EP0842248B1 - Milchige reinigungs- und/oder desinfektionsmittelzusammensetzungenfür harte oberflächen. - Google Patents

Milchige reinigungs- und/oder desinfektionsmittelzusammensetzungenfür harte oberflächen. Download PDF

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Publication number
EP0842248B1
EP0842248B1 EP96926853A EP96926853A EP0842248B1 EP 0842248 B1 EP0842248 B1 EP 0842248B1 EP 96926853 A EP96926853 A EP 96926853A EP 96926853 A EP96926853 A EP 96926853A EP 0842248 B1 EP0842248 B1 EP 0842248B1
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EP
European Patent Office
Prior art keywords
ammonium
alkyl
pine oil
water
composition according
Prior art date
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EP96926853A
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English (en)
French (fr)
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EP0842248A1 (de
Inventor
Alan Francis Richter
Frederic Albert Taraschi
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Reckitt Benckiser LLC
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Reckitt Benckiser LLC
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Priority claimed from GB9516072A external-priority patent/GB2304111A/en
Priority claimed from GB9516081A external-priority patent/GB2304112A/en
Application filed by Reckitt Benckiser LLC filed Critical Reckitt Benckiser LLC
Publication of EP0842248A1 publication Critical patent/EP0842248A1/de
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0084—Antioxidants; Free-radical scavengers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/65—Mixtures of anionic with cationic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/66—Non-ionic compounds
    • C11D1/72—Ethers of polyoxyalkylene glycols
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/94—Mixtures with anionic, cationic or non-ionic compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2068—Ethers
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/48—Medical, disinfecting agents, disinfecting, antibacterial, germicidal or antimicrobial compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/50—Perfumes
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/06—Ether- or thioether carboxylic acids
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/02—Anionic compounds
    • C11D1/04—Carboxylic acids or salts thereof
    • C11D1/08—Polycarboxylic acids containing no nitrogen or sulfur
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/38—Cationic compounds
    • C11D1/62—Quaternary ammonium compounds
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
    • C11D1/88—Ampholytes; Electroneutral compounds
    • C11D1/90—Betaines

