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
• • 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
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites

Definitions

• the subject of the present invention is a new washing product which can be used in particular for washing fabrics, of the type of those which have no phosphate content and which contain at least one zeolite.
• 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
• NTA sodium nitrilotriacetate
• compositions can be free of phosphates and contain less than 20% by weight of zeolites.
• zeolites we associate with zeolites, in addition to said polycarboxylic polymers, clays and NTA.
• acrylic polymers and in particular to homopolymers of acrylic acid or of methacrylic acid or their salts, in particular polyacrylic acid (PA) and sodium polyacrylates (PNa).
• PA polyacrylic acid
• PNa sodium polyacrylates
• acrylic polymers in particular polyacrylic acid and its salts, have the major drawback of being non-biodegradable.
• document EP-A-0 395 970 describes a washing product containing an oxidized disaccharide and document EP-A-0 425 369 describes washing products comprising at least one phosphate.
• the Applicant Company had the merit of finding that this goal was achieved as soon as a washing product, in particular for fabrics having a zero phosphate content, as well as at least one zeolite and at least one oxidized polysaccharide, is constituted, said oxidized polysaccharide being chosen from the oxidation products of trisaccharides, oligosaccharides, starch hydrolysates, cellulose and hemicellulose and mixtures of at least two of these oxidation products which have a terminal function of aldonic type (and aldehic type before oxidation) which, only among all of the potentially oxidizable functions of these oxidation products, is substantially oxidized.
• 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 between 5 and 14 and which are obtained by oxidation of starch hydrolysates having a DE between 20 and 65.
• oxidized polysaccharides will be used which have an acid number between 8 and 14 and which are obtained by oxidation of starch hydrolysates having a DE between 35 and 65.
• the oxidized polysaccharide is an oxidized product having, in particular by its level of reducing sugars, good stability, in particular in terms of its coloring, when said oxidized product is used (when the washing product is prepared or used in accordance with the invention), at any time and for example during spraying operations, in an environment with an alkaline pH and / or a high temperature, an environment capable of coloring (more or less pronounced yellowing) any composition containing it.
• oxidized "stabilized" polysaccharides having low levels, generally less than 0.6%, preferably less than 0.1% and again 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 regards 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 gases, for example alkali metal borohydrides, in particular sodium borohydride.
• Oxidized polysaccharides in particular of the oxidized starch hydrolyzate type, "stabilized” following the implementation of these hydrogenation techniques, in particular those having a DE of between 5 and 90, an acid number I of between 1 and 20 and “stabilized” by catalytic hydrogenation, also give compositions and detergents in which they are introduced, performances comparable to those observed with the same oxidized but not “stabilized” products, or even improved performances for certain parameters.
• the Applicant Company attributes the excellence of these performances in this field to the stabilizing action which the oxidized polysaccharides would play vis-à-vis the oxidizing agents.
• the oxidizing agent is a perborate, in particular of sodium
• the product in accordance with the invention comprises, as oxidized polysaccharide, an oxidized starch hydrolyzate.
• the weight ratio between on the one hand the zeolite and on the other hand the oxidized polysaccharide is between 0.5 / 1 and 4/1, preferably between 1/1 and 2/1.
• 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 EP 70 079 and EP 193 360 mentioned above. Such products are, for 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 silico-aluminate of the "zeolite A" type.
• the washing product according to the invention which constitutes a new industrial product, also comprises one or more other constituents chosen, in particular, from the group comprising detergents, surface-active agents, anti-deposition agents , oxidizing agents, structuring agents, anticorrosion agents, anti-foaming agents, enzymes, perfumes, dyes and solubilizing agents, for example as described in the abovementioned patents EP 70,079 and EP 319,053.
• the detergents may, for example, be chosen from synthetic anionic detergents, such as the water-soluble alkali metal salts of organic sulfates and sulfonates comprising alkyl radicals of 8 to 22 carbon atoms, such as, for example, sodium dodecylbenzene sulfonates or potassium.
• synthetic anionic detergents such as the water-soluble alkali metal salts of organic sulfates and sulfonates comprising alkyl radicals of 8 to 22 carbon atoms, such as, for example, sodium dodecylbenzene sulfonates or potassium.
• nonionic detergents such as in particular alkylpolyglucosides or ethoxylated fatty alcohols.
• Oxidizing agents i.e. products capable of releasing peroxide ions in such quantities that they allow bleaching of wine, tea, coffee stains, etc.
• the structuring agents 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 or glucose syrups.
• washing product in accordance with the invention may contain commonly used detergency builders such as polyacrylic acid (PA), nitrilotriacetic acid (NTA) and / or their respective salts, in particular their sodium salts.
• PA polyacrylic acid
• NTA nitrilotriacetic acid
• the characteristic presence of at least one oxidized polysaccharide within the washing products in accordance with the invention makes it possible, in a remarkable manner, for said products to be, at zeolite levels not higher, or even lower than those of the prior art products, effective for constitutive levels of NTA, in AP or in their respective salts, lower than those commonly encountered in said products of the prior art, in particular for levels not greater than 2 % by weight, and in particular substantially zero.
• Washing products according to the invention useful in particular for washing fabrics, machine or “by hand", will preferably be in the form of particles flowing freely and in particular in the form of powders or granules.
