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
  • C11D3/0005—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
  • C11D3/02—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
• • 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
• • 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
  • C11D3/36—Organic compounds containing phosphorus
  • C11D3/361—Phosphonates, phosphinates or phosphonites

Definitions

• the present invention relates to a powdered detergent that is largely free of phosphates, has little or no detergent substances with alkyl aromatic residues and is therefore to be classified as particularly environmentally friendly.
• the prefabricated grains or prills are then coated with a coating material, which can consist of the compounds used as the carrier material.
• the coating is intended to counteract the sticking of the grains and to prevent interactions with other detergent components, in particular surfactants.
• the patent application does not recommend a method of production in which the polysiloxane component is sprayed onto a granular carrier, for example sodium tripolyphosphate, and is incorporated into the detergent in this form, since this results in an unfavorable foam profile.
• a process for the preparation of the powder component (E) is the subject of the earlier patent application P 29 29 359.2.
• Salt mixtures which contain at least two of the aforementioned salts are preferably used. Such salt mixtures are sprayed from an aqueous slurry containing 50 to 70 percent by weight of anhydrous salt.
• the spraying can be used in customary spray drying plants take place, for example in so-called S p rühtmen in which sprays the slurry through nozzles, and mixed with the aid of heated in co-current or, preferably, counter-current gas, in particular air or air combustion gases are dried.
• the inlet temperature of the dry air is 120 ° to 300 ° C, preferably 150 ° to 250 ° C, the outlet temperature is generally 75 ° to 95 ° C.
• Salt mixtures have proven to be particularly suitable, the proportion of sodium silicate of which is 3 to 75 percent by weight, in particular 5 to 15 percent by weight, based on anhydrous salt. Such salt mixtures result in a particularly abrasion-resistant and at the same time readily soluble granular carrier substance.
• the sodium silicate used in the aforementioned weight ratios preferably has a ratio of 1: 2.
• a further improvement in the grain structure is achieved if a salt mixture is used which, in addition to the aforementioned sodium silicate, also contains sodium tripolyphosphate and sodium sulfate in a weight ratio of 10: 1 to 1:10, in particular 5: 1 to 1: 5, based on anhydrous sodium tripolyphosphate and anhydrous sodium sulfate.
• the sodium tripolyphosphate is used - regardless of the calculated relationship - preferably as hexahydrate.
• the carrier substance (E1) therefore preferably has the following composition (calculated as anhydrous salt)
• Carrier substances with a high tripolyphosphate content have a higher water content (10 - 20%), those with a high sodium sulfate have a lower water content (5 - 8%).
• the water content is approximately 8-12 percent.
• up to 0.3% by weight, preferably 0.05 to 0.2% by weight, of the mixture of polysiloxane and silica can be added to the aqueous slurry, based on anhydrous salts.
• this portion added before spraying loses a certain part of its foam-suppressing effect, as stated at the beginning, this loss can be accepted, since it affects only a small percentage of the total polysiloxane defoamer to be used.
• this additive significantly improves the sprayability of the concentrates, the grain structure of the carrier grains in the sense of an improved absorption capacity for polysiloxanes, and in particular the wettability of the powder component loaded with further polysiloxane defoamer when used later in the washing bath. If, instead, as suggested in the previous literature, the entire amount of the polysiloxane-silica mixture is incorporated into the concentrate and sprayed with it, the wettability in the washing bath deteriorates and residue formation can result from undissolved particles. In addition, the foam-suppressing effect is reduced overall.
• the carrier substance (E1) should be free of surfactants because surfactants also weaken the foam-suppressing effect.
• it should be free of water-insoluble or sparingly soluble compounds such as the clays, diatomaceous earth, fuller's earth and cellulose recommended in the previous literature, since these substances also lead to a loss of activity, which may be due to a partial separation of the polysiloxane from the silica.
• the carrier (E1) prepared in the manner described is of granular nature and has a grain size range of 0, 05 mm to 2.5, preferably from 0.1 to 1.6 mm with an average grain size of 0.2 to 0.8 mm on. It is characterized by a good absorption capacity for the polysiloxane-silica component on the one hand and for a quick and complete dissolution in the wash bath even at low wash bath temperatures.
