EP1451280B1 - Tensidgranulate und verfahren zur herstellung von tensidgranulaten - Google Patents

Tensidgranulate und verfahren zur herstellung von tensidgranulaten Download PDF

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Publication number
EP1451280B1
EP1451280B1 EP02804199A EP02804199A EP1451280B1 EP 1451280 B1 EP1451280 B1 EP 1451280B1 EP 02804199 A EP02804199 A EP 02804199A EP 02804199 A EP02804199 A EP 02804199A EP 1451280 B1 EP1451280 B1 EP 1451280B1
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Prior art keywords
weight
acid
acids
sodium
composition
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German (de)
English (en)
French (fr)
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EP1451280A2 (de
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Bernhard Orlich
Wilfried Rähse
Hans-Friedrich Kruse
Gerhard Blasey
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/0082—Special methods for preparing compositions containing mixtures of detergents one or more of the detergent ingredients being in a liquefied state, e.g. slurry, paste or melt, and the process resulting in solid detergent particles such as granules, powders or beads
    • 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
    • C11D11/00—Special methods for preparing compositions containing mixtures of detergents
    • C11D11/04—Special methods for preparing compositions containing mixtures of detergents by chemical means, e.g. by sulfonating in the presence of other compounding ingredients followed by neutralising
    • 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

