New Zealand No 320930 International No PCT/US96/15588
TO BE ENTERED AFTER ACCEPTANCE AND PUBLICATION
Priority dates 1411 1995,
Complete Specification Filed 27 09 1996
Classification (6) C11D1/68.72.835, C11D3/43.44
Publication date 28 October 1999
Journal No 1445
NEW ZEALAND PATENTS ACT 1953
COMPLETE SPECIFICATION
Title of Invention
Improved compositions containing organic compounds
Name, address and nationality of applicant(s) as in international application form
RECKITT & COLMAN INC , 1655 Valley Road, Wayne, New Jersey 07474, United States of America
la
4Sh W
c
Improved Compositions Containing Organic Compounds
The present invention relates to improvements in cleaning comDositions More particularly, the present invention is directed to improved pine oil type cleaning compositions and concentrates thereof, which find particular use in hard surface cleaning applications
One particular category of cleaning compositions are those which are classed as pine oil type cleaning compositions, such typically contain one or more resins or oils derived from coniferous species of trees, and typically generate a milky or cloudy appearance when diluted with water in dilutions useful for cleaning applications Such pine oil type cleaning compositions are generally provided in a concentrated composition which is subsequently diluted with water by an end user/consumer to form a cleaning composition therefrom However, pine oils also are known to leave undesirable surface residues, particularly on hard surfaces and are further known irritants particularly to the eyes, skin and mucocus tissues Also, pine oil, while known to have cleaning efficacy is not generally considered useful as a broad spectrum antibacterial or santizing agent
It is among the objects of the present invention to provide improved pine oil type cleaning compositions in a "concentrate" form which exhibit one or more of the identifying characteristics outlined above, especially a pronounced blooming effect, and an effective sanitizing effect and a long lasting scent while having reduced amounts of pine oil in such compositions*,
to provide "cleaning compositions", le, aqueous dilutions of these improved pine oil type cleaning compositions which exhibit good blooming upon being produced, and whicn provide an effective cleaning and/or sanitizing benefit to hard surfaces* or at least to provide the public with a useful choice
These and other objects of the invention will become apparent from the following detailed descnption of the invention
In one aspect, the present invention provides a blooming type, pme oil type cleaning composition comprising the following constituents
A) 0 001 - 15% by weight of a pine oil preparation containing at least about 60% alpha-terpmeol,
B) 0 001 - 15% by weight of a co-solvent,
C) 0 001 - 15% by weight of a non-ionic surfactant system which desirably includes two or more non-ionic surfactants wherein at least one of which exhibits a cloud point of 20°C or less in water,
D) 0 5-5% by weight of a cationic quaternary ammonium surfactant which exhibits germicidal activity,
f i hUrLHi V QfMnf 1
*these are at least the objects of the preferred embodiments of the/invention 0F(£qllovveci Dupage lb)
R E" P P I \/ Cr r\
- lb-
E) 0 000001 - 15% by weight of a fragrance/fragrance enhancer, and
F) to 100% by weight of water
In a further aspect, the present invention provides an aqueous cleaning composition comprising the pine oil type cleaning concentrate composition of the invention dispersed m water m a weight ratio of concentrate composition water of from 1 0 1 to 1 1000
In a ye: further aspect, the present invention provides a process for cleaning and disinfecting a hard surface requiring such treatment which process includes the step of applying the composition of the invention in an amount effective for providing cleaning and/or disinfecting treatment
In addition to the above described constituents, the compositions according to the invention may optionally further include known art additives m conventional amounts
/ ~ 8 SEP jggg
LJ1§CE/Vpd
The inventors have found that it is now possible to produce certain concentrate compositions utilizing these selected constituents in particular formulations which provide pine oil type cleaning compositions m a concentrated liquid form which unlike many known prior art composition further include a germicidal effect, good blooming and a high concentration of fragrance and/or fragrance solubihzer constituents Surprisingly however, these inventive compositions still exhibit many of the desirable characteristics of pine oil type cleaning compositions described above, especially "blooming", notwithstanding the relatively high levels of fragrance and/or fragrance solubihzer constituents which they comprise This is an important and surprising feature of the invention as the use of relatively higher amounts of fragrance and/or fragrance solubihzer constituents, which are known to be organic constituents, would be expected to significantly diminish or deactivate the desirable "blooming" effect when such concentrates are further diluted with water 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 or milky yellowish white, cloudy appearance That such behaviour is achieved in the compositions according to the present invention, which contain relatively high amounts of fragrance and/or fragrance solubihzer constituents, is surprising to say the least
