WO2003091375A1

WO2003091375A1 - Cleaning & disinfecting compositions

Info

Publication number: WO2003091375A1
Application number: PCT/GB2003/001764
Authority: WO
Inventors: Robert Zhong Lu; Andrew Arno Kloeppel
Original assignee: Reckitt Benckiser Inc; Reckitt Benckiser (Uk) Limited
Priority date: 2002-04-23
Filing date: 2003-04-23
Publication date: 2003-11-06
Also published as: AU2003224306A1; GB0209198D0

Abstract

Disclosed are concentrated liquid cleaning and disinfecting compositions as well as general purpose cleaning compositions which are normally diluted in a larger volume of water to form a working solution therefrom, and which exhibit a blooming effect when diluted. These compositions comprise: (a) a fatty acid methyl ester solvent, (b) one or more nonionic delusive surfactant, (c) an amphoteric surfactant, (d) one or more alkanolamides, (e) a major proportion of water, (f) optionally, one or more further components, and (g) a germicidal constituent selected from at least one cationic surfactant having germicidal properties and 2-benzyl-4-chlorophenol, in the case of cleaning and disinfecting compositions.

Description

CLEANING & DISINFECTING COMPOSITIONS

The present invention relates to cleaning and disinfecting compositions. More particularly the present invention relates to concentrated liquid cleaning and disinfecting compositions which are normally diluted in a larger volume of water to form a working solution therefrom, and which exhibit a blooming effect when diluted. The present invention also relates to concentrated liquid cleaning compositions which are normally diluted in a larger volume of water to form a working solution therefrom, and which exhibit a blooming effect when diluted.

Blooming is a property exhibited by dilutable compositions such as known cleaning compositions, specifically pine-oil type cleaning compositions which contain a significant amount (generally at least about 5% and more) of pine oil. Blooming may be characterized as the formation of milky, creamy or cloudy appearance which is manifested when a dilutable composition is added to a larger volume or quantity of water. Blooming is an important characteristic from a consumer standpoint as it provides a visual indicator and impression to the consumer that the concentrated product contains active cleaning and/or disinfecting constituents which are released upon addition of the concentrate to a volume of water. Such is an important visual indicator of apparent efficacy of a concentrated product. However, the inclusion of the fraction of pine oil can be detrimental as the fragrance of the pine oil may not be particularly desired.

It has now been found that it is now possible to produce certain concentrate compositions utilizing these selected constituents in particular formulations which provide blooming type cleaning compositions in a concentrated liquid form which provide both a germicidal effect and a good blooming effect. The "blooming" observed may be described as the change of the water's appearance from essentially colorless and transparent to that of a milky white, cloudy appearance. This effect is also sometimes referred to as the "break". Such blooming is a highly desirable in blooming type cleaning compositions as consumer/end user expectations associate cleaning effectiveness with the extent and degree of this blooming upon formation of a cleaning composition. Such blooming is particularly desirable in compositions where the blooming characteristic in an aqueous dilution is long lasting. Accordingly it is an object of the invention to provide an aqueous concentrated liquid cleaning and disinfecting composition which blooms when added to a larger volume of water which comprises the following constituents:

(a) fatty acid methyl ester solvent; (b) a germicidal constituent selected from at least one cationic surfactant having germicidal properties and 2-benzyl-4-chlorophenol;

(c) one or more nonionic detersive surfactant, preferably one or more nonionic detersive surfactants based on alkoxylated alcohols;

(d) an amphoteric surfactant, preferably based on one or more aminopropionates or alkylampho(mono-), or (di-)propionates;

(e) one or more alkanolamides;

(f) a major proportion of water;

(g) optionally, one or more further detersive surfactants, preferably selected from amphoteric or nonionic detersive surfactants; (h) optionally an organic solvent constituent; and optionally, one or more constituents selected from: chelating agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, pH buffers, as well as others known the art and useful in similar compositions. Any optional constituents, when selected to be present, are included in amounts which do not undesirably affect the overall blooming characteristics of the present inventive compositions.

Another object of the present invention is to provide an aqueous general purpose cleaning, but not disinfecting, composition which blooms when added to a larger volume of water which comprises the following constituents: (a) fatty acid methyl ester solvent; (b) one or more nonionic detersive surfactants, preferably one or more nonionic detersive surfactants based on alkoxylated alcohols;

(c) an amphoteric surfactant, preferably based on one or more aminopropionates or alkylampho mono- or di-propionates;

(d) one or more alkanolamides; (e) a major proportion of water;

(f) optionally, one or more further detersive surfactants, preferably selected from amphoteric or nonionic detersive surfactants;

(g) optionally an organic solvent constituent; These compositions may include one or more further conventional optional constituents such as cleaning agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, and pH buffers, and the like.