Definitions

  • the present invention is directed to improved hard surface cleaning compositions and concentrates thereof, which feature blooming when the concentrate is added to a larger volume of water.
  • Cleaning compositions are commercially important products and enjoy a wide field of utility in assisting in the removal of dirt and grime from surfaces, especially those characterized as useful with "hard surfaces".
  • One particular category of cleaning compositions are those which are classed as pine oil type cleaning compositions which typically contain a significant amount, e.g, 5%wt. of naturally derived and/or synthetically produce pine oils. Such compositions generate a milky or cloudy appearance when diluted with water in dilutions useful for cleaning applications, and are generally provided as concentrated composition which is subsequently diluted with water by an end user/consumer 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 attendant shortcomings.
  • pine oil in a cleaning composition are known to leave undesirable surface residues, particularly on hard surfaces.
  • pine oils require the inclusion of surfactants which are useful in solubilizing and stabilizing the pine oil.
  • surfactants which are useful in solubilizing and stabilizing the pine oil.
  • the pine oil itself are categorized as undesired volatile organic compounds ("VOC").
  • VOC undesired volatile organic compounds
  • This blooming effect (also sometimes referred to as "break" in the United Kingdom and in other countries) is an important indicia for consumer acceptance for certain products, those which traditionally use pine oil to providing the 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.
  • compositions which exhibit blooming when added to a larger volume of water, but which may be selectively imparted with any of a number of different appearances 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 concentrated cleaning and/or disinfecting compositions which exhibit blooming when diluted in water.
  • the concentrate compositions contain no pine oil or pine oil fraction (such as a terpineol fraction) in any significant amount, other than minor amounts such a might be used in a fragrance constituent, 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 disinfecting concentrate compositions which comprise the following constituents which provide a "blooming system" which may be incorporated in these compositions:
  • the concentrate compositions may include further optional constituents which do not undesirably reduce or which diminish 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, chelating agents, germicidal compositions including those based on phenolic compounds, as well as other conventional additives.
  • further surfactants including anionic, cationic, nonionic, zwitterionic and/or amphoteric as well as mixtures thereof
  • organic solvents such as lower alkyl alcohols, lower alkyl diols and glycol ethers
  • fragrances such as one or more fragrances
  • coloring agents such as chelating agents
  • germicidal compositions including those based on phenolic compounds, as well as other conventional additives.
  • compositions 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 fragrance materials especially those which provide a pine type scent may be 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 cleaning composition which has the physical appearance and blooming characteristic of a conventional pine oil type cleaning composition may be provided without the presence of pine oil.
  • blooming type cleaning and/or disinfecting compositions may be produced such as by including different fragrances, i.e., those characteristic of lemon, various flora, in conjunction with a desired coloring additives, i.e., green, yellow, amber, red, etc. may be added as desired.
  • a blooming type cleaning and/or disinfecting compositions may produced. "Blooming" 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.
  • the lack of the overall amounts of pine oil typically found in prior art pine oil type cleaning concentrates, as well as the necessary compatibilizing agents required to solubilize the pine oil in such prior art cleaning concentrate provides the benefits of reduced volatile organic content of a concentrate or cleaning composition, as well as reduces the propensity of such compositions to form undesirable residues, especially pine oil residues upon cleaned surfaces.
  • compositions according to this second aspect of the invention comprises the following constituents on a percentage weight basis based on a 100%wt. concentrate composition:
  • compositions according to the invention may include further optional constituents which do not undesirably reduce or which diminish 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, chelating agents, germicidal compositions including those based on phenolic compounds, as well as other conventional additives.
  • further surfactants including anionic, cationic, nonionic, zwitterionic and/or amphoteric as well as mixtures thereof
  • organic solvents such as lower alkyl alcohols, lower alkyl diols and glycol ethers
  • fragrances such as one or more fragrances
  • coloring agents coloring agents, chelating agents
  • germicidal compositions including those based on phenolic compounds, as well as other conventional additive
  • the concentrate compositions according to the second aspect of the invention exhibit the desired "blooming" characteristic of pine oil type cleaners, 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 preferred embodiments also provide a germicidal effect in both concentrate composition, and in cleaning composition dilutions.
  • compositions according to this second aspect of the invention comprises the following constituents on a percentage weight basis based on a 100%wt. concentrate composition:
  • concentrate compositions according to the preferred aspect of the invention may include the same further optional constituents described in conjunction with the second aspect of the invention noted above.
  • 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 preferred embodiments also provide a germicidal effect.
  • the at least one cationic quaternary ammonium surfactant useful in forming the blooming system according to 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 quarternary ammonium compounds and salts thereof. These include quarternary ammonium germicides which may be characterized by the general structural formula: where at least one or R 1 , R 2 , R 3 and R 4 is a hydrophobic, aliphatic, aryl aliphatic or aliphatic aryl radical of from 6 to 26 carbon atoms, and the entire cation portion of the molecule has a molecular weight of at least 165.