Constituent A) Compositions according to the invention compnse a pine oil constituent
Pine oil is an organic solvent, and is a complex blend of oils, alcohols, acids, esters, aldehydes and other organic compounds These include terpenes which include a large number of related alcohols or ketones Some important constituents include terpineol, which is one of three isomeric alcohols having the basic molecular formula C ] oH j 7OH Useful pine oils include synthetic pine oil, and also include steam distilled and sulfate pine oils, and will generally contain a higher content of turpentine alcohols Other important compounds include alpha- and beta-pinene (turpentine), abietic acid (rosm), and other isoprene derivatives
Particularly effective pine oils which are presently commercially available include Glidco® Pine Oil™ 60 (believed to contain approximately 60% terpene alcohols), Glidco® Pine Oil 80 (believed to contain approximately 80% terpene alcohols) Glidco® Pine Oil 150 (believed to contain approximately 85% terpene alcohols), Glidco® Terpene SW (believed to contain approximately 75% terpene alcohols), as well as Glidco® Terpineol 350 (believed to contain approximately 100%
terpene alcohols) Each of these may be obtained from available from Glidco Organics Corp , Jacksonville, FL (USA) Other products which can contain up to 1 00% pure alpha-terpineol, may also be used jn the present invention
As stated, the pine oil constituent is present in the concentrate compositions in amounts of from about 0 001% by weight to up to about 15% by weight However, it is prefe 3,L -
weight, most
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preferably in amounl of between 6 - 10 % pine oil bv weight Preferred of these are pine oil preparations which comprise at least about 60% terpene alcohols and more preferably those which comprise at least about 80% terpene alcohols As with all of the weight percentages of the constituents described, the weight percentages are indicative of the weight percentages of the actives 5 in a constituent containing preparation
Constituent B) A further constituent according to the imention is a co-solvent which is present in addition to the pine oil which is itself known to be an organic solvent and assists in improves the dispersability andA>r miscibilirv of the water insoluble pine oil in water 1 he co-solvent may also improve the miscibility of further constituents according to the present invention, including 10 any water insoluble or poorly soluble constituents Many useful co-solvents which are known to be useful in dispersing pine oil water may be used as Constituent B, especially those based on are based on organic solvents virutalK an\ may be used as long as it does not undesirably disrupt the favorable characteristics of the invention, especiallv the blooming characteristic Mixtures of two or more co solvents may also he used as Constituent B 15 Lxemplary co-solvents useful as Constituent B include certain glycols and gl>col ethers which exhibit the above described properties Examples of such glycol ethers include those having, the general structure R9-O-R.10-OH, wherein R9 is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms and Rjo is an ether condensate of propylene glvcol and/or ethylene glvcol having from one to ten glycol monomer units Examples of such useful glycol ethers include 20 propylene glycol methyl ether, dipropylene gl>col methyl ether tripropylene glycol methyl ether propylene glycol isobutyl ether, ethylene gKcol methyl ether, ethylene glycol ethvl ether ethylene glycol but\l ether, diethvlene glycol phenyl ether, propylene glycol phenol ether, and mixtures thereof Preferred are ethylene gKcol n butyl ether, d(ethylene glycol n butyl ether and mixtures thereof Such glycol ethers arc presently commercially available from a number of sources 25 including in the DOWANOL™ glycol ether from The Dow Chemical Company, Midland MI (USA) Further exemplary co-solvents useful as Constituent D include C ] -Cg alcohols, especially C1-C3 alcohols, of which isopropanol is preferred
It has generally been found the addition of only a minimum effective amount which is found to be effective .n dispersing or solubilizing the pine oil constituent and any other aqueous insoluble 30 or poorly soluble constituents in the concentratc compostions is desirably used Such is due to desire to reduce the amount of volatile organic constituents in the concentrate compositions of the invention which volatile organic constituents are desirably minimized from an environmental standpoint The present inventors have found that inclusion of the solubilizing agent according to Constituent B in amounts of about 0 001% by weight to about 15 % by weight have heen found to be
