, it is desirable to employ concentrations of hypochlorite at the lower end of the preferred range along with relat~ively high proportions of hydroxycarboxylate ion/hypochlorite ion to promote rapid conversion of the hypochlorite. For such uses, we prefer a hydroxycarboxylate ion/hypochlorite ion ratio of at least 2/1. Where hypochlorite ion concentrations of 0.05% or less are employed, a ratio as high as 13.5/1 . . .
: may be used.
Where higher concentrations of hypochlorite and longer contact times can be tolerated, for example in commercial or home ; . .
laundering applications, lower ratios of hydroxycarboxylate îon to hypochlorite ion may be employed, as low as 1/1.
! The proportion of the combined total of hypochlorite salt ., .
;~ and hydroxycarboxylic acid salt to surface active agent is nut critical as long as sufficient hypochlorite is used to achieve rapid sanitization.
While the combined total of the hypochlorite salt and hydroxycarboxylic acid salt may be as high as 10.0% by weight o-f the compositions of this invention, it may be as low as 1.0%.
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1~87~55 -As mentioned herelnabove, it -is necessary to acidify the hypochlorite solution to a pH o~ 5.0 to 8.0, preferably 6.5 to 7.5 to generate the active germicidal species. It is known, however, that hypochlorite solutions are unstable within such a pH range. Hence, commercially available products are generally quite alkaline, having a pH above lO.0, usually about 10.5 to 11.5.
Whlle it is broadly possible to practice our invention by combining just prior to use suitable quantities of the three essential components i.e. (1) a nonionic, anionic or amphoteric surface active i lO agent or mixture thereof, (2) a water soluble9 inorganic hypochlorite salt, and (3) a water soluble, inorganic salt of a hydroxycarboxylic acid, a preferred form of the invention includes a single package adapted to keep separate until the time of use the two chem~cally reactive portions. When such package is employed, surface active agents may be included in either or both portions of the composition. When, however, a surface active agent is included in the portion of the composition containing the hypochlorite salt, care must be taken to select an agent which will be chemically stable in alkaline, oxidizing `:~:,1 , :
' media.
, 20 Virtually any of the dispensing containers, having a plurality of compartments, disclosed in the prior art may be used in j; packaging the compositions of this invention. Where a single use product . .
application is involved, there may be used a container of the type disclosed in U.S. Patent No. 3,402,855 in which complete mixing of the two components takes place prior to dispensing. For multiple use product applications, there may be used multiple chambered containers `; of the types shown in U.S. Patent Nos. 3,635,375 and 3,651,990 in which the f:low rate from each chamber is controlled by proper choice of orifice l size and by adjustment of the rheological properties of the contained ,;'-;.i ~:
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i A preferred form of multiple use packaging employs multiple compartmented pressurized containers which may be const~ucted t~
carefully meter desired proportions of the separate components: and mix them together at the time of use. Such packages are described in U,S.
Patent No. 3,241,722.
The following specific examples are intended to illustrate the nature of this invention without acting as a limitation upon its scope.
Example I. Hard Surface Cleaner/Disinfectant Part A
Ingredient Parts by Weight Modi~ied oxyethylated straight chain alcohol (Plurafac~ D-25 - Wyandotte Chemicals Corp.) 3.00 Polyoxyethylene polyme~hylsiloxane (Dow Corning 471A) 0.60 Ethylene glycol monobutyl ether 20.00 Citric acid 0.57 Sodium citrate dihydrate 2.61 Preservative 0.02 H20 To 100.0 Part B
Sodium hypochlorite (5.5% aqueous solution, pH 11.5) - 10.9 H20 To 100.0 ~ uantities of Parts A and B were packaged in the saparate compartments of a container of the type shown in U.S. Patent 3,651~990 in which the orifice dimensions were chosen to simultaneously dispense equal volumes of each composition. The mixed composition dispensed from thls container was tested against Bacillis subtillis spores deposited on a variety of surfacesincluding ceramic tile, vinyl floor tile, polyvinyl chloride sheet, and wood surfaces coated with high gloss enamel, shellac, and polyurethane varnlsh. In all cases a virtually total kill was achieved in as little as fifteen seconds contact time.
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` '¦ Ingredient Parts by W~igh~ ¦
~I Sodium dioc~ylsu3.fosuccinate 1.90 , Polyoxyethylene pol~ethysiloxane '. tDoW Corning 471A) 0.30 '! Sodium citrate dihydrate2.Z
Citric acid 0.5 . I, Preser~ative 0.02 l .