Definitions

  • the present invention relates to a process for the preparation of surfactant granules and to specific surfactant granules.
  • it relates to a process which makes it possible to produce easily soluble surfactant granules or detergent and cleaner compositions in a cost-optimized manner.
  • anionic surfactants fall in the course of the manufacturing process in their acid form and must be converted with suitable neutralizing agents in their alkali or alkaline earth metal salts.
  • This neutralization step can be carried out with solutions of alkali metal hydroxides or else with solid alkaline substances, in particular sodium carbonate.
  • the surfactant salts are obtained in the form of aqueous formulations, wherein water contents in the range of about 10 to 80 wt .-% and in particular in the range of about 35 to 60 wt .-% are adjustable. Products of this type have at room temperature paste-like to cuttable nature, the flowability and pumpability of such pastes is already limited in the range of about 50 wt .-% of active substance or even lost, so that in the further processing of such pastes, especially when incorporated into solid mixtures For example, in solid detergents and cleaners, considerable problems arise.
  • anionic detergent surfactants in a dry, in particular free-flowing form.
  • FAS fatty alcohol sulfates
  • anionic fat-chemical surfactant compounds include the known sulfofatty acid methyl esters (fatty acid methyl ester sulfonates, MES), by ⁇ -sulfonation of methyl esters of fatty acids of vegetable or animal origin having predominantly 10 to 20 carbon atoms in the fatty acid and subsequent neutralization to water-soluble mono-salts, in particular the corresponding alkali metal salts.
  • MES fatty acid methyl ester sulfonates
  • European patent application EP-A-0 678 573 (Procter & Gamble) describes a process for producing free-flowing surfactant granules having bulk densities above 600 g / l in which anionic surfactant acids with an excess of neutralizing agent form a paste containing at least 40% by weight of surfactant be reacted and this paste with one or more powder (s), at least one of which must be spray-dried and contains the anionic polymer and cationic surfactant is mixed, wherein the resulting granules can be optionally dried.
  • this document reduces the proportion of spray-dried granules in the detergents and cleaners, but does not completely avoid the spray-drying.
  • European Patent Application EP-A-0 438 320 discloses a batch process for the preparation of surfactant granules having bulk densities above 650 g / l.
  • a solution of an alkaline inorganic substance in Water is added with the addition of other solids with the Anionentensidklare and granulated in a high-speed mixer / granulator with a liquid binder.
  • neutralization and granulation occur in the same apparatus, but in separate process steps, so that the process can be operated nurchargenweise.
  • European patent application EP-A-0 402 112 discloses a continuous neutralization / granulation process for producing FAS and / or ABS granules from the acid in which the ABS acid is at least 62% pure NaOH is neutralized and then granulated with the addition of auxiliaries, for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000.
  • auxiliaries for example ethoxylated alcohols or alkylphenols or a above 48.9 ° C melting polyethylene glycol having a molecular weight between 4000 and 50,000.
  • European Patent Application EP-A-0 508 543 discloses a process in which a surfactant acid is neutralized with an excess of alkali to form an at least 40 wt% surfactant paste, which is subsequently conditioned and granulated, with a Direct cooling with dry ice or liquid nitrogen takes place.
  • the liquid surfactant mixtures disclosed in this document contain sodium or potassium salts of alkylbenzenesulfonic acids or alkylsulfuric acids in amounts of up to 80% by weight, ethoxylated nonionic surfactants in amounts of up to 80% by weight and at most 10% by weight of water.
  • the surfactant mixtures to be sprayed contain between 40 and 92% by weight of a surfactant mixture and more than 8 to at most 60% by weight of water.
  • the surfactant mixture is in turn at least 50% of polyalkoxylated nonionic surfactants and ionic surfactants.
  • a process for producing a liquid surfactant mixture from the three components anionic surfactant, nonionic surfactant and water is described in EP 507 402 (Unilever).
  • the surfactant blends disclosed herein, which are said to contain little water, are prepared by combining equimolar amounts of neutralizing agent and anionic surfactant acid in the presence of nonionic surfactant.
  • German laid - open specification DE-A-42 32 874 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of anionic surfactants in their acid form.
  • the neutralizing agent there are disclosed solid powdery substances, especially sodium carbonate, which reacts with the anionic surfactant acids to form anionic surfactant, carbon dioxide and water.
  • the granules obtained have surfactant contents of about 30% by weight and bulk densities of less than 550 g / l.
  • the European patent application EP 642 576 (Henkel KGaA) describes a two-stage granulation in two successive mixers / granulators, wherein in a first, low-speed granulator 40-100 wt .-%, based on the total amount of the ingredients used, the solid and liquid components vorgranuliert and in a second, high-speed granulator, the pregranulate is optionally mixed with the remaining ingredients and transferred into a granule.
  • German Offenlegungsschrift DE-A-43 14 885 discloses a process for preparing washing and cleaning-active Anionentensidgranulate by neutralization of the acid form of anionic surfactants with a basic compound, wherein the hydrolysis-sensitive acid form of a hydrolysis-sensitive anionic surfactant with the neutralizing agent without release is converted by water.
  • the neutralizing agent used is sodium carbonate, which reacts in this process to form sodium bicarbonate.
  • German laid-open specification DE-A-39 30 791 discloses a detergent containing, for example, 7% by weight of Na dodecylbenzenesulfonate, 10% by weight of C 12 -C 18 fatty acid Na salt, 30% by weight of Na carbonate and 10% by weight. %. Sodium bicarbonate.
  • the process to be provided should also allow the direct and economically attractive processing of the acid forms of detergent raw materials, but to the greatest possible extent avoid the disadvantage of energy-consuming evaporation of water.
  • the bulk densities of the granules to be produced should be variable within wide limits, and it was a particular object of the present invention to be able to achieve the low bulk densities of conventional spray-drying products by means of a non-tower process.
  • the solubilities of the process end products should also be equal or superior to the end products of the processes known from the prior art.
  • the present invention in a first embodiment is an agent containing the neutralized form of an anionic surfactant acid and sodium carbonate and sodium bicarbonate containing the neutralized form of fatty acids, wherein the ratio of anionic surfactant to side is 10/1 to 20/1 and the ratio of weight average is 5: 1 to 2: 1 proportions of sodium carbonate to the weight percent of sodium bicarbonate contained in the middle.
  • the reaction between anionic surfactant acid (s) and sodium carbonate is conducted so that the reaction Na 2 CO 3 + 2 anionic surfactant H ⁇ 2 anionic surfactant Na + CO 2 + H 2 O is largely suppressed and in their place the reaction Na 2 CO 3 + anionic surfactant H ⁇ anionic surfactant Na + NaHCO 3 entry.
  • the sodium carbonate is used here in excess, so that unreacted sodium carbonate remains in the product, while sodium bicarbonate is additionally formed in the reaction.
  • the amount of sodium carbonate on average (based on the agent, without taking into account any existing Hydratwassergehalte) is set to the amount of sodium bicarbonate on average (based on the agent, without taking into account any water of hydration content) in accordance with the invention and 5: 1 to 2: 1 be.
  • 2 to 5 grams of Na 2 CO 3 are contained per gram of NaHCO 3 contained in the compositions according to the invention.
  • the mass ratio of sodium carbonate to sodium bicarbonate is within narrower limits, with preferred agents being characterized in that the weight ratio of sodium carbonate to sodium bicarbonate is 4.5: 1 to 2: 1, preferably 4: 1 to 2.1: 1, more preferably 3.5: 1 to 2.2: 1, and especially 3.25: 1 to 2.25: 1.
  • the content of the inventive compositions of sodium bicarbonate may vary.
  • the content of the agent of sodium hydrogencarbonate is 0.5 to 20% by weight, preferably 1 to 15% by weight, particularly preferably 2.5 to 12.5% by weight and in particular 3 to 10% by weight. -%, in each case based on the weight of the agent.
  • the neutralized form of the anionic surfactant acids in short the anionic surfactants, can also be present in varying amounts in the compositions according to the invention.
  • Suitable anionic surfactant acids are all acids known from the prior art. These are described in detail below.
  • Preferred agents according to the invention contain the neutralized form of the acids used in amounts of from 10 to 50% by weight, preferably from 15 to 45% by weight, particularly preferably from 20 to 40% by weight and in particular from 25 to 30% by weight, in each case based on the weight of the agent.
  • compositions of the invention may contain other ingredients. These may either have been part of the solid bed or of the anionic surfactant component prior to the neutralization reaction.
  • additional acidic components such as phosphonic acids, whose neutralizates act as complexing agents, is preferred for the anionic surfactant acids.
  • compositions according to the invention can have different bulk densities. Preference is given to compositions according to the invention whose apparent density is from 300 to 800 g / l, preferably from 350 to 650 g / l and in particular from 400 to 500 g / l.
  • the agents according to the invention are preferably low in water.
  • Preferred agents according to the invention are characterized in that the water content of the agents determined by drying loss at 120 ° C, ⁇ 15 wt .-%, preferably ⁇ 10 wt .-%, particularly preferably ⁇ 5 wt .-% and in particular ⁇ 2.5 wt .-%, is.
  • the neutralization reaction between the / the Aniotensidklare (n) and the sodium carbonate is conducted so that the formation of water and carbon dioxide is suppressed and the formation of sodium bicarbonate is promoted.
  • the reaction of the sodium carbonate "at least partially to sodium bicarbonate" to understand that on the one hand at least a portion of the sodium carbonate ever reacted to sodium bicarbonate, on the other hand, the proportion of reacting sodium carbonate, which does not react to sodium bicarbonate, is minimized.
  • "at least partially” means that a certain amount of sodium carbonate must react at all to sodium bicarbonate (otherwise the definition of Na 2 CO 3 / NaHCO 3 ratio would be nonsense), but on the other hand, that for the same reasons unreacted sodium carbonate in the Product is available.
  • the proportion of sodium carbonate, which indeed reacts, but forms no sodium bicarbonate in the reaction should be as low as possible.
  • at least 70%, preferably at least 80%, more preferably at least 90% and in particular the total amount of reacting sodium carbonate is converted to sodium bicarbonate.
  • the proportion of reacting sodium carbonate can be determined by stoichiometric calculation of the amount of anionic acid used. Alternatively, from the formation of carbon dioxide and its quantitative determination, the proportion of "incorrectly" reacting sodium carbonate can be measured.
  • the water content of the process end products, determined by drying loss at 120 ° C, according to the invention is ⁇ 15 wt.%, Preferably ⁇ 10 wt.%, Particularly preferably ⁇ 5 wt .-% and in particular ⁇ 2.5 wt .-%.
  • the low-water process procedure to ensure the desired reaction to sodium bicarbonate is preferred.
  • the raw materials used should therefore be used as far as possible dry, dry or water-poor.
  • the anionic surfactant acids preferably the highest possible concentrations are to be selected according to the invention, as long as the technical process control (agitation of the anionic surfactant acid and application to the sodium carbonate) is perfectly guaranteed.
  • Another way to promote the formation of sodium bicarbonate and to avoid the formation of carbon dioxide and water is to maintain the lowest possible temperatures. This can be achieved, for example, by cooling, but also by suitable process control or the coordination of the amounts of the reactants.
  • Processes according to the invention are characterized in that the reactants are used in amounts relative to one another such that in the process end products the ratio of the proportions by weight of sodium carbonate to sodium bicarbonate is 2: 1 or more. Preferably, this weight ratio is within narrower limits, so that preferred methods are characterized in that the weight ratio of sodium carbonate to sodium bicarbonate in the process end products 50: 1 to 2: 1, preferably 40: 1 to 2.1: 1, particularly preferably 35: 1 to 2.2: 1 and in particular 30: 1 to 2.25: 1.
  • Very particularly preferred process end products of The method according to the invention are the agents according to the invention described above.
  • processes according to the invention are particularly preferred which are characterized in that the weight ratio of sodium carbonate to sodium bicarbonate in the process end products is 5: 1 to 2: 1, preferably 4.5: 1 to 2: 1, particularly preferably 4: 1 to 2 , 1: 1, more preferably 3.5: 1 to 2.2: 1, and especially 3.25: 1 to 2.25: 1.
  • compositions according to the invention certain contents of sodium carbonate, sodium bicarbonate and anionic surfactants may also be preferred for the end products of the process according to the invention.
