WO2000009642A1 - Hard surface cleaning and disinfecting compositions - Google Patents

Abstract

Provided are aqueous hard surface cleaning and disinfecting compositions which comprise the following constituents: (a) at least one cationic surfactant having germicidal properties; and (b) a fluorosurfactant selected from the group of nonionic fluorosurfactant, cationic fluorosurfactant, and mixtures thereof. Optionally, the compositions may further include (c) one or more detersive surfactants particularly selected from carboxylate surfactants, as well as nonionic, cationic, amphoteric surfactants, and mixtures thereof; (d) one or more organic solvents; (e) one or more alkanolamines; and further conventional additives.

Description

HARD SURFACE CLEANING AND DISINFECTING COMPOSITIONS

3

The present invention geneially relates to haid suiface treatment compositions which impart a cleaning and sanitizing effect, as w ell as piocesses for their use

Cleaning compositions aie commeicially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially 0 those characterized as useful with "hard surfaces" Hard surfaces are those which are frequently encountered in lavatones such as lavatory fixtmes such as toilets, shower stalls, bathtubs, bidets, sinks, etc , as well as in kitchen and food preparation facilities, such as countertops, cabinet and appliance surfaces, as well as walls, floors, etc

The prior art has suggested many aqueous compositions which are directed to l -> provide a cleaning or disinfecting benefit to such hard surfaces Certain of the provide both effective cleaning and disinfection of a treated surfaces These compositions piedommanfly are aqueous pieparations which include one or more detersive surfactants, one or more organic solvents and in minor amounts, conventional additives included enhance the attractiveness of the product, typically 20 fragrances and coloπng agents

While these known-art compositions may provide advantages, there is a continuing need in the art for such hard surface treatment compositions which include reduced amounts of active constituents, and which minimize or eliminate the amounts of organic solvents which need be present m such compositions 23 It is yet a further object of the invention to provide a readily pourable and readily pumpable cleaning composition which features the benefits descπbed above

It is a further object of the invention to provide a process for cleaning or samtization of hard surfaces, which process comprises the step of providing the composition as outlined above, and applying an effective amount to a hard surface 30 requiring such treatment

These and other objects of the invention shall be moie apparent from a reading of the specification and of the claims attached According to a first aspect of the invention there is piovided a haid surface cleaning and disinfecting composition w hich compπses (preferably, consisting essentially of) the tollow ing constituents

(a) at least one cationic sm factant having geπmcidal properties, ι (b) a fluorosurfactant selected fiom the gioup of nonionic fluorosurfactants cationic fluorosuifactants and mixtures thereof, (c) optionally, one or more deteisive surfactants particularly selected from carboxylate surfactants, nonionic. cationic and amphoteric surfactants and mixtuies thereof 0 (d) optionally one or moie organic solvents,

(e) optionally one or more alkanolamines,

(f) a major proportion of watei

The compositions described aboλ e may further include (g) one or more further conventional optional constituents such as pH buffering agents, perfumes, perfume carriers, colorants, hydrotropes. germicides, fungicides, anti-oxidants, anti- coιτosιon agents, and the like

Preferred compositions according to the invention are largely aqueous, and are readily pourable and pumpable when packaged from a manually operable pump, such as a 'trigger spray' dispenser The preferred compositions of the invention feature 0 good cleaning, disinfection of hard surfaces and little or not buildup of residue on treated hard surfaces

According to a second aspect of the invention, there is provided a hard surface cleaning and disinfecting composition w hich comprises (preferably, consisting essentially of) the following constituents ^<ϊ (a) at least one cationic surfactant having germicidal properties,

(b) a fluorosurfactant selected from the group of carboxylate surfactants, as well as nonionic fluorosurfactants, cationic fluorosurfactants and mixtures thereof,

(c) one or more detersive surfactants particularly selected from nonionic, 0 cationic and amphoteric surfactants and mixtures thereof,

(f) a major proportion of water, characterized in that the composition is essentially free of (d) one or more oiganic solvents, such as water soluble alcohols etheis, and glycol etheis and furthei is essentially free of (e) one 01 moie alkanolamines These compositions

include (g) one 01 moie furthei com entional optional constituents such as pH butfeπng ^•^ agents, perfumes, perfume caπieis, coloiants, hydiotropes, germicides, fungicides anti-oxidants, anti-corrosion agents, and the like

According to a thud aspect of the invention, there is provided a hard suiface cleaning and disinfecting composition which compnses (pieferably, consisting essentially of) the following constituents 0 (a) at least one cationic suifactant having germicidal properties

(b) a fluorosurfactant selected fiom the group of nonionic fluorosurfactants, cationic fluorosurfactants and mixtures thereof (d) one or more oi game solvents, (f) a major proportion of water ^s! characterized m that the composition is essentially free of (c) one or more detersive surfactants particularly selected from caiboxylate surfactants, nonionic, cationic and amphoteric surfactants as well as being essentially free of (e) one or more alkanolamines The compositions may optionally include (g) one or more further conventional optional constituents such as pH buffering agents, perfumes, perfume 0 carriers, colorants, hydrotropes, germicides, fungicides, anti-oxidants. anti-corrosion agents, and the like

In accordance with a fourth aspect of the invention there is provided a hard surface cleaning and disinfecting composition which comprises (preferably, consisting essentially of) the following constituents ι (a) at least one cationic surfactant having germicidal properties,

(b) a fluorosurfactant selected from the group of nonionic fluorosurfactants, cationic fluorosurfactants and mixtures thereof, (f) a major proportion of watei, wherein the compositions are essentially free of (c) detersive surfactants, particularly 0 carboxylate surfactants, as well as nonionic, cationic and amphoteπc surfactants, of (d) organic solvents, as well as being essentially free of (e) one or more alkanolamines These compositions may optionally include (g) one or more further conventional optional constituents such as pH buffering agents perfumes, perfume caiπeis, colorants, hydiotropes, germicides, fungicides, anti-oxidants, anti- corrosion agents, and the like

In accoi dance with a fifth aspect of the invention there is pi ovided a hard ^ suiface cleaning and disinfecting composition which compπses (pi efei ably, consisting essentially of) the following constituents

(a) at least one cationic surfactant having germicidal pioperties,

(b) a fluorosurfactant selected fiom the gioup of nonionic fluorosuifactants, cationic fluoiosurfactants and mixtures thereof,

10 (d) one 01 moie organic solvents,

(e) an alkanolamine,

(f) a majoi proportion of water, wherein the compositions are essentially fiee of (c) detersive surfactants, particulaily carboxylate surfactants, as well as nonionic, cationic and amphoteric surfactants l _^ These compositions may optionally include (g) one or more further conventional optional constituents such as pH buffering agents, perfumes, perfume carriers, colorants, hydrotropes, germicides, fungicides, anti-oxidants, anti-corrosion agents, and the like

A sixth aspect of the present invention provides for a hard surface cleaning

20 and disinfecting composition which comprises (preferably, consisting essentially of) the following constituents

(a) at least one cationic suifactant having germicidal properties,

(b) a fluorosurfactant selected from the group of nonionic fluorosurfactant, cationic fluoiosurfactant, and mixtuies theieof,

2_^ (c) one or more detersive surfactants particularly selected from carboxylate surfactants, as well as nonionic, cationic, amphoteric surfactants, and mixtures thereof,

(e) an alkanolamine.

