EP0137615B1 - Compositions de nettoyage de tissus pour enlever des taches - Google Patents

Compositions de nettoyage de tissus pour enlever des taches Download PDF

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Publication number
EP0137615B1
EP0137615B1 EP84305316A EP84305316A EP0137615B1 EP 0137615 B1 EP0137615 B1 EP 0137615B1 EP 84305316 A EP84305316 A EP 84305316A EP 84305316 A EP84305316 A EP 84305316A EP 0137615 B1 EP0137615 B1 EP 0137615B1
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EP
European Patent Office
Prior art keywords
solvent
compositions
composition according
solvents
weight
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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EP84305316A
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German (de)
English (en)
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EP0137615A1 (fr
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 GB838321680A external-priority patent/GB8321680D0/en
Priority claimed from GB838325103A external-priority patent/GB8325103D0/en
Priority claimed from GB848409053A external-priority patent/GB8409053D0/en
Application filed by Procter and Gamble European Technical Center, Procter and Gamble Co filed Critical Procter and Gamble European Technical Center
Priority to AT84305316T priority Critical patent/ATE32230T1/de
Publication of EP0137615A1 publication Critical patent/EP0137615A1/fr
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Publication of EP0137615B1 publication Critical patent/EP0137615B1/fr
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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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/261—Alcohols; Phenols
    • 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
    • C11D1/42—Amino alcohols or amino ethers
    • C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
    • 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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/26—Organic compounds containing nitrogen
    • C11D3/30—Amines; Substituted amines ; Quaternized amines
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5013—Organic solvents containing nitrogen
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/24—Hydrocarbons
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/263—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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/26—Organic compounds containing oxygen
    • C11D7/266—Esters or carbonates
    • 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/22—Organic compounds
    • C11D7/32—Organic compounds containing nitrogen
    • C11D7/3227—Ethers thereof

