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
  • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
  • C11D11/02—Preparation in the form of powder by spray drying
• • 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
  • C11D3/04—Water-soluble compounds
  • C11D3/10—Carbonates ; Bicarbonates
• • 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
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
  • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

• the present invention relates to a granular, phosphate-free cleaning additive which is suitable for cleaning hard surfaces, for example as an additional component in dishwashing detergents. Due to its good lime binding properties, it can be used as an additive to wash water in hard water areas and can replace the polymer phosphates commonly used for this purpose. Agents of this type are also suitable for the pretreatment of hard water intended for hashing, rinsing and cleaning purposes. They are usually stored separately from granular hash and cleaning agents and, if necessary, used together with them in hash or cleaning processes. In the sense of an additional builder effect, they improve the cleaning ability of the actual hash and cleaning agent and prevent the formation of hard limescale deposits on the heating elements or on the textile fiber. In special cases, the detergents can be added to granular detergents or further processed together with them, whereby they advantageously influence their pouring properties and flushing behavior or enable trouble-free further processing.
• salts of polymeric aliphatic carboxylic acids include in particular salts of poly acrylic acid and polymethacrylic acid and copolymers of these two acids with maleic acid and / or vinyl esters. It is not difficult to produce storage-stable granules which contain up to about 15% by weight of such polymer salts. This applies in particular if the granules contain water-insoluble, finely divided zeolites or clays. To the best of our knowledge, granules with higher proportions of such salts cannot readily be converted into stable granules, especially if they do not contain any water-binding or water-repellent mixture constituents or are mixed exclusively with water-soluble neutral salts or builder salts.
• DE 21 00 500-82 (US Pat. No. 3,933,673) proposes using the polymers as free acids or partially neutralized salts with a degree of neutralization of at most 60% or converting them from their aqueous solutions into granular products by hot spray drying.
• the polymeric carboxylic acids develop their full activity only as completely neutralized salts.
• the alkali required for neutralization must therefore be subsequently added to the acidic granules, which requires an additional process step and carries the risk that the mixtures partially separate during transport.
• Component (a) consists of homopolymeric or copolymeric carboxylic acids in the form of the sodium salts.
• Suitable homopolymers are polymethacrylic acid and preferably polyacrylic acid, for example those with a molecular weight of 800 to 150,000 (based on acid).
• Suitable copolymers are those of acrylic acid with methacrylic acid and preferably of the copolymers of acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid as are characterized, for example, in EP 25551-81, have proven to be particularly suitable. These are copolymers containing 50 to 90% by weight. Contain acrylic acid and 50 to 10 wt .-% maleic acid. Copolymers in which 60 to 85% by weight of acrylic acid and 40 to 15% by weight of maleic acid are present are particularly preferred.
• Your molecular weight, based on free acids, is generally 5,000 to 200,000, preferably 10,000 to 120,000.
• Mixtures of different homo- and copolymers can also be used with advantage, in particular mixtures of homopolymeric acrylic acid and the copolymers of 50 to 90% by weight of acrylic acid and 50 to 10 96 maleic acid described above.
• Such mixtures which are characterized by favorable grain properties and high storage stability, can consist, for example, of 10 to 50% by weight of homopolymeric acrylic acid and 90 to 50% by weight of acrylic acid-maleic acid copolymers.
• Highly polymeric polyacrylic acids can also be used in these mixtures which, when used alone, have a slightly greater tendency to stick or melt than the low molecular weight polyacrylates.
• the sodium carbonate (b) and the sodium sulfate (c) are used in anhydrous form. With proportions of sodium carbonate of approx. 40% by weight and more, it is advisable to reduce the hate content (d) of the compositions to less than 6% by weight or to choose a somewhat higher proportion of sodium sulfate, for example in the range 8 to 15% by weight. Sodium sulfate contents of more than 10% by weight, for example 15 to 20% by weight, fundamentally improve the grain properties and the shelf life of the compositions. On the other hand, sodium sulfate is ineffective fiber when using the agents, which is why its proportion should be as low as possible.
• fractions of 5 to 6% by weight (c) are sufficient to contain agents with a content of approx. 50% by weight (a), approx. 40% by weight (b) and approx To stabilize 4% by weight (d) and to ensure good flow properties.