(f) a major portion of water,

30 characterized in that the compositions are essentially free of (d) one or more organic solvents The compositions described above may fui thei include (g) one 01 more further conventional optional constituents such as pH buffeπng agents, pei fumes, pei fume caπieis, colorants hydiotropes, viscositv modifving agents, furthei germicides, fungicides, anti-oxidants, anti-coπosion agents, and the like ^• _^ A seventh aspect of the present invention piovides toi a hard sui ice cleaning and disinfecting composition which comprises (pi eferablv. consisting essentially of) the following constituents

(a) at least one cationic surfactant having germicidal properties,

(b) a fluorosurfactant selected from the group of nonionic fluorosurfactant, 0 cationic fluorosurfactant, and mixtures thereof,

(c) one or more detetsive suifactants particulaily selected fiorn carboxylate surfactants, as well as nonionic, cationic, amphoteπc surfactants, and mixtures thereof,

(d) one or more organic solvents, and ^ (f) a major portion of water, characteπzed in that the compositions are essentially free of (e) alkanolamines

The compositions described above may further include (g) one or more furthei conventional optional constituents such as pH buffering agents, perfumes, 0 pei fume carπeis, colorants, hydrotropes, viscosity modifying agents, further germicides, fungicides, anti-oxidants, anti-corrosion agents, and the like

In accoidance with an eighth aspect of the invention there is provided a hard surface cleaning and disinfecting composition which comprises (preferably, consisting essentially of) the following constituents -> (a) at least one cationic surfactant having germicidal properties,

(b) a fluorosurfactant selected from the group of nonionic fluorosurfactants, cationic fluorosurfactants and mixtures thereof,

(e) an alkanolamine,

(f) a major proportion of water,

30 wherein the compositions are essentially free of (c) detersive surfactants, particularly carboxylate suifactants, nonionic, cationic and amphoteric surfactants, as well as being essentially free of (d) one or more organic solvents These compositions may optionally include (g) one or more furthei conventional optional constituents such as pH buffering agents, perfumes, perfume carπeis, colorants hydi otiopes. genmcides, fungicides,

anti-corrosion agents, and the like

The aqueous compositions taught heiem pi ovide surpi isingly good cleaning and disinfection of haid sui faces merely with the inclusion of the pi efeπed germicidal constituents and the fluoiosui factant constituents These excellent results are surprisingly obtained without the inclusion of certain further constituents as described m the second, third, fourth, fifth, sixth and seventh aspects of the invention discussed previously It is particularly surprising that excellent cleaning and disinfecting results are obtained with the various aspects of the invention

The mventiλ e compositions necessarily include (a) at least one cationic surfactant having genmcidal properties

Particularh preferred for use as the (a) at least one cationic suifactant having germicidal properties are those which provide a bioad antibacterial or sanitizing function Any cationic surfactant which satisfies these requirements may be used and are considered to be within the scope of the present invention, and mixtures of two or more cationic surface active agents, i iz cationic surfactants may also be used Cationic surfactants are well kno n, and useful cationic surfactants may be one or more of those know n to the art Examples of prefeπed cationic surfactant compositions useful in the practice of the instant invention are those hich provide a genmcidal effect to the concentrate compositions, and especially preferred, are quaternary ammonium compounds and salts thereof, which may be characteπzed by the geneial structural formula

where at least one of Ri , R₂, Ri and R4 is a alkyl, aryl or alkylaryl substituent of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165 The alkyl substituents may be long-chain alkyl, long-chain alkoxyaryl, long-chain alkylaryl, halogen-substituted long-chain alkylaryl, long-cham alkylphenoxyalkyl. arylalkyl, etc The remaining substituents on the nitrogen atoms othei than the abovementioncd alkvl substituents are hvdiocarbons usually containing no mote than 12 carbon atoms The substituents R|, Ri, R? and R₄ may be straight- chained 01 may be branched but aie preferably straight-chained and may include one or moie amide, ether 01 estei linkages The countenon X mav be any salt-forming amon which permits watei solubility of the quaternaiy ammonium complex

Exemplaiy quatemai} ammonium salts within the abo\ e description include the alkyl ammonium hahdes such as

tπmethyl ammonium bromide, alkyl aryl ammonium hahdes such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyπdimum hahdes such as N-cetyl pyπdmium bromide, and the like Other suitable types of quaternary ammonium salts include those in which the molecule contains eithei amide, ether or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chlonde, N-(laurylcocoaminofonnylmethyl)-pyndimum chloπde, and the like Othei veiy effective types of quaternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is

\ characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltπmethyl ammonium chloride, cetylaminophenyltnmethyl ammonium methosulfate, dodecylphenyltπmethyl ammonium methosulfate, dodecylbenzyltiimefhy] ammonium chloride, chlorinated dodecylbenzyltπmethyl ammonium chloride, and the like

20 Prefeπed quaternaiy ammonium compounds which act as germicides and which aie be found useful in the practice of the present invention include those which have the structural formula

25 wherein R₂ and R₃ are the same or different C₈-Cι₂alkyl, or R₂ is C_{) 2} ι₆alkyl, C_{8 18}alkylethoxy, C_b ι₈alkylphenoxyethoxy and R₃ is benzyl, and X is a hahde, for example chloride, bromide or iodide, or is a methosulfate amon The alkyl groups recited in R₂ and Ri may be stiaight-chamed or branched, but are preferably substantially linear Particularly useful quatemai y germicides include commercially available preparations which include a single quaternaiy compound, as w ell as mixtures of two or moie different quaternary compounds Particulailv useful quaternary germicides include those which are presently commeicially

ailable undei the tradenames ϊ BARDAC®. BARQUAT®, BTC® , LONZABACα? ONYXIDE® and HYAMINE® such as aie presently marketed by Stepan Co (Chicago ID 01 Lonza Ine (Basle, CH) Exemplaiy useful commeicial preparations containing such quaternary compounds are more fully described in the literature, for example, in McCutcheons 's Functional Materials (Vol 2) North American Edition 1998 and m the respective 0 product literatuie from the supplies identified herein These commercial preparations are piedominantly based on aqueous oi aqueous/alcohol mixtures which function as cameis for the actι\ e constituents By way of non-limiting example useful commercial pieparations include BARD AC® 205M (50% active) and BARD AC® 208M (80% active) are described as being a liquid preparation contaimng alkyl 1 dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloπde, didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloπde, BARDAC® 2050 (50% active) and BARDAC® 2080M described to be a combination of octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloπde, BARDAC® 2250 0 (50% active) descπbed to be didecyl dimethyl ammonium chloride, BARQUAT® MB-50, BARQUAT® MX-50 and BARQUAT® OI-50 each a liquid preparation (50% actives) described to be an alkyl dimethyl benzyl ammonium chloride, BARQUAT® MB-80 or BARQUAT® MX- 80 each a liquid preparation (80% actives) each of which is descπbed to be an alkyl dimethyl benz\ l ammonium chloride; S BARDAC® 4250, BARQUAT® 4250Z (each 50%

es) or BARQUAT® 4280, BARQUAT® 4280Z (each 80% actives) each of which is described as being alkyl dimethyl benzyl ammonium chloπde/alkyl dimethyl ethvl benzyl ammonium chloride Also useful is HYAMINE® 1622 descπbed to be a liquid preparation dnsobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (available

30 either as 100% actives or a 50% actives solution), HYNMINE® 3500 (50% active) and HYAMINE® 3500-80 (80% active) each described as being alkyl dimethyl benzyl ammonium chloπde Further useful are BTC® 50 NF or BTC® 65 NF each described as a liquid prepaiation containing alkyl dimethvl benzyl ammonium chloride (50% active), BTC® 776 descπbed as alkyl dimethyl ben/yl ammonium chloπde/dialkvl methyl benzyl ammonium chloπde (50% active). BTC® 818 (50% actn e) as well as BTC(i< 818-80 (80% actives) each descnbed to be octyl decyl

