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
• • 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
  • C11D3/02—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
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in solid 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
  • C11D3/02—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 invention relates to a granular detergent additive containing liquid to pasty nonionic surfactants which are adsorbed on a granular carrier material.
• the agent is particularly suitable for use in phosphate-free or low-phosphate detergents and cleaning agents. It has a significantly improved flushing behavior, i. H. it does not form undissolved residues in the washing-in devices of automatic washing machines and moreover improves the washing-in behavior of detergent mixtures in such devices.
• nonionic surfactants have a very high cleaning ability, which makes them particularly suitable for use in cold detergents or 60 ° C. detergents.
• their proportion cannot be increased significantly beyond 8 to 10 percent by weight in the generally customary production of detergents by spray drying, since otherwise there is excessive smoke formation in the exhaust air from the spray towers and poor pouring properties of the spray powder.
• Methods have therefore been developed in which the liquid or melted nonionic surfactant is mixed onto the previously spray-dried powder or sprayed onto a carrier substance.
• phosphate-free carrier grains which consist of 25 or 52% sodium carbonate or hydrogen carbonate, 10 to 50% zeolite, 0 to 18% sodium carbonate and 1 to 20% bentonite or 0.05 to 2% polyacrylate .
• DE 34 44 960-A1 discloses a granular adsorbent which is able to absorb high proportions of liquid to pasty detergent constituents, in particular nonionic surfactants, and (based on anhydrous substance) from 60 to 80% by weight of zeolite, 0.1 to 8% by weight .-% sodium silicate, 3 to 15 wt .-% of homo- or copolymers of acrylic acid, methacrylic acid and / or maleic acid, 8 to 18 wt .-% water and optionally up to 5 wt .-% of nonionic surfactants and by spray drying is available.
• EP 149 264 teaches that known spray-dried zeolites and their mixtures with inorganic salts, such as sodium sulfate, can also be used for this purpose, the grain size and bulk density of these spray products being within the usual range.
• the object was therefore to improve the washing-in behavior of such detergent additives.
• the invention thus relates to a granular detergent additive with improved washing-up behavior, consisting of a granular, porous, water-soluble or water-dispersible carrier material and water-soluble or water-dispersible nonionic surfactants adsorbed thereon, characterized in that (a) the adsorbed nonionic surfactant is present in a homogeneous mixture with (b) a hydrophobic substance having polar groups, the weight ratio of (a) to (b) being 99: 1 to 60 to 40.
• water-soluble nonionic surfactants are suitable as the granular carrier material. They can be built up from water-soluble salts, ie from carbonates, bicarbonates, sulfates, silicates, borates and, where this is justifiable for ecological reasons, phosphates, diphosphates and triphosphates and mixtures thereof.
• carrier grains which consist wholly or partly of water-insoluble detergent constituents, since they have a higher adsorption capacity compared to nonionic surfactants. These include zeolites and layered silicates and their mixtures.
• Carrier grain mixtures which contain zeolites or layered silicates in a mixture with water-soluble salts, such as sodium sulfate, sodium carbonate, sodium hydrogen carbonate and sodium citrate, have proven particularly suitable.
• the carrier grains can also be polyme re contain polycarboxylates, which improve the abrasion resistance of the grains and at the same time act as a co-builder.
• Suitable zeolites are those of the zeolite A type. Mixtures of zeolite NaA and NaX can also be used, the proportion of the zeolite NaX in such mixtures advantageously being less than 30%, in particular less than 20%. Suitable zeolites have no particles larger than 30 ⁇ m and consist of at least 80% particles smaller than 10 ⁇ m. Their average particle size (volume distribution, measurement method: Coulter Counter) is 1 to 10 ⁇ m. Their calcium binding capacity, which is determined according to the information in DE 24 12 837, is in the range from 100 to 200 mg Ca0 / g.
• Suitable layered silicates are of natural and synthetic origin, such as those used for. B. from DE 23 34 899-B2, EP 26 529-A1 and DE 35 26 405-A1 are known. Their usability as a component of carrier grains is not limited to a special composition or structural formula.
