WO1997028240A1 - Systeme a base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin - Google Patents
Systeme a base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin Download PDFInfo
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- WO1997028240A1 WO1997028240A1 PCT/FR1997/000152 FR9700152W WO9728240A1 WO 1997028240 A1 WO1997028240 A1 WO 1997028240A1 FR 9700152 W FR9700152 W FR 9700152W WO 9728240 A1 WO9728240 A1 WO 9728240A1
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- alkali metal
- metal silicate
- dispersion
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- 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
- C11D3/04—Water-soluble compounds
- C11D3/08—Silicates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/83—Mixtures of non-ionic with anionic compounds
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/04—Carboxylic acids or salts thereof
- C11D1/06—Ether- or thioether carboxylic acids
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/38—Cationic compounds
- C11D1/42—Amino alcohols or amino ethers
- C11D1/44—Ethers of polyoxyalkylenes with amino alcohols; Condensation products of epoxyalkanes with amines
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- 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
- C11D1/52—Carboxylic amides, alkylolamides or imides or their condensation products with alkylene oxides
- C11D1/526—Carboxylic amides (R1-CO-NR2R3), where R1, R2 or R3 are polyalkoxylated
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/72—Ethers of polyoxyalkylene glycols
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/722—Ethers of polyoxyalkylene glycols having mixed oxyalkylene groups; Polyalkoxylated fatty alcohols or polyalkoxylated alkylaryl alcohols with mixed oxyalkylele groups
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/66—Non-ionic compounds
- C11D1/74—Carboxylates or sulfonates esters of polyoxyalkylene glycols
Definitions
- the subject of the present invention is a system based on at least one liquid, waxy or pasty nonionic surfactant and an alkali metal silicate, said system being in the form of a stable aqueous dispersion or of granules.
- This system can be used as a component of liquid or powder detergent compositions.
- the invention also relates to powder or liquid detergent compositions based on said system. It is known to transform organic materials, in particular surfactants, liquids under normal temperature and pressure conditions, into pulverulent products by adsorption and / or absorption on a solid support, generally a more or less porous mineral.
- the bicomponent product obtained has the drawback of being only very little concentrated in organic matter, the support taking up considerable space.
- nonionic surfactants / sodium carbonate, nonionic surfactants / sodium sulfate or nonionic surfactants / powdered sodium silicate contain at best 30% of their weight of organic matter considered.
- porous supports such as precipitation silicas, clays, sodium silicoaluminates, magnesium or calcium silicates, crystalline or amorphous aluminosilicates such as zeolites, makes it possible to obtain more concentrated mixtures of organic matter. , which can contain up to 65% of their weight of organic matter.
- Another solution consists in using a crosslinked absorbent organic polymer (absorbent crosslinked polyacrylate, etc.) or a hydrocolloid (starch, guar, etc.); it is however more expensive and can also have drawbacks in terms of denaturing interactions between the support and the organic matter.
- a crosslinked absorbent organic polymer absorbent crosslinked polyacrylate, etc.
- a hydrocolloid starch, guar, etc.
- the Applicant has found a means for preparing stable dispersions of nonionic surfactants, the continuous phase of which consists of a concentrated aqueous solution of alkali metal silicate and the dispersed phase of droplets or particles of non-ionic surfactant.
- liquid, waxy or pasty ionics, dispersions which, by simple drying, transform into granules by encapsulation of the droplets or particles of nonionic surfactant in a rigid shell of alkali metal silicate.
- This placing in solid form has the advantage of leading to a soluble product, of easy availability, stable in storage, which can contain high contents of non-ionic surfactant and which can ensure a controlled release of said surfactant.
- the system formed by the nonionic surfactant and the alkali metal silicate whether in the form of an aqueous dispersion or of granules, has detergent and detergency builder properties, which give it the capacity to be used as a constituent of liquid or solid detergent compositions, household or industrial, in particular for washing machines.
- it is a system (S), in the form of an aqueous dispersion or of granules, based on at least one liquid, waxy or pasty nonionic surfactant and a silicate. of alkali metal, system characterized in that it is capable of being obtained
- NIA nonionic surfactant
- TAS nonionic or anionic surfactant
- nonionic surfactant (NIA) liquid, pasty or waxy immiscible or slightly miscible with an aqueous solution of alkali metal silicate is understood to mean any nonionic surfactant in its liquid, pasty or waxy form as it is. normal conditions of temperature and pressure (generally temperature of the order of -10 to 45 ° C and pressure of the order of 0.8 to 1.2 bar) and not liable to dissolve, to hydrate (by solvation hydrophilic part) or hydrolyze more than 10% of its weight in said concentrated silicate solution.