  • the above-mentioned% by weight statements also apply to the process end products.
  • processes according to the invention are preferred in which the content of the process end products of sodium hydrogencarbonate is from 0.5 to 20% by weight, preferably from 1 to 15% by weight, particularly preferably from 2.5 to 12.5% by weight and in particular 3 to 10 wt .-%, each based on the weight of the final process products, is.
  • the process of the invention is based on the reaction of anionic surfactant acids with solid neutralizing agents.
  • anionic surfactant acids with solid neutralizing agents.
  • anionic surfactant acid and sodium carbonate are reacted with each other.
  • other substances may also be present in the reaction mixture which may or may not be involved in the reaction.
  • reactive or inert species may be admixed with either the sodium carbonate or the anionic surfactant acid (s) prior to the reaction; Alternatively, both reactants may contain other reactive or inert ingredients.
  • excipients which do not take part in the reaction may also be added to the sodium carbonate. These should then have sufficient stability against the added acids in order to avoid local decomposition and thus unwanted discoloration or other contamination of the product.
  • the sodium carbonate or the mixture of sodium carbonate and further additives is mixed with agitation with at least one anionic surfactant acid.
  • anionic surfactants in acid form are one or more substances from the group of carboxylic acids, sulfuric acid half esters and sulfonic acids, preferably from the group of fatty acids, fatty alkyl sulfuric acids and alkylaryl sulfonic acids.
  • the compounds mentioned should have longer-chain hydrocarbon radicals, ie at least 6 carbon atoms in the alkyl or alkenyl radical.
  • the C chain distributions of the anionic surfactants are in the range of 6 to 40, preferably 8 to 30 and especially 12 to 22 carbon atoms.
  • Preferred processes according to the invention are characterized in that one or more substances from the group of the carboxylic acids, the sulfuric monoesters and the sulfonic acids, preferably from the group of the fatty acids, the fatty alkyl sulfuric acids and the alkylaryl sulfonic acids, are used as anionic surfactant in acid form. These are described below.
  • Carboxylic acids which are used in the form of their alkali metal salts as soaps in detergents and cleaners, are obtained industrially, for the most part, from native fats and oils by hydrolysis. While the alkaline saponification already carried out in the last century led directly to the alkali salts (soaps), today becomes industrial scale For cleavage only water is used, which splits the fats into glycerine and the free fatty acids. Examples of industrially applied processes are the autoclave cleavage or continuous high pressure cleavage.
  • hexanoic acid caproic acid
  • heptanoic acid enanthic acid
  • octanoic acid caprylic acid
  • nonanoic acid pelargonic acid
  • decanoic acid capric acid
  • undecanoic acid etc.
  • fatty acids such as dodecanoic acid (lauric acid), tetradecanoic acid (myristic acid), hexadecanoic acid (palmitic acid), octadecanoic acid (stearic acid), eicosanoic acid (arachidic acid), docosanoic acid (behenic acid), tetracosanic acid (lignoceric acid), hexacosanoic acid (cerotic acid), triacotanoic acid (melissic acid) and unsaturated secies 9c-hexadecenoic acid (palmitoleic acid), 6c-octadecenoic acid (petroselinic acid), 6t-octadecenoic acid (petroselaidic acid), 9c-octadecenoic acid (oleic acid), 9t-octadecenoic acid ((elaidic acid), 9c, 12c-oc
  • Such mixtures are for example coconut oil (about 6 wt .-% C 8 , 6 wt .-% C 10 , 48 wt .-% C 12 , 18 wt .-% C 14 , 10 wt .-% C 16 , 2 wt % C 18 , 8% by weight C 18 ' , 1% by weight C 18 ..), palm kernel oil fatty acid (about 4% by weight C 8 , 5% by weight C 10 , 50% by weight).
  • % C 16 ' 1 wt% C 17 , 2 wt% C 18 , 70 wt% C 108' , 10 wt% C 18 " , 0.5 wt% C 18"' technical palmitic / stearic acid (about 1% by weight C 12 , 2% by weight C 14 , 45% by weight C 16 , 2% by weight C 17 , 47% by weight C 18 , 1 % By weight C 18 ' ) and soybean oil fatty acid (about 2% by weight C 14 , 15 g % by wt. C 16 , 5 wt.% C 18 , 25 wt.% C 18 , 45 wt.% C 18 " , 7 wt.% C 18"' ).
  • Sulfuric acid semi-esters of relatively long-chain alcohols are likewise anionic surfactants in their acid form and can be used in the context of the process according to the invention.
  • Their alkali metal, in particular sodium salts the fatty alcohol sulfates are industrially available from fatty alcohols, which with sulfuric acid, chlorosulfonic acid, sulfamic acid or Sulfur trioxide are reacted to the respective alkyl sulfuric acids and subsequently neutralized.
  • the fatty alcohols are thereby obtained from the relevant fatty acids or fatty acid mixtures by high-pressure hydrogenation of fatty acid methyl esters.
  • alkylsulfuric acids The quantitatively most important industrial process for the production of fatty alkylsulfuric acids is the sulfation of the alcohols with SO 3 / air mixtures in special cascade, falling film or tube bundle reactors.
  • anionic surfactant acids which can be used in the process according to the invention are the alkyl ether sulfuric acids whose salts, the alkyl ether sulfates, are characterized by a higher water solubility and lower sensitivity to water hardness (solubility of the Ca salts) compared to the alkyl sulfates.
  • Alkyl ether sulfuric acids like the alkyl sulfuric acids, are synthesized from fatty alcohols which are reacted with ethylene oxide to give the fatty alcohol ethoxylates in question. Instead of ethylene oxide, propylene oxide can also be used. The subsequent sulfonation with gaseous sulfur trioxide in short-term sulfonation reactors yields over 98% of the relevant alkyl ether sulfuric acids.
  • Alkane sulfonic acids and olefin sulfonic acids can also be used in the context of the present invention as anionic surfactants in acid form.
  • Alkanesulfonic acids may contain the sulfonic acid group terminally bound (primary alkanesulfonic acids) or along the C chain (secondary alkanesulfonic acids), with only the secondary alkanesulfonic acids having commercial significance. These are prepared by sulfochlorination or sulfoxidation of linear hydrocarbons.
  • alkanesulfonic acids Another process for producing alkanesulfonic acids is sulfoxidation in which n-paraffins are reacted with sulfur dioxide and oxygen under UV light irradiation.
  • This radical reaction produces successive alkylsulfonyl radicals, which react further with oxygen to form the alkylsulfonyl radicals.
  • the unreacted paraffin reaction yields an alkyl radical and the alkylpersulfonic acid which is converted to an alkyl peroxysulfonyl radical and a hydroxyl radical decomposes.
  • the reaction of the two radicals with unreacted paraffin provides the alkylsulfonic acids or water, which reacts with alkylpersulfonic acid and sulfur dioxide to form sulfuric acid.
  • this reaction is usually carried out only up to degrees of conversion of 1% and then terminated.
  • Olefinsulfonates are produced industrially by reaction of ⁇ -olefins with sulfur trioxide. Intermediate zwitterions form, which cyclize to form so-called sultones. Under suitable conditions (alkaline or acid hydrolysis), these sultones react to give hydroxylalkanesulfonic acids or alkensulfonic acids, both of which can likewise be used as anionic surfactant acids.
  • Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
  • petroleum fractions are separated on a large scale with molecular sieves in the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
  • the resulting olefins are then reacted in the presence of acidic catalysts with benzene to the alkylbenzenes, the choice of the Friedel-Crafts catalyst has an influence on the isomer distribution of the resulting linear alkylbenzenes:
  • the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5- and other isomers at about 30 wt.%
  • hydrogen fluoride is used as the catalyst, the content of 2-phenyl isomer can be reduced to about 20 wt .-%.
  • alkylbenzenesulfonates By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred in this case to prepare and use the alkali metal salts and, among these, preferably the sodium salts of ABSS. These can be described by the general formula I: in which the sum of x and y is usually between 5 and 13. Processes according to the invention in which C 8-16 , preferably C 9-13, alkylbenzenesulfonic acids are used as the anionic surfactant in acid form, are preferred.
  • C 8-16 preferably C 9-13 , alkylbenzenesulfonic acids derived from alkylbenzenes which have a tetralin content of less than 5% by weight, based on the alkylbenzene.
  • alkylbenzenesulfonic whose alkylbenzenes were prepared by the HF process, so that the C 8-16 -, preferably C 9-13- alkylbenzenesulfonic used a content of 2-phenyl isomer below 22 wt .-%, based to the alkylbenzenesulfonic acid.
  • anionic surfactants in their acid form may be used alone or in admixture with each other in the process of the present invention.
  • the anionic surfactant in acid form before addition to the / the solid neutralizing agent (s) further, preferably acidic, ingredients of detergents and cleaning agents in amounts of 0.1 to 40 wt.%, Preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing mixture, are admixed.
  • Suitable acid reactants in the context of the present invention are, in addition to the "surfactant acids", the fatty acids, phosphonic acids, polymer acids or partially neutralized polymer acids and “builder acids” and complex builders “alone and in any desired mixtures
  • acidic detergents and cleansing ingredients for example phosphonic acids, which in neutralized form (phosphonates) as incrustation inhibitors are part of many detergents and cleaners, are particularly suitable
  • acid-stable ingredients with the anionic surfactant acid, for example so-called small components, which otherwise are added in complicated further steps en would have, so for example, optical brighteners, dyes, etc., in which case the acid stability is to be checked.
  • the anionic surfactant in acid form nonionic surfactants in amounts of 0.1 to 40 wt .-%, preferably from 1 to 15 wt .-% and in particular from 2 to 10 wt .-%, each based on the weight of the anionic surfactant acid-containing Mixture, mixed.
  • This addition can improve the physical properties of the anionic surfactant-containing mixture and make subsequent incorporation of nonionic surfactants into the surfactant granules or the entire detergent and cleaning agent superfluous.
  • the temperature of the mixture to be applied as low as possible is.
  • the anionic surfactant acids have a temperature of from 15 to 70.degree. C., preferably from 20 to 60.degree. C., particularly preferably from 25 to 55.degree. C. and in particular from 40 to 50.degree. C., when added to the solid bed , Analogously, it is also preferred that the solid bed has the lowest possible temperature. Preference is given here to temperatures between 0 and 30 ° C., preferably between 5 and 25 ° C. and in particular between 10 and 20 ° C.
  • the process according to the invention can be carried out in all devices in which neutralization with simultaneous granulation can be carried out.
  • Examples of this are mixers and granulators, in particular granulators of the type Turbo dryer® (device from Vomm, Italy).
  • mixer granules can be carried out in a variety of conventional mixing and granulating.
  • Mixers suitable for carrying out the process according to the invention are, for example, Eirich® mixers of the R or RV series (trademark of the Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixers (trademarks 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 KT (trademark of Drais-Werke GmbH, Mannheim).
  • the process according to the invention in a low-speed mixer / granulator at peripheral speeds of the tools of 2 m / s to 7 m / s.
  • the process can be carried out in a high-speed mixer / granulator at peripheral speeds of 8 m / s to 35 m / s.
  • a liquid granulation assistant in the present case the anionic surfactant acid (s) with optionally contained additives
  • a liquid granulation assistant in the present case the anionic surfactant acid (s) with optionally contained additives
  • a first, low-speed mixer / granulator on a moving solid bed sodium carbonate in the process according to the invention with optional other ingredients
  • 40 to 100 wt .-%, based on the total amount of the ingredients used pre-granulated the solid and liquid components and mixed in a second, high-speed mixer / granulator, the pregranulate from the first stage optionally with the remaining solid and / or liquid components, and is transferred into a granule.
  • a granulation aid is added to a solid bed in the first mixer / granulator and the mixture is pregranulated.
  • the composition of the granulation aid and the solid bed introduced in the first mixer are selected such that from 40 to 100% by weight, preferably from 50 to 90% by weight and in particular from 60 to 80% by weight, of the solid and liquid constituents are obtained on the total amount of ingredients used, are in the "pre-granules”.
  • This "pre-granulate" is then mixed in the second mixer with other solids and granulated with the addition of further liquid components to the finished surfactant granules.
  • the said order of low-speed high-speed mixer can be reversed according to the invention, so that a method according to the invention results in which the liquid Granulationshüfskar in a first, high-speed mixer / granulator on a moving solid bed is added, wherein 40 to 100 wt .-%, based on the total amount of the ingredients used, pre-granulated the solid and liquid components and in a second, low-speed mixer / granulator, the pregranulate from the first stage, optionally with the remaining solid and / or liquid ingredients and is transferred to a granule.
