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
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/04—Water-soluble compounds
  • C11D3/044—Hydroxides or bases
• • 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
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • 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
  • C11D3/06—Phosphates, including polyphosphates
• • 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
  • C11D3/02—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
  • C11D3/39—Organic or inorganic per-compounds
  • C11D3/3942—Inorganic per-compounds

Definitions

• the present invention relates to a detergent and cleaning agent Contains alkalizing agents and possibly other common ingredients.
• the controlled release of individual detergent components to be determined is advantageous from an economic and ecological point of view and accordingly subject to intensive research.
• One is playing important role in which order the soiling with the individual Ingredients come into contact, but also the interaction of individual Ingredients are important, especially the interplay of bleach and enzymatic cleaning.
• Detergent and bleach compositions containing a source of hydrogen peroxide and contain a peroxyacid bleach precursor (bleach activator) and in the Wash liquor provide an initial alkaline pH (pH 10-11), as well as the delayed release of acid in the wash liquor to bring about a lowered pH to arrive in the fleet are described in the prior art and for example in European patent applications EP-A-0 290 081 (Unilever) and EP-A-0 396 287 (Clorox) or EP 0 651 053 (P&G).
• alkalizing agents are bleaching agents such as Sodium percarbonate, which can be coated with a coating material, which slowly dissolves in water regardless of pH, while being special coated ingredient a bleach activator, preferably tetraacetylethylenediamine (TAED), is used.
• TAED tetraacetylethylenediamine
• the present invention was based on the object of a washing and cleaning agent to develop that through the targeted and defined release kinetics and Combination of ingredients during the wash cycle a pH shift from weakly acidic or neutral into the usual alkaline range, so that the soiling first in a weakly acidic to neutral environment and are then treated in an alkaline medium, especially in the case of low Washing temperatures to achieve an improvement in washing performance.
• the present invention relates to detergents and cleaning agents Alkalizing agent, characterized in that the alkalizing agent completely or is partially coated with a coating material or compounded so that this in the Wash liquor after a period t1 of 1 min. up to 25 min. at most 10% and after t1 plus 3 min. up to 30 min. is released to at least 90%.
• the alkalizing agent is preferably used in a period t1 of 3 minutes. up to 20 min. and particularly preferably from 5 min. up to 15 min. at most 10% and preferably after t1 plus 5 min. up to 15 min. and particularly preferably from 7 min. up to 10 min. at least 90% released.
• Alkalizing agents come in the field of detergents and cleaning agents known substances into consideration which have an alkaline reaction in water. It can be soluble Alkalizing agents, such as alkali carbonates and their hydrates and perhydrates, phosphates such as. Sodium tripolyphosphate, soluble silicates such as e.g. Water glasses, alkali hydroxides, Carboxylates or Na perborate can be used. Suitable examples are also also known as insoluble alkali silicates as builders, as described in more detail below become.
• To release the alkalizing agent according to the invention Set the defined period of time, it has proven to be advantageous, the solubility to be retarded by a suitable coating and / or by a coarseness.
• the release of the alkalizing agent in the period defined according to the invention it has proven to be suitable to use these agents with wrapping materials provided that dissolve in the wash liquor with a defined kinetics. According to them If possible, a step-shaped, ideally sudden, dissolution occurs Release of the coated alkali carrier.
• Fatty alcohols are preferred as coating materials or fatty acids, which may be mixed with other coating materials can.
• a mixture of fatty alcohols and aluminum stearate is an example called.
• envelope materials known from the prior art are as follows summarized in key words: magnesium sulfate and sodium hexaphosphate, Dihydrogen phosphate or pyrophosphates, phosphonic acids, sodium metaborate and - Silicate, water glass and sodium polyphosphate, sodium sulfate, and silicate, or Sodium bicarbonate, borax and magnesium sulfate, boric acid, but also in part organic components such as fat derivatives, paraffins and waxes (melting temperature of the compounds between 25 and 90 ° C), polyethylene glycols and fatty acid esters thereof with a molecular weight of 300 to 1,700, combinations with magnesium oxide, Vinyl chloride-ethylene copolymer emulsions or vinyl chloride-ethylene methacrylate copolymer emulsions. Polycarboxylates or other water-soluble polymers.
• the coating materials can be applied from the melt or from solutions or Dispersions take place, the solvent or emulsifier being evaporated Will get removed. Also application as a fine powder, for example by electrostatic techniques are possible, although this method is too irregular and poorly adhering coatings.
• the wrapping materials can be stirred, Mixing and pelletizers are applied to particles. However, one is preferred Application of the enveloping materials in a fluidized bed, at the same time one Size classification of the particles can be done. Should the wrapping materials under certain circumstances lead to sticky products, it may be useful to to coat coated alkalizing agents with finely divided substances ("Powdering"). All fine-particle substances can be used as powdering agents, other detergent ingredients such as builder substances are also used can. Preferred additional powdering agents are zeolites, silicates, polymeric polycarboxylates, carbonates, citrates, starch, cellulose derivatives, etc. used. Part of the buffer system, if present, can also be used for powdering become.
• the coating materials for the alkalizing agent are used in such amounts that that an optimal interaction of the individual components and thus an exact controlled release is enabled. Depending on the period within which the Release should be largely suppressed and depending on the size de coated Particles will measure the amount of shell material.
