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
  • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets
• • 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
  • C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
  • C11D1/66—Non-ionic compounds
  • C11D1/72—Ethers of polyoxyalkylene glycols
• • 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

Definitions

• the present invention relates to a particulate, nonionic surfactant and Builder-containing washing and cleaning agent or compound therefor, and a Process for its manufacture.
• detergents and cleaning agents contain especially against dust / skin oil stains, non-ionic Surfactants.
• nonionic surfactants are liquid at room temperature, which makes it difficult to process them in powder form.
• the liquid nonionic surfactants are often in the form of so-called Compounds used, which are usually wet granulation with zeolite or a other solid detergent builders, and granulating liquid. in the After granulation, the particles obtained must be dried.
• the Granulation requires the use of a granulating liquid, which increases the proportion liquid nonionic surfactants reduced.
• the mixer through the Liquid easily forms caking and it occurs at high levels on it liquid nonionic surfactants in the dryer further granulation to larger Particles.
• the additional drying step also extends the manufacturing process and additionally increases the costs.
• DE-A-41 24 701 describes a process for the production of solid washing and cleaning agents discloses, wherein solid and liquid detergent raw materials under simultaneous or subsequent shaping and possibly drying.
• solid and liquid detergent raw materials under simultaneous or subsequent shaping and possibly drying.
• anionic surfactants As an integral part are anionic surfactants, builder substances and alkalizing agents and as liquid components non-ionic surfactants used.
• the liquid nonionic surfactants are intimately mixed with a Structure breaker mixed in a weight ratio of 10: 7 to 1: 1.
• Structural breakers are polyethylene glycol or polypropylene glycol, sulfates and / or Disulfates of polyethylene glycol or polypropylene glycol; Sulfosuccinates and / or Disulfosuccinate from polyethylene glycol or polypropylene glycol or mixtures of used this.
• the present invention was therefore based on the object of using particles in To provide detergents and cleaning agents that are as possible as possible Dry granulation or agglomeration using smaller amounts of Granulation aids can be obtained as usual in the prior art and the known solubility problems in powder detergents and cleaning agents exhibit.
• the present invention accordingly relates to particulate washing and Detergents or compounds therefor, containing 20 to 94% by weight of builder and 5 up to 60% by weight nonionic surfactant, characterized in that 1 to 20% by weight cellulose are included.
• the particles according to the invention can either be used as the sole detergent component are used or with other particles, the other detergent components contain mixed and assembled.
• the cellulose contained in the claimed agents according to the invention has the formal gross composition (C 6 H 10 O 5 ) n and, formally speaking, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose .
• Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
• the cellulose used usually has a particle size of less than 150 ⁇ m, preferably less than 100 ⁇ m. The particle size should not be too large, because if they are deposited on the textiles as a residue, they are clearly visible and are regarded as contamination.
• Cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions can also be used as celluloses in the context of the present invention.
• Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
• celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound via an oxygen atom can also be used as cellulose derivatives.
• the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
• Another cellulose derivative that can be used is microcrystalline cellulose.
• the cellulose derivatives mentioned are preferably not alone but in a mixture used with cellulose.
• the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the total cellulose content.
• pure is particularly preferred Cellulose used, which is free of cellulose derivatives.
• the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
• EO ethylene oxide
• alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
• the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 EO or 4 EO, C 9 -C 11 alcohols with 7 EO, C 13 -C 15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12 -C 18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 7 EO.
• the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
• Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
• nonionic surfactants such as alkyl polyglycosides, alkoxylated, preferably ethoxylated or ethoxylated and propoxylated alkyl C 8 -C 18 fatty acids, N-fatty alkyl amine oxides, polyhydroxy fatty acid amides or mixtures thereof can also be used.
• fatty alcohol alkoxylates in combination with alkyl polyglycosides, since it has been found that such mixtures do not show the known solubility problems of compounds of nonionic surfactants with a high bulk density.
• the total content of the nonionic surfactants in the finished compositions is preferably from 10% by weight to 50% by weight, the content of fatty alcohol ethoxylates alone preferably being above 20% by weight, in particular 30 to 40% by weight.
• alkyl alkoxylate to alkyl polyglycoside in a weight ratio of 2: 1 to 6: 1.
• the range of the gel phase which delays the dissolution of alcohol alkoxylates, is significantly reduced compared to the phase diagrams of pure alcohol alkoxylates. Because of this effect, such mixtures show a greatly improved dissolving behavior.
• the processability is further improved by the addition of alkyl polyglycosides to alcohol alkoxylates, since such mixtures usually have a lower viscosity than the pure alcohol alkoxylates.
• All builders suitable for detergents and cleaning agents can be used as builders that have a sufficiently large inner surface to absorb the nonionic surfactant to be able to.
• examples of this are zeolites, crystalline layered silicates, amorphous Silicates, soda, phosphates and mixtures thereof, zeolite being preferred.
• Fine zeolite can be, for example, finely crystalline, synthetic and bound water containing zeolite, such as zeolite A, zeolite P and mixtures of A and P used become.
• zeolite P is, for example, Zeolite MAP® (Trade product of the company Crosfield) to name.
• Zeolites of the faujasite type may be mentioned as further preferred and particularly suitable zeolites.
• the mineral faujasite belongs to the faujasite types within the zeolite structure group 4, which is characterized by the double six-ring subunit D6R (compare Donald W. Breck: Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, page 92).