- nonionic surfactants which are liquid, pasty or waxy
- alkoxylated nonionic surfactants there may be mentioned in particular alkoxylated nonionic surfactants.
- TERGITOL 15-S-9 TERGITOL 24-L-6 NMW sold by Union Carbide Corp.
- NEODOL 45-9 NEODOL 23-65
- NEODOL 45-7 NEODOL 45-4 marketed by Shell Chemical Cy.
- KYRO EOB marketed by The Procter
- alkoxylated terpene hydrocarbons such as ethoxylated and / or propoxylated ⁇ - or ⁇ -pinenes, containing from 1 to 30 oxyethylene and / or oxypropylene units; - the products resulting from the condensation of ethylene oxide or propylene oxide with propylene glycol, ethylene glycol, of molecular weight by weight of the order of 2000 to 10000, such as the PLURONIC sold by BASF;
- aqueous solutions of alkali metal silicate with a Si ⁇ 2 / M2O molar ratio which can range from 1.5 to 4, preferably from 2 to 3.5 and containing about from 35 to 50% of active material, M representing sodium or potassium; Mention may very particularly be made of commercial solutions of sodium silicate with a ratio of around 2 containing around 45 to 50% of active material, as well as those of sodium silicate with a ratio of around 3 containing of the order of 35 to 40% of active material.
- the small amounts of free water present in these concentrated silicate solutions are not sufficient to dissolve, hydrate (solvate) or hydrolyze the non-ionic surfactant (s) (NIA).
- the dispersing operation of the surfactant (s) (NIA) in the said concentrated solution of alkali metal silicate can be carried out using any nonionic or anionic surfactant compatible with the concentrated solution of alkali metal silicate, that is to say capable of dissolving or of hydrating (solvating) giving a homogeneous isotropic phase with the concentrated solution of alkali metal silicate.
- This operation can be carried out in particular using at least one nonionic or anionic surfactant (TAS), the hydrophilic part of which contains one or more saccharide unit (s).
- TAS nonionic or anionic surfactant
- Said saccharide units generally contain from 5 to 6 carbon atoms. These can be derived from sugars such as fructose, glucose, mannose, galactose, talose, gulose, allose, altose, idose, arabinose, xylose, Iyxose and / or ribose.
- nonionic or anionic surfactants whose hydrophilic part has a saccharide structure containing from 5 to 6 carbon atoms, one can mention:
- alkylpolyglycosides which can be obtained by condensation (for example by acid catalysis) of glucose with primary fatty alcohols (US-A-3,598,865;
- glucosamides such as lauryl-N-methylglucosamide
- - sophorolipids such as those in acid or lactone form, derived from 17-hydroxyoctadecenic acid;
- NIA nonionic surfactant
- TAS nonionic or anionic surfactant
- the content of nonionic surfactant (s) represents of the order of 5 to 60% by weight, preferably of the order of 5 to 55% by weight, very particularly of the order of 5 to 45% by weight of the dry matter content of said dispersion
- the content of concentrated solution of alkali metal silicate, expressed as dry represents of the order of 20 to 70% by weight, preferably of the order of 30 to 60% by weight of the dry matter content of said dispersion
- the content of nonionic or anionic surfactant (s), expressed as dry matter represents of the order of 5 to 40% by weight, preferably of the order from 10 to 30% by weight of the dry matter content of said emulsion or dispersion, the dry matter content of said dispersion being of the order of 30 to 90%, preferably of the order of 40 to 80% by weight .
- the operation of dispersing the surfactant (s) (NIA) in said concentrated solution of alkali metal silicate using at least one nonionic or anionic surfactant (TAS) can be carried out according to all the methods of preparation of dispersions known to those skilled in the art.
- a dispersion can be prepared by using high shear colloid mills, such as MENTON GAULIN®, MICROFLUIDIZER® (MICROFLUIDICS) etc ... It is however preferable to prepare a dispersion according to methods employing stirring means moderate.
- a first well-suited method is direct phase emulsification, consisting in preparing a mixture of concentrated solution of alkali metal silicate and nonionic or anionic surfactant (TAS), then in introducing the non-ionic surfactant.
- -ionic (NIA) in liquid form (melted if necessary), with stirring.
