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
  • C11D3/16—Organic compounds
  • C11D3/20—Organic compounds containing oxygen
  • C11D3/22—Carbohydrates or derivatives thereof
  • C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
  • C11D3/223—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin oxidised

Definitions

• the present invention relates to a washing product, in particular for washing dishes, with a reduced or zero zeolite content and containing essentially a chlorine-releasing agent.
• phosphates have played a predominant role in detergents, in particular as sequestrants of cations which form salts insoluble in water, in particular calcium and magnesium ions; the excellent performances which they allow to achieve reside in their particular structure.
• NTA nitrilotriacetic acid
• sodium nitrilotriacetate sodium nitrilotriacetate
• zeolites have the major drawback of not being soluble in washing baths and thus of remaining at least partially deposited on certain objects, notably glassware. , on which they remain visible after machine washing and evaporation of the washing water.
• zeolite (s) in high doses is generally not recommended, in practice, in the context of washing dishes, in particular glassware.
• the presence of oxidized polysaccharide within the washing product according to the invention makes it possible, remarkably, to dispense with any use of phosphates and, according to another embodiment.
• said product has a content of less than 1% and, preferably, substantially zero in phosphates.
• tabletteware more particularly means all of the objects used, in a domestic or non-domestic setting (communities, hospitals, schools, various industries, etc.), for presentation and / or the absorption of food and / or drinks and in particular, without this list being nonlimiting, plates, dishes, cutlery, glasses, cups, saucers, bottles, pans and other food containers, objects similar to those mentioned above but not necessarily used to come into contact with food (cutlery, glassware, porcelain, pots, flasks, vases, etc.) as well as objects intended to contain, at least temporarily, non-food substances of all kinds and requiring to be, at some point, rid of said substances such as laboratory glassware (vials, test tubes, test tubes, pipettes, flasks, etc.).
• the oxidized polysaccharide can in particular consist of the product resulting from the oxidation of a starch hydrolyzate obtained by the acid and / or enzymatic route, said hydrolyzate generally having a DE (Dextrose-Equivalent) of approximately 5 to approximately 90 and containing varying proportions of dimers, trimers, oligomers and polymers of glucose. It can also be constituted by the product resulting from the oxidation of a hemicellulose hydrolyzate such as a D-galacto-D-mannane, a D-gluco-D-mannane, an L-arabino-D-xylane or a D-xylo-arabinan.
• a hemicellulose hydrolyzate such as a D-galacto-D-mannane, a D-gluco-D-mannane, an L-arabino-D-xylane or a D-xylo-arabinan.
• the above-mentioned oxidation products may be present, in whole or in part, in the form of acid salts, in particular in the form of alkali metal salts.
• the oxidized polysaccharides which can be used in the context of the present invention are those which are obtained from products - and in particular tri-, oligosaccharides, starch hydrolysates, cellulose and hemicellulose-- of which only, among all of the potentially oxidizable functions which they comprise, the terminal function (of aldehyde type before oxidation) is substantially oxidized and this, in a function of aldonic type.
• Such oxidized polysaccharides can, in particular if an oxidation truly qualifying as "selective" is sought at the level of the terminal function of aldonic type, can be obtained according to the catalytic oxidation process described by the Applicant Company in its patent EP 232 202.
• oxidized polysaccharides which have an acid number of between approximately 5 and approximately 14 and which are obtained by oxidation of starch hydrolysates having a DE between about 20 and about 65.
• the oxidized polysaccharide is an oxidized product having, in particular by its level of reducing sugars, good stability, in particular at the level of its coloring, when said oxidized product is used (when the the washing product according to the invention is prepared or used), at any time and for example during spraying operations, in an environment having an alkaline pH and / or a high temperature, environment suitable for color (more or less pronounced yellowing) any composition containing it.
• oxidized "stabilized" polysaccharides having low levels, generally less than about 0.6%, preferably less than 0.1% and even more preferably less than 0.05% by weight, in reducing sugars.
• the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the oxidized starch hydrolysates type, make it possible to obtain such products, in particular oxidized products having a practically zero level of reducing sugars , "stabilized” as to a possible yellowing in the presence of an environment (alkaline pH, high temperature) favoring this type of phenomenon.
• hydrolysis techniques means in particular the catalytic hydrogenation techniques using, continuously or batchwise, at least one catalyst chosen from groups IB, IIIB, IVB, VI, VII and VIII of the periodic table and in particular in the group comprising nickel, platinum, palladium, cobalt, molybdenum and combinations of these metals.