Definitions

  • the present invention relates to compositions and processes for removing clay-based soils and stains from fabrics.
  • the compositions are particularly adapted for removing cosmetic stains, which comprise a mixture of clay-based material and an oily or greasy binder material.
  • Compositions which comprise a solvent ingredient to disperse the binder and a polyamine material to disperse the clay are provided. These compositions can be used in the form of a simple fabric pre-spotter, or in fully-formulated laundry detergents comprising a mixture of various ingredients designed to remove a broad spectrum of stains and soils from fabrics, with particularly noteworthy benefits on stains caused by cosmetics.
  • Detergent formulators are faced with the task of devising products to remove a broad spectrum of soils and stains from fabrics. Chemically and physico-chemically, the varieties of soils and stains range the spectrum from primarily oily, through proteinaceous and carbohydrate, to inorganic, and detergent compositions have become more complex as formulators attempt to provide products which handle all types, concurrently. For example, protease ensymes are commonly used in detergents for blood and gravy stains; amylase enzymes are used for carbohydrate stains; nonionic surfactants are used for hydrocarbon oils; and anionic surfactants and builders are used for particulate soil. Bleach is used to chemically degrade stains that are not amenable to removal by less rigorous treatment.
  • many cosmetics comprise a clay base which serves in part as a filler, thickener, carrier for color bodies, and the like, blended with an oily material which serves partially as a binder, gloss agent and emollient.
  • Cosmetics are typically manufactured with great care, such that the clay and color bodies are in the form of very fine particles, and are very thoroughly and completely mixed with, and coated by, the oily material, which may be a hydrocarbon oil, silicone, lipid, or complex mixtures thereof.
  • the'modern cosmetic product causes major problems for the detergent formulator, since cosmetics constitute a mix of widely divergent soil types (oily, particulate, ⁇ lay) all in intimate admixture and often brightly colored. No single detergent ingredient can reasonably be expected to handle such a complex milieu.
  • the present invention employs oil-removal solvents and clay-removal polyamines.
  • the solvents dissolve the oil base of the cosmetics, thereby exposing their clay component to the polyamine materials which disperse and remove it from fabrics.
  • Clay-removal alkoxylated polyamines are disclosed in EP-A-0111984 published 27.06.84, and their use in detergent compositions is disclosed in EP-A-0112593, published 04.07.84.
  • the present invention relates to a detergent composition
  • a detergent composition comprising from 1% to 40% by weight of water-soluble detersive surfactant and at least 5% by weight of a mixture of:
  • 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 moieties 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 terpends and d-limonene.
  • Excellent solvents for use herein are 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 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.
  • 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 molecules comprising at least 2, preferably from 2-20, most preferably 3-5 recurring units having the formula: or wherein R is a hydrocarbyl group, usually of 2-6 carbon atoms; R' is a C 1 -C 20 hydrocarbon; the alkoxy groups are polyethoxy or polypropoxy, with polyethoxy preferably having a degree of polymerization of 2-10, most preferably, 10 to 20; and X e is an anion such as halide or methylsulfate, resulting from the quaternization reaction.
  • 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.
  • the detergent compositions herein contain water-soluble organic surface-active agents ("surfactants") to provide the usual cleaning benefits associated with the use of such materials.
  • surfactants water-soluble organic surface-active agents
  • Water-soluble 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.
  • detersive surfactants contain an alkyl group in the C 97 -C la range; the anionic detersive surfactants are most commonly used in the form of their sodium, potassium or triethanolammonium salts; the nonionics 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.
  • C 11 -C 16 alkyl benzene sulfonates, C 12- C 18 paraffin-sulfonates and alkyl sulfates, and the ethoxylated alcohols and alkyl phenols are especially preferred in the compositions of the present type.
  • the surfactant component comprises from 1% to 40%, preferably 5% to 30%, of the compositions herein. Mixtures of the ethoxylated nonionics with anionics such as the alkyl benzene sulfonates, alkyl sulfates and paraffin sulfonates are preferred for through-the-wash cleansing of a broad spectrum of soils and stains from fabrics.
  • Fatty acids generally Clo-C,,3 chain length
  • water-soluble salts i.e., common "soaps", especially alkali metal soaps
  • fatty acids and soaps are particularly useful when preparing fully-formulated, homogeneous oil-in-water liquid detergents comprising the solvent and polyamine in an aqueous carrier. Usage levels of 0.5-50% are typical.
  • 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.