  • a mixer is used as a high-speed mixer, which has both a mixing and a crushing device, wherein the mixing shaft at rotational speeds of 50 to 150 revolutions / minute, preferably from 60 to 80 revolutions / Minute and the shaft of the crushing device at rotational speeds of 500 to 5000 revolutions / minute, preferably from 1000 to 3000 revolutions / minute, is operated.
  • Preferred granulation processes for producing mixer granules are carried out in mixer granulators in which some mixer parts or the entire mixer are designed to be coolable, in order to be able to remove the heat released during the neutralization reaction (in particular at high throughputs and when using undiluted raw materials).
  • the process according to the invention can also be carried out in a fluidized bed.
  • the invention provides that the process according to the invention is carried out in a batchwise or continuously flowing fluidized bed. It is particularly preferred to carry out the process continuously in the fluidized bed.
  • the liquid anionic surfactants in their acid form or the various liquid components can be introduced simultaneously or successively via one, for example via a nozzle with a plurality of openings, or via a plurality of nozzles in the fluidized bed.
  • the nozzle or the nozzles and the spray direction of the products to be sprayed can be arranged as desired.
  • the solid carriers which are the neutralizing agent and optionally other solids, can be via one or more lines simultaneously (continuous process) or sequentially (batch process), preferably pneumatically via blowing lines, dusted, wherein the neutralizing agent is dusted in the batch process as a first solid.
  • Preferably used fluidized bed apparatus have bottom plates with dimensions of at least 0.4 m.
  • fluidized bed apparatuses are preferred which have a bottom plate with a diameter between 0.4 and 5 m, for example 1.2 m or 2.5 m.
  • fluid bed apparatuses are also suitable which have a bottom plate with a diameter larger than 5 m.
  • the bottom plate is preferably a perforated bottom plate or a Conidurplatte (commercial product of the company Hein & Lehmann, Federal Republic of Germany) used.
  • the process according to the invention is preferably carried out at fluidized air velocities of between 1 and 8 m / s and in particular between 1.5 and 5.5 m / s, for example up to 3.5 m / s.
  • the discharge of the granules from the fluidized bed is advantageously carried out by a size classification of the granules.
  • This classification can be carried out, for example, by means of a screening device or by a countercurrent air stream (classifier air), which is regulated so that only particles of a certain particle size are removed from the fluidized bed and smaller particles are retained in the fluidized bed.
  • the incoming air is composed of the preferably unheated classifier air and the preferably only slightly or not heated bottom air.
  • the bottom air temperature is preferably between 10 and 70 ° C, preferably between 15 and 60 ° C, more preferably between 18 and 50 ° C. Temperatures between 20 and 40 ° C are particularly advantageous.
  • the fluidizing air generally cools due to heat losses and possibly due to the heat of vaporization of the components. However, this heat loss can be compensated or even exceeded by the heat of neutralization in the process according to the invention. It is even possible that the air outlet temperature exceeds the temperature of the fluidized air about 5 cm above the bottom plate. In a particularly preferred embodiment, the temperature of the fluidized air is about 5 cm above the bottom plate 30 to 100 ° C, preferably 35 to 80 ° C and especially 40 to 70 ° C. The air outlet temperature is preferably between 20 and 100 ° C, in particular below 70 ° C and with particular advantage between 25 and 50 ° C.
  • a starting material which serves as an initial support for the sprayed anionic surfactants in its acid form.
  • the neutralizing agent sodium carbonate for example, ingredients of detergents and cleaners, in particular those which can also be used as solids in the process according to the invention and which have a particle size distribution which corresponds approximately to the particle size distribution of the finished granules, are suitable as starting material.
  • sodium carbonate it is preferred to use sodium carbonate as starting material.
  • mixer granulation and fluidized bed processes can also be combined with each other.
  • the reactants can be reacted with each other in a mixer and the resulting neutralizate for carrying out a "maturation" of a fluidized bed apparatus are supplied.
  • the surfactant granules obtained by the process according to the invention have in preferred processes a bulk density of 300 to 1000 g / l, preferably from 350 to 800 g / l, more preferably from 400 to 700 g / l and in particular from 400 to 500 g / l and are dust-free, ie in particular they contain no particles with a particle size below 50 microns. Otherwise, the particle size distribution of the granules corresponds to the usual particle size distribution of a washing and cleaning agent of the prior art.
  • the granules have a particle size distribution in which a maximum of 5 wt .-%, with particular advantage at most 3 wt .-% of the particles have a diameter below 0.1 mm, in particular below 0.2 mm.
  • the particle size distribution is influenced by the nozzle positioning in the fluidized bed plant.
  • the granules are characterized by their light color and by their flowability. In this case, a further measure to prevent the sticking of the granules according to the invention is not required.
  • a process step are followed, wherein the granules for the purpose of further increasing the bulk density in a known manner with finely divided materials, such as zeolite NaA, soda, powdered. This powdering can be carried out, for example, during a rounding step.
  • preferred granules already have such a regular, in particular approximately spherical, structure that a rounding step is generally not necessary and therefore also not preferred.
  • the process end products of the process according to the invention can be added directly to detergents or cleaners; for certain applications they can also be packaged directly as detergents or cleaners and marketed.
  • the process end products of the process according to the invention can also serve as a basis for further refined compounds.
  • the final process products of the neutralization process - optionally after mixing with other solids - are granulated with the addition of liquid active substances.
  • This granulation can in turn be carried out in a variety of apparatuses, with mixer granulators being preferred for this post-treatment step.
  • methods according to the invention are preferred in which the addition of liquid active substances takes place shortly before or during the post-maturation. This can be done in a mixer with preferably short residence times of 0.1 to 5 seconds or in a fluidized bed. Prior complete neutralization is preferred, but is not mandatory.
  • liquid active substances for the subsequent Aufgranulierung the process end products of the process according to the expert granulating liquids ie in particular water or aqueous solutions of salts, water glass, alkylpolyglycosides, carbohydrates (mono-, oligo- and polysaccharides), synthetic polymers (PEG, PVAL, Polycarboxylates), bio-polymers, etc. serve.
  • nonionic surfactants with water, silicone oil and water, supersaturated solvents or surfactant / air mixtures.
  • soaps, nonionic surfactant / polymer solutions, nonionic surfactant / pigment mixtures are used as low-water or -free granulation liquids.
  • aqueous solutions of silicates and / or polymers preferably aqueous solutions of water glasses and / or (meth) acrylic acid polymers and / or copolymers, are used as liquid active substances.
  • the granules can be dried and / or subjected to further substances.
  • process variants are preferred in which the process end products of the granulation process are agglomerated in a fluidized bed and optionally dried.
  • the process products of the process according to the invention which have been subsequently treated have a high absorption capacity for liquid substances, in particular for nonionic surfactants, without losing their excellent solubility.
  • a further preferred variant of the method according to the invention therefore provides that the granules discharged from the fluidized bed are subjected to further substances, in particular nonionic surfactants.
  • nonionic surfactants are preferably used alkoxylated, preferably ethoxylated, especially 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 is linear or preferably methyl-branched in the 2-position may contain or linear and methyl-branched radicals in the mixture, as they are usually present in Oxoalkoholresten.
  • alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
  • Preferred ethoxylated alcohols include, for example, C 12-14 -alcohols containing 3 EO or 4 EO, C9-11 alcohol containing 7 EO, C 13-15 alcohols containing 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures of these, 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 means which, for a particular product, may be an integer or a fractional number.
  • 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 and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
  • nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain.
  • Nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallowalkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides may also be suitable.
  • the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half thereof.
  • polyhydroxy fatty acid amides of the formula (III) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 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 (IV) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with 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 propoxylated Derivatives of this residue.
  • R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
  • R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having
  • [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 be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • nonionic surfactants can be applied.
  • Low-foaming nonionic surfactants are used as preferred surfactants.
  • the agents prepared according to the invention preferably contain a nonionic surfactant which has a melting point above room temperature. Accordingly, preferred agents prepared according to the invention are characterized in that they contain nonionic surfactant (s) having a melting point above 20 ° C, preferably above 25 ° C, more preferably between 25 and 60 ° C and especially between 26.6 and 43.3 ° C, included.
  • Suitable nonionic surfactants which have melting or softening points in the temperature range mentioned are, for example, low-foaming nonionic surfactants which may be solid or highly viscous at room temperature. If high-viscosity nonionic surfactants are used at room temperature, it is preferred that they have a viscosity above 20 Pas, preferably above 35 Pas and in particular above 40 Pas. Nonionic surfactants which have waxy consistency at room temperature are also preferred.
  • Preferred nonionic surfactants to be used at room temperature are from the groups of the alkoxylated nonionic surfactants, in particular the ethoxylated primary alcohols, and mixtures of these surfactants with structurally complicated surfactants such as polyoxypropylene / polyoxyethylene / polyoxypropylene (PO / EO / PO) surfactants.
  • Such (PO / EO / PO) nonionic surfactants are also characterized by good foam control.
  • the nonionic surfactant having a melting point above room temperature is an ethoxylated nonionic surfactant consisting of the reaction of a monohydroxyalkanol or alkylphenol having 6 to 20 carbon atoms, preferably at least 12 mol, more preferably at least 15 mol, especially at least 20 moles of ethylene oxide per mole of alcohol or alkylphenol emerged.
  • a particularly preferred room temperature solid nonionic surfactant is obtained from a straight chain fatty alcohol having 16 to 20 carbon atoms (C 16-20 alcohol), preferably a C 18 alcohol and at least 12 moles, preferably at least 15 moles and especially at least 20 moles of ethylene oxide , Of these, the so-called “narrow range ethoxylates" (see above) are particularly preferred.
  • particularly preferred agents prepared according to the invention contain ethoxylated nonionic surfactant (s) consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • ethoxylated nonionic surfactant consisting of C 6-20 monohydroxyalkanols or C 6-20 alkylphenols or C 16-20 fatty alcohols and more than 12 mol, preferably more than 15 Mol and in particular more than 20 moles of ethylene oxide per mole of alcohol was won (n).
  • the nonionic surfactant preferably additionally has propylene oxide units in the molecule.
  • such PO units make up to 25 wt .-%, more preferably up to 20 wt .-% and in particular up to 15 wt .-% of the total molecular weight of the nonionic surfactant from.
  • Particularly preferred nonionic surfactants are ethoxylated monohydroxyalkanols or alkylphenols which additionally have polyoxyethylene-polyoxypropylene block copolymer units.
  • the alcohol or alkylphenol part of such nonionic surfactant molecules preferably constitutes more than 30% by weight, more preferably more than 50% by weight and in particular more than 70% by weight of the total molecular weight of such nonionic surfactants.
  • Preferred process end products of the process according to the invention with aftertreatment step are characterized in that they contain ethoxylated and propoxylated nonionic surfactants in which the propylene oxide units in the molecule have up to 25% by weight, preferably up to 20% by weight and in particular up to 15% by weight. the total molecular weight of the nonionic surfactant.