Isopropanol 10.00 Ethylene glycol monobutyl e~her 10.00 H2O To 100.0 1 Part B
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' Sodium hypochlorite (5.5% aqueous !
solution, pH 11.5) 16.4 ` H2O To 100.0 e two parts of ~he composition were packaged in a container of . ;
- ~! -*he type shown in U. S. Patent No. 3,241,722, there being placed in the ''! outer con*ainer 74 parts by weight of Part A along with 6.0 parts by weight j of a 40~60 mixture of Propellants 12/114 and 20 parts by weight of Part B
, being pl~ced in the inner container.
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j ¦ Example Ill. Low Foaming, Hard Surface Cleaner/n;.sinfectant ' ''Part A
. ¦ Ingredient''Parts'by`~'eight . j - ___ Oxyethyla~ed linear alcohol .
~Plurafa~Yb-25; Wyandotte Chemicals 105 il Polyoxyethylene polym0thylsioxane 0O3 ! Sodium Citrate dihydTate l.S
'i¦ Citric acid 0O3 . Preservative , OoOl Ethyleno glycol mollobu~yl ether 10.0 1 To 100.0 1 Part B
`I Sodium hypochlori~e (5.5% aqueous lS ,; solution, pH 11.5) 1604 ~l ,' H 0 To 100.0 , I
The two parts of the composition were packaged in a container of . iI type shown in UO S. Patent No. 3,241,722~ there being placed in the outer ontainer 74 pa~ts by weight of Part A along wi~h 5.0 par~s by weight of a ." 20 85/15 mixture of isobutane/propane and 20 parts by weight of Part B being ,I placed in the inner container '.' 11 1 :
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ii lll ~l - 10t~'79 IY. ~ligh Foaming All~Purpose CleanerlDisinfectant !l Part A ¦ .
I In~ ient Parts by Weight Polyethylene glycF~ ether of a linear alcohol (Tcrgitol~ S-S 9; Union Carbide Corp. ) . 4 . 0 Sodium l ar alkyl sulfonate (Ultrawe ~ ; ARC0 Chemical Co.) 4.5 . Polyoxyethylene polymethysiloxane (Dow Corning 471A) 1.0 ' Sodiwn citrate dihydrate 1.5 !
Citric acid 0.3 ,l Preservative - 0.01 ,l ~thylene glycol monobutyl ether 15.0 ! -~ 1S H20 loo . Part B ¦
I Sodium hypochlorite ~5D5% aqueous .i solution~ pH 11.5) 16.4 To lO0~0 1l ;. The two parts of the composition were packaged in a container of the type shown in U. S. Patent No. 3,241,722, there being placed in the ., , outer container 76 parts by weight of Part A along with ~.0 parts by weight `
of 85/lS mixture o isobutane/propane and 20 parts by weight of Part B
` ~~ being placed in the inner container.
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!IExample V. All-Purpose ~brasive Cl~aner/Disinfcctant ' I! _ I
In~redient Parts by Weight , ,j Polyethylenc gly 1 ether of linear ¦
alcohol (Tergito ~15-S-9; Union Carbide Corp.) 47 0 'I Sodium 1 ~ ar alkyl sulfonate Il (Ultrawe ; ARC0 Chemical CoO) 4.5 ,i Polyoxyethylene polyme*hysiloxane :l 10 (Dow Corning 471A) . 1.0 Uncalcinated diatomite celite , mineral filler 12.0 ! Sodiu~;i citrate dihydrate 105 ~. Citric acid 0O3 Pr~servative . 0,01 ,' Ethylene glycol ~ionobutyl ether 10.0 - ,. H20 To 100;0 Part B
~ Sodium hypochlorite (5~5 aqueous . solu~ion, pH 11.5) .16.4 j . H20 To 100.0 `
The two parts of the composition were packaged in a container of .~ the type shown in U. S~ Patent No~ 3,241,722, there being placed in the .
outer container 76 parts by weight of Part A along with 4.0 parts by - weight of 85/15 mixture of isobutanetpropane and 2.0 parts by weight of ,, Part B being placed in the inner container " I j . -13-I
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379~5 il I ~' ' Example VI. ~uick Breakin~ Foam Skin Cleansing Lotion~Disinfectant Part A
: ¦ Ingredient Parts by Weight ,¦ Oxyethyl~ted lanolin alcohol . .
Solula~16; Amerchol Chemical Co.) 1.5 . Il .
Oxyethy ~ted lanolin alcohol . !i (Solula~ 8; Amerchol Chemical Co.) 1.0 Il Propylene glycol 5.0 Polyoxyethylene (2) stearyl ether l.O
, Sodium citTate dihydrate 4.4 Cit~ic acid lo0 'Z
P~eservative 0O03 Ethanol 40.0 . 15 H2O To lOOo Part B
.j .i Sodium hypochlorite (5.5% aqueous solution, pH 11.5) 7.3 .
