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WO1998001527A1 - Compositions proches du point tri-critique contenant un agent de blanchiment et/ou un agent biostatique - Google Patents

Compositions proches du point tri-critique contenant un agent de blanchiment et/ou un agent biostatique Download PDF

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Publication number
WO1998001527A1
WO1998001527A1 PCT/US1997/011600 US9711600W WO9801527A1 WO 1998001527 A1 WO1998001527 A1 WO 1998001527A1 US 9711600 W US9711600 W US 9711600W WO 9801527 A1 WO9801527 A1 WO 9801527A1
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WIPO (PCT)
Prior art keywords
polar solvent
phase
water
composition according
composition
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PCT/US1997/011600
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English (en)
Inventor
Louis Oldenhove Deguertechin
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Colgate-Palmolive Company
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Application filed by Colgate-Palmolive Company filed Critical Colgate-Palmolive Company
Priority to AU35913/97A priority Critical patent/AU3591397A/en
Publication of WO1998001527A1 publication Critical patent/WO1998001527A1/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
    • 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
    • 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
    • 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
    • C11D3/39—Organic or inorganic per-compounds
    • C11D3/3947—Liquid 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
    • C11D3/43—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
    • C11D7/02—Inorganic 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
    • C11D7/00—Compositions of detergents based essentially on non-surface-active compounds
    • C11D7/50—Solvents
    • C11D7/5004—Organic solvents
    • C11D7/5022—Organic solvents containing oxygen
    • 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

Definitions

  • the present invention relates to an aqueous bleach or disinfecting, cleaning composition which is optionally surfactant-free and is useful for the control of bacteria, fungus, molds, spores, viruses and germs as well as for the removal of grease, soap scum or tar without any mechanical action.
  • the instant compositions comprise a bleachant system incorporated in three liquid phases which merge together in the vicinity of a tricritical point to form one continuum, wherein each of the three phases essentially contain a polar solvent, a non-polar solvent or a weakly polar solvent and a water soluble or water dispersible low molecular weight amphiphile.
  • Liquid aqueous synthetic organic detergent compositions have long been employed for human hair shampoos and as dishwashing detergents for hand washing of dishes (as distinguished from automatic dishwashing, machine washing of dishes). Liquid detergent compositions have also been employed as hard surface cleaners, as in pine oil liquids, for cleaning floors and walls. More recently, they have proven successful as laundry detergents too, apparently because they are convenient to use, are instantly insoluble in wash water, and may be employed in "pre-spotting" applications to facilitate removal of soils and stains from laundry upon subsequent washing. Liquid detergent compositions have comprised anionic, cationic and nonionic surface active agents, builders and adjuvants including, as adjuvants, lipophilic materials which can act as solvents for lipophilic soils and stains. The various liquid aqueous synthetic organic detergent compositions mentioned above serve to emulsify lipophilic materials including oily soils in aqueous media, such as wash water, by forming micellar dispersions and emulsions.
  • a cleaning action can be regarded as a more-or-less complex process resulting in the removal of soils from a given surface.
  • the driving forces generally involved in this process are mechanical energy (friction, attrition, sonification, suction etc.), solvation by a liquid, thermal agitation, soil-solvent interfacial tension reduction, chemical modifications (caustic, acidic, oxidative, reductive, hydrolysis, perhydrolysis, condensation, complexation, assisted or not by photoinduction, catalysts or enzymes), soil or soil residual suspension (e.g. in emulsions), and so on.
  • auxiliary cleaning agents especially surfactants
  • surfactants are generally required to get rid of hydrophobic soils.
  • the success of the cleaning mechanism is based on the reduction of the water/oil interfacial tension.
  • the generally admitted theory is that the oily soil is easily dispersed or emulsified in the composition because of the low interfacial tension existing between the washing liquor and the oil; due to the low interfacial tension, the liquid detergent composition easily wets the soil, diffuses through the soil or between the support and the soil, thereby weakening all bonding forces; the soil is then spontaneously removed from the substrate. This explains the removal of oily soil without a real solubilization of the soil.
  • microemulsions Although emulsification is a mechanism of soil removal, it has been recently discovered how to make microemulsions which are much more effective than ordinary emulsions in removing lipophilic materials from substrates.
  • microemulsions are described in British Patent Specification No. 2,190,681 and U.S. Patent Applications Serial Nos. 06/866,029, 07/085,902, 07/120,250 and 07/267,872 most of which relates to acidic microemulsions useful for cleaning hard surface items such as bathtubs and sinks, which microemulsions are especially effective in removing soap scum and lime scale from them.
  • microemulsions may be essentially neutral and as such are also thought to be effective for microemulsifying lipophilic soils from substrates.
