CA2228427A1 - Blooming type, hard surface cleaning and/or disinfecting compositions - Google Patents

Abstract

Blooming type, hard surface cleaning concentrate compositions feature substantially reduced amounts of pine oil, or contain no pine oil. The cleaning concentrates exhibit a characteristic bloom when admixed to a larger volume of water, yet are substantially clear and shelf stable as concentrate compositions.

Description

W O 97/06230 PCT~US96/12613 BLOOMING TYPE, HARD SURFACE CLEANING AND/OR DISINFECTING COMPOSITIONS
The present invention is directed to improved hard surface cleaning compositions and conce"ll,lles thereof, which feature blooming when the concel~LIal~ is added to a larger volume of water.
Cleaning compositions are commercially hllpol l~l products and enjoy a wide field of utility in ~ccictinp in the removal of dirt and grime from surfaces, especially those characterized as useful with 10 "hard surfaces". One particular category of cleaning cl,lllposilions are those which are classed as pine oil type cleaning compositions which typically contain a signific~nt amount, e.g, 5%wt. of naturally derived and/or synthetically produce pine oils. Such cu~posilions generate a milky or cloudy al~peal~,ce when diluted with water in dilutions useful for cleaning applications, and are generally provided as concentrated composition which is ~ùbse~luelllly diluted with water by an end user/consumer 15 to form a cleaning composition therefrom. While such pine oil type cleaning compositions are commercially significant and in popular use, their use is not without ~t~en~l~nt shortcomings. For example, high levels of pine oil in a cleaning composition are known to leave undesirable surface residues, particularly on hard surfaces. Also, such pine oils require the inclusion of ~ulÇ~ which are useful in solubilizing and stabilizing the pine oil. Also, frequently the pine oil itself, are cal~gol;~d 20 as undesired volatile organic compounds ("VOC"). However, the removal of the pine oil itself is not desired nor in most case feasible as its presc;nce is associated with the formation of the blooming effect when the concentrate is added to a larger volume of water. This blooming effect (also sometimec referred to as "break" in the United Kingdom and in other countries) is an hllpoll~llL indicia for consumer acce~ ce for certain products, those which traditionally use pine oil to providing the 25 blooming effect, as well as other products which do not contain pine oil but which nonetheless exhibit this very desirable blooming behavior when added to a larger volume of water to form a cleaning and/or disinfecting composition therefrom.
Therefore, there exist a need in the art for the production of blooming type hard surface cleaning compositions, including pine oil type cleaners, which exhibit the desirable blooming characteristics 30 expected by the consumer, but in which little or no pine oil need be present. Such compositions would contain no pine oil, or would contain significantly reduced amounts of pine oil as col"~aled to known art compositions. There is also a need in the art for blooming type hard surface cleaning compositions which provide a cleaning, as well as germicidal effect to a treated surface.
In accordance with a first aspect of the present invention, there has been made the surprising 35 discovery that successful blooming type hard surface cleaners may be produced which do not include pine oil, but which nonetheless exhibits the much desired blooming behaviour which is associated with , pine oil cleaners. This ~ul~fi~illg discovery now permits for the production of conc~ aLe compositions which are transparent or relatively clear in al~pealallce~ but which when added to a greater volume of water such as to form a cleaning and/or disillfe.;lil g composition the.crl~lll, exhibits a blooming behaviour. This discovery permits for the production of cleaning and/or di~hlre;~;ling compositions and concellLlal~s thereof which contain no pine oil, yet which exhibit this hll~ L~IL identifying characteristics of pine oil type cleaning compositions. This discovery also permits for the production of aqueous cleaning and/or disinfecting compositions which exhibit blooming when added to a larger volume of water, but which may be selectively imparted with any of a number of dirr~ ll- a}~pcalallces and fragrances which is possible by the judicious selection of any of a number of dyes, fragrances, other colorants which may be added to the concentrate compositions to provide a desired color and a desired scent. Such compositions are commercially acceptable, shelf stable conc~.lL-~L~d cleaning and/or disinfecting c~,lllposilions which exhibit blooming when diluted in water. According to this first aspect of the invention, the blooming behaviour is provided although the concentrate compositions contain no pine oil or pine oil fraction (such as a terpineol fraction) in any .cignifiç~nt amount, other than minor amounts such a might be used in a fragrance conctih~nt as the compositions do not rely upon pine oil or pine oil fractions to provide their blooming characteristic when diluted with water. Accordingly there are provided aqueous blooming type, hard surface cleaning and/or di~hl~e~;lillg conc.,.lL~te compositions which comprise the following essential conctit~ ntc which provide a "blooming system" which is incorporated in these compositions:
a cationic quaternary ammonium surfactant, an anionic carboxylated alcohol alkoxylate surfactant;
a surfactant compatibilizing agent, and, water.
According to this first inventive aspect, the concentrate compositions may include further optional conctitnentc which do not undesirably reduce or which 11iminich the operation ofthe blooming system described herein especially one or more further surfactants including anionic, cationic, nonionic, zwitterionic and/or amphoteric as well as mixtures thereof, one or more organic solvents such as lower alkyl alcohols, lower alkyl diols and glycol ethers, as well as one or more fragrances, coloring agents, chelating agents, germicidal compositions including those based on phenolic compounds, as well as other conventional additives.
Such compositions accordillg to the first aspect of the invention exhibit the desired "blooming"
characteristic of pine oil type cleaners, but do not require the presence of pine oil to provide the blooming effect. Rather, selected known art dyes or other coloring agents, in conjunction with minor amounts of one or more ~ragrance materials especially those which provide a pine type scent may be _ W O 97106230 PCTnUS96/12613 included to the blooming system, as well as further optional surfactants and or organic solvents which are included to provide a detersive property to the compositions. In this way, a ele~ning composition which has the physical appeal~lce and blooming ~hala~;le;li~lic of a collvc;,llional pine oil type cleaning composition may be provided without the presence of pine oil. Similarly, other blooming type eleaning and/or disinfeeting eompositions may be produeed sueh as by ineluding different r~aglallces7 i.e., those characteristic of lemon, various flora, in eonjunetion with a desired eoloring additives, i.e., green, yellow, amber, red, etc. may be added as desired. In each case, a blooming type cleaning and/or disinfecting eompositions may produced. "Blooming" may be deseribed as the ehange of the water's appealance from eccf~nti~lly eolorless and transparent to that of a milky white or milky yellowish white, cloudy appea,~llce. Also, in the concentrate compositions acco,ding to any aspect of the invention, the lack of the overall amounts of pine oil typieally found in prior art pine oil type c~ ning conce"L~ales~ as well as the necessary eompatibilizing agents required to solubilize the pine oil in such prior art cleaning coneentrate provides the benefits of redueed volatile organie eontent of a eoneentrate or c!e:lning composition, as well as reduces the p,ope"siLy of sueh eul,lposilions to form undesirable residues, especially pine oil residues upon cleaned surfaees.
In a seeond aspect of the invention, there is provided a blooming, pine oil type hard surface cleaning composition which has redueed amounts of pine oil as eompared to known art pine oil eont:lining eompositions whieh inelude the following çcc~onti~l concti~ ntc The eompositions aeeording to this seeond aspect of the invention collll,l ;ses the following con~
on a pelc~ll~ge weight basis based on a 100%wt. eoncentrate composition:
pine oil in an amount of from 0.01 - 3%wt., preferably 0.01 - 2.5% by weight, but most preferably 0.75-1.5%wt.1;
at least one pine oil solubilizing agent in an amount of to 15% and less by weight, preferably 0.01-10% by weight, and most preferably in an amount of 0.1-5% by weight and the blooming system as deseribed with respeet to the first aspeet of the invention whieh blooming system includes:
a cationic 4LIal~ al y ammonium surfactant;
an anionic carboxylated alcohol alkoxylate surfactant;
a surfactant cOlllpalibilizing agent; and, water.
The compositions accoldillg to this second aspect of the invention the eoneentrate eompositions may inelude further optional eonctitllç~tC which do not undesirably reduce or which ~1iminich the operation of the blooming system described herein especially one or more further surfactants ineluding anionie, eationie, nonionie, zwitterionie and/or amphoteric as well as mixtures thereof, one or more -W O 97/06230 PCT~US96/12613 organic solvents such as lower alkyl alcohols, lower alkyl diols and glycol ethers, as well as one or more fragrances, coloring agents, chelating agents, germicidal compositions including those based on phenolic compounds, as well as other conventional additives. The conctillLldl~ compositions acc~ g to the second aspect of the invention exhibit the desired "blooming" characteristic of pine oil type cleaners, 5 although do not require the presence of pine oil to provide the blooming effect which is primarily provided by the blooming system previously described. These concentrate compositions are pine oil type cleaning compositions which include reduced amounts of pine oil as compared to known art compositions, and in plcr~ ,d embodiments also provide a germicidal effect in both concentrate coll,posilion, and in cleaning colllposilion ~iihltionc In accol.lhlg to a third aspect of the invention, there is also provided a blooming, pine oil type hard surface cleaning colllpo~ilion with reduced amounts of pine oil. The compositions accc,l ii lg to this second aspect of the invention COlll~ es the following con~l;l u ~ on a pelcelllage weight basis based on a 100%wt. concentrate colllpo~ilion:
pine oil, in amount of 0.1-5% by weight, preferably in amounts of 0.1 - 4% by weight, but most preferably in amount of between 2 - 4% by weight;
at least one pine oil solubilizing agent effective in enhancing the miscibility of the pine oil constituent in water which may be present in any effective amount found but desirably is present in amounts of up to about 15% by weight, pl ~;rt;l dbly in amounts of 0.1 - 15% by weight, but most preferably from 5 - 15% by weight a nonionic ~ulrd.;l~ with a cloud point of 20~C or less;
and, water.
The concentrate compositions according to the third aspect of the invention may include the same further optional consliluel~l~ described in conjunction with the second aspect of the invention noted above. Similarly, the concentrate compositions in the third aspect of the invention provide pine oil type cleaning compositions with reduced amounts of pine oil as noted above, and in ,ort;r~.l.,d embodiments also provide a germicidal effect.
In a still further aspect of the invention there are provided processes for cleaning and/or disinfecting hard surfaces by applying effective amounts of a cleaning composition as taught in this specification to a hard surface in need of cleaning and/or disinfection.
The at least one cationic quaternary ammonium surfactant useful in forming the blooming system according to the first and second aspects of the invention, and which ma y be used as an optional germicidal constituent in the second aspect of the invention may be any of those which are known to the art, but preferably are 4uall~lndlr ammonium compounds and salts thereof. These include 4uallt~ lr ammonium germicides which may be characterized by the general structural formula:

.
where at least one or Rl, R2, R3 and R4 is a hydrophobic, aliphatic, aryl aliphatic or ~liph~tic 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 S aryl, halogen-substitu~od long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, etc. The remz~ining radicals on the nitrogen atoms other than the hydrophobic radicals are ~ub~l ;1..~ ul~; of a hydrocarbon ~Llu~;lult; usually cont~ining a total of no more than 12 carbon atoms. The radicals Rl, R2, R3 and R4 may be straight chained or may be branched, but are preferably straight çh~in~?~l and may include one or more amide or ether link~ge~ The radical X may be any salt-forming anionic radical.
Exemplary quarternary 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 benyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl wridinium bromide, and the like. Other suitable types of 4Ucu L~ l y ammonium salts include those in which the molecule contains either amide or ether linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl 15 ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like. Other very effective types of qu~l L~ll,al y ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a ~ul..,~ ;d aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methos--lf~, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenyltrimethyl ammonium chloride, 20 chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
Preferred quarternary 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:

R~ R X

, wherein R2 and R3 are the same or different C8-C~2alkyl, or R2 is C~2 ~6alkyl, C8 l8alkylethoxy, C8 l8alkylphenolethoxy and R3 is benyl, 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.

W O 97/06230 PCT~US96/12613 Such quartenary germicides are usually sold as mixtures of two or more different yu~ ,nal ies, such as BARDAC~ 205M, (~ clllly commercially available from Lonza, Inc., Fairlawn, NJ) which is believed to be a 50% aqueous solution containing 20% by weight of an alkyl dimethyl benzylammonium chloride (50% C14, 40% C16 alkyl); 15% by weight of an octyl decyl dimethylammonium chloride;
7.5% by weight of dioctyl dimethylammonium chloride; and 7.5% by weight of didecyl dimethylammonium chloride. A further useful 4ùaltc.ll~l y germicide is CYNCAL~ 80% (p.csc~lly commercially available from Hilton Davis Chemical Co., Cincinnati, OH) which is believed to CUIIlpll:.C
80% by weight of an alkyl dimethyl benzylammonium chloride (50% C14, 40% C12 and 10% C16 alkyl), 10% water and 10% ethanol. Further useful 4U~llLClllaly germicidal agents include BTC-8358~, an alkyl benzyl dimethyl ammonium chloride (80% active), BTC-835(~) an alkyl benzyl dimethyl ammonium chloride (53% active), and BTC-818~}), a dialkyl dimethyl ammonium chloride (commercially available from the Stepan Chemical Co., Chicago, IL). Additional suitable commercially available 4ual ICIIIdlY ammonium germicides of the alkyl dimethyl benzylammonium chloride type ct-nt~ining the same alkyl dimethyl benzylammonium chloride mixture as that of CYNCAL~ and which are generally referred to as quarternium salts include BARQUAT~) MB-80, (plcsellLly commercially available from Lonza, Inc., Fairlawn, NJ) which is believed to be and 80% by weight solution (20%
ethanol) of the qual Lclllaly, HYAMrNE~) 1622 believed to be an aqueous solution of ben7~thonil-m chloride, and HYAMlNE~ 3500, which is believed to be a 50% aqueous solution ofthe 4u~llLcll~aly ( both presently commercially available from Lonza Inc., Fairlawn, NJ).
The cationic quaternary ammonium surfactant may be present in any amount which are found to exhibit the desirable characteristics according to a respective aspect of the invention; in the first or second aspect the surfactant forms part of the blooming system, and should be present in amounts wherein the concentrate compositions are relatively clear appe~allce in concentrated solution, but which exhibit blooming when diluted with further water to form a cleaning composition. In accordance with the third aspect of the invention, the addition of the preferred cationic 4uaLelll~ y ammonium :~UI r21C
which exhibits germicidal activity are included in plcrcllcd embodiments where a germicidal effect is intended to be provided by the compositions. The amounts in a respective composition are noted above, and it is to be noted that the preferred amounts are in part dictated by toxocological considerations as an excess of the cationic component may pose an increasing risk of irritation to the eyes, skin and mucocous tissues of a consumer. The preferred amounts are also in part dicated by economic considerations as an excess of the cationic component above these amounts generally requires a col,~,ollding increase in the amount of the anionic component used in a blooming system as noted above.