- Another method is emulsification by phase inversion, consisting in introducing dropwise, with stirring, into the nonionic surfactant (NIA) in liquid form (molten if necessary), a mixture of concentrated solution of alkali metal silicate. and nonionic or anionic surfactant (TAS).
- the operation of dispersing by emulsification of the nonionic surfactant (NIA) in the concentrated solution of alkali metal silicate using the nonionic or anionic surfactant (TAS) is carried out at a temperature at which said nonionic surfactant (NIA) is liquid.
- Surface active agent droplets non-ionic (NIA) obtained during this operation can have diameters of the order of 0.5 to 10 ⁇ m, preferably of the order of 0.7 to 5 ⁇ m.
- the possible operation of drying the dispersion to obtain granules is carried out under conditions such that the continuous liquid matrix of alkali metal silicate is transformed by elimination of water into a continuous solid film coating the droplets or the particles d 'nonionic surfactant (NIA), the amount of water remaining corresponding to a weight ratio of water remaining in the silicate / silicate in the dry range of 5/95 to 25/75.
- NIA nonionic surfactant
- This operation can be carried out by any known means.
- Preferably, rapid drying of the dispersion is carried out.
- This latter mode of drying can be carried out in any known spray drying apparatus, such as atomization towers associating a spraying of the dispersion by a nozzle or a turbine with a stream of hot air, under conditions such as the temperature of the product during drying does not exceed 105 ° C.
- Said optional drying operation can also be carried out in the open air in a thin layer in an oven.
- the granules thus obtained comprise of the order of - 5 to 60% of their weight, preferably 5 to 55% of their weight, very particularly 5 to 45% of their weight of non-surfactant (s). monkey (s) (NIA)
- said system (S) is in the form of an aqueous dispersion additionally containing glycerol.
- glycerol makes it possible in particular to improve the stability on hot storage (40 ° C.) of said system in dispersion.
- the amount of glycerol that may be present is of the order of 3 to 20% by weight, preferably of the order of 4 to 20% by weight, very particularly of the order of 6 to 14% by weight relative to the total weight of said dispersion.
- Said system (S) in the form of a dispersion can be obtained by carrying out the dispersing operation according to the methods described above, in particular of emulsification in direct phase or by phase inversion, after prior introduction of the glycerol.
- the system (S) forming the subject of the invention can be used in household or industrial detergents, as a constituent of a detergent composition, for washing laundry in particular.
- the term “constituent” is understood here to mean both a simple component for a detergent composition and the complete detergent composition proper.
- the present invention therefore also relates to the use of the system (S) forming the subject of the invention as a constituent of a detergent composition, as well as the detergent compositions comprising or consisting of said system (S).
- said system (S) may be a simple component of a detergent powder composition or alone constitute a detergent powder composition.
- said system (S) in the form of granules is a simple component of a powdered detergent composition, it can be added in post-addition to the other components of said composition, and in an amount corresponding to that desired by the manufacturer.
- This amount expressed as a nonionic surfactant (NIA), is generally of the order of 5 to 25 parts by weight per 100 parts of final composition.
- detergency builders in an amount such that the total amount of detergency builder is of the order of 5 to 50% of the weight of said composition, detergency builders such as
- polyphosphates tripolyphosphates, pyrophosphates, orthophosphates, hexametaphosphates of alkali metals, ammonium or alkanolamines - tetraborates or borate precursors
- alkali metals sodium, potassium
- ammonium such as zeolites A, P, X, ...
- - water-soluble polyphosphonates ethane 1-hydroxy- 1, 1-diphosphonates, methylene salts diphosphonates, ...) - water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids of molecular order from 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, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates of molecular weight l '' from 2,000 to 10,000 (US-A-3,308,067), copolymers of acrylic acid and maleic anhydride with a molecular weight of about 5,000 to 75,000 (EP-A-66,915)
- - aminophosphonates such as nitrilotris (methylene phosphonates)
- polyfunctional aromatic compounds such as dihydroxydisulfobenzenes of anionic surfactants. in the order of 1 to 50%, such as
- R-CH (S ⁇ 3M) -COOR ' where R represents an alkyl radical containing 8 "20> preferably C10-C16 R.
- R represents an alkyl radical containing 8 "20> preferably C10-C16 R.
