EP0678117B1 - Copolymeres sequences utilises comme regulateurs de mousse dans des detergents ou des nettoyants - Google Patents

Copolymeres sequences utilises comme regulateurs de mousse dans des detergents ou des nettoyants Download PDF

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Publication number
EP0678117B1
EP0678117B1 EP94904187A EP94904187A EP0678117B1 EP 0678117 B1 EP0678117 B1 EP 0678117B1 EP 94904187 A EP94904187 A EP 94904187A EP 94904187 A EP94904187 A EP 94904187A EP 0678117 B1 EP0678117 B1 EP 0678117B1
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EP
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Prior art keywords
weight
foam
block copolymer
glycol
polyethylene glycol
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Lifetime
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EP94904187A
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German (de)
English (en)
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EP0678117A1 (fr
Inventor
Thomas Möller
Herbert Fischer
Winfried Emmerling
Ulrich Eicken
Christian Block
Wolfgang Seiter
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/0034—Fixed on a solid conventional detergent ingredient
    • 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
    • C11D3/0005—Other compounding ingredients characterised by their effect
    • C11D3/0026—Low foaming or foam regulating compositions
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3715—Polyesters or polycarbonates
    • 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
    • C11D3/37—Polymers
    • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3726—Polyurethanes

Definitions

  • the invention relates to the use of block copolymers containing propylene glycol ether and optionally ethylene glycol ether units as foam regulators in detergents and / or cleaning agents containing surfactants, a pourable and free-flowing, particulate foam inhibitor, comprising water-soluble or water-dispersible carrier material and block copolymer adsorbed thereon, and processes for producing such Block copolymers as well as such particulate foam inhibitors.
  • polysiloxanes are known to be comparatively complex to produce with a known good defoaming action and have the disadvantage that they are often perceived as completely unsatisfactory in their biodegradability, especially in recent times.
  • Silicone-free foam regulators are also known.
  • European Patent EP 87 233 describes a process for producing a low-foaming detergent in which mixtures of an oily or waxy substance and bisamides are applied to a carrier powder, in particular a spray-dried detergent containing surfactants.
  • the oily or waxy substance can consist, for example, of petroleum jelly with a melting point of 20 ° C to 120 ° C.
  • foam control component In this type of packaging, namely the spraying of the agent onto the spray-dried detergent-containing detergent, there is Risk that the manufacturing process will adversely affect the shelf life of the foam control component, with the result that its activity will decrease with increasing storage time.
  • further foam inhibitors are often added to these defoamers, in particular the known polysiloxanes or polysiloxane / silica mixtures.
  • Further foam-regulated detergents are known from European patents EP 75 433 and EP 94 250.
  • foam control agents described there also contain silicones and are out of the question for the reasons mentioned.
  • German published patent application DT 28 57 155 discloses detergents with a foam regulating agent which contains hydrophobic silicon dioxide and a mixture of solid and liquid hydrocarbons, optionally in a mixture with fatty acid esters. Due to the high content of hydrocarbon which is liquid at room temperature, from 22.5% by weight to about 98% by weight, there is a risk of clumping in such foam regulating agents.
  • Foam control agents containing paraffin wax mixtures and hydrophobized silica, optionally in combination with branched-chain alcohols, are known from German published patent application DE 34 00 008.
  • Powdered defoamers which contain a liquid mixture of higher molecular weight, branched-chain alcohols with hydrophobized silica in combination with a water-insoluble wax on a water-soluble, powdery carrier, are known from German published patent application DE 31 15 644.
  • European patent application EP 309 931 foam regulating agents were described which contain a relatively complex mixture of paraffin wax and microcrystalline paraffin wax.
  • the task was therefore to provide a silicone-free foam regulator, which is effective in aqueous washing and cleaning liquors, packaged in the form of a free-flowing foam regulating agent can and used in detergents and cleaning agents unfolds its effect over a wide temperature range, that is in the cold wash range, at medium wash temperatures and also in the hot wash range suppresses a disruptive foam development. Furthermore, both the foam regulator and the foam regulating agent containing it should remain stable in storage and effect in a mixture with conventional detergent or cleaning agent components and should not have any adverse effects on the material to be treated and the environment.