  • U.S. Patent Application Serial No. 07/313,664 there is described a light duty microemulsion liquid detergent composition which is useful for washing dishes and removing greasy deposits from them in both neat and diluted forms.
  • Such compositions include complexes of anionic and cationic detergents as surface active components of the microemulsions.
  • the various microemulsions referred to include a lipophile which may be a hydrocarbon, a surfactant which may be an anionic and/or a nonionic detergent(s), a co-surfactant which may be a poly-lower alkylene glycol lower alkyl ether, e.g. tripropylene glycol monomethyl ether, and water.
  • a lipophile which may be a hydrocarbon
  • a surfactant which may be an anionic and/or a nonionic detergent(s)
  • a co-surfactant which may be a poly-lower alkylene glycol lower alkyl ether, e.g. tripropylene glycol monomethyl ether, and water.
  • aqueous cleaning compositions which are optionally surfactant-free, provide increased grease, soap scum and tar removal capabilities without or with a minimum mechanical action as compared to the water-based microemulsions as disclosed in U.S. Patents Nos. 5,075,026, 5,108,643; 4,919,839 and 5,082,584. These water-based microemulsions all contain a surfactant as compared to the preferred surfactant-free compositions of the instant invention.
  • Kohnstamm rose the theoretical possibility of a critical point "of the second order" in a ternary liquid mixture, a point at which three co-existing fluid phases merge and become identical, Kohnstamm (Ph.). Handbuch der physik, 1926, Vol. 10, Kap. 4, Thermodynamik der Gemische, pp. 270-271 , H. Geiger and K. Scheel (SPRINGER, BERLIN). Kohnstamm also stressed the extreme difficulty to find such a point.
  • Bleaching cleaning, oxidizing and disinfectant and compositions have been used in home and industrial applications for hard surface care and fabric care.
  • hypochlorite bleaches are very effective at removal of stains, when they are used in relatively high concentrations, but these hypochlorite, as well as other active chlorine bleaches, can cause rather severe damage to fabric colors as well as damaging textile fibers. Additionally, these hypochlorite liquid bleaches can present handling and packaging problems. Color and fabric damage can be minimized by the use of milder oxygen bleaches such as potassium monopersulfate; however, stain removal characteristics of these peroxygen bleaches are much less desirable than those of the harsher halogen bleaching agents.
  • Commercial bleaching compositions which contain peroxygen bleaches commonly utilize activators; which are compounds that enhance the performance of the peroxygen bleachant.
  • Bleaching compositions which have employed various types of bleach activators have been disclosed in: Popkin, U.S. Patent 1 ,940,768, Dec. 26, 1933; Baevsky, U.S. Patent 3,061 ,550, October 30, 1962; Mackellar et al, U.S. Patent 3,338,839, August 29, 1967; and Woods, U.S. Patent 3,556,711 , January 19, 1971.
  • the instantly disclosed bleachant activators represent an improvement over these previously disclosed activators for the cleaning of fabrics and hard surfaces because of the ability of the formulator to formulation bleachant compositions which are activate at room temperature while causing less damage to the fabric being cleaned.
  • Hydrogen peroxide and surfactant mixtures have been disclosed in European Patent Application and Patent Nos: EP 0376,704B1 ; EP 0376706A1 and EP 0009839B2.
  • the present invention brings a new and different technical benefit: it has been found that it is possible to deliver, independently of an optional disinfection taking place at the point of use, a preventive action able to considerably retard further strain growth on the treated porous surface.
  • This can be achieved by incorporating in a composition a well selected "biostatic" molecule which acts as a "surface preservative” and delays new germs development; this composition can optionally incorporate a bleaching agent.
  • Ideal compositions are those presenting excellent wetting properties to allow a deep penetration of the composition in pores and fractures, and thus an improved in depth active delivery.
  • compositions are able to deliver both a cleaning action and a remanant prevention against further strain growth.
  • Derived products contain user friendly ingredients compared to the currently used aggressive chlorine based compositions. Such products which confer to the cleaning action a sanitizing secondary benefit would also permit a less frequent cleaning whilst maintaining the surfaces longer clean and hygienic. Such products should especially be useful in bathroom where it is very difficult to get rid of colored molds such as Aspergillus niger.-Rhodotorula minuta and various Penicilium species.
  • the bleach or disinfecting aqueous and biostatic agent containing cleaning near tricritical point compositions which of the instant invention are applicable for use in concentrated household care products.
  • the instant near tricritical point compositions permit the preparation of cleaning or liquid products which are optionally surfactant- free.