  • More particularly preferred nonionic surfactants having melting points above room temperature contain from 40 to 70% of a polyoxypropylene / polyoxyethylene / polyoxypropylene block polymer blend containing 75% by weight of a reverse block copolymer of polyoxyethylene and polyoxypropylene with 17 moles of ethylene oxide and 44 moles of propylene oxide and 25% by weight. % of a block copolymer of polyoxyethylene and polyoxypropylene initiated with trimethylolpropane and containing 24 moles of ethylene oxide and 99 moles of propylene oxide per mole of trimethylolpropane.
  • Nonionic surfactants which may be used with particular preference are available, for example, under the name Poly Tergent® SLF-18 from Olin Chemicals.
  • a further preferred aftertreated process end product according to the invention contains nonionic surfactants of the formula R 1 O [CH 2 CH (CH 3 ) O] x [CH 2 CH 2 O] y [CH 2 CH (OH) R 2 ], in which R 1 is a linear or branched aliphatic hydrocarbon radical having 4 to 18 carbon atoms or mixtures thereof, R 2 denotes a linear or branched hydrocarbon radical having 2 to 26 carbon atoms or mixtures thereof and x for values between 0.5 and 1.5 and y is a value of at least 15.
  • nonionic surfactants are the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) [CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, n- Butyl, 2-butyl or 2-methyl-2-butyl radical, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5.
  • each R 3 in the above formula may be different.
  • R 1 and R 2 are preferably linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 6 to 22 carbon atoms, with radicals having 8 to 18 carbon atoms being particularly preferred.
  • R 3 H 1 -CH 3 or -CH 2 CH 3 are particularly preferred.
  • Particularly preferred values for x are in the range from 1 to 20, in particular from 6 to 15.
  • each R 3 in the above formula may be different if x ⁇ 2.
  • the alkylene oxide unit in the square bracket can be varied.
  • the value 3 for x has been selected here by way of example and may well be greater, with the variation width increasing with increasing x values and including, for example, a large number (EO) groups combined with a small number (PO) groups, or vice versa ,
  • R 1 , R 2 and R 3 are as defined above and x is from 1 to 30, preferably from 1 to 20 and in particular from 6 to 18.
  • Particularly preferred are surfactants in which the radicals R 1 and R 2 has 9 to 14 C atoms, R 3 is H and x assumes values of 6 to 15.
  • agents prepared and post-treated according to the invention are preferred, the end-capped poly (oxyalkylated) nonionic surfactants of the formula R 1 O [CH 2 CH (R 3 ) O] x [CH 2 ] k CH (OH) 2 ] CH 2 ] j OR 2 in which R 1 and R 2 are linear or branched, saturated or unsaturated, aliphatic or aromatic hydrocarbon radicals having 1 to 30 carbon atoms, R 3 is H or a methyl, ethyl, n-propyl, iso-propyl, x is n-butyl, 2-butyl or 2-methyl-2-butyl, x are values between 1 and 30, k and j are values between 1 and 12, preferably between 1 and 5, surfactants of the type R 1 O [CH 2 CH (R 3 ) O] x CH 2 CH (OH) CH 2 OR 2 in which x is from 1 to 30, preferably from 1 to 20 and especially from 6 to 18, are particularly preferred.
  • Cationic and / or amphoteric surfactants can also be used in conjunction with the surfactants mentioned, these having only minor importance and usually only in amounts below 10% by weight, in most cases even below 5% by weight, for example from 0, 01 to 2.5 wt .-%, each based on the agent used.
  • the compositions prepared according to the invention and optionally post-treated may thus contain as surfactant and cationic and / or amphoteric surfactants.
  • anionic surfactant granules prepared according to the invention can, as described above, be processed directly into detergents or cleaners by admixing other customary ingredients of detergents or cleaners. But they can also serve as a carrier base for liquid or pasty substances, in particular nonionic surfactants and are then anionic surfactant / nonionic surfactant mixed compounds, which can also be mixed into detergents or cleaners.
  • Another object of the present invention are therefore detergents or cleaning agents containing a Maschinensendecks of the method according to the invention.
  • detergents or cleaners containing these process end products usually contain further substances from the groups of builders, co-builders, bleaches, bleach activators, dyes and bleaches Perfumes, optical brighteners, enzymes, soil-release polymers, etc. These substances are described below for the sake of completeness.
  • Builders are used in detergents or cleaners especially for binding calcium and magnesium.
  • Usual builders which are preferred in the context of the invention in amounts of 22.5 to 45 wt .-%, preferably from 25 to 40 wt .-% and in particular from 27.5 to 35 wt .-%, each based on the total agent which also contains the process end products of the process according to the invention are the low molecular weight polycarboxylic acids and their salts, the homopolymeric and copolymeric polycarboxylic acids and their salts, the carbonates, phosphates and sodium and potassium silicates.
  • trisodium citrate and / or pentasodium tripolyphosphate and silicatic builders from the class of alkali metal isilicates.
  • the potassium salts are preferable to the sodium salts because they often have a higher water solubility.
  • preferred Water-soluble builders are, for example, tripotassium citrate, potassium carbonate and the potassium water glasses.
  • Washing or cleaning agents may contain as builders phosphates, preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • builders phosphates preferably alkali metal phosphates with particular preference of pentasodium or Pentakaliumtriphosphat (sodium or potassium tripolyphosphate).
  • Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
  • the phosphates combine several advantages: they act as alkali carriers, prevent limescale deposits and also contribute to the 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 powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid 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 arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
  • Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
  • KH 2 PO 4 is a white salt of 2.33 gcm -3 density, 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 slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles; (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 the loss of 5 H 2 O), becomes anhydrous at 100 ° C. and on more intense heating passes into the diphosphate Na 4 P 2 O 7 .
  • Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator produced.
  • Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
  • Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate 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 under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
  • Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred in the detergent industry compared to corresponding sodium compounds.
  • Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
  • Na 4 P 2 O 7 is formed on heating of 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 agents 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 being 1% Solution at 25 ° 10.4.
  • Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: fused or annealed phosphates, Graham's salt, Kurrolsches 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
  • 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° about 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
  • pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry.
  • Preferred washing or cleaning agents contain from 20 to 50% by weight of one or more water-soluble builders, preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • water-soluble builders preferably citrates and / or phosphates, preferably alkali metal phosphates with particular preference of pentasodium or pentapotassium triphosphate (sodium or potassium tripolyphosphate).
  • the level of water-soluble builders is within narrower limits.
  • compositions according to the invention may contain phosphates condensed as water-softening substances. These substances form a group of - because of their production also mentioned melting or annealing phosphates - phosphates, which can be derived from acidic salts of orthophosphoric acid (phosphoric acids) by condensation.
  • the condensed phosphates can be classified into the metaphosphates [Mnn (PO 3 ) n ] and polyphosphates (M l n + 2 P n O 3n + or M l n H 2 P n O 3n + 1 ).
  • Metaphosphates are obtained as accompanying substances of the - erroneously designated as Natriumhexametaphosphat -Graham's salt by melting of NaH 2 PO 4 to temperatures above 620 ° C, wherein also intermediately so-called Maddrell's salt is formed.
  • This and Kurrolsches salt are linear polyphosphates, which are usually not one of the metaphosphates today, but also in the context of the present invention are also used with preference as water-softening substances.
  • the quenched, glassy melt is, depending on the reaction conditions, the water-soluble Graham's salt, (NaPO 3 ) 40-50 , or a glassy condensed phosphate of the composition (NaPO 3 ) 15-20 , known as Calgon.
  • the misleading term hexametaphosphate is still in use.
  • Kurrol's salt (NaPO 3 ) n with n »5000, is also produced from the 600 ° C hot melt of Maddrell's salt, if this is left for a short time at about 500 ° C. It forms high polymer water-soluble fibers.
  • Particularly preferred water-softening substances from the abovementioned classes of condensed phosphates are the "hexametaphosphates" Budit® H6 or H8 from Budenheim.
  • bleaches, bleach activators, enzymes, silver protectants, dyes and fragrances, etc. are particularly preferred ingredients.
  • further ingredients may be present, with agents being preferred, in addition to the end products of the process according to the invention additionally one or more substances from the Group of Acidactusstoff, chelating agents or the deposit-inhibiting polymers.
  • Acidifying agents are both inorganic acids and organic acids, provided that they are compatible with the other ingredients.
  • the solid mono-, oligo- and polycarboxylic acids are used. Again preferred from this group are citric acid, tartaric acid, succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid and also polyacrylic acid.
  • anhydrides of these acids can be used as Acidisersstoff, in particular maleic anhydride and succinic anhydride are commercially available.
  • Organic sulfonic acids such as sulfamic acid are also usable.
  • Commercially available and likewise preferably usable as acidifying agent in the context of the present invention is Sokalan® DCS (trademark of BASF), a mixture of succinic acid (maximum 31% by weight), glutaric acid (maximum 50% by weight) and adipic acid ( at most 33% by weight).
  • Chelating agents are substances which form cyclic compounds with metal ions, with a single ligand occupying more than one coordination site on a central atom, i. H. at least "bidentate". In this case, normally stretched compounds are closed by complex formation via an ion into rings. The number of bound ligands depends on the coordination number of the central ion.
  • chelating agents in the context of the present invention are, for example, polyoxycarboxylic acids, polyamines, ethylenediaminetetraacetic acid (EDTA) and nitrilotriacetic acid (NTA).
  • complex-forming polymers ie polymers which carry functional groups either in the main chain itself or laterally to it, which can act as ligands and react with suitable metal atoms usually with the formation of chelate complexes, can be used according to the invention.
  • the polymer-bound ligands of the resulting metal complexes can originate from only one macromolecule or belong to different polymer chains. The latter leads to the crosslinking of the material, provided that the complex-forming polymers were not previously crosslinked via covalent bonds.
  • Complexing groups (ligands) of common complex-forming polymers are iminodiacetic acid, hydroxyquinoline, thiourea, guanidine, dithiocarbamate, hydroxamic acid, amidoxime, aminophosphoric acid, (cyclic) polyamino, mercapto, 1,3-dicarbonyl and Crown ether residues with z. T. very specific. Activities towards ions of different metals.
  • Base polymers of many also commercially important complex-forming polymers are polystyrene, polyacrylates, polyacrylonitriles, polyvinyl alcohols, polyvinylpyridines and polyethyleneimines. Natural polymers such as cellulose, starch or chitin are also complex-forming polymers. In addition, these can be provided by polymer-analogous transformations with other ligand functionalities.
  • polycarboxylic acids a) are understood as meaning carboxylic acids, including monocarboxylic acids, in which the sum of carboxyl groups and the hydroxyl groups contained in the molecule is at least 5.
  • Complexing agents from the group of nitrogen-containing polycarboxylic acids, in particular EDTA are preferred.
  • these complexing agents are at least partially present as anions. It is irrelevant whether they are introduced in the form of acids or in the form of salts.
  • alkali metal, ammonium or alkylammonium salts, in particular sodium salts are preferred.
  • Scale-inhibiting polymers can likewise be present in the agents according to the invention. These substances, which could be constructed chemically different, for example, from the groups of low molecular weight polyacrylates having molecular weights between 1000 and 20,000 daltons, with polymers having molecular weights below 15,000 daltons are preferred.
  • Scale-inhibiting polymers may also have co-builder properties.
  • organic cobuilders in the agents which comprise the process end products according to the invention, in particular polycarboxylates / polycarboxylic acids, polymeric polycarboxylates, aspartic acid, polyacetals, dextrins, other organic cobuilders (see below) and phosphonates are used. These classes of substances are described below.
  • Useful organic builder substances are, for example, the polycarboxylic acids which can be used in the form of their sodium salts, polycarboxylic acids meaning those carboxylic acids which carry more than one acid function. These are, for example, citric acid, adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if such use is not objectionable for ecological reasons, 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 thereof.