2 To 100O0 .. 20 ~ The two parts of the composition were.packaged in a container of .
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the type shown in U. S. Patent No. 3,241,722, there being placed in the ~, outer container 70 parts by weight of Part A along with 10~0 parts by weight o~ 40/60 mixture of Propellants 12/114 and 20 parts by weight of " Part B being placed in the inner container. i I`
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; Example VII. ~ligh Foaming Skin Cleanser/Disinfectant Part A
Ingredient Parts by Weight Sodium lauryl sulfate 6.0 ; Polyoxyethylene (20) cetyl ether 2.5 Polyoxyethylene polymethylsiloxane , (Dow Corning 472) 1.0 Oxyethyla~ed lanolin alcohol - (Solulan~98; Amerchol Chemical Co.) 3.0 Sodium citrate dihydrate 2.2 Citric acid 0-5 Preservative 0.02 H20 To 100.~
Part B ;
Sodium hypochlorite (5.5% aqueous solution, pH 11.5) 7.3 H20 To 100.0 The two parts of the composition were packaged in a container " .
of the type shown in U.S. Patent No. 3,241,722, there being placed in the outer container 77 parts by weight of Part A along with 3.0 parts by weight of a 85!15 mixture of isobutane/propane, 20 parts by weight Qf Part B being placed in the inner container.
The cleaning efficiency of the compositions of Examples I-VII
was ~udged to be good to excellent. Sporicidal activity against Bacillis subtillis was virtually total in a very short period of time for the compositions o~ Examples I-V. Compositions dispensed as foams, such as those of Examples VI-VII require mechanical agitation over the surEace to be treated to achieve comparable levels of activity.
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~ I It has recently been found that aqu~ous hypochlorite solutions can ~, . ..
bo used for routine sanitizing of sensitive ma~erials includlng human skin if 25 such solutions contain an inorganic salt of a hy1roxycarboxyiic acid and `~ sufficient added acid to adjust the pH to a value of 5.0 to 8.0, preferably ~ . , , .
:.
~ -2--~L~8~9S5 ." ',`i, ' , , ,, , 6.5 to 7.5. The preparation and use o such compositions in disinfecting ,I human skin and clo~hing contaminatcd with Bacillis subtillis var. niger is il described in Echols et al. ~,S. Pa~ent No. 3,717,580. l i l~ Since hypochlorous acid is believed to be the active ~ermicidal component in aqueous hypochlorite solutions~ the purpose of lowering the ,, ! pH o commercially available solutionsJ which have a pH of 10.5 to 11, is to jl snift the equilibrium OCl- ~ H = HOCl - ;I to the right. Whereas the ratio of HOCl/OCl- in aqueous solution at 25 is ~ 0.00026 at a pH of 11, i~ increases to 2.7 at a pH o 7, consistent with the vast difference in sanitizing capability between the two solutions. For example, a 0.2% aqueous calcium hypochlorite solution acidified to a pH of 7.0 has been found capable of a disinfection efficiency better than 99.9% in ~ ~ive seconds against Bacillis subtillis var niger deposited on a cottont nylon fabric.
Advantage is taken of the rapidity of actlon of such compositions " by incorporating an inorganic salt of a hydroxycarboxylic acid such as citric i1 . . .
'~ or malic acid to bring about the rapid and spontaneous conversion of hypo-Il chlorite ion to innocuous products, presumably Cl-, HC03 and H20. The rate ~f this reaction between the hypochlorite and hydroxycarboxylate ions is controlled by the concentrations and proportions of the two species.
I,', We have ~ound that a wide variety of surfaces and materials can be l; efectively cleaned and sanitized by the short term application of a Il suitably packaged aqueous composition containing conventional cleansing surface active agents along with an inorganic hypochlorite salt and an ,~
" ; i inorganic salt of a hydroxycarboxylic acid, the composition having a pH of .. ..
5.0 to 8.0, preferably 6.5 to 7.5 at the time of application.
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3_ .'" ' ' . I
, - 1~)8'7~S5 Although U.S. Patent No. 3,717,580 discloses that small quantities of anionic or nonionic detergents may be incorporated in hypochlorite disinfecting solutions as wetting agents, there is no suggestion that such solutions might be used in preparing cleansing compositions in which the quantity of surfactant employed is many fold greater than ~he quantity of disinfectant composition.