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effective to solubilize the pine oil, as well as in solubilizing other less water soluble constituents present in the concentrate compositions of the invention Preferably, the solubilizing agent of Constituent B is present in amounts 4 - 12% by weight and most preferably 8-10% by weight Constituent C) The concentrate compositions according to the invention include a nomonic surfactant system which comprises a mixture of two or more, nomonic surfactants which includes a first nomonic surfactant constituent which is a single or is a mixture of noninonie surfactants which exhibit a cloud point of 20°C or less in water, and a second nomonic surfactant constituent which includes a single nomonic surfactant or mixture of surfactants which are useful in solubilizing the first nomonic surfactant constituent in water The first said nomonic surfactant constituent is generally selected to be one or more aqueous insoluble or poorly soluble nomonic, which optionally, but further very desirably exhibit a cloud point of 20°C or less in water The second nomonic to solubilize the first nomonic surfactant Such a solubilizing cffcct aids in the long term shelf stability of prepared concentratcd compositions, and in ensuring the optical clarity of concentrated compositions especially during the shelf life of prepared concentrated compositions
Generally, suitable nomonic surface active agents which may be used in the nomonic surfactant system according to Constituent C includes condensation products of one or more alkylene oxide groups with an organic hydrophobic eompound, such as an aliphatic or alkyl aromatic compound Exemplary suitable nomonic surface active agents include surfactant compositions based upon pol>ethoxylated, polvpropxylated, or polyglycerolated alcohols, alkylphenols or fatty acids
One exemplary class of nomonic surfactants useful in Constituent C according to the instant invention include certain alkoxylated linear aliphatic alcohol surfactants which are believed to be the condensation products of a Cg-C]0 hydrophilic moiety with polyethyJenc oxide/polypropylene oxide moieties Such alkoxylated linear alcohol surfactants are presently commercially available under the tradename Poly-Tergent© (Olin Chemical Co Stamford CT) and of these particularly useful are those which are marketed as Poly-Tergent® SL-22, Poly-Tergent© SL-42, Poly-Tcrgent® SL-62 and Poly-Tergent® SL-29, of which Poly-Tergent® SL-62 is particularly advantageous Poly-Tergent® SL-42 is described as being a moderately foaming biodegradable alkoxylated linear alcohol surfactant having on average 5 moles of oxyethylene groups per molecule Poly-Tergent® SL-62 is described as being a moderately foaming, biodegradable alkoxylated linear alcohol surfactant having on average 8 moles of oxyethylene groups per molecule These alkoxylated linear alcohol surfactants provide good detersive action in the removal of manv types of fats and greases such as are frequently found in soils on hard surfaces, as well as providing a further solubilizing cffects
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PCI7US96/I5588
A further exemplary class of nomonic surfactants which finds use are alkoxylated alcohols especially alko\>lated fatty alcohols These include ethoxylated and propoxy lated fatty alcohols, as well as clhovylated and propnxylated alkyl phenols, having both withalkvl chains of about 7-16, more preferably about 8-13 carbon chains in length Exemplary alkoxylated alcohols include certain ethoxylated alcohol compositions presently commercially available from the Shell Chemical Company, (Houston TX) under the general trade name Neodol®, which are described to be linear alcohol ethoxy lates Of these, those exhibiting a cloud point of 20aC or less may be used Specific compositions include Neodol® 91-2 5 which is described as an ethoxylated alcohol having an a\ crage molar ratio of 2 7 1 ethoxy groups/alcohol groups per molecule a molecular weight of 281 and a cloud point in water of ?0°C and less Neodol® 23-3 which is described is an ethoxylated alcohol ha\ ing an average molar ratio of 2 9 1 I 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 compositions commercially available from the Union Carbide Co , (Danbury, CT) under the general trade name Tergitol® which are 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 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, Tergitol3?> 15-S-5 described as an ethoxylated secondary alcohol having an average molar ratio of 5 1 ethoxy groups/alcohol groups per molecule and a cloud point in water of less than 20aC
Further exemplary nomonic surfactants which may be used in Constituent C include certain alkanolamides including monoethanolamides and diethanolamides, partirularlv fatt> monoalkanolamides and fatty dialkanolamides Commercially available monoeihanol amides and dicthanol amides include thost marketed under the trade names AlakamidtSL and Cycloinide® by Rhonc-Poulenc Co , (Cranbury, NJ) These include surfactants based on coconut diethanolamides coconut monoethanolamides, 2 1 modified coconut monoethanolamide, fatty acid diethanolamides, lauric/linoleic diethanolamides, linoleic diethanolamides, lauric monoethanolamides, launc diethanolamides, lauric/myristic diethanolamides, olcic diethanolamidc, stearic diethanolamides, coconut diethanolamides, lauric monoisopropanolamides, stearic monoethanolamides diethanolamides of unsaturated fatt\ acids, alkanolamides which may be used singl> or in mixtures Particularly useful are lmeolic diethanolamides and lauric diethanolamides
Exemplary alkoxylated alkyl phenols useful in Constituent C include certain compositions presently commercially available from the Rhone-Poulenc Co , (Cranbury, NJ) under the general trade name Igepal®, which arc described to be octyl and nonyl phenols Again, those exhibiting a