• Preferred Embodiments use less than 20% by weight wrapping material based on the Amount of coated particles, in particular less than 10% by weight Wrapping materials preferred.
• a preferred "physical" method to delay the alkalizing agent releasing is to make it worse compared to the other ingredients to provide soluble form. This can be done, for example, by varying the Particle size can be achieved because there are finely divided detergents or cleaning agents dissolve faster due to the larger surface. Also the A combination of different densities is preferred Way to realize different solubilities. For example powdery ingredients with more compacted, for example extruded, and so that slower soluble alkalizing agents can be combined.
• the "physical Release delay "within a molded body For this purpose, washing or detergent tablets are produced, which consist of several phases exist, where one phase is less compressed than another phase. The the more easily compressed phase breaks down more quickly into the previous one in the washing or cleaning cycle pressed premix, which increases the solubility to a harder pressed phase is increased.
• two-layer tablets are particularly preferred, where one layer is pressed more softly than the other, the hardest one Layer containing the alkalizing agent.
• the retardation of a phase also about a lower content of a de-integration aid contained in it can be achieved.
• the agents according to the invention can include a buffer system, nonionic and anionic surfactants, builders, bleaches and other common Components included.
• the agent according to the invention contains Buffer system. Due to the buffer system, the pH in the wash liquor is increased when the Detergent composition comparatively low, i.e. it is between 6 and 8, preferably between 6.3 and 7.7, particularly preferably between 6.5 and 7.5. With this pH value comes in particular the washing effect of the surfactants compared to bleachable ones Soiling such as tea, coffee, red wine or fruit and vegetable juices Wear.
• the buffer system is preferably used in amounts of 0.1 to 40, preferably 1 to 25 wt .-%, based on the finished agent, used.
• a buffer system everyone can water-soluble substances are used, which are suitable for the pH value buffer aqueous solution below the value 8.
• Preferred buffer systems are partially neutralized inorganic and organic acids, for example the solid mono-, oligo- and polycarboxylic acids such as citric, wine and Succinic acid, polycarboxylic acids such as polyacrylic acid or acrylic acid-maleic acid copolymers, but also acids such as malonic acid, adipic acid, maleic acid, fumaric acid, Oxalic acid, boric acid or amidosulfonic acid and mixtures of the acids mentioned.
• Substances such as hydrogen sulfates or carbonates can also be used as a buffer system are, again only paying attention to the compliance with the pH conditions must become.
• the Select buffer systems so that they dissolve quickly and quickly adjust the pH to bring desired values.
• a coating that delays detachment would be undesirable for the buffer systems within the scope of the present invention.
• the buffer capacity of the buffer system must be chosen so high that different Amounts of residual alkalinity in the washing machine or laundry from previous ones Washes can be neutralized.
• the buffer system has to meet the requirement that they are not volatile. From this point of view, fixed buffer systems are one low tendency to sublimation and a high melting point with a good one Agree on water solubility, clearly preferred. Liquid or pasty buffer system can only in minor amounts below 5 wt .-% of Overall composition must be used and must be used Packaging measures are taken to ensure formulation and storage stability To ensure even with increased humidity. Of course at Selection of the buffer system (s) also ensure that the resulting Washing liquor does not harm textiles or human skin.
• Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
• Preferred surfactants of the sulfonate type are C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates, and disulfonates such as are obtained, for example, from C 12-18 monoolefins with a terminal or internal double bond by sulfonating with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis of the sulfonation products.
• alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
• the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
• Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
• Fatty acid glycerol esters are the mono-, di- and triesters as well as their mixtures understand how they are produced by esterification of a monoglycerin with 1 up to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerin be preserved.
• Preferred sulfonated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example the Caproic acid, caprylic acid, capric acid, myristic acid, lauric acid, palmitic acid, Stearic acid or behenic acid.
• Alk (en) yl sulfates are the alkali and in particular the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned which contain a synthetic, straight-chain alkyl radical prepared on a petrochemical basis and which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
• C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
• 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
• the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
• Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
• Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
• Particularly preferred sulfosuccinates contain a fatty alcohol residue which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
• alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
• Soaps are particularly suitable as further anionic surfactants.
• saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
• the anionic surfactants including the soaps can be in the form of their sodium, potassium or ammonium salts and as soluble salts of organic bases, such as mono-, di- or triethanolamine.
• the anionic surfactants are preferably in the form their sodium or potassium salts, especially in the form of the sodium salts.
• carrier material Preferably at least a portion, preferably at least 50%, of the anionic Surfactants applied to a carrier material.
• carrier materials are Alkali carbonates, alkali sulfates, alkali citrates, alkali phosphates, silicas, Zeolites, citric acid and their mixtures.
• pH-neutral carrier materials such as silica gel, starch, cellulose and Cellulose derivatives, neutral reacting phosphates, alkali sulfates, polyacrylate derivatives, etc.
• agents according to the invention can also use other agents Surfactants, e.g. B. contain nonionic and amphoteric surfactants.
• 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 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 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).
• fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
• nonionic surfactants which either as sole nonionic surfactant or in combination with other nonionic Surfactants used are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably with 1 to 4 Carbon atoms in the alkyl chain, especially fatty acid methyl esters, such as them are described for example in Japanese patent application JP 58/217598 or preferably according to that in international patent application WO-A-90/13533 described methods are produced.
• alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
• Alkypolyglycosides which can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
• the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
• Linear alkyl polyglucosides, ie alkyl polyglycosides, in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical are preferably used.
• nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the Fatty acid alkanolamides can be suitable.
• the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, in particular not more than half of it.
• Suitable surfactants are polyhydroxy fatty acid amides of the formula (II), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
• the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
• the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propylated Derivatives of this rest.
• R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
• R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical
• [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
• the N-alkoxy or N-aryloxy substituted compounds can then, for example according to the teaching of international application WO-A-95/07331 by implementation with Fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired Polyhydroxy fatty acid amides are transferred.
• Surfactants are preferred in the cleaning or washing agents according to the invention in total in an amount of 5% by weight to 50% by weight, in particular 8% by weight up to 30 wt .-%, based on the finished agent.
• the agents according to the invention generally contain one or more builders, especially zeolites, silicates, carbonates, organic cobuilders and - where none There are ecological prejudices against their use - including phosphates. Latter are especially in detergent tablets for automatic dishwashing preferably used builders.
• the builders mentioned below are as described above, also suitable as an alkalizing agent.
• the builders insofar as they are insoluble, are usually in particulate form, i.e. in a particle size of 0.1 to 10 ⁇ m.
• Many builders show latent alkaline Properties, i.e. overall, they are pH neutral due to their insolubility but alkaline groups on your surface. Since the particles from the Textiles are filtered out and therefore in intensive contact with the soiling come, create an alkaline milieu there locally, as this negatively affects the Washability affects bleachable stains in particular, though macroscopically there can be a neutral pH. Another increase in Washing effect can be achieved if the insoluble, finely divided builders too larger agglomerates are granulated using neutral granulation aids or they exist as coarser particles.
• agglomerates disintegrate during of the washing process slowly and release the primary particles. By the coarser ones Particles become a fine dispersion in the first minutes of the wash cycle prevented.
• cellulose derivatives Polyvinyl alcohols, polycarboxylates, polyvinyl pyrrolidone and their copolymers are suitable.
• Suitable crystalline, layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 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 preferred values for x 2, 3 or 4.
• Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular, both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred.
• the delay in dissolution compared to conventional amorphous sodium silicates can have been caused in various ways, for example by surface treatment, compounding, compacting / compaction, by overdrying or by coating.
• 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 deliver 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.
• Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
• the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
• zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
• zeolite X and mixtures of A, X and / or P are also suitable.
• Commercially available and can preferably be used in the context of the present invention for example a co-crystallizate of zeolite X and zeolite A (approx ), which is sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula n Na 2 O (1-n) K 2 O Al 2 O 3 (2 - 2.5) SiO 2 (3.5 - 5.5) H 2 O can be described.
• Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
• Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can distinguish between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
• the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in tissues and also contribute to cleaning performance.
• Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders, which lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
• NaH 2 PO 4 is acidic; it occurs when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
• Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
• Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to the diphosphate Na 4 P 2 O 7 when heated to a greater extent. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
• Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
• Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
• Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when heating Thomas slag with coal and potassium sulfate. Despite the higher price, the more easily soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
• Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also given 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) .
• Substances are colorless crystals that are soluble in water with an alkaline reaction.
• Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
• the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
• Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4. Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher moles.
• Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
• pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
• sodium tripolyphosphate sodium tripolyphosphate
• n 3
• Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
• pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
• sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
• organic cobuilders in the washing and Detergent tablets in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic Cobuilder (see below) and phosphonates are used. These substance classes are described below.
• Usable organic builders are, for example, those in the form of their Polycarboxylic acids that can be used are sodium salts, with polycarboxylic acids being such Carboxylic acids are understood that carry more than one acid function.
• these are citric acid, adipic acid, succinic acid, glutaric acid, Malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, Nitrilotriacetic acid (NTA), provided that such use is not for ecological reasons objectionable, and mixtures of these.
• Preferred salts are the salts of Polycarboxylic acids such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids and mixtures of these.
• the acids themselves can also be used.
• the acids have besides theirs Builder effect typically also the property of an acidifying component and thus also serve to set a lower and milder pH value of Detergents or cleaning agents.
• Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70,000 g / mol.
• the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), using a UV detector. The measurement was made against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
• Suitable polymers are in particular polyacrylates, which preferably have a molecular weight have from 2000 to 20,000 g / mol. Because of their superior solubility, can this group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
• copolymeric polycarboxylates especially those of Acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
• Copolymers of acrylic acid with maleic acid have proven particularly suitable proven that 50 to 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid contain.
• Their relative molecular weight, based on free acids, is in general 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 up to 40,000 g / mol.
• the (co) polymeric polycarboxylates can either be as a powder or as an aqueous Solution are used.
• the content of the agents in (co) polymeric polycarboxylates is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
• the polymers can also contain allylsulfonic acids, such as allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer contain.
• allylsulfonic acids such as allyloxybenzenesulfonic acid and methallylsulfonic acid
• Biodegradable polymers of more than two are also particularly preferred various monomer units, for example those which are salts of the monomers Acrylic acid and maleic acid as well as vinyl alcohol or vinyl alcohol derivatives or the as monomers, salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
• copolymers are those which preferably contain acrolein as monomers and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
• Polymeric aminodicarboxylic acids are also further preferred builder substances. to name their salts or their precursors. Are particularly preferred Polyaspartic acids or their salts and derivatives.
