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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/1213—Oxides or hydroxides, e.g. Al2O3, TiO2, CaO or Ca(OH)2

Definitions

• the invention relates to a detergent composition containing titanium dioxide in the form of elementary particles of size less than 100 nm and of specific surface greater than 150 m 2 / g.
• titanium dioxide as a bactericidal and photo-oxidizing agent in a detergent composition.
• any type of detergency whether for washing clothes or for industrial surfaces such as tiles, windows, etc., it is essential to be able to destroy microorganisms such as bacteria, algae, microscopic fungi, animal cell residues or plants .... which may cause risks to human health.
• a certain number of techniques are known for eliminating these microorganisms, such as irradiation under gamma or UV radiation, freezing, sterilization by heating, etc.
• the object of the present invention is to provide a means other than chemical agents for eliminating microorganisms in detergency.
• the invention relates to a detergent composition comprising titanium dioxide, as well as the use of titanium dioxide as a bactericidal and photo-oxidizing agent in a detergent composition.
• the invention relates first of all to a detergent composition characterized in that it contains titanium dioxide in the form of elementary particles of size less than 100 nm, preferably less than 70 nm, very particularly of the order of 20 to 60 nm and with a specific surface greater than 150 rrvVg, preferably greater than 200 m / g, very particularly of the order of 200 to 300 m 2 / g.
• Titanium dioxide has a photocatalytic action in an aqueous medium and in the presence of UV rays, with the release of oxidizing species, which can have a bactericidal or soil degradation effect. Titanium dioxide is also a bleaching activator, in particular an activator of the decomposition of hydrogen peroxide with release of more oxidizing species.
• the specific surface described above is a BET surface.
• O means BET surface, the specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established from the method
• the failure of elementary titanium dioxide particles according to the invention is measured by transmission electron microscopy (TEM).
• TEM transmission electron microscopy
• the nature of the elementary particles of titanium dioxide is preferably the anatase.
• Said elementary titanium dioxide particles can be present, within the detergent composition, both in the form of aggregates and of individualized particles, as in colloidal dispersion depending on the physical nature of the detergent composition.
• the detergent composition is a powder
• the elementary particles of titanium dioxide will generally be present in the form of aggregates. They can also be deposited on the surface of an inorganic substance inert with respect to titanium dioxide such as alkali metal carbonate.
• the elementary particles of titanium dioxide can be perfectly individualized and well separated from each other.
• said elementary particles of titanium dioxide can be in the form of a colloidal dispersion.
• colloidal dispersion is meant here and for the entire description any system consisting of fine particles of colloidal size based on titanium oxide and / or hydrated oxide (hydroxide), suspended in a liquid phase, in particular an aqueous phase.
• Titanium can be found either completely in the form of colloids, or simultaneously in the form of ions and colloids, without however the proportion represented by the ionic form not exceeding approximately 10% of the total of titanium in the colloidal dispersion.
• colloidal dispersions are preferably used in which the titanium is completely in colloidal form.
• This colloidal dispersion generally has a solids content of between 5 and 30%, preferably between 10 and 20% by weight.
• the elementary particles of titanium dioxide according to the invention either in the form of aggregates, or in the form of individualized particles, can be obtained by any means known to those skilled in the art.
• the hydrolyzed titanium compound can be chosen from halides, oxyhalides, nitrates, alkoxides or titanium sulfates.
• the hydrolysis operation can be carried out by heating the solution of titanium compound. It can, in certain cases, be carried out in the presence of titanium dioxide seeds or in the presence of specific compounds making it possible to obtain titanium dioxide of higher purity, such as those described in
• EP-A-0351 270 EP-A-0351 270.
• the precipitated titanium dioxide is separated from the mother liquors, then dried, the titanium dioxide powder obtained can be used directly or be redispersed in a liquid medium so as to obtain a colloidal dispersion of titanium dioxide .
• the level of titanium dioxide expressed in dry terms, may be at least about 0.1%, preferably of the order of 0.1 to 5%, very particularly of the order of 0.4 to 3% by weight of said composition.
• the invention also relates to the use of titanium dioxide in the form of elementary particles having a size less than 100 nm, preferably less than 70 nm, very particularly of the order of 20 to 60 nm and a specific surface greater than 150 m 2 / g, preferably greater than 200 m 2 / g, very particularly of the order of 200 to 300 m 2 / g, as a bactericidal and photo-oxidizing agent in a detergent composition.