  • a bleach or disinfecting and biostatic agent containing near tricritical point cleaning composition suitable at room temperature or colder or at a higher temperature for pre-treating and cleaning materials soiled with a lipophilic soil, comprises a bleachant system and biostatic agent together with a polar solvent such as water, a water soluble or dispersible low molecular weight amphiphile, and a non-polar solvent, or weakly polar solvent wherein the three phases have merged into one continuum at the tricritical point.
  • a polar solvent such as water, a water soluble or dispersible low molecular weight amphiphile
  • the invention also relates to the killing as well as the prevention of the formation of fungus, molds, spores, viruses, germs and bacteria as well as to a processes for treating items and materials soiled with soils such as lipophilic soil, with compositions of this invention, to loosen and to remove without mechanical action such soil by applying to the locus of such soil on such material a soil loosening or removing amount of the near tricritical point compositions of the instant invention.
  • Disinfecting and preventing means obtaining a germ killing and preventing effect or microorganism killing effect.
  • the instant bleach or disinfecting and biostatic agent containing aqueous cleaning composition exists at or in the vicinity of the tricritical point which is the terminus of three lines of critical points.
  • the tricritical point is a thermodynamical point at which all three co-existing phases become identical simultaneously.
  • the interfacial tension between the merging phases in which the polar solvent and the low molecular weight amphiphile are respectively at their highest concentrations is substantially zero, and the interfacial tension between the merging phases in which the low molecular weight amphiphile and the non-polar or weakly polar solvent (oil) are respectively at their highest concentrations is substantially zero, and the interfacial tension between the merging phases in which the polar solvent and the non-polar or weakly polar solvent are respectively at their highest concentrations, is substantially zero.
  • the cleaning mechanism of the cleaning compositions of the instant invention is based on the reduction of the polar solvent/non-polar solvent interfacial tension as it approaches the value of zero.
  • compositions of the instant invention have a phase inversion temperature (PIT) of about 0 to about 80°C, more preferably about 15 to about 40°C.
  • the phase inversion temperature is the temperature at which there is an equal affinity of the low molecular weight amphiphile for water and for oil. It is the temperature at which the partition of the low molecular weight amphiphile between the water-rich phase and the non-polar-solvent-rich phase or weakly-polar-solvent-rich phase equals unity. That is, the weight fraction of the low molecular weight amphiphile in the water-rich phase is equal to the weight fraction of the low molecular weight amphiphile in the non-polar- solvent-rich phase.
  • composition 100 wt % of composition
  • ⁇ wt % of additive wt % of water + wt. % of additive
  • the weight fraction of the water is equal to (1- ⁇ ) (1 - ⁇ ) (1- ⁇ ) and ⁇ is about 0.01 to about 0.50 more preferably about 0.05 to about 0.30, ⁇ is about 0.01 to about 0.40, more preferably about 0.03 to about 0.25, and ⁇ is about 0 to about 0.20, more preferably about 0.01 to about 0.05
  • the additive is a water soluble additive, a polar cosolvent or an electrolyte which has as essential function to adjust the phase configuration.
  • the additives are water soluble molecules (electrolytes or organics) that are able to modify the structure of water so as to strengthen or disrupt the solvent structure. Addition of such chemicals will therefore modify the solubility of uncharged organic ingredients in water and, among others, of amphiphilic molecules.
  • the above chemicals are divided into two classes: Salting-out (or kosmotropic) agents reinforce the structure of water and make it less available to hydrate organic molecules. Salting- in (or chaotropic) agents, on the other hand, disorder the structure of water, thereby creating an effect comparable to "holes". As a consequence they increase the solubility of polar organic molecules in water. (Salting-out and -in agents are also referred to as lyotropes and hydrotropes, respectively.)
  • lyotropic agents make water more incompatible with both oil and amphiphile. The result is a decrease of the PIT and an increase of the supertricritical character. The amount of low molecular weight amphiphile needed to "congregate" water and oil generally increases in the presence of salting-out agents. Hydrotropic agents have the opposite effects.
  • the instant invention relates to an aqueous near tricritical point composition having an apparent viscosity at 10 2 sec *1 and 25°C, of about 1 to 10,000 cps, more preferably about 1 to 1 ,000 cps, most preferably about 1 to 100 cps, and a surface tension of about 10 to about 35 mN/m, which comprises approximately by weight: 55 to 95 wt. % of a polar solvent; 1 to 15 w. % of a non-polar solvent or a weakly polar solvent, and about 1 to about 23 wt. % of water soluble or water dispersible low molecular weight amphiphile, about 0 to about 60 wt. %, more preferably about 1 to about 60 wt.