  • the invention thus relates to the use of block copolymers containing glycol ether units, which can be obtained by reacting polypropylene glycol with a molecular weight in the range from 1000 to 8000 and optionally polyethylene glycol with a molecular weight in the range from 200 to 20,000 with diisocyanates and / or dicarboxylic acids each with 2 to 44 carbon atoms, in the case of dicarboxylic acids a molar ratio of hydroxyl groups to carbonyl groups of 1: 1 to 1.9: 1 being present as foam regulators in detergents and / or cleaning agents containing surfactants.
  • Block copolymers are preferably used which, by reacting diisocyanate with the glycol or the glycols, in a molar ratio of hydroxyl groups to carbonyl groups of from 1: 2 to 2: 1, in particular from 1: 1 to 2: 1 and particularly preferably from 1.1: 1 to 1.9: 1 are available.
  • block copolymers are used which can be obtained by reacting diisocyanate and / or dicarboxylic acid with a mixture of polypropylene glycol and polyethylene glycol in which the molar ratio of polyethylene glycol to polypropylene glycol up to 1: 1, in particular from 0.1: 1 to 0.9: 1.
  • the molar ratio can, however, also be significantly above 1: 1.
  • Such block copolymers contain the blocks ([-C 3 H 6 O] a -X) n - and ([-C 2 H 4 O] b -X) o -, in which the numbers a and b are derived from the molecular weights of the polypropylene glycol or polyethylene glycol and in the case of degree of ethoxylation b can also be 0, X is a bisacyl or bisurethane group, n is a number greater than 0 and o is a number of at least 0.
  • the number of these blocks in the polymer, the molecular ratio of the blocks to one another and the sizes n and o form a complex system which is difficult to illustrate in a general formula.
  • Another object of the invention is a granular, free-flowing foam regulating agent which adsorbs 0.5% by weight to 30% by weight of a block copolymer to be used according to the invention to 70% by weight to 99.5% by weight of a granular , contains essentially inorganic phosphate-free carrier material.
  • the block copolymers to be used according to the invention are substances with ester and / or urethane groups, which can be obtained by reacting polypropylene glycols, optionally in a mixture with polyethylene glycols, with diisocyanates and / or dicarboxylic acids. These are preferably compounds which, by reacting 1 mol equivalent of diisocyanate and / or dicarboxylic acid with 1 mol equivalent to 2 mol equivalents, in particular 1.1 mol equivalents to 1.9 mol equivalents, of polypropylene glycol and up to 1 mol equivalent, in particular 0.05 mol equivalent to 0 , 9 mole equivalents of polyethylene glycol are available.
  • urethane block copolymers are those which can be obtained by reacting the glycols with diisocyanates in OH: NCO molar ratios of 1: 1 to 1.5: 1.
  • the molar ratio of polypropylene glycol to polyethylene glycol is preferably 0.1: 1 to 0.9: 1, in particular 0.2: 1 to 0.8: 1.
  • Polyethylene glycol preferably has a molecular weight from 500 to 15,000 and polypropylene glycol preferably a molecular weight of 1000 to 2000.
  • polyethylene glycol and polypropylene glycol in the stated ratio, in which at least part, in particular not more than 90 mol% and particularly preferably 5 mol% to 50 mol%, of the polypropylene glycol and / or the polyethylene glycol is replaced by longer-chain aliphatic vicinal diols with 10 to 20 C atoms, in particular 12 to 18 C atoms, and / or a, w-diols with 3 to 22 C atoms.
  • X represents a bisacyl or a bisurethane grouping, as is obtained by formal condensation with two molar equivalents of an alcohol from a dicarboxylic acid or by formal addition of two molar equivalents of an alcohol from a diisocyanate.
  • the bisacyl groups contain a total of 2 to 44, preferably 2 to 12, carbon atoms which can be arranged between the acyl or isocyanate ends as an alkylene, alkenylene or arylene group.
  • the formal derivatives of linear ⁇ , w-dicarboxylic acids and of double-carboxyl-substituted aromatics are particularly preferred.
  • ester derivatives of oxalic acid, malonic acid, succinic acid, maleic acid, fumaric acid, adipic acid, pimelic acid, suberic acid, azelaic acid, brassylic acid, phthalic acid, isophthalic acid, terephthalic acid and mixtures thereof are therefore particularly useful.
  • Block copolymers which are particularly useful according to the invention, in which X denotes a bisurethane group, are, in addition to the optionally alkyl-substituted alkylene diisocyanates, for example trimethylhexamethylene diisocyanate, that of isophorone diisocyanate, ortho-, meta- and para-phenylene diisocyanate, the methylene diphenyl diisocyanates, the methylene dicyclohexyl diisocyanate diisocyanate diisocyanate diisocyanate diisocyanate, and the tetramethylxylylene diisocyanates and their mixtures of derivable compounds.
