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
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2082—Polycarboxylic acids-salts thereof
• • 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
  • C11D3/2075—Carboxylic acids-salts thereof
  • C11D3/2086—Hydroxy carboxylic acids-salts thereof
• • 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
  • C11D3/225—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin etherified, e.g. CMC
• • 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
• • 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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3902—Organic or inorganic per-compounds combined with specific additives
  • C11D3/3937—Stabilising agents
  • C11D3/394—Organic compounds

Definitions

• EP 0 037 026-81 discloses a process for producing a readily soluble granulate which contains 90 to 98% by weight of a bleach activator.
• the pulverulent bleach activator is homogeneously mixed with cellulose or starch ether or starch, which is also in powder form, and then sprayed with water or a dilute aqueous solution of the cellulose ether and granulated at the same time. The granules are then dried.
• Tetraacetylethylenediamine (TAED) is preferably used as the bleach activator and sodium carboxymethylcellulose (CMC) is preferably used as the cellulose ether.
• EP 0 070 474 (US 4,457,858).
• an aqueous slurry containing the bleach activator and the cellulose ether in a weight ratio of 97: 3 to 93: 7 is spray-dried.
• the products are comparable to those according to EP 0 027 026.
• a dispersion aid must therefore be added to the mixtures, such as sodium tripolyphosphate, nitrilotriacetate, sodium sulfate or salts of polymeric or copolymeric carboxylic acids, such as polyacrylate or a copolymer of acrylic acid and maleic acid as the sodium salt.
• these additives also do not significantly improve the dispersing properties, which applies in particular to the (co) polymers.
• phosphates and nitrilotriacetate are often undesirable from an ecological point of view, while sodium sulfate is a fiber.
• the invention described below leads to a significant improvement in the dispersing and solubility properties of the granules.
• the storage stability of the granules in mixtures with washing powder containing saline is increased considerably. It is particularly advantageous that the substances used are completely harmless from an ecological point of view and additionally increase the cleaning effect of the detergents due to their sequestering properties.
• the required amount of these auxiliaries is so small that the active substance content of the agents is not or only slightly reduced. In addition, this reduction in bleach activator content is more than compensated for by the significantly improved shelf life.
• the invention relates to granular bleaching aids containing bleach activators from the class of the N-acyl and O-acyl compounds and at least one pelletizing aid from the class of water-soluble, film-forming polymers, characterized by a content of 2 to 15% by weight of one polyvalent carboxylic acid, hydroxycarboxylic acid or ether carboxylic acid with 3 to 6 carbon atoms in the molecule.
• polyvalent carboxylic acids examples include malonic acid, succinic acid, glutaric acid, adipic acid, maleic acid, malic acid, tartaric acid, citric acid, diglycolic acid and carboxymethyloxysuccinic acid.
• Preferred acids are citric acid and carboxymethyl succinic acid.
• Their proportion, based on the bleach activator granules, is preferably 4 to 12% by weight.
• Polyvalent carboxylic acids containing amino groups such as nitrilotriacetic acid, are unsuitable because they are oxidizable and reduce the bleaching activity.
• N-acylated amines, diamines, amides, glycolurils, diketopiperazines, hydantoins and acylated polyols and acylated p-hydroxybenzoates or p-hydroxybenzenesulfonates are suitable as bleach activators.
• TAED tetraacetylmethylene diamine
• pentaacetyl glucose hexanoyloxybenzenesulfonate
• octanoyloxybenzenesulfonate octanoyloxybenzenesulfonate
• nonanoyloxybenzenesulfonate with linear or branched acyl radicals, the sulfonate groups being in the form of sodium.
• TAED is particularly preferred.
• the content of bleach activators in the granules is 80 to 96% by weight, preferably 85 to 94% by weight.
• Water-soluble, film-forming polymers such as water-soluble cellulose ethers, water-soluble starch or water-soluble starch ethers and mixtures thereof are used as granulation aids.
• cellulose ethers are methyl cellulose, ethyl cellulose, hydroxyethyl cellulose, methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, carboxymethyl cellulose (as sodium salt) and methyl carboxymethyl cellulose (sodium salt).
• Suitable starch ethers are, for example, carboxymethyl starch, hydroxyethyl starch and methyl starch. From this group, sodium carboxymethyl cellulose (CMC) has proven to be particularly suitable.
• homopolymeric or copolymeric carboxylic acids such as polyacrylic acid, polymethacrylic acid, polymaleic acid, copolymers of acrylic acid or methacrylic acid with maleic acid and maleic acid with vinyl methyl ether, these polymeric acids being present as free acids or preferably as sodium salts.
• Preferred representatives of this group are sodium polyacrylate and sodium salts of acrylic acid-maleic acid copolymers with a weight ratio of acrylic acid: maleic acid of 10: 1 to 1: 1, preferably 7: 1 to 2: 1.
• These compounds generally have molecular weights of 3,000 to 150,000 , preferably 5000 to 100000.
• a third group of film-forming polymers are carbon chain polymers with nonionic hydrophilic groups or polyether groups.
• examples include polyvinyl alcohol, partially saponified polyvinyl acetate, polyvinyl pyrrolidone, polyacrylamide and polyethylene glycol ether.