• the granular carrier substance (E1) is mixed with conventional polysiloxane-silica mixtures (E2), the weight ratio of carrier substance (calculated as anhydrous salt) to polysiloxane-silica mixture 50: 1 to 6: 1, preferably 25: 1 to 8: 1.
• Suitable polysiloxanes are conventional compounds such as dimethyl, diethyl, dipropyl, dibutyl, methylethyl, methylphenyl, methylcyclohexyl and hydroxyalkyl polysiloxanes.
• Crosslinked polysiloxanes are also suitable.
• the polysiloxanes are used in a mixture with finely divided silica, for example Aerosil, it also being possible to use silanized silica which can be obtained by reacting silica containing hydroxyl groups with chlorosilanes.
• the weight ratio of polysiloxane to silica is 50: 1 to 5: 1, preferably 25: 1 to 7: 1.
• the granular carrier substance can be mixed with the polysiloxane / silica mixture in customary mixing devices, it being possible for batchwise and continuous operation.
• customary mixing devices for example, drum mixers, spray mixers, cascade mixers or mixing devices which consist of a vertical downpipe with an axially arranged rotating shaft equipped with mixing tools (so-called Schugi mixers).
• the carrier substance (E1) is such that the polysiloxane / silica mixture (E2) is absorbed quickly and completely.
• the pore structure of the carrier grain leads to an optimal distribution state of the foam damper. This optimum manifests itself through the following properties.
• the carrier substance (powder component E) loaded with the polysiloxane / silica mixture has a bulk density of 450 to 700, preferably 500 to 650 g / l. It is of the same order of magnitude as the bulk density of spray-dried detergent powder, which is why the powder mixtures cannot separate during transport and storage.
• the powder component (E) is mixed with other powdery to granular detergent components in a manner known per se, the proportions being such that - depending on the strength of the desired effect - 0.01 to 0.5, preferably 0.05 to 0 , 2 percent by weight of polysiloxane-silica mixture are contained in the detergent.
• the detergent according to the invention consists of at least one further powder component, which advantageously also has a particle size of 0.05 to 2.5 mm, preferably 0.1 to 1.6 mm. It contains the detergent ingredients listed under (A) to (D) as well as other non-bleaching detergent additives, which include washing alkalis, graying inhibitors, optical brighteners, stabilizers, neutral salts and dyes. Other powder components may also be present, per compounds or bleaches containing active chlorine, bleach activators and enzymes which are not stable under the conditions of hot spray drying.
• cation-exchanging alkali alumosilicates are synthetically produced crystalline compounds which generally have particle sizes below 50 ⁇ , essentially below 40 ⁇ and mostly in the range from 20 to 0.1 ⁇ .
• the agents according to the invention are advantageously used crystalline sodium aluminosilicates containing bound water and having the composition 0.7 to 1.1 Na 2 0. 1.0 Al 2 O 3 . 1.3 to 2.4 SiO 2 , the water content of which can vary depending on the processing conditions and is generally 18 to 22 percent by weight in the finished washing powder.
• Such aluminosilicates are also referred to as "zeolite NaA".
• such products are used, in the production of which a suitable selection of the starting conditions ensured that the resulting crystallites have rounded corners and edges and their particle size is below 30 ⁇ and at least 80% in the range from 8 to 0.01 ⁇ and the mean particle diameter Is 3 to 6 ⁇ .
• Examples of other suitable sodium aluminosilicates of the composition 0.7 to 1.35 Na 2 O. 1.0 Al 2 O 3 . 1.3 to 2.4 SiO 2 are binary mixtures of 40 to 90% particles of the zeolite NaA and 10 to 60% particles of the zeolite HS (hydrosodalite).
• Such an aluminosilicate already has a calcium binding capacity of 100 to 165 mg CaO / g and a magnesium binding capacity of 50 to 110 mg MgO / g - in each case based on the anhydrous substance - in the heated wash liquor from a temperature of 50 ° C.
• These aluminosilicate mixtures, their preparation and their use in detergents and cleaning agents are described in DE-OS 25 43 941, which is also expressly referred to as a disclosure within the scope of this invention.