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PCT/11S96/1S588
cloud point of20°C or less may be used These include Igepal® CA-21 0 an ethoxylatid octyl phenol 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 an ethoxylated octyl phenol having an average of 3 ethox\ groups groups per molecule and a cloud point in water of less than 20CC
Especially preferred for use as the first nomonic surfactant constituent which comprises Constituent C according to the instant invention is Neodol® 91-2 5 which is described as an ethoxylated alcohol having an average molar ratio of 2 7 I ethoxy groups/alcohol groups per molecule, a molecular weight of 281, and a cloud point in water of 20°C and less
Of course a mixture of two or more nomonic surfactants having a cloud point of 20DC or less may be incorporated into the inventive compositions Other known nomonic surface active agents not particularly enumerated here may also be used
The cloud point of the first nomonic surfacant constituent according to Constituent C of the present invention may be determined by known methods such as by ASTM 1)2024 (reappro\ed 1986) for "Standard Test method for Cloud Point ofNonionic Surfactants" An even simpler test method for effectively determining which nomonic surfactants may be used as the first nomonic surfactant constituent in the compositions of the invention is as follows to a clean beaker or other glass vessel is added 99 parts bv weight of dcionized 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 ind the temperature permitted to drop to 20°C, if this test sample is observed to be murU or cloudy in appearance as the test sample's temperature achieves 20°C and drops below 20°C it is considered to have a suitable cloud poirvt of 20°C and less and may be used as Constituent B in the concentrate compositions according to the invention
Constituent C, may be present in any effectiv e amount but desirably is present in the concentrate compositions from about 0 001 % by weight to about 25% by weight preferably 0 I -20% by weight, and most preferably from 8% and 15% by weight Desirabl), particularly wnere Constituent C includes an alkanolamidc, dialkanolamide or tnalkanolamide, Constituent C) is present in a weight percentage about equal to, or greater than the amount of Constituent E) present in the concentrate composition
Constituent D) The concentrate compositions according to the invention include as a necessary constituent at least one canonic quaternary ammonium surfactant which is found to provide a broad antibacterial or sanitizing function Such materials are per se known to the art
Exemplary useful and preferred compounds are quartemary ammonium compounds and -alts thereof, which may be characterized by the general structural formula
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7-
where at least one or R] R2 R3 and R4 is a hydrophobic, aliphatic aryl aliphatic or aliphatic aryl radical of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular ■weight of at least 165 The hydrophobic radicals ma\ be long-chain alkyl, long-chain alkoxy aryl long-chain alkyl aryl, halogen-substituted long-chain alk>l aryl, long-chain alkyl pheno\y alkyl, aryl alkyl, etL The remaining radicals on the nitrogen atoms other than the hydrophobic radicals arc substituents of a hydrocarbon structure usually containing a total of no more than 12 carbon atoms The radicals Rj. R2 R3 and R4 mav be straight chamcd or may be branched, but are preferably straight chained, and may include one or more amide or ether linkage The radical \ ma) be anv salt-forming anionic radical
Exemplar) quaternary ammonium salts within the above description include the alkyl ammonium halides such as cetyl trimethyl ammonium bromide alkyl aryl ammonium halides such as octadecv1 dimethyl benzyl ammonium bromide, ls-alkyl p\ridimum halides such as N-cetyl pyndinium bromide and the like Other suitable types of quartemaiy ammonium salts include those in which the molecule contains either amide or ether linkages such as octyl phenoxy ethow ethyl dimethyl benzyl ammonium chloride N-(laurylcocoaminoformylmethyl)-pynd]nium chloride, and the like Other very effective tvpes of quartemaiy ammonium compounds which are useful as gcrmtcidcs include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of laury lowphenyltrimethyl ammonium chloride, cctylammophenyltnmethy I ammonium methosulfate, dodecylphenvltrimeth)! ammonium methosulfatt dodecvlbcnzNltrimcthy] ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like
Especially Preferred quarternary ammonium compounds which act as germicides and which are be found useful in the practicc of the present invention include those which have the structural formula
■wherein R2 and R3 arc the same or different Cg-C^a'kyl, or R2 is C 12-igalkyl, Cg. ] galkylethoxy, Cg.igalkylphenolethoxy and R3 is bciuyl, anil X is a hahde, for example chloride, bromide or
OH,
R2—Ivl—R3 X"
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iodide, or methosulfale The alk> 1 groups rccitcd in Rt and Rl may be straight chained or branched but arc preferably substantially linear
Such quartenary germicides are commercially availahle either as single quaternary ammonium compounds or as mixtures of two or more different quartenaries Suitable materials include germicidal quaternary ammonium compounds include those sold under the tradenames BARDAC BARQUAT and IH'AMINE (Lonza lnc , Fairlawn KJ (USA)) as well as those designated "BTC" (Stepan Co Northficld II (USA))