It is a further object of the invention to provide such a concentrated liquid cleaning and disinfecting composition wherein the composition exhibits a blooming effect when diluted in a larger volume of water.

It is a yet further object of the invention to provide such a concentrated liquid cleaning and disinfecting composition wherein the composition exhibits a germicidal effect in both its concentrated form, and in an aqueous diluted form. It is a still further object of the invention to provide such a concentrated liquid cleaning and disinfecting composition which in a diluted form provides disinfection of surfaces wherein the presence of gram positive type pathogenic bacteria such as Staphylococcus aureus, and/or the presence of gram negative type pathogenic bacteria such as Escherichia coli and/or Salmonella choleraesuis is suspected on said surfaces. It is a still further object of the invention to provide working solutions formed from concentrated liquid cleaning and disinfecting compositions which exhibit a blooming effect when diluted in a larger volume of water, particularly where the dilutions retain their blooming characteristic over an extended period, for example, several days.

A yet further object of the invention is to provide a process for the cleaning or cleaning and disinfecting treatment of surfaces, especially hard surfaces which process contemplates the use of the concentrate compositions or of aqueous dilutions of the concentrate compositions described herein.

It is among the further object of the invention to provide such a concentrated liquid cleaning and disinfecting composition wherein the composition exhibits good long term stability at moderate temperatures (20 - 30°C) i.e., shelf stability in its concentrated form.

The concentrate compositions of the invention include (a) a fatty acid methyl ester solvent which consists solely of, or includes a significant proportions of one or more fatty acid methyl esters. Generally these fatty acid methyl ester solvents are based on compounds according to the formula:

O II R— C— O— CH3 ^J wherein R is a fatty alkyl moiety, such as a C₆-C₃₂, especially a C₈-C₂ alkyl moiety. These solvents may be based on a single monoester of an fatty acid or on a blend of fatty acid monoesters. The fatty acids may be saturated, unsaturated or polyunsaturated. Exemplary esters, without limitation thereto, include methyl linoleate, methyl linolenate and monoesters of any of a number of vegetable oils. Such vegetable oils are the commonly available vegetable triglycerides in which the preponderance of the fatty acid ester moieties have a chain length of 12 or more carbon atoms, particularly having a chain length of 16 or more carbon atoms. Exemplary vegetable oils contemplated herein are those which may be derived from soybean, cottonseed, linseed, safflower, sunflower, corn, sesame, rung, canola (rapeseed). Exemplary vegetable oil methyl esters derivable from such sources include: linseed oil methyl ester, safflower oil methyl ester, tung oil methyl ester and preferably soybean oil methyl ester. Further exemplary fatty acid methyl esters are derived from one or more 'cuts' of coconut, such as C₈-Cιo methyl esters, C₁₂ methyl esters, as well as C₁₄ methyl esters. It is further contemplated that fatty acid methyl esters from synthetic sources may also be used. Examples of synthetic ester oils include, e.g., isopropyl myristate, cetyl octanate, octyldodecyl myristate, isopropyl palmitate, butyl stearate, hexyl laurate, myristyl myristate, decyl oleate, hexyldecyl dimethyloctanate, cetyl lactate, myristyl lactate, lanolin acetate, isocetyl stearate, isocetyl isostearate, cholesteryl 12-hydroxystearate, ethylene glycol di-2- ethylhexylate, dipentaerythritol fatty acid ester, N-alkylglycol monoisostearate, neopentylglycol dicaproate, diisostearyl malate, glycerin di-2-heptyl undecanoate, trimethylopropane tri-2-ethylhexylate, trimethylopropane triisostearate, pentaerythritol tetra- 2-ethylhexylate, glycerin tri-2 -ethylhexylate, trimethylopropane triisostearate, cetyl-2- ethylhexanoate, 2-ethylhexyl palmitate, glycerin trimyristate, glyceride tri-2- heptylundecanoate, castor oil fatty acid methyl ester, oil oleate, cetostearyl alcohol, acetoglyceride, 2-heptylundecyl palmitate, diisobutyl adipate, N-lauroyl-L-glutamate-2-octyl dodecyl ester, di-2-heptylundecyl adipate, ethyl laurate, di-2-ethylhexyl sebatate, 2- hexyldecyl myristate, 2-hexyldecyl palmitate, 2-hexyldecyl adipate, diisopropyl sebatate, 2- ethylhexyl succinate, ethyl acetate, butyl acetate, amyl acetate, triethyl citrate, etc. may be mentioned.

The use of both a single fatty acid methyl ester, as well as mixtures of two or more different fatty acid methyl esters are contemplated. Desirably the fatty acid methyl ester solvent is a vegetable oil methyl ester, and is most preferably is either a soybean oil methyl ester or a fatty acid methyl ester which includes a fatty acid derived from coconut, particularly those demonstrated in the Examples, below.