W O 97/06230 PCT~US96/12613 In accordance with the first and second inventive aspects described above, there is also included at least one anionic carboxylated alcohol alkoxylate surfactant. This anionic ~ulÇa~ l which has been found to be effective in forming a water insoluble or poorly miscible complex when mixed with the quaternary ammonium compound de~c. ibed above, which due to said insolubility or poor miscibility of the forrned complex, renders an aqueous mixture containing the anionic carboxylated alcohol alkoxylate surfactant and the 4ualclllaly ammonium compound such an aqueous mixture turgid, milky or cloudy.
Particularly useful carboxylated alcohol alkoxylate compounds which are advantageously incorporated into the co---po~iLions of the invention include carboxylated alcohol alkoxylate surfactants according to the following general formula:
R--O--(CH--CH--~)n~Z
X Y
wherein R is a hydrophobic group, more preferably a C6-C,8 alkyl group, n is a number in the range of I
to 24, X and Y are independently selected from the group consisting of hydrogen,succinic acid radical, hydroxysuccinic acid radical, citric acid radical, and mixtures thereof, wherein at least one of X or Y is a succinic acid radical, hydroxysuccinic acid radical, or citric acid radical, and Z is H or -CH2COOH Certain anionic surfactants accolJing to the immediately precee~ling general formula are ~. ~sc--lly commercially available as the PolyTergent~ C series of anionic surfactants from the Olin Chem Co, ( Stamford, CT) Particularly plC~ .cd amongst these are the PolyTergentTM CS- I
compounds which is believed to be in accu,.l~lce with the formula above wherein R is a C6-CI8 alkyl group, X and Y are independently H, CH3 or the succinic acid radical with at least one succinic acid radical being present, and where Z is H. Also useful is PolyTergentrM C9-62P a further carboxylated alcohol alkoxylate surfactant also available from the Olin Chemical Co.
Other known anionic surfactants, while not particularly enumerated here may also find use in the present inventive co--lposilions, as well as mixtures of one or more anionic surfactants.
According to the first and second aspects of the invention, the carboxylated alcohol alkoxylate is present in any amount which is found to exhibit the desirable characteristics of the invention, that of a relatively clear appea. ance in an aqueous solution when in the presence of an effective amount of the quaternary ammonium compound described above and further with an effective amount of the surfactant compatiblizing agent described below, but that of blooming when diluted with further water to form a cleaning composition. This anionic surfactant compound is included in the amounts noted above.
In the blooming system according to the first and second aspect of the invention described previously, particular attention is to be paid to the relative proportions of the cationic surfactant to the anionic surfactant. It is a feature of the invention that both the cationic 4u~1~,.1.aly ammonium ~ulra~;lalll and the anionic carboxylated alcohol alkoxylate surfactant, and surfactant compatibilizing agent be W 097t06230 PCTAJS96/12613 present in such amounts such that the concentrate composition be relatively clear when present in the concentrate composition. Such a concentrate composition is relatively clear and is p.cr~ bly transparent. However, upon the addition of the said cvnc~ l-ale composition to a further amount of water, the solubility of these cationic ~u. r~ lL~ and the anionic ~UI fa~ ulL~ in the new larger volume of S water is sufficiently reduced or disrupted which causes the newly formed co--~posilion to become turgid, or cloudy and thus imitate the "blooming" behaviour of prior art pine oil cleaner type compositions.
While not wishing to be bound by any theory, it is hypothesized that in the absence of a sufficient amount of the surfactant compatabilizing agent, the pendant carboxylic acid or carboxylic acid moieties ofthe preferred species of anionic surfactants effectively complex with the 4Ualt~,~llal,y ammonium in the quarternary ammonium colll~)vu~.d and become insoluble or immiscible in an aqueous mixture, which then become visible due to the presence of the sufficiently long alkyl chain moieties which also con~titllte part of the preferred anionic surf~ct~nt.c This effect may however be reversed by the addition of an additional, sufficient amount of the surfactant compatibilizing agent to such a mixture, which addition solubilizes at least the anionic surfactant and/or the complexed cationic and anionic ~1l r~
Such solubilization effectively restores the clear app~ ce of the aqueous mixture cont~ining the cationic and anionic surf~ct~ntc It is contemplated that other anionic surface active agents having a first functional portion or group effective in forming a complex with the UUal L~llaly ammonium compound in water, and which has a second functional portion or group which is hydluphobic in nature and which is insoluble or poorly miscible in water when such a complex is formed and in the absence of any further compatabilizing agent(s) become visible to the eye, may also be used.
In accordance with the first and second aspect of the invention, the blooming system includes a surfactant compatibilizing agent which solubilizes the at least one cationic 4u~lelll~lr ammonium :jUI r~1Lallt and the at least one anionic carboxylated alcohol alkoxylate surfactant may be any known art material which exhibits the properties described above. A variety of surfactant compatibilizing agents are believed ~o be determinable by routine experimental techniques, such as by providing a volume of water having mixed therein amounts of the cationic quaternary ammonium su. r~cl~.l compound and the anionic carboxylated alcohol alkoxylate surfactant compound which renders the volume of water to be non-transparent, especially turgid or milky in appeal~llce, and adding thereto an amount of a compound or composition which may be used to compatibilize the anionic and cationic ~ulr~il~ll compounds.
Afterwards, an aliquot of this mixture may then be added to a larger volume of water, such as a mixture:water dilution ratio of 1:64 at room temperature (approx. 20~C) to determine if such mixture evidences a blooming effect.