• polyacetals which are obtained by converting Dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 Have hydroxyl groups can be obtained.
• Preferred polyacetals will be from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and their Mixtures and from polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid receive.
• Suitable organic builder substances are dextrins, for example Oligomers or polymers of carbohydrates by partial hydrolysis of starches can be obtained.
• the hydrolysis can be carried out according to conventional methods, for example acid or enzyme-catalyzed processes are carried out. It is preferably Hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
• a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, particularly preferred from 2 to 30, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which a DE out of 100.
• DE dextrose equivalent
• oxidized derivatives of such dextrins are theirs Reaction products with oxidizing agents that are capable of at least one To oxidize the alcohol function of the saccharide ring to the carboxylic acid function.
• oxidizing agents capable of at least one To oxidize the alcohol function of the saccharide ring to the carboxylic acid function.
• an oxidized oligosaccharide e.g. B. an oxidized at C6 of the saccharide ring Product.
• Ethylene diamine disuccinate are other suitable cobuilders. This is ethylenediamine-N, N'-disuccinate (EDDS) preferred in the form of its sodium or magnesium salts used. Also preferred in this context Glycerol disuccinates and glycerol trisuccinates. Suitable amounts are in Zeolite-containing and / or silicate-containing formulations at 3 to 15% by weight.
• organic cobuilders are, for example, acetylated Hydroxycarboxylic acids or their salts, which may also be in lactone form and which have at least 4 carbon atoms and at least one Contain hydroxy group and a maximum of two acid groups.
• phosphonates are, in particular, hydroxyalkane or aminoalkane phosphonates.
• hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) of particular importance as a cobuilder.
• HEDP 1-hydroxyethane-1,1-diphosphonate
• Preferred aminoalkane phosphonates are ethylenediaminetetramethylenephosphonate (EDTMP), diethylene triamine pentamethylene phosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral reacting sodium salts, e.g.
• the Class of phosphonates preferably uses HEDP.
• the aminoalkane phosphonates also have a strong ability to bind heavy metals. Accordingly, it is preferred, especially if the agents also contain bleach, Aminoalkanephosphonate, especially DTPMP to use, or mixtures of the to use the named phosphonates.
• the amount of builders is usually between 10 and 70% by weight, preferably between 15 and 60% by weight and in particular between 20 and 50 % By weight.
• the agents according to the invention are particularly suitable for washing delicate textiles and / or for washing textiles at low Temperatures, preferably up to 40 ° C, the use at higher temperatures is also possible.
• the washing and Detergent used as a so-called full detergent i.e. for washing any textiles and at any temperature.
• Detergent included Usually, in addition to the surfactants and builder materials, organic and / or especially inorganic bleaches.
• bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracid salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
• Bleaching agents from the group of organic bleaching agents can also be used.
• Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
• organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
• Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoxy acid perooxyperaproic acid ( ⁇ -phthalimidoperoxy-capoic acid) )], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid,
• the bleaching agent content of the compositions can be 1 to 40% by weight and in particular 10 to 20% Wt .-%, wherein advantageously perborate or tetrahydrate or Percarbonate is used.
• the bleaching agents which may be present can also serve as alkalizing agents, since many react alkaline in an aqueous medium. It has proven to be beneficial Use bleach in coated form. Dissolves during the washing process the coating on and releases the alkaline bleaching agent, whereby the step-wise increase in pH takes place according to the invention.
• the same coating materials can be used to coat the bleaching agents for coating the alkalizing agents.
• the application of the wrapping materials can also done in the same way.
• bleach activators can be incorporated.
• bleach activators can be compounds that are under perhydrolysis conditions aliphatic peroxocarboxylic acids with preferably 1 to 10 carbon atoms, in particular 2 up to 4 carbon atoms, and / or optionally substituted perbenzoic acid, be used.
• Substances containing O and / or N-acyl groups of the number of carbon atoms mentioned are suitable and / or optionally substituted benzoyl groups.
• Multiple are preferred acylated alkylenediamines, especially tetraacetylethylenediamine (TAED), acylated Triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), Carboxylic anhydrides, especially phthalic anhydride, acylated polyvalent Alcohols, especially triacet
• bleach catalysts can be included.
• These substances are bleach-enhancing transition metal salts or transition metal complexes such as for example Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
• Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands as well as Co, Fe, Cu and Ru amine complexes are suitable as bleaching catalysts, such compounds are preferably used which are described in DE 197 09 284 A1 are described.
• the washing and cleaning agent according to the invention can be used as a further conventional one Ingredients in particular enzymes, sequestering agents, electrolytes, and others Auxiliaries, such as optical brighteners, graying inhibitors, color transfer inhibitors, Foam regulators, additional bleach activators, colors and fragrances included.
• Enzymes that can be used in the agents come from the class of oxidases, Proteases, lipases, cutinases, amylases, pullulanases, cellulases, hemicellulases, Xylanases and peroxidases and mixtures thereof, for example proteases like BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Esperase® and / or Savinase®, amylases such as Termamyl®, Amylase-LT®, Maxamyl®, Duramyl® and / or Purafect® OxAm, lipases such as Lipolase®, Lipomax®, Lumafast® and / or Lipozym®, cellulases such as Celluzyme® and or Carezyme®.