• Examples of homopolymeric and / or copolymeric carboxylic acids or their water-soluble salts contained in the carrier grains, of which the sodium salts are preferably used, are polyacrylic acid, polymethacrylic acid and polymaleic acid, copolymers of acrylic acid with methacrylic acid or copolymers of acrylic acid, methacrylic acid or maleic acid with vinyl ethers, such as vinyl methyl ether or vinyl ethyl ether, further with vinyl esters such as vinyl acetate or vinyl propionate, acrylamide, methacrylamide and with ethylene, propylene or styrene.
• polyacrylic acid polymethacrylic acid and polymaleic acid
• copolymeric acids in which one of the components has no acid function the proportion thereof, in the interest of sufficient water solubility, is not more than 50 mole percent, preferably less than 30 mole percent.
• Copolymers have proven particularly suitable acrylic acid or methacrylic acid with maleic acid, as described in more detail, for example, in EP 25 551-B1. These are copolymers which contain 40 to 90% by weight of acrylic acid or methacrylic acid and 60 to 10% by weight of maleic acid. Copolymers in which 45 to 85% by weight of acrylic acid and 55 to 15% by weight of maleic acid are present are particularly preferred.
• the molecular weight of the homo- or copolymeric polycarboxylates is generally 2,000 to 150,000, preferably 5,000 to 100,000.
• Their proportion of the adsorbent is 1 to 10% by weight, preferably 2 to 8% by weight and in particular 2 5 to 7% by weight, calculated as the sodium salt.
• the resistance of the grains to abrasion increases with an increasing proportion of polyacid or its salts. A sufficient abrasion resistance is already achieved with a proportion of 2% by weight. Mixtures with 2.5 to 7% by weight of sodium salt of polyacid have optimal abrasion properties.
• Another preferred constituent of the carrier grains is sodium sulfate, which can contribute to an improvement in the grain structure and an increase in the bulk density of the compositions.
• composition of the carrier grains can be of any type, but those with 40 to 80% by weight of zeolite and / or layered silicate (calculated as anhydrous), 2.5 to 7% by weight of (co) polymeric polycarboxylates and 0 to 30 % By weight, preferably 3 to 25% by weight, of sodium sulfate (remainder: water), preferably suitable for the purposes of the invention, since these have a high adsorption capacity and are particularly noticeable in connection with the adsorbed mixture of nonionic surfactants and water-insoluble, fat-like compound show the effect of improved washability.
• Nonionic surfactants are alkoxylation products with 10 to 20 carbon atoms in the hydrophobic radical and 3 to 20 glycol ether groups. These include ethoxylation products of alcohols, vicinal diols, ami nen, thio alcohols, fatty acid amides and fatty acids. Alkylphenol polyglycol ethers with 5 to 12 carbon atoms in the alkyl radical and 3 to 10 ethylene glycol ether groups can also be used. Finally, block polymers of ethylene oxide and propylene oxide, which are commercially available under the name Pluronics, are also suitable.
• Preferred detergent constituents which are bound to the granular adsorbent and are present together with the latter as a free-flowing mixture are liquid to pasty nonionic surfactants from the class of the polyglycol ethers, derived from alcohols with 12 to 18 carbon atoms. These alcohols can be saturated or olefinically unsaturated, linear or methyl-branched in the 2-position (oxo radical).
• EO ethylene oxide
• PO propylene oxide
• the number of EO or PO groups corresponds to the statistical mean.
• ethoxylated fatty alcohols examples include C12 ⁇ 18 coconut alcohols with 3 to 12 EO, C 16 ⁇ 18 tallow alcohol with 4 to 16 EO, oleyl alcohol with 4 to 12 EO and ethoxylation products of corresponding chain and EO distribution available from other native fatty alcohol mixtures. From the series of ethoxylated oxo alcohols, for example, those of the composition C12 ⁇ 15 + 5 to 10 EO and C14-C15 + 6 to 12 EO are suitable.
• Mixtures of low and highly ethoxylated alcohols are distinguished by increased detergency against both greasy and mineral stains, for example those made from tallow alcohol + 3 to 6 EO and tallow alcohol + 12 to 16 EO or C13 ⁇ 15 oxo alcohol + 5 EO and C12 ⁇ 14 -Oxo alcohol + 8 to 12 EO.
