EP0137616B1 - Flüssige Detergentien mit einem Lösungsmittel - Google Patents

Flüssige Detergentien mit einem Lösungsmittel Download PDF

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Publication number
EP0137616B1
EP0137616B1 EP84305317A EP84305317A EP0137616B1 EP 0137616 B1 EP0137616 B1 EP 0137616B1 EP 84305317 A EP84305317 A EP 84305317A EP 84305317 A EP84305317 A EP 84305317A EP 0137616 B1 EP0137616 B1 EP 0137616B1
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EP
European Patent Office
Prior art keywords
solvent
compositions
alkyl
composition according
mixtures
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired
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EP84305317A
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English (en)
French (fr)
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EP0137616A1 (de
Inventor
Ivan Herbots
James Pyott Johnston
John Richard Walker
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Procter and Gamble European Technical Center
Procter and Gamble Co
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Priority claimed from GB838321682A external-priority patent/GB8321682D0/en
Priority claimed from GB838325105A external-priority patent/GB8325105D0/en
Priority claimed from GB848409052A external-priority patent/GB8409052D0/en
Application filed by Procter and Gamble European Technical Center, Procter and Gamble Co filed Critical Procter and Gamble European Technical Center
Priority to AT84305317T priority Critical patent/ATE32231T1/de
Publication of EP0137616A1 publication Critical patent/EP0137616A1/de
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Publication of EP0137616B1 publication Critical patent/EP0137616B1/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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0008—Detergent materials or soaps characterised by their shape or physical properties aqueous liquid non soap compositions
    • C11D17/0017—Multi-phase liquid compositions
    • C11D17/0021—Aqueous microemulsions
    • 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
    • C11D10/00—Compositions of detergents, not provided for by one single preceding group
    • C11D10/04—Compositions of detergents, not provided for by one single preceding group based on mixtures of surface-active non-soap compounds and soap
    • 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
    • C11D3/43—Solvents
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/14—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aliphatic hydrocarbons or mono-alcohols
    • 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
    • C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
    • C11D1/28—Sulfonation products derived from fatty acids or their derivatives, e.g. esters, amides
    • 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

Definitions

  • the present invention relates to compositions and processes for laundering fabrics which employ high levels of solvent to enhance the removal of greasy soils and stains.
  • the liquid compositions herein are provided in the form of clear, or substantially clear, homogeneous, stable emulsions which not only provide excellent pretreatment cleaning performance, but also exhibit improved detergency and fabric whiteness maintenance when used in an aqueous laundry liquor.
  • the compositions herein also are excellent for removing particulate soils from fabrics.
  • the compositions are formulated and stabilized at a pH in the range near neutrality to alkaline.
  • Citrus juices which contain relatively low amounts of terpenes, have been suggested for use in hand soaps and dish-washing liquids. US ⁇ A ⁇ 3,650,968, 1972; Memoire descriptif 873,051 (relating to GB-A-2010892).
  • Terpineols e.g. from pine oil
  • pine oil terpineol such as alpha terpineol and fatty acid soap or free acid neutralized in situ to alkaline pH.
  • EP-A-0 072 488 suggests that terpenes such as d-limonene can be incorporated into fabric pre-treating compositions as a non-homogeneous emulsion.
  • terpenes such as d-limonene
  • Such emulsions are apparently designed to be packaged in relatively small volume containers which can be shaken immediately prior to use to restore some semblance of homogeneity, then dispensed directly onto fabrics by spraying.
  • the present invention provides fully-formulated heavy duty liquid laundry detergents comprising as much as 20% by weight of essentially water-insoluble solvent, in the form of homogeneous, fatty acid-built liquids that are quite suitable for use in both the fabric pre-treatment and through-the-wash modes.
  • compositions are formulated as stable microemulsions at pH's of from 6.5 to 8.0.