  • 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 pH regulants, perfumes, dyes, optical brighteners, soil suspending agents, hydrotropes and gel-control agents, freeze-thaw stabilizers, bactericides, preservatives, suds control agents and the like.
  • Water-alcohol e.g., ethanol, isopropanol, etc.
  • alkylated polysaccharides can be used to increase the stability and performance characteristics of the compositions.
  • compositions herein are preferably formulated in the neutral to alkaline pH range, generally in the range of pH 6.5-9.0, preferably about 6.8-7.5.
  • Materials such as sodium hydroxide, potassium hydroxide, the alkanol amines such as triethanol-amines, or magnesium hydroxide, can be used to adjust the pH, as desired.
  • Preferred pH adjusting agents are described hereinafter.
  • compositions herein are in liquid form, which can be prepared by simply blending the essential and optional ingredients in a fluid (preferably aqueous) carrier.
  • a fluid preferably aqueous
  • fatty acid or soap can be used in such liquid compositions to provide clear, homogeneous microemulsions of the solvent in an aqueous carrier.
  • Solid or granular compositions can be prepared by adsorbing the solvent and polyamine in a suitable granular carrier, for example, in a sodium sulfate, sodium perborate (bleach) or spray-dried detergent granule carrier.
  • the compositions herein in the form of liquids or pastes 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 6.5-10 to launderfabrics.
  • the laundering can be carried out over the range from 5°C to the boil, with excellent results.
  • a spot remover in stick form is prepared by blending the following ingredients, extruding the resulting mass through a 1.25 cm die, and packaging the resulting stick in an aluminum foil wrapper.
  • the foil wrapper is peeled away from a portion of the stick, which is then rubbed briskly onto the area of a garment soiled with cosmetic, or the like, stains.
  • the garment is thereafter brushed, or optionally laundered, to remove the stain, together with residues from the stick.
  • a liquid fabric pre-treatment and through-the-wash detergency booster is prepared by blending the following ingredients.
  • Example II In a preferred method of use, a few (1-10) milliliters of the composition of Example II are applied directly to an area of fabric stained with claylgrease soil and rubbed briskly into the stained area. The fabric is thereafter laundered with a commercial laundry detergent (e.g., VIZIR@) according to label instructions.
  • a commercial laundry detergent e.g., VIZIR@
  • Example II is added directly to an aqueous laundry bath, generally at a level of 500-5000 ppm, depending on the desires of the user and the soil load, together with a commercial laundry detergent, to enhance cleaning performance.
  • Example II can be diluted (1:1) with water or water-ethanol and packaged in an aerosol or manual pump dispenser for use as a spot remover.
  • a granular detergent composition comprising the solvent/polyamine compositions of the present invention can be prepared by blending the solvent/polyamine with a spray-dried commercial laundry detergent.
  • the solvent/polyamine is admixed with non-neutralized anionic surfactant, which is then admixed with alkaline detergency builder and other optional detergency ingredients, whereby the surfactant is neutralized in situ in the product.
  • This method of formulating solvent-containing granular detergents is described by A. Davidsohn in the report of the original lectures, 3rd International Congress of Surface Activity Cologne, pages 165 to 172 at 171 (1960).
  • Example III The composition of Example III is used in standard fashion to launder fabrics.
  • ca. 2g. of the composition is admixed with ca. 5ml. water to form a paste which is then rubbed into heavily soiled areas of fabrics, prior to laundering with the composition.
  • compositions within the scope of this invention with solvents which 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. In Examples IV-IX, all ingredients are listed as parts by weight.
  • compositions in accordance with the invention special attention is now directed to highly preferred formulations which are particularly useful as 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, and wherein the solvent/polyamine contributes significantly to the removal of clay/grease and dirty motor oil stains from fabrics.
  • formulations can be prepared as water-in-oil emulsions, they are preferably prepared in the form of oil-in-water emulsions (wherein the solvent is considered the "oil" phase) and are most preferably in the form of substantially clear, homogeneous oil-in-water microemulsions.
  • the formulator of heavy duty liquid detergents will appreciate that using water as the carrier phase in such compositions is a significant cost saving, and will further appreciate that an aqueous carrier phase contributes importantly to ease-of-formulation, since water-soluble detersive ingredients can be more readily incorporated into oil-in-water emulsions than in water-in-oil emulsions.
  • the oil-in-water emulsions herein are comparable in grease-cutting performance to water-in-oil emulsions, which have much higher concentrations of solvent.
  • compositions herein with high concentrations of surfactant and fatty acid/soap may be packaged in high density polyethylene bottles without solvent loss.
  • a heavy-duty liquid detergent in the form of a clear, homogeneous oil-in-water emulsion which shows excellent performance with a wide variety of clay soil types of stain is prepared as follows:
  • the above composition is prepared by blending the indicated ingredients to provide a dear, stable microemulsion.
  • the composition gives excellent performance on a wide variety of stains, including cosmetics and dirty motor oil.
  • compositions of the foregoing microemulsion type will generally contain 10-20% of the fatty acid mix and be formulated at pH 6.6-7.3.
  • Example X The composition of Example X is modified slightly by using 0.6 parts of weight of magnesium hydroxide in place of 1.2 parts of potassium hydroxide (50%) to adjust pH to 7.0.
  • the resulting product is a homogeneous microemulsion.
  • composition of Examples X and XI are modified by replacing the orange terpene by a mixture of deodorized paraffin oil (iso-C 10 -C 12 ) (7.5% of the total composition) and orange terpenes (2.5% of the 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 6 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.
  • the above technique indicates that mixed solvent/solvent compositions with Hansen Parameters in the range 6 d (7 to 9), ⁇ p (0 to 4), 5 h (0 to 7) allow the formulation of microemulsions with superior greasy stain removal performance.
  • the solvent combination can be targeted against particular greasy stains, such as motor oil, where the optimum Hansen Parameter range is 6 d (7 to 9), 6 h (0 to 4) 6p (0 to 3) to marker ink, where the optimum range is 6 d (769), 6 h (2 to 11), 6p (2 to 7), or targeted more broadly against mixed stains by selecting an intermediate point in the range of Hansen Parameters.
  • Some 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.
  • solvents and solvent mixtures are typically used at concentrations of 5-20%, preferably 5-10%, in the present compositions.
  • Slightly polar solvents such as benzyl alcohol or n-hexanol can be used with water-immiscible solvents such as terpenes and paraffin oil at levels of 0-10%.
  • water-immiscible solvents such as terpenes and paraffin oil at levels of 0-10%.
  • Various other solvent mixtures are disclosed in Example XIX, hereinafter.
  • 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 XIII 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 6 -C9 alkyl aromatic solvents especially the C 6 ⁇ C 9 alkyl benzenes, preferably octyl benzene, exhibit excellent grease-removal properties and have a low, pleasant odor.
  • alkyl-aromatic 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 XVII the use of the 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.
  • Example XIV is a stable, oil-in-water microemulsion suitable for use as a laundry detergent.
  • Example XIV The composition of Example XIV is modified by replacing the 1-Decene by the same amount (9.1% total formulation) of n-octyl benzene.
  • Example XIV The composition of Example XIV 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 (5.9%)/Benzyl alcohol (3.2%); n-octyl benzene (6.2%)/Diethyl phthalate (2.9%); n-octyl benzene (5.0%)/Butyl carbitol (4.1%); Diethyl phthalate (6%)/liquid C, o iso-paraffin (2%)/ orange terpene (2%).
  • compositions of Examples XIV, XV, and XVI are modified by adding sufficient cyclohexyl amine or 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.
  • An extra-heavy duty laundry additive composition which can be used in the detergent compositions of the invention is as follows.
  • P-4 is an isomer mix of the condensation product of 4-moles of propylene, i.e., C 12 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 include the "cello-solves” e.g. alkoxyl alkanols such as 2-butoxyethanol; C 6 -C 12 alkanols (including benzyl alcohol) such as dodecanol, phenethyl alcohol, diglycolether acetates, hexyl cellosolve and hexyl carbitol, and the like.
  • cello-solves e.g. alkoxyl alkanols such as 2-butoxyethanol
  • C 6 -C 12 alkanols including benzyl alcohol
  • dodecanol phenethyl alcohol
  • diglycolether acetates hexyl cellosolve and hexyl carbitol, and the like.
  • compositions herein are used in an aqueous laundering liquor 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.
  • any of the well-known base materials can be used, 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.
  • Dioctyl dimethyl ammonium chloride is a highly preferred quaternary used herein as a pH regulant, but there can also be mentioned the following quaternaries in increasing order of preference of use: coconut trimethyl ammonium chloride (6.66); di-coconut dimethyl ammonium chloride (6.84); coconut benzyl dimethyl ammonium chloride (6.84); and dihexyl dimethyl ammonium chloride (6.89).
  • the numbers in paretheses denote the pH achievable by adding the respective quaternaries to a liquid oil-in-water microemulsion containing fatty acid and formulated at an "as is" pH of 6.5.
  • the pH figure is 6.94.
  • Suitable alkyl and cyclo-alkyl amines useful herein include: coconutalkyl diethanol amine (6.65); coconutalkyl dimethyl amine (6.75); trioctyl amine (7.0); and cyclohexyl amine (7.5).
  • Suitable amine oxides herein include coconutalkyl dimethylamine oxide (6.7) and dioctyl methylamine oxide (est. 7).
  • compositions herein comprise:
  • Microemulsion stability of such comprising can be estimated visually by watching for phase separation, or can be monitored quantitatively by standard turbidometric techniques.
  • 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.
  • 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 XX 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).

