GB2320030A - Disinfecting and cleaning compositions - Google Patents

Abstract

Aqueous disinfecting and cleaning compositions and concentrates which are efficacious against gram positive and gram negative bacteria, have relatively low volatile organic content ("VOC") and are mild to the user of the compositions. These compositions include a quaternary ammonium compound as its primary germicidal active agent, have a low content of active constituents, and do not include organic solvents such as alcohols, glycols, or glycol ethers in significant amounts.

Description

IMPROVEMENTS IN OR RELATING TO ORGANIC COMPOSITIONS The present invention relates to improvements in cleaning and disinfectant compositions. More particularly the present invention is directed to improved cleaning compositions which find particular use in hard surface cleaning applications.

Notwithstanding the presence of known cleaning and disinfecting compositions, there is a real and continuing need in the art for such improved compositions.

The new and useful compositions according to the present invention provide at least one, but most desirably feature a plurality of the following characteristics: low volatile organic content, low irritancy to the end user of the composition, phase stability in storage, ease of fabrication, low cost, efficacy against gram positive bacteria, efficacy against gram negative bacteria, good cleaning characteristics, relatively low percentage actives required in an aqueous formulation. In preferred embodiments these compositions also feature a relatively low volatile organic content ("VOC") and are mild to the user of the compositions. That these results are concurrently achieved with a composition which includes a quatemary ammonium compound as its primary germicidal active agent is surprising, and indicates a synergistic effect not apparent from the prior art. These compositions also provide good cleaning and disinfecting properties with low amounts of active constituents, and desirably do not include organic solvents such as low molecular weight alcohols, glycols or glycol ethers, in significant amounts, i.e., amounts of about It or more.

In accordance with a first aspect of the invention there is provided an aqueous disinfecting and cleaning composition in a concentrated form which comprises, but desirably consists essentially of: a disinfecting effective amount of a quaternary ammonium compound having germicidal properties, desirably in an amount of from about 0.001 - 5% wt.; 0.01 - I 0%wt. of a nonionic surfactant compound which includes as a major portion of the molecule a block polymeric alkylene oxide block; 0.01 - 10%wt. of a nonionic surfactant; 0 - 3%wt. of a polymeric cationic surfactant based on a polyquaternary ammonium salt; 0 - 3%wt. of a builder, desirably present in an amount of about 0.1 - 0.5%wt.; optionally, minor amounts of up to about 5%wt. of one or more conventional additives particularly coloring agents, fragrances and fragrance solubilizers, viscosity modifying agents such as thickeners, pH adjusting agents and pH buffers including organic and inorganic salts; and, water to form 1 00%wt. of the concentrate form of the inventive compositions.

Another aspect of the present invention also comprises a process for cleaning and/or disinfecting surfaces in need of such treatment which includes contacting a surface with a composition as taught herein.

The compositions of the invention include a disinfecting effective amount of a quaternary ammonium compound having germicidal properties. Useful quaternary ammonium compounds and salts thereof include quaternary ammonium germicides which may be characterized by the general structural formula:

where at least one or R1, R2, R3 and R4 is a hydrophobic, aliphatic, aryl aliphatic or aliphatic aryl radical of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165. The hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substituted long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, etc. The remaining radicals on the nitrogen atoms other than the hydrophobic radicals are substituents of a hydrocarbon structure usually containing a total of no more than 12 carbon atoms.

The radicals R1, R2, R3 and R4 may be straight chained or may be branched, but are preferably straight chained, and may include one or more amide or ester linkages.

The radical X may be any salt-forming anionic radical.

Exemplary quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide, alkyl aryl ammonium halides such as octadecyl dimethyl benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like. Other suitable types of quaternary ammonium salts include those in which the molecule contains either amide or ester linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very 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 lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.

Preferred quaternary ammonium compounds which act as germicides and which are be found useful in the practice of the present invention include those which have the structural formula:

wherein R2 and R3 are the same or different Cs-Cl2alkyl, or R2 is C1216alkyl, C8 18alkylethoxy, C8,8alkylphenolethoxy and R3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or methosulfate. The alkyl groups recited in R2 and R3 may be straight chained or branched, but are preferably substantially linear.

Particularly useful quaternary germicides include compositions which include a single quaternary, as well as mixtures of two or more different quaternaries.

