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 subject of the present invention is a product of washing, especially for washing dishes, reduced or zero in zeolite and containing essentially a chlorine-releasing agent.
• Phosphates have long played a role predominant in washing products, especially in as sequestrants of the cations that form salts insoluble in water, in particular calcium ions and magnesium; the excellent performance they allow to reach resident in their particular structure.
• NTA nitrilotriacetic acid
• sodium nitrilotriacetate such as recommended in patents FR 2 208 975 and EP 82 564.
• these products are believed to fix heavy metals, which could get into the drinking water.
• the zeolites contribute by their cation exchange power, especially calcium and magnesium, upon elimination of said cations, their substitution with phosphates does not allow to reach a degree of washing satisfying the requirements of the practice.
• zeolites have the disadvantage major not to be solubilizable in the baths of washing and thus, to remain at least partially deposited on certain objects, among others the articles of glassware, on which they remain visible after machine washing and evaporation of washing water.
• zeolite (s) incorporation of zeolite (s) into reduced contents, i.e. at doses lower than about 5% by weight in the detergents, can be beneficial in some cases, according to the teachings of Patent EP 30,986 and CH 673,033 describing the use of these products respectively as abrasive agents of dry soiling and anti-corrosion / anti-caking agents.
• washing products which may be free of phosphates and zeolites and containing starches which must be strongly oxidized have been described in following patents FR-A-2,074,026, FR-A-2,126,386 and FR-A-2 063 914, the products described in this latter patent being intended for washing fabrics.
• Patent application DE-A-2023944 recommends increasing the number of functions starch hydrolysate acids oxidized by carboxymethylation, said hydrolysates being used in detergent compositions.
• the presence of oxidized polysaccharide within the product of washing according to the invention makes it possible, remarkably, to get rid of any use of phosphates and, according to another advantageous embodiment of the invention, said product has a lower content at 1% and preferably substantially zero in phosphates.
• the oxidized polysaccharide can in particular be consisting of the product resulting from the oxidation of a starch hydrolyzate obtained by the acid route and / or enzymatic, said hydrolyzate generally having a DE (Dextrose-Equivalent) from about 5 to about 90 and containing varying proportions of dimers, trimers, glucose oligomers and polymers. It can also be consisting of the product resulting from the oxidation of a hemicellulose hydrolyzate such as D-galacto-D-mannan, a D-gluco-D-mannane, an L-arabino-D-xylane or a D-xylo-arabinane.
• the above-mentioned oxidation products may be present, in whole or in part, in the form of salts acids, in particular in the form of metal salts alkaline.
• Such oxidized polysaccharides can, in particular if we are looking for a truly qualifiable oxidation of "selective" at the level of the terminal function of aldonic type, obtained by the oxidation process catalytic described by the Applicant Company in its Patent EP 232 202.
• oxidized polysaccharides who have an acid number between about 5 and about 14 and which are obtained by oxidation of hydrolysates starch having an ED of between about 20 and about 65.
• the oxidized polysaccharide is an oxidized product presenting, especially by its level of reducing sugars, good stability, in particular in terms of its coloring, when said oxidized product is used (when the correct detergent is prepared or used to the invention), at any time and for example during atomization operations, in an environment presenting alkaline pH and / or high temperature, environment suitable for coloring (more or less yellowing pronounced) any composition containing it.
• the Applicant Company has designed and implemented to develop, as new products, polysaccharides oxidized "stabilized” with low rates, generally less than about 0.6%, preferably less than 0.1% and even more preferably less at 0.05% by weight, in reducing sugars.
• the Applicant Company has found that the hydrogenation techniques applied to oxidized polysaccharides, in particular of the hydrolysate type oxidized starch, allowed to obtain such products, in particular oxidized products having a rate practically zero in reducing sugars, "stabilized” as to possible yellowing in the presence of an environment (pH alkaline, high temperature) favoring this type of phenomenon.
• hydrogenation techniques we mean especially the techniques of catalytic hydrogenation using, continuously or discontinuously, at least a 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.
• Oxidized polysaccharides in particular of the type oxidized starch hydrolyzate, "stabilized” following the implementation of these hydrogenation techniques, in particular those with an ED between 5 and 90, a acid number I between 1 and 20 and “stabilized” by catalytic hydrogenation, further impart to the compositions and washing products in which they are introduced, performance generally comparable to that observed with the same oxidized products but not “stabilized”, or even improved performance for certain parameters.