• Titanium dioxide is capable of destroying living organic matter, so it acts as a bactericidal agent. It also destroys dead organic matter, it is a photo-oxidizing agent. These two functions of titanium oxide may be due to the photocatalytic process and or the bleach activating process described above.
• detergent composition is understood to mean both detergent formulations, in particular for household or industrial washing of linen, as well as compositions for cleaning or maintaining hard surfaces exposed to light.
• surfactants such as anionic surfactants
• alkyl ester sulphonates of formula R-CH (S ⁇ 3M) -COOR ' where is an alkyl radical containing 8 "20> preferably C-
• R' an alkyl radica Ci-C ⁇ , preferably C1 C3 and M an alkali cation (sodium potassium, lithium), substituted or unsubstituted ammonium (methyl-, dimethyl- trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...)
• Mention may very particularly be made of methyl ester sulfonates whose radicals R is C 1 -C 16 ;
• alkyl sulfates of formula ROSO3M where R represents a C10-C24 alkyl or hydroxyalkyl radical. preferably C12-C20 and most preferably C12-C18 'M representing a hydrogen atom or a cation with the same definition as above, and their ethoxylenated (EO) and / or propoxylenated (PO) derivatives, having on average of 0.5 to 6 units, preferably 0.5 to 3 OE and / or OP units;
• alkylamide sulfates of formula RCONHROSO3M where R represents a C2-C22 alkyl radical. preferably C ⁇ -C20. R ' a C2- alkyl radical
• C3, M representing a hydrogen atom or a cation of the same definition as above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 60 OE units and / or OP;
• the salts of C8-C24 preferably C14-C20 saturated or unsaturated fatty acids.
• 'C9-C20 alkylbenzenesulfonates primary alkyl sulfonates or secondary in C8-C22.
• alkyl glycerol sulfonates sulfonated polycarboxylic acids such as those described in GB-A-1 082 179, paraffin sulfonates, N-acyl N-alkyltaurates, alkylphosphates, isethionates, alkylsuccinamates, alkylsulfosuccinates, monoesters or diesters of sulfosuccinates, N-acyl sarcosinates, alkyl glycoside sulfates, polyethoxycarboxylates, the cation being an alkali metal (sodium, potassium, lithium), a substituted or unsubstituted ammonium residue (methyl-, dimethyl-, trimethyl-, tetramethylammonium, dimethylpiperidinium ...) or derived from an alkanolamine (monoethanolamine, diethanolamine, triethanolamine ...); non-ionic surfactants polyoxyalkylenated (
• polyoxyalkylenated C8-C22 aliphatic alcohols containing from 1 to 25 oxyalkylene units oxyethylene, oxypropylene
• amine oxides such as alkyl oxides C10-C18 dimethylamines, alkoxy oxides C8-C22 ethyl dihydroxy ethylamines;
• builders in amounts corresponding to about 5-50%, preferably about 5-30% by weight for liquid detergent formulas, or about 10-80%, d preferably 15-50% by weight for detergent formulas in powders, such as inorganic Cbuilders ")
• polyphosphates tripolyphosphates, pyrophosphates, orthophosphates hexametaphosphates of alkali metals, ammonium or alkanolamines. tetraborates or borate precursors
• silicates in particular those having a Si ⁇ 2 / Na2 ⁇ ratio of the order of 1.6 / 1 to 3.2 / 1 and the lamellar silicates described in US-A-4,664,839.
• alkali or alkaline earth carbonates (bicarbonates, sesquicarbonates)
• crystalline or amorphous aminosilicates of alkali metals (sodium, potassium) or ammonium, such as zeolites A, P, X ...; zeolite A with a particle size of the order of 0.1-10 micrometers is preferred organic agents ("builders") water-soluble polyphosphonates (1-hydroxy-1 ethane, 1-diphosphonates, methylene salts diphosphonates ...)
• polycarboxylate ethers oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts.
• hydroxypolycarboxylate ethers oxidisuccinic acid and its salts, monosuccinic acid tartrate and its salts, disuccinic acid tartrate and its salts.