- An alkyl radical 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
- R represents an alkyl or hydroxyalkyl radical in C ⁇ o c 24> preferably in C12-C20 and very particularly in C12-C18 ' M representing a hydrogen atom or a cation of the same definition as ci above, as well as their ethoxylenated (OE) and / or propoxylenated (OP) derivatives, having on average from 0.5 to 6 units, preferably from 0.5 to 3 OE and / or OP units;
- RCONHROSO3M where R represents an alkyl radical in C2-C22. preferably Cg-C20.
- C8-C24 preferably C14-C20 saturated or unsaturated fatty acids, C9-C20 alkylbenzenesulfonates. 'primary or secondary C8-C22 alkylsulfonates.
- alkylglycerol sulfonates the sulfonated polycarboxylic acids 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 having the same definition as above.
- anti-fouling agents in amounts of the order of 0.01-10%, preferably of the order of 0.1 to 5%, and very particularly of the order of 0.2-3% by weight , agents such as
- cellulose derivatives such as cellulose hydroxyethers, methylcellulose, ethylcellulose, hydroxypropyl methylcellulose, hydroxybutyl methylcellulose - polyvinylesters 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 of units) 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 to 5000, preferably of the order of 600 to 5000 (US-A-3,959,230, US-A-3,893,929, US-A-4,116,896, US-A-4,702,857, US-A-4,770,666);
- polyester oligomers terminated by alkylpolyethoxy groups (US-A-4,702,857) or anionic sulfopolyethoxy groups (US-A-4,721,580), sulfoaroyl (US-A-4,877,896)
- polyesters with a molecular mass of less than 20,000 obtained from a diester of terephthalic acid, a diester of sulfoisophthalic acid and a diol (FR-A-2 720400)
- polyesters-polyurethanes obtained by reaction of a polyester with a molecular mass of 300-4000 in number obtained from adipic acid and / or terephthalic acid and / or sulfoisophthalic acid and a diol, on a prepolymer with terminal isocyanate groups obtained from a polyoxyethylene glycol with a molecular mass of 600-4000 and a diisocyanate (FR-A-2 334 698) of the antiredeposition agents. in amounts of about 0.01-10% by weight for a powdered detergent composition, about 0.01-5% by weight for a liquid detergent composition, agents such as
- - peroxygenated compounds such as sodium carbonate peroxyhydrate, pyrophosphate peroxyhydrate, failed peroxyhyd urea, sodium peroxide, sodium persulfate
- 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.
- percarbonates such as magnesium monoperoxyphthalate hexahydrate, magnesium metachloroperbenzoate, 4-nonylamino-4-oxoperoxybutyric acid, 6-nonylamino-6-oxoperoxycaproic acid, diperoxydodecanedioic acid, nonylamide peroxysuccinic acid, decyldiperoxysuccinic acid.
- a bleach activator generating in situ in the washing medium, a peroxycarboxylic acid; among these activators, there may be mentioned, tetraacetylethylene diamine, tetraacetyl methylene diamine, tetraacetyl glycoluryl, sodium p-acetoxybenzene sulfonate, pentaacetyl glucose, octaacetyl lactose, ... fluorescent agents, in an amount of about 0.05-1.2% by weight, agents such as stilbene derivatives , pyrazoline, coumarin, fumaric acid, cinnamic acid, nitrogen, methinecyanin, thiophene, ... foam suppressants, in amounts up to 5% by weight, agents such as
- silica particles softening agents in amounts of about 0.5-10% by weight, agents such as clays of enzymes in amounts up to 5 mg by weight, preferably of the order of 0.05-3 mg of active enzyme / g of detergent composition, enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139,
- the amount of alkali metal silicate expressed in dry terms represents around from 30 to 70%, very particularly of the order of 40 to 60% of the weight of said system expressed as dry, and that of nonionic surfactant (NIA) represents of the order of 10 to 35%, very particularly of the order of 15 to 30% of the weight of said system expressed in sec.
- said system (S) constitutes the liquid detergent composition itself. He can then present as is (i.e. composed of its three basic constituents, alkali metal silicate, nonionic surfactant (NIA) and nonionic or anionic surfactant (TAS), water and optionally glycerol) or with the addition of other detergency components introduced during its preparation.
- NIA nonionic surfactant
- TAS nonionic or anionic surfactant
- said system (S) in the form of an aqueous dispersion contains an amount of alkali metal silicate expressed as dry, of the order of 30 to 70 %, preferably of the order of 40 to 60% of the weight of said system expressed in dry terms, and an amount of nonionic surfactant (NIA) of the order of 5 to 35%, preferably of the order from 5 to 30% of the weight of said system expressed in sec.