• the Applicant Company attributes, at least in part, the excellent performance of washing products according to the invention, to the stabilizing action that would play oxidized polysaccharides with respect to said agents whitening as well as a certain complexing / dispersing action oxidized polysaccharides in baths detergents.
• zeolite includes all ion exchange materials aluminosilicate type, whether they are crystalline in nature or amorphous, of natural or synthetic origin, as described, for example, in the FR patents 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”.
• zeolite A silico-aluminate crystalline sodium type
• the detergent conforming to the invention which constitutes a new industrial product, also includes one or more other constituents chosen, without this list being exhaustive, in the group comprising detergents, sequestering agents other than zeolites and phosphates, surfactants, bleaching, anti-foaming agents, anti-deposition agents, alkaline agents, structuring agents, flow agents, thickening agents, anticorrosive agents, abrasive agents, agents solubilizers, bulking agents, enzymes and agents for stabilizing enzymes, bactericides, agents opacifiers, optical brighteners, coloring agents, perfumes, for example those described in terms of patents 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 can, for example, be chosen from anionic products synthetics, such as water-soluble metal salts alkali sulfates and organic sulfonates including alkyl radicals of about 8 to 22 carbon atoms, such as sodium dodecylbenzene sulfonates or potassium.
• anionic products synthetics such as water-soluble metal salts alkali sulfates and organic sulfonates including alkyl radicals of about 8 to 22 carbon atoms, such as sodium dodecylbenzene sulfonates or potassium.
• They can also be chosen from non-ionic products, such as in particular alkylpoly-glucosides or ethoxylated fatty alcohols.
• the sequestering agents may, for example, be chosen from mono- or polyphosphates, in particular ortho-, pyro-, tripoly- and hexametaphosphates, and more particularly the tripolyphosphates of sodium (TPP-Na), phosphonic acids and / or their salts respective, citric acid, polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, especially their sodium salts, EDTA.
• TPP-Na tripolyphosphates of sodium
• PA polyacrylic acid
• NDA nitrilotriacetic acid
• EDTA nitrilotriacetic acid
• the presence characteristic of at least one oxidized polysaccharide, in particular oxidized "selectively" at the level of its terminal function, within detergents in accordance with the invention, allows, remarkably, said products to be effective for constituent rates in phosphates, NTA, AP (or their respective salts) generally lower than those commonly encountered on the market, even for substantially zero rates in each of these compounds.
• the implementation work of at least one oxidized polysaccharide, in particular "selectively" oxidized at its terminal function achieves washing efficiency (dishes especially but also linen) complies with the requirements of practice even for rates substantially zero in both phosphates and zeolites.
• the bleaching agents that can be used call in the constitution of compliant washing products to the invention are in particular the liberating agents chlorine, such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) acids chlorocyanurics and their salts, dichlorodimethylhydantoin.
• chlorine such as chlorinated trisodium phosphates, alkali metal hypochlorites, (poly) acids chlorocyanurics and their salts, dichlorodimethylhydantoin.
• the chlorine-releasing agent when it is present, will be used in the form trichloroisocyanuric acid (ATCC) and / or dichloroisocyanurates sodium (DCC-Na) or potassium (DCC-K), hydrated or not.
• ATCC trichloroisocyanuric acid
• DCC-Na dichloroisocyanuric acid
• DCC-K dichloroisocyanurates sodium
• DCC-K potassium
• the alkaline agent may, among other things, be chosen in the group comprising sodium hydroxide, the borates, carbonates and meta- or disilicates of alkali metals, and in particular be made of carbonate and / or sodium metasilicate, the latter product having further protective action against metals and other hard surfaces (enamels, fine porcelain patterns).
• the thickening agent may, purely indicative, consist of a colloidogenic mineral clay, in particular of the smectite, montmorillonite, bentonite type, attapulgite, hectorite or saponite.
• the structuring agent may, in particular, be chosen, as recommended in patent EP 215 637, from sugars, hydrogenated sugars and any mixtures of these 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 hydrogenation products of these.
• the structuring agents may in particular be consisting of or containing, at least in part, sorbitol and in particular be in the form of hydrogenated products obtained by hydrogenation of starch hydrolysates DE variables.
• Washing products according to the invention useful especially for washing dishes done “at by hand” or in industrial or domestic machines, preferably present in solid form, in particular in the form of free flowing particles such as granules or powders. They can however also present themselves in more agglomerated aspects (compact powders, lozenges) or in the form of liquids, gels or pasta.