SUMMARY OF THE INVENTION
In one particular aspect the present invention provides a cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing a water soluble inorganic salt of a hydroxycarboxylic acid, the other part of said composition comprising an aqueous solution containing a water soluble inorganic salt of hypochlorous acid, at least one of said parts containing, in addition, a cleansing surface active agent, the two parts of the composition, when mixed together, having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weight of the water soluble inorganic salt of hydrochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxycarboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having 1 to 20 percent by weight of the cleansing surface active agent.
' 1 In another particular aspect the present invention provides a cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing sodium citrate and cleansing surface active agent, the other part of said composition comprising an aqueous solution containing sodium hypochlorite, the two parts of the composition, when mixed together, having a pH of 6.5 to 7.5, containing 0.05 to 2.0 percent by weight sodium citrate, having a molar ratio of citrate ion to hypochlorite ion of 2/1 to 13.5/1, and having 1 to 20 percent by weight of cleansing surface ,:
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In a further particular aspect the present invention provides a method for cleansing and saniti~ing a ~acterially contaminated surface comprising the application of an aqueous composition containing a water soluble inorganic salt of a hydroxycarboxylic acid, a water soluble inorganic salt of hypochlorous acid and a cleansing surface active agent, the composition having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weigh~ of the water soluble inorganic salt of hypochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxycarboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having l to 20 percent by weight of the cleansing surface active agent.
DETAILED DESCRIPTION OF THE INVE~TIO~
In its broadest form our invention comprises conducting a simultaneous cleansing-disinfecting operation by the application of a conventional cleansing composition containing a water soluble salt of hypochlorous acid, the pH of the composition being adjusted to 5.0 to 8.0, preferably 6.5 to 7.5, to increase bactericidal activity, and also containing a quantity of a water soluble inorganic salt of a hydroxy-carboxylic acid to provide for rapid and spontaneous conversion of the hypochlorite ion to innocuous products.
The invention is broadly applicable to all types of cleansing products based upon anionic or nonionic or ampholytic ,~
. ` 30 `
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1(~8~955 ~-~urface active agen~s, both syn~hetlc and naturally derived.
Included are domestic and industrial products for dishwashing, ~ carpet and upholstery cleansers, laundry products, floor and wall cleansers, and products for the cosmetic or medical treatment of human or animal skin or hair. The formulation of such products is well within the purview of those skilled in the art and involves the combina~ion of suitable ampholytic, nonionic and/or anionic surface active agents with adjuvants chosen to fit the requirements of the particular product type involved. Useful s~rface ~ctive a8ents iDcl~de the following:
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_ Anionic Surfactants Nonionic Surfactants fatty taurat~s fatty alkanolamides isethionates alkoxylated amides sarcosinates amine oxides alkyl and aryl sulfonates sorbitan esters alkyl-aryl sulfonates phosphate esters napthalene sulfonates fatty esters sulfosuccinates glycerol fatty esters fatty ester sulfates fatty alcohols fatty acid sulfates alkoxylated alcohols alcohol sulfates alkoxylated fatty acids ethoxylated alcohol sulfates and sulfonates i ethoxylated alkyl-arylphenol sulfates ethoxylated fatty sulfates ether sulfates alkyl and aryl phosphates salts of fatty acids ' Ampholytic Surfactants betaines sulfobetaines carboxyimidazoles ., .
Just as the species of surface active agent used is 1 ~ dictated by the type of cleànsing product involved, so is the .j quantity to be employed. Where an aggresive and thorough cleansing result is desired, a higher proportion of surface active agent will be required than when a more gentle .! .
cleansing result is sufficient. In general, the amount of surface active agent in the compositions of this invention may range from 1 to 20%.
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The sanitiæing capabilities of the compositions of this invention are derived from the inclusion of a mixture .
, of an inorganic hypochlorite salt and an inorganic salt of ; a hydroxycarboxylic acid. Although any inorganic ~ hypochlorite salt may be used without affecting the sanitizing ., .
capabilities of the compositions, the preferred salts are sodium, calcium, potassium, and lithium.
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79~5 The inorganic salt of the hydroxycarboxyl:ic acld is the eomponent in the compositions of this invention which reacts with the aetive germicidal species, the hypochlorite, to bring about spontaneous conversion of hypochlorite ion to innocuous produets, the ra~e of conversion being controlled by the concentration and proportions of the two species. Although any inorganic salt of any hydroxy-eontaining earboxylie aeid is effeetive, the water soluble salts of eitric and malic acid are preferred, especially the sodium, potassium, lithium, and calcium salts.
As alluded to above, aqueous hypochlorite compositions when aeidified to a pH of 5.0 to 8.0 are eapable of aehieving essentially total disinfection efficiency in very short contact times and . .