W O 97/06230 PCT~US96/12613 One class of such useful surfactant compatibilizing agents are water soluble salts including, but not limited to monovalent alkali and/or polyvalent alkaline earth metal salts and ammonium salts. Non-limiting examples of such useful salts include: NaCI, MgCI2, NaHCO3, Na2CO3 NH4CI.
A further class of useful ~ulra~iL~ll compatabilizing agents include certain amphoteric 5 surf~t~ntc Useful amphoteric ~ulr~ lL~ include betaine compounds which exhibit the following general formula:
( ) ( ) R--N(R~2-R2COO
wherein R is a hydrophobic group selected from the group selected from alkyl groups cont~ining from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkylaryl and 10 arylalkyl groups cont~ining a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar sll u~iLul~;S hlL~ll u~t~d by amido or ether link~ec, each Rl is an alkyl group cont~ininE from I to about 3 carbon atoms; and R2 is an alkylene group cont~inin~
from 1 to about 6 carbon atoms.
Examples of preferred betaines include lauramidopropyl betaine, a col~ l pl~,p~uaLion of 15 which is available under the tradename Mirataine~ BB (from Rhône-Poulenc, Cherry Hill, NJ), and cocamidopropyl betaine available under the trade name MackamTM DZ (from McIntyre Group Ltd., University Park, IL).
As noted previously, effective amounts of the surfactant comp~t~hilizing agent may be any amount which, when included in the blooming systems in the first and second aspects of the invention 20 compatibilize in the concentrate composition dilution the least one cationic ~uaL~;lllaly ammonium surfactant and the at least one anionic carboxylated alcohol alkoxylate surfactant, but do not ~liminich the blooming characteristic of the collcellllal~ composition when it is added to water. The ~ulÇa~iL~llL
compatibilizing agent may be present in any effective amount, and good culllpaLibilizing behaviour has been observed with amounts of 10% by weight and less, with preferred amounts being 0.01 - 6% by 25 weight of the compatibilizing agent.. While amount less than 6% are to be preferred from an economic standpoint, it is to be understood that other amounts, including those greater than 6% by weight may be neces~iL~l~d due to the selected cationic surfactant, and anionic surfactant, their relative amounts used, and their miscibility in water.
In accordance with the third aspect of the invention, in the place of the blooming system 30 according to the first and second aspects of the invention there is included one or more nonionic surfactants which are characterized in exhibiting a cloud point of 20~C or less. Suitable nonionic surface active agents include condensation products of one or more alkylene oxide groups with an organic hydrophobic compound, such as an aliphatic or alkyl aromatic compound. Suitable nonionic surface active agents include surfactant compositions based upon polyethoxylated, polypropxylated, or polyglycerolated alcohols or alkylphenols or fatty acids. It is contemplated that one or more nonionic surfactants which are cha~ . i2ed in exhibiting a cloud point of 20~C or less may also be used as the sole blooming agent in an aqueous hard surface cleaning and/or disinfecting colllpo~ilion, i.e., absent the 5 pine oil discussed herein.
One exemplary class of nonionic SUI~C~ which finds use are alkoxylated alcohols especially alkoxylated fatty alcohols. These include ethoxylated and propoxylated fatty alcohols, as well as ethoxylated and propoxylated alkyl phenols, having both with alkyl chains of about 7-16, more preferably about 8- 13 carbon chains in length.
Exemplary alkoxylated alcohols include certain ethoxylated alcohol colnpo~ilions pres~lllly commercially available from the Shell Chemical Company, (Houston, TX) under the general trade name Neodol g), which are described to be linear alcohol ethoxylates. Of these, those exhibiting a cloud point of 20~C or less may be used. Specific compositions include: Neodol~) 91-2.5 which is described as an ethoxylated alcohol having an average molar ratio of 2.7: 1 ethoxy groups/alcohol groups per molecule; a molecular weight of 281, and a cloud point in water of 20~C and less; Neodol~) 23-3 which is described as an ethoxylated alcohol having an average molar ratio of 2.9: 1 1 ethoxy groups/alcohol groups per molecule; a molecular weight of 322, and a cloud point in water of 20~C and less.
Exemplary alkoxylated alcohols further include certain compositions presently commercially available from the Union Carbide Co., (Danbury, CT) under the general trade name Tergitol~), which are 20 described to be secondary alcohol ethoxylates. Again, those exhibiting a cloud point of 20~C and less may be used. Specific compositions include: Tergitol~ 15-S-3 which is described as an ethoxylated secondary alcohol having an average molar ratio of 3.2: 1 ethoxy groups/alcohol groups per molecule, and a cloud point in water of less than 20~C; Tergitol~ 15-S-5 which is described to be an ethoxylated secondary alcohol having an average molar ratio of 5: 1 ethoxy groups/alcohol groups per molecule, and 25 a cloud point in water of less than 20~C.
Exemplary alkoxylated alkyl phenols include certain compositions presently commercially available from the Rhône-Poulenc Co., (Cranbury, NJ) under the general trade name Igepal~), which are described to be octyl and nonyl phenols. Again, those exhibiting a cloud point of 20~C or less may be used. Specific compositions include: Igepal~ CA-210 which is described as an ethoxylated octyl phenol 30 having an average of 1.5 ethoxy groups groups per molecule and a cloud point in water of less than 20~C
and, Igepal~ CA-420 which is described as an ethoxylated octyl phenol having an average of 3 ethoxy groups groups per molecule and a cloud point in water of less than 20~C.

W O 97/~6230 PCT~US96/12613 Of course, a mixture of two or more nonionic surfactant compounds having a cloud point of 20~C or less may be incorporated into the inventive compositions. Other known nonionic surfactants not particularly enumerated here may also be used.
The cloud point of the nonionic surfactant may be determined by known methods. For ~ mple, ASI'M D2024 (lGapp~ ed 1986) for "Standard Test method for Cloud Point of Nonionic Su.r~ L~
According to this test method which is particularly useful for nonionic surfactants of a dGI~ GllL systems which are characterized of less soluble in water at higher le.ll~JclaLulcs than at lower lG~ dlul~s wherein the cloud point occurs within water at a IGIIIP~alUIe range of between 30-95~C. According the test protocol, a one percent test solution is prepared by weighing one gram of the ~l .. r~ 1 into a 150 ml. beaker to which 100 mls. of distilled dimineralized water at a temperature of less than 30~C is added. The sample is agitated until solution is reached, after which a 50 ml. aliquot of the solution is placed into a test tube. While agitating the sample solutions slowly with the thermometer, the test tube is heated with a bunsen burner until the sample solution becomes definitely cloudy, at which point it is removed from the heat. While stirring with the thermometer c~ntinl~ec~ the test tube and its sample solution are allowed to cool slowly until the sample solution clarifies at which point the L~"lp~,.a~u,G is noted. Such a test method provides a simple, yet reliable, means for determining the cloud point of a surfactant in water.
An even simpler test method for effectively determining which nonionic surfactants may be used in the compositions of the invention is as follows: to â clean beaker or other glass vessel is added 99 parts by weight of deionized water at 20~C +0.5~C, and 1 part by weight (by weight of the actives) of a surfactant composition to be tested. This test sample is stirred and the temperature permitted to drop to 20~C; if this test sample is observed to be murky or cloudy in apl,ed,allce as the test sample's temperature achieves 20~C and drops below 20~C, it is considered to have a suitable cloud point of 20~C and less and may be used in the concentrate compositions acco,ding to this aspect of the invention.
In accordance with the third inventive aspect, such a nonionic surfactant may be present in any effective amount, but desirably is present in the concentrate compositions in amounts of up to about 10%
by weight, preferably in amounts of 0.1 and 6% by weight, but most preferably in amount of between 4 and 6% by weight.
Water is included in the concentrate compositions and 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.
If the water is tap water, it is preferably appropriately filtered in order to remove any undesirable impurities such as organics or inorganics, especially minerals salts which are present in hard water which may thus hll~,. r~, G with the operation of one or more conctitl~ntc of the blooming system, as well as any other optional components of the liquid concentrates according to the invention. Generally, water is present in the concentrate compositions in amounts in excess of about 50% by weight, preferably in amounts of in excess of 70% by weight, but most preferably in amounts in excess of 80% by weight of the concentrate compositions according to the invention. ,.
In accordance with the second and third aspects of the invention described above, there is also included as an ece~nti~l constituent an amount of a pine oil C~ ;l u~,.l, while in the first aspect of the invention such a pine oil conctitllent is to be understood as an optional c~m~tit~l~?nt Pine oil is a complex blend of oils, alcohols, acids, esters, aldehydes and other organic compounds, and is sometimes used as a solvent for certain types of stains. An illlpOlL~.l col,~ of pine oil are terpene alcohols, especially alpha-terpineol. When included, the pine oil generally 10 col..~.ises at least about 60% terpene alcohols, especi~lly alpha L.~ineol. Particularly effective presently commercially available pine oils Glidco~) Pine Oil~M 60 (available from Glidco Organics Corp., Jacksonville, FL, believed to contain applu2~i~..ately 60% terpene alcohols), Glidco~) Pine Oil 60 (available from Glidco Organics Corp., Jacksonville, FL, believed to contain ~,.02~i...ately 60% terpene alcohols); Glidco~) Pine Oil 140 (available from Glidco Organics Corp., Jacksonville, FL, believed to 15 contain ap~ i...ately 70% terpene alcohols); Glidco~) Pine Oil 80 (available from Glidco Organics Corp., Jacksonville, FL, believed to contain a~.~.xi...~tely 80% terpene alcohols) Glidco~}) Pine Oil 150 (available from Glidco Organics Corp., Jacksonville, FL, believed to contain al,l,lo~h~ately 85% terpene alcohols); Glidco~ Terpene SW (available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 75% terpene alcohols); as well as Glidco(~) Terpineol 350 (available from Glidco Organics Corp., Jacksonville, FL, believed to contain a~pl~xi-l.ately 100% terpene alcohols). Other products which can contain up to 100% pure alpha-terpineol, may also be used in the present invention.
When included, the pine oil con~titl~ent need be present in only minor amounts as they are not required to produce the blooming characteristics of the inventive compositions. Generally, they are present in reduced amounts in any of the concentrate compositions, i.e., in amounts of up to about 3% by weight, and if present are preferably included in amounts of from 0.01 - 2.5% by weight, but most preferably in amount of between 0.75-1.5% pine oil by weight. As with all of the weight p~,. ce-~Ldges of the constituents described, the weight percentages are indicative of the weight p~ .gt?s of the actives in a constituent containing p.epd~dLion.
Further in accordance with the second and third aspects of the invention, in addition to the pine oil con~titllent there is also included an effective amount of at least one pine oil solubilizing agent.
Exemplary pine oil solubilizing agents include certain nonionic alkoxylated linear alcohol ~ul ra~iLdllL~ which aid in the dissolution of the pine oil in the water of the concentrate composition. Such useful nonionic alkoxylated linear alcohol nonionic surfactants are known, and may be commercially obtained from the Olin Chemical Co., (Stamford, CT) under the product line name of "PolyTe.~ ,L~3)".