  • alkyl-substituted alkylene diisocyanates for example trimethylhexamethylene diisocyanate, that of isophorone diisocyanate, ortho-, meta- and para-phenylene diisocyanate, the methylene diphenyl diisocyanates, the m
  • reaction products obtainable by reaction of the diisocyanates or dicarboxylic acids mentioned with the diols mentioned in molar ratios of about 2: 1 or isocyanate group-terminated or carboxylic acid group-terminated reaction products are also useful. Because of their excellent defoamer performance, the block copolymers which can be derived from 2,4- or 2,6-tolylene diisocyanate are particularly preferred.
  • Hydroxyl group-terminated compounds of the abovementioned type can also be reacted in a manner known in principle with monocarboxylic acids having 1 to 22 carbon atoms, in particular fatty acids with 12 to 20 carbon atoms, or their reactive derivatives, for example acid chlorides, anhydrides or methyl or ethyl esters, and so at least partially end groups are closed.
  • monocarboxylic acids having 1 to 22 carbon atoms, in particular fatty acids with 12 to 20 carbon atoms, or their reactive derivatives, for example acid chlorides, anhydrides or methyl or ethyl esters, and so at least partially end groups are closed.
  • the defoaming performance of such compounds is also excellent.
  • the polymers to be used according to the invention are preferably prepared by reacting polypropylene glycols and, if appropriate, polyethylene glycols with difunctional isocyanates or difunctional carboxylic acids or reactive carboxylic acid derivatives, for example anhydrides or acid chlorides, in the abovementioned molar ratios, if desired with the addition of acidic catalysts, at temperatures from 20.degree 140 ° C and, if desired, in a solvent inert under the reaction conditions. It is also possible to use the lower alkyl esters of carboxylic acids, especially their methyl or ethyl esters, under preferably acidic transesterification conditions.
  • block copolymers to be used according to the invention which contain both polyethylene and polypropylene groupings, it is also possible to react previously prepared polyethoxylated polypropylene glycols with the difunctional compounds mentioned.
  • the production of certain polyglycol esters is described, for example, in US Pat. No. 2,950,310.
  • reaction with monocarboxylic acids or their reactive derivatives can then take place, so that end-capped products are formed.
  • the use according to the invention can be achieved in its simplest form by adding a block copolymer as described above to a washing or cleaning liquor in bulk without this addition, which tends to cause undesirable strong foaming, dissolved in a preferably water-miscible organic solvent or in aqueous suspension.
  • the block copolymers to be used according to the invention are preferably in In the form of granular, free-flowing foam regulators, which contain the block copolymers mentioned.
  • the phosphate-free carrier material for converting the block copolymers to be used according to the invention into a free-flowing foam regulating agent which is particularly suitable for use in powdered detergents and cleaning agents, has a granular structure and consists of water-soluble or water-dispersible compounds, primarily of inorganic and optionally additional organic salts, which are suitable for use in detergents and cleaning agents.
  • organic carrier materials such as starch or cellulose and customary neutral salts, for example alkali sulfates or alkali chlorides, in particular customary washing alkalis, for example alkali carbonates or silicates, inorganic builder substances, for example aluminosilicates, layered silicates, for example bentonites, and inorganic bleaches based on oxygen, for example - alkali perborates percarbonates, the latter bleaching agents in particular being preferred in one embodiment of the foam regulating agent according to the invention as carrier material or constituent of the carrier material.
  • customary neutral salts for example alkali sulfates or alkali chlorides
  • customary washing alkalis for example alkali carbonates or silicates
  • inorganic builder substances for example aluminosilicates, layered silicates, for example bentonites
  • inorganic bleaches based on oxygen for example - alkali perborates percarbonates, the latter bleaching agents in particular being preferred in one embodiment of
  • organic carrier materials preferably not containing more than 20% by weight, in particular in amounts of 2% by weight to 15% by weight, based in each case on the total carrier material are.
  • the carrier material preferably contains both alkali carbonate and alkali silicate.