• proteases like BLAP®, Optimase®, Opticlean®, Maxacal®, Maxapem®, Alcalase®, Es
• fungi or bacteria such as Bacillus subtilis, Bacillus licheniformis, Streptomyces griseus, Humicola lanuginosa, Humicola insolens, Pseudomonas pseudoalcaligenes or Pseudomonas cepacia obtained enzymatic active substances.
• the possibly Enzymes used can, as for example in the European Patent EP 0 564 476 or in international patent applications WO 94/23005 described, adsorbed on carriers and / or embedded in coating substances to protect them against premature inactivation. They are in the invention Detergents preferably in amounts up to 10 wt .-%, in particular from 0.2% by weight to 2% by weight, with particular preference against oxidative Degradation-stabilized enzymes are used.
• inventive Detergents a variety of other compounds are used, for example be called foam inhibitors, phosphonates, or optical brighteners.
• Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
• Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
• the foam inhibitors in particular silicone or paraffin-containing foam inhibitors, are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred. If the carrier substance of the foam inhibitor reacts alkaline in aqueous solution, it is an alkali carrier for the purposes of the invention, so this can be treated as described above and used as an alkalizing agent. Conversely, a foam inhibitor with an alkaline carrier in the sense of the invention should be delayed in solubility in order to maintain the required pH conditions at the start of the washing cycle.
• foam inhibitors acting carrier e.g. Use starch or cellulose derivatives.
• the salts of polyphosphonic acids are preferably the neutral ones Sodium salts of, for example, 1-hydroxyethane-1,1-diphosphonate, diethylene triamine pentamethylene phosphonate or ethylenediaminetetramethylenephosphonate in Amounts of 0.1 to 1.5 wt .-% used.
• the agents according to the invention can be used as optical brighteners Contain diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g.
• the agent according to the invention preferably contains from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight nonionic surfactants, 5 to 70% by weight builder materials, 1 to 40% by weight bleach, 1 to 10% by weight bleach activators, 0.1 to 5% by weight enzymes and from 1% by weight to 30 % By weight pH regulators (buffering agents), in addition other active ingredients, such as optical brighteners
• the agent according to the invention is used as So-called mild detergent or color detergent for washing delicate Textiles used especially at temperatures up to 40 ° C.
• a mild detergent preferably contains from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight nonionic surfactants, 5 to 70% by weight builder materials, 0.1 to 5% by weight enzymes and from 1% to 30% by weight pH regulators (buffering agents).
• Color detergents are characterized by the fact that they are especially the colors of protect delicate textiles and prevent staining.
• Color detergent preferably contain from 5 to 25% by weight of anionic surfactants, 1 to 25% by weight nonionic surfactants, 5 to 70% by weight builder materials, 0.1 to 5% by weight enzymes and from 1% by weight to 30% by weight pH regulators (buffering agents), in addition to others Active ingredients such as discoloration inhibitors.
• the detergents and cleaning agents according to the invention can be in liquid bisgel form and can also be used in solid form, solid aggregate states being preferred are.
• the agents can be in the form of powders, granules, extrudates or as Shaped bodies, so-called tablets, are present.
• the powders can be spray dried and in a manner known per se can be produced by simply mixing the powdered components.
• the agents are to have higher bulk densities, they are preferably in compact form.
• the compacts include e.g. B. the granules, extrudates and Molded body.
• the granules can be obtained by granulating the components in a variety of ways Detergents and cleaning agents industry usually used equipment become. For example, it is possible to close the rounders common in pharmacy use. The residence time of the granules is in such turntable apparatuses usually less than 20 seconds. Also conventional mixers and Mixed granulators are suitable for granulation. As a mixer, both High-intensity mixers (“high-shear mixer”) as well as normal mixers with less Orbital speeds are used.
• Suitable mixers are, for example Eirich® mixers of the R or RV series (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (Trademark of Lödige Maschinenbau GmbH, Paderborn) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).
• the dwell times of the Granules in the mixers are in the range of less than 60 seconds, with the Dwell time also depends on the speed of rotation of the mixer. Here the dwell times are reduced accordingly the faster the mixer runs.
• P refers the residence times of the granules in the mixer / rounder are less than one minute, preferably less than 15 seconds.
• dwell times of up to 20 minutes are set, dwell times below 10 minutes are preferred because of the economics of the process.
• the surfactant-containing granules are under pressure and compacted under the influence of shear forces and thereby homogenized and then discharged form-giving from the apparatus.
• the technically The most important press agglomeration processes are extrusion Roll compaction, pelleting and tableting.
• Press agglomeration processes used are extrusion, roller compacting and pelleting.
• the granules obtained can be powdered with an oil absorption component in order to further improve their processability and meterability.
• This final powdering step with a finely divided component binds the liquids to the surface of the granules so that the granules cannot clump together during storage.
• the oil absorption component should have an oil absorption capacity of at least 20g / 100g, more preferably at least 50g / 100g, preferably at least 80g / 100g, particularly preferably at least 120g / 100g and in particular at least 140g / 100g.
• the oil absorption capacity is a physical property of a substance that can be determined using standardized methods. For example, the British standard methods BS1795 and BS3483: Part B7: 1982 exist, both of which refer to the ISO 787/5 standard.