• hydrogenation techniques may be used, using, in the absence of hydrogenation catalyst, sources of hydrogen other than hydrogen gas, for example alkali metal borohydrides, in particular sodium borohydride.
• Oxidized polysaccharides in particular of the oxidized starch hydrolyzate type, "stabilized” following the use of these hydrogenation techniques, in particular those having a DE between 5 and 90, an acid number I included between 1 and 20 and “stabilized” by catalytic hydrogenation, also give the compositions and washing products into which they are introduced, performances generally comparable to those observed with the same oxidized products but not “stabilized”, or even improved performance for certain parameters.
• the remarkable effectiveness of the washing products according to the invention in this regard concerns the elimination of stains of an oxidizable or proteinaceous nature.
• the Applicant Company attributes, at least in part, the excellence of the performance of the washing products according to the invention, to the stabilizing action which the oxidized polysaccharides would play with respect to said agents bleaching as well as a certain complexing / dispersing action of the oxidized polysaccharides in the washing baths.
• zeolite includes all ion-exchange materials of the aluminosilicate type, whether they are of crystalline or amorphous nature, of natural or synthetic origin, as described, for example, in the patents FR 2 620 727, CH 673 033, EP 30 986 and EP 249 163 mentioned above. Such products are, by way of example, commercially available under the designations "zeolite A”, “zeolite B”, “zeolite X” or "zeolite HS”.
• Use may in particular be made of a crystalline sodium silicoaluminate of the "zeolite A" type, in combination or not with another zeolite.
• the washing product in accordance with the invention which constitutes a new industrial product, also comprises one or more other chosen constituents, and this, without this list being exhaustive, in the group comprising detergents, sequestering agents other than zeolites and phosphates, surface-active agents, bleaching agents, anti-foaming agents, anti-redeposition agents, alkaline agents, structuring agents, flow agents, thickening agents, anti-corrosion agents, abrasive agents, solubilizing agents, bulking agents, enzymes and enzymes stabilizing agents, bactericides, opacifying agents, optical brighteners, coloring agents, perfumes, etc., for example those described in FR 2 208 975, FR 2 608 168, FR 2 620 727 and EP 30 986, EP 82 564 and EP 267 371 mentioned above.
• Detergents and surfactants may, for example, be chosen from synthetic anionic products, such as water-soluble metal salts alkali metal sulfates and organic sulfonates comprising alkyl radicals of about 8 to 22 carbon atoms, such as, for example, sodium or potassium dodecylbenzene sulfonates.
• synthetic anionic products such as water-soluble metal salts alkali metal sulfates and organic sulfonates comprising alkyl radicals of about 8 to 22 carbon atoms, such as, for example, sodium or potassium dodecylbenzene sulfonates.
• They may also be chosen from nonionic products, such as in particular alkylpoly-glucosides or ethoxylated fatty alcohols.
• the sequestering agents may, by way of example, be chosen from mono- or polyphosphates, in particular ortho-, pyro-, tripoly- and hexametaphosphates, and more particularly sodium tripolyphosphates (TPP-Na), phosphonic acids and / or their respective salts, citric acid, polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts, EDTA, etc.
• mono- or polyphosphates in particular ortho-, pyro-, tripoly- and hexametaphosphates, and more particularly sodium tripolyphosphates (TPP-Na), phosphonic acids and / or their respective salts, citric acid, polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts, EDTA, etc.
• the use of at least one oxidized polysaccharide, in particular oxidized "selectively" at the level of its terminal function makes it possible to achieve an efficiency of washing (especially dishes but also washing) in accordance with the requirements of practice and even for substantially zero levels of both phosphates and zeolites.
• the bleaching agents which can be used in the constitution of the washing products in accordance with the invention are in particular the liberating agents chlorine, such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) chlorocyanuric acids and their salts, dichlorodimethylhydantoin.
• chlorine such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) chlorocyanuric acids and their salts, dichlorodimethylhydantoin.
• the chlorine-releasing agent when it is present, will be used in the form of trichloroisocyanuric acid (ATCC) and / or sodium dichloroisocyanurates (DCC-Na) or potassium dichloroisocyanurates (DCC-K ), hydrated or not.
• ATCC trichloroisocyanuric acid
• DCC-Na sodium dichloroisocyanurates
• DCC-K potassium dichloroisocyanurates
• peroxygen bleaches and in particular perborates percarbonates, persilicates, persulfates or perphosphates of alkali metals, and in particular sodium perborate.