• the water-soluble organic complexing agents listed under (B) from the group of substituted alkanedi- and triphosphonic acids, which also includes heterocyclically substituted compounds, include those alkanedi- and triphosphonic acids or their salts, the alkane group of which is substituted by the hydroxyl, amino, phenyl or is substituted by a phenyl group carrying hydroxyl, amino or halogen groups.
• the alkane and triphosphonates from the group consisting of 1-hydroxyethane-1,1-diphosphonic acid, 1-aminoethane-1,1-diphosphonic acid, 3-amino-1-hydroxypropane-1,1-diphosphonic acid, 1- Amino-1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-p-chlorophenylmethane-1,1-diphosphonic acid, 1-hydroxy-1-phenylmethane-1,1-diphosphonic acid, 1-hydroxybutane-1, 1-diphosphonic acid and aminotrimethylene triphosphonic acid in the form of their alkali, magnesium or calcium salts, in particular the sodium salts.
• the sodium salt of 1-hydroxyethane-1,1-diphosphonic acid is particularly preferred, in particular in amounts of 0.2 to 2 percent by weight, based on the detergent.
• Suitable phosphonic acids also include those which additionally have one or more carboxyl groups, for example 1,1-diphosphonoethane-2-carboxylic acid, 1,1-diphosphonopropane-3-carboxylic acid, 1-phosphonopropane-1,2,3-tricarboxylic acid, 1 , 1-diphosphonopropane-2,3-dicarboxylic acid, 1-phosphonobutane-2,3,4-tricarboxylic acid, 2-phosphonobutane-2,3,4-tricarboxylic acid, 2,2-diphosphonobutane-3,4-dicarboxylic acid, 2,4 -Diphosphonobutane-1,2-dicarboxylic acid and 3,3-di-phosphonopentane-1,5-dicarboxylic acid.
• These phosphonocarboxylic acids can replace all or part of the aforementioned di- and triphosphonic acids having hydroxyl or amino groups and are also preferably present as sodium salts.
• the anionic surfactants (component C) present in amounts of 3 to 12 percent by weight should consist of 50 to 100 percent by weight of sulfonate and sulfate surfactants with predominantly linear hydrocarbon radicals having 10 to 20 carbon atoms.
• Suitable sulfonate surfactants are n-alkanesulfonates, as are obtainable by sulfochlorination or sulfoxidation of paraffin hydrocarbons, olefin sulfonates which are obtained by reacting linear olefins having a terminal or internal double bond with sulfur trioxide and subsequent hydrolysis and ⁇ -sulfofatty acid alkyl esters, such as those obtained by sulfonating sulfonates from fatty acid esters monohydric alcohols containing 1 to 3 carbon atoms can be obtained with SO 3 .
• Suitable sulfate surfactants are primary alkyl sulfates or fatty alcohol sulfates and alkyl or fatty alcohol glycol ether sulfates with 1 to 3 ethylene glycol ether groups which are derived from alcohols of natural origin or synthetically produced, for example alcohols obtained by ethylene polymerization or oxosynthesis. The latter can be partially methyl-branched in the 2-position, which does not seriously impair the biodegradability.
• the proportion of anionic surfactants in alkylbenzenesulfonates, which usually have 9 to 13, in particular 12, C atoms in the linear alkyl group should not be more than 50 percent by weight, preferably less than 25 percent by weight.
• the anionic surfactants can consist of up to 25 percent by weight of soap, which are derived from saturated or monounsaturated fatty acids having 12 to 22, preferably 12 to 18, carbon atoms. They suppress unwanted foaming while rinsing the laundry with fresh water.
• the anionic surfactants are present as alkali metal salts, preferably as sodium salts.
• the sulfates of coconut and tallow alcohols in particular the sodium salt of hydrogenated tallow alcohol sulfate, and the sulfofatty acid esters based on coconut and tallow fatty acids are ideally suited for the production of light and free-flowing powders and are therefore particularly preferred.
• sulfate and sulfonate surfactants can be present individually or in a mixture or in a mixture with soap. Although these are extremely high-foaming compounds, their use in conjunction with the foam-regulating powder component in washing machines is problem-free.