  • the present invention provides a liquid detergent composition
  • a liquid detergent composition comprising an aqueous carrier, from 10% to 40% by weight of non-soap detersive surfactant, and from 5% to 20% by weight of grease-removal solvent comprising a non-polar solvent component selected from terpene and terpenoids, paraffins, halogenated hydrocarbons, C s -Cg alkyl aromatics, liquid olefins and mixtures thereof, characterized in that the composition comprises from 5% to 30% by weight of C 12 -C, S fatty acid or soap thereof and a microemulsion stabilizer, the stabilizer being a water-soluble high ionic strength ingredient selected from formate, sulfate or citrate salts, an ingredient soluble in the non-polar solvent and having an HLB (hydrophilic lipophilic balance) of from 2-5, a nitrogen-functional compound, or a mixture thereof, wherein the composition has a pH of from 6.5 to 8.0 and is in the form of a stable oil
  • solvents employed herein are well-known "degreasing" solvents commonly known for use in, for example, the commercial laundry and drycleaning industry, in the hard-surface cleaner industry and the metalworking industry.
  • solvents comprise hydrocarbon or halogenated hydrocarbon moieities of the alkyl or cycloalkyl type, and have a boiling point well above room temperature.
  • compositions of the present type will be guided in the selection of solvent partly by the need to provide good grease-cutting properties, and partly by aesthetic considerations.
  • kerosene hydrocarbons function quite well in the present compositions, but can be malodorous. Kerosene can be used in commercial laundries.
  • the formulator would be more likely to select solvents which have a relatively pleasant odor, or odors which can be reasonably modified by perfuming.
  • solvents include, for example, the terpenes and terpenoid solvents obtainable from citrus fruits, especially orange terpenes and d-limonene. Mixtures of orange terpene and benzyl alcohol are especially suitable for removing certain types of stains, e.g., marker ink, shoe polish, and dirty motor oil.
  • Excellent solvents for use herein are the paraffins and the mono- and bicyclic mono-terpenes, i.e., those of the hydrocarbon class, which include, for example, the terpinenes, limonenes and pinenes, and mixtures thereof.
  • Highly preferred materials of this latter type are d-limonene and the mixture of terpene hydrocarbons obtained from the essence of oranges (e.g. cold-pressed orange terpenes and orange terpene oil phase ex fruit juice).
  • terpenes such as dipentene, alpha-pinene, beta-pinene and the mixture of terpene hydrocarbons expressed from lemons and grapefruit.
  • Fatty acids such as lauric, myristic, palmitic, stearic and oleic acids, and poly-unsaturated fatty acids, as well as their water-soluble salts (i.e., "soaps") are employed in the present compositions to provide clear, homogeneous formulations containing the solvent and water.
  • Mixtures of fatty acids (or soaps) including palm oil acids, coconut oil acids, and the like, in the C12-C18 carbon chain length, can be used.
  • the concentration of fatty acid (or soap) is from 5% to 30%, and the weight ratio of fatty acid (or soap):solvent is preferably in the range of 4:1 to 1:4, more preferably 3:1 to 1:2.
  • the potassium and sodium salt forms are preferred, but any convenient water-soluble salt may be used.
  • these fatty acid/soap materials provide an important detergency builder function in the present compositions.
  • these fatty acid/soap materials provide an important detergency builder function in the present compositions.
  • compositions herein may properly be characterized as "water-based", in contrast with organic solvent-based cleaners known in the art.
  • water can interfere with the ability of solvents such as terpenes to remove greasy stains from fabrics.
  • solvents such as terpenes
  • a fabric stained with motor oil and dampened with water prior to treatment with neat terpene is not very well de-greased by the terpene, if at all.
  • the present compositions wherein non-polar solvent such as the terpenes are microemulsified in water are excellent greasy stain removers when used directly on dry or damp fabrics.
  • water-based heavy duty liquid detergents offer ease-of-formulation advantages with respect to ingredients such as most detergency builders, sanitiziers, chelants, soil-suspending agents, pH-control agents, and the like, which are usually water-soluble.
  • compositions herein exhibit the advantages of water-based formulation flexibility, together with the superior grease removal qualities of solvent-based compositions.
  • compositions generally comprise from 10% to 70%, preferably 20% to 50% water.
  • the weight ratio of water:solvent is generally 10:1 1 to 1:1, preferably 5:1 to 2:1.