The quaternary ammonium compound of Constituent C) is desirably present in a minimum amount to provide the desired germicidal and sanitizing effects as the blooming effect of the concentrate compositions when added to a larger volume of water have been found to be hindered by the inclusion of e\cessi\e amounts of the such quaternary ammonium compounds in the concentratc compositions Generalh Constituent C is present in the conccntrate coinpostions in amounts of up to 5 % by weight and less, preferabK from 0 S - 2 6/o by weight, and most preferably from 0 8 - 1 2 % by weight It has also been found by the inventors that the preferred amounts are in part dictated by toxicological considerations as an excess of the canonic eomponent may pose an increasing risk of irritation to the eyes, sk >n and mucocous tissues of a consumer
Constituent Q A further constituent of the concentrate compositions according to the invention are fragrances and/or fragrance enhancers which provide a characteristic pine oil scent and and scent longevity, particularly wherein the conccntrate compositions are diluted to form cleaning compositions therefrom As is described in the specification under claims, llic term "fragrance" is used to refer to and to include any non-water soluble fragrance substance or mixture of such substances including those which are naturally derived (i e , obtained by extraction of flower herb blossom or plant) those which arc artificially derived or produced (l e , mixture of natural oils and/or oil constituents), and those whieli are synthetically produced substances (odiferous substances) Generally fragrances are complex mixtures or blends various organic compounds including, but not limited to, certain alcohols, aldehydes, ethers, aromatic compounds and varying amounts of essential oils such as from about 0 to about 85% by weight, usually from about 10 to about 70% by weight the essential oils themselves being volatile odiferous compounds and also functioning to aid in the dissolution of the other components of the perfume In the present invention the precise composition of the perfume is of no particular conscquence to cleaning performance so long as it may be effectively included as a constituent of the compositions Generally however, one or more fragrances characteristic of pine oil type compositions, such as natural or synthetically produced fragrancc compositions, especially those which are intended to mimic the scent of one or more resins or oils derived from coniferous species of trees, viz, asccnt characteristic of pine oil type cleaning
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(^1
WO 97/182B5 PCTa1s96/15588
concentnstes are used Fragrance effects atypical of pine oil t)pc cleaning concentrates ma> be used as well T ragrance adjuvants for enhancing the scent effect of a fragrance, and/or for improving the miscibility of such fragrance compositions include known art fragrance adjuvants, for example fenchoi
lri any type of composition the pine oil scent is the characteristic scent which is emitted bv pine oil, and the longe\ lty of such a pine oil scent is understood to be closely related to the pine oil cunten' if a concentrate composition or a cleaning composition as described in this specification Thub, it is normally expected that an increase in the pine oil provides an increase in the characteristic pin oil scent and in the scent longevity, however, for reasons noted earlier in this specification, the 10 inclusion of increased amounts of pine oil is not always desirable from other standpoints To provide a desired characteristic pine oil scent and pine oil scent longevity without requiring an increased amount of pine oil, the present inventors have found that by careful selection of fragrances and/or fragrance enhancers a reduction m the amount of pine oil may be achieved while maintaining a characteristic pine oil scent and a scent longe\ it> At the same time, this has been achieved w ithout 15 undesirably effect the blooming behavior of pine oil cleaning compositions taught herein Also a further undesired characteristic is an e pectation of increased irritancy especially to the eyes skin and mucocous tissues which an increase in an organic solvent such as a fragrance/fragiance solubili?er which is known to emit a volatile fraction has been avoided Constituent H Water is added in order to provide 100% by weight of the concentratc
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 25 Generally, water is present in the concentrate compositions in amounts in excess of about 80°/o by weight, preferably in amounts of in excess of 75% by weight, but most preferably in amount of between 60 -70 % by weight based on the total weight of Constituents A - F in the concentrate compositions taught herein Optional constituents
I urther optional, but 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 stabiliser constituents which act to retain the appearance characteristics of the concentrate
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PCr/US96/15588