^■ _^ dimethyl ammonium chloπde didecyl dimethyl ammonium chlonde and dioctyl dimethyl ammonium chlonde BTC® 824 and BTC® 815 each described as being alkyl dimethyl benzyl ammonium chlonde (50% ac es), BTC® 885 (50% actives) and BTC® 888 (80% actives) each described as being alkyl dimethyl benzyl ammonium chloπde, octyl decyl dimethyl ammonium chloride, didecyl dimethyl

10 ammonium chloride and dioctvl dimethyl ammonium chloride, Bl C® 1010 (50% active) as well as BTC® 1010-80 (80% active) each described to be didecyl dimethyl ammonium chloride, BTC® 2125 (50% active) and BTC® 2125M (50% active), and BTC® 2125-80 (80% active) each descπbed to be alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride, BTC® 2565 (50% l-i active) and BTC® 2568 (80% active) each described to be alkyl dimethyl benzyl ammonium chlorides, BTC® 8248 (80% active), BTC® 8358 (80% active) or BTC® 8249 (90% actι\ e) each described to be alkyl dimethyl benzyl ammonium chloride, as well as ONYXIDE® 3300 (95% active) described to be an n-alkyldimethyl benzyl ammonium saccharmate

20 The genmcidal constituent may be present in am effective amount, but generally need not be present in amounts m excess of about 10%wt based on the total weight of the composition The prefeπed germicidal cationic surfactant(s) may be present m the concentrated liquid disinfectant compositions m amounts of from about 0 001 % by weight to up to about 10% by weight, preferably about 0 01-8% by

25 weight, most preferably m amount of between 0 5-6 % bv weight It is particularly advantageous that the prefeπed germicidal cationic surfactant(s) are present in amounts of at least 200 parts per million (ppm), preferably in amounts of 200 - 700 ppm, more pieferably in amounts of from 250 - 500 ppm

The inventive compositions necessarily include (b) at least a fluorosurfactant

30 selected from the group of nonionic fluorosurfactant, cationic fluorosurfactant, and mixtures thereof which compounds are soluble or miscible in the aqueous compositions being taught herein, particularly compositions which do not include furthei deteisive surfactants, 01 compositions which do not include further organic solvents, 01 compositions whei e both fuithei e sui f actants and further organic solvents ai e absent

Particulai ly useful nonionic fluoi osui factant compounds are found among the ^■^ mateπals piesently commeicially maiketed undei the tiadename Fluorad® (ex 3M Corp )

Especially useful nonionic fluoiosui factant compounds include those which ai e believed to conform to the following stiuctural formula

C_nF2_n+1SO₂N(C₂H₅)(CH₂CH₂O)_xCH₃ 0 wherein n has a value of from 1 -12, pi eferably from 4-12, most preferably 8, x has a value of fiom 4- 18, pieferably fiom 4-10, most preferably 7, which is descπbed to be a nonionic fluoi mated alkyl alkoxvlate and which is sold as Fluoiad® FC- 171 (ex 3M Coip , fonnei ly Minnesota Mining and Manufactuπng Co ) Furthei useful nonionic fluorosui factant compounds are certain mateπals - marketed undei the tradename ZONYL® (ex DuPont Corp ) Particularly useful examples include ZONYL® FSO and ZONYL® FSN each of which is believed to be represented by the following structural foiτnula

F(CF₂CF₂)yCH₂CH₂O(CH₂CH₂O)_xH wherein foi ZONYL® FSO, 0 x has a value of from 0 to about 15 and y has a value of from 1 to about 7, wherein for ZONYL® FSN,

X has a value of from 0 to about 25, and y has a value of from 1 to about 9 *> An example of a useful cationic fluorosurfactant compound is one according to the following structural formula

C_nF₂n₊iSO₂NHC₃H₆N⁺(CH₃)₃r

This cationic fluorosurfactant is available under the tradename Fluorad® FC- 30 135 (ex 3M Corp )

A further example of a useful cationic fluorosurfactant is one according to the following stiuctural fonmila F₃-(CF2)n-(CH2)_mSCH₂CHOH-CH2-N⁺R₁R₂R₃Cr

Ri . R? and R-, π e -CH 1 his cationic fluoiosurfactant is available under the ti adenamc ZONYL ι FSD

aιlable from DuPont, and is described as 2-hydroxy-3- ((gamma-omega-pei fluoio-Cft 2o-alkyl)thιo)-N,N,N-tπmethyl-l -propyl ammonium chlonde)

Other cationic fluorosurfactants suitable for use in the present invention are also described in EP 866 1 15, as well as in US the contents of w hich aie mcorpoi ated by refei ence

The amount of fluorosurfactant present in the inventive formulations range m amounts of from about 0 001 to about 5%wt, preferably fiom about 0 001 to about 5%wt, and more preferably from about 0 01 to about 2.5%wt According to the certain aspects of the invention , the compositions necessarily include (c) one or more surfactants which pi ovide a further detersive benefit to the compositions, ( but it is to be understood that according to further certain specific particularly embodiments these one or moie surfactants are specifically absent ) Useful surfactants which provide a further detersive benefit which may be piesent in the inv entive compositions include detersive surfactants particularly selected from carboxylate surfactants, as well as nonionic, cationic and amphoteπc surfactants as well as mixtures of two or more thereof

Suitable nonionic surfactants include, inter aha, condensation products of alkylene oxide groups with an organic hydrophobic compound, such as an aliphatic compound or with an alkyl aromatic compound. The nonionic synthetic organic detergents generally are the condensation products of an organic aliphatic or alkyl aromatic hydrophobic compound and hydrophihc ethylene oxide groups Practically any hydrophobic compound having a carboxy, hydroxy, amido, or ammo group with a free hydrogen attached to the nitrogen can be condensed with ethylene oxide or with the polyhydration product thereof, polyethylene glycol, to form a water soluble nonionic detergent Fui thei , the length of the polyethenoxx hydiophobic and hydrophihc elements may be \ aned to adjust these properties

One example of such a nonionic sui factant is the condensation product of one mole of an alkyl phenol having an alkyl group containing f i om 6 to 12 carbon atoms ^ with fiom about 5 to 25 moles of an alkylene oxide Anothei example of such a nonionic surfactant is the condensation product of one mole of an aliphatic alcohol w hich may be a primary, secondary oi tertiary alcohol having from 6 to 18 carbon atoms with from 1 to about 10 moles of alkylene oxide Pi efcrred alkylene oxides are ethylene oxides or propylene oxides which may be present singly, or may be both 1 piesent

Preferred nonionic surfactants include primary and secondary linear and branched alcohol ethoxylates, such as those based on Q, to Cι « alcohols which further include an average of from 2 to 80 moles of ethoxylation per mol of alcohol Particularly prefeπed nonionic surfactants are Cn linear pi imary alcohol ethoxylates l ~> averaging about 9 moles of ethylene oxide per mole of alcohol These surfactants are available, foi example, under the commercial name of Neodol 1 -9, (from Shell Chemical Company, Houston, TX) , or in the Genapol® series of linear alcohol ethoxylates. particularly Genapol® 26-L-60 or Genapol® 26-L-80 (from Claπant Corp , Charlotte, NC) A further class of nonionic surfactants which are 20 advantageously present in the inventive compositions aie those presenth marketed under the Genapol® tiadename