  • the acids themselves can also be used.
  • the acids typically also have the property of an acidifying component and thus also serve for setting a lower and milder pH of detergents or cleaners.
  • Citric acid, succinic acid, glutaric acid, adipic acid, gluconic acid and any desired mixtures of these can be mentioned here ,
  • polymeric polycarboxylates are suitable, these are, for example, the alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those having a molecular weight of 500 to 70000 g / mol.
  • the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
  • Suitable polymers are, in particular, polyacrylates which preferably have a molecular weight of 2,000 to 20,000 g / mol. Because of their superior solubility, the short-chain polyacrylates, which have molar masses of from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, may again be preferred from this group.
  • copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and of acrylic acid or methacrylic acid with maleic acid.
  • Copolymers of acrylic acid with maleic acid which contain 50 to 90% by weight of acrylic acid and 50 to 10% by weight of maleic acid have proven to be particularly suitable.
  • Their relative molecular weight, based on free acids is generally from 2000 to 70000 g / mol, preferably from 20,000 to 50,000 g / mol and in particular from 30,000 to 40,000 g / mol.
  • the (co) polymeric polycarboxylates can be used either as a powder or as an aqueous solution.
  • the content of (co) polymeric polycarboxylates in the compositions is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
  • biodegradable polymers of more than two different monomer units for example those which contain as monomers salts of acrylic acid and maleic acid and vinyl alcohol or vinyl alcohol derivatives or as monomers salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives.
  • Further preferred copolymers are those which preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
  • polymeric aminodicarboxylic acids their salts or their precursors.
  • polyaspartic acids or their salts and derivatives which, in addition to cobuilder properties, also have a bleach-stabilizing action.
  • polyacetals which can be obtained by reacting dialdehydes with polyolcarboxylic acids which have 5 to 7 C atoms and at least 3 hydroxyl groups.
  • Preferred polyacetals are made Dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Polyolcarbon Textren such as gluconic acid and / or glucoheptonic acid.
  • dextrins for example oligomers or polymers of carbohydrates, which can be obtained by partial hydrolysis of starches.
  • the hydrolysis can be carried out by customary, for example acid or enzyme catalyzed processes.
  • it is hydrolysis products having average molecular weights in the range of 400 to 500,000 g / mol.
  • a polysaccharide with a dextrose equivalent (DE) in the range from 0.5 to 40, in particular from 2 to 30 is preferred, DE being a common measure of the reducing action of a polysaccharide compared to dextrose, which has a DE of 100 , is.
  • DE dextrose equivalent
  • maltodextrins having a DE of between 3 and 20 and dry glucose syrups having a DE of between 20 and 37 and also yellow dextrins and white dextrins having relatively high molecular weights in the range from 2000 to 30 000 glmol.
  • the oxidized derivatives of such dextrins are their reaction products with oxidizing agents which are capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
  • a product oxidized to C 6 of the saccharide ring may be particularly advantageous.
  • Oxydisuccinates and other derivatives of disuccinates are other suitable co-builders.
  • ethylenediamine-N, N'-disuccinate (EDDS) is preferably used in the form of its sodium or magnesium salts.
  • glycerol disuccinates and glycerol trisuccinates are also preferred in this context. Suitable amounts are in zeolithissen and / or silicate-containing formulations at 3 to 15 wt .-%.
  • organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
  • phosphonates are also classes of substances with cobuilder properties. These are, in particular, hydroxyalkane or aminoalkanephosphonates.
  • 1-hydroxyethane-1,1-diphosphonate is of particular importance as a co-builder. It is preferably used as the sodium salt, the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
  • Preferred aminoalkanephosphonates are ethylenediamine tetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologs. They are preferably in the form of neutral sodium salts, eg. B. as the hexasodium salt of EDTMP or as hepta- and octa-sodium salt of DTPMP used.
  • the builder used here is preferably HEDP from the class of phosphonates.
  • the aminoalkanephosphonates also have a pronounced heavy metal binding capacity. Accordingly, in particular if the agents also contain bleach, it may be preferable to use aminoalkanephosphonates, in particular DTPMP, or to use mixtures of the phosphonates mentioned.
  • the agents according to the invention may contain further customary ingredients of cleaning agents, in particular bleaching agents, bleach activators, enzymes, silver protectants, dyes and fragrances being of importance. These substances will be described below.
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
  • Detergents or cleaning agents according to the invention may also contain bleaching agents from the group of organic bleaching agents. Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
  • peroxyacids examples of which include the alkyl peroxyacids and the aryl peroxyacids.
  • 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, s-phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenz-amidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidoper-succinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9
  • Chlorinating or bromine-releasing substances can also be used as bleaching agents in dishwasher detergents according to the invention.
  • suitable chlorine or bromine releasing materials are, for example, heterocyclic N-bromo- and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with cations such as potassium and sodium.
  • DICA dichloroisocyanuric acid
  • Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydantoin are also suitable.
  • Bleach activators aid the action of the bleaching agents.
  • Known bleach activators are compounds which contain one or more N- or O-acyl groups, such as substances from the class of the anhydrides, the esters, the imides and the acylated imidazoles or oximes. Examples are tetraacetylethylenediamine TAED, tetraacetylmethylenediamine TAMD and tetraacetylhexylenediamine TAHD, but also pentaacetylglucose PAG, 1,5-diacetyl-2,2-dioxo-hexahydro-1,3,5-triazine DADHT and isatoic anhydride ISA.
  • bleach activators it is possible to use compounds which, under perhydrolysis conditions, give aliphatic peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid.
  • Suitable substances are those which carry O- and / or N-acyl groups of the stated C atom number and / or optionally substituted benzoyl groups.
  • polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular tetraacetylglycoluril (TAGU), N- Acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular phthalic anhydride, acylated polyhydric alcohols, in particular triacetin, ethylene glycol diacetate, 2,5-diacetoxy- 2,5-dihydrofuran, n-methyl-morph
  • Hydrophilic substituted acyl acetals and acyl lactams are also preferably used.
  • Combinations of conventional bleach activators can also be used.
  • so-called bleach catalysts can also be present in the agents according to the invention.
  • These substances are bleach-enhancing transition metal salts or transition metal complexes such as, for example, Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes.
  • Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
  • Bleach activators from the group of the polyacylated alkylenediamines in particular tetraacetylethylenediamine (TAED), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, in particular n-nonanoyl or isononanoyloxybenzenesulfonate (n- or iso-NOBS), are preferred -Methyl-morpholinium acetonitrile-methyl sulfate (MMA), preferably in amounts of up to 10 wt .-%, in particular 0.1 wt .-% to 8 wt .-%, particularly 2 to 8 wt .-% and particularly preferably 2 to 6 wt .-% based on the total agent used.
  • TAED tetraacetylethylenediamine
  • N-acylimides in particular N-nonanoylsuccinimide (NOS
  • Bleach-enhancing transition metal complexes in particular having the central atoms Mn, Fe, Co, Cu, Mo, V, Ti and / or Ru, preferably selected from the group of manganese and / or cobalt salts and / or complexes, particularly preferably the cobalt (ammine) Complexes of the cobalt (acetate) complexes, the cobalt (carbonyl) complexes, the chlorides of cobalt or manganese, manganese sulfate are used in conventional amounts, preferably in an amount up to 5 wt .-%, in particular of 0.0025 wt % to 1 wt .-% and particularly preferably from 0.01 wt .-% to 0.25 wt .-%, each based on the total agent used. But in special cases, more bleach activator can also be used.
  • Suitable enzymes in the detergents or cleaners according to the invention are, in particular, those from the classes of the hydrolases, such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as proteinaceous, fatty or starchy stains. To bleach can Oxidoreductases are also used. Particularly suitable are bacterial strains or fungi such as Bacillus subtilis, Bacillus licheniformis, Streptomyceus griseus, Coprinus cinereus and Humicola insolens, as well as enzymatically-derived variants derived from their genetically modified variants.
  • the hydrolases such as the proteases, esterases, lipases or lipolytic enzymes, amylases, glycosyl hydrolases and mixtures of the enzymes mentioned. All of these hydrolases contribute to the removal of stains such as protein
  • subtilisin-type proteases and in particular proteases derived from Bacillus lentus are used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or lipolytic enzymes or from protease, amylase and lipase or lipolytic enzymes or protease, lipase or lipolytic enzymes, but in particular protease and / or lipase-containing mixtures or mixtures with lipolytic enzymes of particular interest.
  • lipolytic enzymes are the known cutinases.
  • Peroxidases or oxidases have also proved suitable in some cases.
  • Suitable amylases include, in particular, alpha-amylases, iso-amylases, pullulanases and pectinases.
  • the enzymes may be adsorbed to carriers or embedded in encapsulants to protect against premature degradation.
  • the proportion of enzymes, enzyme mixtures or enzyme granules may be, for example, about 0.1 to 5 wt .-%, preferably 0.5 to about 4.5 wt .-%, each based on ready-made detergent or cleaning agent.
  • Dyes and fragrances can be added to the washing or cleaning agents according to the invention in order to improve the aesthetic impression of the resulting products and to provide the consumer with a visually and sensory "typical and unmistakable" product in addition to performance.
  • perfume oils or fragrances individual perfume compounds, for example the synthetic products of the ester type, ethers, aldehydes, ketones, alcohols and hydrocarbons can be used.
  • Fragrance compounds of the ester type are, for example, benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, phenylethyl acetate, linalyl benzoate, benzylformate, ethylmethylphenylglycinate, allylcyclohexylpropionate, styrallylpropionate and benzylsalicylate.
  • the ethers include, for example, benzyl ethyl ether to the aldehydes z. B.
  • the linear alkanals with 8-18 C-atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamen aldehyde, hydroxycitronellal, lilial and bourgeonal
  • the ketones such as the ionone, ⁇ -isomethylionone and methyl cedrate
  • the alcohols include anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol
  • the hydrocarbons mainly include the terpenes such as limonene and pinene.
  • mixtures of different fragrances are used, which together produce an attractive fragrance.
  • perfume oils may also contain natural fragrance mixtures as are available from vegetable sources, eg pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Also suitable are muscatel, sage, chamomile, clove, lemon balm, mint, cinnamon, lime, juniper, vetiver, olibanum, galbanum and labdanum, and orange blossom, neroliol, orange peel and sandalwood.
  • the fragrances can be incorporated directly into the compositions of the invention, but it may also be advantageous to apply the fragrances on carriers, which enhance the adhesion of the perfume on the laundry and provide by a slower release of fragrance for long-lasting fragrance of the textiles.
  • carrier materials for example, cyclodextrins have been proven, the cyclodextrin-perfume complexes can be additionally coated with other excipients.
  • compositions made according to the invention may (or parts thereof) be colored with suitable dyes.
  • suitable dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the agents and against light and no pronounced substantivity to the substrates to be treated with the agents such as glass, ceramic or plastic dishes, not to stain them.
  • the detergents or cleaners according to the invention may contain corrosion inhibitors for the protection of the items to be washed or the machine, with silver protectants in particular being of particular importance in the field of automatic dishwashing. It is possible to use the known substances of the prior art. In general, silver protectants selected from the group of triazoles, benzotriazoles, bisbenzotriazoles, aminotriazoles, alkylaminotriazoles and transition metal salts or complexes can be used in particular. Particularly preferred to use are benzotriazole and / or alkylaminotriazole. In addition, cleaning agent formulations often contain active chlorine-containing agents which corrode the silver surface can significantly reduce.
