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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/33—Amino carboxylic acids
• • 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 invention relates to powdered and / or granular additives for powdered detergent and cleaning agent preparations.
• Polymeric polycarboxylic acids and their salts are common additives for detergent and cleaning agent preparations which improve the primary washing action and the incrustation and graying inhibitor action in an outstanding manner.
• the polymer carboxylic acids or their salts are generally added to the detergent slurries in the form of aqueous solutions and then dried.
• This additive increases the viscosity of the slurries and, in the worst case, precipitation can occur.
• the polymer carboxylic acids or their salts in solid form and to subsequently add the solid product obtained as powder or granules to the detergents in powder or granule form.
• the solid polymer carboxylic acids in particular in the form of the salts, have the disadvantage of high hygroscopicity and low bulk density.
• the object of this invention is to largely reduce these disadvantages in order to enable better technical processing of polymer carboxylic acids and their salts in powder form, i.e. reduce hygroscopicity and bulk density.
• the solution to the problem consists in the surprising finding that the disadvantages described can be overcome in the mixture with nitrilotriacetic acid or its sodium salts.
• this powdered or granular mixture as an additive for powdered or granular detergent and cleaning agent preparations.
• Powdery is to be understood as meaning a finely divided powder up to a granular or granular mass, both in the case of the additive according to the invention and in the case of detergents and cleaning agents.
• the powdery additives according to the invention can be characterized by particle sizes with an average diameter of 10 to 500 microns. preferably 50 to 300 microns, with a high proportion in the distribution of sizes from 100 to 300 microns.
• the granules generally have average grain sizes of 0.2 to 10 mm, preferably 0.3 to 5 mm and particularly preferably 0.5 to 2 mm.
• the particle sizes depend in particular on the type of drying process, spray drying and fluidized bed drying, in particular in the form of spray granulation, being preferred.
• the (meth) acrylic acid-maleic acid copolymers indicated contain 45 to 85% (meth) acrylic acid and 55 to 15% halic acid as monomer units, based on the total weight of the copolymer.
• (Heth) acrylic acid means acrylic acid or methacrylic acid or mixtures of the two acids.
• the preferred copolymers with hydroxyalkyl (meth) acrylates contain, based on the total weight of the copolymer, 10 to 40% by weight (meth) acrylic acid, 10 to 40% by weight maleic acid and 20 to 50% by weight of at least one hydroxyalkyl ( meth) acrylate with 2 to 6 carbon atoms in the hydroxyalkyl group.
• the hydroxyalkyl ester groups of the hydroxyalkyl (meth) acrylates are derived, for example, from alkanediols, such as 1,2-ethanediol, 1,3 and 1,2-propanediol, and their technical mixtures, neopentylglycol, 1,5-pentanediol or 1-hexanediol, 6 from.
• alkanediols such as 1,2-ethanediol, 1,3 and 1,2-propanediol
• neopentylglycol 1,5-pentanediol or 1-hexanediol
• Examples include hydroxyethyl methacrylate, hydroxypropyl methacrylate, butanediol monomethacrylate, neopentyl glycol monoacrylate, 1,5-pentanediol monoacrylate and 1,6-hexanediol monoacrylate.
• the preferred hydroxyalkyl esters are hydroxyethyl acrylate, 1,4-butanediol monoacrylate and the hydroxypropyl acrylates.
• the particularly preferred hydroxyalkyl esters are the hydroxypropyl acrylates, the isomer mixtures of 2-hydroxy-1-propyl acrylate and 1-hydroxy-2-propyl acrylate which are prepared by reacting acrylic acid with propylene oxide being of particular technical importance.
• the copolymers are preferably used in the form of the water-soluble alkali metal salts, such as the sodium or potassium salts, in particular the sodium salts.
• they can also be used in the form of the water-soluble ammonium salts or organic amine salts, such as, in particular, the salts of trialkylamines with alkyl radicals of 1 to 4 carbon atoms or the salts of mono-, di- and trialkanolamines with 1 to 4 carbon atoms in the alkanol radical will.
• Mixtures of the amine salts mentioned may also be suitable. Examples include: mono-, di- and trihydroxyethylamine. It may be appropriate to use different salts, such as sodium and potassium salts or sodium and alkanolamine salts together.
• the water-soluble salts are expediently partially to completely neutralized salts.
• 50 to 100 z of the carboxyl groups are generally neutralized.
• the (meth) acrylic acid-maleic acid copolymers are known and according to known manufacturing processes, e.g. according to EP-A-75 820 or DE-A 3 233 777, 3 233 778, 3 233 775 and 3 233 776.
• the copolymers with hydroxyalkyl (meth) acrylates can be obtained, for example, according to German patent application P 34 26 368.
• the copolymers to be used according to the invention have K values of 8 to 150, preferably 10 to 100, measured in 1% aqueous solution adjusted to pH 7 with sodium hydroxide solution at 25 ° C. according to Fikentscher, cellulose chemistry 13, 58 ff ( 1932).
• the K value is a suitable characterization for these polymeric polycarboxylic acids.
• the preferred mixing ratios for the additives according to the invention are 30 to 70 and very particularly preferably 60 to 40% by weight a) and 70 to 30 and very particularly preferably 40 to 60% by weight b).
• a mixing ratio of about 1: 1 has proven to be particularly suitable in the art.
• the substances c) which are usually additives which are not surface-active for detergents and cleaning agents and which do not necessarily have to be present in the mixture according to the invention, generally include detergent and cleaning agent additives, such as, for example, sodium sulfate, sodium tripolyphosphate, soluble and insoluble sodium silicates.