Particular members of this product line which have been found useful include; PolyTergent(~) SL-42 and PolyTergentg) SL,62. Further useful nonionic surfactants include alkoxylated linear secondary alcohols, as well as alkoxylated alkylphenolic nonionic surf~rt~ntc Such nonionic ~wr~ also provide a detersive effect to the compositions.
Further exemplary pine oil solubilizing agents include Cl-C8 alcohols, especially Cl-C3 alcohols, of which isopropanol is p~G~ d.
The pine oil solubilizing agents are included in effective, often minor amounts, with specific ple~,.d weight proportions having been described previously.
The compositions accul.lhlg to the first, second or third aspects of the invention in many cases which comprise any of a number of further optional con~ u~ which do not undesirably reduce or which ~limini~h the operation of the blooming system described herein especially one or more further surfactants including anionic, cationic, nonionic, zwitterionic and/or amphoteric as well as mixtures thereof, one or more organic solvents such as lower alkyl alcohols, lower alkyl diols and glycol ethers, as well as one or more fragrances, coloring agents, ~ hPl~ting agents, antioxi-l~nt~ germicidal compositions including those based on phenolic compounds, as well as other co~ enlional additives.
Such further optional con~l;luc~ may be included in amounts found not to ~ lly ;IILGIr~.C or detract from the blooming chala~ Lics provided by the invention. Such materials are known to the art, and are described in McCutcheon 's Emulsifiers and Detergents ~VoL 1), McCutcheon 's Functional Materials (Yol. 2), North American Edition, 1991, Kirk-Othmer, Encyclopedia of Chemical Technology, 3rd Ed., Vol. 22, the contents of which are herein inco",." alGd by reference.
Known surfactants which provide a further detersive effect to the concGlllldl~ co,.,posilions and especially to the cleaning compositions formed therefrom may be where such do not :"lb~ lly interfere or detract from the blooming chal~ l istics provided by the invention, and further desirably do ~limini~h the germicial nature of the l,lcre,l ~d cationic ~ualtilllal y arnmonium compounds which are included in the blooming system being taught herein. Such include anionic, cationic, nonionic, zwitterionic and/or amphoteric as well as mixtures thereof.
Useful anionic ~ulra~ include the water-soluble salts, particularly the alkali metal, ammonium and alkylolammonium (e.g., monoethanolammonium or triethanolammonium) salts, of organic sulfuric reaction products having in their molecular ~llu~;Lule an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group. (Included in the term "alkyl" is the alkyl portion of aryl groups.) Examples of this group of synthetic surfactants are the alkyl sulf~t~, especially those obtained by snlf~ting the higher alcohols (C8-CI8 carbon atoms) such as those produced by reducing the glycerides of tallow or coconut oil; and the alkylbenzene sulfonates in which the alkyl group contains from about 9 to about 15 carbon atoms, in straight chain or branched chain.

W O 97/06230 PCT~US96/12613 Especially valuable are linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
Other anionic surfactants herein are the water soluble salts of: paraffin sulfonates cont~ining from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C8 l8 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about I to about 4 units of ethylene oxide per molecule and from about 8 to about 12 carbon atoms in the alkyl group; and alkyl ethylene oxide ether sulfates Cont~ining about I to about 4 units of ethylene oxide per molecule and from about 10 to about 20 carbon atoms in the alkyl group.
Other useful anionic surfactants herein include the water soluble salts of esters of a-sulfonated fatty acids co,~L~ini"g from about 0 to 20 carbon atoms in the fatty acid group and from about 1 to 10 carbon atoms in the ester group; water soluble salts of 2-acyloxy-alkane- 1 -sulfonic acids Co~f ni~ g from about 2 to 9 carbon atoms in the acyl group and from about 9 to about 23 carbon atoms in the alkane moiety; water-soluble salts of olefin sulfonates containing from about 12 to 24 carbon atoms; and ,13 alkyloxy alkane sulfonates containing from about I to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
Care should be exercised however in the selection of the anionic surfactants as it is known to the art that many anionic form insoluble complexes with cationic u,ua~ la~ y ammonium su. ~ ; and their use in most cases is to be limited to minor amounts or wholly avoided.
Useful nonionic surfactants which may be included in the concentrate compositions include known art nonionic surfactant compounds. Such nonionic surfactant compounds provide a further detersive effect to the concentrate compositions and cleaning c~u~posiLions formed thc~cL~m.
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 surfactant compound. Further, the length of the polyethenoxy hydrophobic and hydrophilic elements may various. Exemplary nonionic compounds include the polyoxyethylene ethers of alkyl aromatic hydroxy compounds, e.g., alkylated polyoxyethylene phenols, polyoxyethylene ethers of long chain aliphatic alcohols, the polyoxyethylene ethers of hydrophobic propylene oxide polymers, and the higher alkyl amine oxides.
To be mentioned as particuarly useful nonionic surfactants are alkoxylated linear primary and secondary alcohols such as those commercially available under the tr~1en~mes PolyTergent~) SL series (Olin Chemical Co., Stamford CT), Neodol~) series (Shell Chemical Co., Houston T~), as alkoxylated alkyl phenols including those commercially available under the tradename Triton~ X series (Union Carbide Chem. Co., Danbury CT). Also to be noted as useful are the nonionic surfactants ~liccll~sed W O 97/06230 PCT~US96/12613 above with regard to the third aspect of the invention, namely the çss~nti~l nonionic surfactant co~
Known organic solvents which may be useful in providing a further cleaning benefit, especially in the loosening of stains may be added to the concentrate c~ lpo~iLions of the invention. Such should 5 be selected and be present in amounts which do not ~ 11y hlLe.rc.G or detract from the blooming characteristics provided by the invention. Exemplary organic solvents include lower alkyl alcohols, lower alkyl diols and glycol ethers.
Lower alkyl alcohols which may be included are generally the water soluble Cl-C8 alchols as well as the water miscible Cl-C8 diols examples of which include methanol, ethanol, propanol, 10 isopropanol, butanol including t-butanol.
Exemplary glycol ethers water miscible glycol ethers inclll~ing those having the general structure Ra-O-Rb-OH, wherein Ra is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and Rb is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units. Preferred are glycol ethers having one to five glycol monomer units. These are 15 C3-C20 glycol ethers. Examples of more preferred solvents include propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, propylene glycol isobutyl ether, ethylene glycol methyl ether, ethylene glycol ethyl ether, ethylene glycol butyl ether, diethylene glycol phenyl ether, propylene glycol phenol ether, and mixtures thereof. Further useful as the organic solvent are water-miscible ethers such as. diethylene glycol diethylether, diethylene glycol dimethylether, 20 propylent glycol dimethylether, as well as lower esters of monoalkylethers of ethyleneglycol or propylene glycol such as. propylene glycol monomethyl ether acetate. Such are co..,l"c,cially available from Union Carbide, Dow Chemic~ or Hoescht. Mixtures of organic solvents can also be used.A further optional, but in some cases advantageous organic solvent which may be included are one or more terpene solvents, especially monocyclic monoterpene and bicyclic terpenes which include 25 terpinene, terpinolenes, limonenes, pinenes and mixtures thereof. Some may be found in fractions of pine oils noted above, but preferred are those which may be obtained from the essence of citrus fruits of various types including from oranges, lemons and grapefruit. These are generally mixtures which include one or more of the following: d-limonene, dipentene, alpha-pentene, beta-pinene of which d-limonene is most ~ler~ ,d and may for example be obtained by distilling orange rind oil. Such a 30 material is readily commercially available, has a very pleasant citrus fragrance, is known to have favorable cleaning properties and is derived from a naturally occuring material. If present such materials, especially materials which comprise 90%wt. and greater of d-limonene, need be present in only minor amounts, i.e., about 7%wt. and less, preferably about 5%wt, and less, and preferably about 3%wt. and less of the concentrate composition.