- alkali metal silicate expressed as dry
- NIA nonionic surfactant
- Said system (S) in the form of an aqueous dispersion, added during its preparation of at least one detergency component can constitute a liquid detergent composition, for washing machines in particular.
- the nature and the quantity of the components as well as the possible quantity of water introduced via these components are chosen so as not to destructure the liquid dispersion. It is preferable that the total amount of these components does not exceed 10% of the weight of the final detergent composition.
- the mode of introduction of said additive (s) into said system (S) in the form of a dispersion depends on the behavior of said additive (s) with respect to the concentrated solution of silicate and of non-ionic surfactant (NIA).
- NIA non-ionic surfactant
- soluble or dispersible but non-hydrolyzable detergency additives in the concentrated solution of alkali metal silicate such as the water-soluble salts of carboxylic polymers or copolymers such as the water-soluble salts of polycarboxylic acids of molecular weight of the order from 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, mesaconic acid, citraconic acid, methylenemalonic acid, and very particularly polyacrylates of molecular mass of the order of 2,000 to 10,000 (US-A-3,308,067), the copolymers of acrylic acid and maleic anhydride of molecular weight of the order of 5,000 to 75,000 (EP-A-66 915), they can be used in an amount (expressed in dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry.
- polypeptides such as polyaspartic acid, polyglutamic acid and their salts, in an amount (expressed in dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry .
- water-soluble polyphosphonates (1-hydroxy-1-ethane, 1-diphosphonates, methylene salts, diphosphonates, etc.
- water-soluble polyphosphonates (1-hydroxy-1-ethane, 1-diphosphonates, methylene salts, diphosphonates, etc.
- salts of polyacetic acids ethylenediaminetetraacetates, nitrilotriacetates, N- (2 hydroxyethyl-nitrilodiacetates), in quantity (expressed as dry) of the order of 0.5 to 6% of the weight of detergent composition expressed in dry
- polycarboxymethylated derivatives of glutamic acid such as N, N-bis (carboxymethyl) glutamic acid and its salts, especially of sodium
- glutamic acid such as N, N-bis (carboxymethyl) glutamic acid and its salts, especially of sodium
- other amino acids in quantity (expressed as dry) of the order of 0 , 5 to 6% of the weight of detergent composition expressed in dry
- alkali carbonates (bicarbonates, sesquicarbonates), in quantity (expressed in dry) of the order of 1 to 10% of the weight of detergent composition expressed in dry.
- optical brighteners such as stilbene derivatives, pyrazoline, coumarin, fumaric acid, cinnamic acid, nitrogen, methinecyanins, thiophenes, in dry quantity of the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
- This type of additive can be introduced into said system (S) by prior mixing of the additive (s) with the alkali metal silicate solution, the nonionic surfactant (NIA) being then dispersed in said mixture using the surfactant (TAS).
- NIA nonionic surfactant
- TAS surfactant
- detergency additives soluble or dispersible in the nonionic surfactant such as in particular enzymes such as proteases, amylases, lipases, cellulases, peroxidases (US-A-3,553,139, US- A-4 101 457, US-A-4 507 219, US-A-4 261 868), in quantity expressed as dry of the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
- NIA nonionic surfactant
- This type of additive can be introduced into said system by dispersion or solubilization in the liquid nonionic surfactant (NIA), before dispersing said nonionic surfactant (NIA) in the silicate solution.
- NIA liquid nonionic surfactant
- aliphatic, alicycic, aromatic or heterocyclic saturated or unsaturated hydrocarbons such as paraffins, waxes. monostearylphosphates, monostearyl alcohol phosphates. polyorganosiloxane oils or resins optionally combined with silica particles in quantity expressed as dry of the order of 0.1 to 0.5% of the weight of detergent composition expressed in dry
- This type of additive can be introduced into the system (S) by dispersing it in the silicate solution via the surfactant (TAS), then adding the nonionic surfactant (NIA).
- TAS surfactant
- NIA nonionic surfactant
- the system formed here is a codispersio ⁇ .
- the detergent composition formed by said system (S) in the form of an aqueous dispersion can be used both for the main washing of laundry and as a stain removing agent before washing.
- stain remover before washing means a product which, deposited before washing, without prior dilution, on the soiled area of the laundry, allows better removal of the soil during the main wash.