Particulai ly useful aie those in the Genapol® "26-L" series which include for example C P-C_K, linear alcohols condensed with 1 mole of ethylene oxide (Genapol® 24-L-3); Cι ;-C](, linear alcohols condensed with 1.6 moles of ethylene oxide 2^ (Genapol® 26-L-1.6), Ci ₂-Cu, linear alcohols condensed with 2 moles of ethylene oxide (Genapol® 26-L-2), C] ₂-Cκ, linear alcohols condensed with 3 moles of ethylene oxide (Genapol® 26-L-3). Cι₂-C , linear alcohols condensed with 5 moles of ethylene oxide (Genapol® 26-L-5), as well as C₁₂-Cj linear alcohols condensed with varying amounts of ethylene oxide to provide specific cloud points of the surfactant (i.e., 30 Genapol® 26-L-60, Genapol® 26-L-60N. and Genapol® 26-L-98N) These matenals are commercially available from a variety of sources, including Claπant Corp. (Charlotte, N.C ). A fui thei particulaily useful and pieferred alcohol ethoxylate is Genapol® UD- 079 w hich is described to be a Cn lincai alcohol condensed w ith 7 moles of ethylene oxide to foim a nonionic suifactant

It is to be understood that othei nonionic sui factants othei than those descπbed abo\ e ma\ also be used By way of illustration, and not by w ay of limitation, examples include secondaiy Cp to G alcohol ethoxylates. including those which e from about 3 to about 10 moles of ethoxylation Such are available in the Teigitol® seπes of nonionic surfactants (Union Carbide Corp , Danbury, CT), particulaily those in the Tergitol® "15-S-" series Further exemplary nonionic

10 suifactants include hneai primaiy Cl 1 to C15 alcohol ethoxylates, including those which ha\ e fiom about 3 to about 10 moles of ethoxylation Such are available m the Neodol® seπes of nonionic surfactants (Shell Chemical Co )

A fuithei class of nonionic sui factants which mav find use m the present inventive compositions include ethoxylated octyl and nonyl phenols include those l -> having one of the following general stiuctuial formulas

CH₃ CH₃ H₃C C CH₂— C < 7 (OCH₂CH₂)_x — OH

CH, CH,

01 ,

C₉H_B % (OCH₂CH₂)_x— OH

m which the C₉Hι₉ group m the lattei formula is a mixture of branched chamed 20 isomeis, and x indicates an average number of ethoxy units in the side chain

Particularly suitable non-ionic ethoxylated octyl and nonyl phenols include those having from about 7 to about 13 ethoxy units Such compounds are commercially available under the trade name Triton® X (Union Carbide, Danbury CT), as well as under the tradename Igepal® (Rhodia Ine , Princeton, NJ) One exemplary and 2*> particularly prefeπed nonylphenol ethoxylate is Igepal® CO-630

A further useful class of surfactants include amine oxide compounds Exemplary useful amine oxide compounds may be defined as one or more of the following of the four general classes ( 1 ) Alkyl di (low er alkyl) amme oxides in w hich the alkyl gioup has about 6-24, and preiei bly 8-18 caibon atoms, and can be stiaight or branched chain, satuiated oi unsaturated The lowei alkyl gioups include between 1 and 7 carbon atoms, but piefeiably each include 1 3 caibon atoms Examples include octyl

1 amme oxide, mynstyl dimethyl amme oxide, and those in hich the alkyl group is a mixture of diffeient amme oxides, such as dimethyl cocoamme oxide, dimethyl (hydiogenated tallow ) amme oxide, and mynstyl/palmityl dimethyl amme oxide,

(2) Alkyl di (hydroxy low ei alkyl) amme oxides m which the alkyl group 10 has about 6-22, and preferably 8-18 carbon atoms, and can be straight or branched chain, saturated or unsaturated Examples include bιs-(2-hydroxyethyl) cocoamme oxide, bιs-(2-hydroxyethyl) tallowamine oxide, and bιs-(2-hydroxyethyl) steal ylamine oxide,

(3) Alkylamidopiopyl dι( loweι alkyl) amme oxides in which the alkyl l *> group has about 10-20. and pieferably 12-16 carbon atoms, and can be straight or blanched chain, saturated or unsatuiated Examples are cocoamidopropyl dimethyl amme oxide and tallowamidopropyl dimethyl amme oxide, and

(4) Alkylmorpholine oxides in which the alkyl group has about 10-20, and preferably 12-16 carbon atoms, and can be straight or branched chain, saturated or

20 unsatuiated

While these amme oxides lecited above may be used, preferred are amme oxides which may be represented by the follow ing structural representation.

R₂ — N — »-O

Ri

2^ wherein each R] independently is a stiaight chained Cι-C₄ alkyl group, preferably both R] groups are methyl groups; and.

R₂ is a straight chained C₆-C ₂ alkyl group, preferably is C₆-Ci₆ alkyl group, most prefei ably is a C ₁0 alkyl group, especially a C» alkyl group, Each oi the alkyl groups may be linear 01 branched, but most preferably are linear Most pi elerably the amme oxide constituent is lauryl dimethyl amine oxide Technical grade mixtures of two or more amme oxides may be used, wherein amme oxides of varying chains of the R₂ group are present Preferably, the amme oxides used in the present invention include R₂ groups which comprise at least 50%wt., preferably at least 75% t of C₈ alkyl group

Exemplai y and preferred amme oxide compounds include N-alkyl dimethyl amine oxides, particularly octyl dimethyl amme oxides as well as lauryl dimethyl 10 amme oxide 1 hese amme oxide compounds are a\ ailable as surfactants from

Mclntyre Group Ltd under the name Mackamme® C-8 which is described as a 40% by weight

e solution of octyl dimethyl amme oxide, as well as from Stepan Co , under the tradename Ammonyx® LO which is described to be as a 30%wt. active solution of laui yl dimethyl amme oxide, l ^ A furthei class of materials surfactants which may be advantageously included in the inventive compositions are alkoxy block copolymers, and in particular, compounds based on ethoxy/propoxy block copolymers. Polymeπc alkylene oxide block copolymers include nonionic surfactants m hich the major portion of the molecule is made up of block polymeric C₂-C₄ alkylene oxides. Such nonionic 20 surfactants, while preferably built up from an alkylene oxide chain starting group, and can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols

One group of such useful nonionic surfactants containing the characteπstic alkylene oxide blocks are those which may be generally represented by the formula 2 (A)-

HO-(EO)_x(PO)y(EO)_z-H (A) where EO represents ethylene oxide, PO represents propylene oxide, y equals at least 15, 30 (EO)_λ+ equals 20 to 50% of the total weight of said compounds, and, the total molecular weight is preferably in the range of about 2000 to 15,000. Anothei gi oup of nonionic sui factants appropriate for use in the new compositions can be lepi esented by the fonnula (B)

R— (EO,PO)_a(EO,PO)b-H (B) whei ein R is an alkv 1, an 1 oi ai alkyl group, whei e the R group contains 1 to 20

^ caibon atoms, the eight percent of EO is within the range of 0 to 45% m one of the blocks a, b, and w ithin the range of 60 to 100% in the othei of the blocks a b, and the total numbei of moles of combined EO and PO is in the lange of 6 to 125 moles, with 1 to 50 moles in the PO πch block and 5 to 100 moles in the EO rich block

Further nonionic surfactants which m general are encompassed bv Fonnula B 10 include butoxy denvati es of propylene oxide/ethylene oxide block pol mers having molecular vv eights within the range of about 2000-5000

Still furthei useful nonionic surfactants containing polymeπc butoxy (BO) gioups can be repi esented by formula (C) as follows

RO-(BO)_n(EO)χ-H (C) l ^•> wherein R is an alkv 1 group containing 1 to 20 carbon atoms, n is about 5- 15, and x is about 5-15

Also useful as the nonionic block copolymer surfactants, which also include polymeπc butoxy groups, are those which may be lepresented by the following

20 foπriula (D)

HO-(EO)χ(BO)_π(EO)y- H (D)

wherein n is about 5-15, pieferably about 15,

\ is about 5- 15, preferably about 15, and 25 y is about 5-15, preferably about 15