• the nonionic component (D) present in amounts of 1 to 15 percent by weight preferably consists of saturated or simply non-ethoxylation products saturated aliphatic primary alcohols having 12 to 24, preferably 12 to 18 carbon atoms and 2 to 20 s, in particular 3 to 15 ethylene glycol ether groups.
• Suitable alcohols, from which the present ethoxylation products are derived are in particular those of natural origin, such as coconut oil or tallow fatty alcohols or oleyl alcohol, and also oxo alcohols or synthetic alcohols obtained by ethylene polymerization.
• Fatty acid mono- and dialkanolamides which are derived from saturated or monounsaturated fatty acids with 12 to 20 carbon atoms, such as lauric, myristic, palmitin, stearic, oil, coconut palm kernel, have also proven to be useful. or tallow fatty acids and derived from monoethanolamine, diethanolamine or the corresponding mono or dipropanol or isopropanol amines. Although this class of compounds is known to greatly increase the foam formation rate and foam stability in conjunction with sulfate and sulfonate surfactants, there is no foaming in the presence of the foam-regulating component (E) in washing machines.
• E foam-regulating component
• nonnicnic surfactants are ethoxylation products of secondary alcohols, vicinal diols and amino alcohols each having 12 to 18 carbon atoms, the number of glycol ether groups likewise being 3 to 20, preferably 4 to 15.
• the abovementioned ethoxylated alcohols and amino alcohols can also be replaced in whole or in part by those which are prepared with 0.5 to 3 moles of propylene oxide per mole of starting compound and only in the second stage the envisaged amount of ethylene oxide is added.
• the components listed under (A) to (D) are preferably in the form of homogeneous powder components or granules, as can be obtained by spray drying or granulation.
• This powder component can also contain other common detergent ingredients, such as Alkaline detergents, neutral salts, graying inhibitors, optical brighteners, stabilizers such as magnesium silicate, advising substances and dyes, further additives which improve the sprayability, for example alkali metal salts of toluene, xylene or cumene sulfonic acid.
• Suitable washing alkalis are alkali carbonates, bicarbonates, borates and silicates with a Na 2 O: SiO 2 ratio of 1: 1 to 1: 3.5.
• Sodium sulfate and sodium chloride are suitable as neutral salts.
• Suitable graying inhibitors are, in particular, carboxymethyl cellulose and cellulose mixed ethers which have varying amounts of carboxymethyl, methyl and / or hydroxyethyl, hydroxypropyl and hydroxybutyl groups, in particular methylhydroxypropyl cellulose and methylhydroxybutyl cellulose, and also colloidally water-soluble polymers or copolymers of vinyl alcohol and vinyl alcohol and vinyl alcohol, vinyl alcohol and vinyl alcohols, vinyl alcohol and vinyl alcohols, vinyl alcohol and vinyl alcohols Acrylonitrile.
• Suitable optical brighteners are the alkali salts of 4,4-bis (-2 "-anilino-4" -morpholino-1,3,5-triazinyl-6 "-amino) -stilbene-2,2'-disulfonic acid or compounds of the same structure which carry a diethanolamino group, a methylamino group or a .beta.-methoxyethylamino group instead of the morpholino group.
• brighteners for polyamide fibers are those of the diarylpyrazoline type, for example 1- (p-sulfonamidophenyl) -3- (p-chlorophenyl) - ⁇ 2 -pyrazoline and compounds of the same structure which carry a carboxymethyl or acetylanino group instead of the sulfonamido group
• substituted aminocoumarins for example 4-methyl-7-dimethylamino- or 4-methyl-7-diethylaminocoumarin.
• the compounds 1- (2-benzimidazolyl) -2- (1-hydroxyethyl-2-benzimidazolyl) ethylene and 1-ethyl-3-phenyl-7-diethylamino-carbostyryl are also useful as polyamide brighteners.
• the brighteners for polyester and polyamide fibers are the compounds 2,5-di- (2-benzoxazolyl) -thiophene, 2- (2-benzoxazolyl) -naphto- [2,3-b] -thiophene and 1,2-di- (5-methyl-2-benzoxazolyl) ethylene suitable. Brighteners of the type of the substituted diphenylstyryls can also be present.