  • the hydrophobic radicals may be long-chain alkyl, long-chain alkoxy aryl, long-chain alkyl aryl, halogen-substitued long-chain alkyl aryl, long-chain alkyl phenoxy alkyl, aryl alkyl, etc.
  • the remaining radicals on the nitrogen atoms other than the hydrophobic radicals are substituents of a hydrocarbon structure usually containing a total of no more than 12 carbon atoms.
  • the radicals R 1 , R 2 , R 3 and R 4 may be straight chained or may be branched, but are preferably straight chained, and may include one or more amide or ether linkages.
  • 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 benzyl ammonium bromide, N-alkyl pyridinium halides such as N-cetyl pyridinium bromide, and the like.
  • quarternary ammonium salts include those in which the molecule contains either amide or ether linkages such as octyl phenoxy ethoxy ethyl dimethyl benzyl ammonium chloride, N-(laurylcocoaminoformylmethyl)-pyridinium chloride, and the like.
  • quarternary ammonium compounds which are useful as germicides include those in which the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
  • the hydrophobic radical is characterized by a substituted aromatic nucleus as in the case of lauryloxyphenyltrimethyl ammonium chloride, cetylaminophenyltrimethyl ammonium methosulfate, dodecylphenyltrimethyl ammonium methosulfate, dodecylbenzyltrimethyl ammonium chloride, chlorinated dodecylbenzyltrimethyl ammonium chloride, and the like.
  • Preferred 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: wherein R 2 and R 3 are the same or different C 8 -C 12 alkyl, or R 2 is C 12-16 alkyl, C 8-18 alkylethoxy, C 8-18 alkylphenolethoxy and R 3 is benzyl, and X is a halide, for example chloride, bromide or iodide, or methosulfate.
  • the alkyl groups recited in R 2 and R 3 may be straight chained or branched, but are preferably substantially linear.
  • Such quartenary germicides are usually sold as mixtures of two or more different quartenaries, such as BARDAC® 205M, (presently 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.
  • BARDAC® 205M presently commercially available from Lonza, Inc., Fairlawn, NJ
  • a further useful quarternary germicide is CYNCAL® 80% (presently commercially available from Hilton Davis Chemical Co., Cincinnati, OH) which is believed to comprise 80% by weight of an alkyl dimethyl benzylammonium chloride (50% C14, 40% C12 and 10% C16 alkyl), 10% water and 10% ethanol.
  • Further useful quarternary 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).
  • quarternary ammonium germicides of the alkyl dimethyl benzylammonium chloride type containing the same alkyl dimethyl benzylammonium chloride mixture as that of CYNCAL® and which are generally referred to as quarternium salts include BARQUAT® MB-80, (presently commercially available from Lonza, Inc., Fairlawn, NJ) which is believed to be and 80% by weight solution (20% ethanol) of the quarternary, HYAMINE® 1622 believed to be an aqueous solution of benzethonium chloride, and HYAMINE® 3500, which is believed to be a 50% aqueous solution of the quarternary ( both presently commercially available from Lonza Inc., Fairlawn, NJ).
  • BARQUAT® MB-80 (presently commercially available from Lonza, Inc., Fairlawn, NJ) which is believed to be and 80% by weight solution (20% ethanol) of the quarternary
  • HYAMINE® 1622 believed to be
  • 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 appearance in concentrated solution, but which exhibit blooming when diluted with further water to form a cleaning composition.
  • the addition of the preferred cationic quaternary ammonium surfactants which exhibits germicidal activity are included in preferred 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 corresponding increase in the amount of the anionic component used in a blooming system as noted above.
  • At least one anionic carboxylated alcohol alkoxylate surfactant there may also be included at least one anionic carboxylated alcohol alkoxylate surfactant.
  • This anionic surfactant which has been found to be effective in forming a water insoluble or poorly miscible complex when mixed with the quaternary ammonium compound described above, which due to said insolubility or poor miscibility of the formed complex, renders an aqueous mixture containing the anionic carboxylated alcohol alkoxylate surfactant and the quaternary ammonium compound such an aqueous mixture turgid, milky or cloudy.
  • R is a hydrophobic group, more preferably a C 6 -C 18 alkyl group
  • n is a number in the range of 1 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
  • Certain anionic surfactants according to the immediately preceeding general formula are presently commercially available as the PolyTergent® C series of anionic surfactants from the Olin Chem. Co., (Stamford, CT). Particularly preferred amongst these are the PolyTergentTM CS-1 compounds which is believed to be in accordance with the formula above wherein R is a C 6 -C 18 alkyl group, X and Y are independently H, CH 3 or the succinic acid radical with at least one succinic acid radical being present, and where Z is H. Also useful is PolyTergentTM C9-62P a further carboxylated alcohol alkoxylate surfactant also available from the Olin Chemical Co.
  • anionic surfactants While not particularly enumerated here may also find use in the present inventive compositions, as well as mixtures of one or more anionic surfactants.
  • a carboxylated alcohol alkoxylate may be present in any amount which is found to exhibit the desirable characteristics of the invention, that of a relatively clear appearance 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.
  • the pendant carboxylic acid or carboxylic acid moieties of the preferred species of anionic surfactants effectively complex with the quarternary ammonium in the quartemary ammonium compound 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 constitute part of the preferred anionic surfactants.
  • 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 surfactants.
  • Such solubilization effectively restores the clear appearance of the aqueous mixture containing the cationic and anionic surfactants.
  • anionic surface active agents having a first functional portion or group effective in forming a complex with the quarternary ammonium compound in water, and which has a second functional portion or group which is hydrophobic 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.