• ethoxylates containing EO groups and PO groups e.g. B. C12 ⁇ 18 alcohols of the formula R- (PO) a - (EO) b or R- (EO) b - (PO) c , wherein a numbers from 1 to 3, b such from 5 to 20 and c mean those from 1 to 10 (b greater than c).
• Component (b) according to the definition of the invention, the addition of which surprisingly improves the solubility properties and the flushing-in behavior of the adsorbents impregnated with nonionic surfactants, consists of compounds with polar end groups which are sparingly or not soluble in water, but which are dispersible, but which are dispersible. Examples include soap-forming fatty acids and their derivatives.
• fatty acid esters such as partial esters of polyhydric alcohols, partial glycerides and fatty acid glycol esters, fatty acid amides including fatty acid ethanolamides and fatty acid propanolamides, fatty acid partial amides of alkylenediamines, fatty amines, quaternary ammonium bases or their salts, fatty alcohols and poorly soluble anionic surfactants, such as the di-salts of alpha-sulfates. Mixtures of such poorly soluble or insoluble compounds can also be used.
• the number of carbon atoms in the hydrophobic radicals should be at least 10, usually 12 to 22.
• the weight ratios of nonionic surfactant to hydrophobic additive compound is 99: 1 to 60:40, preferably 98: 2 to 80:20. It is essential for the success that the nonionic surfactant and additive form a homogeneous mixture. A successive application of the individual substances on the carrier grains does not lead to an improvement in the solubility and flushing behavior.
• Preferred examples from the group of hydrophobic compounds are coconut, tallow and rapeseed oil fatty acids, which can also be hardened, mixtures as tallow fatty acid partial glyceride and the tallow fatty acid partial amide of hydroxyethyl-ethylenediamine and quaternary ammonium salts which contain at least one hydrophobic C12 ⁇ 18 radical, such as C12 ⁇ 18-alkyl-trimethyl-ammonium chloride and di-tallow alkyl-dimethyl-ammonium chloride.
• Saturated fatty acids with 12 to 20 carbon atoms such as lauric acid, myristic acid, palmitic acid, stearic acid and arachic acid and mixtures thereof, are particularly preferred.
• Unsaturated fatty acids, such as oleic acid can also be present, but their proportion of the fatty acid mixture is preferably at most 70% by weight, in particular at most 50% by weight.
• the mixtures should be as free as possible from fatty acids with less than 12 carbon atoms.
• water which usually remain in the product during such a deodorization treatment and in the present case are between 1 and 6% by weight, usually 2 to 5% by weight (based on the deodorized mixture), do not have to be removed, but can remain in the mixture.
• These amounts of water have the effect that the mixtures of nonionic surfactant and fatty acid remain liquid and have a comparatively low viscosity and do not have to be heated or melted before being applied to the adsorbent carrier grain.
• the water content is so low that it increases the adsorption capacity and the pouring properties of the fer final product.
• the liquid, optionally heated, mixtures can be applied to the granular carrier material by admixing, preferably spraying, the carrier material advantageously being kept in motion by suitable mixing devices. Further treatment of the granular adsorbate is not necessary. However, it may be advisable to leave the product to rest for several hours at high contents of the applied liquid material, since its diffusion into the interior of the grain takes some time. The determination of the pourability and the induction behavior is therefore expediently carried out after 24 hours.
• Suitable powdering agents have a grain size of 0.001 to at most 0.1 mm, preferably less than 0.05 mm and can be present in proportions of 0.03 to 3, preferably 0.05 to 2% by weight, based on that with the additive loaded adsorbents are used. For example, B.
• finely powdered zeolites silica airgel (Aerosil (R) ), colorless or colored pigments, such as titanium dioxide and other powder materials already proposed for powdering granules or detergent particles, such as finely powdered sodium tripolyphosphate, sodium sulfate, magnesium silicate and carboxylmethyl cellulose.
• an aftertreatment is superfluous, especially since it does not improve the rinsing behavior.
• the detergent additives can be mixed with the granular or powder detergent, for example a tower spray powder its mixtures with other powder components, such as persalts, enzyme granules, bleach activators or defoamers, are combined and mixed in a known manner.