Certain of the optional constituents, such as the derivatives of citrus fruit may be provided with, or benefit from the addition of minor amounts of a stabilizer such as an antioxidant material, such as butylated hydroxytoluene.
Further optional, but desirable co~ include fragrances, natural or synthetic~lly produced 5 cont~ining synthetic fragrance col--posilions, especially those which are int~?nfl.qd to mimic the scent of one or more resins or oils derived from coniferous species of trees, viz., a scent chala~iL~ Lic of pine oil type cleaning concentrates as well as scents characteristic of other forms of flora, such as flowers. Other desired fragrance materials may also be included in the compositions, and such are generally included in minor amounts, i.e, less than about 5%wt. of a conc~ compositions and care should be exercised so 10 as not to undesirably inhibit the operation of the blooming system according to the invention and as described above. Many organic materials which providing a rla~,lan'illg effect may be used and these include those described at columns 9 - 11 of US Patent 5,336,445 the contents of which are herein incorporated by reference. Particularly with regard to non-pine oil containing concentrate compositions, such fragrances may be added in any conventional manner, ~tlmixing to a conc.,..LIate co~posiLion or 15 blending with other c~ L;I--~ used to form a conccllLlaLc composition, in amounts which are found to be useful to enhance or impart the desired scent chala~;L~ Lic to the concentrate composition, and/or to cleaning compositions fonned LL~rcLulll. However, they should not be included in excessive amounts.
Further optional, but advantageously included co~ lu~.l; are one or more coloring agents which find use in modifying the appealallce of the concentrate compositions and enhance their 20 a~J~ucdlallce from the p~- " ecLi~e of a consumer or other end user. Known coloring agents, may be incorporated in the compositions in effective amount to improve or impart to concentrate compositions an a~ealdllce characteristic of a pine oil type concentrate composition, such as a color ranging from colorless to a deep amber, deep amber yellow or deep amber reddish color. Other coloring agents, such as those which may impart a yellow color, such as may be associated with a lemon colored cleaning 25 composition, or other colors may also be included. Such a cûloring agent or coloring agents may be added in any useful amount in a conventional fashion, i.e., ~11mixing to a concentrate composition or blending with other con~tit~ nt~ used to form a concentrate composition.
Still further conventional additives which may be included are one or more hydl~t,~Jes such as sodium toluene sulfonate and sodium cumene sulfonate; one or more ~ntib~ct~rial agents such as 30 orthobenzyl-para-chlorophenol although in preferred embodiments wherein the cationic 4uaL~Ilal y ammonium compound has gerrnicidal activity a further ~ntih~ct~rial agent is not normally required, detergent builder compositions, chelating agent especially useful as hard water ion sequestrants, as well as others. Each of such materials is generally only included in very minor amounts, i.e., each generally not exceeding 0.1 5%wt of the concentrate composition, but desirably even less.

WO g7r06230 PCTAUS96/12613 Generally the total weight of such further conventional additives may comprise up to 30% by weight of a concentrated composition formulation, but preferably comprise not in excess of 15%wt., and are typically significantly less.
What is to be understood by the term "concentrate" and "concelll~al~ composition" in this S specification and claims is the pre-consumer dilution and composition of the cleaning composition which is the e~nti~lly the form of the product prepared for sale to the COn~ .. or other end user.
Such a consumer or other end user would then normally be expected to dilute the same with water to form a cleaning composition. It is to be understood however that nothing in this invention would bar its use as cleaning composition witbout any further dilution and it may be used in the concentrations in 10 which it was prepared for sale. Similarly, what is to be understood by the term "cleaning compositions"
are the water diluted compositions which are expected to be prepared by the consumer or otber end user by mixing a measured amount of the "concenl~al~" with water in order to form an al.~,r~,p.;dlely diluted cleaning composition which is suitable for use in cleaning applications, especially in the cleaning of hard surfaces.
As generally denoted above, the formulations according to any of tbe aspects of the invention described above include both cleaning compositions and conct;llllal~s as outlined above which differ only in the relative proportion of water to that of the other constituents forming such form~ tions.
While tbe concentrated form of the cleaning colllpo~ilions find use in their original form, they are more frequently used in the formation of a cleaning co...posiLion therefrom. Such may be easily prepared by diluting measured amounts of ~he concelllldle: compositions in water by the consumer or other end user in certain weight ratios of concel~ ater, and optionally, agit~ting tbe 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, tbe 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. 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 is to be expected at lower relative dilutions of the concentrate in water.
F~mples:
Fvaluation of Cloud Points of non-ionic surfactant compostions:
An evaluation of the cloud point for Neodol(~) 91-2.5, a nonionic surfactant composition based on linear alcohol ethoxylates was evaluated according to tbe following protocol. To a clean glass beaker was added 99 parts by weight of deionized water at 20~C iO.5~C, to which was subsequently added I
part by weight (by weight of the actives) of a Neodol(~) 91-2.5 composition. Tbis test sample was stirred and the sample was immediately observed to be murky or cloudy in &l yea~allce. The sample was allowed to drop to 20~C and it was observed to remain in its cloudy form. The surfactant composition was considered to be useful as as the nonionic surfactant in the concentrate compc-~iti~ ns according to the third aspect of the invention.
In a similar manner, the cloud point of Neodol~) 23-6.5, a nonionic surfactant composition based on linear alcohol ethoxylates was evaluated. To a clean glass beaker was added 99 parts by weight of deionized water at 20~C ~0.5~C, to which was subsequently added I part by weight (by weight of the actives) of the Neodol~) 23-6.5 composition. The test sample was stirred and the sample was observed to be clear and transparent in ~Jealance~ The sample was allowed to drop to 20~C and no change in its appealallce was noted. The ~ulr~ul~lll composition was considered not to be useful as as the nonionic surfactant in the third aspect of the inventon.

Prep~ration of F.~mple Formulations:
Exemplary concentrate composition formulations accoldillg to the first aspect of the invention were prepared in accordance with the following general procedure.
Into a suitably sized vessel, the following concti~lentc were added in the sequence: water, cationic and anionic surfactant compositions of the blooming system, the sllf~rt~nt compatibilizing agent, and then any rem~ining constituents. All of the con~titllentC were supplied at room temperature, and mixing of the constituents was achieved by the use of a magnetic stirrer. These con~tituent~ were used "as is" as supplied from their respective supplier. Mixing, which generally lasted from I minute to 5 minnt~c, was m~int~ined until the formulation attained uniform color and uniform clarity. The example formulations were readily pourable, and retained well mixed characteristics indicative of stability.