Particularly useful quaternary germicides include BARDACR 205M, and BARDAC 208M or BTC 885which is described to be a blend of alkyl dimethyl benzyl ammonium chlorides; BARDAC(D 2050 and BARDACX 2080 or BTC 818 which is described to be based on dialkyl(C8-C,0)dimethyl ammonium chloride; BARDAC 2250 and BARDACR 2280 or BTC 1010 which is described as a composition which includes didecyl dimethyl ammonium chloride; BARDACX LF and BARDACR LF 80 which is described to be based on dioctyl dimethyl ammonium chloride; BARQUAT) MB-50, HYAMINE 3500, BARQUAT MB-80, BTC 835 or BTC 8358 each described to be based on alkyl dimethyl benzyl ammonium chloride; BARQUATX MX-50, BARQUAT MX-80, BTCR 824 or BTCR 8248 each described to be a composition based on alkyl dimethyl benzyl ammonium chloride; BARQUATt) OJ-50, BARQUAT) 0J-80, BTC 2565, or BTCX 2658 each described to be a composition based on alkyl dimethyl benzyl ammonium chloride; BARQUATt) 4250, BARQUAT 4280, BARQUAT 4250Z, BARQUAT(D 4280Z, BTCX 2125, or BTC 2125M each described to be a composition based on alkyl dimethyl benzyl ammonium chloride and/or alkyl dimethyl ethyl benzyl ammonium chloride; BARQUATt) MS-100 or BTCX 324-P100 each described to be based on myristyl dimethyl benzyl ammonium chloride; HYAMINE 2389 described to be based on methyl dodecyl benzyl ammonium chloride and/or methyl dodecyl xylene-bix-trimethyl ammonium chloride; HYAMINE 1622 described to be an aqueous solution of benzethonium chloride; HYAMINE 3500-NF or BTCX 50 each described to be based on alkyl dimethyl benzyl ammonium chloride; as well as BARQUAT(t 1552 or BTCX 776 described to be based on alkyl dimethyl benzyl ammonium chloride and/or dialkyl methyl benzyl ammonium chloride. (Each of these recited materials are presently commercially available from Lonza, Inc., Fairlawn, NJ and/or from Stepan Co., Northfield IL). It is to be understood that these quaternary ammonium compounds may be used singly or in mixtures of two or more. These quaternary ammonium compounds are desirably present in the concentrate compositions in an amount of from about 0.001 - 5% wt., but are desirably present in an amount of from 0.1 - 3%wt.

When diluted in a larger volume of water to form a cleaning and disinfecting composition, the quaternary ammonium compounds should be present in sufficient amount such that they are in a concentration of at least about 150 parts per million (p.p.m.), more desirably at least about 175 p.p.m. and most desirably about 200 p.p.m.

The present inventors have surprisingly found that certain of their formulations exhibited effective cleaning and disinfecting with less than 200 p.p.m. of the quatemary ammonium compounds in cleaning compositions which is an amount below that which is generally believed to be necessary for disinfecting efficacy.

A further constituent of invention is a nonionic surfactant compound wherein a major portion of the molecule is based on polymeric alkylene oxide block copolymer.

Polymeric alkylene oxide block copolymers include nonionic surfactants in which the major portion of the molecule is made up of block polymeric C2-C4 alkylene oxides, with alkylene oxide blocks containing C3 to C4 alkylene oxides. Such nonionic surfactants, while preferably built up from an alkylene oxide chain starting group, can have as a starting nucleus almost any active hydrogen containing group including, without limitation, amides, phenols, thiols and secondary alcohols.

One group of nonionic surfactants containing the characteristic alkylene oxide blocks are those which may be generally represented by the formula (A): HO-(EO)x(PO)y(EO)z-H (A where EO represents ethylene oxide, PO represents propylene oxide, y equals at least 15, (EO)x+z 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.

Another group of nonionic surfactants appropriate for use in the new compositions can be represented by the formula (B): R-(EO,PO)a(EO,PO)b-H (B wherein R is an alkyl, aryl or aralkyl group, where the R group contains 1 to 20 carbon atoms, the weight percent of EO is within the range of 0 to 45% in one of the blocks a, b, and within the range of 60 to 100% in the other of the blocks a, b, and the total number of moles of combined EO and PO is in the range of 6 to 125 moles, with 1 to 50 moles in the PO rich block and 5 to 100 moles in the EO rich block.

Further nonionic surfactants which in general are encompassed by Formula B include butoxy derivatives of propylene oxide/ethylene oxide block polymers having molecular weights within the range of about 2000-5000.

Still further useful nonionic surfactants containing polymeric butoxy (BO) groups can be represented by formula (C) as follows: RO-(BO)n(EQ)x-H (C wherein R is an alkyl group containing 1 to 20 carbon atoms, n is about 15 and xis about 15.

Also useful as the nonionic block copolymer surfactants, which also include polymeric butoxy groups, are those which may be represented by the following formula (D): HO-(EO)x(BO)n(EO)yH (D) wherein n is about 15, x is about 15 and y is about 15.

Still further useful nonionic block copolymer surfactants include ethoxylated derivatives of propoxylated ethylene diamine, which may be represented by the following formula:

where (EO) represents 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)y is such as to provide about 20% to 90% of the total weight of said compound.

Of these, the most preferred materials are those which are represented by formula (A) above; specific examples of particularly useful nonionic surfactant compounds which include as a major portion of the molecule a block polymeric alkylene oxide block are those materials presently commercially available under the tradename "Pluronict", and in particular the PluronictF series, Pluronic(g)L series, Pluronic( P series, as well as in the PluronicXR series, each of which is generally described to be a block copolymer of propylene oxide and ethylene oxide. Generally those of the PluronicRL series and the Pluronict)R series are preferred 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 intermediate HLB values such as from about 12.0 - 18.0 are found to be particularly advantageous. These materials are presently commerically available from BASF AG (Ludwigshafen, Germany) as well as from BASF Corp. (Mt. Olive Township, New Jersey).