An exemplary and preferred source for the fatty acid methyl ester solvent are commercially products available under the tradename SOYGOLD®, for example, SOYGOLD® 1000, a soybean oil methyl ester solvent, (ex. Ag Environmental Products Co.) A further useful and preferred source for the fatty acid methyl ester solvent is commercially available material marketed under the tradename Emery® (ex. Henkel Corp.) which is described to be a fatty acid methyl ester solvent wherein the fatty acid is derived from coconut oil and is available in three chain lengths of C₈-Cιo (Emery® 2209), Cι₂ (Emery® 2296), and C_H (Emery® 2214).

The fatty acid methyl ester solvent is generally present (on an actives weight basis) in an amount of from 0.1 - 20%wt. based on the total weight of the concentrate composition of which it forms a part. Desirably the fatty acid methyl ester solvent is present in amounts of from 1 - 18%wt. and more preferably in amounts of from 2 - 12%wt. The concentrate compositions according to the invention include as a necessary constituent (b) germicidal constituent selected from at least one cationic surfactant having germicidal properties, and 2-benzyl-4-chlorophenol, each of which are found to provide a broad 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, viz., cationic surfactants may also be used. Examples of preferred cationic surfactant compositions useful in the practice of the instant invention are those which provide a germicidal effect to the concentrate compositions, and especially preferred are quaternary ammonium compounds and salts thereof, which may be characterized by the general structural formula:

where at least one of R**, R₂, R₃ 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-chain alkylphenoxyalkyl, arylalkyl, etc. The remaining substituents on the nitrogen atoms other than the abovementioned alkyl substituents are hydrocarbons usually containing no more than 12 carbon atoms. The substituents R-* , R₂, R₃ and R-t may be straight-chained or may be branched, but are preferably straight-chained, and may include one or more amide, ether or ester linkages. The counterion X may be any salt-forming anion which permits water solubility of the quaternary ammonium complex.

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, ether 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 to be particularly useful in the practice of the present invention include those which have the structural formula:

wherein R₂ and R₃ are the same or different and are selected from C₈-Cι₂alkyl, or R₂ is Cι₂. _lβalkyl, C₈.₁₈alkylethoxy, or C₈.ι₈alkylphenoxyethoxy when R₃ is benzyl, and X is a halide, for example chloride, bromide or iodide, or is a saccharide or methosulfate anion. Desirably however, the R₂ and R₃ may be as defined but neither is benzyl. The alkyl groups recited in R₂ and R₃ may be straight-chained or branched, but are preferably substantially linear.

Exemplary useful quaternary germicides include commercially available preparations which include a single quaternary compound, as well as mixtures of two or more different quaternary compounds. Particularly useful quaternary germicides include those which are presently commercially available under the tradenames BARD AC®, BARQUAT®, BTC®, LONZABAC® and HYAMINE® such as are presently marketed by Stepan Co. (Chicago, EL) or Lonza Inc. (Basle, CH). Exemplary useful commercial 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 in the respective product literature from the supplies identified herein. These commercial preparations are predominantly based on aqueous or aqueous/alcohol mixtures which function as carriers for the active constituents. By way of non-limiting example useful commercial preparations include: BARDAC® 205M (50% active) and BARDAC® 208M (80% active) are described as being a liquid preparation containing alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride; BARDAC® 2050 (50% active) and BARDAC® 2080M (80% active) described to be a combination of octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride, and dioctyl dimethyl ammonium chloride; BARDAC® 2250 (50% active) described to be didecyl dimethyl ammonium chloride; BARQUAT® MB-50, BARQUAT® MX-50 and BARQUAT® OJ-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 described to be an alkyl dimethyl benzyl ammonium chloride; BARDAC® 4250, BARQUAT® 4250Z (each 50% actives) or BARQUAT® 4280, BARQUAT® 4280Z (each 80% actives) each of which is described as being alkyl dimethyl benzyl ammonium chloride/alkyl dimethyl ethyl benzyl ammonium chloride. Also useful is HYAMINE® 1622 described to be a liquid preparation diisobutyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride (available as 100% or 50% active); HYAMINE® 3500 (50% active) and HYAMINE® 3500-80 (80% active) each described as being alkyl dimethyl benzyl ammonium chloride. Further useful are BTC® 50 NF or BTC® 65 NF each described as a liquid preparation containing alkyl dimethyl benzyl ammonium chloride (50% active); BTC® 776 described as alkyl dimethyl benzyl ammonium chloride/dialkyl methyl benzyl ammonium chloride (50% active); BTC® 818 (50% active) as well as BTC® 818-80 (80% actives) each described to be octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride; BTC® 824 and BTC® 835 each described as being alkyl dimethyl benzyl ammonium chloride (50% actives); BTC® 885 (50% actives) and BTC® 888 (80% actives) each described as being alkyl dimethyl benzyl ammonium chloride, octyl decyl dimethyl ammonium chloride, didecyl dimethyl ammonium chloride and dioctyl dimethyl ammonium chloride; BTC® 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 described to be alkyl dimethyl benzyl ammonium chloride and alkyl dimethyl ethylbenzyl ammonium chloride; BTC® 2565 (50% 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% active) each described to be alkyl dimethyl benzyl ammonium chloride.