• a balanced sample of the substance in question is placed on a plate and refined flaxseed oil (density: 0.93 gcm -3 ) from a burette is added dropwise. After each addition, the powder is thoroughly mixed with the oil using a spatula, the addition of oil being continued until a paste of smooth consistency is obtained. This paste should flow or run without crumbling.
• the oil absorption capacity is now the amount of the added oil, based on 100g absorbent and is given in ml / 100g or g / 100g, whereby conversions about the density of the linseed oil are possible without any problems.
• the oil absorption component preferably has the smallest possible mean Particle size, since the active surface increases with decreasing particle size.
• Preferred Detergents and cleaning agents contain a component with one Oil absorption capacity of at least 20g / 100g, which has an average particle size of less than 50 microns, preferably less than 20 microns and especially less than 10 microns.
• a large number of substances are suitable as an oil absorption component.
• inorganic and organic substances that suffice have large oil absorption capacity.
• examples include finely divided substances that to be obtained by precipitation.
• silicates Use of aluminosilicates, calcium silicates, magnesium silicates and calcium carbonate.
• diatomaceous earth diatomaceous earth
• finely divided cellulose fibers or derivatives of these can be used in the context of the present invention.
• Preferred Detergents are characterized in that the component contained in them an oil absorption capacity of at least 20g / 100g is selected from silicates and / or aluminosilicates, in particular from the group of silicas and / or Zeolites.
• finely divided zeolites can be used, but also pyrogenic ones Silicas (Aerosil®) or silicas obtained by precipitation.
• a method for producing extrudates is preferred, in which a Premix made from detergent ingredients.
• This fixed preferred homogeneous premix is over using a plasticizer and / or lubricant Hole shapes with opening widths of the predetermined extrudate dimension at high Pressures between 25 and 200 bar extruded.
• the strand goes right after the exit from the hole shape by means of a cutting device to the predetermined Cut to size.
• the application of the high working pressure causes the Plasticizing the pre-mix during granulation and provides the cutting ability of the freshly extruded strands safely.
• the premix consists at least in part from solid, preferably finely divided common ingredients of washing and Detergents, to which liquid components may be added.
• the solid ingredients can, however, also tower powder obtained by spray drying Agglomerates, the selected mixture components as pure substances, which in the finely divided state are mixed together, as well as mixtures of these. Then the liquid ingredients are added and then optionally mixed with a plasticizer and / or lubricant.
• a plasticizer and / or lubricants are aqueous solutions of polymeric polycarboxylates as well highly concentrated anionic surfactant pastes and nonionic surfactants are preferred.
• Shaped bodies are produced in accordance with the state of the art Method. Usually the individual components, all or part can be pre-granulated, mixed dry and then shaped, in particular by pressing into tablets, using conventional methods can be used. For the production of moldings, the premix is in a so-called matrix between two stamps to form a solid compact condensed. This process, which is briefly referred to below as tabletting, is divided into four sections: dosing, compression (elastic deformation), plastic deformation and ejection.
• the premix is introduced into the die, the filling quantity and so that the weight and shape of the resulting molded body by the position of the lower stamp and the shape of the press tool can be determined.
• the constant dosing is preferred, even with high molding throughputs achieved by volumetric metering of the premix.
• the upper plunger touches the premix when tabletting and descends further of the lower stamp. With this compression, the particles of the premix pressed closer together, the void volume inside the filling between the stamps decreases continuously. From a certain position of the The upper stamp (and thus from a certain pressure on the premix) begins plastic deformation, in which the particles flow together and it to form the Shaped body comes.
• the premixed particles are crushed and it comes at even higher pressures to sinter the premix.
• the phase of elastic deformation is shortened more and more, so that the resulting shaped bodies have more or less large cavities can.
• the finished molded body is removed by the Lower stamp pressed out of the die and by subsequent ones Transport equipment transported away. At this point, only the weight of the Shaped body finally determined because the compacts due to physical processes (Stretching, crystallographic effects, cooling etc.) their shape and size still can change.
• Tableting takes place in commercially available tablet presses, which are basically or double stamps can be equipped. In the latter case, not only Upper stamp used to build up pressure, the lower stamp also moves during of the pressing process towards the upper punch, while the upper punch is down presses.
• Eccentric tablet presses are preferred for small production quantities used, in which the stamp or stamps are attached to an eccentric, the in turn is mounted on an axis with a certain rotational speed. The Movement of this ram is with the operation of a conventional reciprocating piston engine comparable. The pressing can be done with an upper and lower stamp However, several stamps can also be attached to an eccentric disc, the Number of die holes has been expanded accordingly.
• the throughputs of Eccentric presses vary from a few hundred to a maximum of 3000 tablets depending on the type per hour.
• rotary tablet presses are selected, on which one so-called die table a larger number of dies is arranged in a circle.
• the number of matrices varies between 6 and 55, depending on the model, with larger ones Matrices are commercially available.
• Each die on the die table is a top and Lower stamp assigned, whereby again the pressure is active only by the upper or lower stamp, but can also be built up by both stamps.
• the Matrix table and the stamp move around a common vertical Axis, the stamp with the help of rail-like cam tracks during circulation in the positions for filling, compression, plastic deformation and discharge to be brought.
• the stamp is necessary (filling, compacting, ejecting), these will be Curved tracks by additional low pressure pieces, low tension rails and Lifting lanes supported.
• the matrix is filled with a rigid one arranged feed device, the so-called filling shoe, which with a Storage container for the premix is connected.