• the zeolite structure group 4 also includes the minerals chabazite and gmelinite and the synthetic zeolites R (chabazite -Type), S (Gmelinite type), L and ZK-5. The latter two synthetic zeolites have no mineral analogues.
• Faujasite-type zeolites are composed of ⁇ -cages, which are linked tetrahedrally via D6R subunits, the ⁇ -cages being arranged in the diamond in a manner similar to the carbon atoms.
• the three-dimensional network of the faujasite-type zeolites used in the process according to the invention has pores of 2.2 and 7.4 ⁇ , the unit cell also contains 8 cavities with a diameter of approx. 13 ⁇ and can be determined by the formula Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] .264 H 2 O.
• the network of zeolite X contains a void volume of approximately 50%, based on the dehydrated crystal, which represents the largest empty space of all known zeolites (zeolite Y: approx. 48% void volume, faujasite: approx. 47% void volume). (All data from: Donald W. Breck: Zeolite Molecular Sieves ", John Wiley & Sons, New York, London, Sydney, Toronto, 1974, pages 145, 176, 177).
• the term characterizes Zeolite of the faujasite type "all three zeolites which form the faujasite subgroup of the zeolite structure group 4.
• zeolite Y and faujasite and mixtures of these compounds can also be used according to the invention, the pure zeolite X being preferred.
• Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites which do not necessarily have to belong to the zeolite structural group 4 can also be used according to the invention, the advantages of the process according to the invention being particularly evident when at least 50% by weight of the zeolites Faujasite type zeolites.
• the aluminum silicates used in the process according to the invention are commercially available, and the methods for their representation are in Standard monographs described.
• Examples of commercially available X-type zeolites can be described by the following formulas: Na 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, K 86 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, Ca 40 Na 6 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, Sr 21 Ba 22 [(AlO 2 ) 86 (SiO 2 ) 106 ] x H 2 O, in which x can have values between 0 and 276 and the pore sizes range from 8.0 to 8.4 ⁇ .
• the zeolite A-LSX described in European patent application EP-A-816 291 which corresponds to a co-crystallizate of zeolite X and zeolite A and in its anhydrous form has the formula (M 2 / n O + M ' 2 / n O) .Al 2 O 3 .zSiO 2 , where M and M' can be alkali or alkaline earth metals and z is a number between 2.1 and 2.6.
• This product is commercially available under the brand name VEGOBOND AX from CONDEA Augusta SpA
• Y-type zeolites are also commercially available and can be expressed, for example, by the formulas Na 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, K 56 [(AlO 2 ) 56 (SiO 2 ) 136 ] x H 2 O, in which x stands for numbers between 0 and 276 and have a pore size of 8.0 ⁇ .
• the particle sizes of the zeolites used in the process according to the invention of The faujasite type is in the range from 0.1 to 100 ⁇ m, preferably between 0.5 and 50 ⁇ m and especially between 1 and 30 ⁇ m, each with standard particle size determination methods measured.
• Suitable builders are, for example, crystalline, layered sodium silicates of the general formula NaMSi x O 2x + 1.yH 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and is preferred Values for x are 2, 3 or 4.
• Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
• both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
• amorphous sodium silicates with a module Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, can also be used as builder substances are used, which are preferably delayed release and have secondary washing properties.
• the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
• the term “amorphous” is also understood to mean “X-ray amorphous”.
• silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
• it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
• Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024. Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the agents according to the invention may also contain anionic surfactants, such as C 8 -C 22 alkyl sulfates, C 8 -C 22 alkanesulfonates, C 8 -C 22 olefin sulfonates, C 8 -C 22 alkylbenzenesulfonates, C 8 - C 22 fatty acid ether sulfates, C 8 -C 22 fatty acid ester sulfonates, sulfated fatty acid glycerol esters, 2,3-C 8 -C 22 alkyl sulfates, salts, monoesters and / or diesters of alkyl sulfosuccinic acid (sulfosuccinates), sulfuric acid monoesters of those ethoxylated with 1 to 6 moles of ethylene oxide straight-chain or branched C 7 -C 21 alcohols, fatty acid soaps or mixtures thereof.
• anionic surfactants such as C 8 -C 22
• agents according to the invention can all usually be used in detergents and cleaning agents contain substances, such as inorganic salts, bleaches, Bleach activators, graying inhibitors, foam inhibitors, salts of polyphosphonic acids, optical brighteners, enzymes or mixtures thereof.
• Another object of the present invention is a method for manufacturing of the particulate detergent and cleaning agent according to the invention or Compounds for this.
• the individual components intimately mixed together and in a manner known per se in shape be agglomerated.
• the nonionic surfactant is first applied to the builder in a manner known per se, usually the builder impregnated with the nonionic surfactant.
• the impregnated builders mixed with the cellulose and agglomerated.
• the cellulose acts as a granulating / compacting aid.
• the Agglomeration can take place according to known methods, such as extrusion, pelleting or roller compaction, with roller compaction being preferred.
• the agglomeration can optionally be carried out with the addition of auxiliaries such as organic Builders, e.g. B. polycarboxylic acids, citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), polymeric carboxylates, the alkali salts, especially the sodium salts, the the aforementioned carboxylic acids and mixtures thereof provided that the auxiliaries are not the solubility of the agents according to the invention affect.
• organic Builders e.g. B. polycarboxylic acids, citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), polymeric carboxylates, the alkali salts, especially the sodium salts, the the aforementioned carboxylic acids and mixtures thereof provided that the auxiliaries are not the solub

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• 1997
  • 1997-12-22 DE DE1997157217 patent/DE19757217A1/de not_active Withdrawn
• 1998
  • 1998-12-11 EP EP98123664A patent/EP0926232A3/fr not_active Ceased

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