Other useful exemplary nonionic block copolymers based on ethoxy/propoxy units which may also be used are those presently commercially available in the Poly Tergent g) E, and Poly-Tergent P series of materials from Olin Chemicals Corp., (Stamford CT) which are similarly described to be nonionic surfactants based on ethoxy/propoxy block copolymers and which are also conveniently available in a liquid form from the supplier.

It is to be understood that these nonionic surfactants based on polymeric alkylene oxide block copolymers may be used singly or in mixtures of two or more such compounds. These nonionic surfactant compounds are desirably present in the concentrate compositions in an amount of from about 0.01 - 10%wt., and most desirably in an amount of 0.1 - 3%wt.

The present inventive compositions also include a nonionic surfactant which desirably provides effective cleaning performance. Further desirably, the nonionic surfactant further exhibits a low level of irritancy to the eyes.

One class of nonionic surfactants are alkoxylated alcohols. These include the condensation products of a higher alcohol (e.g., an alkanol containing about 8 to 18 carbon atoms in a straight or branched chain configuration) condensed with about 2 to 30 moles of ethylene oxide, for example, lauryl or myristyl alcohol condensed with about 16 moles of ethylene oxide, tridecanol condensed with about 6 moles of ethylene oxide, myristyl alcohol condensed with about 10 moles of ethylene oxide per mole of myristyl alcohol, the condensation product of ethylene oxide with a distillation or separation fraction of coconut fatty alcohol containing a mixture of fatty alcohols with alkyl chains varying from 10 to about 14 carbon atoms in length and wherein the condensate contains either about 6 moles of ethylene oxide per mole of total alcohol or about 9 moles of ethylene oxide per mole of alcohol and tallow alcohol ethoxylates containing 6 ethylene oxides to 11 ethylene oxides per mole of alcohol.

A preferred group of the foregoing nonionic surfactants are the Neodolt ethoxylates (Shell Chemical Co., Houston TX); which are higher aliphatic, primary alcohols containing about 9-15 carbon atoms, such as a C, l alkanol condensed with 7 moles of ethylene oxide (NeodoltW 1-7), Cg-Cll alkanol condensed with an average of 2.5 moles of ethylene oxide (Neodol(g) 91-2.5); C9-C11 alkanol condensed with 6 moles of ethylene oxide (Neodol 91-6), Cg-Cl l alkanol condensed with 8 moles of ethylene oxide (Neodol 91-8), C12.13 alkanol condensed with 6.5 moles ethylene oxide (Neodol 23-6.5), C12-13 alkanol condensed with 7 moles ethylene oxide (Neodol 23-7), C12.15 alkanol condensed with 7 moles of ethylene oxide (Neodol 25-7), C12.15 alkanol condensed with 9 moles ethylene oxide (Neodol 25-9), C12-15 alkanol condensed with 12 moles ethylene oxide (NeodolR 25-12), C14.15 alkanol condensed with 13 moles ethylene oxide (Neodol 45-13), and the like.

Additional useful nonionic surfactants based on alcohol and ethylene oxide condensates are the condensation products of a secondary aliphatic alcohol containing 8 to 18 carbon atoms in a straight or branched chain configuration with 5 to 30 moles of ethylene oxide. Examples of commercially available nonionic detergents of the foregoing type are Cll-C15 secondary alkanol condensed with either 9 ethylene oxide (TergitolR 15-S-9) or 12 ethylene oxide (TergitolR 15-S-12) marketed by Union Carbide Corp. (Danbury CT). It is to be understood that these nonionic alkoxylated alcohol surfactant compounds may be used singly or in mixtures of two or more such compounds.

Further useful nonionic surfactants include alkoxylated, and particularly ethoxylated octyl and nonyl phenols according to the following general structural formulas:

in which the CgHl9 group in the latter formula is a mixture of branched chained isomers, and x indicates an average number of ethoxy units in the side chain. 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 Tritons X (Union Carbide, Danbury CT).

Exemplary alkoxylated alkyl phenols useful useful as a nonionic surfactant include certain compositions presently commercially available from the Rhone Poulenc Co., (Cranbury, NJ) under the general trade name Igepal, which are described to be octyl and nonyl phenols. These include Igepalt) C0730 which is described as an ethoxylated nonyl phenol having an average of 15 ethoxy groups per molecule.

A further useful class of nonionic surfactants is those based on alkylpolyglycosides. Suitable alkyl polyglycosides are known nonionic surfactants which are alkaline and electrolyte stable. Alkyl mono and polyglycosides are prepared generally by reacting a monosaccharide, or a compound hydrolyzable to a monosaccharide with an alcohol such as a fatty alcohol in an acid medium. Various glycoside and polyglycoside compounds including alkoxylated glycosides and processes for making them are disclosed in U.S. Patent No. 2,974,134; U.S. Patent No.3,219,656; U.S. Patent No. 3,598,865; U.S. Patent No. 3,640,998; U.S. Patent No.

3,707,535; U.S. Patent No.3,772,269; U.S. Patent No.3,839,318; U.S. Patent No.

3,974,138; U.S. Patent No.4,223,129; and U.S. Patent No.4,528,106.