• the pressure on the premix is individually adjustable via the press paths for upper and lower punches, whereby the Pressure build-up by rolling the stamp shaft heads past adjustable ones Print rolls happen.
• Rotary presses can also be used with two filling shoes to increase the throughput be provided, with only a semicircle to produce a tablet must be gone through.
• For the production of two- and multi-layer moldings several filling shoes arranged one behind the other without the slightly pressed first Layer is ejected before further filling. Through suitable process control In this way, coated and dot tablets can also be produced have onion-shell-like structure, with the top in the case of the point tablets the core or core layers is not covered and thus remains visible.
• Rotary tablet presses can be equipped with single or multiple tools, see above that, for example, an outer circle with 50 and an inner circle with 35 holes can be used for pressing at the same time. The throughputs are more modern Rotary tablet presses are over one million tablets per hour.
• stamps known non-stick coatings.
• Plastic coatings plastic inserts or plastic stamps.
• spinning Stamps have proven to be advantageous, with upper and Lower stamp should be made rotatable.
• rotating stamps one can Plastic inserts are usually dispensed with.
• stamp surfaces be electropolished.
• the compression is usually carried out at pressures from 0.01 to 50 kNcm -2 , preferably from 0.1 to 40 kNcm -2 and in particular from 1 to 25 kNcm -2 .
• Suitable tableting machines are available, for example, from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA packaging systems GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
• Other providers include Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
• the hydraulic double pressure press HPF is particularly suitable 630 from LAEIS, D.
• Tableting tools are, for example, from the companies Adams tableting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
• Other providers are e.g. Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
• the moldings can be in a predetermined spatial shape and a predetermined size are manufactured, whereby they always consist of several phases, i.e. Layers, inclusions or cores and rings. Practically all of them come in useful form manageable configurations, for example the training as Blackboard, the shape of bars or bars, cubes, cuboids and corresponding room elements flat side surfaces and in particular cylindrical configurations with circular or oval cross section.
• This last embodiment covers the Presentation form from tablets to compact cylinder pieces with one Ratio of height to diameter above 1.
• the portioned compacts can each be separated Individual elements can be formed which correspond to the predetermined dosage of the washing and / or detergent. But it is also possible to use compacts to train that connect a plurality of such mass units in a compact, the ease of separation, in particular by predetermined breaking points portioned smaller units is provided.
• the formation of the portioned compacts as tablets in the shape of a cylinder or cuboid be appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
• Commercial hydraulic presses, eccentric presses or Rotary presses are suitable devices, particularly for manufacturing such compacts.
• the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the moldings can be dosed directly into the induction chamber without a dosing aid, where it dissolves during the induction process.
• a dosing aid for example, a dosing aid is also a Use of the detergent tablets.
• Another preferred multi-phase molded body that can be produced has a plate or plate-like structure with alternating thick long and thin short Segments, so that individual segments from this "multiphase bar" to the Predetermined breaking points, which represent the short thin segments, broken off and into the Machine can be entered.
• This principle of the "bar-shaped" Molded detergent can also be in other geometric shapes, for example vertically standing triangles that are only along one side on the other connected, can be realized.
• Triangular base that connects the individual segments together as one phase form while the triangle tip forms the second phase. A different one Staining of both phases is particularly attractive in this embodiment.
• the detergent tablets After pressing, the detergent tablets have a high Stability on.
• the detergent tablets can be packaged after production, the use of certain packaging systems having proven particularly useful, since these packaging systems on the one hand increase the storage stability of the ingredients, and on the other hand surprisingly also significantly improve the long-term adhesion of the tray filling.
• the detergent tablets are combined with a packaging system containing the detergent tablet or tablets, the packaging system having a moisture vapor permeability rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day if the packaging system is stored at 23 ° C and a relative equilibrium humidity of 85%.
• the packaging system of the combination of detergent tablets (s) and packaging system preferably has a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is at 23 ° C and a relative Equilibrium moisture of 85% is stored.
• the specified temperature and humidity conditions are the test conditions that are mentioned in the DIN standard 53122, whereby according to DIN 53122 minimal deviations are permitted (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
• the moisture vapor permeability rate of a given packaging system or material can be determined according to further standard methods and is, for example, also in the ASTM standard E-96-53T ("Test for measuring Water Vapor transmission of Materials in Sheet form") and in the TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at high temperature an Humidity").
• the measuring principle of current methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container being closed at the top with the material to be tested.
• the moisture vapor permeability rate can be determined from the surface of the container which is closed with the material to be tested (permeation surface), the weight gain of the calcium chloride and the exposure time calculate, where A is the area of the material to be tested in cm 2 , x is the weight gain of calcium chloride in g and y is the exposure time in h.
• the relative equilibrium humidity is 85% at 23 ° C. when measuring the moisture vapor transmission rate in the context of the present invention.
• the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is given in g / m 3 .
• saturation content For example, 1 m 3 of air at 17 ° is saturated with 14.4 g of water vapor; at a temperature of 11 ° there is saturation with just 10 g of water vapor.
• the relative humidity is the ratio of the actual water vapor content to the saturation content corresponding to the prevailing temperature.
• the relative equilibrium humidity of 85% at 23 ° C can be found, for example, in Laboratory chambers with humidity control to +/- 2% RH depending on the device type. I agree to adjust. Even over saturated solutions of certain salts form in closed systems at a given temperature constant and well defined relative air humidity based on the phase balance between partial pressure of water, saturated solution and soil body.