  • the carrier material preferably contains 1% by weight to 50% by weight of alkali carbonate, up to 70% by weight of alkali sulfate, up to 50% by weight of alkali alumosilicate and 10% by weight to 50% by weight of alkali silicate , but can additionally contain other water-soluble or water-insoluble, water-dispersible substances.
  • the materials which can additionally be used include, in particular, alkali metal chlorides and layered silicates, for example bentonite.
  • the alkali silicate is preferably a compound with a molar ratio of alkali oxide to SiO 2 of 1: 1.5 to 1: 3.5.
  • Foam control agents that can be used for aluminosilicates include, in particular, the zeolites, for example zeolite NaA and NaX.
  • Examples of possible organic components of the carrier material are starch, acetates, tartrates, citrates, succinates, carboxymethylsuccinates and the alkali metal salts of aminopolycarboxylic acids, such as NTA or EDTA, hydroxyalkane phosphonates and aminoalkane polyphosphonates, such as 1-hydroxyethane1,1-diphosphonate phosphonate aminophthalonate and ethylenediophosphonate pentamphonate amine.
  • Water-soluble salts of polymeric or copolymeric carboxylic acids for example polyacrylates and copolymers of acrylic acid and maleic acid, can also be used.
  • the preferred alkali metal in the alkali salts mentioned is sodium in all cases.
  • the carrier material can also contain, as an organic component, film-forming polymers, for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones and cellulose derivatives.
  • film-forming polymers for example polyethylene glycols, polyvinyl alcohols, polyvinylpyrrolidones and cellulose derivatives.
  • Usable cellulose ethers are, in particular, alkali carboxymethyl cellulose, methyl cellulose, ethyl cellulose, hydroxyethyl cellulose and so-called cellulose mixed ethers, such as, for example, methyl hydroxyethyl cellulose and methyl hydroxypropyl cellulose, and mixtures thereof.
  • the carboxymethyl cellulose usually having a degree of substitution of 0.5 to 0.8 carboxymethyl groups per anhydroglucose unit and the methyl cellulose having a degree of substitution of 1.2 to 2 methyl groups per anhydroglucose unit.
  • the mixtures preferably contain alkali carboxymethyl cellulose and nonionic cellulose ethers in weight ratios from 80:20 to 40:60, in particular from 75:25 to 50:50.
  • Such cellulose ether mixtures can be used in solid form or as aqueous solutions, which can be pre-swollen in the usual way.
  • the foam regulating agents according to the invention can, preferably not more than 10 wt .-% and in particular from 0.5 wt .-% to 3.5 wt .-%, surfactant.
  • Surfactants are to be understood as meaning surface-active compounds with a hydrophobic part of the molecule and hydrophilic anionic, ampholytic, zwitterionic, cationic and nonionic groups which, in aqueous solution or dispersion, have a cleaning or emulsifying effect Make an impact.
  • Surfactants are usually the foam-causing components of washing and cleaning liquors. It is all the more surprising that these foaming constituents can be contained in the foam regulating agents according to the invention without the effectiveness of the agents being impaired.
  • the hydrophobic molecular part of surfactants generally consists of a hydrocarbon radical or a substituted hydrocarbon radical or a polyglycol ether radical which is poorly soluble in water, for example a polypropylene glycol or polybutylene glycol ether radical.
  • the foam control agents according to the invention preferably contain synthetic anionic surfactants of the sulfate or sulfonate type, in particular alkylbenzenesulfonates and / or alkyl sulfates, because these enable particularly good dispersion of the block copolymers in the course of the preparation of the foam control agents described below via aqueous dispersions of the block copolymers.
  • a foam regulating agent according to the invention can be produced by applying the liquid block copolymer, optionally heated to room temperature, to the granular carrier material, for example by successive admixing, in particular as a spray, to the carrier material.
  • the carrier grain which can be produced in the customary manner by granulation or by spray drying an aqueous slurry of the carrier materials, is kept in motion by mixing elements or by fluidization in order to ensure a uniform loading of the carrier material.
  • the spray mixers used for this can be operated continuously or discontinuously.
  • an aqueous dispersion of the block copolymer to be used according to the invention which preferably contains a film-forming polymer and / or surfactant listed above as a dispersion aid.
  • a dispersion aid e.g., a film-forming polymer and / or surfactant listed above.
  • the foam regulating agent is produced by dissolving or slurrying the carrier materials in water, dispersing the block copolymer to be used according to the invention therein and then spray-drying this slurry.