A preferred group of alkyl glycoside surfactants suitable for use in the practice of this invention may be represented by formula I below: RO-(R1 O)y-(G)xZb wherein: R is a monovalent organic radical containing from about 6 to about 30, preferably from about 8 to about 18 carbon atoms; R, is a divalent hydrocarbon radical containing from about 2 to about 4 carbon atoms; O is an oxygen atom; y is a number which has an average value from about 0 to about 1 and is preferably 0; G is a moiety derived from a reducing saccharide containing 5 or 6 carbon atoms; and x is a number having an average value from about 1 to 5 (preferably from 1.1 to 2); ZisO2M',

O(CH2), CO2M', OSO3Ml, or O(CH2)SO3M'; R2 is (CH2)CO2Ml or CH=CHCO2M; (with the proviso that Z can be O2M only if Z is in place of a primary hydroxyl group in which the primary hydroxylbearing carbon atom, CH2OH, is oxidized to form a

group); b is a number of from 0 to 3x+1 preferably an average of from 0.5 to 2 per glycosal group; p is 1 to 10, M is H or an organic or inorganic cation, such as, for example, an alkali metal, ammonium, monoethanolamine, or calcium.

As defined in Formula I above, R is generally the residue of a fatty alcohol having from about 8 to 30 and preferably 8 to 18 carbon atoms. Examples of such alkylglycosides as described above include, for example, APGTM 325 CS GLYCOSIDE which is described as being a 50% C9-C alkyl polyglycoside, also commonly referred to as D-glucopyranoside, (commercially available from Henkel Corp, Ambler PA) and GLUCOPONTM 625 CS which is described as being a 50% C10-C16 alkyl polyglycoside, also commonly referred to as a D-glucopyranoside, (available from Henkel Corp., Ambler PA).

These nonionic surfactant compounds may be used singly or in mixtures.

They comprise 0.01 - 10%wt. of the concentrate compositions, and desirably comprise 0.1 - 7%wt. and most desirably comprise about 5%wt. of the concentrate compositions taught herein.

The inventive compositions optionally but desirably include a builder constituent. Such constituent may be present in an amount of from 0 - 3%wt. based on the total weight of the concentrate compositions taught herein. Such include water soluble inorganic builders which can be used alone, in admixture with other water soluble inorganic builders, as well as in conjunction with one or more organic alkaline sequestrant builder salts.

Exemplary builders include alkali metal carbonates, phosphates, polyphosphates and silicates. More specific examples include sodium tripolyphosphate, sodium carbonate, potassium carbonate, sodium polyphosphate, potassium pyrophosphate, potassium tripolyphosphate, and sodium hexametaphosphate. Further exemplary builders also include organic alkaline sequestrant builder salts such as alkali metal polycarboxylates including water-soluble citrates such as sodium and potassium citrate, sodium and potassium tartarate, sodium and potassium ethylenediaminetetraacetate, sodium and potassium N-(2hydroxyethyl)-ethylene diamine triacetates, sodiurn and potassium nitrilo triacetates, as well as sodium and potassium tartrate mono- and di-succinates. Also useful are gluconate or glucoheptonate salts particularly sodium gluconate and sodium glucoheptonate. Particularly advantageously used are di-, tri- and tetrasodium salts of ethylenediaminetetraacetic acid, especially tetrasodium salts thereof. As noted, these organic builder salts may be used individually, as a combination of two or more organic builder salts, as well as in conjunction with one or more detergency builders, including those indicated above.

As is noted above, the compositions according to the invention are aqueous in nature. Water is added to the constituents in order to provide 100% by weight of the composition.

An optional but in certain embodiments particularly desirable further constituent which is included in the inventive compositions is based on a polymeric polyquaternary ammonium salt, especially a halogen salt such as a chloride salt. Such a material is one which includes at least one repeating monomer unit wherein such monomer includes as part of its structure a quaternary ammonium. A particularly useful class of such materials are those sold under the trade designation "Mirapolt)" and are available from Rhne-Poulenc Surfactant & Specialty Chemicals Co.

(Cranbury, NJ). These materials are highly cationic in nature, and are believed to be in accordance with the following general structure:

wherein n is an integer greater than 2, and is desirably in the range of 2 - 12, more desirably is about 6. Such a material is commercially available as Mirapol A15 from from Rhne-Poulenc, identified above. The inventors have found that the inclusion of such material provides a useful soil suspending benefit which is desirable from a cleaning standpoint, although it has also been observed by the inventors that inclusion of such a material may have detrimental effect on the disinfecting properties of the compositions. Thus, its inclusion in the compositions and use is to be carefully chosen and in effective amounts to be determined in view of the inventive teaching presented herein, particularly in one or more of the Example formulations.

The constituents which may be used in the compositions according to the invention are individually known, and many are described in McCutcheon 's Detergents and Emulsifiers, North American Edition, 1991; Kirk-Othmer, Encyclopedia Chemical Technology, 3rd Ed., Vol. 22, pp. 346-387, the contents of which are herein incorporated by reference.