~ relatively low concentrations. While we have found that as little as ;~ 0.01% by weight hypochlorite salt in the mixed compositions of this invention is eapable of useful disinfection, we prefer to employ 0.05 to 2.0~. While even higher concentrations may be employed, up to 5.5~, there is usually little need to employ more than 2.0~.
The rate at which the hypochlorite species is converted by the hydroxyearboxylate to innoeuous produets is a funetion of ~he 20 eoncentrations of the two species, their relative proportions, and the ~, nature of the other components in any given formulation.
~` When all variables are held constant except the eoncentration of hydroxyearboxylate ion, it is found that an increase in its eoneentration will yield a corresponding reduction in the half life of the hypochlorite.
` For example, a eomposition having a molar ratio of citrate ion/hypochlorite ion of 0.5~1.0 has a hypoehlorite eoneentration half liEe of about 10 minutes whereas a similar eomposition having a eitrate ion/hypoehlorite ioA ratio of 7.0/1.0 has a half life of 0.8 minutes.
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When the proportions of hypochlorite/hydroxycar~oxylate are held constant, but the concentrations of the two species varled, it is foùnd that an increase in concentrations will yield a corresponding reduction in the half life of the hypochlorite. For example a composition having a molar ratio of citrate ion/hypochlorite ion of 2/1 and a hypochlorite concentration of 0.05% has a half life of 8.0 minutes. Doubling the concentrations of the two species reduces the half life to 2,25 minutes. Doubling the concentrations again further reduces the half life to 0.9 minutes.
Where the compositions of this invention are to be used for personal care or where hypochlorite corrosivity may be a problem, it is desirable to employ concentrations of hypochlorite at the lower end of the preferred range along with relat~ively high proportions of hydroxycarboxylate ion/hypochlorite ion to promote rapid conversion of the hypochlorite. For such uses, we prefer a hydroxycarboxylate ion/hypochlorite ion ratio of at least 2/1. Where hypochlorite ion concentrations of 0.05% or less are employed, a ratio as high as 13.5/1 . . .
: may be used.
Where higher concentrations of hypochlorite and longer contact times can be tolerated, for example in commercial or home ; . .
laundering applications, lower ratios of hydroxycarboxylate îon to hypochlorite ion may be employed, as low as 1/1.
! The proportion of the combined total of hypochlorite salt ., .
;~ and hydroxycarboxylic acid salt to surface active agent is nut critical as long as sufficient hypochlorite is used to achieve rapid sanitization.
While the combined total of the hypochlorite salt and hydroxycarboxylic acid salt may be as high as 10.0% by weight o-f the compositions of this invention, it may be as low as 1.0%.
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1~87~55 -As mentioned herelnabove, it -is necessary to acidify the hypochlorite solution to a pH o~ 5.0 to 8.0, preferably 6.5 to 7.5 to generate the active germicidal species. It is known, however, that hypochlorite solutions are unstable within such a pH range. Hence, commercially available products are generally quite alkaline, having a pH above lO.0, usually about 10.5 to 11.5.
Whlle it is broadly possible to practice our invention by combining just prior to use suitable quantities of the three essential components i.e. (1) a nonionic, anionic or amphoteric surface active i lO agent or mixture thereof, (2) a water soluble9 inorganic hypochlorite salt, and (3) a water soluble, inorganic salt of a hydroxycarboxylic acid, a preferred form of the invention includes a single package adapted to keep separate until the time of use the two chem~cally reactive portions. When such package is employed, surface active agents may be included in either or both portions of the composition. When, however, a surface active agent is included in the portion of the composition containing the hypochlorite salt, care must be taken to select an agent which will be chemically stable in alkaline, oxidizing `:~:,1 , :
' media.
, 20 Virtually any of the dispensing containers, having a plurality of compartments, disclosed in the prior art may be used in j; packaging the compositions of this invention. Where a single use product . .
application is involved, there may be used a container of the type disclosed in U.S. Patent No. 3,402,855 in which complete mixing of the two components takes place prior to dispensing. For multiple use product applications, there may be used multiple chambered containers `; of the types shown in U.S. Patent Nos. 3,635,375 and 3,651,990 in which the f:low rate from each chamber is controlled by proper choice of orifice l size and by adjustment of the rheological properties of the contained ,;'-;.i ~:
~¦ 30 composition.
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i A preferred form of multiple use packaging employs multiple compartmented pressurized containers which may be const~ucted t~
carefully meter desired proportions of the separate components: and mix them together at the time of use. Such packages are described in U,S.
Patent No. 3,241,722.