Another germicidal constituent useful in the present invention is 2-benzyl-4- chlorophenol (also known as orthobenzylparachlorophenol or OBPCP) which is available from Bayer under the tradename Preventol® BP.

The germicidal constituent selected from at least one cationic surfactant having germicidal properties and 2-benzyl-4-chlorophenol described above may be present in any germicidally effective concentration. Preferably, the germicidal cationic surfactant may be present in the concentrate compositions in amounts of from about 0.01 % by weight to up to about 10% by weight, preferably about 0.1-6% by weight, most preferably in amount of between about 0.5-3% by weight. The 2-benzyl-4-chlorophenol is present in the concentrate compositions in amounts of from about 0.01% by weight up to about 10% by weight, and preferably from about 0.1% by weight to about 6% by weight.

The inventive compositions further necessarily include (c) one or more nonionic detersive surfactants, preferably one or more nonionic detersive surfactants based on alkoxylated alcohols Exemplary useful nonionic surfactants include, inter alia, 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 hydrophilic ethylene oxide groups. Practically any hydrophobic compound having a carboxy, hydroxy, amido, or amino 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. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may be varied to adjust these properties. One example of such a nonionic surfactant is the condensation product of one mole of an alkyl phenol having an alkyl group containing from 6 to 12 carbon atoms with from about 5 to 25 moles of an alkylene oxide. Another example of such a nonionic surfactant is the condensation product of one mole of an aliphatic alcohol which may be a primary, secondary or tertiary alcohol having from 6 to 18 carbon atoms with from 1 to about 10 moles of alkylene oxide. Preferred alkylene oxides are ethylene oxides or propylene oxides which may be present singly, or may be both present.

Preferred nonionic surfactants include condensation products of a Cg-C₂o alkanols with a mixture of ethylene oxide and/or propylene oxide. Such are commercially available under the tradename POLYTERGENT® (BASF Corp., Mt. Olive Township., NJ), such as, for example, POLYTERGENT SL-22, POLYTERGENT SL-42, POLYTERGENT SL-62, and POLYTERGENT SL-92. Other similar types of nonionics include Plurafac surfactants from BASF, which are identified to be straight chain primary alkoxylated alcohols, such as, for example, Plurafac B-26, Plurafac C-17, and Plurafac D-25; as well as Surfonic JL-80X (Huntsman) which is identified to be an alkyl polyoxyalkylene ether and Triton XL-80N (Union Carbide) which is identified to be an alkoxylated alcohol.

Desirably the inventive compositions comprise at least two nonionic surfactants, a first nonionic surfactant which either has a cloud point of 25°C or greater or an HLB of greater than 10 or exhibits good solubility in water, and, a second nonionic surfactant which has a cloud point of 25°C or less or an HLB lesser than 10 or exhibits poor solubility in water. Examples of the first nonionic surfactant which has a cloud point of 25°C or more include POLYTERGENT® SL-62 (ex. BASF) and Plurofac B-26 (BASF). Examples of the second nonionic surfactant which has a cloud point of 25°C or less include POLYTERGENT® SL-22 (ex. BASF). By exhibits good solubility in water is meant that the material has a solubility in water which is greater than 0.5wt% in water. By exhibits poor solubility in water is meant that the material has a solubility in water which is less than 0.5wt.% in water.

The cloud points of such suitable first and second nonionic surfactants may be determined by known methods, such as by ASTM D2024 (reapproved 1986) for "Standard Test method for Cloud Point of Nonionic Surfactants". An even simpler test method for effectively determining which nonionic surfactants may be used as the first and second nonionic surfactant constituents in the compositions of the invention is as follows: to a clean beaker or other glass vessel is added 99 parts by weight of deionized water and 1 part by weight (by weight of the actives) of a surfactant composition to be tested. This test sample is heated above 25°C (preferably at least several degrees higher) stirred and the temperature permitted to drop to 25°C; if this test sample is observed to be murky or cloudy in appearance as the test sample's temperature achieves 25°C and drops below 25°C, it is considered to have a suitable cloud point of 25 °C and less and may be used as the second nonionic surfactant as described above. Alternately, for the first nonionic surfactant, 1 part by weight (by weight of the actives) of a surfactant is added 99 parts by weight of deionized water at approximately 25°C in a clean beaker or other glass vessel. This test sample is then slowly heated to above 25°C; if this test sample is observed to be murky or cloudy in appearance as the test sample's temperature achieves 25°C and at higher temperatures, it is considered to have a suitable cloud point of 25°C and more and may be used as the first nonionic surfactant as describe above.