The compositions according to the invention are useful in the disinfecting and/or cleaning of surfaces, especially hard surfaces in need of such treatment. These in particular include surfaces wherein the presence of gram positive and/or gram negative bacteria are suspected. In accordance with the present inventive process, cleaning and/or disinfecting of such surfaces comprises the step of applying a stain or soil releasing and a disinfecting effective amount of a composition as taught herein to such a stained and/or soiled surface. Afterwards, the compositions are optionally but desirably wiped, scrubbed or otherwise physically contacted with the hard surface, and further optionally, may be subsequently rinsed from such a cleaned and disinfected hard surface. Such a hard surface cleaning and disinfecting composition according to the invention may be provided as a ready to use product which may be directly applied to a hard surface, but is desirably provided in a concentrated form intended to be diluted in water to form a cleaning composition therefrom.

The hard surface cleaner composition provided according to the invention can be desirably provided as a ready to use product in a manually operated spray dispensing container, and is thus ideally suited for use in a consumer "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 thereafter, wipes off the treated area with a rag, towel, or sponge, often a disposable paper towel or sponge. For particularly heavy deposits of such undesired stains, multiple applications may also be used.

In a yet a further embodiment, the compositions according to the invention may be formulated so that they may be useful in conjunction with a "aerosol" type product wherein they are discharged from a pressurized aerosol container.

Whereas the present invention is intended to be used in the types of liquid forms described, the compositions according to the invention are desirably diluted with a further amount of water to form a cleaning solution therefrom. In such a proposed diluted cleaning solution, the greater the proportion of water added to form said cleaning dilution, the greater may be the reduction of the rate and/or efficacy of the thus formed cleaning solution in the cleaning of a hard surface, as well as a reduction in disinfectant efficacy. Accordingly, longer residence times upon the stain or soils to effect their loosening and/or the usage of greater amounts may be necessitated. Conversely, nothing in 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 composition is essentially the same as the compositions described above with the exception of the inclusion of a lesser amount of water.

Cleaning compositions may be easily prepared by diluting measured amounts of the compositions in further amounts of water by the consumer or other end user in certain weight ratios of composition:water, and optionally, agitating the same to ensure even distribution of the composition in the water. The aqueous compositions according to the invention may be used without further dilution, but may also be used with a further aqueous dilution, i.e., in composition:water concentrations of 1:0, to extremely dilute d most desirably is about 1:64. The actual dilution selected is in part determinable by the degree and amount of dirt and grime to be removed from a surface(s), the amount of mechanical force imparted to remove the same, as well as the observed efficacy of a particular dilution. Generally better results and faster removal are to be expected at lower relative dilutions of the composition and the water.

Other conventional optional additives, although not particularly elucidated above may also be included in the present inventive compositions.

The following examples illustrate exemplary and preferred formulations of the concentrate 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 which 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 spirit 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.

Example Formulations.

Preparation of Example Formulatlons Exemplary formulations illustrating certain preferred embodiments of the inventive compositions and described in more detail in Table 1 below were formulated generally in accordance with the following protocol.

Into a suitably sized vessel, a measured amount of water was provided after which the constituents were added in no specific or uniform sequence, which indicated that the order of addition of the constituents was not critical. All of the constituents were supplied at room temperature, and any remaining amount of water was added thereafter. Certain of the nonionic surfactants were gelled at room temperature and were first preheated to render them pourable liquids prior to addition and mixing. Mixing of the constituents was achieved by the use of a mechanical stirrer with a small diameter propeller 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, even in excess of 120 days.

The exact compositions of the example formulations are listed on Table 1, below where are described the weights of the actives provided.

Table 1 Example: Ex.1 Ex.2 Ex.3 Ex.4 Ex.5 Ex.6 Ex.7 Ex.8 Ex.9 Ex.10

Mirapol A-15 0.25 0.25 0.25 0.25 0.25 0.25 0.25 0.25 Pluronic L-64 6.00 2.00 4.00 4.00 6.00 5.00 2.00 2.00 2.00 2.00 Neodol 23-6.5 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 4.00 4.00 Neodol 25-7 Neodol 91-2.5 Tergitol 15-S-9 other nonionic surfactants sodium carbonate sodium sesquicarbonate sodium citrate EDTA sodium salt 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 1.00 BTC-8358 2.50 1.25 1.25 2.50 1.25 2.00 2.00 2.00 2.00 2.00 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Dl water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Table 1 Example: Ex.11 Ex.12 Ex.13 Ex.14 Ex.15 Ex.16 Ex.17 Ex.18 Ex.19 Ex.20

Mirapol A-15 0.25 Pluronic L-64 2.00 2.00 1.28 6.00 4.00 4.00 4.00 4.00 4.00 4.00 Neodol 23-6.5 8.00 8.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Neodol 25-7 4.00 Neodol 91-2.5 Tergiol 15-S-9 other nonionic surfactans sodium carbonate 1.00 2.00 3.00 sodium sesquicarbonate sodium citrate EDTA sodium salt 1.00 1.00 0.15 0.15 0.50 1.00 BTC-8358 2.00 2.00 1.28 2.00 1.30 1.30 1.30 1.30 1.30 1.30 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Dl water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Table 1 Example: Ex.21 Ex.22 Ex.23 Ex.24 Ex.25 Ex.26 Ex.27 Ex.28 Ex.29 Ex.30