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
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  • Oil, Petroleum & Natural Gas (AREA)
  • Wood Science & Technology (AREA)
  • Life Sciences & Earth Sciences (AREA)
  • Health & Medical Sciences (AREA)
  • Emergency Medicine (AREA)
  • Detergent Compositions (AREA)
  • Details Of Garments (AREA)
  • Chemical Or Physical Treatment Of Fibers (AREA)
  • Treatments For Attaching Organic Compounds To Fibrous Goods (AREA)

Claims (9)

1. Composition détergente comprenant de 1% à 40% en poids de tensio-actif détersif hydrosoluble, caractérisée en ce qu'elle contient au moins 5% en poids d'un mélange:
(a) d'un solvant éliminant les graisses comprenant un ou plusieurs terpènes ou terpénoïdes, paraffines, solvants hydrocarbonés halogénés, solvants aromatiques alkylés en C6-C9 ou oléfines liquides; et
(b) d'une polyamine alcoxylée ayant au moins deux motifs récurrents de formule
Figure imgb0019
où R est un groupe hydroxycarbyle, R1 est un hydrocarbure en Cl-C20, alcoxy représente un groupe polyéthoxy ou polypropoxy et X- est un anion.
2. Composition selon la revendication 1, dans laquelle la polyamine alcoxylée est le produit de réaction polymérisé de l'oxyde d'éthylène avec l'éthylène-imine.
3. Composition selon la revendication 2, dans laquelle la polyamine alcoxylée comporte de 3 à 5 motifs récurrents de formule suivante:
Figure imgb0020
dans laquelle y est un nombre entier de 10 à 20.
4. Composition selon l'une quelconque des revendications 1 à 3, dans laquelle le rapport pondéral du solvant à la polyamine alcoxylée est dans l'intervalle de 100:1 à 1:20.
5. Composition selon la revendication 1, qui contient au moins 5% en poids du solvant éliminant les graisses et au moins 0,2% en poids de la polyamine alcoxylée.
6. Composition selon la revendication 5, qui est sous la forme d'une microémulsion huile dans l'eau.
7. Composition selon la revendication 6, qui contient en outre de 0,5% à 50% en poids d'acide gras ou de savon.
8. Composition selon la revendication 7, dans laquelle le solvant est choisi parmi les terpène, l'huile de paraffine, les alkyl(en C6―C9)benzènes, les oléfines liquides et leurs mélanges.
9. Composition selon la revendication 7, dans laquelle le solvant est choisi parmi un mélange:
(a) de terpènes, d'isoparaffines, d'alkyl(en C6―C9)benzènes ou d'oléfines liquides; et
(b) d'alcool benzylique, de phtalate de diéthyle, de phtalate de dibutyle ou de butylcarbidol, en un rapport pondéral (a):(b) de 1:10 à 10:1.
EP84305316A 1983-08-11 1984-08-06 Compositions de nettoyage de tissus pour enlever des taches Expired EP0137615B1 (fr)

Priority Applications (1)

Application Number Priority Date Filing Date Title
AT84305316T ATE32230T1 (de) 1983-08-11 1984-08-06 Gewebereinigungsmittel-zusammensetzungen fuer schmutzflecke.