  • a water-soluble dispersion stabilizer in the form of a surfactant and / or water-swellable polymers is preferably added to the dispersion since the block copolymers to be used according to the invention are generally insoluble or only slightly soluble in the aqueous slurry.
  • water-swellable polymers examples include the cellulose ethers mentioned, homo- and copolymers of unsaturated carboxylic acids, such as acrylic acid, maleic acid and copolymerizable vinyl compounds, such as vinyl ether, acrylamide and ethylene.
  • the addition of such compounds which act as dispersion stabilizers in the aqueous slurry is preferably not more than 5% by weight, in particular 1% to 3% by weight, based on the foam regulating agent formed.
  • the water content of the slurry can be 30% to 60% by weight, depending on the type or solubility of the carrier material.
  • the spray drying of the dispersion can be carried out in a known manner in systems provided for this purpose, so-called spray towers, using hot drying gases conducted in cocurrent or countercurrent.
  • a foam regulating agent according to the invention preferably consists of particles with particle sizes not more than 2 mm, in particular from 0.1 mm to 1.6 mm. It preferably has a bulk density in the range from 300 grams per liter to 1100 grams per liter, in particular from 450 grams per liter to 900 grams per liter. It is preferably used for the production of powdered detergents or cleaning agents, a further advantage of the foam regulating agents according to the invention being their small amount required with good defoamer performance.
  • polyethylene glycols PEG, the number given means the molecular weight
  • polypropylene glycols PPG, the number given means the molecular weight
  • diisocyanates listed in Tables 2 to 5 below were converted to the block-copolymeric urethanes U1 to U20 .
  • the parts by weight used for the polyglycols are given in the tables; for the diisocyanate component, this is the equivalent weight ratio with regard to the alcohol components (ratio OH: NCO).
  • the defoamer performance of block copolymers according to Example 1 was determined using the free-fall cycle method.
  • Table 6 shows the times (in seconds) until 1000 ml of foam build up. The longer these times are the better the foam-regulating effect of the block copolymer. It was largely irrelevant whether the block copolymers were absorbed in bulk or on carrier materials (sodium carbonate, zeolite Na-A, starch, partially hydrolyzed starch and a sodium sulfate / sodium carbonate / sodium silicate / carboxymethyl cellulose / methyl cellulose combination were used).
  • Table 7 shows the amounts of foam (in ml) formed in the free-fall cycle method described above as a function of time. Block copolymers in concentrations of 0.5% by weight were used in the liquor. Table 7: Foam amounts [ml] Block copolymer (0.5% by weight) Amount of foam after 10 min 15 minutes 25 min - 1480 1450 1580 U3 720 720 780 U6 740 800 900 U7 700 780 1120 U8 980 1120 920 U9 1160 1360 1280 U10 860 980 1540 U11 940 940 980 U12 720 740 760 U13 780 860 920 U14 740 820 1380 U17 720 760 1000 U18 940 920 880 U20 1020 1000 980
  • Granular foam control agents were obtained by simply mixing in each case 1% by weight of part of the block copolymers E1 , E2 and U1 to U20 with 10% by weight of powdered sodium sulfate. This was incorporated into foam detergent-free universal detergent formulations and, under conditions of use in a household washing machine at concentrations of 1% by weight to 4% by weight, based on the total detergent, defoamer performance comparable to that of a commercially available silicone foam inhibitor (used with the same weight based on active substance) in no way inferior.
  • An alkaline cleaning agent for metal sheets in the automotive industry consisting of 18% by weight borax, 32% by weight sodium phosphate, 25% by weight sodium silicate, 15% by weight of sodium hydroxide, 9% by weight of nonionic surfactant and 1% by weight of block copolymer U11 was tested in an intensive foam test according to Götte.
  • the procedure was such that the test solution (concentration 0.3% by weight) in the presence of a foaming agent (concentration 0.03% by weight) made of mineral oil, alkylbenzenesulfonate, fatty acid and polyethylene glycol was placed in a cylindrical vessel with a rotating spray arm pumped around and sprayed.
  • the amount of foam formed was read off after the times given below (switch off the pump, the foam height is the distance between the foam surface and the liquid surface).
  • the value for the foam regulator-free agent was set as 1. After a pumping and spraying time of 30 minutes, the foam height when using the foam regulator-containing agent was 0.5 units, after 3.5 hours 0.4 units.
  • the foam regulator used according to the invention has not been found to have a negative influence on the ability to be painted over with customary automotive paints or the cleaning effect of the agent.