• the agents can also contain minor components such as dyes and color pigments and can be colored uniformly or speckled.
• the proportion of such minor components is well below 1% by weight.
• the average grain size of the agent is usually 0.2 to 1.2 mm, the proportion of the grains being below 0.1 mm not more than 2% by weight and above 2 mm not more than 20% by weight.
• at least 80% by weight, in particular at least 90% by weight, of the grains have a size of 0.2 to 1.6 mm, the proportion of the grains between 0.1 and 0.05 mm not more than 3% by weight %, in particular not more than 1% by weight and the proportion of the grains between 1.6 and 2.4 mm is not more than 20% by weight, in particular not more than 10% by weight. Larger proportions of fine grain generally lead to a deterioration in the induction behavior.
• the bulk density is 350 to 550 g / l.
• the granules are produced by spray drying an aqueous slurry.
• the slurry concentration is between 50 and 68% by weight (non-aqueous fraction), preferably between 55 and 60% by weight, the decisive factor being the viscosity of the paste, which should not exceed 10,000 mpa.s and advantageously 2,500 to 6,000 mpa ⁇ s.
• the temperature of the slurry is usually between 50 and 100 ° C.
• the pressure at the spray nozzles is generally 30 to 80 bar, preferably 40 to 70 bar.
• the temperature of the counter-current dry gases. in the entrance zone of the spray tower, ie in the so-called ring channel is advantageously between 200 and 320 ° C, in particular between 220 and 300 ° C.
• the drying is preferably carried out in such a way that the hater bond is reduced to less than 1 mol of H2O per mol of sodium carbonate, in particular to 0.3 to 0.7 mol of H2O per mol of sodium carbonate.
• Conventional spray drying systems can be used for spray drying, it being possible for the spray nozzles to be arranged in one or more levels.
• the spray material leaving the tower can, if necessary after cooling with flowing air, be immediately further processed or packaged.
• the granules are exceptionally free-flowing and can be washed into residue-free washing machines and dishwashers and retain these advantageous properties even after a long storage period.
• a granular composition (in% by weight) 50.0% acrylic acid-maleic acid copolymer (MW 70,000) in the form of the Na salt 36.3% sodium carbonate 10.0% sodium sulfate 3.7% haters was made as follows:
• a slurry which contained the abovementioned solids and 44.5% by weight of water and had a viscosity of 4,500 mpa ⁇ s at a processing temperature of 63 ° C. was sprayed into a drying tower at a pressure of 40 bar via nozzles.
• the counter-current dry gas had a temperature of 240 ° C in the ring channel and 120 ° C in the area of the tower outlet.
• the spray product was extremely free-flowing and had a bulk density of 450 g / l.
• the dust content ( ⁇ 0.05 mm) was less than 0.02% by weight.
• the water binding was 0.6 moles of water per mole of sodium carbonate.
• Example 2 As described in Example 1, a free-flowing, storage-stable granulate of the following composition was produced by spray drying: 50.0% by weight Na salt of the acrylic acid-maleic acid copolymer, 40.8% by weight sodium carbonate, 5.0% by weight sodium sulfate, 4.2% by weight haters.
• the dust content was less than 0.02% by weight.
• the spray product showed an equally good flowability as the product according to Example 1, but it decreased slightly over a period of several weeks.
• the product is therefore particularly suitable as an admixture component for granular detergents or for further processing into granular dishwashing detergents, this small tendency toward reduced free-flowing ability, which only develops after long storage, no longer occurs.
• experiment A the same spray conditions were used as described in example 1, in experiment B the tower outlet temperature of the dry gases was 90 ° C. Both spray products consisted of sticky grains that could already be deformed under slight pressure. The flow behavior was unsatisfactory and when trying to process the products together with other detergent components into stable granules, problems occurred due to sticking to the mixing elements and the inner wall of the granulating mixer.

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• Chemical & Material Sciences (AREA)
• Life Sciences & Earth Sciences (AREA)
• Engineering & Computer Science (AREA)
• Chemical Kinetics & Catalysis (AREA)
• Oil, Petroleum & Natural Gas (AREA)
• Wood Science & Technology (AREA)
• Organic Chemistry (AREA)
• Inorganic Chemistry (AREA)
• Detergent Compositions (AREA)

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Citations (4)

• 1989
  • 1989-11-10 DE DE3937469A patent/DE3937469A1/de not_active Withdrawn
• 1990
  • 1990-11-02 DE DE59009767T patent/DE59009767D1/de not_active Expired - Fee Related
  • 1990-11-02 AT AT90121008T patent/ATE129008T1/de not_active IP Right Cessation
  • 1990-11-02 ES ES90121008T patent/ES2077619T3/es not_active Expired - Lifetime
  • 1990-11-02 EP EP90121008A patent/EP0432437B1/fr not_active Expired - Lifetime

Patent Citations (4)

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