CA2190839A1

CA2190839A1 - Disinfectants and sanitizers with reduced eye irritation potential

Info

Publication number: CA2190839A1
Application number: CA002190839A
Authority: CA
Inventors: Larry K. Hall; Michael Yao-Chi Chiang; Judith Meszaros Meyer
Original assignee: Individual
Current assignee: Lonza LLC
Priority date: 1994-05-20
Filing date: 1995-05-19
Publication date: 1995-11-30
Also published as: AU2606095A; AU2656095A; US5547990A; MX9605701A; WO1995032269A1; WO1995031958A1

Abstract

It has been found that certain combinations of substituted imidazoline-based amphoterics and quaternary ammonium compounds show markedly reduced irritation profile in addition to providing excellent cleaning detergency. Moreover, it has further been found that certain substituted imidazoline amphoteric surfactants in combination with didecyl dimethyl ammonium chloride (DIDAC) show unexpected synergistic irritation compared to that observed when the quaternary is an ADBAC type. This allows the formulation of disinfectants and sanitizers with the favored antimicrobial agent while at the same time affording the optimum reduction in irritation potential.

Description

W0 95131958 ~ P~ . r -DISlNFECTANTS AND SANITIZERS WIT~
~;uU(~I) EYE IRRlTATION POTENTIAL
BACKGROUND OF T~li INVE~ON
Sanitizers and ,- r ' ' are r ~ ' intended to Teduce or destroy pathogenic bacteria, fungi and viTuses. Quaternary ~ serve as the active: ul,;~l agent in a wide variety of these r '- cuTrently used im the household, industrial and 1 markets. They are effective at low ~
S and provide a broad spectTum of b-~ riri~1~1 activity, against both gram positive amd gram negative bacteria. In addition to the Jb;~l agent, the r '- usually contain CO ~ r ' ' to assist in --~ soil 1 - as well as chelating agents to overcome ~ associated with hard water, and builders or acids to aid in cleaning p r . Over the years, these r '- have been optimized to afford excellent 10 ~-- r '- and sanitizing efficacy as well as providing good cleaning ~, r Aslabor costs have been increasimg substantially, there has been a trend toward the one-step . r ' /cleaners. Modern ,r " both clean and disinfect or sanitize in one ., ' T~is concept has also become attractive for the household market as well, where reducing cleaning time is desirable.
Tr r ' ' l~"standard~, ofchoice,beingcationic r . .
are quite irTitating to ocular tissue. rl'his is especially so of dialkyl quaternaTy chlorides which are very effficient as a ,- r ' ' With increased concerns overpathogens in the household e... t, the need for safe ~- r ' ' and sanitizers hasincreased. Therefore, there is heightened imterest im safe and mild household 1~ r . .
20 and sanitizers and it is desirable to obtain a ,- r . . r '- that is less irTitatmg but still efficient as a r The co, r ' ' used in most ,r '- also contribute to the overall irritation profile. The commonly used co r ' ' can be classified imto two categories:
nonyl phenol Cl~lu~ and linear alcohol t;LI~u~ T r ' ' ~ NPE's, 25 especially those with the best detergency, exhibit high Draize eye scores and are Wo 95/319~8 2 1 ~ 0 8 3 9 .. .. .2 , ..
a~ / labelled severely to moderately itritating. Linear alcohol ethoxylates are themselves less irritating, but do little to mitigate the itritation of the quaternary.
Several methods have been employed in the prior att to address the issue of reduced ocular irritation for ,~ r ' ' and sanitizer r, ' - Tr r ~ ~ l 5 none have combined a cost effective way to reduce irritation and enhance the overall clearling IJ~ r of the r~ inn Many co~ , while lessening the itritation of the quaternary, impact negatively on the biocidal efficacy of the quatemary.
While it is well known that anionic surfactants cannot be used in the presence of cationics, other surfactants including ethoxylates can dramatically reduce the biocidal effficacy of 10 ~ (Futura, Taro, ~Effect of AL~aline Builders amd Surfact~mts on the p~^tPriri~l~l Activity of Dh:l~y - '-J- Chloride", J. Ant~bac. Anti~ng.
Agents (1992) 20:12, pp. 617-22 (Japanese)) An early patent, U.S. Patent No. 3,402,242, assigned to Parachlo}
Chemical, describes the use of borax (sodium i 1 ) as an additive to a quatemaryr~ .. bemg applied as a spray or in nebulized form. The borax was described as reducing the irritation to eyes, nose amd throat of nebulized sprays in hospital rooms, nursing homes, etc. However, in a . form, the botax would not be effective in reducing the irritation of the quatematy amd would leave a residue upon ~1in~tinn Today most of the use of quaternary ~ r ' ' and sanitizers is in the area of dilutable . , where a small amount of concentrate is diluted with water and then used to disinfect walls, floors, furniture, etc. or im the product category called RTU, or ready-to-use. RTU products contain the quaternary at use ~ and are a widely used type of ,.- r ' ' for the household market.
It has been recognized that at use dilution ~ ;, e.g., 30 - 100 ppm, the itritability of quaternary: compounds can be reduced by the addition of: ,' surfact~mts and certain nonionic surractants at 1:1 and 10:1 surfactant /
quaternary ratios. "D- r ' ' and Sanitizers - Global Issues 1992" presented by L.
Hall, M.Chiang and D. Dutton of Lonza Inc. at CSMA/AOCS Detergent Industry 30 (' r l~ce~ September 13, 1992. EIowever, ~L~r~ techniques havenotbeenfound to mitigate the irtitation of r ~ nnC havmg a high of quaternary, ~uli~ ul~l.y above the critical micelle, (CMC).