  • the blooming system may include a surfactant compatibilizing agent which solubilizes the at least one cationic quaternary ammonium surfactant and the at least one anionic carboxylated alcohol alkoxylate surfactant may be any known art material which exhibits the properties described above.
  • surfactant compatibilizing agents are believed to be determinable by routine experimental techniques, such as by providing a volume of water having mixed therein amounts of the cationic quaternary ammonium surfactant compound and the anionic carboxylated alcohol alkoxylate surfactant compound which renders the volume of water to be non-transparent, especially turgid or milky in appearance, and adding thereto an amount of a compound or composition which may be used to compatibilize the anionic and cationic surfactant 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.
  • 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.
  • Nonlimiting examples of such useful salts include: NaCI, MgCl 2 , NaHCO 3 , Na 2 CO 3 , NH 4 Cl.
  • a further class of useful surfactant compatabilizing agents include certain amphoteric surfactants.
  • Useful amphoteric surfactants include betaine compounds which exhibit the following general formula: wherein R is a hydrophobic group selected from the group selected from alkyl groups containing from about 10 to about 22 carbon atoms, preferably from about 12 to about 18 carbon atoms, alkylaryl and arylalkyl groups containing a similar number of carbon atoms with a benzene ring being treated as equivalent to about 2 carbon atoms, and similar structures interrupted by amido or ether linkages; each R 1 is an alkyl group containing from 1 to about 3 carbon atoms; and R 2 is an alkylene group containing from 1 to about 6 carbon atoms.
  • betaines examples include lauramidopropyl betaine, a commercial preparation of 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).
  • effective amounts of the surfactant compatabilizing agent may be any amount which, when included in the blooming systems compatibilize in the concentrate composition dilution the least one cationic quaternary ammonium surfactant and the at least one anionic carboxylated alcohol alkoxylate surfactant, but do not diminish the blooming characteristic of the concentrate composition when it is added to water.
  • the surfactant compatibilizing agent may be present in any effective amount, and good compatibilizing behaviour has been observed with amounts of 10% by weight and less, with preferred amounts being 0.01 - 6% by weight of the compatibilizing agent..
  • 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.
  • nonionic surfactants which are characterized 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 composition, i.e., absent the pine oil discussed herein.
  • 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 compositions presently commercially available from the Shell Chemical Company, (Houston, TX) under the general trade name Neodol®, which are described to be linear alcohol ethoxylates. Of these, those exhibiting a cloud point of 20°C or less may be used.
  • 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 described to be secondary alcohol ethoxylates. Again, those exhibiting a cloud point of 20°C and less may be used.
  • 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 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.
  • compositions include: Igepal® CA-210 which is described as an ethoxylated 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 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.
  • 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.
  • a test method for effectively determining which nonionic surfactants may be used in the compositions of the invention is as follows: to a clean beaker or other glass vessel is added 99 parts by weight of deionized water 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 appearance 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 according to this aspect of the invention.
  • 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 interfere with the operation of one or more constituents of the blooming system, as well as any other optional components of the liquid concentrates according to the invention.
  • 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.
  • 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 important constituent of pine oil are terpene alcohols, especially alpha-terpineol.
  • the pine oil generally comprises at least about 60% terpene alcohols, especially alpha-terpineol.
  • Glidco® Pine OilTM 60 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 60% terpene alcohols
  • Glidco® Pine Oil 60 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 60% terpene alcohols
  • Glidco® Pine Oil 140 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 70% terpene alcohols
  • Glidco® Pine Oil 80 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 80% terpene alcohols
  • Glidco® Pine Oil 150 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 85% terpene alcohols
  • Glidco® Terpene SW available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 75% terpene alcohols
  • Glidco® Terpineol 350 available from Glidco Organics Corp., Jacksonville, FL, believed to contain approximately 100% terpen
  • the pine oil constituent 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 percentages of the constituents described, the weight percentages are indicative of the weight percentages of the actives in a constituent containing preparation.
  • pine oil solubilizing agents include certain nonionic alkoxylated linear alcohol surfactants which aid in the dissolution of the pine oil in the water of the concentrate composition.
  • 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 "PolyTergent®". Particular members of this product line which have been found useful include; PolyTergent® SL-42 and PolyTergent® SL-62.
  • Further useful nonionic surfactants include alkoxylated linear secondary alcohols, as well as alkoxylated alkylphenolic nonionic surfactants. Such nonionic surfactants also provide a detersive effect to the compositions.
  • pine oil solubilizing agents include C 1 -C 8 alcohols, especially C 1 -C 3 alcohols, of which isopropanol is preferred.
  • pine oil solubilizing agents are included in effective, often minor amounts, with specific preferred weight proportions having been described previously.