• washing products according to the invention does not impose the implementation of any process and / or equipment other than those commonly used by skilled in the art and may, for example, call upon conventional drying techniques for aqueous suspensions by atomization and / or conventional techniques granulation.
• the use of at least one polysaccharide oxidized in the washing products according to the invention and its possible presence with a zeolite can be operated in a variety of ways, in the form of powders, liquids or powder / liquid mixtures, in one or more steps, each of said stages taking place in the presence or not of all or part of the other constituents of said products.
• compositions of matter intended for the preparation of washing products according to the invention said composition already associating said polysaccharide oxidized to 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 appear as free 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.
• the granulation can be performed for example on an AEROMATIC granulator or a plate granulator.
• washing products obtained in forms "non-solid” such as liquids, gels or pastes will have generally a dry matter content of around 15 to about 80%, in particular 30 to 50% and may, as an example, be obtained by increasing, by a any means and in particular by simple dissolution or suspended in water or other liquid, moisture of detergents according to the invention beforehand 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 whose constitution 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.
• the Applicant Company used as an oxidized polysaccharide contained in the detergents according to the invention, a product resulting from the oxidation of a starch hydrolyzate having a DE of about 37, said product having an index of acid I of about 8.6.
• Said comparative tests consist of tests which have been carried out using a washing machine wash MIELE LUXE G 540 brand dishes with capacity of 12 place settings.
• the machine is supplied with running water with a hardness of 22 ° TH. Water hardness checked after passage on resin is 4 ° TH. Resins are regenerated every six tries. Average water temperature supply temperature 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 did not been used.
• the parts are arranged in the machine according to the manufacturer's information, unchangeable for all attempts.
• a washing cycle includes: a 4 min prewash, a wash at 55 ° C for 27 min, an intermediate rinse of 2 min, rinsing at 70 ° C for 22 min and drying for 16 min.
• the total duration of the washing cycle is approximately 1 hour 20 minutes min.
• the soiling is that recommended in the NF C 73176 standard, namely egg, margarine, tea, milk reconstituted from powder, semolina and spinach.
• the cups are clean except for a few slight traces of tea coloring.
• the glasses are very clean with traces of dried water and remnants of minor soiling.
• the Applicant Company has, on the occasion of 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 (implementation works with 38 g of detergent, the duration total washing cycle being approximately 1 h 10 min).
• dishes washed with product B according to the invention has a clean and shiny appearance with relatively little residue of dirt and traces of water dried.
• Dishes washed with product C according to the invention has a very clear and very bright general appearance, showing very slight traces of dirt and Few dried water droplets. We observe only light remains of spinach and semolina and some traces of dried water on some plates. The cutlery is generally clean with slight traces of dirt and dried water spots for some people.
• the cups are very sharp, without coloring of tea or dirt or traces of dried water and clean glasses with a number only limited soiling and traces of dried water.
• washing products according to the invention by the characteristic presence of at least one polysaccharide oxidized, in particular from an oxidized starch hydrolyzate, in their composition, show washing performance quite remarkable, and this while allowing significantly reduce the need for implementation concomitant with phosphates and / or other likely additives to harm the environment.
• an oxidation product of a starch hydrolyzate having an ED of about 37 said oxidation product with an acid number I of 8.6 approximately and having, moreover, been "stabilized” by Raney nickel catalytic hydrogenation.
• Said comparative tests consist of washing tests which were carried out using a washing machine brand VEDETTE 8596 CHOICE SYSTEM top loading.
• the tests are carried out at a temperature of 60 ° C. with a temperature rise of 21 minutes, then a stop at 60 ° C for 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 consists of 2.2 kg of pieces of white fabric (cotton) whose dimensions are 55 cm x 70 cm.
• 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 by formulation.
• washing product P according to the invention proves, for certain parameters, slightly less efficient than the control product T 1 , 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)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Detergent Compositions (AREA)
• Silicates, Zeolites, And Molecular Sieves (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)

Applications Claiming Priority (2)

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• 1991
  • 1991-04-22 FR FR9104952A patent/FR2675514A1/fr active Granted
• 1992
  • 1992-04-21 AT AT92401122T patent/ATE180825T1/de not_active IP Right Cessation
  • 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 EP EP92401122A patent/EP0511081B1/fr not_active Expired - Lifetime
  • 1992-04-21 ES ES92401122T patent/ES2132112T3/es not_active Expired - Lifetime
  • 1992-04-21 DK DK92401122T patent/DK0511081T3/da active
  • 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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