• Examples include 4,4 1- bis- (2-sulfostyryl) biphenyl and 4,4'-bis- (4-chloro-3-sulfostyryl) biphenyl as disodium salts. Mixtures of the aforementioned brighteners can also be used.
• a further powder component which may be present preferably contains per compounds, for example sodium percarbonate, but in particular sodium perborate tetrahydrate.
• Additional powder components may also be present, which may contain enzymes or bleach activators, for example.
• the enzymes and bleach activators can be coated with water-soluble or dispersible coating substances.
• the various powder components are combined by mixing in conventional mixing devices, which preferably operate continuously or on the free-fall principle. Before or during the mixing process, further constituents, for example fragrances, can also be introduced or onto one of the powder components or the powder mixture be sprayed on. Finally, the sodium perborate - as described in the patent applications DE-OSS 27 48 970 and 27 53 680 - can be treated with nonionic surfactants in order to improve the washing-in behavior of the washing powder.
• the detergents according to the invention have good washing and cleaning properties both in the 60 0 washing area and in the boil washing area.
• the formation of laundry incrustations and deposits on the heating elements in the washing machines is largely prevented. They are also characterized by favorable foaming behavior. It is advantageous that the foam-suppressing effect of the siloxanes does not suffer any significant losses in the production process according to the invention or during storage, but that on the other hand, when the agents are used, there is no graying of the tissues or no exposure of the washing machine parts to a siloxane film which is very difficult to remove. Another advantage is their favorable environmental behavior due to the largely absence of phosphates and detergent substances with alkyl aromatic residues.
• the spray products (temperature 20 ° C.) were mixed in a drum mixer with step by step with a homogeneous mixture of 10 parts by weight of polydimethylsiloxane and 1 part by weight of silanized silica heated to 50 ° C.
• the viscosity of the polysiloxane-silica mixture was 1300 cP at 20 ° C and 750 cP at 50 ° C.
• examples a, b, d and e 5 parts by weight of polysiloxane-silica mixture per 95 parts by weight of carrier were used.
• this ratio was 10 to 90 and in example f (spray product containing 0.2 percent by weight polysiloxane) 4.8 to 95.2 parts by weight.
• the polysiloxane / silica mixture was completely absorbed by the carrier substance.
• the impregnated granules proved to be dry, pourable, non-sticky and non-greasy.
• Their liter weight was between 560 and 590 g / l.
• the granules were dry-mixed with a spray-dried detergent, per compounds, bleach activators and enzyme-containing granules.
• the enzyme granules were produced by spraying (prilling) a mixture of 25 percent by weight of proteolytic enzyme, 60 percent by weight of a tallow fatty alcohol reacted with 80 mol of ethylene oxide and 15 percent by weight of sodium sulfate in accordance with the specifications of US Pat. No. 3,801,463.
• the composition of the detergents is shown in Table 2.
• the components "tallow alcohol sulfate" to "optical brightener” were available as spray powder.
• a zeolite A with the following parameters was used as sodium aluminosilicate: composition 1.04 Na 2 O.1 Al 2 O 3 2.05 SiO 2 ; Water content 21.2%; Calcium binding capacity at 20 ° C: 170 mg Ca0 / g (according to the method of determination specified in DE-OS 24 12 837); Particle size range 15 to 1 ⁇ , average particle diameter (Coulter counter, volume distribution): 4.8 ⁇ .
• anionic surfactants were used as sodium salts.
• the mixtures had a water content of between 7.8 and 9.4 percent by weight.
• the difference up to 100 percent by weight consisted of sodium sulfate.
• the detergents listed below did not tend to foam when used in drum washing machines with a detergent concentration of 5 to 7.5 g / 1 and a water hardness of 5 ° to 20 ° dH in the temperature range between 20 ° and 96 ° C.
• the detergents proved to be equivalent to a phosphate-rich heavy detergent.

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• Chemical & Material Sciences (AREA)
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• 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 (1)

• 1980
  • 1980-03-17 DE DE19803010192 patent/DE3010192A1/de not_active Withdrawn
• 1981
  • 1981-03-09 EP EP81101716A patent/EP0036162A1/fr not_active Withdrawn

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