  • compositions according to the invention in many cases which comprise any of a number of further optional constituents which do not undesirably reduce or which diminish 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, chelating agents, antioxidants, germicidal compositions including those based on phenolic compounds, as well as other conventional additives.
  • Such further optional constituents may be included in amounts found not to substantially interfere or detract from the blooming characteristics provided by the invention.
  • Known surfactants which provide a further detersive effect to the concentrate compositions and especially to the cleaning compositions formed therefrom may be where such do not substantially interfere or detract from the blooming characteristics provided by the invention, and further desirably do diminish the germicial nature of the preferred cationic quaternary ammonium 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 surfactants 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 structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • 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 structure an alkyl group containing from about 10 to about 20 carbon atoms and a sulfonic acid or sulfuric acid ester group.
  • alkyl is the alkyl portion of aryl groups.
  • alkylsulfates especially those obtained by sulfating the higher alcohols (C 8 -C 18 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.
  • linear straight chain alkylbenzene sulfonates in which the average number of carbon atoms in the alkyl group is from about 11 to 14.
  • anionic surfactants herein are the water soluble salts of: paraffin sulfonates containing from about 8 to about 24 (preferably about 12 to 18) carbon atoms; alkyl glyceryl ether sulfonates, especially those ethers of C 8-18 alcohols (e.g., those derived from tallow and coconut oil); alkyl phenol ethylene oxide ether sulfates containing from about 1 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 containing about 1 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 ⁇ -sulfonated fatty acids containing 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 containing 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 ⁇ -alkyloxy alkane sulfonates containing from about 1 to 3 carbon atoms in the alkyl group and from about 8 to 20 carbon atoms in the alkane moiety.
  • anionic surfactants as it is known to the art that many anionic form insoluble complexes with cationic quaternary ammonium surfactants, 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 that provide a further detersive effect to the concentrate compositions and cleaning compositions formed therefrom.
  • 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.
  • the length of the polyethenoxy hydrophobic and hydrophilic elements may various.
  • 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.
  • nonionic surfactants are alkoxylated linear primary and secondary alcohols such as those commercially available under the tradenames PolyTergent® SL series (Olin Chemical Co., Stamford CT), Neodol® series (Shell Chemical Co., Houston TX); 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 other nonionic surfactants described above.
  • organic solvents which may be useful in providing a further cleaning benefit, especially in the loosening of stains may be added to the concentrate compositions of the invention. Such should be selected and be present in amounts which do not substantially interfere 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 C 1 -C 8 alchols as well as the water miscible C 1 -C 8 diols examples of which include methanol, ethanol, propanol, isopropanol, butanol including t-butanol.
  • Exemplary glycol ethers water miscible glycol ethers including those having the general structure R a -O-R b -OH, wherein R a is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms, and R b is an ether condensate of propylene glycol and/or ethylene glycol having from one to ten glycol monomer units.
  • R a is an alkoxy of 1 to 20 carbon atoms, or aryloxy of at least 6 carbon atoms
  • R b 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 C 3 -C 20 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, propylent glycol dimethylether, as well as lower esters of monoalkylethers of ethyleneglycol or propylene glycol such as. propylene glycol monomethyl ether acetate. Such are commercially available from Union Carbide, Dow Chemicals 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 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 preferred and may for example be obtained by distilling orange rind oil.
  • Such a 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.
  • a stabilizer such as an antioxidant material, such as butylated hydroxytoluene.
  • 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.
  • a stabilizer such as an antioxidant material, such as butylated hydroxytoluene.
  • fragrances natural or synthetically produced containing synthetic fragrance compositions, especially those which are intended to mimic the scent of one or more resins or oils derived from coniferous species of trees, viz., a scent characteristic 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 concentrate compositions and care should be exercised so as not to undesirably inhibit the operation of the blooming system according to the invention and as described above.
  • fragrances may be added in any conventional manner, admixing to a concentrate composition or blending with other constituents used to form a concentrate composition, in amounts which arc found to be useful to enhance or impart the desired scent characteristic to the concentrate composition, and/or to cleaning compositions formed therefrom. However, they should not be included in excessive amounts.
  • constituents are one or more coloring agents which find use in modifying the appearance of the concentrate compositions and enhance their appearance from the perspective of a consumer or other end user.
  • coloring agents may be incorporated in the compositions in effective amount to improve or impart to concentrate compositions an appearance 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 composition, or other colors may also be included.
  • Such a coloring agent or coloring agents may be added in any useful amount in a conventional fashion, i.e., admixing to a concentrate composition or blending with other constituents used to form a concentrate composition.
  • Still further conventional additives which may be included are one or more hydrotopes such as sodium toluene sulfonate and sodium cumene sulfonate; one or more antibacterial agents such as orthobenzyl-para-chlorophenol although in preferred embodiments wherein the cationic quaternary ammonium compound has germicidal activity a further antibacterial 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 0.15%wt of the concentrate composition, but desirably even less.