W09SI31958 - 2 ~ 9 0 8 3 9 r~l,u~ - -Two patents assigned to American Cyanamid address reducing the ilfitation of household ,l . r ' ' In the first, US 4,336,151, the mvention describes the use of ~ u~y' ' ~o~ lUAy- ' ~ lanolin, hydrolyzed anunalprotein, aUantoin, dextrose sugar and/or imidazole to mitigate the ir~itation of, While the frst 5 two agents are effective at reducing ocular irritation, both are ethoxylates based on ethylene oxide, which have been shown to contain residual traces of I ,4-dioxane, a known ~- inngen .A~ , the protein, aUantoin, dextrose sugar and imidazole, while aU
being effective at reducing ocular irritation of quaternary-based r, l~ nc, offer no other p~,lr~ benefits. Indeed, residual sugar, for instance, unless totaUy and 10 completely rinsed, leads to sticky residues, attracting ants and providing a food supply for I~UIU~ _ ' Thus, while the r ~ ~ described do offer reduced ocular irritation, it does not come without drawbacks.
In US 4,336,152, the use of 1 as an irritation reducing compound for d-limonene containing ~ r ' is described. The use of rn~ Ytrin 15 reduced the irritation profile from a Draize score of 74 to 2, a very substantial change in irritationpotential. However, ' ' likedextrosecitedinUS4,336,151,provides nothing in the way of cleaning ' or lower cost and can contribute to residue or other deposits.
In none of the c( ' patents have all the critical objectives (i.e., 20 low cost, enhanced cleaning ~_ r , no post-application cleanup) been achieved.
Therefore, there is a long standing need to provide a cost 1rl~1i.~, quaternary-based 1 " that is both low in ocular irritation, while providing exceUent in-use clearling and detergency. AdditionaUy, the r " should provide one-step cleaning and (. r_ ~" and not require post-treatment rinsing nor cleanup in order to keep labor costs contained. FinaUy, it would be ~I~ if the r " could be based on readily available raw materials commonly used in detergent and cleaner r . . _ STJMMARY QF 1~ INVEI~ON
The present invention is based upon the unexpected discovery that the 30 1 of (1) certain substituted ' ' based: ,- with (2) quaterrlary , produce that have reduced ocular irritation, exhibit efficient cleaning and wetting and, most , '~y, are biocidaUy active. ,~
the cleaning efficiency of the is superior to the cleaning efficiency of th~

WO95131958 ~1 90839 r~
quaternary compound alone. These products can be used as, but are not limited to, hard surface 1~ r ' ' cleaners and dips for workers in fields which require direct ,, of their hands. The ~ nc can also be used to make at use dilution products, such as RTUs. : r Without intending to be bound to any theory, it is oelieved that the amphoteric surfactant is successful in reducing the irritation of the quaternary, above the critical micelle ~ - by , ,, the quaternary molecules into associative structures or micelles. By tightly binding the quaternary into these associative structures, the amphoteric structure reduces the cationic charge of the quaternary within the micelle, 10 making the quaternary less irritating on contact with animal tissue. Upon subsequent dilution and below the critical micelle . (CMC), the quaternary exists dissociated from the surfactant and can perform unimpeded in its ~)b;al efficacy.
r, , because rnany of the amphoteric surfactants exhibit two charged sites, one mole of surfactant can effectively reduce the irritation profile of two 15 moles of quaternary, thereby making the amphoteric extremely cost effective.
D~T~II.F.D DESCR~PrION OF T~. I~Y~.NTTON
The quaternary: ~ , ' that can be used in the present invention include d;lL~y- ' ~' chloride (DIDAC), alh~ ILYI
20: chloride(ADBAC),r~ ,.h~ . chloride(ethylbenzyl quat), ~ chloride or any ' of these, The general formula for the quaternary ammonium compound useful in the present invention has the following structure:
R