- the emulsion obtained is stable; it has a homogeneous drop diameter less than a micrometer and a viscosity lower than that of the starting silicate solution.
- the emulsion is dried in a thin layer of 1 cm on a glass slide in an oven at 60 ° C for 24 hours.
- the product obtained contains 4% by weight of water; it is grindable and flows freely, although it contains more than 50% of nonionic surfactant.
- Example 2
- the whole is homogenized at 1000 revolutions / minute avoiding the introduction of air.
- the test simulates a simplified machine wash, using a tergotometer. It consists of washing, at 40 ° C in water with a hardness of 30 ° TH, test pieces of soiled fabrics in a standard and uniform manner, with the formulation to be tested. The washing lasts thirty minutes and the detergency is evaluated by measuring the whiteness of the pieces of fabric, before and after washing, using a colorimeter. In addition, white, unsoiled control fabrics are incorporated, which make it possible to evaluate the redeposition of soiling by measuring the reflectances before and after washing.
- Standard fabrics are manufactured by the CFT (Center For Test materials) or by the company “Test Fabric”. They have the following characteristics:
- the tergotometer is a device made up of 4 2-liter stainless steel pots on which are fitted stirrers which are adjusted to 50 cycles per minute (100 back and forth). The pots are placed in a water tank regulated at 40 ° C.
- the pots When the water is at temperature, the pots are introduced into the thermostatically controlled bath, simultaneously stirring and a stopwatch.
- the baths are recovered (250 cc) for pH control.
- the fabrics are rinsed three times with tap water, then wrung by hand and dried flat individually between two sheets of white absorbent paper.
- the fabrics are again placed between two sheets of clean absorbent paper, and ironed in the freezer at a temperature in the region of 110 ° C. Color measurement
- the measurements are carried out with the "LUCI 100" colorimeter before and after washing according to the "L", “a”, “b” system (scale from black to white, from green to red, and from blue to yellow) to measure the detergent power of the surfactants tested (increase the whiteness of the pieces of soiled tissue). Detergency calculation
- the anti-redeposition power of the tested products is demonstrated using standard white soiled cotton CN1 and polyester / cotton PCN1 fabrics, which color is measured before and after washing. Redeposition is the difference in reflectance between the initial white fabric and the white fabric that has been washed in the presence of soiled fabrics.
- the measurement of the incrustation inhibiting effect is measured after 6 washes at 60 ° C. in hard water at 40 ° TH, in the absence of soiled fabrics on the following unsoiled test tubes: cotton CN1.
- Terry cotton 12A The mineral incrustation is calculated from the ash rate (in% relative to the total weight of the cotton) of the fabrics washed, dried and burned at 950 ° C for 3 hours.
- the stability of the emulsions is observed after 1 day, 3 days, 5 days and 20 days of storage in closed bottles, in an oven at 40 ° C.
- the emulsion not containing glycerol (3a) or 1% (3b) of glycerol has a phase shift of 60% after 5 days.
- emulsions containing 4% (3c) or 19% (3d) by weight of glycerol do not yet show a phase shift after 20 days.
- Example 4 The following liquid detergent formulation
- the whole is homogenized at 1000 revolutions / minute avoiding the introduction of air.
- Two detergent powder compositions are prepared, one consisting of 100% of granules prepared in Example 1, the other consisting of 80% of said granules and 20% of other additives mentioned in Table 3.
- the detergent and anti-scaling power of these two compositions is compared to that of a commercial powder detergent, containing more than 35 constituents, including a complex detergency builder system based on zeolite, sodium carbonate and polymers. , a surfactant system (18%) composed of 4 different products, an enzymatic system and an activated bleaching system.
- the detergent power is measured in a Tergotometer according to the method described in the example.
- wash time 20 minutes (instead of 30 minutes) - 5g / l of composition to be tested (instead of 8.2g / l) on the following soils Standard soiled fabrics (soiling) number of pieces per test
- Example 3 An aqueous emulsion containing as in Example 3 is prepared
- the agent to be tested is deposited in a concentrated state on the soiled tissue and spread locally using a spatula.
- a contact time of 5 minutes between the textile and the product is respected, before proceeding to the actual washing using a detergent in a household washing machine of AEG brand, cycle 40 ° C.
- DETAILS 10x10cm specimens of standard soiling prepared by specialized laboratories are used, namely
- test pieces (on their towel holder) are introduced into an AEG household washing machine, accompanied by a load of 3 kg of linen consisting of clean sponge towels.