Applications Claiming Priority (6)

Application Number Priority Date Filing Date Title
GB838321680A GB8321680D0 (en) 1983-08-11 1983-08-11 Fabric cleaning compositions
GB8321680 1983-08-11
GB838325103A GB8325103D0 (en) 1983-09-20 1983-09-20 Fabric cleaning compositions
GB8325103 1983-09-20
GB848409053A GB8409053D0 (en) 1984-04-07 1984-04-07 Fabric cleaning compositions
GB8409053 1984-04-07

Publications (2)

Publication Number Publication Date
EP0137615A1 EP0137615A1 (fr) 1985-04-17
EP0137615B1 true EP0137615B1 (fr) 1988-01-27

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EP84305316A Expired EP0137615B1 (fr) 1983-08-11 1984-08-06 Compositions de nettoyage de tissus pour enlever des taches

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Country Link
EP (1) EP0137615B1 (fr)
JP (2) JPS60106897A (fr)
AT (1) ATE32230T1 (fr)
CA (1) CA1230533A (fr)
DE (1) DE3469036D1 (fr)
ES (1) ES8606477A1 (fr)
FI (1) FI73731C (fr)
GR (1) GR80086B (fr)
IE (1) IE57571B1 (fr)

Families Citing this family (32)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB8409055D0 (en) * 1984-04-07 1984-05-16 Procter & Gamble Cleaning compositions
GB8512638D0 (en) * 1985-05-18 1985-06-19 Procter & Gamble Laundry detergent compositions
US5075026A (en) * 1986-05-21 1991-12-24 Colgate-Palmolive Company Microemulsion all purpose liquid cleaning composition
DE4012380A1 (de) * 1990-04-18 1991-10-24 Koch Christian Reinigungsmittelkonzentrat zur reinigung von sanitaeren einrichtungen
JPH08508536A (ja) * 1993-04-02 1996-09-10 ザ ダウ ケミカル カンパニー 微小エマルジョン及びエマルジョン洗剤組成物
NZ260144A (en) * 1993-04-12 1995-10-26 Colgate Palmolive Co Cleaning composition; contains three liquid phases which merge at a tricritical point; use for removing tar or grease from articles
US5883066A (en) * 1993-06-28 1999-03-16 The Procter & Gamble Company Liquid detergent compositions containing cellulase and amine
US5763386A (en) * 1993-08-04 1998-06-09 Colgate Palmolive Company Microemulsion all purpose liquid cleaning compositions comprising ethoxylated polyhydric alcohols with at least partial esters thereof, and optional dralkyl sulfosuccinate
US5741769A (en) * 1994-11-23 1998-04-21 Colgate Palmolive Company Microemulsion light duty liquid cleaning compositions
EP0794245B1 (fr) * 1996-03-04 2003-07-09 The Procter & Gamble Company Procédé de prétraitement pour le lavage du ligne et compositions de blanchiment
US5759290A (en) * 1996-06-13 1998-06-02 Colgate Palmolive Company Liquid crystal compositions
US5834417A (en) * 1996-06-13 1998-11-10 Colgate Palmolive Co. Light duty liquid cleaning compositions
US5700331A (en) * 1996-06-14 1997-12-23 Colgate-Palmolive Co. Thickened cleaning composition
US5703028A (en) * 1996-06-14 1997-12-30 Colgate-Palmolive Co Liquid crystal detergent compositions based on anionic sulfonate-ether sulfate mixtures
US5719114A (en) * 1996-06-28 1998-02-17 Colgate Palmolive Company Cleaning composition in various liquid forms comprising acaricidal agents
US5756441A (en) * 1996-08-07 1998-05-26 Colgate Palmolive Company High foaming nonionic surfactant based liquid detergent
US5714454A (en) * 1996-08-07 1998-02-03 Colgate-Palmolive Co. Light duty liquid cleaning compositions comprising alkyl sulroglycerides
US6194371B1 (en) 1998-05-01 2001-02-27 Ecolab Inc. Stable alkaline emulsion cleaners
US6159925A (en) * 2000-04-06 2000-12-12 Colgate-Palmolive Co. Acidic liquid crystal compositions
GB0016847D0 (en) * 2000-07-10 2000-08-30 Unilever Plc Fabric conditioning composition
GB0216173D0 (en) * 2002-07-12 2002-08-21 Fabric Care Res Ass Ltd A laundry preparation
US7018968B2 (en) 2003-09-17 2006-03-28 Unilever Home & Personal Care Usa Liquid laundry detergent with polyanionic ammonium surfactant
US7037883B2 (en) 2003-09-17 2006-05-02 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Process of making a liquid laundry detergent with polyanionic ammonium surfactant
US6969700B2 (en) 2004-02-12 2005-11-29 Unilever Home & Personal Care, Usa Division Of Conopco, Inc Liquid detergent with polyanionic ammonium surfactant and a high pKa solid inorganic base
GB0428202D0 (en) * 2004-12-23 2005-01-26 Fabric Care Res Ass Ltd A method of disinfecting textile articles during laundering and a laundry preparation for use in said method
US7387992B2 (en) 2005-03-15 2008-06-17 Unilever Home & Personal Care Usa Division Of Conopco, Inc. Laundry detergent with polyamine mono-anionic surfactant
AR072859A1 (es) 2008-05-23 2010-09-29 Colgate Palmolive Co Metodos y composiciones liquidas de limpieza
ES2633247T3 (es) * 2013-02-28 2017-09-20 Basf Se Uso de polipropilenimina alcoxilada para el cuidado de la colada y composiciones para esto
PL2961819T3 (pl) 2013-02-28 2018-02-28 Basf Se Wodne preparaty, ich wytwarzanie i ich zastosowanie do czyszczenia twardych powierzchni
JP6275864B2 (ja) * 2014-03-27 2018-02-07 ザ プロクター アンド ギャンブル カンパニー ポリエーテルアミンを含有する洗浄組成物
EP3540052A1 (fr) 2018-03-14 2019-09-18 Indian Oil Corporation Limited Composition d'enzyme lignocellulolytique stable
CA3136357C (fr) * 2019-04-12 2023-10-17 Ecolab Usa Inc. Solution de nettoyage de surface dure avec activite viricide rapide