These one or more nonionic surfactants may be present in any amount which is found to provide a beneficial detersive effect. Generally, these one or more nonionic surfactants do not comprise more than about 30%wt. (on an actives weight basis) of the inventive compositions. The nonionic surfactants, particularly the preferred first and second nonionic surfactants as described above are desirably present in the concentrate compositions in amounts of from about 0.001 % by weight to up to about 25% by weight, preferably about 1 - 25% by weight, most preferably in amount of between about 2 - 15% by weight. Further, according to preferred embodiments wherein both a first nonionic surfactant which has a cloud point of 25 °C or greater, and, a second nonionic surfactant which has a cloud point of 25°C or less, are present, the first nonionic surfactant comprises from 0.01 - 15%wt., preferably 0.1 - 12%w , and most preferably l-10%wt., while the second nonionic surfactant comprises from 0.1 - 12%wt., preferably 1 - 10%wt., and most preferably from 1 - 8%wt.

The compositions of the invention also include (d) one or more amphoteric surfactants, preferably such amphoteric surfactants based on one or more aminopropionates or alkylampho mono-, or di-propionates, which are believed to enhance the bloom properties of the present invention. Contemplated as useful are one amphoteric surfactant selected from alkylampho(mono)- and (di)-acetates, alkylampho(mono)- and (di)-propionates, and aminopropionates. These amphoteric surfactants may be used singly, or in combination with further other amphoteric surfactants, but desirably are the sole amphoteric surfactants present in the compositions. Salt forms of these amphoteric surfactants may also be used. Exemplary useful alkylampho(mono)acetates include those according to the general structure:

Exemplary useful alkylampho(di)acetates include those according to the general structures:

Exemplary useful alkylampho(mono)propionates include those according to the general structure:

Exemplary useful alkylampho(di)propionates include those according to the general structure:

Exemplary useful aminopropionates include those according to the following general structure:

In each of the above indicated structures, R represents a C₈-C₂₄ alkyl group and desirably is a Cio-Ciβ alkyl group.

Specific useful and commercially available amphoteric surfactants which may be used include certain surfactants presently commercially available under the tradename Miranol® (Rhodia, Cranbury NJ). Specific examples include Miranol® C2M-NPLN described to be disodium cocoamphodiacetate; Miranol® FA-ΝP which is described to be sodium cocoamphoacetate, Miranol® DM described to be sodium stearoamphoacetate; Miranol® HMA described to be sodium lauroamphoacetate; Miranol® C2M described as being cocoamphodiproponic acid; Miranol® C2M-SF described as being disodium cocoamphodipropionate; Miranol® CM-SF Cone, described as being cocoamphopropionate; and especially Mirataine® H2C-HA described as being sodium lauriminodipropionate which is preferred.

Of these amphoteric surfactants, those based on aminopropionates, alkyl(ampho)monopropionates or alkyl(ampho)diropionatesare preferred. Specific and particularly preferred are the amphoteric surfactants demonstrated in the Examples, below. The amphoteric surfactant constituent may be present in the concentrate compositions in amounts of from about 0.001 % by weight to up to about 15% by weight, preferably about 0.1-10% by weight, most preferably in amount of between about 1.0-8% by weight.

The compositions of the invention further include (e) one or more alkanolamides. Such alkoxylated alkanolamides include C₈-C₂₄ alkyl di(C₂-C₃ alkanol amides), particularly as represented by the following formula:

wherein Rς is a branched or straight chain C₈-C₂₄ alkyl radical, preferably a Cιo-Cι₆ alkyl radical and more preferably a C₁₂-C₁₄ alkyl radical, and R_d and R_e are a Cι-C₄ alkyl radical, preferably an ethyl radical; Rj and R_e may be the same or different.

Particularly useful alkoxylated alkanolamides include cocoamide diethanol amide, and especially soyamide diethanolamide. Exemplary and particularly preferred alkoxylated alkanolamides are described with reference to the Examples.

The alkoxylated alkanolamides are included in the concentrate compositions in amounts of from about 0.001 % by weight to up to about 8% by weight, preferably about 0.1 - 5 % by weight, most preferably in amount of between about 0.5 - 3 % by weight. According to preferred embodiments of the invention, the (d) amphoteric surfactant constituent and the (e) alkanolamide surfactant constituent are present in relative weight ratios of about 2-16:1 and a more preferred ratio being of about 2-6:1.