• citric acid and its salts citric acid and its salts, mellitic acid, succinic acid and their salts
• salts of polyacetic acids ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyD-nitrilodiacetates), C5-C20 alkyl succinic acids and their salts (2-dodecenylsuccinates, lauryl succinates,)
• polyacetal carboxylic esters polyaspartic acid, polyglutamic acid and their salts. polyimides derived from the polycondensation of aspartic acid and / or glutamic acid
• polycarboxymethylated derivatives of glutamic acid or other amino acids - WHITENING AGENTS in amounts of about 0.1-20%, preferably about 1-10% by weight, optionally combined with WHITENING ACTIVATORS, in amounts of about 0.1-60%, preferably about 0.5-40% by weight, agents and activators such as bleaches
• perborates such as sodium perborate monohydrate or tetrahydrate
• peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, urea peroxyhydrate, sodium peroxide, sodium persulfate preferably combined with a bleach activator generating in situ in the washing medium, a peroxyacid carboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, p-acetoxybenzene sodium sulfonate, pentaacetyl glucose, octaacetyl lactose ...
• percarboxylic acids and their salts such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide peroxysuccinic acid, decyldiperoxysuccinic acid.
• These agents can be combined with at least one of the anti-fouling or anti-redeposition agents mentioned below.
• Non-oxygenated bleaching agents acting by photoactivation in the presence of oxygen, agents such as sulfonated aluminum and / or zinc phthalocyanines
• cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose
• polyvinyl esters grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048).
• polyvinyl alcohols grafted on polyalkylene trunks such as polyvinylacetates grafted on polyoxyethylene trunks (EP-A-219 048).
• polyester copolymers based on ethylene terephthalate and / or propylene terephthalate and polyoxyethylene terephthalate units with a molar ratio (number of units) ethylene terephthalate and / or propylene terephthalate / (number polyoxyethylene terephthalate of the order of 1/10 to 10/1, preferably of the order of 1/1 to 9/1, the polyoxyethylene terephthalates having polyoxyethylene units having a molecular weight of the order of 300 at 5,000, preferably in the range of 600 to 5,000 (US-A-3,959,230, US-A-3,893,929, US-A-116,896, US-A-4,728,857, US-A-4,770,666);
• sulfonated polyester oligomers obtained by sulfonation of an oligomer derived from ethoxylated allyl alcohol, dimethyl terephthalate and 1, propylene diol, having from 1 to 4 sulfonated groups (US-A-4968451)
• polyester copolymers based on propylene terephthalate and polyoxyethylene terephthalate units and terminated with ethyl or methyl units US-A
• polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or anionic sulfopolyethox groups
• the polyesters-polyurethanes obtained by reaction of a polyester of molecular mass in number of 300-4000 obtained from adipiquic acid and / or tereptalic acid and / or sulfoisophthalic acid and a diol of mass less than 300, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-400 and a diisocyanate ((FR-A-2334698) - ANTI-REDEPOSITION AGENTS, in amounts of approximately 0 , 01-10% by weight for a powder detergent composition, of about 0.01 -5% by weight for a liquid detergent composition, agents such as
• the sulfonated polyester oligomers obtained by condensation of isophthalic acid, of dimethyl sulfosuccinate and of diethylene glycol (FR-A-2 23 926)
• polyvinylpyrollidones - CHELATING AGENTS of iron and magnesium in amounts of the order of 0.1-10%, preferably of the order of 0.1-3% by weight, agents such as
• aminocarboxylates such as ethylenediaminetetraacetates, hydroxyethyl ethylenediaminetriacetates, nitrilotriacetates
• aminophosphonates such as nitrilotris (methylene phosphonates) polyfunctional aromatic compounds such as dihydroxydisulfobenzenes - POLYMERIC DISPERSING AGENTS, in an amount of the order of 0.1-7% by weight. to control the hardness of calcium and magnesium, agents such as
• the water-soluble salts of polycarboxylic acids of molecular mass of the order of 2000 to 100,000 obtained by polymerization or copolymerization of ethylenically unsaturated carboxylic acids such as acrylic acid, maleic acid or anhydride, fumaric acid, itaconic acid, aconitic acid, mesaconic acid, citraconic acid, methylenemalonic acid, and in particular polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), copolymers of arylic acid and maleic anhydride of mass molecular of the order of 5,000 to 75,000 (EP-A-66,915)
• polyethylene glycols of molecular mass of the order of 1000 to 50,000
• agents such as
• aliphatic, alicyclic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as paraffins, waxes.
• monostearylphosphates monostearyl alcohol phosphates
• proteases, amylases, lipases, cellulases, peroxidases US-A-3 553 139, US-A-4 101 457, US-A-4 507 219, US-A-4261 868)
• alcohols methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin
• buffering agents methanol, ethanol, propanol, isopropanol, propanediol, ethylene glycol, glycerin
• titanium dioxide according to the invention can also be done in detergent compositions for the maintenance of hard surfaces exposed to light.