  • detergent compositions As is well-known in the detergency arts, it is preferred for detergent compositions to be in the near-neutral to alkaline pH range, i.e., pH 6.5, and above. This is for a variety of reasons. For example, many soils are partly peptized or emulsified by alkalinity, itself. And, many commercially available detersive enzymes (e.g., the "alkaline proteases”) function optimally in alkaline laundering liquors.
  • formulation stability could theoretically be achieved by proper selection of surfactants (discussed hereinafter) with low HLB's.
  • nonionic surfactants such as C 14-15 alcohols with low ethoxylate numbers (1-3) could be used.
  • low HLB surfactants do not function well as detersive surfactants, and the object herein is not only to provide stable microemulsions, but also good pre-treat and through-the-wash detergency.
  • adding water-soluble, high ionic strength ingredients selected from formate, sulfate and citrate increases stability.
  • adding water-soluble, low ionic strength materials such as ethanol has no stabilizing effect.
  • ionic strength ingredients Conjointly adding the ionic strength ingredients and the solvent-soluble ingredients further enhances stability.
  • the formulator can select ingredients with a view towards not only increasing microemulsion stability, but also providing optimal cleaning benefits.
  • citrate as an ionic strength agent which also has detergency builder properties
  • formate as an ionic strength agent which also stabilizes detergent enzymes
  • n-hexanol or benzyl alcohol as a low HLB ingredient which also serves a useful grease-cutting function.
  • the amount of high ionic strength or low (2-5) HLB solvent-soluble ingredients, or both, used in the compositions will depend somewhat on the pH desired, the concentration of fatty acid, the level of grease-cutting solvent, the composition of the detersive surfactant system, and the like. Microemulsion stability can be monitored rather simply since the true microemulsions are clear, but turn hazy and non-homogeneous, with eventual phase separation at the point of instability.
  • any of the well-known base materials can be used to adjust pH to about 6.5 ⁇ 6.6; for example, triethanolamine, alkali metal hydroxide and the like. Potassium hydroxide is preferred over sodium hydroxide, inasmuch as the ease of formulation of stable systems is increased substantially by the potassium cation.
  • Magnesium hydroxide is another useful neutralizing base. During use, the magnesium cation is believed to associate with anionic surfactants present in the compositions to enhance their grease-removal performance.
  • compositions of this invention contain non-soap organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.
  • surfactants non-soap organic surface-active agents
  • Detersive surfactants useful herein include well-known synthetic anionic, nonionic, amphoteric and zwitterionic surfactants. Typical of these are the alkyl benzene sulfonates, alkyl- and alkylether sulfates, paraffin sulfonates, olefin sulfonates, alkoxylated (especially ethoxylated) alcohols and alkyl phenols, amine oxides, a-sulfonates of fatty acids and of fatty acid esters, and the like, which are well-known from the detergency art.
  • such detersive surfactants contain an alkyl group in the Cg-C '8 range;
  • the anionic detersive surfactants can be used in the form of their sodium, potassium or triethanolammonium salts but it is to be understood that the presence of magnesium cations in the compositions usually means that at least some portion of the anionic surfactant will be in the magnesium salt form;
  • the nonionics such as the ethoxylated alcohols and alkyl phenols generally contain from 5 to 17 ethylene oxide groups.
  • US-A-4.111.855 and US ⁇ A ⁇ 3.995.669 contain detailed listings of such typical detersive surfactants.
  • Cll-C,6 alkyl benzene sulfonates C, 2 -C, 8 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • Polyamine materials are optional ingredients in the present compositions by virtue of their ability to co-act with the solvent to remove the solid material that is present in many greasy stains (e.g., carbon-black in motor oil stain; clay and color bodies in cosmetic stain).
  • greasy stains e.g., carbon-black in motor oil stain; clay and color bodies in cosmetic stain.
  • polyamines as used herein represents generically the alkoxylated polyamines, both in their amine form and in their quaternarized form.