Mirapol A-15 0.50 1.00 0.50 1.00 0.50 Pluronic L-64 4.00 2.00 2.00 2.00 4.00 4.00 4.00 2.00 2.00 2.00 Neodol 23-6.5 2.00 Neodol 25-7 4.00 4.00 4.00 2.00 2.00 2.00 8.00 8.00 7.00 Neodol 91-2.5 Tergitol 15-S-9 other nonionic surfactans sodium carbonate 0.50 sodium sesquicarbonate sodium citrate EDTA sodium salt 0.50 0.10 0.10 0.10 BTC-8358 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Dl water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Table 1 Example: Ex.31 Ex.32 Ex.33 Ex.34 Ex.35 Ex.36 Ex.37 Ex.38 Ex.39 Ex.40

Mirapol A-15 0.50 0.13 0.50 0.50 0.75 0.50 0.50 0.50 Pluronic L-64 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Neodol 23-6.5 Neodol 25-7 7.00 6.00 6.00 5.00 5.00 6.00 6.00 5.00 6.00 Neodol 91-2.5 Tergitol 15-S-9 5.00 other nonionic surfactants sodium carbonate sodium sesquicarbonate sodium citrate EDTA sodium salt 0.10 0.10 0.10 0.10 0.10 0.10 0.38 1.00 0.10 0.10 BTC-8358 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 DI water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Table 1 Example: Ex.41 Ex.42 Ex.43 Ex.44 Ex.45 Ex.46 Ex.47 Ex.48 Ex.49 Ex.50

Mirapol A-15 Pluronic L-64 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Neodol 23-6.5 Neodol 25-7 5.00 5.00 5.00 3.50 6.00 5.00 5.00 5.00 5.00 Neodol 91-2.5 1.50 Tergitol 15-S-9 5.00 other nonionic surfactants sodium carbonate sodium sesquicarbonate sodium citrate 0.50 0.50 0.50 0.50 0.50 EDTA sodium salt 0.10 0.10 0.10 0.10 0.10 BTC-8358 1.30 1.14 1.14 1.30 1.30 1.30 0.98 1.30 1.30 1.30 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 DI water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s.

Table 1 Example: Ex.51 Ex.52 Ex.53 Ex.54 Ex.55 Ex.56 Ex.57 Ex.58 Ex.59 Ex.60

Mirapol A-15 0.50 0.25 0.25 0.25 0.25 0.25 Pluronic L-64 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 2.00 Neodol 23-6.5 Neodol 25-7 5.00 5.00 5.00 6.00 6.00 Neodol 91-2.5 Tergitol 15-S-9 5.00 other nonionic 2.50 0.40 3.00 6.00 APG 325 Pluronic surfactans Neodol Neodol L-64 91-2.5 25-9 and and 3.00 3.60 Neodol Pluronic 91-6 P103 sodium carbonate sodium 1.00 1.00 sesquicarbonate sodium citrate EDTA sodium salt 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 0.10 BTC-8358 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 1.30 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 0.20 Dl water q.s. q.s. q.s. q.s. q.s. q.s. q.s. q.s q.s. q.s.

Table 1 Example: Ex.61 Ex.62 Ex.63 Ex.64 Ex.65 Ex.66

Mirapol A-15 0.25 0.25 0.25 0.25 0.25 Pluronic L-64 2.00 2.00 2.00 2.00 2.00 1.28 Neodol 23-6.5 Neodol 25-7 6.00 4.00 Neodol 91-2.5 Tergitol 15-S-9 other nonionic 5.00 6.00 5.00 5.00 surfactants Surfonic Neodol lgepal Triton N95 1-7 CO730 X-100 sodium carbonate sodium sesquicarbonate sodium citrate EDTA sodium salt 0.10 0.10 0.10 0.10 0.10 0.15 BTC-8358 1.30 1.30 1.30 1.30 1.30 1.28 fragrance (+dye) 0.20 0.20 0.20 0.20 0.20 0.20 Dl water q.s. q.s. q.s. q.s. q.s. q.s.

APG 325 which is described as a nonionic alkylpolyglucoside surfactant (Henkel Corp., Gulph Mills, PA) Pluronic L-64 described previously Pluronic P103 described to be a nonionic surfactant based on block ethoxy/propoxy copolymers Surfonic N95 described to be a nonionic nonylphenol surfactant Igepal CO730 described to be a nonionic nonylphenol surfactant As is indicated, to all of the formulations of Table 1 was added sufficient deionized water in "quantum sufficient" to provide 100 parts by weight of a particular formulation.

The identity of the constituents of Table 1 above are described in more detail on Table 2, below.

TABLE 2

constituent: identity: MirapolR A-15 cationic polymeric polyquaternary ammonium compound (Rhne-Poulenc Inc.) PluronicS L 64 . nonionic ethoxy/propoxy block copolymer surfactant (BASF Corp.) NeodolR 23-6.5 nonionic C12-13 alkanol condensed with 6.5 moles ethylene oxide (Shell Chemical Co.) NeodolR 25-7 nonionic C12-15 alkanol condensed with 7 moles ethylene oxide (Shell Chemical Co.) NeodolE 91-2.5 nonionic C9-11 alkanol condensed with an average of 2.5 moles ethylene oxide (Shell Chemical Co.) TergitolE 15-S-9 .- nonionic C11-15 alkanol condensed with 8 moles of ethylene oxide (Union Carbide Corp.) sodium . sodium sesquicarbonate sesquicarbonate sodium citrate sodium citrate, anhydrous sodium carbonate sodium carbonate monohydrate sodium salt of ethylene diamine tetraacetic acid EDTA sodium salt (Dow Chemical Co.) BTC-8358 . alkyl dimethyl benzyl ammonium chloride Fragrance ,. proprietary composition It is to be noted that the formulations according to Examples 48 - 53 were substantially the same, but for different dyes and/or fragrances which varied between these formulations.