  • aqueous near tricritical point cleaning composition which is useful in a cleaning operation without or with a minimum of mechanical action for the control and prevention of the formation of bacteria, fungus, molds and germs as well as for removal of grease, soap scum and tar and especially for the penetration of the near tricritical composition into a porous surface thereby destroying the adhesion of soil to the substrate.
  • the present invention relates to an aqueous near tricritical point composition having an apparent viscosity at 10 2 sec -1 and 25°C, of about 1 to 10,000 cps, more preferably about 1 to 1 ,000 cps, most preferably about 1 to 100 cps, and a surface tension of about 10 to about 35 mN/m, which comprises approximately by weight: a) 1 to 15% of a non-polar solvent or a weakly polar solvent or mixtures thereof, more preferably 2 to 12% and most preferably 2 to 10%; b) 1 to 23%, more preferably 2 to 20% and most preferably 3 to 18%, of a water soluble or water low molecular weight dispersible amphiphile; c) 55 to 95%, more preferably 70 to 94% and most preferably 74 to 94%, of a polar solvent, wherein the composition is optionally surfactant-free;.
  • composition 0 to 20%, more preferably 0.5 to 15% and most preferably 1.0 to 10% of a water soluble additive, wherein the composition can optionally contain at least one solid particle and/or immiscible solvent which is not the non-polar or weakly polar solvent in the composition;
  • the bleach or disinfecting and biostatic agent containing near tricritical point compositions of the instant invention have three coexisting liquid phases that are capable of being converted into one single phase by weak mechanical action according to a reversible equilibrium or to make the three co-existing liquid phases merge together into one continuum to form the tricritical point composition.
  • wt. % concentrations (Xi , X2, X3, X, Y1 , Y2. Y3, Y. Z1 , Z2, Z3, Z) are expressed with reference to the whole composition and not reference to the considered singular phase.
  • the wt. % concentration of the polar solvent in the first phase is represented by X1
  • the wt. % concentration of the polar solvent in the second phase is represented by X2
  • the wt. % concentration of the polar solvent in the third phase is represented by X3, wherein the total wt.
  • % concentration (X) of the polar solvent in the composition is equal to X1 +X2+X3, wherein Xi , X2 and X3 are approximately equal to each other.
  • the concentration of the polar solvent in each of the three phases is about 22 wt. % to about 32 wt. %, more preferably about 25 wt. % to 29 wt. % and most preferably about 26 wt. % to about 28 wt. %, wherein X ⁇ >X2 or X3.
  • the wt. % concentration of the water soluble or water dispersible low molecular weight amphiphile in the first phase is represented by Y1 and the wt. % concentration of the amphiphile in the second phase is represented by Y2 and the wt. % concentration of the amphiphile in the third phase is represented by Y3, wherein the total wt. % concentration (Y) of the amphiphile in the composition is equal to Y1+Y2+Y3, wherein Y1 , Y2 and Y3 are approximately equal to each other.
  • the concentration of the low molecular weight amphiphile can tolerate variations of ⁇ 2 absolute wt. % and more preferably ⁇ 1 absolute wt. % in each of the three phases.
  • the concentration of the low molecular weight amphiphile in each of the three phases is about 1 wt. % to about 5 wt. %, more preferably about 2 wt. % to 4 wt. %, wherein Y2>Y ⁇ or Y3.
  • the wt. % concentration of the non-polar solvent (also weakly polar solvent) in the first phase is represented by Z1 and the wt. % concentration of the non-polar solvent in the second phase is represented by Z2 and the wt. % concentration of the non-polar solvent in the third phase is represented by Z3, wherein the total wt. % concentration (Z) of the non-polar solvent in the composition is equal to Z1+Z2+Z3, wherein Z- ⁇ , Z2 and Z3 are approximately equal to each other.
  • the concentration of the nonpolar solvent can tolerate variations of ⁇ 5 absolute wt. %, more preferably ⁇ 2 absolute wt. % and most preferably ⁇ 1 absolute wt. % in each of the three phases.
  • the concentration of the non-polar solvent in each of the three phases is about 1 wt. % to about 5 wt. %, more preferably about 2 wt. % to 4 wt. %, wherein Z3>Z ⁇ or Z2.
  • the bleach or disinfecting and biostatic agent containing near tricritical point compositions unlike true microemulsions which are optically clear exhibit a critical opalescence in that the tricritical point composition appears opalescent.
  • the bleach or disinfecting aqueous and biostatic agent containing near tricritical point compositions of the instant invention can be used as a basic formulation for the production of both commercial and industrial applications by the incorporation of selective ingredients in the tricritical point composition.