  • Such materials can conveniently be represented as m'olecules comprising at least 2, preferably from 2-20, most preferably 3-5 recurring units having the formula: Amine form and Quaternarized form wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R' may be a C 1 -C 20 hydrocarbon; the alkoxy groups are polyethoxy, polypropoxy, and the like, with polyethoxy having a degree of polymerization of 2-30, most preferably 10 to 20; and X e is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • the anion X e is of no particular consequence to performance of the polyamine in the present context, and is mentioned only for completeness in the above formula.
  • polyamines for use herein are the so-called ethoxylated polyethylene imines, i.e., the polymerized reaction product of ethylene oxide with ethylene-imine, having from 3 to 5 recurring units of the formula: wherein y is an integer of 10 to 20.
  • Polyamines typically will comprise at least 0.2% of the preferred compositions herein, generally 0.5%-5%.
  • compositions herein can contain other ingredients which aid in their cleaning performance.
  • through-the-wash detergent compositions contain a detergent builder and/or metal ion sequestrant.
  • detergent builders include the nitrilotriacetates, polycarboxylates, citrates, water-soluble phosphates such as tripolyphosphate and sodium ortho- and pyro-phosphates, silicates, and mixtures thereof.
  • Metal ion sequestrants include all of the above, plus materials like ethylenediaminetetraacetate, the amino-0 polyphosphonates and phosphates (DEQUEST (RTM)) and a wide variety of other poly-functional organic acids and salts too numerous to mention in detail here. See US-A-3.579.454 for typical examples of the use of such materials in various cleaning compositions. In general, the builder/sequestrant will comprise 0.5% to 15% of the composition. Citrate is one of the most preferred builders since it is readily soluble in the aqueous phase of heavy-duty liquid detergent compositions. Such ingredients are also useful in 5 hard-surface cleaners.
  • a source of magnesium ions can be used in the compositions, for the reasons stated hereinabove.
  • magnesium hydroxide water-soluble salts such as magnesium chloride, acetate, sulfate, and the like, can be used.
  • the laundry compositions herein also preferably contain enzymes to enhance their through-the-wash cleaning performance on a variety of soils and stains.
  • Amylase and protease enzymes suitable for use in detergents are well-known in the art and in commercially available liquid and granular detergents.
  • Commercial detersive enzymes preferably a mixture of amylase and protease
  • Ingredients such as propane diol and/or formate and calcium can be added to help stabilize the enzymes in well-known fashion, according to the desires of the formulator.
  • compositions herein can contain, in addition to ingredients already mentioned, various other optional ingredients typically used in commercial products to provide aesthetic or additional product performance benefits.
  • Typical ingredients include perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents and the like at levels of 0.1-15%.
  • Water or water-alcohol (e.g., ethanol, isopropanol, etc.) mixtures are used as the carrier vehicle, and alkylated polysaccharides can be used to increase the stability and performance characteristics of the compositions.
  • compositions herein are in liquid form, which can be prepared by simply blending the essential ; and optional ingredients in the aqueous carrier.
  • Microemulsion stability can be estimated visually by watching for phase separation, or can be monitored more quantitatively by standard turbidometric techniques.
  • the compositions can be used to pre-treat soiled fabrics by rubbing a few milliliters of the composition directly onto and into the soiled area, followed by laundering, in standard fashion.
  • the compositions are typically used at a concentration of at least 500 ppm, preferably 0.1% to 1.5% in an aqueous laundry bath at pH 6.5 and above to launder fabrics.
  • the laundering can be carried out over the range from 5°C to the boil, with excellent results.
  • compositions are diluted with water, or used full-strength, all in standard fashion.
  • heavy duty liquid detergents that are suitable for laundering all manner of fabrics in a typical home laundering operation.
  • the heavy duty liquid detergents disclosed hereinafter are formulated with a variety of detersive ingredients to provide excellent cleaning of a wide variety soils and stains, with particularly noteworthy benefits with regard to cosmetic and dirty motor oil stains.
  • the following formulations are in the form of oil-in-water emulsions (wherein the solvent is considered the "oil" phase) and are substantially clear, homogeneous, stable microemulsions.
  • the oil-in-water microemulsions herein are comparable in grease-cutting performance to water-in-oil emulsions, which have much higher concentrations of solvent.