Evaluation of Antimicrobial Efficacy: Several of the exemplary formulations described in more detail on Table 1 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", 16th 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", s Edition, of the Association of Official Analytical Chemists; or American Society for Testing and Materials (ASTM) E 1054-91 the contents of which are herein incorporated by reference. This test is also commonly referred 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 indicate the number of test substrates wherein the tested organism remains viable after contact for 10 minutes with a 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 for lesser amount of test substrates such as for 10, 20, 30 or 40 test substrates provide useful screening results, although insufficient to satisfy the requirement of 60 test substrates as dictated by the AOAC Use-Dilution Test.

Results of the antimicrobial testing are indicated on Table 3, 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. Table 3 - Antimicrobial Efficacy

Formulation: Staphylococcus Salmonella Pseudomonas aureus choleraesuis aeruginosa Ex.1 0/60 0/60 2/60 Ex.2 1/60 1/70 -- Ex.3 0/60 2/90 -- Ex.4 0/60 0/60 -- Ex.6 1/60 0/60 -- Ex.8 0/60 0/60 -- Ex.10 0/40 0/40 -- Ex.13 0/30 0/30 -- Ex.14 0/30 0/30 -- Ex.32 --- 15/20 -- Ex.34 0/30 21/30 -- Ex.36 0/30 20/30 -- Ex.54 --- 0/10 -- Ex.37 --- 0/10 -- Ex.38 --- 0/10 -- Ex.39 0/30 0/30 -- Ex.40 --- 0/20 -- Ex.41 0/30 0/30 -- Ex.55 0/20 0/20 -- Ex.42 0/20 0/20 -- Ex.43 0/20 0/20 -- Ex.44 0/20 0/20 -- Ex.45 1/40 0/40 -- Ex.49 0/60 0/60 -- Ex.51 0/60 0/60 -- Ex.52 1/60 0/60 -- Ex.53 0/60 0/60 -- -' indicates not tested Evaluation of Ocular Irritation: The ocular irritation characteristics of formulations according to the invention were evaluated using the known Draize Eye test protocol. Evaluation was performed on several formulations according to the invention and described more fully in Table I above.

As known to those skilled in the art, the Draize Eye Test measures eye irritation for the grading of severity of ocular lesions, measuring three dimensions: scores obtained for the cornea, iris and conjunctiva. For the cornea, after exposure to the composition, A the cornea opacity is graded on a scale from 1 to 4; B the area of cornea involved is graded on a scale from 1-4 (where the score = A x B x 5 may be a total maximum of 80). For evaluation of the iris, after exposure the composition, A the involvement of the iris is graded on a scale of 1-2 (where the score = A x 5 may be a total maximum of 10). For a evaluation of the conjunctiva, A Redness is graded on a scale of 1-3; B Chemosis is graded on a scale of 14; and C Discharge is measured on a scale of 1-3 [where the score = (A + B + C) x 2 may be a maximum of 20]. The maximum total score is the sum of all scores obtained for the cornea, iris and conjunctive (a maximum of 110).

The results of the Draize test are reported below. These indicate that an EPA classification Category "3" was appropriate, where corneal involvement or irritation cleared in "21" days or less. These results are in accordance with the guidelines of the Environmental Protection Agency (EPA), 40 C.F.R. Ch. 1, ≈162.10, (1986).

TABLE 4 - DRAIZE RESULTS

Formulation: Corneal opacity in test subjects / number of days Ex.1 0/21 Ex.6 2/21 Ex.13 0/21 Ex.14 1/21 Ex.39 0/21 Evaluation of Cleaning Efficacy: Various formulations amongst those listed above were evaluated for their cleaning efficacy on tile surfaces utilizing the following protocols. "Standard soiled tiles" were prepared for use in the tests. These were prepared in accordance with the protocol described in ASTM 4488-87, Annex A2 "Greasy Soil/Painted Masonite Wallboard Test Method" as well as Annex A5 "Particulate and Oily Soil/Vinyl Tiles Test Method". This preparation of standard soiled tiles and cleaning protocol was performed for a number of cleaning compositions formed from the formulations described in more detail on Table 1.

Evaluation was performed utilizing a Gardner Washability Apparatus, using standard soil tiles prepared in accordance with the protocol described above at a standard pressure and sponge stroke settings in order to determine or quantify the cleaning efficiency of the formulations. These formulations were used formed into a cleaning composition wherein 1 part of a formulation of Table 1 was diluted with 64 parts water. For comparative purposes, a 1:64 dilution of a commercially available concentrated cleaning and disinfecting preparation, LysolQ) Deodorizing Cleaner "Country Scent" variety was also prepared and evaluated in the same test. In determining the cleaning efficiency of each of the formulations, reflectance values were determined using a Minolta Chromameter where each tile was measured three times and the mean reflectance value are reported below on Table 5. For each of these tiles, there were at least four replicates, each of which was evaluated and used to determine the mean reflectance value of Table 5. Testing was performed for each of the following: a clean unsoiled tile, a soiled tile, and a soiled tile following Gardner Washability Apparatus scrubbing. Such reflectance values were then employed to calculate cleaning efficiency according to the following formula: Cleaning Efficiency = Lo-Ls wherein: Lt = reflectance average after scrubbing soiled tile; Ls = reflectance average before cleaning soiled tile; Lo = reflectance average original tile before soiling.