compositions over longer intervals of time may also be used Further optional constituents may also be used which, bv way of non-limiting example include pH adjusters, pH buffering agents, foaming agents further surfactants including anionic canonic, non ionic amphoteric and zwitterionic surfactants, especially those useful in providing further detersive effects and water softening agents 1 hese optional, i e , non-essential constituents should be selected so to have little or no detrimental effect upon the desirable characteristics of the present invention namely the blooming behaviour cleaning efficacy disinfectant activity, and low toxicity as provided bv the inventive compositions an in most cases anionic surfactants which may deactivate the quaternary canonic surfactant are to be avoided Generally the total weight of such further conventional additives may comprise up to 10% by weight of a concentrated composition formulation
The term "concentrate' as used in this specification is the pre-consumer dilution and the composition of the cleaning composition which is the ty picallv Ihc 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 bv the consumer or other end user bv mixing a measured amount of the "concentrate" with water in order to form an appropriatelv diluted cleaning composition which is suitable for use in cleaning ap^'ications, especially in the cleaning of hard surfaces Such mav 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 conccntrate in the water As noted, the concentrate may be used without dilution i e , in concentratc 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 lft-1 100 His to be understood however that the ' concentrate ' composition without any further dilution and it mas be 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, the following constituents were added in the following sequence pine oil co-solvent, nomonic surfactant system, fragrance/fragrance enhancer, cationic surfactants, water and lastly, optional constituents The order of mixing is not critical in order to achieve
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concentrate compositions exhibiting the desired results All of the constituents wert supplied at as weight percentages, as room temperature, and mixing of the constituents was achieved b\ the use of <1 magnetic stirrer Mixing which general!) lasted from 1 minute to 15 minutes, was maintained until the particular exemplary formulation attained uniform color and uniform eljrit) Each of the formulations exhibited the following physical characteristics transparent appearance, light orange to medium orange-brown color, and a noticeable pine oil odor TI.e exemplar)' formulations were readily pourable and retained well mixed charaeterislics (i c stable mixtures') upon standing at room temperature (about 68°F) for periods m excess of sc\ual weeks The stability of the concentrate formulations was also evaluated at by heating to 120^ determine if clouding or phase separation occurred none was observed
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Table 1 Formulations
Constituent
El
E2
E3
E4
E5
E6
E7
E8
P\ne Oil 1
a
—
-
-
--
B
8
8
Pine Oil 2
—
8
6
-
-
-
Isopropanol
9 25
9
4
9 25
9 25
9 25
diethylene glycol n-butyl ether
—
—
6
6
—
—
Poly-Tergent® SL-62
8
8
8
8
8 75
8
8
8
Neodol® 91-2 5
4
4
1 75
alkyldiethanolamide
1 4
1 2
1
-
1
1 18
1 5
1 8
BTC-8358
09
09
1
1
1
09
09
09
BTC-818
0 5
05
05
05
05
05
05
05
Fragrance I
1 2
—
-
-
-
-
1 2
1 2
Fragrance II
—
0 1
0 1
0 1
0 1
«
-
-
Fragrance III
—
—
-
-
--
06
-
-
fenchol
0 1
0 1
01
0 1
0 1
0 1
0 1
0 1
coloring agent
0 001
0 0008
0 0008
0 0008
0 0008
0 0008
0 0008
0 0008
Deiomzed water
65 65
67 2
69 29
70 29
71 8
66 47
65 55
65 25
Pine Oil 1 is a pine oil preparation coniaining at least about 60% terpene alcohols Pine Oil 2 is a pine oil preparation containing at least about 80% terpene alcohols Po(v-Tergen(® SL-62 is a nomonic alkoxylated linear alcohol surfactant
Neodol® 91-25 is is a nomonic surfactant composition based on linear alcohol eihowlaies featuring a cloud pomt <20°C BIC-8358 is an alkyl ben7yl dimeth>l ammonium chlondt (80% active) available from stepan Chemical Co BTC-818 IS a dialk>l dimethyl ammonium chloride (^0% acti\c) a%ailablc trom Stepan Chemical Co
PCT/US9fi/|55R8
- n -
The determination of the amount of a solubilizing agent, here isopropy I alcohol required in order to clarify the formulations of Table ) provides a useful indication of the. amount of required co-solvents which are required in rvpical concentrate formulations The weight percent of isopropyl alcohol (100%) which was added to each of the formulations is also indicated on Table 1 It is to be noted that the values indicated on Table. 1 art on d 100% total weight basis of the actual weight percentages of the constituents added Preparation of Cleaning Compositions
Cleaning testing was performed utilizing one or more of the exemplary compositions within the scope of the invention as illustrated on Table I and cleaning compositions prepared from known commercially available cleaning products, which arc indicated as comparative examples
Comparative Example "Cl"
A cleaning composition was formed b> forming an aqueous dilution of one part by weight of Lysol® Pine Action Cleaner a commercially available cleaning concentrate with 64 parts bv weight of water at approximate!} 20°C and subsequentl> manually stirring the same to form a uniform mixture
Comparative Example "C2'