f ~ a ~ O

~herein Rl u~d R9 may be ~lcyl or dlco~cy groups of I to 4 c~ons; R, ~ay be ~ straight or b~anch~o cha~ of 6 to 18 ca~bon~; asui R~ may be citSor a ~tr~ht or branchod cbais~
of 6 to 18 ca~bon~, or a benzyl o~ aUcylbenzyl, v.~heleln tho allyl l roup may bo of 2 to 8 car~on~ atom~.
Exarnples of DD~AC quater~y ' _ , ' that can bo usod in th~ prosent inv~ntion inclute dloctyl ~ chloride, u~L~ld~yl~ii~-LL~ chlorido, dhl_y!.~' ~ ' chloride, ~yll~ - ~' y' ~ chloride, d;;~ ' chloride, a~l c-~ roof.
Spccific Q~ampl~ of AD~AC quaten~y l ~' Cf ~ for u~e in the pTesent invontion include aLtcyl (C~, sa~, cli 4096, c,~ lO~
chloride and allyl (CL 60%, C~ 30%, C,i 5~, Cl, 59~) " yll~l c~o.
~.~ av~ilable ,~ h 1 ~ulf;u tants cl~n be uscd ln 15 the p~t invent~ aDd are ~enerally " 1 ~y reacting a fatty aci~l with ~ amino ethyl ethanol unino to form an ami~. Watcr i5 efficiontty romoved to form an , which i~ then ~actod with methyl ac~ylate ~nd 1j7rrl to produce the ' ~ sodium ~t~.
The ;n-~ - g"~p~ sur~actants u30d in tho p~t invontion h~ve 20 she ~ollowinE general ~tructure, accordlnls to ~o CTEIA Co~r~c Ingrodient Dictiou Iy, Thlrd Edition, publi~hed by t~o Co~r~tic, Toilotry and ~agraDce ~ ' Inc.,~iVs~ , D.C.:
O lC21-140R
R--C--NH--C2H4--N--C2H~.R~
w~er~n R may be ~ faSty acid ~lkyl of 6 to 22 carhons; R~
may oo X or C~H~COOX or C7E~COO~a; ~ may be COONa ~r t~t~co~Na OX
or r~E~.COONa or C~COOC}~,COO~ or CHICOOC~COO~a.

WO95/31958 ; 21 9 3839 .~ r - ~

Specific examples of , ' surfactants that can be used im the presentinvention imclude sodium ~ ~: . ' , disodium c ~ , ' - ' , sodium ~~~ 1 r l~j ' ~ and disodium . "li ~r These ~ surfactants can also be ~ ti... ~,lly ~y ' ' usimg well known methods and are produced by reacting methyl acrylate and aLk~
at 1:1 to 2.5:1 ratios.
For use as a ~ r 5 t, the quatemary; compounds and amphoteric surfactants listed above can be blended im a weight ratio ranging about 10:1 10 to about 0.1:1 on a 100% active basis. Useful and preferred r ~ " in the present invention are listed in Table 1.
TABLE I
QUATERNARY/ CONCENTRATE, % Active USE
SURPACTANT DILUTION
` (RAT~O) QUATERNARY AMPHOTERIC PPM
15 Useful 10:1- 0.1:1 0.25 - 25 0.1- 30 10~10,000 Preferred 5:1- 0.3:1 0.5 -10 0.3 -10 100 -1000 For use im a system with reduced ocular irritation, the quaternary ~~~ r and: n surfactants listed above can be blended in a molar 20 ratio that ranges from 1:0.1 to l :S, with the preferred r;mge beimg 1:0.25 to 1:1. A blend of quaternary amd amphoteric surfactant at these molar ratios result im an ' decrease in ocular irritation, even at high of active quaternary (i.e., 10,000 ppm of active ~1 y). Because quaternary ammonium compounds and amphoteric surfact;mts are aqueous solutions, any method for blending such solutions 25 known in the art can be used. Cold mixing in a tar~ is a sufficient method.
The final ,r ~ " can also include chelators, builder salts, and dyes and fragrances such as those commonly used in the art in cleaning and ,-- r ..1 solutions. The pPlrfnt~, by weight, of chelators that may be used in the fnal ~ ~ ranges from 0.1 to 10 wt. %, with the preferred range being O.S to S wt. %.30 Examples of chelators that may be used are sodium and potassium salts of ~ W0 95/31958 : . 2 1 9 0 8 3 9 ~hy~ acid (EDTA), citric acid, niffil-~-rPfi~ acid, and various acids and zeolites.
The p~r~nt~eP, by weight, of building salts that may be used in the final ~ ranges from 0.1 to 15 wt. %, with the preferred range being 0.1 to 0.5 wt. %.
5 Examples of building salts that may be used include sodium ' , sodium ,' , sodium nifril ' ' , sodium carbonate, sodium silicate, citric acid salts amd zeolites.
In addition, noDionic surfactants can be included in the fnal f~ ' The percentage of these r ' ', by weight, im the final f( ' may be from about 10 0.1 to 25 wt.%, with a preferred range beimg 0.5 to 10 wt.%. When such nonionic surfactants are used at the use-dilution ~ an I ~ synergistic effect with r_gard to cleaning efficiency is obtained. In such r ~ '- where both nonionic and ,' surfactant are used along with the quaternary, less total surfactant, on an active weight percentage basis, is necessary to obtain a r l ~ n with greater cleaning 15 efficiency and less ocular irritation. Additionally, r ~ ' comprising only the nonionic surfactant with the , ' - surfactant, in a weight ratio of 0.1 to 10, are also part of the present invention.
Nonionic surfactants can be broadly defned as ~ , ' produced by the of a ll~h~ l ' aL~ylene oxide group with an aliphatic o} aLIcyl aromatic 20 h.~dlulJllubh, compound. Examples of preferred classes of nonionic surfactants are:
1. Long chain tertiary anune oxides ~ -n ~ , to the following general formula:
R~R2R3N O
wherein R, contains an aL~yl, aL~enyl or ~u~-y aL~yl radical of from about 8 to 25 about 18 carbon atoms, up to about 10 ethylene oxide moieties, and up to 1 glyceryl moiety, and R~ and R3 contain from 1 to about 3 caTbon atoms and up to about 1 hydroxy group, e.g., methyl, ethyl, propyl, hJd~u~lhyl~ or hy~ul~ylJlu~Jyl radicals. Examples of amine oxides suitable for use in this invention include:
- yl~de~y- oxide, 30 oleyldi(2 ~ u~l~l)amime oxide, ' - JlU- I~- oxide, d;,_llyld~- oxide, - - yl~ll~l~y- oxide, WO95~31958 `~ ~ 2190839 P ~
di('2-t~.ydlu~ )t~ oxide, 3-dodecoxy-2-h.~Lv~.y~lu~l~ii(3-1..~ u~jl)amine oxide, and ' ' ~" ' .y' oxide.