The evaluation procedure noted above was performed in groups of test tiles, wherein the cleaning compositions formed from formulations according to Table 1 were compared to tiles treated with the cleaning composition formed using the Lysol Deodorizing Cleaner "Country Scent" formulation. These cleaning efficiency results are shown in the Table 5, following.

TABLE 5- CLEANING EFFICACY

Formulation: Greasy Oily Group A

LysolR Country 0.61 0.75 Scent Ex.1 0.59 0.87 Ex.2 0.56 0.77 Ex.3 0.61 0.76 Ex.4 0.61 0.87 Ex.6 -- 0.87 Ex.7 -- 0.83 Ex.8 -- 0.77 Ex.9 -- 0.83 Ex.10 -- 0.79 Ex.11 -- 0.78 Ex.12 -- 0.75 Group B

LysolR -- 0.63 Country Scent Ex.66 -- 0.53 Ex.14 -- 0.57 Group C

LysolR -- 0.73 Country Scent Ex.15 -- 0.64 Ex.16 -- 0.7 Ex.17 -- 0.6 Ex.18 -- 0.64 Ex.19 -- 0.68 Ex.20 -- 0.6 Ex.21 -- 0.57 Group D

LysolR -- 0.72 Country Scent Ex.22 -- 0.58 Ex.23 -- 0.56 Ex.24 -- 0.75 Ex.25 -- 0.42 Ex.26 -- 0.66 Ex.27 -- 0.66 Group E

LysolR -- 0.76 Country Scent Ex.28 -- 0.68 Ex.29 -- 0.75 Ex.30 -- 0.72 Ex.31 -- 0.81 Ex.33 -- 0.85 Ex.34 -- 0.85 Ex.35 -- 0.84 Ex.39 -- 0.81 Ex.40 -- 0.78 Group F

LysolR -- 0.57 Country Scent Ex.56 -- 0.21 Ex.57 -- 0.46 Ex.58 -- 0.71 Ex.59 -- 0.73 Ex.60 -- 0.74 Ex.61 -- 0.77 Ex.62 -- 0.80 Ex.63 -- 0.80 Ex.64 -- 0.82 As shown, the measurement of the cleaning effectiveness of the test samples involved the ability of the cleaning composition to remove the test soil from the test substrate. This was expressed by Cleaning Efficiency; as numerical values for a Cleaning Efficiency increase, higher cleaning effectiveness is achieved for the cleaning composition tested. As the results show, the inventive composition showed excellent cleaning characteristics which favorably compare to the commercially available products.

Claims (10)

1. Claims: 1.An aqueous disinfecting and cleaning composition which comprises per 100% wt., a disinfecting effective amount of a quaternary ammonium compound having germicidal properties (component I); 0.01 - 10% wt of a nonionic surfactant compound which includes as a major portion of the molecule a block polymeric alkylene oxide block (component II); 0.01 - 10% wt of a nonionic surfactant (component III); 0 - 3% wt of a builder (component IV); 0%wt. to about 5%wt. of one or more conventional additives.
2. 2. A composition according to claim 1 wherein the quaternary ammonium compound having germicidal properties is present in an amount of from 0.001 to 5% wt, preferably about 0.1 - 3% wt.
3. 3. A composition according to claim 1 or 2 wherein the nonionic surfactant compound based on a block polymeric alkylene oxide block is present in an amount of from 1-8% wt, preferably about 1.25% - 4%wt.
4. 4. A composition according to claim 1, 2 or 3 wherein the nonionic surfactant compound based on a block polymeric alkylene oxide block has the general formula: HO-(EO)x(PO)y(EO)z-H (A where EO represents ethylene oxide, PO represents propylene oxide, y equals at least 15, (EO)x+z 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.
5. 5. A composition as claimed in any of claims 1 to 4 wherein the nonionic surfactant (component III) is based on an alkoxylated alcohol.
6. 6. A composition as claimed in any of claims 1 to 5 wherein the nonionic surfactant (component III) is present in an amount of from 0.1 to 8% wt, preferably 1 - 7% wt.
7. 7. A composition according to any of claims 1 to 6 further comprising 0.1 2% wt of a polymeric cationic surfactant compound based on a polyquaternary ammonium salt;
8. 8. A composition according to claim 7 wherein polymeric cationic surfactant compound based on a polyquatemary ammonium salt is a compound according to the formula:

   wherein n is an integer greater than 2.
9. 9. A process for cleaning and/or disinfecting of hard surfaces which includes the step of: applying to the surface an effective amount of a composition according to any ofclaims 1 to 8.
10. 10. A composition substantially as herein before described with reference to any of Examples 1 to 66.