The following specific examples are intended to illustrate the nature of this invention without acting as a limitation upon its scope.
Example I. Hard Surface Cleaner/Disinfectant Part A
Ingredient Parts by Weight Modi~ied oxyethylated straight chain alcohol (Plurafac~ D-25 - Wyandotte Chemicals Corp.) 3.00 Polyoxyethylene polyme~hylsiloxane (Dow Corning 471A) 0.60 Ethylene glycol monobutyl ether 20.00 Citric acid 0.57 Sodium citrate dihydrate 2.61 Preservative 0.02 H20 To 100.0 Part B
Sodium hypochlorite (5.5% aqueous solution, pH 11.5) - 10.9 H20 To 100.0 ~ uantities of Parts A and B were packaged in the saparate compartments of a container of the type shown in U.S. Patent 3,651~990 in which the orifice dimensions were chosen to simultaneously dispense equal volumes of each composition. The mixed composition dispensed from thls container was tested against Bacillis subtillis spores deposited on a variety of surfacesincluding ceramic tile, vinyl floor tile, polyvinyl chloride sheet, and wood surfaces coated with high gloss enamel, shellac, and polyurethane varnlsh. In all cases a virtually total kill was achieved in as little as fifteen seconds contact time.
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` '¦ Ingredient Parts by W~igh~ ¦
~I Sodium dioc~ylsu3.fosuccinate 1.90 , Polyoxyethylene pol~ethysiloxane '. tDoW Corning 471A) 0.30 '! Sodium citrate dihydrate2.Z
Citric acid 0.5 . I, Preser~ative 0.02 l .
Isopropanol 10.00 Ethylene glycol monobutyl e~her 10.00 H2O To 100.0 1 Part B
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' Sodium hypochlorite (5.5% aqueous !
solution, pH 11.5) 16.4 ` H2O To 100.0 e two parts of ~he composition were packaged in a container of . ;
- ~! -*he type shown in U. S. Patent No. 3,241,722, there being placed in the ''! outer con*ainer 74 parts by weight of Part A along with 6.0 parts by weight j of a 40~60 mixture of Propellants 12/114 and 20 parts by weight of Part B
, being pl~ced in the inner container.
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j ¦ Example Ill. Low Foaming, Hard Surface Cleaner/n;.sinfectant ' ''Part A
. ¦ Ingredient''Parts'by`~'eight . j - ___ Oxyethyla~ed linear alcohol .
~Plurafa~Yb-25; Wyandotte Chemicals 105 il Polyoxyethylene polym0thylsioxane 0O3 ! Sodium Citrate dihydTate l.S
'i¦ Citric acid 0O3 . Preservative , OoOl Ethyleno glycol mollobu~yl ether 10.0 1 To 100.0 1 Part B
`I Sodium hypochlori~e (5.5% aqueous lS ,; solution, pH 11.5) 1604 ~l ,' H 0 To 100.0 , I
The two parts of the composition were packaged in a container of . iI type shown in UO S. Patent No. 3,241,722~ there being placed in the outer ontainer 74 pa~ts by weight of Part A along wi~h 5.0 par~s by weight of a ." 20 85/15 mixture of isobutane/propane and 20 parts by weight of Part B being ,I placed in the inner container '.' 11 1 :
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ii lll ~l - 10t~'79 IY. ~ligh Foaming All~Purpose CleanerlDisinfectant !l Part A ¦ .
I In~ ient Parts by Weight Polyethylene glycF~ ether of a linear alcohol (Tcrgitol~ S-S 9; Union Carbide Corp. ) . 4 . 0 Sodium l ar alkyl sulfonate (Ultrawe ~ ; ARC0 Chemical Co.) 4.5 . Polyoxyethylene polymethysiloxane (Dow Corning 471A) 1.0 ' Sodiwn citrate dihydrate 1.5 !
Citric acid 0.3 ,l Preservative - 0.01 ,l ~thylene glycol monobutyl ether 15.0 ! -~ 1S H20 loo . Part B ¦
I Sodium hypochlorite ~5D5% aqueous .i solution~ pH 11.5) 16.4 To lO0~0 1l ;. The two parts of the composition were packaged in a container of the type shown in U. S. Patent No. 3,241,722, there being placed in the ., , outer container 76 parts by weight of Part A along with ~.0 parts by weight `
of 85/lS mixture o isobutane/propane and 20 parts by weight of Part B
` ~~ being placed in the inner container.