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  • Engineering & Computer Science (AREA)
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  • Emulsifying, Dispersing, Foam-Producing Or Wetting Agents (AREA)

Claims (15)

  1. Utilisation, comme régulateurs de mousse dans des détergents et/ou des nettoyants à teneur tensioactive, de copolymères séquencés contenant des unités de glycoléther, qui sont obtenables par mise en réaction de polypropylèneglycol possédant une masse molaire comprise dans l'intervalle de 1000 à 8000 et, le cas échéant, de polyéthylèneglycol présentant une masse molaire située dans la plage de 200 à 20 000, en particulier jusqu'à 8000, avec des diisocyanates et/ou des acides dicarboxyliques comportant chacun 2 à 44 atomes de C, le rapport moléculaire entre les groupes hydroxyle et carbonyle étant compris entre 1:1 et 1,9:1, en cas d'utilisation d'acides dicarboxyliques.
  2. Utilisation selon la revendication 1, caractérisée en ce que le copolymère séquencé est obtenable par mise en réaction du diisocyanate avec le ou les glycols, avec un rapport molaire entre les groupes hydroxyle et carbonyle compris entre 1:2 et 2:1, en particulier entre 1:1 et 1,9:1.
  3. Utilisation selon la revendication 1 ou 2, caractérisée en ce que le copolymère séquencé est obtenable par mise en réaction de diisocyanate et/ou d'acide dicarboxylique avec un mélange de polypropylèneglycol et de polyéthylèneglycol, dans lequel le polyéthyléneglycol et le polypropylèneglycol sont entre eux dans un rapport molaire allant jusqu'à 1:1, en particulier compris entre 0,1:1 et 0,9:1.
  4. Utilisation selon une des revendications 1 à 3, caractérisée en ce que le copolymère séquencé est obtenable à partir de polyéthylèneglycol possédant un poids moléculaire de 500 à 15 000 et de polypropylèneglycol présentant un poids moléculaire de 1000 à 2000.
  5. Utilisation selon une des revendications 1 à 4, caractérisée en ce que le copolymère séquencé est obtenable par mise en réaction de diisocyanates avec un mélange constitué de polypropyléneglycol et de polyéthyléneglycol dans un rapport molaire OH:NCO de 1:1 à 1,5:1.
  6. Utilisation selon une des revendications 3 à 5, caractérisée en ce que les copolymères séquences sont obtenables à partir d'un mélange de polypropylèneglycol et de polytéthylèneglycol, dans lequel au moins une partie, en particulier pas plus de 90 moles % et, avec une préférence particulière, 5 à 50 moles % du polypropylèneglycol et/ou du polyéthyléneglycol, sont remplacés par des diols vicinaux aliphatiques à chaîne plus longue comportant 10 à 20 atomes de C, en particulier 12 à 18 atomes de C, et/ou des diols a,w possédant 3 à 22 atomes de C.
  7. Procédé de fabrication des copolymères séquencés à mettre en oeuvre conformément à une des revendications 1 à 6, par mise en réaction de polypropylèneglycols et, éventuellement, de polyéthylèneglycols avec des isocyanates difonctionnels et/ou des acides carboxyliques difonctionnels ou des dérivés d'acides carboxyliques réactifs difonctionnels, le cas échéant sous adjonction de catalyseurs acides, à des températures comprises entre 20 et 140 °C et, si on le souhaite, dans un solvant inerte dans les conditions de réaction.