  • the compositions also exhibit excellent whiteness maintenance on cotton fabrics, apparently because the solvent reduces fatty acid soap build-up on fabric surfaces. These performance advantages are particularly noticeable after multi-cycle washings.
  • the above composition is prepared by blending the indicated ingredients to provide a clear, stable microemulsion.
  • the composition gives excellent performance on a wide variety of stains, especially cosmetics and dirty motor oil.
  • Example I The composition of Example I is modified slightly by using 0.6 parts by weight of magnesium hydroxide as replacement for 2 parts of the 50% KOH and adjusting pH to 7.5.
  • the resulting product is a clear, stable, homogeneous microemulsion.
  • Example I and II are each modified by the addition of 1.5 parts by weight of tetraethylene pentamine ethoxylated with an average of 15 moles of ethylene oxide per nitrogen atom.
  • the resulting composition is a clear, stable, homogeneous microemulsion at pH's above 6.9.
  • any of the foregoing compositions may be modified by replacing the orange terpene solvent by a mixture of deodorized paraffin oil (iso-C 10 -C 12 ; 7.5% of the total composition) and orange terpenes (2.5% of total composition).
  • This change in the solvent component in no way detracts from the performance attributes of the compositions, but allows the perfumer more latitude for introducing non-citrus perfume notes.
  • Anionic optical brightener (0.01-0.5%) may be added, as desired.
  • the solvent should be substantially water immiscible; and, it should of course be capable of solubilizing a broad range of problem greasy soils.
  • thermodynamic solubility parameters Hansen Parameters
  • any solvent can be described by the Hansen Parameters 6 d , ⁇ p , ⁇ h : 6 d being the dispersion component; ⁇ p the polarity component; and ⁇ h the hydrogen bonding component.
  • key greasy problem soils can be described by "pseudo" Hansen Parameters. In order to do this the solubility of each greasy stain in a broad range of solvents of different Hansen Parameters is first assessed. This can be done by immersing the greasy stain on a range of different fabric types (cotton, polyester cotton, acrylic) in each solvent in turn for a fixed time (say, 5 minutes) under fixed agitation.
  • Preferred solvents and solvent mixtures herein especially: orange terpenes (d-limonene), paraffins (especially iso-C 10 ⁇ C 12 ); cyclohexane; kerosene; orange terpene/benzyl alcohol; (60/40), n-paraffins (C 12-15 )/hexanol (50/50) fall within the Hansen Parameters, as stated.
  • any of the foregoing examples may be modified by replacing the solvents listed with the foregoing, especially by mixtures of terpenes or paraffin oil with benzyl alcohol, n-hexanol or 1-butanol.
  • Preferred pH's for the heavy-duty detergent are 6.6-7.3.
  • Product "as is" pH is measured at ambient (23°C) temperature using a commercial pH meter. The electrode is immersed in the product and the meter is allowed to stabilize before reading.
  • compositions within the scope of this invention with solvents that are particularly suitable in industrial, heavy-duty laundry and cleaning plants, and the like. It will be appreciated by the formulator that some of the solvents employed in such compositions may be unsuitable for general home use, due to malodors, potential for skin irritation, low flash points, and the like. However, such compositions are entirely suitable for use under properly controlled conditions by professional operators who take such matters into consideration.
  • the pH is adjusted in all compositions with magnesium hydroxide, as indicated. All the other ingredients are listed as parts by weight.
  • a superior heavy duty liquid detergent composition can also be prepared using a solvent system comprising diethyl phthalate (preferred) or dibutyl phthalate in combination with the terpenes (preferably, orange terpene) or dipentene, or paraffin oils, or (most preferably) mixtures thereof.
  • a solvent system comprising diethyl phthalate (preferred) or dibutyl phthalate in combination with the terpenes (preferably, orange terpene) or dipentene, or paraffin oils, or (most preferably) mixtures thereof.
  • terpenes preferably, orange terpene
  • paraffin oils or (most preferably) mixtures thereof.
  • the following is a representative example of such a composition.
  • Example IX the dibutyl phthalate can be replaced by an equivalent amount of diethyl phthalate.