  • 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.
  • concentrate and “concentrate composition” in this specification and claims is the pre-consumer dilution and composition of the cleaning composition which is the essentially the form of the product prepared for sale to the consumer 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 without any further dilution and it may be used in the concentrations in which it was prepared for sale.
  • cleaning compositions are the water diluted compositions which are expected to be prepared by the consumer or other end user by mixing a measured amount of the "concentrate” with water in order to form an appropriately diluted cleaning composition which is suitable for use in cleaning applications, especially in the cleaning of hard surfaces.
  • the formulations according to any of the aspects of the invention described above include both cleaning compositions and concentrates as outlined above which differ only in the relative proportion of water to that of the other constituents forming such formulations. While the concentrated form of the cleaning compositions find use in their original form, they are more frequently used in the formation of a cleaning composition therefrom. Such may be easily prepared by diluting measured amounts of the concentrate compositions in water by the consumer or other end user in certain weight ratios of concentrate:water, and optionally, agitating the same to ensure even distribution of the concentrate in the water. As noted, the concentrate may be used without dilution, i.e., in concentrate:water concentrations of 1:0, to extremely dilute dilutions such as 1:10,000.
  • the concentrate is diluted in the range of 1:0.1 - 1:1000, preferably in the range of 1:1 - 1:500 but most preferably in the range of 1:10 - 1:100.
  • 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.
  • Neodol® 91-2.5 a nonionic surfactant composition based on linear alcohol ethoxylates was evaluated according to the following protocol. 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 1 part by weight (by weight of the actives) of a Neodol® 91-2.5 composition. This test sample was stirred and the sample was immediately observed to be murky or cloudy in appearance. 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 compositions according to the third aspect of the invention.
  • 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 1 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 appearance. The sample was allowed to drop to 20°C and no change in its appearance was noted.
  • the surfactant composition was considered not to be useful as as the nonionic surfactant in the third aspect of the inventon.
  • Exemplary concentrate composition formulations according to the first aspect of the invention were prepared in accordance with the following general procedure.
  • the following constituents were added in the sequence: water, cationic and anionic surfactant compositions of the blooming system, the sufactant compatibilizing agent, and then any remaining constituents. All of the constituents were supplied at room temperature, and mixing of the constituents was achieved by the use of a magnetic stirrer. These constituents were used "as is” as supplied from their respective supplier. Mixing, which generally lasted from 1 minute to 5 minutes, was maintained until the formulation attained uniform color and uniform clarity. The example formulations were readily pourable, and retained well mixed characteristics indicative of stability.
  • 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.
  • the following constituents were added in the sequence: water, pine oil, nonionic surfactants, other surfactants, pine oil solubilizing agent, and if present BTC-8358®, a quarternary ammonium compound preparation. All of the constituents were supplied at room temperature (approximately 20°C), mixing of the constituents was achieved by the use of a magnetic stirrer. Stirring, which generally lasted from approximately 2 minutes to approximately 5 minutes continued and was maintained while the particular formulation attained uniform color and uniform clarity or translucency. Each of the formulations exhibited the following physical characteristics: transparent appearance, light to medium yellowish amber color, and an appreciable pine oil odor. The exemplary compositions were readily pourable, and retained well mixed characteristics, demonstrating excellent shelf stability.
  • Neodol® 91-2.5 is a nonionic surfactant composition 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 > 20°C available from Shell Chemical Co., Houston TX.
  • MackamTM DZ is a surfactant composition containing cocoamidopropyl betaine
  • formulation designated as “Comp.1” is 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.1C”, “Ex.2C” are formulations demonstrating the blooming feature according to the present invention, and considered with in the present inventive scope. Each of these formulations appeared to be translucent and varying little in color.
  • Each of the example formulations 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 1 into 63 parts by weight of tap water (1:64 by weight dilution) at 20°C and in some instances at 40°C.
  • aqueous dilutions were prepared to evaluate the degree of light transmittance, a measure of the opacity as well as of the blooming of each of the aqueous dilutions. Certain of these aqueous dilutions were also evaluated to determine the antimicrobal efficacy of the aqueous dilution.
  • the results of the light transmittance evaluation was determined as a percentage of light transmitted through a sample of a particular aqueous dilution wherein the transmisson of a like sample of water is assigned a percentage of 100%. Testing was performed by mixing a 5g aliquot of a particular example formulation with 315 g of tap water (with approx.
  • the formulations according to the invention provided excellent blooming characteristics, although containing little or no pine oil in their formulations.
  • the absence of pine oil, or its presence in reduced amounts also required a substantial 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.
  • the exemplary formulations featured good blooming behaviour as cleaning composition, but were substantially clear in the form of concentrate compositions.