  • Typical compositions which can be formed for a variety of applications are fabric cleaners, shampoos, floor cleaners carpet cleaners, cleaning pastes, tile cleaners, bath tub cleaners, bleach compositions, disinfecting cleaners, ointments, oven cleaners, stain removers, bleach pre-spotters, dishwashing prespotters, automatic dishwashing compositions, laundry pre-spotters, and cleaning pre-spotters and graffiti or paint removers and mildew cleaner for grouts.
  • the present invention relates to a bleach or disinfecting and biostatic agent containing liquid cleaning composition which is optionally surfactant-free having a surface tension of about 10 to about 35 mN/m at 25°C deriving from three co-existing liquid phases which are almost chemically identical to each other and the three coexisting liquid phases have merged together into one continuum to form the composition, wherein the first phase has the highest polar solvent concentration, the second phase has the highest water soluble or water dispersible amphiphile concentration and the third phase has the highest non-polar solvent or weakly polar solvent concentration and the interfacial tension between said first phase and said second phase is 0 to about 1 x 10 * 3 mN/m and the interfacial tension between the second phase and the third phase is 0 to about 1 x 10 ⁇ 3 mN/m, and the interfacial tension between the first phase and the third phase is 0 to about 1 x 10 -3 mN/m.
  • the polar solvent is water at a concentration of about
  • the low molecular weight amphiphile is an organic compound having a water insoluble hydrophobic portion which has a partial Hansen polar parameter and hydrogen bonding parameter, both of which are less than about 5 (MPa) 1 /2 , and a water soluble hydrophilic portion which has a partial Hansen hydrogen bonding solubility parameter greater than about 10 (MPa) 1 '' 2 ; the amphiphile is present at a concentration of about 1 to about 23 wt %; and non-polar solvent or weakly polar solvent has a Hansen dispersion solubility parameter greater than about 10 (MPa) 1 /2 and a Hansen hydrogen bonding solubility parameter of less than about 15(MPa) 1 /, 2, being present at a concentration of about 1 to about 15 wt %.
  • the main characteristic of the polar solvent is that it has the ability to form hydrogen bonding with the low molecular weight amphiphile and the polar solvent has a dielectric constant of higher than 35.
  • other polar solvents suitable for use in the instant composition are formamide, glycerol, glycol and hydrogen peroxide and mixtures thereof.
  • the aforementioned polar solvents can be mixed with water to form a mixed polar solvent system.
  • the concentration of the polar solvent such as water in the near tricritical point composition is about 55 to 95 wt %, more preferably about 70 to about 94 wt %.
  • the organic non-polar or weakly polar solvent component of the present bleach or disinfecting and biostatic agent containing aqueous near tricritical point compositions includes solvents for the soils, is lipophilic.
  • the non-polar solvent or weakly polar solvent has a Hansen dispersion solubility parameter at 25°C of at least 10 (MPa) 1/2 , more preferably at least about 14.8 (MPa) 1/2 , a Hansen polar solubility parameter of less than about 10 (MPa) 1/2 and a Hansen hydrogen bonding solubility parameter of less than about 15 (MPa) 1/2 .
  • non-polar solvent or weakly polar solvent important parameters to be considered are the length and configuration of the hydrophobic chain, the polar character of the molecule as well as its molar volume.
  • the non-polar solvent or weakly polar solvent which at 25°C is generally less than 5 wt % soluble in water, can be selected from the group consisting of alkylene glycol alkyl ethers having the formula:
  • R" is an alkylene group having about 4 to about 14 carbon atoms and x is 1 to 13 and y is about 2 to about 7 and can be selected from the group consisting of weakly water soluble polyoxyethylene alkyl ethers derivatives having the formula:
  • Ri and R2 are alkyl groups having about 2 to about 10 carbon atoms, more preferably about 3 to about 8 carbon atoms and x is about 1 to 12, y is 0 to 2 and z is about 0 to 2 and terpenes or oxygenated terpenes.
  • Some typical non-polar solvents or weakly polar solvents are decylacetate, ethylene glycol monohexyl ether, diethylene glycol monohexyl ether, disopropyl adipate, octyl lactate, dioctyl maleate, dioctyl malate, diethylene glycol mono octyl ether, Dobanol® 91 - 2.5 EO, limonene, pinene, dipentene, terpineol and mixtures thereof.
  • the concentration of the non-polar solvent or weakly polar solvent in the bleach or disinfecting near tricritical point composition is about 1 to about 5 wt. %, more preferably about 2 to about 12 wt. %.
  • the concentration of the low molecular weight amphiphile in the bleach or disinfecting and biostatic agent containing near tricritical point composition is about 1 to about 23 wt. %, more preferably about 2 to about 20 wt. %.