  8. Procédé selon la revendication 7, caractérisé en ce que l'on met en oeuvre comme dérivés d'acides carboxyliques réactifs difonctionnels, des anhydrides, des chlorures d'acides et/ou des alkylesters inférieurs d'acides dicarboxyliques, en particulier des diméthyl- et/ou des diéthylesters.
  9. Agent régulateur de mousse granuleux, coulant, contenant une substance active antimoussante et une matière porteuse, sans phosphates, essentiellement inorganique, caractérisé en ce qu'il contient
    0,5 à 30 % en poids d'un copolymère séquencé, qui est obtenable par mise en réaction de polypropylèneglycol possédant une masse molaire comprise dans l'intervalle de 1000 à 8000 et, le cas échéant, de polyéthylèneglycol présentant une masse molaire située dans la plage de 200 à 8000, avec des diisocyanates et/ou des acides dicarboxyliques comportant chacun 2 à 44 atomes de C,
    adsorbés sur
    70 à 99,5 % en poids d'une matière porteuse granuleuse, sans phosphates et soluble ou dispersible dans l'eau.
  10. Agent selon la revendication 9, caractérisé en ce qu'il renferme 1 à 25 % en poids, en particulier 2 à 12 % en poids d'un copolymère séquencé et 75 à 99 % en poids, en particulier 88 à 98 % en poids de matière porteuse.
  11. Agent selon la revendication 9 ou 10, caractérisé en ce que la matière porteuse contient des alcalis détergents, en particulier du carbonate et/ou du silicate de métal alcalin, des substances adjuvantes inorganiques, en particulier de l'aluminosilicate, du silicate stratifié, en particulier de la bentonite, et/ou un agent de blanchiment inorganique à base d'oxygène, en particulier du perborate ou du percarbonate de métal alcalin.
  12. Procédé de fabrication d'un agent régulateur de mousse granuleux, conforme à une des revendications 9 à 11, caractérisé en ce que l'on applique le copolymère séquencé sur la matière porteuse granuleuse maintenue en mouvement, si on le souhaite à des températures supérieures à la température ambiante.
  13. Procédé selon la revendication 12, caractérisé en ce que l'on met en oeuvre une suspension ou une dispersion aqueuse du copolymère séquencé, confectionnée si on le souhaite en utilisant un adjuvant de dispersion, et que l'on soumet, le cas échéant, l'agent régulateur de mousse obtenu à une étape de séchage postérieure.
  14. Procédé de fabrication d'un agent régulateur de mousse granuleux conforme à une des revendications 9 à 11, caractérisé en ce que l'on disperse le copolymère séquencé dans une solution ou une suspension aqueuse de la matière porteuse, le cas échéant sous adjonction d'un adjuvant de dispersion, en particulier d'un polymère soluble ou gonflable dans l'eau, et en ce que l'on sèche la dispersion par pulvérisation.
  15. Utilisation d'un agent régulateur de mousse granuleux, conforme à une des revendications 9 à 11, pour la fabrication de détergents ou de nettoyants en poudre.
EP94904187A 1993-01-07 1993-12-27 Copolymeres sequences utilises comme regulateurs de mousse dans des detergents ou des nettoyants Expired - Lifetime EP0678117B1 (fr)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE4300087 1993-01-07
DE4300087A DE4300087A1 (de) 1993-01-07 1993-01-07 Blockcopolymere als Schaumregulatoren in Wasch- oder Reinigungsmitteln
PCT/EP1993/003697 WO1994016044A1 (fr) 1993-01-07 1993-12-27 Copolymeres sequences utilises comme regulateurs de mousse dans des detergents ou des nettoyants