• Combinations of detergent tablets and packaging system can of course in turn in secondary packaging, for example Cardboard boxes or trays, are packed, but none of the secondary packaging further requirements must be made.
• the secondary packaging is accordingly possible but not necessary.
• Packaging systems preferred in the context of the present invention have a moisture vapor permeability rate of 0.5 g / m 2 / day to less than 15 g / m 2 / day.
• the packaging system encloses one or several detergent tablets. It is preferred either to design a shaped body so that it is an application unit of the washing and Detergent includes, and to package this molding individually, or the number to pack in a packaging unit, the sum of one Application unit includes. With a nominal dosage of 80 g washing and So it is possible to use a detergent and an 80 g detergent Produce detergent tablets and pack them individually, but it is also possible, two 40 g heavy detergent tablets in one Pack packaging to get a combination. This principle leaves expand naturally, so that combinations also three, four, five or even more more detergent tablets in one packaging unit can. Of course, two or more molded articles can be in one package have different compositions. In this way it is possible to separate certain components from each other, for example To avoid stability problems.
• the packaging system described above can be of the most varied Materials exist and take on any external shape. From economic However, there are reasons and reasons of easier processing Preferred packaging systems where the packaging material is low Weight, easy to work with and inexpensive. In preferred combinations the packaging system consists of a sack or bag made of single-layer or laminated paper and / or plastic film.
• the detergent tablets can be unsorted, i.e. as loose Fill, be filled into a bag from the materials mentioned. But it is for aesthetic reasons and to sort the combinations in Secondary packaging preferred, the detergent tablets individually or to fill several in sacks or bags.
• the term "flow pack” has become common in technology. Such "flow packs” can then - again preferably sorted - optionally in Outer packaging can be packed, which is the compact offer form of the molded body underlines.
• the sacks or bags made of single-layer or laminated paper or plastic film which are preferably to be used as a packaging system, can be designed in a wide variety of ways, for example as a blown-up bag without a central seam or as a bag with a central seam which is sealed by heat (hot fusion), adhesives or adhesive tapes become.
• Single-layer bag or sack materials are the known papers, which may or may not be impregnated, and plastic films, which may or may not be co-extruded.
• Plastic films that can be used as a packaging system in the context of the present invention are specified , for example, in Hans Domininghaus "The plastics and their properties", 3rd edition, VDI Verlag, Düsseldorf , 1988, page 193 .
• Figure 111 shown there also provides information on the water vapor permeability of the materials mentioned.
• packaging system features always the primary packaging of the Molded articles, i.e. the packaging that is directly on the inside with the Molded surface is in contact.
• An optional secondary packaging no requirements, so here all the usual materials and systems can be used.
• the detergent tablets contain molded articles the combination described depending on its intended use other ingredients of detergents and cleaning agents in varying amounts. Independent of Purpose of use of the moldings, it is preferred that the washing or washing and Detergent tablets have a relative equilibrium moisture content of less than 30% at 35 ° C.
• the relative equilibrium moisture content of the detergent tablets can are determined according to common methods, whereby within the scope of the present Investigations following procedure was chosen: A water impermeable 1 liter container with a lid, which has a closable opening for insertion of samples, was washed with a total of 300 g Detergent tablets filled and kept at a constant 23 ° C for 24 h to ensure uniform temperature of the vessel and substance. The Water vapor pressure in the room above the molded body can then be measured with a hygrometer (Hygrotest 6100, Testoterm Ltd., England). The water vapor pressure is now measured every 10 minutes, until two successive values none Show deviation (equilibrium moisture). The above Hygrometer allows one direct display of the recorded values in% relative humidity.
• packaging system is resealable.
• Combinations where the Packaging system has a microperforation can be realized with preference.
• Detergents with the composition shown in Table 1 were produced.
• component Quantity /% by weight C 12 -C 18 alkyl benzene sulfonate 11.58 C 12 -C 18 alkyl sulfate 3.17 Texapon Z 65 0.79 C 12/18 fatty alcohol x 7 EO 3.88 Tallow alcohol x 5 EO 0.59 Na stearate 0.60 Aerosil 8.03 Sodium sulfate 8.03 Sokalan CP 5 1.41 Na percarbonate 13.75 Stearic acid 0.35 Zeolite A 22.58 Polyvinyl alcohol 2.99 Hydroxyethyl diphosphonate 0.69 Sodium citrate 6.68 Citric acid 1.17 TAED 6.44 enzyme 1.54 water ad 100
• Standard fabrics were provided with standard soiling and washed in a Miele Novotronic W 918 household washing machine with a dosage of 81.5 g / wash load, 18 l of water, a load of 3.5 kg of dry laundry and a water hardness of 15 dH at 30 ° C.
• the reflectance values obtained are shown in Table 2.
• the following soiling was examined: Bleachable soiling: JB Currant juice on cotton TB Tea on cotton BB B Blueberry on cotton RB Red wine on cotton Enzymatic soiling: BMT Blood / milk / ink on cotton BMR Blood / milk / soot on cotton BLB Blood on cotton

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• 1999
  • 1999-11-26 DE DE1999157038 patent/DE19957038A1/de not_active Ceased
• 2000
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