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043622A1 (fr) * 1980-01-07 1982-01-13 THE PROCTER & GAMBLE COMPANY Composition d'adoucissement pour matières textiles
EP0111984A2 (fr) * 1982-12-23 1984-06-27 THE PROCTER & GAMBLE COMPANY Polymères d'amines éthoxylées ayant des propriétés pour enlever des taches et la contre-redéposition utilisables dans des compositions détergentes

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
BE754989A (fr) * 1969-04-11 1971-02-18 Pechiney Saint Gobain Sechage et nettoyage de surfaces
US3839234A (en) * 1973-01-26 1974-10-01 C Roscoe Multi-purpose cleaning concentrate
EP0106266B1 (fr) * 1980-05-27 1988-02-24 The Procter & Gamble Company Mélange terpène-solvant utilisable pour la préparation de compositions détergentes liquides
DE3380216D1 (en) * 1982-12-23 1989-08-24 Procter & Gamble Detergent compositions containing ethoxylated amines having clay soil removal/anti-redeposition properties

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0043622A1 (fr) * 1980-01-07 1982-01-13 THE PROCTER & GAMBLE COMPANY Composition d'adoucissement pour matières textiles
EP0111984A2 (fr) * 1982-12-23 1984-06-27 THE PROCTER & GAMBLE COMPANY Polymères d'amines éthoxylées ayant des propriétés pour enlever des taches et la contre-redéposition utilisables dans des compositions détergentes

Also Published As

Publication number Publication date
IE57571B1 (en) 1992-12-16
IE842066L (en) 1985-02-11
CA1230533A (fr) 1987-12-22
FI73731B (fi) 1987-07-31
GR80086B (en) 1984-10-30
ATE32230T1 (de) 1988-02-15
ES8606477A1 (es) 1986-04-01
ES535068A0 (es) 1986-04-01
FI843158A (fi) 1985-02-12
EP0137615A1 (fr) 1985-04-17
JPH05271694A (ja) 1993-10-19
JPS60106897A (ja) 1985-06-12
JPH0564200B2 (fr) 1993-09-14
FI843158A0 (fi) 1984-08-10
FI73731C (fi) 1987-11-09
DE3469036D1 (en) 1988-03-03

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