2. The pul~ h.yl."l~, oxide, ' of aL~cyl phenols, e.g., the s . ' products of aLIcyl phenols having an aLkyl group eontaining from about 6 to 12 earbon atoms in either a straight chain or branehed eh~un .~ with ethylene oxide, the said ethylene oxide being present in amounts equal to 6 to 60 moles of ethylene oxide per mole of aLkyl phenol. The alkyl substi¢uent in such compounds may be derived from ~,oly",~ lpropylene, ~ h",~" oetane, ornonane.

3. Those derived from the ' of ethylene oxide with the produet resulting from the reaetion of propylene oxide and ethylene diamime produets whieh may be varied in; , depending upon the balanee between the h.~dl,.' ' - and hydrophilic elements which is desired. For example, . . ' ~ contauling from about 40% tû about 80% polyu~ , by weight and having a molecular weight of from 15 about 5,000 to about ll,000 resulting from the reactiûn of ethylene oxide groups with a IIJ.- II ' base constituted of the reaction produet of ethylene diamine amd exeess propylene oxide, said base having a molecular weight of the order of 2,500 to 3,000, are D~ r~,~Luly.

4. The ,. ' product of straight or brdnched chain aliphatic alcohols 20 having from 8 ¢o 18 earbon atoms with ethylene oxide, e.g., a coeonut alcohol ethylene oxide eondensate having from 10 to 30 moles of ethylene oxide per mole of eoeonut aleohol, the eoconut aleohol fraction havmg from 10 ¢o 14 earbon atoms.
The preferred surfaetants to be used in the invention are nonyl phenol ethoxylates (6-12 moles), primary alcohol ethoxyla¢es (3-12 moles), and secondary alcohol 25 ethoxylates (3-12 moles).
Three cri¢eria are used ¢o test the r l ~ nc microbial efficiency; ocular irritation po¢ential; and cleaning efficiency. Tes¢s for these three eriteria are set forth below.
30 ~NT~ RORT~T ET~ CY
The crr~ DD of the r ~ '- of the mvention in reducing and des¢roying pathogenic baeteria, fungi, or viruses is .' ' by ¢esting ¢ne various W09S131958 ~ 9 0 8 3 '~ P~ sr g solutions against Sabnonella ~' ' I UGDI~;D and St~ lococcl D aureus at 1:33 dilution ratc, following the AOAC Use Dilution Test, a test protocol accepted by the EPA.
OCIJL~R TRRlTATloN
'! Ocular irritation is measured two ways, in vivo by the Drai7e and in vitro by the Bovine Corneal Opacity and ~ '.y Test ("BCOP").
D~i7~ R~;hit Eye Test Ocular irritation is measured by the Drai_e rabbit eye test, an acute eye irlitation evaluation method currently accepted by the EPA (See Pnnciples and Procedures 10 for Evaluanng the rOxicity of Household Products, National Academy of SciencePublication 1138 (1977)). Three or six rabbits are used for each test. The test solution is ~ t ~ to one eye of the rabbit. The other eye is used as a control. Tne eyes were compared at 1 hour, 1 day, 2 day, 3 day, 7 day, 14 day and 21 day timepoints, for the following three I cornea opacity; damage to the iris; and damage to the 15 ~; '-v~.
B~ Cnrn~1 O~ ity ~-~i r ~ ~ ~ Test The BCOP test (Gautheron, P. "Bovine Corneal Opacity and r, 1ity Test: an In Vitro Assay of Ocular Irritancy", Fund. and Appl. Toxicol. (1992) 18, pp.
442-49) is used to assess the ocular irritancy of the test materials to isolated bovine0 corneas. An in vitro score is ~ based on the test material's induced opacity and to fluorescein in the isolated bovine corneas.
The corneas of bovine eyes are excised and mounted in a corneal holder.
They are exposed to 750 microliters of test materials then incubated for 10 minutes at 32C, rinsed three times and imcubated again for 2 hours. As the positive control, 25 corneas are dosed with acetone, in the same fasbion as with the test materials. An opacity is performed on each cornea. The corrected opacity values for each treated comea is calculated by subtracting the pre-treatment opacity readings from the post-treatment opacity readings. The mean opacity value of each cornea is calculated 'oy averaging the corrected opacity values of the treated corneas for each treatment condition.
The BCOP assay is accepted when the positive control, acetone, causes an in vitro score that falls witbin two standard deviations of the historical mean. The following ~ system is used to rank the BCOP scores:

wo 95/31958 ` 2 109 8 3 ~ r~.,o.. ~ c - ~
In ~.~o S~ r-P.
0 - 25 Mild irritant over 25 - 55 ~ Moderate irritant above 55.0 Severe irritant 5t~r~F.~ G ~ CY
t~ W~C~ ility TP~t (ASTM #D4488-85) The "Hard Surface Cleanirlg Using Pigrnent-Clay Soil" method is a test in which synthetic particulate and oily soil is applied to vinyl tiles and then the vimyl tiles are cleaned with detergent r ' '- using the Gardner Str~ught Line W ' ' ' ~/
10 Apparatus. The efficiency of soil removal is based on tne color difference between soiled and washed tiles, which is measured by reflectmce readings from a: ' . The result are expressed as percent soil removal ( % SR).
The use of these r 1-~if~nc is also part of the present imvention. It is li' l that there would be many uses for a r ~ '- with a quaternary of 0.25 to 25 wt. %, which cause little or no irritation to ocular and other animal tissue. Such uses would include hard surface ,- r ' /sanitizers, a hand dip for workers in such areas as the meat and poultry industry and the medical fields, ~;al handsoaps and saTutizing laundrv rinses. These, r ~ -can also be used as a starling material for other products, at use dilution, such as RTUs.
The followirlg examples are iUustrative of the present invention, however, it wiL be understood that the invention is not limited to the specific details set forth in the examples.
l~xarn~le I
r~ consisting of blends of DIDAC quatemary:
, ' and disodium: . i . (~, ` K-2, a registered trademark of Lonza, Inc.,Fair Lawn, N.J.) were tested by the in vi~ro BCOP method to rank ocul.rr irritation. Quatemary ammonium , to surfactant molar ratios of 1:0.25, 1:0.5, and 1:1, at 10,000 ppm active quatemary, were evaluated.

~Wo95r3l958 . . 2 1 ~ 08 3 9 P~

% % O~uaternmy: Surfactant In Yuro Toxici~
DIDAC, Surfactant, Active Active Molar Wt, Actives BcOP Score Irritation Rating

5 1 ~ 0 -- 89 Severe 0.33 1:0.25 1:0.33 58 Moderate 0.65 1:0.50 1:0.65 24 Mild 1.31 1:1 1:1.31 8 very Mild rrhe quaternary to surfactstnt molar ratio of 1:0.25 was sufficient to reduce the in vitro ocular toxicity ratirtg frAvm a severe irritant to a moderate irritant.
U~ ~t~ly, with 1:0.5 and 1:1 molar ratios of the DIDAC to the amphoteric surfactant, the in vitro ocular toxicity ratirtg of the DIDAC is reduced to "mild irritartt"
artd "very mild irritant."
Example 2 The identical chemical r ~ that were tested by BCOP in Example 1 were tested usirtg the Draize test, and the results are m Table 3.
TA~3LE 3 1" Vlw Toxicity O~uaternar~v: Surfactant Drnze Score Molar wt~ Activec DAY 1 DAY 7 DAY 2 1:0 -- 38 28 12 251:0.25 1:0.33 7 s 0.3 1:0.50 1:0.66 13 4 3.3 1:11:1.31 10 2 o WO95/31958 `~ ~ 2 1 9 0 ~ 3 q ~ ~
Similar to the BCOP scores, the one, seven and twenty-one day Draize scores all showed reduction in irrihtion by the DIDAC quaternary with the addition of the substituted ' ' based amphoteric surfactant.
5 ~Lm~le 3 I7. ' consisting of blends of ADBAC quaternary ammonium compounds and disodium ~ , ' 'ii . I were tested by the in ~itro BCOP Test.
The results are shown in Table 4. I~. ' with quaternary ammonium, to surfactant molar ratios of 1:0, 1:0.5, and 1:1, in which there is 10,000 ppnn (1%) 10 active quaternary, were evaluated.