W O 97106230 PCT~US96/12613 The exact compositions of the example forrnulations according to the first aspect of the invention are listed on Table lA, below.
" TABLE lA: EXAMPLE FORMULATIONS
F~- mple Forrn~ tion: (in % weight) Con~tituent~ ~ E~ Ex.3A
PolyTergent~) CS-1 3. 6.0 --PolyTergent(g C9-62P -- -- 4.0 BTC-8358 3.0 -- --BTC-8 18 -- 6.0 4.2 sodium chloride 2.0 -- --Mackam~) DZ -- 5.6 11.4 PolyTergent~ SL-42 -- 1.25 --deionizedwater to 100 to 100 to 100 PolyTergent(~) CS-I is a polycarboxylated alcohol alkoxylate (50% active) ava lable from Olin (~ l~mir~l Corp.
PolyTergent~ C9-62P is a polycarboxylated alcohol alkoxylate (50~/0 active) available from Olin ('.h~mir~l Corp.
BTC-835 is an aLkyl benzyl dimethyl ammonium chloride (53% active) available from Stepan ~hPmir~l Co.
BTC-8 18 is a diaLIcyl dirnethyl ammonium chloride (50% active) available from Stepan ~'h~mir~l CO.
Ma-,lual.,~ DZ is cocoamidopropyl betaine (30% active) available from McIntyre Group Ltd.
Poly-Tergent~ SL-42 is a nonionic alcohol alkoxylate available from Olin Ch~mic~l Corp.
Exemplary concentrate composition formulations according to the second aspect of the invention were prepared in accordance with the general procedure outlined above, and are illustrated on Table lB following.

WO 97/06230 PCT~US96/12613 o ~ , ~n ~ o . ~ , ~ ~
K ~ ~ O ~ ~ ~

00 0 ~ D O I I ~ ~ ~~

~ O ~D~ ~ ~ O I ~ ~

,_ ~ ~ o ~ o ~ ~ ~ oo ~ ~
3 K --' -- ~ " o~ ~

.~ ~ o. o ~ o. ~ I
' ~ ' ~ .~ C E-~ ~ o ~ o ~ o C
G ~ o ~ ~ , ~ x ~

c o ~ ~ U~ ~ O ~ ~ ~ O
ô ~ ~ - 2 c ~ ~ .
o o ~ o o ~ o o K ~ ~ ~ ~ ~
~ o ~, d~ '~ ~ ~ ~
~ ~ ~ 5 ~ o ~, ~ I ~ . s --~, ~ ,., 0: V~

= o c oo C E ~ D ~ ~ ~ w ~ ~ eo o s~ ~ ~ x ~ ~ ~~

, W O 97/~6230 PCTAUS96/12613 .; ~, j, I ~ I '.

Comparative formulations according to the prior art and example formulations according to the third aspect of the invention were prepared in accordance with the following general procedure.
Into a suitably sized vessel, the following constituents were added in the sequ~n~e: water, pine 5 oil, nonionic surfactants, other surftlct~nt~, pine oil solubilizing agent, and if present BTC-8358(~, a qud, L~. I,a~ y ammonium compound ~ al dlion. All of the conctitu~ntc were supplied at room le;lnp~l dLUI C~ (approximately 20~C), mixing of the conctihle.lt~ was achieved by the use of a magnetic stirrer. Stirring, which generally lasted from ap~,lo~i"lately 2 minutes to a~ o~illldlt~ly 5 minutes continued and was m~int~inf?d while the particular formulation attained uniform color and uniform 10 clarity or translucency. Each of the forrnulations exhibited the following physical cllal~el~;l ;slics:
hdlls~udl~nL appealdnce, light to medium yellowish amber color, and an appreciable pine oil odor. The exemplary compositions were readily pourable, and retained well mixed chdldcLel;sLics, demon:,L,dLi"g excellent shelf stability.
The exact compositions of the example formulations are listed on Table I C, below wherein the values in~lic zlt~d for each of the forrnulations are indicative of weight pC.~i~i.lL:i of the respective con~tih-ent in the formulation.

TABLE lC: FOR~ULATIONS
COmP.1 COnlP.2 E~.1C E~h2~ EX.3C
Conc~titue~t Pine Oil 60 8 4 4 4 4.1 Neodol 91-2.5 -- -- 4 4.1 4.1 Neodol23-6.5 4 4 4 9.0 6.3 BTC-8358 1.87 1.87 1.87 -- --MackarnTM DZ -- -- -- -- 5.2 iSo~ 10l (100%)23.8 6.8 9.6 15.0 15.0 deionized water62.32 83.32 76.52 62.32 83.32 Pine Oil 60 is a pine oil ~ ,pllld~iUII available ~rom the Glidco Organics Corp., Jac csonville, FL
BTC-8358 is an alkyl benzyl dimethyl ammonil.nn chloride (80% active) available from Stepan Chemical Co.
Neodol~ 91-2.5 is a nonionic surfactant .,c".ll.o~i~ion based on linear alcohol ethoxylates featuring a cloud point <
20~C available from Shell Chemical Co., Houston TX.
Neodol~ 23-6.5 is nonionic surfactant composition based on linear alcohol ethoxylates featuring a cloud point >
20OC available from Shell Ch~rni~ l CO., Houston TX.
MackamTM DZ is a surfactant composition containing coco~rnidopropyl betaine With reference to Table lC, formulations designated as "Comp.1" and "Comp.2" are indicative of illustrative formulations which did not comprise the nonionic surfactant having a cloud point less than 20~C, while the formulations designated as "Ex.lC", "Ex.2C" and "Ex.3C" are formulations demonsL,dling the blooming feature according to the present invention, and considered with in the W O 97/06230 PCT~US96/12613 present inventive scope. Each of these formulations appeared to be translucent and varying little in color.
The determination of the the amount of a solubilizing agent, isopropyl alcohol, required in order to clarify the formulations of Table I C provides a useful indication of the amount of required organic 5 solvents/compatabilizers which are required in typical collc~ dl~ formulations. The weight percent of isopropyl alcohol (100%) which was added to each ofthe formulations is also indicated on Table IC.
A further forrnulation according to the third aspect of the invention was produced in which no pine oil was present, but in which the sole blooming agent was the nonionic surfactant having a cloud point less than 20~C, and is illustrated on Table ID following:

TABLE lD: FOR~ULATION
Con~tihle~t wei~ht percent Neodol~) 91-2.5 5.66 Neodol~) 91-8 5.66 Dowanol(~) PM 5.66 deionized water 83.02 Neodol~9 91-2.5 is a nonionic ~u- rd~ cc,...po~i~ion based on linear alcohol ethoxylates featuring a cloud point < 20~C available from Shell ~ht?mir~l CO., Houston I7~.
Neodol~ 91-8 is a nonionic surfactant composition based on linear alcohol ethoxylates available from Shell Chemical Co., Houston 17~.
Dowanol(~ PM is a propylene glycol methyl ether available from Dow Chemical Co.,Midland, Michigan.
Although the formulation on Table ID did not include any pine oil, significant blooming was observed when diluted into a greater volume of water at room temperature at a ratio of formulation:water of 1:64. No pine oil was present in the composition.