- a washing cycle is then carried out at 40 ° C., with 100 g of commercial brand ARIEL standard detergent.
- test pieces After washing, the test pieces are visually examined to assess the additional detergent effect due to the local presence of a stain-removing agent. Clearer areas, located where the agent is stored, allow this effect to be seen.
- aqueous emulsion tested as a stain-removing agent before washing is compared with a commercial product rich in surfactants, of the following composition: anionic surfactant 15% non-ionic surfactant 5% pearlescent base 1% water 19%
- protease enzyme system (savinase) 0.5 amylase (termamyl) 0.5
Abstract
Description
Claims
Priority Applications (6)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
US09/117,475 US6291420B1 (en) | 1996-01-31 | 1997-01-27 | System containing a non-ionic surfactant and an alkali metal silicate |
DE69728448T DE69728448D1 (de) | 1996-01-31 | 1997-01-27 | Verfahren zur herstellung eines systems enthaltend ein nichtionisches tensid und ein alkalimetallsilikat |
JP52734897A JP3179502B2 (ja) | 1996-01-31 | 1997-01-27 | ノニオン系界面活性剤とアルカリ金属珪酸塩とを基とする系 |
EP97901676A EP1019474B1 (fr) | 1996-01-31 | 1997-01-27 | Procede de preparation d'un systeme a base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin |
AU15495/97A AU1549597A (en) | 1996-01-31 | 1997-01-27 | System containing a non-ionic surfactant and an alkali metal silicate |
AT97901676T ATE263228T1 (de) | 1996-01-31 | 1997-01-27 | Verfahren zur herstellung eines systems enthaltend ein nichtionisches tensid und ein alkalimetallsilikat |
Applications Claiming Priority (4)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
FR9601124A FR2744131B1 (fr) | 1996-01-31 | 1996-01-31 | Systeme a base d'un agent tensio-actif non-ionique et d'un silicate de metal alcalin, sous forme d'une dispersion ou de granules et son utilisation en detergence |
FR9611092A FR2744132B1 (fr) | 1996-01-31 | 1996-09-11 | Systeme de base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin, sous forme d'une dispersion ou de granules et son utilisation en detergence |
FR96/01124 | 1996-09-11 | ||
FR96/11092 | 1996-09-11 |
Publications (1)
Publication Number | Publication Date |
---|---|
WO1997028240A1 true WO1997028240A1 (fr) | 1997-08-07 |
Family
ID=26232485
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/FR1997/000152 WO1997028240A1 (fr) | 1996-01-31 | 1997-01-27 | Systeme a base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin |
Country Status (8)
Country | Link |
---|---|
US (1) | US6291420B1 (fr) |
EP (1) | EP1019474B1 (fr) |
JP (1) | JP3179502B2 (fr) |
AT (1) | ATE263228T1 (fr) |
AU (1) | AU1549597A (fr) |
DE (1) | DE69728448D1 (fr) |
FR (1) | FR2744132B1 (fr) |
WO (1) | WO1997028240A1 (fr) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2766838B1 (fr) * | 1997-07-29 | 2003-06-13 | Rhodia Chimie Sa | Procede de preparation d'un systeme solide divise a base d'un agent tensioactif non-ionique et d'un silicate de metal alcalin et utilisation dudit systeme en detergence |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
FR2135285A1 (fr) * | 1971-05-05 | 1972-12-15 | Miles Lab | |
GB1346227A (en) * | 1970-05-18 | 1974-02-06 | Desoto Inc | Detergent compositions |
US3920586A (en) * | 1972-10-16 | 1975-11-18 | Procter & Gamble | Detergent compositions |
US4115308A (en) * | 1976-12-27 | 1978-09-19 | The Procter & Gamble Company | High-shear process for preparing silicate-containing paste-form detergent compositions |
US4457854A (en) * | 1982-06-04 | 1984-07-03 | Colgate Palmolive Company | High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent |
WO1993023522A1 (fr) * | 1992-05-18 | 1993-11-25 | Henkel Kommanditgesellschaft Auf Aktien | Concentres de nettoyants alcalins susceptibles d'etre pompes |