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!IExample V. All-Purpose ~brasive Cl~aner/Disinfcctant ' I! _ I
In~redient Parts by Weight , ,j Polyethylenc gly 1 ether of linear ¦
alcohol (Tergito ~15-S-9; Union Carbide Corp.) 47 0 'I Sodium 1 ~ ar alkyl sulfonate Il (Ultrawe ; ARC0 Chemical CoO) 4.5 ,i Polyoxyethylene polyme*hysiloxane :l 10 (Dow Corning 471A) . 1.0 Uncalcinated diatomite celite , mineral filler 12.0 ! Sodiu~;i citrate dihydrate 105 ~. Citric acid 0O3 Pr~servative . 0,01 ,' Ethylene glycol ~ionobutyl ether 10.0 - ,. H20 To 100;0 Part B
~ Sodium hypochlorite (5~5 aqueous . solu~ion, pH 11.5) .16.4 j . H20 To 100.0 `
The two parts of the composition were packaged in a container of .~ the type shown in U. S~ Patent No~ 3,241,722, there being placed in the .
outer container 76 parts by weight of Part A along with 4.0 parts by - weight of 85/15 mixture of isobutanetpropane and 2.0 parts by weight of ,, Part B being placed in the inner container " I j . -13-I
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379~5 il I ~' ' Example VI. ~uick Breakin~ Foam Skin Cleansing Lotion~Disinfectant Part A
: ¦ Ingredient Parts by Weight ,¦ Oxyethyl~ted lanolin alcohol . .
Solula~16; Amerchol Chemical Co.) 1.5 . Il .
Oxyethy ~ted lanolin alcohol . !i (Solula~ 8; Amerchol Chemical Co.) 1.0 Il Propylene glycol 5.0 Polyoxyethylene (2) stearyl ether l.O
, Sodium citTate dihydrate 4.4 Cit~ic acid lo0 'Z
P~eservative 0O03 Ethanol 40.0 . 15 H2O To lOOo Part B
.j .i Sodium hypochlorite (5.5% aqueous solution, pH 11.5) 7.3 .
2 To 100O0 .. 20 ~ The two parts of the composition were.packaged in a container of .
.. . .
the type shown in U. S. Patent No. 3,241,722, there being placed in the ~, outer container 70 parts by weight of Part A along with 10~0 parts by weight o~ 40/60 mixture of Propellants 12/114 and 20 parts by weight of " Part B being placed in the inner container. i I`
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; Example VII. ~ligh Foaming Skin Cleanser/Disinfectant Part A
Ingredient Parts by Weight Sodium lauryl sulfate 6.0 ; Polyoxyethylene (20) cetyl ether 2.5 Polyoxyethylene polymethylsiloxane , (Dow Corning 472) 1.0 Oxyethyla~ed lanolin alcohol - (Solulan~98; Amerchol Chemical Co.) 3.0 Sodium citrate dihydrate 2.2 Citric acid 0-5 Preservative 0.02 H20 To 100.~
Part B ;
Sodium hypochlorite (5.5% aqueous solution, pH 11.5) 7.3 H20 To 100.0 The two parts of the composition were packaged in a container " .
of the type shown in U.S. Patent No. 3,241,722, there being placed in the outer container 77 parts by weight of Part A along with 3.0 parts by weight of a 85!15 mixture of isobutane/propane, 20 parts by weight Qf Part B being placed in the inner container.
The cleaning efficiency of the compositions of Examples I-VII
was ~udged to be good to excellent. Sporicidal activity against Bacillis subtillis was virtually total in a very short period of time for the compositions o~ Examples I-V. Compositions dispensed as foams, such as those of Examples VI-VII require mechanical agitation over the surEace to be treated to achieve comparable levels of activity.
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Claims (6)
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:
1. A cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing a water soluble inorganic salt of a hydroxycarboxylic acid, the other part of said composition comprising an aqueous solution containing a water soluble inorganic salt of hypo-chlorous acid, at least one of said parts containing, in addition, a cleansing surface active agent, the two parts of the composition, when mixed together, having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weight of the water soluble inorganic salt of hypochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxy-carboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having 1 to 20 percent by weight of the cleansing surface active agent.
2. A composition as described in Claim 1 in which the salt of a hydroxycarboxylic acid is selected from the group consisting of the sodium, potassium, lithium and calcium salts of citric and malic acids.
3. A composition as described in Claim 1 in which the salt of hypochlorous acid is selected from the group con-sisting of the sodium, potassium, lithium and calcium salts.
4. A composition as described in Claim 1 in which the two parts, when mixed together, contain from 1.0 to 10.0 percent by weight combined salts of a hydroxycarboxylic acid and hypochlorous acid.