  • the low molecular weight amphiphile of the instant composition is a molecule composed of at least two parts which is capable of bonding with the polar solvent and the non-polar solvent. Increasing the molecular weight of the low molecular weight amphiphile increases its water/oil coupling ability which means less low molecular weight amphiphile is needed to couple the polar solvent and the non-polar solvent or weakly polar solvent. At least one part is essentially hydrophobic, with a Hansen partial polar and hydrogen bonding solubility parameters less than 5 (MPa) 1 / 2 . At least one part is essentially water soluble, with Hansen partial hydrogen bonding solubility parameter equal or greater than 10 (MPa) 1/2 .
  • the low molecular weight amphiphilic molecule must be cut according to the following rules:
  • the hydrophobic parts should not contain any nitrogen or oxygen atoms; the hydrophilic parts generally contain the hetero-atoms including the carbon atoms directly attached to an oxygen or nitrogen atom.
  • This table shows the solubility parameters for different groups.
  • the first series can be used as the hydrophilic part of an amphiphile molecule, as the hydrogen bonding solubility parameter is always greater than 10.
  • the last group can be used as the hydrophobic part of an amphiphile, as their polar and hydrogen bonding solubility parameters are below 1.
  • the group in the middle (esters and ketones) cannot be used as a significant contribution to an amphiphile molecule.
  • low molecular weight amphiphiles which are present at a concentration of about 1 to about 23 wt. %, more preferably about 2 to about 20 wt. %, are selected from the group consisting of polyoxyethylene derivatives having the formula: C x H2 ⁇ + ⁇ - O - (CH2CH2 - O -) y - H wherein x and/or y is 1 to 10, more preferably 1 to 6, polyols having 4 to 8 carbon atoms, polyamines having 5 to 7 carbon atoms, polyamides having 5 to 7 carbon atoms, alkanols having 2 to 4 carbon atoms and alkylene glycol alkyl ethers having the formula: CH3
  • R" O - (CH2 CH - 0) y H
  • R" is an alkylene group having about 4 to about 8 carbon atoms and x is 0 to 2 and y is about 1 to about 5
  • the molecular weight of the low molecular weight amphiphile is about 76 to about 300, more preferably about 100 to about 250.
  • ethylene glycol monobutyl ether (EGMBE), diethylene glycol monobutyl ether (DEGMBE), triethylene glycol monohexyl ether and tetraethylene glycol monohexyl ether and mixtures thereof such as ethylene glycol monobutyl ether (EGMBE) and diethylene glycol monobutyl ether (DEGMBE) in a ratio of about 1 :2.
  • bleach or disinfecting and biostatic agent containing near tricritical point compositions can be optionally formed from a polar solvent, a nonpolar or weakly polar solvent and a surfactant or a mixture of a low molecular weight amphiphile and surfactant, when the surfactant is employed without a low molecular weight amphiphile, the surfactant is present in the composition at a concentration of about 3.0 to about 8.0 wt. percent. When the surfactant is employed in the composition with the low molecular weight amphiphile the concentration of the surfactant is about 0.1 to about 6.0 weight percent and the concentration of the low molecular weight amphiphile is about 1 to about 25 wt. percent.
  • the surfactants that are employed in the instant invention are selected from the group consisting of nonionics, anionics, amine oxides, cationics and amphoteric surfactants and mixtures thereof. Especially preferred nonionic surfactants are Dobanol 91-5 and Synperonic 19/4. When the surfactant is used alone and without a low molecular weight amphiphile the surfactant must preferably have an HLB of about 7 to 14. It is to be understood that surfactants are a subset of the set of amphiphiles. The low molecular weight amphiphiles do not form aggregates at an interface for example, the interface of oil and water, but rather the low molecular weight amphiphile is evenly distributed throughout the solution. Whereas a surfactant is proned to concentrate at the interfaces between different phases
  • the instant near tricritical point compositions contain about 0 to about 30 wt. %, more preferably 2.5 to about 25 wt. %, most preferably about 4 to about 20 wt.
  • the preferred bleach is a 35 wt. % solution of hydrogen peroxide in water.
  • the biostatic agents used in the instant composition at a concentration of 0.2 to 10 wt. %, more preferably 0.4 to 8 wt. % are selected from the group consisting essentially of a C ⁇ -Ci ⁇ alkyl dimethyl benzyl ammonium halide such as dodecyl dimethyl benzyl ammonium chloride (Benzalkonium chloride), a C12-C20 alkyl trimethyl ammonium halide such as cetyl trimethyl ammonium chloride (Cetrimonium chloride), polyhexamethylene biguanide hydrochloride (Tradename-Cosmocil CQ), 3-trialkoxysily, C14-C20 alkyl dimethyl ammonium C2-C4 alkyl halide such as 3-tri-methoxysily, propyl octadecyl dimethyl ammonium chloride, (Tradename DC5700 - Dow Corning), cis-1 - acetyl-4-[4[
  • the instant composition can optionally contain about 0.1 to about 15 wt. %, more preferably about 1 to about 5 wt. % of a water soluble chaotropic additive which can be hydrotropic or kosmotropic.