Ev~ tion of Fx~mple Formulation~:
Each of the example forrnulations was used to prepare an aqueous diluted form therefrom at a concentration and dilution typical of conventionally used cleaning and/or disinfecting compositions useful in commercial/residential locations. These aqueous dilutions were simply prepared by pouring one part by weight of each example formulation of Table I into 63 parts by weight of tap water ( 1:64 by weight dilution) at 20~C and in some instances at 40~C. r In each case, the addition of an example formulation to the water was acconll,dllied by a change in the d,opeal dnce of the water from transparent to a translucent cloudy, whitish appearance. '-These aqueous dilutions were prepared to evaluate the degree of light tr~n~mitt~nce, a measure of the opacity as well as of the blooming of each of the aqueous dilutions. Certain of these aqueous dilutions were also evaluated to determine the antimicrobal efficacy of the aqueous dilution. The results W O 97/06230 PCT~US96/12613 of the light tr~n~m itt~nce evaluation was determined as a percentage of light tr~ncmitt~d through a sample of a particular aqueous dilution wherein the tr~n~mi~cc-n of a like sample of water is assigned a percentage of 100%. Testing was performed by mixing a Sg aliquot of a particular example formulation with 315 g of tap water (with approx. 100 ppm hardness), a~er which the sample was mixed for 60 S seconds and a tran~mitt~nce reading at 620 nm waveleng~ was taken using a Brink~nan model PC801 dipping probe colorimeter, which was set at 620 nm to determine the light tr~ncmicsion of eash of the samples. Samples of each formulation at 20~C and in some cases, 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 deter~nined values, reported in Tables 2A, 2B and 2C
10 (colTesonding to the formulations on Tables lA, lB and lC les~,e~ ely) below provide an empirical evaluation, reported in percent tr~ncm itt~nce ("%") of the degree of l~ )alcll~;y of a diluted example forTnulation wherein 0% indicates complete opacity and 100% the LlcL~ alcii~cy of a water sample as noted above. Accordingly, those results indicative of lower tr~ncmitt~nce values identify samples exhibiting desirable turgid or cloudy ~ eâl dnces indicative of desirable blooming effects.

TABLE 2A:TEST RESULTS OF TABLE lA FORMULATIONS
Bloomir~
Dilution of Exampletr~n~mi~ion at 20~C
Form~ tion Ex.lA 9.2 %
Ex.2A 9.7 %
Ex.3A 19.7 %
TABLE 2B: TEST RESULTS OF TABLE lB FORMULATIONS
BloQmir~
Dilution of Exampletr~n~mi~ion at 20~Ctr~n~mic~ion at 40~C
Form~ tion:
Ex.1B 13.0% 10.4%
Ex.2B 10.0 % 8.2 %
Ex.3B 11.1 % 8.7%
Ex.4B 15.8 % 13.1 %
Ex.5B 53.7 % 8.6 %
Ex.6B 15.4 % 7.8 %
Ex.7B 71.8 % 14.8%
Ex.8B 35.6 % 100.2 %
Ex.9B 17.2 % 22.9 %

TABLE 2C: TEST RESULTS - LIGHT TRANSMITTANCE
Formulation: Co~.l Corrlp.2 11~ .lC Ex. 2C E~T i~ht Tr~n~mitt~nce:
%T at 20~C 60.5 99.4 35.5 21.9 26.8 %T at 40~C 34.2 97.2 37.1 28.1 37.9 As may be seen from the above, the formulations according to the invention provided excellent blooming characteristics, although containing little o} no pine oil in their formulations. In certain formulations, the absence of pine oil, or its presence in reduced amounts also required a ~. .l~/;.. .l ;~l 5 reduction in pine oil solubilizing agents as compared to prior art pine oil cleaning compositions, many such agents are considered undesired VOC's and their use is desirably limited.
As can be seen from the results reported above, the exemplary formulations featured good blooming behaviour as cleaning composition, but were s--bst~nti~lly clear in the form of concentrate compositions.
The antimicrobal efficacy of certain of prepared formulations were also evaluated against two representative bacterial species, Salmonella choleraesuis and Staphylococcus aureus. As is known in the art, each of these bacterial species is commonly found and is desirably removed or destroyed during a cleaning procedure of such environments.
Antimicrobial efficacy of the prepared formulations according to examples were evaluated generally in accordance with the standardized AOAC Use-Dilution test method based on AOAC Of ficial Methods of Analysis Procedures 955.14 "Testing disinfectants against Salmonella Choleraesusis, " and Pl oce.lule 955.15 "Testing disinfectants against Staphylococcus Aureus " ( 15th Edition, 1990, pages 135-137, Use Dilution Methods). The results reported on Table 3 indicate the proportion of the number of sample test tubes within which the organism remained alive after 10 minutes of exposure at 20~C over 20 the total number of test tube samples used in testing the exemplary forrnulations of Table I B for their germicidal activity.

Antimic-obal F.fficacy Dilution of Exarnple Staphylococcus Salmonella choleraesuis ForInul~tion: aureus Ex.5B 1/60 1/60 Ex.6B 1/60 1/60 Ex.7B 0/30 0/30 As can be seen from the results reported above, the exemplary forrnulations featured good blooming behaviour and the tested formulations also showed good efficacy as germicidal agents.

WO 97/0~230 PCTAUS96/12613 Generally it is expected that formulations which contain effective amounts of the quaternary ammonium cationic surfactant described above especially with respect to the first and second aspects of the invention and/or which include a germicial active agent such as the phenolic compositions described above are useful in providing germicidal active compositions within the scope of the present inventive t~ hin~

Claims (9)

Claims:

1. An aqueous blooming type, hard surface cleaning composition concentrate comprises a blooming sytem which is selected from:
a blooming system which comprises an effective amount of each of a cationic quaternary ammonium surfactant; an anionic carboxylated alcohol alkoxylate surfactant;
a surfactant compatibilizing agent; and, water, or, a blooming system comprising one or more nonionic surfactants which are characterized in exhibiting a cloud point of 20°C or less in water.

2. The composition according to claim 1 which has incorporated therein a blooming system comprising:
a cationic quaternary ammonium surfactant;
an anionic carboxylated alcohol alkoxylate surfactant;
a surfactant compatibilizing agent; and, water.

3. The composition according to claim 1 which comprises:
pine oil in an amount of from 0.01 - 3%wt., preferably 0.01 - 2.5% by weight, but most preferably 0.75-1.5%wt.1;
at least one pine oil solubilizing agent in an amount of to 15% and less by weight, preferably 0.01-10% by weight, and most preferably in an amount of 0.1-5% by weight and a blooming system which includes:
a cationic quaternary ammonium surfactant;
an anionic carboxylated alcohol alkoxylate surfactant;
a surfactant compatibilizing agent; and, water.

4. The composition according to claim 1 which comprises:
pine oil, in amount of 0.1-5% by weight, preferably in amounts of 0.1 - 4% by weight, but most preferably in amount of between 2 - 4% by weight;

at least one pine oil solubilizing agent effective in enhancing the miscibility of the pine oil constituent in water which may be present in any effective amount found but desirably is present in amounts of up to about 15% by weight, preferably in amounts of 0.1 - 15% by weight, but most preferably from 5 - 15% by weight a nonionic surfactant with a cloud point of 20°C or less;
and, water.

5. A germicidal composition according to claim 1.

6. An aqueous blooming type, hard surface cleaning composition concentrate substantially as described herein with reference to the Examples.

7. A cleaning composition which comprises the aqueous blooming type, hard surface cleaning composition concentrate according to any proceeding claim diluted in a larger volume of water.

8. A process for process for treating a hard surface requiring cleaning which comprises the process step of:
contacting the hard surface with an aqueous blooming type, hard surface cleaningcomposition concentrate according to any proceeding claim an amount effective for providing cleaning treatment.

9. A process for process for treating a hard surface requiring cleaning which comprises the process step of:
forming an aqueous dilution of the composition according to claim I in a larger volume of water, and thereafter, applying the said aqueous dilution in an amount effective for providing cleaningtreatment.