Still furthei useful nonionic block copolymer surfactants include ethoxylated derivatives of piopoxylated ethylene diamme, which may be represented by the following formula

-0 where (EO) repiesents ethoxy, (PO) represents propoxy, the amount of (PO)_x is such as to provide a molecular weight prior to ethoxylation of about 300 to 7500, and the amount of (EO is such as to provide about 20% to 90% of the total weight of said compound. 5 Of these, the most preferred are those which are represented by formula (A) above; specific examples of which include those materials presently commercially available under the tradename PLURONIC®, and in particular the PLURONIC® F seπes, PLURONIC® L series. PLURONIC® P series, as well as in the PLURONIC® R series, each of which are generally described to be block copolymers of propylene 0 oxide and ethylene oxide. Generally those of the PLURONIC® L series and the PLURONIC® R series are prefeπed as these are supplied in liquid form by the manufacturer and are readily formulated into the present inventive compositions. These are also available in a wide range of HLB values, and those having HLB values in the range of 1.0 - 23.0 may be used, although those with mteπnediate HLB values 5 such as from about 12.0 - 18.0 are found to be particularly advantageous. These materials are presently commercially available from BASF AG (Ludwigshafen, Geπriany) as well as from BASF Corp. (Mt. Olive Township, New Jersey).

A further class of surfactants which may be advantageously included in the inventive compositions are carboxylates. particularly one or more 0 alkylpolyoxycarboxylates including alkyletherpolyoxycarboxylates, or alkylarylpolycarboxylates. Exemplary alkylpolyoxycarboxylates and alkylarylpolycarboxylates include alkyl- and alkylaryl-carboxylates which include those which may be represented by the general formula:

R-COO^" M⁺

? wherein R is a straight or branched hydrocarbon chain containing from about 9 to 21 carbon atoms, and which may also include an aromatic ring, especially a phenyl group as part of the hydrocarbon chain, and M is a metal or ammonium ion.

Further examples of particularly useful carboxylate surfactants include compounds according to the formula: H H R— (O)_y— (C - C - O)χ R ^{M +}

R is a C₄-C₂₂ lineai 01 branched alkyl gioup w hich may optionally include at least one aiyl gioup prefeiablv Cs-C] -, linear 01 _^ branched alkyl gioup which may include at least one aryl gioup, and yet moie prefei ablv a C₁₂ n linear or bianched alkyl group which may include at least one an 1 group, x is an integer fiom 1 to 24

10 Ri. Ri and R- is a group selected from H, lower alkyl radicals including methyl and ethyl ladicals, caiboxylate tadicals including acetate and propionate radicals succmate radicals, hydroxysuccinate radicals, oi mixtures thereof wherein at least one R| , R₂ or R, is a carboxylate radical and, l -> M^~ is a counteπon including an alkali metal counteπon (I e , sodium, potassium) or ammonium counteπon

Free acid forms of the alkylethercarboxylate compounds noted above may also be used

Examples of such presently available commercial preparations include 20 SURFINE® WLG (ex Finetex Ine , Elmwood Park NT ) SANDOPAN® DTC

(Claπant Chem Co , Charlotte NC) in salt forms, and free acid forms include those marketed under the tradename NEODOX® (Shell Chemical Co , Houston TX) One particularly prefeπed carboxylate is one which is represented by the formula

- O)₉-COO- M⁺

2 -^Ϊ

Such a material is presently commercially av ailable under the tradename EMCOL®, and specifically as EMCOL® CNP-1 10

- 1 i Othei useful exemplaiv nonionic block copolymeis based on a polymeπc ethoxy/propoxy units w Inch may also be used include those presently commercially available in the POLYTERGENT® E and POLYTERGENT® P seπes of materials from Ohn Chemicals Coip , (Stamfoid CT) These aie descπbed to be nonionic

^•> surfactants based on ethoxy/piopoxv block copolymeis, conveniently av ailable in a liquid form from its supphei

It is to be undei stood that these nonionic surfactants based on polymeric alkylene oxide block copolymers may be used singly 01 in mixtures of two or more such compounds

10 When the compositions of the piesent invention contain one or more furthei detersive surfactants, these may be present in any amount which is found to provide a beneficial detersive effect Generally, these one or more further detersive surfactants do not compπse more than 12%wt (on an actives weight basis) of the inventive compositions When included such one or more further detersive surfactants are l-> advantageously present in an amount from 0 001 - 10%wt , preferably are present fiom 0 01 8%w t , but still more prefeiably aie included in amounts of fiom 0 1 - 8%wt

According to the first, third, fifth and seventh aspects of the invention, the compositions necessaπly include (d) one or more organic solvents, ( but it is to be

20 understood that according to further certain specific particularly embodiments these one or more suifactants are specifically absent)

Exemplary organic solvents which may be included m the inventive compositions include those which aie at least partially water-miscible such as alcohols particularly Cι-C₆ alcohols such as ethanol, n-propanol, isopropanol, water-miscible

2*> ethers (e g diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ethers (e g propylene glycol monomethylether, propylene glycol mono ethylethei, propylene glycol monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether, dipropylene

30 glycol monopropyl ether, dipropylene glycol monobutyl ether), lower esters of monoalkylethers of ethyleneglycol or propylene glycol (e g propylene glycol monomethyl ether acetate) all commercially available such as from Union Carbide (Danbmy, CT), Dow Chemical Co (Midland MI ) 01 Hoechst (Germanv ) Mixtures of several organic solvents can also be used

Useful glycol ethei s include those ha ing the general stiucture R_a-0-R_h-OH, wheiem R , is an alkyl of 1 to 20 caibon atoms, or an aiv l of at least 6 carbon atoms, and Ri, is an alkylene of 1 to 8 caibons or is an ethei or polyether containing from 2 to 20 carbon atoms Examples of certain prefeπ ed glycol ether solvents include propylene glycol methyl ethei, dipiopylene glycol methyl ether, tπpropylene glycol methyl ether, piopylene glycol isobutyl ethei , ethv lene glycol methyl ethei, ethylene glycol ethyl ethei, ethylene glycol butyl ethei , diethylene glycol phenv l ethei, propylene glycol phenol ethei , dipiopylene glycol monobutyl ether and mixtures thereof

In certain embodiments of the mv ention the use of mixtures of organic solvents is contemplated For example a mixture of an alcohol (e g , isopropanol) and a glycol ether (e g , dipropylene glycol monobutyl ether) is contemplated as one such mixture Furthei ex emplaiv organic solv ent mixtures having similar characteπstics (e g , solubility, evaporation late, etc ) are also contemplated

When included, the (d) organic solvent constituent is advantageously present in amounts of fiom 0 001 - 10%wt , more preferably from 0 01%wt to not more than 7%wt , but still more preferably is included in amounts of from 0 1 - 5%wt Certain embodiments of the invention may include (e) one or more alkanolamines Such alkanolamines include mono-, di- and tπ-alkanolammes Such alkanolamines include monoefhanolamme, diethanolamine, tπethanolamme, isopropanolamine and the like Of these, monoefhanolamme is particularly preferred When present, the (e) one or more alkanolamines comprise from 0 001 - 3%wt , of the inventive compositions More preferably, when present, the one or more alkanolamines comprise from 0 1 - 1 0%wt , of the inventive compositions of which they form a part

The compositions are laigely aqueous in nature, and compπse as a further necessary constituent (f) watei Water is added to order to provide to 100% by weight of the compositions of the invention The water may be tap water, but is preferably distilled and is most preferably deiomzed water If the water is tap water, it is preferably substantially free of any undesirable impurities such as orgamcs or inorganics, especially mineials salts w hich are pi esent in haid w atei which may thus undesirably mterteie with the operation of the constituents piesent in the aqueous compositions according to the invention