5. A cleansing-sanitizing composition, one part of said composition comprising an aqueous solution containing sodium citrate and cleansing surface active agent, the other part of said composition comprising an aqueous solution containing sodium hypochlorite, the two parts of the com-position when mixed together, having a pH of 6.5 to 7.5, containing 0.05 to 2.0 percent by weight sodium citrate, having a molar ratio of citrate ion to hypochlorite ion of 2/1 to 13.5/1, and having 1 to 20 percent by weight of cleansing surface active agent.
6. A method for cleansing and sanitizing a bacterially contaminated surface comprising the application of an aqueous composition containing a water soluble inorganic salt of a hydroxycarboxylic acid, a water soluble inorganic salt of hypochlorous acid and a cleansing surface active agent, the composition having a pH of 5.0 to 8.0, containing from 0.01 to 5.5 percent by weight of the water soluble inorganic salt of hypochlorous acid, having a molar ratio of water soluble inorganic salt of hydroxycarboxylic acid to hypochlorite ion of 1/1 to 13.5/1, and having 1 to 20 percent by weight of the cleansing surface active agent.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US64852876A | 1976-01-12 | 1976-01-12 | |
| US648,528 | 1976-01-12 |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CA1087955A true CA1087955A (en) | 1980-10-21 |
Family
ID=24601148
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA266,834A Expired CA1087955A (en) | 1976-01-12 | 1976-11-29 | Cleansing-sanitizing composition |
Country Status (1)
| Country | Link |
|---|---|
| CA (1) | CA1087955A (en) |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908215A (en) * | 1986-03-06 | 1990-03-13 | Brandeis University | Hypochlorite compositions containing thiosulfate and use thereof |
| WO2002097022A1 (en) * | 2001-05-30 | 2002-12-05 | Cognis Deutschland Gmbh & Co. Kg | Surfactant preparations comprising alpha-hydroxy acids |
| US7674473B2 (en) * | 2001-01-04 | 2010-03-09 | Byotrol Plc | Anti-microbial composition |
| US8003593B2 (en) | 2007-09-17 | 2011-08-23 | Byotrol Plc | Formulations comprising an anti-microbial composition |
| US8178484B2 (en) | 2007-07-17 | 2012-05-15 | Byotrol Plc | Anti-microbial composition comprising a siloxane and anti-microbial compound mixture |
| US9029311B2 (en) | 2012-02-17 | 2015-05-12 | The Clorox Company | Targeted performance of hypohalite methods thereof |
-
1976
- 1976-11-29 CA CA266,834A patent/CA1087955A/en not_active Expired
Cited By (13)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US4908215A (en) * | 1986-03-06 | 1990-03-13 | Brandeis University | Hypochlorite compositions containing thiosulfate and use thereof |
| WO1990005529A1 (en) * | 1988-11-21 | 1990-05-31 | Brandeis University | Hypochlorite compositions containing thiosulfate and use thereof |
| US7674473B2 (en) * | 2001-01-04 | 2010-03-09 | Byotrol Plc | Anti-microbial composition |
| WO2002097022A1 (en) * | 2001-05-30 | 2002-12-05 | Cognis Deutschland Gmbh & Co. Kg | Surfactant preparations comprising alpha-hydroxy acids |
| US7253139B2 (en) | 2001-05-30 | 2007-08-07 | Cognis Deutschland Gmbh & Co. Kg | Surfactant preparations comprising α-hydroxy acids |
| US8178484B2 (en) | 2007-07-17 | 2012-05-15 | Byotrol Plc | Anti-microbial composition comprising a siloxane and anti-microbial compound mixture |
| US8575085B2 (en) | 2007-07-17 | 2013-11-05 | Byotrol Plc | Anti-microbial composition comprising a quaternary ammonium biocide and organopolysiloxane mixture |
| US8003593B2 (en) | 2007-09-17 | 2011-08-23 | Byotrol Plc | Formulations comprising an anti-microbial composition |
| US8598106B2 (en) | 2007-09-17 | 2013-12-03 | Byotrol Plc | Anti-microbial composition exhibiting residual anti-microbial properties on a surface |
| US9029311B2 (en) | 2012-02-17 | 2015-05-12 | The Clorox Company | Targeted performance of hypohalite methods thereof |
| US9074163B2 (en) | 2012-02-17 | 2015-07-07 | The Clorox Company | Targeted performance of hypohalite systems thereof |
| US9499774B2 (en) | 2012-02-17 | 2016-11-22 | The Clorox Company | Targeted performance of hypohalite methods thereof |
| US10066193B2 (en) | 2012-02-17 | 2018-09-04 | The Clorox Company | Targeted performance of hypohalite methods thereof |
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