• the alkaline agent may, inter alia, be chosen from the group comprising sodium hydroxide, borates, carbonates and meta- or disilicates of alkali metals, and in particular consist of sodium carbonate and / or metasilicate, the latter product also having a protective action against metals and other hard surfaces (enamels, fine porcelain patterns).
• the thickening agent may, purely as a guide, consist of a colloidogenic mineral clay, in particular of the smectite, montmorillonite, bentonite, attapulgite, hectorite or saponite type.
• the structuring agent may, in particular, be chosen, as recommended in patent EP 215 637, from sugars, hydrogenated sugars and any mixtures thereof and in particular those consisting of or containing, at least in part, a monosaccharide such as glucose or fructose and / or a disaccharide such as maltose or sucrose and / or the hydrogenation products thereof.
• the structuring agents may in particular consist of or contain, at least in part, sorbitol and in particular be in the form of hydrogenated products obtained by hydrogenation of starch hydrolysates of variable DEs.
• the detergents according to the invention useful in particular for washing dishes carried out "by hand” or in industrial or domestic machines, will preferably be in a solid form, in particular in the form of particles flowing freely such as granules or powders. They may however also be present in more agglomerated aspects (compact powders, lozenges) or in the form of liquids, gels or pastes.
• the preparation of the detergents according to the invention does not require the use of any process and / or apparatus other than those commonly used by those skilled in the art and may, for example, use conventional techniques of drying of aqueous suspensions by atomization and / or with conventional granulation techniques.
• oxidized polysaccharide within the washing products according to the invention and its possible contact with a zeolite can be carried out according to very diverse methods, in the form of powders, liquids or powder / liquid mixtures, in one or more stages, each of said stages taking place in the presence or not of all or part of the other constituents of said products.
• compositions of material intended for the preparation of washing products according to the invention said composition already associating said oxidized polysaccharide with at least one of the other constituents of the product. final, including any zeolites and / or phosphates.
• Such a composition of matter may in particular be in the form of freely flowing particles obtained, for example, by granulation of a mixture associating, in the presence or not of third constituents, zeolite (s) and oxidized polysaccharide (s) ) and this, with a weight ratio zeolite (s) / oxidized polysaccharide (s) generally less than 1/1.
• Granulation can be carried out for example on an AEROMATIC type granulator or a plate granulator.
• the detergents obtained in “non-solid” forms such as liquids, gels or pastes will generally have a dry matter content of approximately 15 to approximately 80%, in particular from 30 to 50% and may, for example , be obtained by increasing, by any means and in particular by simple dissolution or suspension in water or another liquid, the humidity of detergents according to the invention previously prepared in the form of powders or granules.
• the Applicant Company carried out comparative tests using, on the one hand, a product of the prior art, designated by the letter T and the constitution of which appears in Table I below and, on the other hand, three washing products according to the invention, designated respectively by the letters A, B and C and whose respective levels of oxidized polysaccharide (s) (s) and possibly in phosphates are listed in Table II with regard to the 40% of phosphates (Na tripolyphosphate) contained in the product T.
• T a product of the prior art
• Table I three washing products according to the invention, designated respectively by the letters A, B and C and whose respective levels of oxidized polysaccharide (s) (s) and possibly in phosphates are listed in Table II with regard to the 40% of phosphates (Na tripolyphosphate) contained in the product T.
• the Applicant Company used, as an oxidized polysaccharide contained in the washing products according to the invention, a product resulting from the oxidation of a starch hydrolyzate having an ED of 37 approximately, said product having an acid number I of approximately 8.6.
• Said comparative tests consist of washing tests which were carried out using a MIELE de LUXE G 540 brand dishwashing machine with a capacity of 12 place settings.
• the machine is supplied with running water with a hardness of 22 ° TH.
• the hardness of the water checked after passing over resin is 4 ° TH.
• the resins are regenerated every six trials.
• the average temperature of the feed water is 20-21 ° C.
• the standard cover used corresponds to that specified in standard NF 73175. For reasons of space, the twelve teaspoons and the large round dish were not used.
• the parts are placed in the machine according to the manufacturer's instructions, unchangeable for all tests.
• a washing cycle includes: a 4 min prewash, a 27 min wash at 55 ° C, a 2 min intermediate rinse, a 22 min rinse at 70 ° C and a drying of 16 min.
• the total duration of the washing cycle is approximately 1 h 20 min.
• the rinse aid and regenerating salt are of the SUN brand.