  • compositions comprising the terpene hydrocarbons will necessarily have a rather strong citrus odor that may not be entirely acceptable to all formulators of such compositions.
  • the C s -Cg alkyl aromatic solvents especially the C s -C 9 alkyl benzenes, preferably octyl benzene, exhibit excellent grease-removal properties and have a low, pleasant odor.
  • the olefin solvents having a boiling point of at least about 100°C, especially alpha-olefins, preferably 1-decene or 1-dodecene are excellent grease-removal solvents.
  • the iso-paraffins especially C 10 -C 12 chain lengths are noteworthy for their low odor and high grease-removal characteristics.
  • alkyl-aromatic or paraffin or olefin solvents with polar liquids such as benzyl alcohol, n-hexanol, Butyl Carbitol (Trade Mark; 2-(2-butoxyethoxy) ethanol) or the phthalic acid esters constitute additional examples of preferred non-polar/polar solvents that are preferred for use in the practice of this invention.
  • Example XIII the use of quaternary ammonium compound to adjust the pH of the formulation to a pH just barely below neutrality contributes importantly to product performance while maintaining long-term microemulsion stability.
  • compositions of Example X is a stable, oil-in-water microemulsion suitable for use as a laundry detergent.
  • Example X The composition of Example X is modified by replacing the 1-Decene by the same amount (9.1 % total formulation) of n-octyl benzene.
  • Example X The composition of Example X is modified by replacing the 1-Decene by any of the following solvent mixtures (percentages of total formulation being specified in parentheses): 1-Decene (6.1 %)/ Diethylphthalate (3.0%); 1-Dodecene (7.3%)/Benzyl alcohol (1.8%); n-octyl benzene (6.2%)/Diethyl phthalate (2.9%); n-octyl benzene (6.0%)/Butyl carbitol (3.1%).
  • compositions of Examples X, XI, and XII are modified by adding sufficient dioctyldimethyl ammonium chloride to adjust the "as is" pH of the compositions from 6.6 to 6.94.
  • the resulting compositions exhibit exceptionally good fabric cleaning and whiteness maintenance.
  • compositions of Examples X-XIII are in the form of true oil-in-water microemulsions. On diluting with water, the compositions appear hazy. In contrast, water-in-oil emulsions tend to gel on dilution, whereas micellar oil-in-water compositions remain clear on dilution.
  • Example XIII illustrates the use of a nitrogen-functional ingredient (the quaternary) to adjust product pH.
  • Other such pH adjusting agents include the following (product pH being indicated in parentheses): coconutalkyldiethanol amine (6.65); coconutdimethyl amine (6.75); trioctylamine (7.0); cyclohexylamine (7.5); coconutalkyl trimethylammonium chloride (6.66); coconutalkyl dimethylamine oxide (6.70); dicoconutalkyl dimethylammonium chloride (6.84); coconutalkyl benzyl dimethylammonium chloride (6.84); dihexyl dimethylammonium chloride (6.89); and dioctyl methyl amine oxide (>7 est.).
  • Such nitrogen-functional materials are used at levels from 0.5-5% in the compositions to adjust pH, and importantly contribute to cleaning and whiteness maintenance of laundered fabrics. Cyclohexyl amine (1-5%) is preferred for this use.
  • P-4" polymer Another preferred olefin solvent herein by virtue of its relatively low odor is the so-called "P-4" polymer, available from a number of petrochemical suppliers to the detergent industry as a raw material for branched alkyl benzene.
  • P-4 is an isomer mix of the condensation product of 4-moles of propylene, i.e., C '2 branched olefins.
  • P-4 is non-polar, and is preferably used in combination with a polar solvent such as benzyl alcohol, diethylphthalate, Butyl Carbitol, or the like.
  • polar solvents herein besides the "Carbitols” (2-(2-alkoxyethoxy)ethanols) include the "Cellosolves” (Trade Mark) e.g. 2-alkoxyl alkanols such as 2-butoxyethanol; C 4 -C 12 alkyl alcohols, such as dodecanol, phenethyl alcohol, and the diglycolether acetates, and the like.