As the inventive compositions are largely aqueous in nature, they include (f) a major proportion of water. Water is added in order to provide 100% by weight of the concentrate composition. The water may be tap water, but is preferably distilled and/or deionized water. Water is added in amounts which are sufficient to form the concentrated compositions which amount is sufficient to ensure the retention of a substantially clear characteristic when produced as a concentrate, but at the same time ensuring good blooming upon the addition of the concentrated composition to a further amount of water, or upon the addition of further water to the concentrate. Generally, water is present in the concentrate compositions in amounts in excess of about 75% by weight, based on the total weight of the concentrate compositions taught herein.

According to certain especially preferred embodiments, the concentrate compositions may be characterized in that when the concentrate compositions are diluted at a ratio of 1 part to 64 parts water at 40°C, the resultant mixture exhibits a percent light transmittance of at most 90%, preferably at most 75%, more preferably at most 50%, and still more preferably at most 25%. This can be determined according to methods well known in the art as well as the method discussed in the Examples below.

The inventive compositions may optionally include one or more further detersive surfactants which may be anionic, cationic, amphoteric but preferably are one or more further nonionic surfactants.

If any further detersive surfactants are included in the compositions, they are desirably selected so to be compatable with the other constituents present and are present in amounts which will not undesirably degrade the blooming characteristics of the compositions. Any such further detersive surfactants, if desirable, are present in amounts of from 0.001 - 10%wt.

The inventive compositions may optionally, but in certain specific formulations desirably, include one or more organic solvents. Useful organic solvents are those which are at least partially water-miscible such as alcohols (e.g., Cι-C₆ alcohols including various positional isomers), polyols such as glycols, water-miscible ethers (e.g. diethylene glycol diethylether, diethylene glycol dimethylether, propylene glycol dimethylether), water-miscible glycol ether (e.g. propylene glycol monomethylether, propylene glycol mono ethylether, propylene glycol monopropylether, propylene glycol monobutylether, ethylene glycol monobutylether, dipropylene glycol monomethylether, diethyleneglycol monobutylether), lower esters of monoalkylethers of ethyleneglycol or propylene glycol (e.g. propylene glycol monomethyl ether acetate) and pyrrolidiones, for example, N-methyl-pyrrolidone, all commercially available from Union Carbide, Dow Chemical Co., Hoechst, or ISP Chemicals. According to certain particularly preferred embodiments, pine oil, terpene or terpineols are substantially or wholly absent from the concentrate compositions.

The concentrate compositions described herein optionally but in some instances desirably further include at least one optional constituent selected from: chelating agents, coloring agent, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, pH buffers, as well as others known the art and useful in similar compositions. The one or more optional constituents are selected to be present, and are included in amounts which do not undesirably affect the overall blooming characteristics of the present inventive compositions. One unique aspect of the present invention is that with the use of the fatty acid methyl ester solvent of the present invention, a variety of fragrances can be used that usually are not used with traditional pine oil products that bloom. This is due to the low odor characteristics of the fatty acid methyl ester solvents used in the present invention which would not interfere with the additional fragrance whereas when pine oil is used in products that bloom, the odor of the pine oil overpower the any fragrance added to that product.

Advantageously included constituents are one or more coloring agents which find use in modifying the appearance of the concentrate compositions especially to impart to concentrate compositions an appearance characteristic of a pine oil type concentrate composition. However, other colors atypical of pine oil type cleaning concentrates may be used as well. Known art light stabilizer constituents which act to retain the appearance characteristics of the concentrate compositions over longer intervals of time may also be used.

Generally the total weight of such further conventional additives may comprise up to 10% by weight of a concentrated composition formulation. Such materials as described above are each individually known to the art, many of which are described in McCutcheon 's Emulsifiers and Detergents (Vol.1), McCutcheon 's Functional Materials (Vol. 2), North American Edition, 1998; Kirk-Othmer, Encyclopedia of Chemical Technology, 4^th Ed., Vol. 23, the contents of which are herein incorporated by reference For any particular composition described above, any optional ingredients should be compatible with the other ingredients present.

The term "concentrate" as used in this specification is the pre-consumer dilution and the composition of the cleaning composition which is the typically the form of the product prepared for sale to the consumer or other end user. The term "cleaning compositions" are the water diluted compositions which are expected to be prepared by the consumer or other end user by mixing a measured amount of the "concentrate" with water in order to form an appropriately diluted cleaning composition which is suitable for use in cleaning applications, especially in the cleaning of hard surfaces. Such may be easily prepared by diluting measured amounts of the concentrate compositions in water by the consumer or other end user in certain weight ratios of concentrate:water, and optionally, agitating the same to ensure even distribution of the concentrate in the water. As noted, the concentrate may be used without dilution, i.e., in concentrate:water concentrations of 1 :0, to extremely dilute dilutions such as 1 : 10,000. Desirably, the concentrate is diluted in the range of 1 :0.1 - 1 : 1000, preferably in the range of 1 : 1 - 1:500 but most preferably in the range of 1:10 - 1:100, and particularly preferably at 1 :64. It is to be understood however that the "concentrate" composition can be used without any further dilution and thus used "as is."