  • chlorine-free cleaners are particularly oxygen and nitrogen-containing organic re-doxzine compounds such as di- and trihydric phenols, eg. As hydroquinone, pyrocatechol, hydroxyhydroquinone, gallic acid, phloroglucinol, pyrogallol or derivatives of these classes of compounds. Also, salt and complex inorganic compounds, such as salts of the metals Mn, Ti, Zr, Hf, V, Co and Ce are often used.
  • transition metal salts which are selected from the group of manganese and / or cobalt salts and / or complexes, more preferably the cobalt (amine) complexes, the cobalt (acetate) complexes, the cobalt (carbonyl) complexes , the chlorides of cobalt or manganese and manganese sulfate.
  • zinc compounds can be used to prevent corrosion on the items to be washed.
  • Detergents according to the invention may contain as optical brighteners derivatives of diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'-disulfonic acid or similarly constructed compounds which, instead of the morpholino group, a diethanolamino group , a methylamino group, an anilino group or a 2-methoxyethylamino group. Furthermore, brighteners of the substituted diphenylstyrene type may be present, e.g.
  • the final process products of the process according to the invention can not only be admixed with particulate detergents or cleaners, but can also be used in detergent tablets. Surprisingly, the solubility of such tablets improved by the use of the process end products of the method according to the invention in comparison to the same hard and identically composed tablets, which do not include end products of the method according to the invention.
  • Another object of the present invention is therefore the use of the process end products of the process according to the invention for the production of detergents, in particular detergent tablets.
  • washing and cleaning active moldings is done by applying pressure to a mixture to be pressed, which is located in the cavity of a press.
  • a mixture to be tableted is injected directly, i. pressed without previous granulation.
  • the advantages of this so-called Maistablett ist are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages.
  • a powder mixture, which is to be tabletted directly have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die.
  • washing and cleaning agent tablets are based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting. In the context of the present invention, this means that the process end products of the process according to the invention are worked up to a premix with further ingredients, which may also be present in granular form.
  • the premix Before the particulate premix is compressed into detergent tablets, the premix can be "powdered” with finely divided surface treatment agents. This may be advantageous for the nature and physical properties of both the premix (storage, compression) and the finished detergent tablets. Fine particulate powdering agents are well known in the art, with mostly zeolites, silicates or other inorganic salts are used. Preferably, however, the premix is "powdered” with finely divided zeolite, with faujasite-type zeolites being preferred. In the context of the present invention, the term “faujasite-type zeolite” denotes all three zeolites which form the faujasite subgroup of the zeolite structure group 4 (cf. Donald W.
  • Mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which need not necessarily belong to the zeolite structure group 4, can be used as a powdering agent, it being advantageous if at least 50 wt .-% of the powdery powder of a zeolite of faujasite Type persist.
  • detergent tablets which consist of a particulate premix containing granular components and subsequently admixed pulverulent substances, the one or more subsequently admixed pulverulent components comprising a faujasite-type zeolite having particle sizes of less than 100 ⁇ m, preferably below 10 ⁇ m and in particular below 5 ⁇ m and makes up at least 0.2% by weight, preferably at least 0.5% by weight and in particular more than 1% by weight of the premix to be tabletted.
  • the premixes to be compressed may additionally contain one or more substances from the group of bleaches, bleach activators, enzymes, pH adjusters, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, grayness inhibitors, dye transfer inhibitors and corrosion inhibitors. These substances have been described above.
  • the production of the shaped bodies according to the invention takes place firstly by the dry mixing of the constituents, which may be completely or partially pre-granulated, and subsequent informing, in particular pressing into tablets, wherein conventional methods can be used.
  • the premix is compacted in a so-called matrix between two punches to form a solid compressed product. This process, hereinafter referred to as tabletting, is divided into four sections: dosing, compaction (elastic deformation), plastic deformation and ejection.
  • the premix is introduced into the die, wherein the filling amount and thus the weight and the shape of the resulting shaped body are determined by the position of the lower punch and the shape of the pressing tool.
  • the constant dosage even at high molding throughputs is preferably achieved via a volumetric metering of the premix.
  • the upper punch contacts the pre-mix and continues to descend toward the lower punch.
  • the particles of the premix are pressed closer to each other, with the void volume within the filling between the punches decreasing continuously. From a certain position of the upper punch (and thus from a certain pressure on the premix) begins the plastic deformation, in which the particles flow together and it comes to the formation of the molding.
  • the premix particles are also crushed, and even higher pressures cause sintering of the premix.
  • the phase of the elastic deformation is shortened more and more, so that the resulting moldings may have more or less large cavities.
  • the finished molded body is pushed out of the die by the lower punch and carried away by subsequent transport means. At this time, only the weight of the shaped body is finally determined because the compacts due to physical processes (re-expansion, crystallographic effects, cooling, etc.) can change their shape and size.
  • the tabletting is carried out in commercial tablet presses, which can be equipped in principle with single or double punches. In the latter case, not only is the top punch used to build up pressure, but also the bottom punch moves toward the top punch during the pressing operation while the top punch presses down.
  • eccentric tablet presses are preferably used in which the die or punches are attached to an eccentric disc, which in turn is mounted on an axis at a certain rotational speed. The movement of these punches is comparable to the operation of a conventional four-stroke engine.
  • the compression can be done with a respective upper and lower punch, but it can also be attached more stamp on an eccentric disc, the number of Matrizenbohritch is extended accordingly.
  • the throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.
  • rotary tablet presses are selected in which a larger number of dies are arranged in a circle on a so-called die table.
  • the number of matrices varies between 6 and 55 depending on the model, although larger matrices are commercially available.
  • Each die on the die table is assigned an upper and lower punch, in turn, the pressing pressure can be actively built only by the upper or lower punch, but also by both stamp.
  • the die table and the punches move about a common vertical axis, the punches are brought by means of rail-like cam tracks during the circulation in the positions for filling, compression, plastic deformation and ejection.
  • these curved paths are supported by additional low-pressure pieces, Nierderzugschienen and lifting tracks.
  • the filling of the die via a rigidly arranged supply device, the so-called filling shoe, which is connected to a reservoir for the premix.
  • the pressing pressure on the premix is individually adjustable via the compression paths for upper and lower punches, wherein the pressure build-up is done by the Vorbeirollen the stamp shank heads on adjustable pressure rollers.
  • Concentric presses can be provided with two Drik to increase the throughput, with the production of a tablet only a semicircle must be traversed.
  • several filling shoes are arranged one after the other without the slightly pressed-on first layer being ejected before further filling.
  • suitable process control coat and point tablets can be produced in this way, which have a zwiebelschalenartigen structure, wherein in the case of the point tablets, the top of the core or the core layers is not covered and thus remains visible.
  • Even rotary tablet presses can be equipped with single or multiple tools, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for pressing.
  • the throughputs of modern rotary tablet presses amount to over one million moldings per hour.
  • Plastic coatings, plastic inserts or plastic stamps are particularly advantageous.
  • Rotary punches have also proved to be advantageous, wherein, if possible, upper and lower punches should be rotatable. With rotating punches can be dispensed with a plastic insert usually. Here, the stamp surfaces should be electropolished.
  • Tableting machines suitable for the purposes of the present invention are obtainable, for example, from Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell on the lake, KORSCH presses AG, Berlin, as well as Romaco GmbH, Worms.
  • Other providers include Dr. med. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy NV, Halle (BE / LU) and Mediopharm Kamnik (SI ).
  • the hydraulic is particularly suitable Double pressure press HPF 630 of the company LAEIS, D.
  • Tablettierwerkmaschinee are for example from the companies Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
  • Other providers include the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).
  • the moldings can be made in a predetermined spatial form and predetermined size.
  • a form of space practically all useful manageable configurations come into consideration, for example, the training as a blackboard, the bar or bar shape, cubes, cuboids and corresponding space elements with flat side surfaces and in particular cylindrical configurations with circular or oval cross-section.
  • This last embodiment covers the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
  • the portioned compacts can be designed in each case as separate individual elements, which corresponds to the predetermined dosage amount of the washing and / or cleaning agent. However, it is also possible to form compacts which connect a plurality of such mass units in a compact, wherein in particular by predetermined predetermined breaking points the easy separability portioned smaller units is provided.
  • the formation of the portioned compacts can be useful as tablets, in cylindrical or cuboidal form, a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
  • Commercially available hydraulic presses, eccentric presses or rotary presses are suitable devices, in particular for producing such compacts.
  • the spatial form of another embodiment of the moldings is adapted in their dimensions of the dispenser of commercial household washing machines, so that the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • the moldings can be metered without dosing directly into the dispenser, where it dissolves during the dispensing process.
  • detergent tablets via a dosing easily possible and preferred in the context of the present invention.
  • Another preferred molded article which can be produced has a plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, which are the short thin segments, broken and in the Machine can be entered.
  • This principle of the "bar-shaped" shaped body wash can also be realized in other geometric shapes, for example vertical triangles, which are joined together only on one side thereof.
  • the various components are not pressed into a single tablet, but that moldings are obtained which have multiple layers, ie at least two layers. It is also possible that these different layers have different dissolution rates. This can result in advantageous performance properties of the molded body. If, for example, components are contained in the moldings which interact negatively, it is possible to integrate one component in the faster soluble layer and to incorporate the other component into a slower soluble layer, so that the first component has already reacted, when the second goes into solution.
  • the layer structure of the moldings can be carried out both in a staggered manner, wherein a dissolution process of the inner layer (s) takes place at the edges of the molded body already when the outer layers are not completely dissolved, but it can also be a complete coating of the inner layer (s ) are reached through the respective outer layer (s), which leads to a prevention of premature dissolution of constituents of the inner layer (s).
  • a shaped body consists of at least three layers, ie two outer and at least one inner layer, at least in one of the inner layers containing a peroxy bleach, while the stacked shaped body, the two outer layers and the envelope-shaped body
  • outermost layers are free of peroxy bleach.
  • peroxy bleach and optionally present bleach activators and / or enzymes spatially in a molding from each other.
  • Such multilayer moldings have the advantage that they can be used not only via a dispensing compartment or via a metering device, which is placed in the wash liquor; Rather, it is also possible in such cases, to give the molding in direct contact with the textiles in the machine without stains caused by bleach and the like to be feared.
  • the detergent tablets After pressing, the detergent tablets have a high stability.
  • ⁇ is the diametrical fracture stress (DFS) in Pa
  • P is the force in N leading to the pressure applied to the molded article causing the breakage of the molded article
  • D is the molded article diameter in meters
  • t the height of the moldings.