As discussed pi ev louslv the inv entiv e compositions mav comprise (g) one or ι more conventional optional additiv es By way of non-hmitmg example these include pH adjusting agents and pH buffeis including oigamc and inorganic salts, non-aqueous solv ents, peifumes, peifume caπiers, optical bπghteners, coloring agents such as dyes and pigments opacifymg agents, hydrotropes, antifoaming agents, viscosity modifv ing agents such as thickeners, enzymes anti-spottmg agents, anti- 0 oxidants, anti corrosion agents as w ell as others not specifically elucidated here

These ingredients may be piesent in anv combinations and in any suitable amount that is sufficient for imparting the desired properties to the compositions These one or more conventional additives w hen present, should be present in minor amounts, preferably in total comprise less than about 5% by weight (on an active vv eight basis) -Ϊ of the compositions, and desnably less than about 3%wt

Such materials described above are known to the art, including those descπbed in McCutcheon s Emulsifiei s and Detei gents (Vol 1), McCutcheon s Functional Matei mis (Vol 2) North Ameiican Edition, 1991 , Kit k Othmei Encyclopedia of Chemical Technology' 4th Ed , Vol 22 pages 478-541 the contents of which are 0 herein incorporated by reference For any particular composition, any optional constituents should be compatible vv ith the other ingredients present

The aqueous compositions according to the invention are desirably provided as a ready to use product which mav be directly applied to a hard surface Hard suifaces which are to be particulaily denoted are lavatory fixtures, lavatory appliances -ι (toilets, bidets, shower stalls, bathtubs and bathing appliances), wall and flooring surfaces especially those which include refiactory materials and the like Further hard surfaces which are particularly denoted are those associated with kitchen environments and other environments associated with food preparation Hard surfaces which are those associated with hospital environments, medical laboratoπes 30 and medical tieatment environments Such hard surfaces descπbed above are to be understood as being recited by vv ay of illustration and not be way of limitation The composition piovided accoid g to the inv ention can be desn ably piovided as a ιead\ to use pioduct in a manually opeiated spiav dispensing container, 01 may be supplied in aeiosohzed pi oduct whei ein it is dischaiged from a pressurized aeiosol containei Known art piopellants such as liquid pi opellants based on ι chloroflmocaibons oi pi opellants of the non-liquid form i e , piessuπzed gases including carbon dioxide, an , nitrogen, as well as othei s may be used, even though it is lealized that the former chloiofluoiocarbons are not generally further used due to environmental considei ations

The composition accoidmg to the invention is ideally suited for use in a 0 consumei "spray and wipe" application In such an application, the consumer generally applies an effective amount of the cleaning composition using the pump and within a few moments theieafter, wipes off the treated ai ea with a rag, towel, or sponge, usually a disposable paper towel or sponge In certain applications, howevei, especially where undesirable stain deposits are heavy, the cleaning composition ^ according to the mv ention may be left on the stained area until it has effectively loosened the stain deposits aftei which it may then be wiped off, rinsed off, or otherwise removed Foi particularly heav y deposits of such undesired stains, multiple applications may also be used It is also to be understood that longei residence time of the inventive compositions on a hard surface may be lequired in order to attain 0 greater degrees of disinfection Where thoiough disinfection is a primary consideration, it may be desired to apply the inventive compositions to the hard surface being treated and to permit the composition to remain on the hard surface for several minutes (2- 10 mm ) pπoi to πnsing or wiping the composition from the hard suiface It is also contemplated that the inventive compositions be applied to a hard ι surface without subsequently wiping or rinsing the treated hard surface

In a yet a furthei embodiment, the product according to the invention may be formulated so that it may be useful in conjunction with a "aerosol" type product wherein it is discharged from a pressurized aerosol container Known art propellants such as liquid propellants based on chloroflurocarbons or propellants of the non-liquid

30 form, l e , pressuπzed gases, including caibon dioxide, an , nitrogen, as well as others, may be used, even though it is realized that the former chlorofluorocarbons are not generally further used due to environmental considerations In such an application, the cleaning composition is dispensed by activating the l elease nozzle of said aerosol t pe contamei onto the stam and/oi stam area, and in accordance w ith a manner as above-described a stam is heated and lemoved

Wheieas the compositions of the piesent mv ention are intended to be used in

-i the types of liquid forms descπbed, nothing in this specification shall be understood as to limit the use of the composition according to the inv ention with a further amount of water to foπn a cleaning solution theiefrom In such a proposed diluted cleaning solution, the gieatei the proportion of water added to foπn said cleaning dilution w ill, the gi eater may be the reduction of the late and/or efficacv of the thus formed

10 cleaning solution Accordingly, longer lesidence times upon the stam to effect their loosening and/oi the usage of greater amounts may be necessitated Conversely, nothing m the specification shall be also understood to limit the forming of a "super- concentrated" cleaning composition based upon the composition described above Such a super-concentrated ingredient composition is essentially the same as the l i cleaning compositions described above except in that they include a lessei amount of watei

The composition of the present invention, hethei as described herein or in a concentrate or super-concentiate foπn can also be applied to a hard suiface by using a wet wipe The wipe can be of a woven or non- woven natuie Fabπc substrates can be

20 used to form the wipe Exemplary fabric substrates can include non-woven and woven pouches, sponges, in the form of abrasive or non-abrasive cleaning pads Such fabrics are known commercially in this field and are often refeπed to as wipes Such substrates can be resm bonded, hydroentangled, thennally bonded, melfblown, needlepunched or any combination of the formei

25 The non-woven fabrics may be a combination of wood pulp fibers and textile length synthetic fibers foπried by well known dry-form or wet-lay processes Synthetic fibers such as Rayon, Nylon, Orion and Polyester as well as blends thereof can be employed

The wood pulp fibers should comprise about 30 to about 60 percent by weight

30 of the non-woven fabπc, pieferably about 55 to about 60 percent by weight, the remainder being synthetic fibers The wood pulp fibers provide for absorbency, abiasion and soil retention whereas the synthetic fibeis piovide for substrate stiength and lesihency

The substrate of the ipe may also be a film foimmg material such as a watei soluble polymei Such substiates include self supporting film substrates including those which may be sandwiched between layeis of fabπc substrates and head sealed to form a useful substrate The fiee standing films can be extruded utilizing standard equipment to devolatilize the blend Casting technology can also be used to form and dry films or a liquid blend can be saturated into a carπei and then dried via any of a vanety of known methods The compositions of the present invention aie absoibed onto the wipe to form a saturated wipe The wipe can then be sealed in individually into a pouch which can then be opened when needed or a multitude of wipes can be placed in a container for use on an as needed basis The container, when closed, sufficiently seals to prevent evaporation of any components from the compositions The following examples below illustrate exemplary and prefeπed formulations of the concentiate composition according to the instant invention It is to be understood that these examples are presented by means of illustration only and that further useful formulations fall within the scope of this invention and the claims may be readily produced by one skilled in the art and not deviate from the scope and spiπt of the invention

Throughout this specification and in the accompanying claims, weight percents of any constituent are to be understood as the weight percent of the active portion of the referenced constituent, unless otherwise indicated

Examples

The following examples illustrate the formulation and performance of various compositions of the invention, as well as certain particularly prefeπed embodiments of the invention

Exemplary formulations illustrating certain prefeπed embodiments of the inventive compositions and described m more detail in Tables 1A, IB, 2 and 3 below were formulated generally in accordance with the following protocol The weight percentages indicated the "as supplied" weights of the named constituent The formulations of Table 1 A illustrate embodiments w hei e alkanolamines aie not present, while the formulations of Table IB illustrate embodiments wherein alkanolamines ai e necessaπly pi esent