It is also to be understood, that the percentages of the constituents have been generally referred to in this specification as percent by weight or as parts by weight based on a measure of 100 % by weight, unless otherwise indicated.

Example Formulations: Preparation of Example Formulations:

Exemplary formulations as illustrated on Table 1 following according to the instant invention were prepared in accordance with the following general procedure.

Into a suitably sized vessel, a measured amount of water was provided after which the constituents were added in the following sequence: surfactants and solvents, and lastly the fragrance constituents. All of the constituents were supplied at room temperature, except for the linear alcohol alkoxylate which was first gently heated and melted. 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.

It is to be noted that the constituents might be added in any order, for example, the order listed of the constituents listed in Table 1. It is also possible that water can be added last, provided the other constituents are thoroughly mixed together prior to addition of water. The exact compositions of the example formulations are listed on Table 1; the weights given are the "as is" weight of materials as supplied by their respective producer.

To all of the compositions of Table 1, sufficient water was added in "quantum sufficient" in order to provide 100% of a particular formulation.

The identity of the specific constituents, and the %wt. actives, is indicated on Table 2.

Cleaning Evaluations:

Cleaning evaluations were also performed in accordance with the testing protocol outlined according to ASTM D4488 A2 Test Method, which evaluated the efficacy of the cleaning compositions on painted masonite wallboard samples, as well as with vinyl tile samples. The test soil applied was to the masonite tiles was a greasy soil sample containing vegetable oil, food shortening and animal fat. The test soil applied to vinyl tiles was a particulate soil.

For the masonite wall board tiles, the sponge (water dampened) of a Gardner Abrasion Tester apparatus was squirted with a 15 gram sample of a tested cleamng and the apparatus was cycled 10 times. The evaluation of cleaning compositions was "paired" with one side of each of the test samples treated with a composition according to the invention, and the other side of the same sample treated with a comparative example's composition, thus allowing a "side-by-side" comparison to be made. For the evaluation on vinyl tiles, the sponge (water dampened) of a Gardner Abrasion Tester apparatus was squirted with a 70 gram sample of a tested cleaning compsition, and the apparatus was cycled 10 times. A similarly prepared sponge was then used with a comparative example composition as a comparative control. Each of these tests were duplicated on several masonite wallboard tiles, or vinyl tiles, as the case may be, and the results statistically analyzed. The cleaning efficacy of the tested compositions was evaluated utilizing a Minolta Chroma Meter CF-110, with Data Processor DP- 100, which evaluated spectrophotomic characteristics of the sample.

The formulation according to Ex. 8, described on Table 1, above was tested. As a first comparative, a commercially available product, Lysol® Disinfectant Cleaner ("Country Scent") was used as supplied from its manufacturer. As a second comparative, a second commercially available product, Spic & Span® Pine Cleaner was diluted and used in the test. For the cleaning test on vinyl tiles, both the formulation according to Ex.8 and the Lysol® Disinfectant Cleaner were first diluted with water to form a 1 :64 aqueous dilution. For the cleaning test on masonite wallboard tiles, both the formulation according to Ex.8 and the Lysol® Disinfectant Cleaner were used 'as supplied', i.e., without any further dilution.

The results of testing a formulation according to the present invention with other commercially available compositions are set forth in Table 3.

With respect to the results reported on Table 3 a value of "100%" is indicative of a white (unsoiled) background, and a "0%" value is indicative of a black background. A soil laden (uncleaned) surface generally provided a result of about 20-30% for masonite wallboard samples, and 40 - 50% for vinyl wallboard samples.

As can be seen from the results of Table 3, the cleaning efficacy of a composition according to the invention provided equivalent or superior results with those of known art cleaning products. Evaluation of Light Transmittance ("Blooming") of Formulations:

Aqueous dilutions of each of the formulations described on Table 1 were prepared to evaluate the degree of light transmittance, a measure of the opacity as well as of the blooming of each of the aqueous dilutions. The results of the light transmittance evaluation was determined as a percentage of light transmitted through a sample of a particular aqueous dilution wherein the transmission of a like sample of water is assigned a percentage of 100%. Testing was performed by mixing a 3 g aliquot of a particular example formulation with 192 g of tap water (with approx. 100 ppm hardness) which formed a 1:64 dilution of the example formulation: water, after which the sample was mixed and a transmittance reading was taken using a Brinkman model PC801 dipping probe colorimeter, which was set at 620 nm to determine the light transmission of each of the samples. Samples of each example formulation was evaluated in warm tap water at 40°C were evaluated, as well as the reference (pure tap water) sample used to calibrate the colorimeter to the reference 100% light transmission sample outlined above. The resulting determined values, reported in Table 4 below provide an empirical evaluation, reported in percent light transmittance ("%T") of the degree of transparency of a diluted example formulation wherein 0% indicates complete opacity and 100% the transparency of a water sample as noted above. Accordingly, a lower %T of a particular aqueous dilution provided a more desirable indication of the blooming characteristic of the particular aqueous dilution.