  • a preferred composition by virtue of its low odor qualities and compatibility with polyethylene containers is prepared by replacing the 1-decene of Example X with a solvent mixture which comprises (as percent total composition) 6% diethylphthalate/2% iso-paraffin liquid (C 10 ⁇ C 12 )/2% orange terpene.
  • microemulsion compositions herein do not affect high density polyethylene and thus can be packaged in high density polyethylene bottles.
  • many solvent-containing cleaners that are not in true microemulsion form must be packaged in the more expensive metal cans or polyvinylchloride bottles.
  • compositions are used in an aqueous laundering liquor (preferably at a liquor pH of 6.5 ⁇ 8.0 measured as 1% of composition in water) to launder fabrics. Excellent cleaning is attained by agitating fabrics in such liquors at this in-use pH range.
  • a highly preferred liquid laundry detergent by virtue of the low odor properties of its grease removal solvent system, its stability in microemulsion form, and its enzymatic cleaning activity (by virtue of its pH) is as follows:
  • Example XVI is used in an aqueous laundry bath at a concentration of 100 ml/10 liters and provides an in-use pH of about 7,2 (varies with water hardness).
  • the most highly preferred cleaning solvent mixtures of paraffins especially iso-C 10-12 (most preferably iso-C io ) paraffin hydrocarbons and diethyl phthalate (or, less preferred, dibutyl phthalate) function exceptionally well in cleaning fabrics, both in a pre-treatment and through-the-wash mode.
  • These particular solvents formulated at a ratio of 5:1 to 1:5, are especially advantageous due to their exceptionally low odor.
  • microemulsion compositions of this invention are noteworthy for their mildness to skin. This unexpected benefit in solvent-containing compositions allows the compositions to be used in hand-washing of fine fabrics, china, glassware, and the like.

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  • Chemical & Material Sciences (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Organic Chemistry (AREA)
  • Detergent Compositions (AREA)

Claims (9)

1. Eine flüssige Detergenszusammensetzung, enthaltend einen wässerigen Träger, 10 Gew.-% bis 40 Gew.-% eines detersiven Nichtseifen-grenzflächenaktiven Mittels und 5 Gew.-% bis 20 Gew.-% Fettlöser, umfassend eine nicht-polare Lösungsmittelkomponente, die aus Terpen und Terpenoiden, Paraffinen, halogenierten Kohlenwasserstoffen, Cs-Cg-Alkylaromaten, flüssigen Olefinen, und Mischungen davon, ausgewählt ist, dadurch gekennzeichnet, daß die Zusammensetzung 5 Gew.-% bis 30 Gew.-% C12-C18-Fettsäure, oder Seife davon, und einen Mikroemulsionsstabilisator enthält, wobei der Stabilisator ein wasserlöslicher Bestandteil hoher lonenstärke, ausgewählt aus Formiat, Sulfat und Citrat, ein in dem nicht-polaren Lösungsmittel löslicher Bestandteil mit einem HLB-Wert von 2-5, eine Stickstoff-funktionelle Verbindung, oder ein Gemisch davon, ist, und wobei die Zusammensetzung einen pH-Wert von 6,5 bis 8,0 hat und in der Form einer stabilen Öl-in-Wasser-Mikroemulsion vorliegt.
2. Eine Zusammensetzung nach Anspruch 1, wobei das detersive Nichtseifen-grenzflächenaktive Mittel aus C9-C18-Alkylbenzolsulfonaten, Parafinsulfonaten, a-Sulfonaten von Fettsäuren, Alkylsulfaten, und ethoxylierten Alkoholen und Alkylphenolen mit 5 bis 17 Ethylenoxidgruppen, und Mischungen davon, ausgewählt ist.
3. Eine Zusammensetzung nach Anspruch 1 oder 2, wobei das Lösungsmittel Terpene, Paraffinöl, Cs-Cg-Alkylaromaten, flüssige Olefine, oder Mischungen davon, oder Mischungen von Terpenen, Paraffinölen, Cs-Cg-Alkylaromaten oder Olefinen, mit Benzylalkohol, C4-C12-Alkoholen, Phthalsäureestern, 2-(2-Alkoxyethoxy)ethanolen oder 2-Alkoxyalkanolen, umfaßt.