• the contacting of at least one zeolite and at least one oxidized polysaccharide within the washing products according to the invention can be carried out according to very diverse methods, in the form of powders, liquids or powder / liquid mixtures. , in one or more stages, in the presence or not of all or part of the other constituents of said products.
• the combination of at least one zeolite and at least one oxidized polysaccharide may also be carried out in washing products which are in a form other than that of freely flowing particles, in particular in the form of liquids, gels or pasta.
• These products which will generally have a dry matter content of 15% to 80%, in particular from 30 to 50%, may, for example, be obtained by increasing, by any means and in particular by simple dissolution or placing suspended in water or another liquid, the water content of washing products according to the invention previously prepared in the form of powders or granules.
• an oxidized polysaccharide contained in the washing products according to the invention is used, an oxidation product of a starch hydrolyzate having an ED of 61, 5 approximately and which has an acid number I of approximately 13.6.
• 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 the following two temperatures: 40 ° C and 60 ° C.
• 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), the dimensions of which 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 per fabric is 4, i.e. 4 measurements (i.e. in four different places on the same piece of fabric)
• x 2 strips of fabric 16 measurements per soiling, per formulation and by temperature.
• the effect of the washing is measured on two coupons of white unsoiled cotton EMPA 221 and on two coupons of polyester / white cotton unsoiled EMPA 213, which are incorporated into the washing bath. On each coupon, 4 measurements are made, which therefore gives 16 measurements per formulation and per temperature studied.
• the washing tests were carried out, on the one hand, on gray cotton and, on the other hand, on synthetic fabrics (polyester / cotton).
• the synthetic fabric used here is a polyester / cotton (dacron / cotton) type fabric from KREFELD; it was soiled with a mixture of animal oil and carbon black (ref. WFK 20C).
• spots caused are those which bleaching reduces or eliminates (other spots of this type are those caused by fruits, coffee, vegetables and others).
• White non-azure cotton of the brand EMPA 221 and polyester / cotton non-azure of the brand EMPA 213 are used to determine whether a given washing product is capable of preserving, increasing or decreasing the initial degree of whiteness of the fabric.
• the detergents in accordance with the invention are, overall, as effective as the washing product of the prior art, said washing products according to the invention making it possible to obtain, after washing, a fabric whose degree of whiteness is greater than that which it had before washing.
• washing product designated by the letter T was used as a control product according to the prior art, the constitution of which has been detailed in Table I above.
• oxidized polysaccharide contained in the washing products according to the invention of an oxidation product of a starch hydrolyzate having a DE of approximately 37, and having an index of acid I of about 8.6, said oxidation product having moreover been treated by catalytic hydrogenation with Raney nickel (residual content of reducing sugars less than 0.05%).
• the tests are carried out at 60 ° C on a wash brand WASCATOR FOM 71 at a rate of 7 g / l of detergent, or 154 g per wash.
• the determination of the DP of the cellulose is carried out by measuring the viscosity of a solution of a cotton sample subjected to the test in an appropriate solvent (cupriethylene diamine) relative to the viscosity of the solvent itself, in accordance with NF T 73-601, paragraph 3.6 or NF G 06-037 standards.
• the aim is that the detergent action does not cause a substantial decrease in the DP so as not to facilitate the tearing of the fabric thus washed.
• the organic incrustation makes it possible to apprehend the deposit of residues of surfactant (s) or soap (s) complexed (s) by calcium in the case of poor sequestration.
• test is carried out in accordance with standards NF T 73-601, paragraph 3.3 and ISO 4312, paragraph 6.
• the organic encrustation rate should not exceed around 1%.
• Table XII gives, for the control washing product T and each of the washing products I, J and K according to the invention, the average degree of polymerization DP and the rate of organic incrustation IO obtained after 25 washes carried out at 60 ° C.
• TABLE XII Washing product T I J K Degree of polymerization DP 1924 1865 1914 1892 IO organic inlay rate (in%) 1.05 0.59 0.64 0.41
• Measuring the ash rate makes it possible to understand the importance of the deposit of mineral salts, in particular of the carbonate, bicarbonate, calcium or magnesium sulfate type, on the laundry at the end of the washing cycle.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Health & Medical Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Molecular Biology (AREA)
• Inorganic Chemistry (AREA)
• Emergency Medicine (AREA)
• Detergent Compositions (AREA)
• Woven Fabrics (AREA)
• Medicines Containing Material From Animals Or Micro-Organisms (AREA)
• Lubrication Of Internal Combustion Engines (AREA)
• Preparation Of Compounds By Using Micro-Organisms (AREA)
• Biological Depolymerization Polymers (AREA)

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• 1990
  • 1990-03-23 FR FR9003758A patent/FR2659979B1/fr not_active Expired - Fee Related
• 1991
  • 1991-03-19 CA CA002038640A patent/CA2038640A1/en not_active Abandoned
  • 1991-03-21 AT AT91400773T patent/ATE141323T1/de not_active IP Right Cessation
  • 1991-03-21 ES ES91400773T patent/ES2090268T3/es not_active Expired - Lifetime
  • 1991-03-21 DK DK91400773.7T patent/DK0455522T3/da active
  • 1991-03-21 EP EP91400773A patent/EP0455522B1/fr not_active Expired - Lifetime
  • 1991-03-21 DE DE69121286T patent/DE69121286T2/de not_active Expired - Fee Related
  • 1991-03-22 FI FI911409A patent/FI911409A/fi not_active Application Discontinuation
  • 1991-03-22 NO NO91911157A patent/NO911157L/no unknown
  • 1991-03-25 JP JP3216730A patent/JPH05214367A/ja active Pending
• 1996
  • 1996-09-04 GR GR960402301T patent/GR3020943T3/el unknown

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