Publications (2)

Publication Number Publication Date
EP0678117A1 EP0678117A1 (fr) 1995-10-25
EP0678117B1 true EP0678117B1 (fr) 1996-08-28

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Application Number Title Priority Date Filing Date
EP94904187A Expired - Lifetime EP0678117B1 (fr) 1993-01-07 1993-12-27 Copolymeres sequences utilises comme regulateurs de mousse dans des detergents ou des nettoyants

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EP (1) EP0678117B1 (fr)
JP (1) JPH08512333A (fr)
AT (1) ATE141944T1 (fr)
DE (2) DE4300087A1 (fr)
ES (1) ES2091132T3 (fr)
WO (1) WO1994016044A1 (fr)

Families Citing this family (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5632860A (en) * 1995-07-05 1997-05-27 Betzdearborn Inc. Method of controlling foam in aqueous systems
DE10339479A1 (de) * 2003-08-27 2005-05-12 Basf Ag Schaumregulierungsmittel auf Basis von kationischen Urethan-Oligomeren
TWI555800B (zh) * 2011-04-04 2016-11-01 拜耳材料科學股份有限公司 聚胺基甲酸酯脲分散體

Family Cites Families (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE1069577B (de) * 1959-11-26 Farbenfabriken Bayer Aktiengesellschaft, Leverkusen-Bayerwerk Entschäumer auf Urethanbasis
GB1465700A (en) * 1974-11-21 1977-02-23 Ici Ltd Surface active compositions
JPS57119807A (en) * 1981-01-19 1982-07-26 Mitsubishi Petrochem Co Ltd Antifoaming agent
MX2781A (es) * 1985-06-27 1993-09-01 Ciba Geigy Ag Inhibidor de espuma para sistemas acuosos

Also Published As

Publication number Publication date
WO1994016044A1 (fr) 1994-07-21
EP0678117A1 (fr) 1995-10-25
DE4300087A1 (de) 1994-07-14
DE59303602D1 (de) 1996-10-02
JPH08512333A (ja) 1996-12-24
ES2091132T3 (es) 1996-10-16
ATE141944T1 (de) 1996-09-15

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