As can be seen from the reported results, the compositions according to the invention, and particulary according to preferred embodiments exhibited excellent blooming characteristics.

Evaluation of Antimicrobial Efficacy:

An example formulation 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) and Salmonella choleraesuis (gram negative type pathogenic bacteria) (ATCC 10708). 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 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 indicates the number of test substrates wherein the tested organism remains viable after contact for 10 minutes with at test disinfecting composition / total number of tested substrates (slides) evaluated in accordance with the AOAC Use-Dilution Test. Thus, a result of "0/30" indicates that of 30 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 5, below. The reported results indicate the number of test slides with live test organisms/number of test slides 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 and disinfecting benefits to hard surfaces, and exhibit good blooming characteristics upon dilution into a larger amount of water. These advantages are further supplemented by the excellent antimicrobial efficacy of these compositions against known bacteria commonly found in bathroom, kitchen and other environments. Such mutual technical properties clearly illustrate the excellent characteristics of the compositions, wherein the concurrent blooming, cleaning and antimicrobial benefits are not believed to have been known to the art.

Claims

Claims:

1. An aqueous concentrated liquid cleaning and disinfecting composition which blooms when added to a larger volume of water which comprises the following constituents: (a) fatty acid methyl ester solvent;

(b) a germicidal constituent selected from at least one cationic surfactant having germicidal properties and 2-benzyl-4-chlorophenol;

(c) one or more nonionic detersive surfactant, preferably one or more nonionic detersive surfactants based on alkoxylated alcohols; (d) an amphoteric surfactant, preferably based on one or more aminopropionates or alkylampho mono-, or di-propionates;

(e) one or more alkanolamides;

(f) a maj or proportion of water;

(g) optionally, one or more further detersive surfactants, preferably selected from amphoteric or nonionic detersive surfactants;

(h) optionally an organic solvent constituent; and optionally, one or more constituents selected from: chelating agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, and pH buffers.

2. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (a) fatty acid methyl ester solvent is a compound according to the formula:

O II R— C— O— CH₃ wherein R is a fatty alkyl moiety.

3. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 2 wherein R is a C6-C₃₂ alkyl moiety.

4. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the fatty acid methyl ester solvent is present in an amount of from 0.1 - 20% wt. based on the total weight of the concentrate composition of which it forms a part.

5. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (b) germicidal constituent is a cationic surfactant having germicidal properties.

6. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 5 wherein the cationic surfactant is a quaternary ammonium compound.

7. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (b) germicidal constituent is 2-benzyl-4-chlorophenol.

8. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (b) germicidal constituent is present from 0.01 - 10% by weight.

9. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (c) nonionic detersive surfactant is an alkoxylated alcohol.

10. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (c) nonionic detersive surfactant constituent comprises at least two nonionic surfactants, a first nonionic surfactant which has either a cloud point of 25°C or greater or an HLB greater than 10 or exhibits good solubility in water, and a second nonionic surfactant which has either a cloud point of 25°C or less or an HLB less than 10 or exhibits poor solubility in water.

11. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (d) an amphoteric surfactant is an aminopropionate compound.

12. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (d) an amphoteric surfactant is present from 0.001 - 10 % by weight.

13. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (e) one or more alkanolamides are one or more C₈-C₂₄ alkyl di(C₂-C₃) alkanol amides.

14. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the (e) one or more alkanolamides are present from 0.001 - 6% by weight.

15. The aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 wherein the dilution of 1 part of said composition to 64 parts water at 40°C results in a percent light transmittance of at most 90%.

16. An aqueous composition comprising: 1 part by weight of the aqueous concentrated liquid cleaning and disinfecting composition according to claim 1 diluted in 10 - 64 parts by weight of water.

17. A process for the cleaning or disinfecting treatment of hard surfaces which process comprises the step or applying a cleaning or disinfecting effective amount of the cleaning and disinfecting composition according to claim 1.

18. An aqueous concentrated general purpose cleaning composition which blooms when added to a larger volume of water which comprises:

(a) fatty acid methyl ester solvent; (b) one or more nonionic detersive surfactants, preferably one or more nonionic detersive surfactants based on alkoxylated alcohols;

(d) one or more alkanolamides; (e) a major portion of water;

(g) optionally an organic solvent constituent; and optionally, one or more constituents selected from: chelating agents, coloring agents, light stabilizers, fragrances, thickening agents, hydrotropes, pH adjusting agents, and pH buffers.

19. An aqueous concentrated general purpose cleaning composition which blooms when added to a larger volume of water substantially as described with reference to the examples.