• the granulation aid content of the granules is 0.3 to 5% by weight, preferably 0.5 to 3% by weight. Despite this reduced content of granulating aids compared to the information in EP-B 0 037 026, the agents according to the invention are notable for good grain stability and a further improved storage capacity resistance in mixtures with detergents containing peroxides and washing alkalis.
• the granules can contain small amounts of moisture, for example up to 3% by weight, preferably less than 2% by weight. In contrast to known granules, this water content is not critical, i. H. even a slightly increased water content does not lead to a significant reduction in shelf life. This proves to be particularly valuable if the agents are stored in unfavorable climatic conditions, such as high air humidity and elevated temperature.
• the production can be carried out by means of conventional granulation processes and granulation devices.
• the procedure is preferably such that an intimate, dry mixture of the bleach activator and the polyvalent carboxylic acid is first prepared and sprayed with an aqueous solution of the granulating aid in a granulating device.
• concentration of the aqueous solution can contain 2 to 20% by weight of the granulation aid.
• the procedure can also be such that a dry mixture of all components, including the powdered granulation aid or part thereof, is first prepared and then sprayed with water or an aqueous solution which contains the rest of the granulation aid in solution.
• Such a procedure is particularly recommended when the aqueous solutions of the granulating aid swell strongly and become so highly viscous that they are difficult to spray and can be distributed in the mixture to be granulated.
• This can e.g. B. then the case when carboxymethyl cellulose in a concentration of more than 1 to 2 wt .-% should be used as a granulating aid.
• carboxymethyl cellulose in a concentration of more than 1 to 2 wt .-% should be used as a granulating aid.
• comparatively large amounts of water are required, which would have to be removed by drying during the granulation or afterwards.
• the proportion of the granulating aid is in the range from 0.3 to 1.5% by weight, in particular 0.5 to 1% by weight, the first-mentioned procedure, i. H. the introduction of the granulating aid as an aqueous solution is preferred.
• additives such as dyes or color pigments can also be mixed in or introduced via the aqueous granulation liquid.
• oxidation-stable complexing agents and stabilizers for per compounds can also be mixed in this process step.
• these are salts of polyphosphonic acids, such as 1-hydroxyethane-1,1-diphosphonate, ethylene diamine tetramethylene phosphonate and diethylene triamine pentamethylene phosphonate, each in the form of the sodium salt.
• the proportion of these additives can be up to 2% by weight, generally up to 0.5% by weight, based on the granules.
• the water content of the granules is then reduced to less than 3, preferably less than 2 and in particular less than 1.5% by weight.
• the excess water can be removed by drying with the addition of heat, the temperature of the granules advantageously not exceeding 80 ° C. and below the melting temperature of the bleach activator and the carboxylic acid. Dryers that do not adversely change the granular structure of the product are suitable, for example tray, vacuum or fluidized bed dryers.
• foam inhibitors are customary known defoamers, preferably polysiloxanes, and mixtures thereof with microfine silica. Examples include polydimethylsiloxane with a content of approx. 1 to 10% by weight, preferably 2 to 4% by weight, based on the finished granulate.
• the defoamer can be added in the first mixing stage; however, the defoamer can also be dispersed in the granulating liquid which, in order to avoid segregation processes, should contain a part of the granulating aid in this case.
• the granules produced in the manner indicated have a favorable grain spectrum. Any coarse and fine fractions that are present can be screened off and returned to the process after the coarse fractions have been ground.
• the granules are easy to pour, non-adhesive and are characterized by superior storage stability. Even at low washing temperatures such as those of 25 to 40 o C they decay very rapidly and completely, so that the full bleaching power is also under such washing conditions within a short time fully available. They can be used to advantage in detergents, sheet metal agents, oxidizers and disinfectants and retain their good properties even when mixed with the active ingredients contained in these agents.
• Tetraacetylethylenediamine with an average grain size of 0.01 to 0.8 mm was used as the bleach activator.
• the grain fraction between 0.8 and 1.6 mm was 5% by weight, the fraction below 0.01 mm 10% by weight.
• the granulation process was then continued for 1 minute.
• the still moist granules were dried in a fluidized bed dryer with air at 50 ° C. to a water content of 1% by weight.
• the content of the granules was thus 88.1 wt% TAED 10.4% by weight of citric acid 0.5% by weight polyacrylate 1.0 wt% water.
• 92% by weight of the granules had a grain size of 0.1 to 1.2 mm. The rest was coarse and very fine, which were screened off.

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• Chemical & Material Sciences (AREA)
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• Oil, Petroleum & Natural Gas (AREA)
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• Detergent Compositions (AREA)

Applications Claiming Priority (2)

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Cited By (8)

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Citations (3)

• 1988
  • 1988-08-01 DE DE19883826092 patent/DE3826092A1/de not_active Withdrawn
• 1989
  • 1989-07-24 EP EP89113631A patent/EP0356700A1/fr not_active Withdrawn
  • 1989-07-24 WO PCT/EP1989/000867 patent/WO1990001535A1/fr not_active Application Discontinuation
  • 1989-07-24 EP EP19890909181 patent/EP0430986A1/fr active Pending

Patent Citations (3)

Non-Patent Citations (1)

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