Into a suitabl} sized v essel a measui ed amount of vv atei w as piovided after w hich the constituents wei e added in no specific 01 uniform sequence, which indicated that the order of addition of the constituents w as not critical All of the constituents vv eie supplied at room tempeiature, and any lemammg amount of water w as added thei eafter Certain of the nonionic surfactants if gels at room temperature w ere first preheated to render them pourable liquids pπoi to addition and mixing Mixing of the constituents w as achiev ed by the use of a mechanical stiπer with a small diametei propellei at the end of its rotating shaft Mixing, which generally lasted from 5 minutes to 120 minutes was maintained until the particular exemplary formulation appeared to be homogeneous The exemplary compositions were readily pourable, and retained well mixed characteristics (I e , stable mixtures) upon standing for extend periods

TABLE 1 A

Ex,1 Ex.2 Ex.3 Ex.4 Ex,5 Ex.7 Ex,8 Ex.9 Ex.10

BTC® 8358 3.6 3.6 3.6 4.0 3.6 ^{" "} 3.6^~ 3.6 3.6 3.6

Fluorad® FC-171 0.64 2.02 0.51 1.28 0.64 0.64 0.64 0.64 0.64

Genapol® UD-079 ~ - - - 1.0 — — — —

Emcol® CNP-110 - - — -- ~ 1.0 - — lgepal®CO-630 - - - ~ - 1.0 —

Pluronic® L-64 — - — ~ - - ~ 1.0 —

Mackamine® C8 —

I " - - ~ - - - 1.0 di water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.S. q.s. I

TABLE 1 B ! ^■ ' , ' I

Ex.11 Ex.12 Ex.13 Ex.14 Ex.15 Ex.16 Ex.17 Ex.18 i Ex.19 Ex.20

^"BTC® 8358 0.027 0.027 0.027 0.027 0.027 0.027 0.027 0.027 | 0.027 0.027

BTCΘ 65NF 0.172 0.172 0.172 0.172 0.172 0.172 0.172 0.172 i 0.172 0.172

Fluorad® FC-171 0.9 0.1 0.05 ^' 0.05 0.04 0.02 0.04 0.02 - ~

Zonyl® FSN 100 ~ ~ - - - - - 0.04 -

Zonyl® FSO 100 - - ~ ~ — — — — 0.04

Dowanol® PnB 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 3.0 isopropanol — — 2.0 — 2.0 2.0 — — n-decanol 6 o ^' ~ monoethanolamine 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 0.5 di water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. ' q.s.

As is indicated, to all of the formulations of Tables 1 A and IB w as added sufficient deionized water in "quantum sufficient" to provide 100 parts by weight of a particular foπnulation.

The identity of the constituents used to produce various formulations described herein are described in Table 2. below, including the "actives'^" percentage of each were a constituent was not 100%w t "actives".

TABLE 2

BTC® 8358 alkyl dimethyl benzyl ammonium chloπde (80%wt. actives) from Stepan Co. BTC® 65NF alkyl dimethyl benzyl ammonium chloride (50%wt. actives) from Stepan Co. Fluorad® FC-171 fluorinated alkyl alkoxylate ( 100%wt. actives) from

3M Corp. Zonyl® FSN 100 alkoxylated nonionic fluorosurfactant (100%wt. actives) from DuPont Corp. Zonyl® FSO 100 alkoxylated nonionic fluorosurfactant (100%wt. actives) from DuPont Corp. Genapol® UD-079 nonionic, C1 1 alcohol ethoxylate, with 7 moles of

EO (ethoxy) groups (90%wt. actives) from Hoechst

Celanese

Emcol® CNP-1 10 anionic, alkylaryl polyoxycarboxylate (100%wt. actives) from Witco Co. _ lgepal®CO-630 nonionic, nonylphenol ethoxylate with 9 moles of

EO groups (100%wt. actives) from Rhone-Poulenc

Pluronic® L-64 nonionic, polypropylene-polyethylene block copolymer (100%wt. actives) from BASF In

Mackamine® C8 nonionic, octamine oxide (40%wt. actives) from

Mclntyre Co. __

Tergitol® 15-S-9 nonionic, polyethylene glycol ether (100%wt. actives) from Union Carbide Co.

Dowanol® DPnB dipropylene glycol n-butyl ether (100%wt. actives) from Dow Chemical Co. _ isopropanol isopropanol, technical grade (95%+ actives) from

Aldrich Chem. Co. or Eastman Chem. Co. n-decanol n-decanol, technical grade (95%+ actives) from

Aldrich Chem. Co or other commercial source monoethanolamine monoethanolamine (100%wt. actives) from Dow

Chemical Co. _

Na4EDTA tetrasodium salt of ethylenediamine tetraacetic acid

(Dow Chem. Co.) di water deionized water Additional formulations, namely aqueous dilutions of the concentrate compositions exemplified by the formulations described in Table 1A were produced, and these are described on Table 3. following:

TABLE 3

Ex.21 Ex.22 Ex.23 :

BTC-8358® 0.05625 0.05625 0.05625 Fluorad® FC-171 0.01 0.03156 0.00795 | di water q.s. q.s. q.s. |

These exemplary aqueous dilutions were prepared by dilution of one part by weight of a concentrated formulation described on Table 1A, with 64 parts by weight of deionized water. Ex. 21 is a 1 :64 dilution of the formulation of Ex.l with water. Ex. 22 is a 1 :64 dilution of the formulation of Ex.2 with water. Ex. 23 is a 1 :64 dilution of the formulation of Ex.3 with water. A comparative formulation which did not include the nonionic fluorosurfactant or quaternary ammonium compound was also produced, and this formulation included of Table 4, from the indicated constituents:

TABLE 4

Comparative Formulation: (C11 %wt.

Tergitol® 15-S-9 5.0 Pluronic® L-64 2.0 Na4EDTA ^"0.25^" di water balance to 100

Certain of the formulations described on Table 1 A and Table 4, as well as the comparative formulation ('Cl ') were subjected to one or more of the following evaluations.

Cleaning Efficacy Certain of the compositions indicated above were diluted with water at a respective weight ratio of composition: water of 1 :64. These diluted compositions were then subjected to the protocol of ASTM D-4488-89 Annex A5 for particulate soil, which evaluated the efficacy of the cleaning compositions on vinyl tile samples. The soil applied was a particulate soil sample containing natural humus, paraffin oil, used crankcase motor oil, Portland cement, silica, lampblack carbon, iron oxide, bandy black clay, stearic acid, and oleic acid, produced according to the protocol. Each of the soiled test vinyl tile samples were placed into the apparatus and the center of each tile was wetted with a 20 milliliter sample of a test formulation and allowed to stand for 1 minute. When approximately 30 seconds had elapsed, a further 50 milliliter sample was applied to the sponge (water dampened, then wrung to remove excess water) of a Gardner Abrasion Tester apparatus. Thereafter the apparatus was cycled 10 times, which provided 20 strokes of the sponge across the face of each of the vinyl test tiles. Each test was replicated three times using three vinyl tile samples. The reflectance values of the cleaned samples were evaluated utilizing a Minolta Chroma Meter CF-1 10, with Data Processor DP- 100, which evaluated spectrophotomic characteristics of the sample. The averaged results of the three readings are reported on Table 5, following.

With respect to the results reported in Table 5 a value of "100" is indicative of a white (unsoiled) background, and a "0" value is indicative of a black background. As can be seen from the results of Table 3, the cleaning efficacy of the composition according to the invention generally provided superior results or were on parity with those of known art cleaning products.