• the soiling is that recommended in standard NF C 73176, namely egg, margarine, tea, milk reconstituted from powder, semolina and spinach.
• the dirt deposited on the cutlery is left to dry for 30 minutes before loading the latter into the washing machine.
• the soiled dishes then remain 15 to 20 hours in the machine with the door closed.
• the cups are crisp except for a few slight traces of tea coloring.
• the glasses are very clear with traces of dried water and small amounts of dirt.
• the Applicant Company during a second series of tests carried out according to standard NF C 73176, compared the effectiveness of washing product B according to the invention to that of product T according to the prior art (setting used at a rate of 38 g of washing product, the total duration of the washing cycle being approximately 1 h 10 min).
• the dishes washed with product B according to the invention have a clean and shiny appearance with relatively little residue of dirt and traces of dried water.
• the dishes washed with product C according to the invention have a very clean and very shiny general appearance, presenting very slight residues of dirt and few dried water droplets. We only observe slight remains of spinach and semolina grains and some traces of dried water on some plates. The cutlery is generally clean with slight traces of dirt and some dried water stains.
• the cups are very clean, with no coloring of tea or stains or traces of dried water and clean glasses with, only for a few, a limited number of stains and traces of dried water.
• the washing products according to the invention due to the characteristic presence of at least one oxidized polysaccharide, in particular of an oxidized starch hydrolyzate, in their composition, show quite remarkable washing performance, and this while making it possible to significantly reduce the need for concomitant use of phosphates and / or other additives liable to harm the environment.
• Example 4 the presence of at least one oxidized polysaccharide makes it possible to completely overcome such an implementation, in particular of phosphates, including in detergents according to the invention, for contents also substantially zero in zeolite (s).
• an oxidized product of a starch hydrolyzate having an ED of approximately 37 is used as the oxidized polysaccharide contained in the washing product P according to the invention.
• Said comparative tests consist of washing tests which were carried out using a VEDETTE 8596 CHOICE SYSTEM top loading washing machine.
• the tests are carried out at a temperature of 60 ° C. with a temperature rise of 21 minutes, then a plateau at 60 ° C. of 22 minutes.
• the complete cycle lasts 90 minutes.
• the volume of washing water is 11 liters.
• the water hardness is 30 ° TH.
• the washing load is made up of 2.2 kg of pieces of white fabric (cotton) whose dimensions are 55 cm x 70 cm.
• a load of 2.2 kg of pieces of white fabric is made to consist of a set of "soiled fabrics" of different natures and which contain predetermined soiling and deposited on these fabrics.
• the dose of detergent is 8 g / l of water.
• the reflectances are determined using the blue trichromatic component.
• the number of measurements made is 6 per soiling and per formulation.
• washing product P according to the invention proves, for certain parameters, slightly less efficient than the control product T1, which has a relatively high rate of zeolites and a higher rate of polyacrylates, the fact remains that the washing product according to the invention has an efficiency as good, or even improved for certain other parameters such as the degree of whiteness and the elimination of certain stains of an oxidizable nature.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Emergency Medicine (AREA)
• Engineering & Computer Science (AREA)
• Molecular Biology (AREA)
• Oil, Petroleum & Natural Gas (AREA)
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• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Measuring Pulse, Heart Rate, Blood Pressure Or Blood Flow (AREA)
• Measurement And Recording Of Electrical Phenomena And Electrical Characteristics Of The Living Body (AREA)
• Silicates, Zeolites, And Molecular Sieves (AREA)

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• 1991
  • 1991-04-22 FR FR9104952A patent/FR2675514A1/fr active Granted
• 1992
  • 1992-04-21 ES ES92401122T patent/ES2132112T3/es not_active Expired - Lifetime
  • 1992-04-21 EP EP92401122A patent/EP0511081B1/de not_active Expired - Lifetime
  • 1992-04-21 FI FI921769A patent/FI921769A/fi not_active Application Discontinuation
  • 1992-04-21 DE DE69229301T patent/DE69229301T2/de not_active Expired - Fee Related
  • 1992-04-21 DK DK92401122T patent/DK0511081T3/da active
  • 1992-04-21 AT AT92401122T patent/ATE180825T1/de not_active IP Right Cessation
  • 1992-04-22 CA CA002066879A patent/CA2066879A1/fr not_active Abandoned
  • 1992-04-22 JP JP4103261A patent/JPH05117688A/ja active Pending
• 1999
  • 1999-08-19 GR GR990402113T patent/GR3031035T3/el unknown

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