• the favorable flushing behavior of the additives according to the invention is also transferred to these complex mixtures regardless of the mixing ratio.
• the mixed detergents generally contain 10 to 40% by weight of the additive according to the invention.
• a spray-dried granular carrier material of the following composition was used (data in percent by weight): 68.0 % Zeolite NaA (calculated anhydrous) 6.2 % Arylic acid-maleic acid copolymer (Na salt) 5.0 % Sodium sulfate 2.1 % ethoxylated C 12-18 alcohol + 5 EO 18.7 % water
• the grain size was (in% by weight): 1.2 - 0.8 mm 3rd % 0.8 - 0.4 mm 34 % 0.4 - 0.2 mm 50 % 0.2 - 0.1 mm 12 % under 0.1 mm 1 %
• the bulk weight was 550 g / l.
• the grains were in a spray mixer, consisting of a horizontally arranged, with mixing and conveying elements and Spray nozzles equipped cylindrical drum (L ⁇ DIGE mixer) with melted non-ionic surfactants and their mixtures sprayed with various additives.
• the temperature of the adsorbent was 20 ° C, that of the surfactant melt 45 ° C.
• the surfactant melts consisted of mixtures of ethoxylated alcohols (4 parts by weight of C12 ⁇ 18 coconut alcohol + 5 EO and 1 part by weight of C12 ⁇ 14 coconut alcohol + 3 EO) and fatty acids (hydrogenated tallow fatty acids, solidification point 35 ° C) of different compositions. 17.7 parts by weight of surfactant melt were applied to 82.9 parts by weight of carrier material.
• a first test series E1 the washing-in behavior of the products produced in this way was examined after a storage period of 24 hours, conditions being simulated which correspond to a washing-in device of a household washing machine operated under critical conditions.
• 100 g of product were introduced into the test device (ZANUSSI induction channel) and, after a rest period of 1 minute, 10 liters of tap water were fed in within 90 seconds. Remaining residues were weighed out while wet and 30% of the weight was calculated as water.
• a second test series E2 mixtures of 25 parts by weight of the products and 75 parts by weight of a conventional household detergent (50 parts by weight of spray-dried powder, 25 parts by weight of sodium perborate tetrahydrate) were tested.
• Example 2 the hydrogenated tallow fatty acid used in Example 1 was replaced by a mixture of 50% oleic acid, 30% stearic acid and 20% palmitic acid under otherwise identical conditions.
• coconut fatty acid (C12 ⁇ 18 mixture) was used as the exchange material.
• Table 2 example relationship Induction behavior Clump test Package test E1 E2 4th 80: 20 13 2nd ++ + 5 80: 20 7 5 ++ +
• Example 2 A mixture heated to 45 ° C 3.5 % By weight C 12-18 coco alcohol + 3 EO 12.0 % By weight C 16-18 tallow alcohol + 5 EO were on 89.5% by weight of the carrier material used in Example 1 were sprayed on (comparative experiment V7).
• the ethoxylate mixture was previously with 0.3% by weight of a 1: 1 mixture of tallow fatty acid amide of the hydroxyethyl-ethylenediamine at 45 ° C and mixed homogeneously 89.2% by weight of the carrier material sprayed on.
• 25 parts by weight of the two samples were dry mixed with 50 parts by weight of a spray-dried, phosphate-free detergent and 25 parts by weight of sodium perborate and subjected to the wash-in test.
• the residue was 2 g, in the comparative experiment 6 g.

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• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (5)

• 1988
  • 1988-07-02 DE DE3822479A patent/DE3822479A1/de not_active Withdrawn
• 1989
  • 1989-06-26 EP EP89907157A patent/EP0425519A1/fr active Pending
  • 1989-06-26 EP EP89111617A patent/EP0354331A1/fr not_active Withdrawn
  • 1989-06-26 WO PCT/EP1989/000716 patent/WO1990000189A1/fr not_active Application Discontinuation
• 1990
  • 1990-02-23 KR KR1019900700404A patent/KR900701998A/ko not_active Application Discontinuation

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