Ouatcrnra~: Surfactant In V~no Toxici~
Molu wt, Active BCOP score IrritutionRating 15 1:0 - 70 sovQe :0.50 1:0.66 47 Modcrlto 1:1 1:1.32 42 Moderate The BCOP scores for all of the r~ illustrate reduction in ocular 20 irritation.
Example 4 Several amphoteric surfactant types were blended with DIDAC at 1:0.5 quaternary to surfactant molar ratio and 10,000 p,om active quaterllary. Ocular irritation 25 was evaluated by the BCOP method. The: , ' used were t~te followmg: sodium ,: ,', ., , disodium ~:: .' 'i ., , sodium ~ ,' and disodium.~ '~' The results are ' in Table 5.

~W0 95/31958 2 1 q O 8 3 q r~

TABLEi S
% Qusternary: surfsct~mt In Vtro Toxicity DIDAC, Surfact~mt Active Type Molar wt, Actives BCOP Score IrritstionR~tmg 5 1 --I:o - 89 severe Sodim~ 1:0.5 1:0.53 32 Moder~te cocoampho-propionate disodium 1:0.5 1:0.65 24 Mild cocoampho-dipropiorlate sodium 1:0.5 1:0.51 ss severe coconmpho-acehte di90dium 1:0.5 1:0.62 51 Moderate cocoampho-diacehte As shown im the Table, each type of amphoteric surfactant reduced the quaternary from a severe irritant to a mild or moderate irritant at a ratio of 1:0.5 quaternary to surfactant, with disodium '~ ,' 'i ,' ' exhibittng the greatest irritation mitigation.
~unple 5 The ' '' '' based ~ surfactmt can also be obtained by leacting dtfferent mole ratios of ' ' to methyl acrylate (MAC) prior to the blending of the surfactant with the quaternary. The irritation mitigation effect of these 20 surfactants on quaternary . , ' were also v, ~i,, ' ' by the BCOP
method.

~J7 F~rf~ g 2 1 9 0 8 3 9 ~P~ JVN f~96 t~Surfu:t~t Ir~ v To~city DIDAC, I~ olW
AcUv~ MAC R-tio Mul-r Wt, AcUve~ BCop 9com ~ Uon R~U~y S I-- 1:0 -- ~9 ~v~
1.3 1:0.5 1:0.57 62 90v 1.6 1:0.5 1:0.60 43 Mo~r lo t.O 1;0.5 1:0.65 19 h~t .. 5 1:0.5 ~ :0.67 28 blo~

A~ shown in Taolo 6, a po~itive corIelat~on be~woo~ irritation mitigation effoct and ' ~ ' ~ '' to MAC r~tio of t~ burfactsnt w~ c ~ ' " ' l, witb tho hi~her the riLtlo, tho groater tho ~nitation reductLon offcct. In thn t~ out of four ca~o~, tho ocular ~ihtion poteut;41 of the quato~y wa~ re~uced from severo ttJ ~odcIate by the addit~on l5 o~ ~o urfactant.

l~;a~pl~6 r~ of di 11ryl disnot~yl ~ ' compound and sur~actant ~t vsr~ou~ lar ratio~, w~e to~ted aga~n~t ~bno~ ', ' (SC) and ZO S~ JZ~-a~.,t, a a~r~u~ ~, at a 1:33 dilution r to, by u~ing AOAC U50 Dilution 're~t.
The ~e~ults ~ ~hown in l~lo 7.

.

~
WO 9~i/31958 ~ 2 1 9 3 8 3 q r~

.
Wt % Wt % Ouaternary: Surfactant AOAC Use Dilution;
DIDAC ~ , deior~ized water Active Molar Wt, Actives S.C. ATCC S.A. ATCC
5 Active ~10708 ~Y6538 --1:0 -- 0/20 0/20 0,331:0.25 1:0.33 0/20 0/20 0.651:0.50 1:0.65 0/20 0/20 1.311:1 1:1.31 0/20 2/20 As shown by the Tables 2 amd 7, an optimum molar ratio of quaternary to surfactant, im terms of balancing irrttancy reduction with microbial efficiency is 1:0.5.
EXamDle 7 As showrt by the previous examples, r '- of the present invention 15 can be expected to have reduced ocular irritation as well as good (i.e., stro~g) microbial efficacy. The following examples ~' the cleaning efficacy of formulated systems, as well as the reduced ocular ir~itation and microbial efficacy.
The results are shown in Table 8.

20cornponent, Actives % A B C D E F
DIDAC 1.9 1.9 1.9 1.9 1.9 1.9 EDTA Na4 0.76 0.76 0.76 0.76 0.76 0.76 Non~ c 6.1+ 6.1+ 3.0+ 3.0+ 6.1~ 3.0 r --1.24 1.24 2.48 -- 1.24 25 I' 'i .
Dl w~ter q.s. to 100 + Tergitol 15~-12 ~ Neodol 25-12 W095/31958 ; ~ ~ ?1 90~39 P~ S- --16:

Component, Actives % A B C D E F
Total Surfact~nt Active 6.1 7.34 4.24 5.48 6.1 4.24 wt %
SIQ wVwt 3.2 3.9 2.2 2.9 3.2 2.2 S/Q mols 1.6 2.1 1.3 1.8 1.6 1.3 5 QunVAmphotcrge -- 1:1.53 1:1.53 1:0.77 - 1:1.53 wVwt Rntio Molar Ratio 1:0 1:0.5 1:0.5 1:1 1:0 1:0.5 BCOP Score 8S 45 56 44 59 48 0 BCOP Rating Severe Moderate Severe Moderate Severe Modcrate Perform,mce nt 1:64 Dilution im D.I. Water, 300 ppm actives Gsdner Cle~ming 58 79 60 75 50 50 (% SR) 15~ Efficacy at 1:64 Dilution SA, DI & 5% Soil 1/20 1/20 0/20 1/20 0/20 1/20 SC, Dl ~ 5% Soil 1/20 l/20 1/20 0/20 0/20 0/20 As shown by Table 8, the r ~ - without disodium 20 ~ r- (I~ ~ - A) gave a BCOP score of 88, a severe irritation rating. The addition of disodium ~ .' 'i , (r. ' ' B) decreased the BCOP score to 45, a modelate irritation rating. U , ' '1~" this r ~ - also showed an imcrease in Gardner Cleaning score of 58% SR to 79% SR with t~te same microbial efficiency.
Another surprisimg result i8 obtained from a r l-~ti~m which contairts two parts nonionic surfactant and one palt amphoteric surfactant . lr-~inm C). While the total surfactant activity weight percentage is 50% less than W0951319S8 t ' ` ' 2 1 9 0 8 3 9 r~l~u~
that in r~ B, r. c still has a lower irrita~ion score without a loss in cleaning abi]ity or microbial efficiency. This shows a synergistic activity between the non-ionic and, ,. . r ~ .
While several nonionic surfactants may be used to obtain the 5 : ~ ' irritation reduction combined with cleaning ~ the desired consisted of secondary alcohol ethoxylate and disodium ~~ . i 1. which gave the best balance of detergency and low irritancy scores.

Claims

181. A sanitizing and disinfecting composition comprising:
a) a quaternary ammonium compound, having the following general formula:
wherein R1 and R2 may be alkyl or alkoxy groups of 1 to 4 carbons; R3 may be a straight or branched chain of 8 to 12 carbons; and R4 may be either a straight or branched chain alkyl group of 8 to 12 carbons, or a benzyl or alkylbenzyl, wherein the alkyl group may be of 2 to 8 carbon atoms; and b) a substituted imidazoline based amphoteric having the following general formula:
wherein R may be a fatty acid alkyl of 6 to 22 carbons; R1 may be H or C2H4COOH or C2H4COONa; R2 may be COONa or CH2CHCH2SO3Na or OH
C2H4COONa or CH2COOCH2COOH or CH2COOCH2COONa; wherein the concentration of said quaternary ammonium compound is about 0.25 to 25 wt.% and the concentration of said imidazoline amphoteric surfactant is about 0.1 to 30 wt.% and the weight ratio of said quaternary ammonium compound to said amphoteric surfactant is about 10:1 to 0.1:1.
2. The composition of claim 1, wherein said concentration of ammonium compound is about 0.5 to 10 wt.%.
3. The composition of claim 1, wherein said concentration of quaternary ammonium compound is greater than the critical micelle concentration.
5. The composition of claim 4, wherein said weight ratio is about 5:1 to 0.3:1.
6. The composition of claim 1, wherein the molar ratio of said quaternary ammonium compound to said amphoretic surfactant is about 1:01 to 1.5.
7. The composition of claim 6, wherein said molar ratio is about 1:0.25 to 1:1.
9. The composition of claim 1, wherein said quarternary ammonium compound is alkyldimethylbenzyl ammonium chloride, dialkyldimethylammonium chloride, alkyldimethylethylbenzyl ammonium chloride, benzethonium chloride or combinations thereof.
10. The composition of claim 9, wherein said dialkyldimethyl ammonium chloride is dioctyldimethylammonium chloride, octyldecyldimethylammonium chloride, didecyldimethylammonium chloride, decylisononyldimethylammonium chloride, diisodecyldimethylammonium chloride or combinations thereof.

12. The composition of claim 1, wherein said imidazoline amphoteric surfactant is sodium cocoamphoacetate, disodium cocoamphodiacetate, sodium cocoamphopropionate or disodium cocoamphodipropionate.
13. The composition of claim 1, wherein said composition further comprises one or more of the following: chelators; builder salts; dyes; fragrances; and nonionic surfactants.
14. The composition of claim 13, wherein the percentage of said chelator is about 0.1 to 10 wt.%.
15. The composition of claim 14, wherein the percentage of said chelator is about 0.5 to 5 wt.%.
16. The composition of claim 13, wherein said chelator is sodium or potassium salts of EDTA, citric acid, nitriloacetic acid, phosphoric acid or zeolite.
17. The composition of claim 13, wherein the percentage of said builder salt is 0.1 to 15 wt.%.
18. The composition of claim 17, wherein the percentage of said builder salt is 0.5 to 5 wt. %.
19. The composition of claim 13, wherein said builder salt is sodium metasilicate, sodium tripolyphosphate, sodium nitriloacetate, sodium carbonate, sodium silicate, citric acid salt or zeolite.
20. The composition of claim 13, wherein the percentage of said nonionic surfactant is 0.1 to 25 wt.%.