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Claims (13)

  1. Wässrige, bei Verdünnung schleierartige Wolken bildende Reinigungszusammensetzung für harte Oberflächen, umfassend:
    A) 0,1 bis 4 Gew.-% einer Pinienölzubereitung, welche mindestens etwa 60 Gew.-% alpha-Terpineol enthält;
    B) 0,1 bis 10 Gew.-% eines nichtionischen, oberflächenaktiven Mittels, welches einen Trübungspunkt von 20 °C oder weniger aufweist, ausgewählt aus Kondensationsprodukten eines oder mehrerer Alkylenoxidreste mit einer organischen, hydrophoben, aliphatischen Verbindung oder mit einer organischen, hydrophoben, alkylaromatischen Verbindung;
    C) 0,1 bis 15 Gew.-% eines Lösungsvermittlers für Pinienöl, ausgewählt aus C1-8-Alkoholen und C1-8-Alkylenglycolen; und
    D) Wasser.
  2. Zusammensetzung gemäß Anspruch 1, wobei;
    B) ein oberflächenaktives Mittel auf Basis eines nichtionischen, alkoxylierten, primären Alkohols oder alkoxylierten, sekundären Alkohols ist, welches einen Trübungspunkt von 20 °C oder weniger aufweist.
  3. Zusammensetzung gemäß Anspruch 1, welche ferner eine keimtötend-wirkende Menge einer quartären Ammoniumverbindung umfasst, gemäß der Formel:
    Figure 00270001
    wobei mindestens einer der Reste R1, R2, R3 und R4 ausgewählt ist aus einem hydrophoben, aliphatischen, arylaliphatischen oder aliphatischen Arylrest mit 6 bis 26 Kohlenstoffatomen, und alle übrigen Reste R1, R2, R3 und R4 Kohlenwasserstoffreste mit 1 bis 12 Kohlenstoffatomen sind, wobei alle Reste R1, R2, R3, und R4 linear oder verzweigt sein können und eine oder mehrere Ester- oder Amidbindungen enthalten können; und X ein salzbildender, anionischer Rest ist.
  4. Zusammensetzung gemäß Anspruch 3, wobei die quartäre Ammoniumverbindung eine Verbindung der Formel
    Figure 00280001
    wobei R2 und R3 gleiche oder verschiedene C8-12-Alkylreste sind oder R2 ein C12-16-Alkylrest ist und R3 eine Benzylgruppe ist und X ein Halogenid oder Methylsulfat ist, ist.
  5. Zusammensetzung gemäß Anspruch 4, wobei die quartäre Ammoniumverbindung ausgewählt ist aus Cetyltrimethylammoniumbromid, Alkylarylammoniumhalogeniden, N-Alkylpyridiniumhalogeniden, Octylphenoxyethoxyethyldimethylbenzylammoniumchlorid, N-(Laurylcocoaminoformylmethyl)-pyridiniumchlorid, Octadecyldimethylbenzylammoniumbromid, N-Cetylpyridiniumbromid, Lauryloxyphenyltrimethylammoniumchlorid, Cetylaminophenyltrimethylammoniummethylsulfat, Dodecylphenyltrimethylammoniummethylsulfat, Dodecylbenzyltrimethylammoniumchlorid, chloriertem Dodecylbenzyltrimethylammoniumchlorid und quartären Ammoniumverbindungen, welche einen hydrophoben Rest enthalten, welcher einen substituierten, aromatischen Kern enthält.
  6. Wässrige, bei Verdünnung schleierartige Wolken bildende Reinigungszusammensetzung für harte Oberflächen, umfassend:
    A) 0,1 bis 4 Gew.-% einer Pinienölzubereitung, welche mindestens etwa 60 Gew.-% alpha-Terpineol enthält;
    B) 0,1 bis 10 Gew.-% eines nichtionischen, oberflächenaktiven Mittels, welches einen Trübungspunkt von 20 °C oder weniger aufweist, ausgewählt aus Kondensationsprodukten eines oder mehrerer Alkylenoxidreste mit einer organischen, hydrophoben, aliphatischen Verbindung oder mit einer organischen, hydrophoben, alkylaromatischen Verbindung;
    C) 0,1 bis 15 Gew.-% eines Lösungsvermittlers für Pinienöl, ausgewählt aus C1-8-Alkoholen und C1-8-Alkylenglycolen;
    D) Wasser; und
    E) eine keimtötend-wirkende Menge einer quartären Ammoniumverbindung gemäß der Formel:
    Figure 00290001
    wobei mindestens einer der Reste R1, R2, R3 und R4 ausgewählt ist aus einem hydrophoben, aliphatischen, arylaliphatischen oder aliphatischen Arylrest mit 6 bis 26 Kohlenstoffatomen, und alle übrigen Reste R1, R2, R3 und R4 Kohlenwasserstoffreste mit 1 bis 12 Kohlenstoffatomen sind, wobei alle Reste R1, R2, R3, und R4 linear oder verzweigt sein können und eine oder mehrere Ester- oder Amidbindungen enthalten können; und X ein salzbildender, anionischer Rest ist.
  7. Zusammensetzung gemäß Anspruch 6, wobei
    B) ein oberflächenaktives Mittel auf Basis eines nichtionischen, alkoxylierten, primären Alkohols oder alkoxylierten, sekundären Alkohols ist, welches einen Trübungspunkt von 20 °C oder weniger aufweist.
  8. Zusammensetzung gemäß Anspruch 7, wobei die quartäre Ammoniumverbindung eine Verbindung der Formel
    Figure 00290002
    wobei R2 und R3 gleiche oder verschiedene C8-12-Alkylreste sind oder R2 ein C12-16-Alkylrest ist und R3 ein Benzylrest ist und X ein Halogenid oder Methylsulfat ist, ist.
  9. Zusammensetzung gemäß Anspruch 8, wobei die quartäre Ammoniumverbindung ausgewählt ist aus Cetyltrimethylammoniumbromid, Alkylarylammoniumhalogeniden, N-Alkylpyridiniumhalogeniden, Octylphenoxyethoxyethyldimethylbenzylammoniumchlorid, N-(Laurylcocoaminoformylmethyl)-pyridiniumchlorid, Octadecyldimethylbenzylammoniumbromid, N-Cetylpyridiniumbromid, Lauryloxyphenyltrimethylammoniumchlorid, Cetylaminophenyltrimethylammoniummethylsulfat, Dodecylphenyltrimethylammoniummethylsulfat, Dodecylbenzyltrimethylammoniumchlorid, chloriertem Dodecylbenzyltrimethylammoniumchlorid und quartären Ammoniumverbindungen, welche einen hydrophoben Rest enthalten, welcher einen substituierten, aromatischen Kern enthält.
  10. Zusammensetzung gemäß Anspruch 1, umfassend die flüssige Reinigungszusammensetzung auf Basis von Pinienöl gemäß Anspruch 1, welche in Wasser in einem Gewichtsverhältnis von Zusammensetzung zu Wasser von 1:0,1 bis 1:1000 dispergiert ist.
  11. Wässrige Reinigungszusammensetzung gemäß Anspruch 6, umfassend die flüssige Reinigungszusammensetzung auf Basis von Pinienöl gemäß Anspruch 1, welche in Wasser in einem Gewichtsverhältnis von Zusammensetzung zu Wasser von 1:0,1 bis 1:1000 dispergiert ist.
  12. Verfahren zur Reinigung einer harten Oberfläche, bei der eine derartige Behandlung notwendig ist, umfassend die Stufe der Verwendung einer Reinigungszusammensetzung gemäß Anspruch 1 in einer Menge, die zum Erzielen einer Reinigungsbehandlung wirksam ist.
  13. Verfahren zur Reinigung einer harten Oberfläche, bei der eine derartige Behandlung notwendig ist, umfassend die Stufe der Verwendung einer Reinigungszusammensetzung gemäß Anspruch 6 in einer Menge, welche zum Erzielen einer Reinigungsbehandlung wirksam ist.
EP96926853A 1995-08-04 1996-08-01 Milchige reinigungs- und/oder desinfektionsmittelzusammensetzungenfür harte oberflächen. Expired - Lifetime EP0842248B1 (de)