  • a hydrotropic agent weakens (salting-in effect) the structure of the water thereby making the water an improved solvent for the amphiphile
  • a kosmotropic (lyotropic) agent strengthens (salting-out effect) the structure of the water thereby making water less of a solvent for the amphiphile.
  • Typical hydrotropic agents are acetic acid, ethanol, isopropanol, sodium benzoate, sodium toluene sulfonate, sodium xylene sulfonate, sodium cumene sulfonate, ethylene glycol, propylene glycol, metal salts of iodide, metal salts of thiocyanates, metal salts of perchlorates, guanidinium salts.
  • the use of the chaotropic additive can change the weight percentage of the polar solvent, amphiphile and non-polar solvent used to form the near tricritical point composition.
  • adjuvant materials for dental, dishwashing, laundering and other detergency applications may include: foam enhancing agents such as lauric or myristic acid diethanolamide; foam suppressing agents (when desired) such as silicones, higher fatty acids and higher fatty acid soaps; preservatives and antioxidants such as formalin and 2,6-ditert-butyl-p-cresol; pH adjusting agents such as sulfuric acid and sodium hydroxide; perfumes; polymeric thickening agents, bleach stabilization agents and colorants (dyes and pigments).
  • foam enhancing agents such as lauric or myristic acid diethanolamide
  • foam suppressing agents when desired
  • silicones such as silicones, higher fatty acids and higher fatty acid soaps
  • preservatives and antioxidants such as formalin and 2,6-ditert-butyl-p-cresol
  • pH adjusting agents such as sulfuric acid and sodium hydroxide
  • perfumes polymeric thickening agents, bleach stabilization agents and colorants (dyes and pigments).
  • compositions can optionally contain an inorganic or organic builder salt provided that the salt is not present at a concentration that destroys the character of the near-tricritical point compositions.
  • the builder salt is generally present at a concentration of about 1 to about 30 wt. %, more preferably about 2 to about 10 wt. %.
  • the builder salt is selected from the group consisting of isoserine diacetate acid, alkali metal carbonates, alkali metal bicarbonates, alkali metal citrates, alkali metal salts of a polyacrylic acid having a molecular weight of about 500 to 4,000, alkali metal tartarates, alkali metal gluconates, alkali metal silicates, alkali metal tripolyphosphates and alkali metal pyrophosphates and mixtures thereof.
  • the maximum concentration of the builder salt in the bleach and biostatic agent containing near tricritical point composition is determined by and limited by the solubility of the builder salt in the most polar phase, wherein the builder salt is completely dissolved in the most polar phase.
  • near tricritical point compositions Pre-spotting and manual cleaning uses of the invented near tricritical point compositions are uncomplicated, requiring no specific or atypical operations. Thus, such near tricritical point compositions may be employed in the same manner as other liquid pre-spotting and detergent compositions.
  • the invented near tricritical point compositions may be applied to such surfaces with a cloth or sponge, or by various other contacting means, but it is preferred to apply them, depending on their viscosity.
  • Such application may be applied onto hard surfaces such as dishes, walls or floors from which lipophilic (usually greasy or oily) soil is to be removed, or may be applied onto fabrics such as laundry which has previously been stained with lipophilic soils such as motor oil.
  • the invented compositions may be used as detergents and as such may be employed in the same manner in which liquid detergents are normally utilized in dishwashing, floor and wall cleaning, and laundering, but it is preferred that they are employed as pre-spotting agents too, in which applications they are found to be extremely useful in loosening the adhesions of lipophilic soils to substrates, thereby promoting much easier cleaning with application of more of the same invented detergent compositions or by applications of different commercial detergent compositions in liquid, bar or particulate forms.
  • compositions A through G were made by first forming with mixing at room temperature a solution of the H2O2 and the water or the water and the optional additive. To this solution at room temperature were added successively with mixing the non-polar solvent or weakly polar solvent (oil) and the amphiphile and then subsequently was added the optional disinfecting agent to form the near tricritical point compositions A through G.
  • Sample H contains only H2 ⁇ 2, Sample I is a tricritical composition without bleach or biostatic agent and Sample J is a pure water blank.