A cleaning composition wis formed by forming an aqueous dilution of one part by weight of Spic and Span® Ultra Pine Deodorizing Cleaner, a commercial!) available cleaning concentrate with 128 parts by weight of water at room temperature (approx 20°( ) and subsequent!) manually stirring the same to form a uniform mixture
Comparative Fxample "C3'
A cleaning composition was formed b\ mixing one part of a commercially available cleaning formulation, PineSol® Cleaner, a pine oil type cleaning concentrate, with 64 parts of water at room temperature, approximate^ 20°C, and manually stirring the same to form a cleaning composition tnerefrom
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 masonite wallboard samples painted with wall paint The soil applied was a grcas) soil sample containing vegetable oil, food shortening and animal fat The sponge (water dampened) of a Gardner Abrasion Tester apparatus was squirted with a 15 gram sample of a tested cleaning composition, 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
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ihus allowing a "side b>-side" comparison to he made fcacli of these tests were duplicated 011 20 wallboard tiles and the results statistically analyzed and the averaged rt-suIts reported on Table 2, below The cleaning tffiiacv 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 results are reported on Tabic 2 following
Table 2
composition | comparative composition
E1 | C1
E1 | C2
El | C3
E2| C3
reflectance reading composition | comparative composition
69 04 | 67 19
63 68 | 62 22
70 93 | 69 B2
65 63 | 65 14
With respect to the results reported on Table 2 a value of' 100 is indicative of a white (unboiled) background and a "0" value is indicative of a bhek background A soil laden (uncleaned) surface gererally provided a result of about 20-30
As can be seen from the results of Table 2, the cleaning efficacy of the composition according to tht invention provided fav orablc results with those ol known art cleaning products I Evaluation of Linht Transmittance (''Blooming") of Formulations
Each of the formulations described on Table 1 was evaluated 10 determine the degree of light transminance, a measure of the opacity of each of these concentrated formulations Also evaluated were comparative formulations designated as ' CI" and "C2" as described above
These aqueous dilutions were prepared to evaluate the degree of light transnittance, a measure of the opacity as well as of the blooming of each of the aqueous dilutions Certain of these iqueous dilutions were also evaluated to determine the antimicrobal cfficac\ of the aqueous dilution The results of the light transmitlance evaluation was determined as a percentage of light transmitted through a sample of a particular aqueous dilution wherein the transmisson 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 for 60 second and a transmittance reading was taken using a Brinkman model PCK0I dipping probe eolonmetcr, which was set at 620 nm to determine the light transmission of each of the samples Samples of each formulation at 20°C and 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 3 below provide an empirical evaluation, reported in percent 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
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Accordingh, a lower %T of a particular aqueous dilution provided a more desirable indication of the blooming characteristic of the particular aqueous dilution
Table 3 - Percentage Light Transmittance (%T)
Light
Transmittance
El
E3
E4
E5
E7
E8
C2
C3
%T at 20°C
40
-40
>80
>80
-30
-20
>80
>80
%T at 40°C
20
-40
—
—
-20
<10
>80
>80
As mav be seen from the results described on Table 3 the formulations according to the invention vere comparable to, but in most cases better than the known art formulations represented by the Comparative examples CI and C2
2 Evaluation of Licht Transmittance ("Rloomine' 1 of Formulations
Further formulations according to the invention as well as further "comparative' 10 formulation"? were produced, their constituents are noted on Table 4 below The indiv idual constituents were the same as used for the formulations of Table 1, but for the use of a different coloring agent (1% indicates weight actives) and a different fragrance
Table 4
C4
C5
E9
E10
Constituents
Pine Oil BO
8 00
8 00
8 00
8 00
Isopropanol
9 25
9 25
9 25
9 25
Polytergent® SL-62
8 00
8 00
8 00
8 00
Neodol® 91-2 5
00
00
00
00
alkyldiethanolamide
0 00
0 50
1 50
2 00
Fenchol
0 10
0 10
0 10
0 10
Fragrance
1 20
1 20
1 20
1 20
BTC-6358
0 90
0 90
0 90
0 90
BTC-818
0 50
0 50
0 50
0 50
coloring agent (1%)
0 11
011
0 11
0 11
Deionized Water
66 94
66 44
65 44
64 94
In a similar manner to that described above, the blooming characteristics of the further compositions according to the invention (designated as' E9' and "E10") as well as further comparative examples (designated as "C4", "C5") were evaluated as to their blooming characteristics by forming formed a 1 64 dilution of a respective example or compartive formulation in water, after which the sample was mixed for 60 seconds and a transmittance reading was taken using a Brinkman 20 model PC801 dipping probe colorimeter set at 620 nm to determine the light transmission of each of
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the samples Samples of cach formulation at 20°C and at 40°C were evaluated and the percentage light transmittance is reported on Table 5 below