Applications Claiming Priority (5)

Application Number Priority Date Filing Date Title
GB9516072A GB2304111A (en) 1995-08-04 1995-08-04 Pine oil cleaning composition
GB9516072 1995-08-04
GB9516081A GB2304112A (en) 1995-08-04 1995-08-04 Pine oil cleaning compositions
GB9516081 1995-08-04
PCT/US1996/012613 WO1997006230A1 (en) 1995-08-04 1996-08-01 Blooming type, hard surface cleaning and/or disinfecting compositions

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EP0842248A1 EP0842248A1 (de) 1998-05-20
EP0842248B1 true EP0842248B1 (de) 2003-05-21

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Application Number Title Priority Date Filing Date
EP96926853A Expired - Lifetime EP0842248B1 (de) 1995-08-04 1996-08-01 Milchige reinigungs- und/oder desinfektionsmittelzusammensetzungenfür harte oberflächen.

Country Status (10)

Country Link
EP (1) EP0842248B1 (de)
CN (2) CN1087770C (de)
AR (1) AR003171A1 (de)
BR (1) BR9609984A (de)
CA (1) CA2228427A1 (de)
DE (1) DE69628302T2 (de)
ES (1) ES2195003T3 (de)
MX (1) MX9800987A (de)
NZ (1) NZ315213A (de)
WO (1) WO1997006230A1 (de)

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WO2023025575A1 (en) * 2021-08-26 2023-03-02 Unilever Ip Holdings B.V. A liquid disinfecting composition

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AU2025797A (en) * 1996-03-15 1997-10-10 Unilever Plc Cleaning gels
GB2320927B (en) * 1997-01-06 2001-04-18 Reckitt & Colman Inc Germicidal hard surface cleaner
GB2322552B (en) * 1997-03-01 2001-05-16 Reckitt & Colman Inc Liquid disinfectant concentrate
GB2331758B (en) 1997-11-28 2002-04-17 Reckitt & Colman Inc Disinfectant compositions
GB2331760B (en) * 1997-11-28 2002-05-15 Reckitt & Colman Inc Hard surface cleaning compositions
EP1034245B1 (de) * 1997-11-28 2003-09-17 Reckitt Benckiser Inc. Konzentriertes flüssiges reinigungsmittel für harte oberflächen
GB2331703B (en) * 1997-11-28 2002-01-23 Reckitt & Colman Inc Disinfectant compositions
GB9807657D0 (en) * 1998-04-14 1998-06-10 Reckitt & Colman Inc Improvements in or relating to organic compositions
GB2336375A (en) * 1998-04-14 1999-10-20 Reckitt & Colman Inc Liquid disinfectant composition
GB9807661D0 (en) * 1998-04-14 1998-06-10 Reckitt & Colman Inc Improvements in or relating to organic compositions
GB2336312B (en) * 1998-04-14 2003-05-21 Reckitt & Colman Inc Improvements in or relating to organic compositions
WO2000038523A1 (en) 1998-12-23 2000-07-06 Rhodia Consumer Specialties Limited Herbicidal compositions and surfactant concentrates
GB9901702D0 (en) * 1999-01-27 1999-03-17 Reckitt & Colman Inc Improvements in or relating to organic compositions
GB0209218D0 (en) * 2002-04-23 2002-06-05 Reckitt Benckiser Inc Improvements in or relating to organic compositions
GB0209198D0 (en) * 2002-04-23 2002-06-05 Reckitt Benckiser Inc Improvements in or relating to organic compositions
GB2393911A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Antimicrobial hard surface cleaner
GB2393907A (en) * 2002-10-12 2004-04-14 Reckitt Benckiser Inc Antimicrobial hard surface cleaner
MX2007008012A (es) 2004-12-30 2007-08-23 Rhone Poulenc Chimie Composicion herbicida que comprende una sal de aminofosfato o de aminofosfonato y una betaina.
RU2411726C2 (ru) 2005-11-14 2011-02-20 Родиа Инк. Сельскохозяйственная вспомогательная композиция, пестицидная композиция и способ для применения таких композиций
FR2914647B1 (fr) 2007-04-05 2011-10-21 Rhodia Recherches Et Tech Copolymere comprenant des unites betainiques et des unites hydrophobes et/ou amphiphiles,procede de preparation,et utilisations.
WO2012021164A2 (en) 2010-08-10 2012-02-16 Rhodia Operations Agricultural pesticide compositions

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Publication number Priority date Publication date Assignee Title
WO2023025575A1 (en) * 2021-08-26 2023-03-02 Unilever Ip Holdings B.V. A liquid disinfecting composition

Also Published As

Publication number Publication date
AR003171A1 (es) 1998-07-08
WO1997006230A1 (en) 1997-02-20
CN1087770C (zh) 2002-07-17
CN1159426C (zh) 2004-07-28
NZ315213A (en) 1999-11-29
BR9609984A (pt) 1999-01-12
ES2195003T3 (es) 2003-12-01
CN1346878A (zh) 2002-05-01
AU6687096A (en) 1997-03-05
CA2228427A1 (en) 1997-02-20
EP0842248A1 (de) 1998-05-20
DE69628302D1 (de) 2003-06-26
DE69628302T2 (de) 2004-04-01
CN1198772A (zh) 1998-11-11
AU700516B2 (en) 1999-01-07
MX9800987A (es) 1998-04-30

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