  • cleaning compositions are basically designed around ternary water/NI amphiphile/oil system; the incorporate C6E2 and C6E2 as amphiphiles, limonene as oil and H2O2 as an optional bleaching agent.
  • the prototypes have been first evaluated in a microbiology lab for both bacteria and molds growth inhibition on two types of natural cultures:
  • a minimum nutrient material (carbohydrate food, stuffing electrolytes%) is also needed to sustain the germs culture; it can be initially present (paper, glue%) or can result from the build-up of external contaminants (soapy water, air condensates, food or beverage stains).
  • boiled orange juice is a very effective nutritive solution for lab purpose.
  • Nutrient solution used in the following experiments is made from orange juice extract; this extract is prepared by boiling 11 orange juice for 1/2 hour and bringing back its volume to 11 by addition of Dl water.
  • the mold spores present on a naturally contaminated shower curtain have been collected. They were previously identified as being mainly Aspergillus niger, Rhodotorula minuta, Candida albicans and various Penicilium strains.
  • Procedyre 1. Bathroom keramic tiles are immersed in a 5% hydrogen peroxide solution to eliminate potential undesirable germs. They are left overnight backside up to allow drying.
  • a 24daysO more than 24 days at least bacteria
  • compositions provide a preventive effect against mold since only the blank (i.e. J) has exhibited a mold proliferation (after 17 days).
  • the germ growth preventive action is increasing when adding in a neartricritical system a peroxide bleach (cf. from I to H).

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Abstract

La présente invention concerne une composition nettoyante aqueuse de blanchiment ou de désinfection qui permet d'éliminer la graisse ou le goudron sans action mécanique. En particulier, ces compositions prêtes à l'emploi sont composées de trois phases liquides qui se mélangent au point tri-critique et forment un continuum constituant la composition aqueuse nettoyante. Ces trois phases comprennent au moins un solvant polaire, un solvant non polaire ou faiblement polaire et un amphiphile de faible poids moléculaire soluble dans l'eau ou dispersable dans l'eau, et ladite composition comprend un agent de blanchiment et un agent biostatique.
PCT/US1997/011600 1996-07-05 1997-06-18 Compositions proches du point tri-critique contenant un agent de blanchiment et/ou un agent biostatique WO1998001527A1 (fr)

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AU35913/97A AU3591397A (en) 1996-07-05 1997-06-18 Near tricritical point compositions containing bleach and/or biostatic agent

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US67857596A 1996-07-05 1996-07-05
US08/678,575 1996-07-05

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AR (1) AR007811A1 (fr)
AU (1) AU3591397A (fr)
CO (1) CO4870790A1 (fr)
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018605A1 (fr) * 2002-08-20 2004-03-04 Givaudan Sa Composition de blanchiment aromatisee
WO2016164545A1 (fr) 2015-04-07 2016-10-13 Indusco, Inc. Articles antimicrobiens et composés associés

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
EP0620270A2 (fr) * 1993-04-12 1994-10-19 Colgate-Palmolive Company Compositions de nettoyage
US5527485A (en) * 1994-02-04 1996-06-18 Colgate-Palmolive Co. Near tricritical point compositions
US5585034A (en) * 1991-11-21 1996-12-17 Colgate-Palmolive Co. Gelled near tricritical point compositions
WO1997019164A1 (fr) * 1995-11-17 1997-05-29 Colgate-Palmolive Company Compositions a point tricritique proche

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5585034A (en) * 1991-11-21 1996-12-17 Colgate-Palmolive Co. Gelled near tricritical point compositions
EP0620270A2 (fr) * 1993-04-12 1994-10-19 Colgate-Palmolive Company Compositions de nettoyage
US5527485A (en) * 1994-02-04 1996-06-18 Colgate-Palmolive Co. Near tricritical point compositions
WO1997019164A1 (fr) * 1995-11-17 1997-05-29 Colgate-Palmolive Company Compositions a point tricritique proche

Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2004018605A1 (fr) * 2002-08-20 2004-03-04 Givaudan Sa Composition de blanchiment aromatisee
WO2016164545A1 (fr) 2015-04-07 2016-10-13 Indusco, Inc. Articles antimicrobiens et composés associés
EP3280578A4 (fr) * 2015-04-07 2019-01-02 Indusco, Ltd. Articles antimicrobiens et composés associés
AU2016245775B2 (en) * 2015-04-07 2020-07-02 Novalent, Ltd. Antimicrobial articles and compounds therefor

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ZA975826B (en) 1998-12-30
AR007811A1 (es) 1999-11-24
CO4870790A1 (es) 1999-12-27
AU3591397A (en) 1998-02-02

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