Family Cites Families (13)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
IS1740B (is) * | 1982-02-05 | 1999-12-31 | Albright & Wilson Uk Limited | Samsetning á hreinsivökva |
DE3708330A1 (de) | 1987-03-14 | 1988-09-22 | Henkel Kgaa | Fluessige, alkalische reinigerkonzentrate |
EP0377807B1 (fr) | 1988-12-07 | 1994-02-09 | Henkel Kommanditgesellschaft auf Aktien | Détergent liquide hautement alcalin et sans phosphate |
CA2092186C (fr) * | 1990-09-28 | 1997-12-09 | Robert Y. Pan | Amides d'acides gras polyhydroxyles dans un detergent renfermant un agent de lavage facilite |
SK25593A3 (en) * | 1990-09-28 | 1993-07-07 | Procter & Gamble | Polyhydroxy fatty acid amide surfactants in bleach containing detergent compositio |
HUT64380A (en) * | 1990-09-28 | 1993-12-28 | Procter & Gamble | Detergents compositions containing n-polyhydroxyalkyl-fatty acid amide and alkoxycarbonylalkyl-sulphate type surface active agents |
US5750485A (en) * | 1991-06-18 | 1998-05-12 | The Procter & Gamble Company | Laundry detergent containing a polyhydroxy fatty amide and insoluble ethoxylated alcohol |
DE4134914A1 (de) * | 1991-10-23 | 1993-04-29 | Henkel Kgaa | Wasch- und reinigungsmittel mit ausgewaehlten builder-systemen |
US5223179A (en) * | 1992-03-26 | 1993-06-29 | The Procter & Gamble Company | Cleaning compositions with glycerol amides |
US5536437A (en) * | 1992-08-19 | 1996-07-16 | Colgate-Palmolive Co. | Hard surface cleaning composition formed from a structured silicate |
US5854196A (en) * | 1994-08-23 | 1998-12-29 | The Procter & Gamble Company | Detergent compositions |
US5858957A (en) * | 1995-01-26 | 1999-01-12 | The Procter & Gamble Company | Process for the manufacture of granular detergent compositions comprising nonionic surfactant |
US5750733A (en) * | 1996-08-06 | 1998-05-12 | Lever Brothers Company, Division Of Conopco, Inc. | Hydroxy containing alkyl glycamides, low foaming detergent compositions comprising such and a process for their manufacture |
-
1996
- 1996-09-11 FR FR9611092A patent/FR2744132B1/fr not_active Expired - Fee Related
-
1997
- 1997-01-27 AU AU15495/97A patent/AU1549597A/en not_active Abandoned
- 1997-01-27 DE DE69728448T patent/DE69728448D1/de not_active Expired - Lifetime
- 1997-01-27 EP EP97901676A patent/EP1019474B1/fr not_active Expired - Lifetime
- 1997-01-27 JP JP52734897A patent/JP3179502B2/ja not_active Expired - Fee Related
- 1997-01-27 US US09/117,475 patent/US6291420B1/en not_active Expired - Fee Related
- 1997-01-27 WO PCT/FR1997/000152 patent/WO1997028240A1/fr active IP Right Grant
- 1997-01-27 AT AT97901676T patent/ATE263228T1/de not_active IP Right Cessation
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB1346227A (en) * | 1970-05-18 | 1974-02-06 | Desoto Inc | Detergent compositions |
FR2135285A1 (fr) * | 1971-05-05 | 1972-12-15 | Miles Lab | |
US3920586A (en) * | 1972-10-16 | 1975-11-18 | Procter & Gamble | Detergent compositions |
US4115308A (en) * | 1976-12-27 | 1978-09-19 | The Procter & Gamble Company | High-shear process for preparing silicate-containing paste-form detergent compositions |
US4457854A (en) * | 1982-06-04 | 1984-07-03 | Colgate Palmolive Company | High bulk density carbonate-zeolite built heavy duty nonionic laundry detergent |
WO1993023522A1 (fr) * | 1992-05-18 | 1993-11-25 | Henkel Kommanditgesellschaft Auf Aktien | Concentres de nettoyants alcalins susceptibles d'etre pompes |
Also Published As
Publication number | Publication date |
---|---|
JPH11506802A (ja) | 1999-06-15 |
AU1549597A (en) | 1997-08-22 |
FR2744132B1 (fr) | 1998-04-24 |
FR2744132A1 (fr) | 1997-08-01 |
EP1019474B1 (fr) | 2004-03-31 |
EP1019474A1 (fr) | 2000-07-19 |
JP3179502B2 (ja) | 2001-06-25 |
DE69728448D1 (de) | 2004-05-06 |
US6291420B1 (en) | 2001-09-18 |
ATE263228T1 (de) | 2004-04-15 |
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