4. Eine Zusammensetzung nach Anspruch 3, wobei das Lösungsmittel ein Gemisch von:
(a) einem nicht-polaren Lösungsmittel, ausgewählt aus Terpenen, Iso-C10-C12-Paraffinölen, C6―C9-Alkylbenzolen oder flüssigen Olefinen; und
(b) einem polaren Lösungsmittel, ausgewählt aus Benzylalkohol, Diethylphthalat, Dibutylphthalat oder 2-(2-Butoxyethoxy)-ethanol,

bei einem Gewichtsverhältnis von (a) zu (b) von 10:1 bis 1:10, ist.
5. Eine Zusammensetzung nach einem der Ansprüche 1 bis 4, wobei die Fettsäure oder Seife ein Gemisch von Laurinfettsäure und Myristinfettsäure, oder Seifen davon, oder aus Kokosnußalkylfettsäuren-oder -fettseifengemisch ist, oder aus Gemischen von Palmfettsäure und Kokosnußfettsäure, oder Seifen davon, besteht.
6. Eine Zusammensetzung nach einem der Ansprüche 1 bis 5, formuliert mit einem pH-Wert von 6,6 bis 7.3.
7. Eine Zusammensetzung nach einem der Ansprüche 1 bis 6, verpackt in einem Behälter aus Polyethylen hoher Dichte.
8. Eine Zusammensetzung nach Anspruch 4, enthaltend ein Gemisch aus Iso-C10-C12-Paraffin und Diethylphthalat oder Dibutylphthalat in einem Gewichtsverhältnis von Paraffin:Phthalat von 5:1 bis 1:5.
9. Eine Zusammensetzung nach Anspruch 8, wobei die Stickstoff-funktionelle Verbindung Cyclohexylamin ist.
EP84305317A 1983-08-11 1984-08-06 Flüssige Detergentien mit einem Lösungsmittel Expired EP0137616B1 (de)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84305317T ATE32231T1 (de) 1983-08-11 1984-08-06 Fluessige detergentien mit einem loesungsmittel.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB838321682A GB8321682D0 (en) 1983-08-11 1983-08-11 Liquid detergents with solvent
GB8321682 1983-08-11
GB8325105 1983-09-20
GB838325105A GB8325105D0 (en) 1983-09-20 1983-09-20 Liquid detergents
GB8409052 1984-04-07
GB848409052A GB8409052D0 (en) 1984-04-07 1984-04-07 Liquid detergents

Publications (2)

Publication Number Publication Date
EP0137616A1 EP0137616A1 (de) 1985-04-17
EP0137616B1 true EP0137616B1 (de) 1988-01-27

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EP84305317A Expired EP0137616B1 (de) 1983-08-11 1984-08-06 Flüssige Detergentien mit einem Lösungsmittel

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EP (1) EP0137616B1 (de)
JP (1) JPH0631420B2 (de)
CA (1) CA1236372A (de)
DE (1) DE3469037D1 (de)
ES (3) ES8609451A1 (de)
FI (1) FI78730C (de)
GR (1) GR80085B (de)
IE (1) IE57570B1 (de)
MX (1) MX160962A (de)

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GR80085B (en) 1984-10-30
FI843159A (fi) 1985-02-12
IE57570B1 (en) 1992-12-16
DE3469037D1 (en) 1988-03-03
JPH0631420B2 (ja) 1994-04-27
ES554199A0 (es) 1987-06-01
ES8609451A1 (es) 1986-09-01
MX160962A (es) 1990-06-27
ES8706200A1 (es) 1987-06-01
ES554200A0 (es) 1987-06-01
ES535067A0 (es) 1986-09-01
IE842065L (en) 1985-02-11
FI78730C (fi) 1989-09-11
CA1236372A (en) 1988-05-10
EP0137616A1 (de) 1985-04-17
FI78730B (fi) 1989-05-31
ES8706199A1 (es) 1987-06-01
FI843159A0 (fi) 1984-08-10
JPS60106898A (ja) 1985-06-12

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