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  • Acyclic And Carbocyclic Compounds In Medicinal Compositions (AREA)
  • Inorganic Compounds Of Heavy Metals (AREA)
  • Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
EP02804199A 2001-12-07 2002-11-28 Tensidgranulate und verfahren zur herstellung von tensidgranulaten Revoked EP1451280B1 (de)

Applications Claiming Priority (3)

Application Number Priority Date Filing Date Title
DE10160319A DE10160319B4 (de) 2001-12-07 2001-12-07 Tensidgranulate und Verfahren zur Herstellung von Tensidgranulaten
DE10160319 2001-12-07
PCT/EP2002/013416 WO2003048286A2 (de) 2001-12-07 2002-11-28 Tensidgranulate und verfahren zur herstellung von tensidgranulaten

Publications (2)

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EP1451280A2 EP1451280A2 (de) 2004-09-01
EP1451280B1 true EP1451280B1 (de) 2006-01-25

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EP02804199A Revoked EP1451280B1 (de) 2001-12-07 2002-11-28 Tensidgranulate und verfahren zur herstellung von tensidgranulaten

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US (1) US20040259755A1 (enExample)
EP (1) EP1451280B1 (enExample)
JP (1) JP2005511820A (enExample)
AT (1) ATE316567T1 (enExample)
AU (1) AU2002356745A1 (enExample)
DE (2) DE10160319B4 (enExample)
ES (1) ES2257598T3 (enExample)
WO (1) WO2003048286A2 (enExample)

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KR101349876B1 (ko) 2007-02-05 2014-01-09 주식회사 엘지생활건강 용해성이 향상된 분말세제 조성물의 제조방법
CN102559401A (zh) * 2011-12-31 2012-07-11 任航 一种环保水基型汽车虫胶清洗剂及其制备方法
US9994799B2 (en) 2012-09-13 2018-06-12 Ecolab Usa Inc. Hard surface cleaning compositions comprising phosphinosuccinic acid adducts and methods of use
US8871699B2 (en) 2012-09-13 2014-10-28 Ecolab Usa Inc. Detergent composition comprising phosphinosuccinic acid adducts and methods of use
US9752105B2 (en) 2012-09-13 2017-09-05 Ecolab Usa Inc. Two step method of cleaning, sanitizing, and rinsing a surface
US20140308162A1 (en) 2013-04-15 2014-10-16 Ecolab Usa Inc. Peroxycarboxylic acid based sanitizing rinse additives for use in ware washing
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KR102014499B1 (ko) * 2019-05-16 2019-08-26 주식회사 비알인포텍 고온 환경에 배치된 cctv 냉각 방법

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Also Published As

Publication number Publication date
US20040259755A1 (en) 2004-12-23
EP1451280A2 (de) 2004-09-01
DE10160319A1 (de) 2003-06-26
ES2257598T3 (es) 2006-08-01
DE10160319B4 (de) 2008-05-15
AU2002356745A1 (en) 2003-06-17
WO2003048286A3 (de) 2003-10-02
ATE316567T1 (de) 2006-02-15
WO2003048286A2 (de) 2003-06-12
DE50205726D1 (de) 2006-04-13
JP2005511820A (ja) 2005-04-28

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