• detergent and cleaning agent additives such as, for example, sodium sulfate, sodium tripolyphosphate, soluble and insoluble sodium silicates.
• Magnesium sulfate, Soda organic phosphonates, sodium aluminum silicates of the zeolite A type and mixtures of the substances mentioned.
• the additive according to the invention is advantageously prepared by mixing the aqueous solution of the polymer carboxylic acid or a water-soluble salt with the aqueous solution of nitrilotriacetic acid or one of its sodium salts and, if appropriate, the aqueous solution or suspension of one or more substances c) and then drying it.
• the individual substances can also be added separately in the solid phase to the aqueous solution.
• These solutions preferably have a pH of 5 to 10, preferably 7 to 9, and a solids content of 20 to 70%.
• Drying takes place according to the usual methods in the known drying devices at temperatures of 70 to 200 ° C and preferably at 80 to 180 ° C.
• Suitable drying processes are, for example, belt drying, drum drying, freeze drying, spray drying or fluidized bed drying. Spray drying is particularly suitable for producing a fine powder, and fluidized bed drying is particularly suitable for producing granules, and spray granulation is particularly suitable in a particular embodiment.
• the particle sizes can be varied within the framework of the drying process used, since the resulting particle sizes depend less on their composition than on the type of drying process.
• a spray-dried powder according to the invention having average particle sizes of 50 to 500 ⁇ m is advantageously introduced and the particles are then enlarged in a fluidized bed by spraying on further solution.
• the additives or mixtures according to the invention for detergents and cleaning agents have the advantage that they are extremely easy to handle, represent little hygroscopic powders or granules with a high bulk density and can be added directly to the powder detergents.
• nitrilotriacetic acid or its sodium salts used to reduce the hygroscopicity and to increase the bulk density are a sequestering agent known for detergents, which has found its way into numerous detergents and cleaning agents and is therefore not a fiber which causes unnecessary stress.
• the following examples illustrate the invention. Parts specified are parts by weight.
• the K values are determined according to H. Fikentscher as stated above.
• the water absorption of the predried powder is determined from a sample of approx. 2 g in a weighing glass of approx. 5 mm diameter after storage for 24 hours at 68% relative atmospheric humidity and 20 ° C.
• the grain sizes are determined by dry screening the respective powder using an electromagnetic screening machine (Analyzer 3 from Fritsch).
• a 45% solution of a copolymer of 70% by weight acrylic acid and 30% by weight maleic acid having a K value of 50 and neutralized with 50% sodium hydroxide is mixed with a 38% solution of nitrilotriacetic acid trisodium salt (NTA) and sprayed with a 2-component nozzle dried at 150 ° C air inlet temperature and at 90 ° C air outlet temperature.
• NTA nitrilotriacetic acid trisodium salt
• the grain sizes of the powders are between 50 and 500 ⁇ m. 70% of them in a range from 100 to 200 ⁇ m.
• a 50% solution of a copolymer of 65% by weight acrylic acid and 35% by weight maleic acid of K value 24 neutralized to 50% with sodium hydroxide is mixed with 38% ZTA NTA solution and dried and tested according to Example 1.
• the grain sizes of the powder are comparable to Example 1.
• a 38% solution of a copolymer of 50% by weight acrylic acid and 50% by weight maleic acid having a K value of 42 and neutralized with 65% sodium hydroxide is mixed with a 38% NTA solution and dried and tested as in Example 1.
• the grain sizes of the powder are comparable to Example 1.
• the grain sizes of the powder are between 25 to 300 ⁇ m, the main proportion of approx. 80% being 70 to 110 ⁇ m.
• a 40% solution of a copolymer of 30% by weight methacrylic acid, 45% by weight acrylic acid and 25% by weight maleic acid having a K value of 98 and neutralized with 90% sodium hydroxide is mixed with a 40% solution of a nitrilotriacetic acid disodium salt.
• Half of the mixture is dried in a spray dryer according to Example 1, placed in a fluidized bed and the rest of the mixture is sprayed on at a gas temperature of approximately 140.degree. This spray granulation leads to granules of approximately 0.5 to 5 mm in diameter.
• the test results are shown in the table below:
• a 38 Zige solution of a copolymer of 40% acrylic acid neutralized to 70% with sodium hydroxide 40% by weight of maleic acid and 20% by weight of hydroxypropyl acrylate (technical isomer mixture of approx. 67% by weight of 2-hydroxy-1-propyl acrylate and approx. 33% by weight of 1-hydroxy-2-propyl acrylate) from K -Value 42 is mixed with a 38% NTA solution and dried and tested according to Example 1, but with a single-component nozzle.
• the grain sizes of the powders are 50 to 500 ⁇ m. approx. 70% of them in the range from 200 to 350 ⁇ m.
• the grain sizes of the powders are comparable to Example 1.

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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)
• Detergent Compositions (AREA)
• Addition Polymer Or Copolymer, Post-Treatments, Or Chemical Modifications (AREA)

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• 1985
  • 1985-02-13 DE DE19853504896 patent/DE3504896A1/de not_active Withdrawn
• 1986
  • 1986-01-27 US US06/822,610 patent/US4698174A/en not_active Expired - Fee Related
  • 1986-01-31 CA CA000500898A patent/CA1248838A/fr not_active Expired
  • 1986-02-05 JP JP61022211A patent/JPS61188497A/ja active Pending
  • 1986-02-10 EP EP86101659A patent/EP0192153B1/fr not_active Expired
  • 1986-02-10 AT AT86101659T patent/ATE35148T1/de not_active IP Right Cessation
  • 1986-02-10 DE DE8686101659T patent/DE3660311D1/de not_active Expired
  • 1986-02-12 ES ES551899A patent/ES8800716A1/es not_active Expired

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