Table 5 - Percentaye Light Transmittance (%T)
C4
C5
E9
E10
Bloom at 20°C
97
97
28
13
Bloom at 40"C
86
92
11
2
As may be seen from Table 5, the formulations according to C4 and C5 having low amounts 5 of dietlianolamide and high levels of fragrance (1 2%\vt ) exhibited high percentages of light transmitted indicating very poor blooming charatenstics In sharp contrast the formulations according to E9 and E10 having the same level of fragrance, but including at least about an equivalent amount of (in %\vt ) of the diethanolamide as the fragrance featured surprisingly and substantially improved blooming characteristics as demonstrated by low high percentages of light 10 transmitted rvaluation of Seen! Longevity
An evaluation of the scent longevity of formulations of Example formulation "El' described on Table 1 above, compared to a comparative formulation "CI' was performed
Individual cleaning composition based on cach of these formulations was produced by 15 mixing 4 grams of a respective formulation with 256 grams of water, which formed a representative
1 64 dilution t> pica! of the dilutions used for such pine oil type products in domestic environments Next, cach of these cleaning compositions was poured onto a floor surfacc in separate rooms and mopped with a sponge mop to cov er approximately 40 square feet of floor surface with a cleaning composition Circulation fans were turned on for 5 minutes and then turned off Within 1/2 hour of 20 mopping two groups each consisting of 20 test panelists vsere asked to enter one of the rooms, stay in the room for 45 seconds, and then exit the room Subsequently, each panelist was asked to evaluate the scent emanated by the floor, and remain outside of both test rooms in order to allow for their nasal passages to clear and become accustomed to the ambient Afterwards, the members of the group were asked to enter the other of the two rooms, again stay in the room for 45 seconds, exit the 25 room, and evaluate the scent emanated b> the floor in the room just visited
After a time interval of 7 hours after mopping, and again after a 24 hour interval after mopping, cach of the members of the groups repeated the above protocol, and again evaluated the scent emanated by the two treated flooring surfaces at these two later time periods In such a manner a meaningful evaluation of the relative pine scent, especially after the longer time periods of 7 and 24 30 hours after application could be obtained, and compared to a presently commericallv available pine oil type cleaning composition
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Table 6 - Scent Duration Characteristics
Cleaning Composition 1 part formulation 64 parts water
Strength of pine scent
1/2 hour after application
Strength of pine scent
7 hours after application
Strength of pine scent
24 hours after application
C1
44%
16%
33%
E1
56%
84%
67%
Thc numbers indicated on Table 6, as well as graphically illustrated on Figure 1 tlie total percentages of the group who indicated preference for one formulation's scent over that of the other As tan be seen while the results following the first one-half hour following application are not 5 dissimilar, the strength of the pine oil scent left by the formulations according to the invention as exemplified by El are significantly stronger, and exhibit a greater duration than that of the prior art formulation CI Evaluation of Ocular Irritation
The occular irritation characteristics of formulations according to the invention were 10 evaluated using the known Draize Eye test protocol Evaluation was performed on a formulation according to Example E7 of Table 1 above in an "as is' composition, namely without any further dilution As known the Draize Eye Test measures eye irritation for the grading of severity of ocular lesions with separate scores obtained for the cornea, iris and conjunctiva For the comca, after exposure 1o the composition, A the comca opacity is grated on a scale from 1-4, B the area of cornea 15 involved is graded on a scale from 1-4 (when, the scon. = A x B \ 5 may be a total maximum of 80)
For evaluation of the iris, after exposure the composition, A the involvement of the iris is graded on a scale of 1-2 (where the score = A \ 5 may be a total maximum of 10) For a evaluation of the conjunctive, A Redness is graded on a scale of 1-3, B Chemosis is graded on a scale of 1-4, and C Discharge is measured on a scale of 1-3 [where the scorc = (A + B + C) x 2 may be a maximum of 20 20J The maximum total scorc is the sum of all scores obtained for the comea, iris and conjunctive (a maximum of 110)
The Draize test score on day 1 of the test was 19 33, and it was further observed that all signs of opacity cleared in all of the 6 subjects by day 7 of the test although conjunctival irritation was observed in 1 of the 6 test subjects by day 7 The Draize score on day 7 of the test was 0 33 By day 25 14, all signs of any irritation, opacity or conjunctival irritation was observed to have cleared The results of the Draize test indicated than an EPA Tox Category "0" was appropriate That these results were achieved with a product known to have a significant content of constituents which individuallv considered are known irritants was particularly surprising
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