• the level of titanium dioxide, expressed on a dry basis, may be at least about 0.1, preferably of the order of 0.1 to 5%, very particularly of the order of
• the specific surfaces exposed to light can be tiles, windows, car bodies, industrial surfaces, etc.
• the bactericidal and / or photo-oxidant effect occurs as soon as the surface exposed to light is in contact with the detergent composition.
• the detergent compositions can be made up of (percentages by weight):
• non-ionic, zwitterionic or ampholytic organic surfactant preferably a low-foaming surfactant, at a rate of 0.5 to 3%
• inert organic solvent such as isopropanol, methanol, ethanol, acetone, 10 to 30%.
• the balance consists of deionized water or a water / solvent mixture.
• the detergent compositions may consist of (percentages by weight):
• composition consists of demineralized water.
• a solution of titanyl sulfate resulting from the attack with illmenite sulfuric acid is hydrolyzed by raising the temperature.
• the solution obtained is centrifuged after hydrolysis so as to separate the acidic mother liquors from the solid which is in the form of a gel.
• a colloidal dispersion of titanium dioxide is obtained in the anatase form, the colloids of which are 40 nm in size and have a specific surface of 250 m 2 / g after drying at 200 ° C.
• Example 2 comparison of the photocatalytic activity of a titanium dioxide according to the invention and another titanium dioxide.
• An aqueous solution of K 2 Cr 2 ⁇ 7 is produced containing 0.05 g / l of Cr at degree of oxidation VI.
• the pH of the solution is 5.3.
• the first is irradiated by a 200 W mercury lamp for 1 h.
• a titanium dioxide powder having a specific surface after heating at 200 ° C. of 9 m 2 / g and a particle size is added. of 200 nm, then irradiate the beaker in the same conditions as the first.
• titanium dioxide having a specific surface area after heating at 200 ° C. of 187 m 2 / g and an elementary particle size of 35 nm is added, then the beaker is irradiated under the same conditions as the other two .
• the titanium dioxide is separated by centrifugation from solutions of the second and third beakers, then the total Cr is measured in each solution obtained by atomic adsorption, as well as the Cr (VI) pa visible UV spectrometry at 346 nm. The percentage of Cr (VI reduced to Cr (III) during the irradiation is thus measured.
• the titanium dioxide does indeed have a photocatalytic actio: the Cr (VI) of yellow color is reduced to Cr (III) of green color and on the other hand, it is observed that the titanium dioxide having the most specific surface area high has a photocatalytic activity significantly higher than that of titanium dioxide of low specific surface.
• Example 3 comparison of the bactericidal effect of a colloidal dispersion of titanium dioxide according to the invention and of another titanium dioxide.
• An S. Cerevisiae mold strain is grown for 12 hrs under aerobic conditions.
• the concentration of the cells is measured by a hemacytometer.
• the titanium dioxide powder obtained in Example 1 (after drying) is introduced and having a specific surface of 250 m 2 / g and an elementary particle size of 45 nm
• the titanium dioxide powders are introduced in such a way that the concentration is 10 4 cells per mg of titanium dioxide. Then the mixtures are irradiated for 90 min by a 300 W Xenon lamp.
• the percentage of cells killed is measured after 60, then 90 min.
• the cells are counted by the colony counting method on a petri dish.
• titanium dioxide according to the invention is much more effective than a titanium dioxide with a smaller specific surface.
• Example 4 Formulation for washing windows.
• a formulation for washing windows is prepared by mixing the following constituents:
• PLURONIC F 48® oxyethylene polyethylene glycol
• Example 5 Formula for cleaning car bodies A formulation for cleaning car bodies is prepared by mixing the following constituents:
• polydimethylsiloxane oil (viscosity 1000 mPas. at 25 ° C) 5% polydimethylsiloxane oil (viscosity 3000 mPas at 25 ° C) 1% camauba wax 5% white spirit essence 15% .

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• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (9)

• 1995
  • 1995-01-25 FR FR9500821A patent/FR2729673A1/fr active Granted
• 1996
  • 1996-01-17 WO PCT/FR1996/000073 patent/WO1996023051A1/fr active Application Filing
  • 1996-01-17 AU AU45437/96A patent/AU4543796A/en not_active Abandoned

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