21. The composition of claim 20, wherein the percentage of said nonionic surfactant is 0.5 to 10 wt.%.
22. The composition of claim 13, wherein said nonionic surfactant is a long chain tertiary amine oxide; a polyethylene oxide condensate of alkyl phenols; a condensation product of ethylene oxide or ethylene oxide and propylene oxide; or a condensation product of alkylene oxides with straight or branched chain aliphatic alcohols.
23. A sanitizing and disinfecting composition comprising:
a) a substituted imidazoline based amphoteric; and b) a nonionic surfactant;
wherein the concentration of said imidazoline amphoteric surfactant is about 0.1 to 30 wt. % and the concentration of said nonionic surfactant is about 0.5 to 10 wt. %.
24. The composition of claim 23, wherein the weight ratio of said amphoteric surfactant to said nonionic surfactant is about 0.1:10.
25. The composition of claim 23, wherein said nonionic surfactant is a long chain tertiary amine oxide; a polyethylene oxide condensate of alkyl phenols; a condensation product of ethylene oxide or ethylene oxide and propylene oxide; or the condensation product of ethylene oxides with straight or branched chain aliphatic alcohols.
26. A method of disinfecting and sanitizing comprising contacting animal skinwith a composition of quaternary ammonium compound, having the following generalformula:

wherein R1 and R2 may be alkyl or alkoxy groups of 1 to 4 carbons; R3 may be a straight or branched chain of 8 to 12 carbons; and R4 may be either a straight or branched chain alkyl group of 8 to 12 carbons, or a benzyl or alkylbenzyl, wherein the alkyl group may be of 2 to 8 carbons atoms and a substituted imidazoline based amphoteric having the following general formula:
wherein R may be a fatty acid alkyl of 6 to 22 carbons; R1 may be H or C2H4COOH
or C2H4COONa; R2 may be COONa or CH2CHCH2SO3Na OH
or C2H4COONa or CH2COOCH2COOH or CH2COOCH2COONa, wherein the concentration of said quaternary ammonium compound is about 0.25 to 25 wt.% and the concentration of said amphoteric is about 0.1 to 30 wt.% and the weight ratio of said quaternary ammonium compound to said amphoteric surfactant is about 10:1to 0.1:1.

27. The method of claim 26, wherein the concentration of said quaternary is about 0.5 to 10 wt.%.
28. The method of claim 26, wherein said concentration of said active quaternary ammonium compound is greater than the critical micelle concentration.
29. The method of claim 26, wherein said animal skin is human.
30. A method of sanitizing and disinfecting comprising contacting a hard surface with a formulation of quaternary ammonium compound, having the followinggeneral formula:
wherein R1 and R2 may be alkyl or alkoxy groups of 1 to 4 carbons; R3 may be a straight or branched chain of 8 to 12 carbons; and R4 may be either a straight or branched chain alkyl group of 8 to 12 carbons, or a benzyl or alkylbenzyl, wherein the alkyl group may be of 2 to 8 carbons atoms and a substituted imidazoline based amphoteric having the following general formula:
wherein R may be a fatty acid alkyl of 6 to 22 carbons; R1 may be H or C2H4COOH
or C2H4COONa; R2 may be COON, or or C2H4COONa or CH2COOCH2COOH or CH2COOCH2COONa, wherein the concentration of said quaternary ammonium compound is about 0.25 to 25 wt. %
and the concentration of said amphoteric is about 0.1 to 30 wt. % and the weightratio of said quaternary ammonium compound to said amphoteric surfactant is about 10:1 to 0.1:1.
31. The method of claim 30, wherein said concentration of said quaternary ammonium compound is about 0.5 to 10 wt, %, 32. A method of making a sanitizing and disinfecting composition comprising adding to a formulation of quaternary ammonium having the following general formula:
wherein R1 and R2 may be alkyl or alkoxy groups of 1 to 4 carbons; R3 may be a straight or branched chain of 8 to 12 carbons; and R4 may be either a straight or branched chain alkyl group of 8 to 12 carbons, or a benzyl or alkylbenzyl, wherein the alkyl group may be of 2 to 8 carbons atoms and substituted imidazoline based amphoteric having the following general formula:

wherein R may be a fatty acid alkyl of 6 to 22 carbons; R1 may be H or C2H4COOH or C2H4COONa; R2 may be COONa or CH2CHCH2SO3Na OH
or C2H4COONa or CH2COOCH2COOH or CH2COOCH2COONa, wherein the concentration of said quaternary ammonium compound is above 0.25 wt.%, and amount of water sufficient to reduce the concentration of said quaternary ammonium compound to below 0.25 wt.% and the weight ratio of said quaternary ammonium compound to said amphoteric surfactant is about 10:1 to 0.1:1.