Antimicrobial Efficacy Several of the exemplary fonmilations described in more detail on Table 1A above were evaluated in order to evaluate their antimicrobial efficacy against Staphylococcus aureus (gram positive type pathogenic bacteria) (ATCC 6538), Salmonella choleraesuis (gram negative type pathogenic bacteria) (ATCC 10708), and Pseudomonas aeruginosa (ATCC 15442). The testing was performed in accordance with the protocols outlined in "Use-Dilution Method", Protocols 955.14, 955.15 and 964.02 described in Chapter 6 of "Official Methods of Analysis", 16^th Edition, of the Association of Official Analytical Chemists; "Germicidal and Detergent Sanitizing Action of Disinfectants", 960.09 described in Chapter 6 of "Official Methods of Analysis", 15^th Edition, of the Association of Official Analytical Chemists; or American Society for Testing and Mateπals ("ASTM") E 1054-91 the contents of which are herein incorporated by reference. This test is also commonly refeπed to as the "AOAC Use-Dilution Test Method^" As is appreciated by the skilled practitioner in the art, the results of the AOAC

Use-Dilution Test Method indicates the number of test substrates wherein the tested organism remains viable after contact for 10 minutes w ith at test disinfecting composition / total number of tested substrates (cylinders) evaluated in accordance with the AOAC Use-Dilution Test. Thus, a result of "0/60" indicates that of 60 test substrates bearing the test organism and contacted for 10 minutes in a test disinfecting composition, 0 test substrates had viable (live) test organisms at the conclusion of the test. Such a result is excellent, illustrating the excellent disinfecting efficacy of the tested composition.

Results of the antimicrobial testing are indicated on Table 6, below. The reported results indicate the number of test cylinders with live test organisms/number of test cylinders tested for each example formulation and organism tested.

As may be seen from the results indicated above, the compositions according to the invention provide excellent cleaning benefits to hard surfaces, including hard surfaces with difficult to remove stains notwithstanding the low solids content of the inventive compositions. These advantages are further supplemented by the excellent antimicrobial efficacy of these compositions against known bacteria commonly found in bathroom, kitchen and other. Such advantages clearly illustrate the superior characteristics of the compositions, the cleaning and antimicrobial benefits attending its use which is not before known to the art. Evaporation and Drying Characteristics The compositions according to formulations 11 through 20 described on Table IB were evaluated for their evaporation and drying characteristics. These compositions were used "as is" (and as described on Table IB) and not further diluted with additional water. As a further comparative example a commercially available product, LYSOL® antibacterial kitchen cleaner was used as supplied by its manufacturer.

As test substrates were used glazed black ceramic tile, and a polished stainless steel tile. Immediately prior to the test the tiles were horizontally positioned with their glazed or polished surfaces facing upwards on a laboratory tabletop. Onto the surface of each was deposited a drop of an example foπnulation, and immediately thereafter the drop was spread into a roughly circular pattern to form a generally uniform thin film on the substrate via the use of a clean, crumpled sheet of a lint free paper wipe (Kimwipe®, ex. Kimberly-Clark Corp.) after which the paper wipe was removed and discarded. The thin film was approximatelv- 1 inch in diameter. The test was repeated for each formulation tested.

Immediately thereafter the drying behavior of the example foπnulation was visually observed. Each formulation according to Examples 11 through 20 were tested, and each was observed to initiate evaporation at the periphery of the thin film, and to in a generally uniform manner advancing towards the center of the thin film. The typical drying time was from approx. 1 to 1.5 minutes. During drying, no discrete rivulets or droplets were observed to form, and at the conclusion of drying the surface was dry and appeared to be streak free. Little or no residue was observed to remain on the glazed black tile substrate for any of the formulations according to Examples 11 through 20. In contrast, the comparative example was observed to deposit a readily visible, hazy whitish residue subsequent to its drying on the black tile substrate. On the polished stainless steel tile substrate, it was observed that subsequent to drying each of the tested formulations were observed a very faint, dark color cast where the thin film was previously present, but this color cast was readily removed by subsequently wiping with a clean dry lint free paper wipe.

Claims

Claims:

1 . A hard surface cleaning and disinfecting composition which comprises:

(a) at least one cationic surfactant having genmcidal properties;

(b) a fluorosurfactant selected from the group of nonionic fluorosurfactant, cationic fluorosurfactant, and mixtures thereof;

(c) optionally, one or more detersive surfactants particularly selected from carboxylate surfactants, as well as nonionic, cationic, amphoteric surfactants, and mixtures thereof;

(d) optionally, one or more organic solvents;

(e) optionally, one or more alkanolamines;

(f) a major portion of water; and (g) optionally, one or more further conventional optional constituents such as: pH buffering agents, perfumes, perfume caπiers, colorants, hydrotropes, viscosity modifying agents, further germicides, fungicides, anti-oxidants, and antι-coιτosιon agents, and the like.

2. A hard surface cleaning and disinfecting composition of claim 1 wherein the

(b) nonionic fluorosurfactant is a compound selected from a compound of the formula

C_nF_2n+1SO₂N(C₂H₅)(CH₂CH₂)_xCH₃ where n has a value of from 4 to 12 and x has a value of from 4 to 18; F(CF₂CF₂)yCH₂CH₂CH₂O(CH₂CH₂O)_)<H where ╬╗ is 0 to about 15 and y is 1 to about 7, or x is 0 to about 25 and y is 1 to about 9.

C_nF_2n+1S╬╕₂NHC₃H₆N⁺(CH₃)₃r where n~8:

F₃-(CF₂)n-(CH₂)mSCH₂CHOH-CH₂-N⁺R₁ R₂R₃Cr where n is 5-9 and m is 2, and Ri , R₂ and R₃ are -CH₃; as well as mixtures thereof. 3 The haid surface cleaning and disinfecting compositions according to claim 1 oi 2 which is characteiized as containing (c) one or more detersive surfactants particularly selected fiom cai boxylate surfactants as well as nonionic, cationic,

^■^ amphoteπc surfactants, and mixtures thereof, (d) one or more organic solv ents, and (e) one oi moi e alkanolamines

4 The hard surface cleaning and disinfecting composition according to claim 1 oi 2 w Inch is chaiactenzed as being essentially fiee of (d) one or more organic 0 solvents

5 The haid surface cleaning and disinfecting composition according to claim 1 oi 2 w Inch is characteiized as being essentially fiee of (c) one or more detersive surfactants 5

6 The hard surface cleaning and disinfecting composition according to claim 1 or 2 w Inch is characteiized as being essentially free of both (c) one or more detersive surfactants and (d) one or more organic solvents

0 7 The hard suiface cleaning and disinfecting compositions according to claim 1 oi 2 w Inch is characteπzed as being essentially free of (e) one or more alkanolamines

8 The hard surface cleaning and disinfecting compositions according to claim 1 D or 2 vv Inch is characteπzed as being essentially free of (c) one or more deteisive surfactants, (d) one or more organic solv ents, and (e) one or more alkanolamines

9 The hard surface cleaning and disinfecting compositions according to claim 1 30 or 2 vv Inch is characterized as being essentially free of (d) one or more organic solvents and (e) one or more alkanolamines The haid surface cleaning and disinfecting compositions according to claim 1 oi 2 which is characterized as being essentially free of (c) one or more detei siv e surfactants and (e) one or more alkanolamines

A haid surface cleaning and disinfecting composition according to claim 1 or 2 w heicm the (d) one or more oiganic solvents are selected from alcohols, etheis, glycol ethers, lower esteis of monoalkylethers of ethylene glycol or propylene glycol, as well as mixtures thereof

A process for the cleaning and sanitizing of a hard surface which comprises the step of providing the composition as outlined above, and applying an effective amount of the composition according to any of the preceding claims to a haid surface requiring such treatment