EP0748369B1 - Melanges complexes a base de composes de silicate alcalin hydrosolubles et leur utilisation - Google Patents

Melanges complexes a base de composes de silicate alcalin hydrosolubles et leur utilisation Download PDF

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Publication number
EP0748369B1
EP0748369B1 EP95911243A EP95911243A EP0748369B1 EP 0748369 B1 EP0748369 B1 EP 0748369B1 EP 95911243 A EP95911243 A EP 95911243A EP 95911243 A EP95911243 A EP 95911243A EP 0748369 B1 EP0748369 B1 EP 0748369B1
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EP
European Patent Office
Prior art keywords
alkali metal
weight
water
solid material
useful materials
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EP95911243A
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German (de)
English (en)
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EP0748369A1 (fr
Inventor
Wilfried Rähse
Johann Friedrich Fues
Kathleen Paatz
Wilhelm Beck
Wolfgang Hlavacek
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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
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/046—Salts
    • 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
    • C11D11/02—Preparation in the form of powder by spray drying
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/06—Phosphates, including polyphosphates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/08—Silicates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/02—Inorganic compounds ; Elemental compounds
    • C11D3/04—Water-soluble compounds
    • C11D3/10—Carbonates ; Bicarbonates
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/20—Organic compounds containing oxygen
    • C11D3/2075—Carboxylic acids-salts thereof
    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
    • C11D3/16—Organic compounds
    • C11D3/37—Polymers
    • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
    • C11D3/3757—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions
    • C11D3/3761—(Co)polymerised carboxylic acids, -anhydrides, -esters in solid and liquid compositions in solid compositions

Definitions

  • the teaching according to the invention relates to the field of solid materials and mixtures of materials based on water-soluble alkali metal silicate compounds, which are also referred to in the specialist literature as water glasses.
  • the ratio of x: y is called the module.
  • Module ranges of water-soluble alkali metal silicate compounds of the type concerned according to the invention are in the range from about 0.8 to 4.
  • Water glasses of the type affected here find the most varied in practice Use.
  • adhesives for paper and cardboard Binder for the production of refractory Kitte, in the enamel and building materials industry as well as in the Foundry as core binder; Corrosion protection agents, in particular to inhibit the alkaline attack on aluminum and zinc; Plasticizer to lower the viscosity of ceramic slurry cores; Stabilizers in the peroxide bleaching of paper and textiles; Binder as part of soil and rock consolidation in the House, tunnel and mining as well as the humusless greening of Dunes and debris piles or flocculants in water treatment.
  • One of the most important areas of application for water glasses is their use as components in detergents and cleaning agents. They have a wide range of functionality to fulfill here which will be discussed in more detail below.
  • zeolite NaA Simultaneously with the development of the zeolite NaA as a builder proposed selected water-soluble amorphous sodium silicate compounds as builder substances in washing and cleaning agents to use.
  • the water content of the products used is approx. 18 to 20% by weight with bulk densities well above 500 g / l.
  • detergents with 5 to 50 wt .-% at least one surfactant, 0.5 to 60 wt .-% of a builder as well as usual washing aids are proposed, with the mark lies in the fact that an amorphous water-poor as a builder Sodium disilicate with a water content of 0.3 to 6% by weight is used becomes.
  • the amorphous sodium disilicate should preferably 0.5 to 2 Wt .-% water.
  • the production of this highly dewatered Amorphous disilicates are made in a multi-stage process, initially the production of a powdered amorphous sodium silicate provides with a water content of 15 to 23 wt .-%.
  • This Material is in a rotary kiln with flue gas at temperatures treated from 250 to 500 ° C in countercurrent. That from the rotary kiln escaping amorphous sodium disilicate is with the help of a mechanical Crushed to grain sizes of 0.1 to 12 mm and then grind to a particle size of 2 to 400 ⁇ m with a mill.
  • EP-A-0 542 131 wants to be considered a Builder component useful dried Sodium silicate containing water of crystallization with a free water content produce between 5 and 12% by weight in one process step, that a 40 to 60 wt .-% aqueous solution of sodium silicate in a turbo dryer equipped with striking tools is treated with hot air.
  • the drying product passes through thereby a pseudoplastic state, which leads to the formation of a Product in granular form is used.
  • the drying up of this Granules are carried out under working conditions, the one Embrittlement of the outer shell of the granules and a related breakage exclude the granulate structure. That way it will - while avoiding the so-called "popcorn effect" - possible, water soluble sodium silicates with specific weights in the range to produce between 0.5 and 1.2, which is characterized by complete Characterize solubility in water at ambient temperature.
  • the teaching according to the invention is essentially based on the example of the builder or builder mixed components described for detergents and cleaning agents. As introduced in the introduction is the area of action according to the invention not on restricted to this particular area of application, but it is special suitable, the characteristic of the teaching of the invention To summarize elements.
  • the teaching of the present invention is based on the task in a large-scale accessible and inexpensive process Water glasses or water glass-based multi-substance mixtures to win in an offer form that meets the varied requirements the product properties in practice.
  • the invention aims to create the possibility of an improved one Access to highly effective builders respectively Finding builder systems for detergents and cleaning agents.
  • the invention relates in a first embodiment to a solid material, the alkali metal silicates with a molar ratio of SiO 2 : M 2 O, where M is an alkali metal, from 0.8 to 4 in homogeneous mixture with further inorganic and / or organic value and / or auxiliary substances, characterized in that it contains at least 10% by weight of water-soluble inorganic and / or organic salts as inorganic and / or organic valuable substances and / or auxiliary substances, a bulk density of at least 150 g / l and a BET surface area of has at least 5 m 2 / g, the alkali metal silicate content has a water content of below 15% by weight and the alkali metal silicates are present in at least 50% by weight in a Q 2 and / or Q 3 structure.
  • the invention relates to the use of the Solid goods as a builder in detergents and cleaning agents.
  • the invention also relates in particular Detergent and cleaning agent in solid preparation form, especially textile detergent, based on a mixture of surfactants, builder components and other usual valuable and / or auxiliary substances, which are characterized are that they contain a solid material - as described above.
  • M alkali
  • the solid material according to the invention is often also referred to as "primary dry good” or dry good ".
  • a crucial core idea lies in the application of the principle drying, in particular spray drying and / or fluidized bed drying, aqueous preparations of valuable materials and Recyclable materials with superheated steam as a hot gas stream Feeding the evaporation energy into the material to be dried and the simultaneous absorption of the evaporated water portion in the stream of superheated steam and the removal of this evaporated water together with the one withdrawn from the drying zone superheated steam flow.
  • the amount of water discharged is condensed and worked up while the rest of the overheated Steam is returned to the drying zone in a closed circuit after the amount of energy removed by drying has been fed again.
  • the teaching according to the invention is based on the knowledge that, particularly in the field of drying water-containing preparations of water glasses of the type described at the outset, this technology of superheated steam drying allows access to a summation and multifunctionality of advantages which have hitherto not been known.
  • the closed circulation system of the superheated steam enables CO 2 -free drying and thus avoids undesired secondary reactions in the material to be dried.
  • the drying conditions can be controlled as required with regard to the residual water content. Dry products with residual water contents in the range of the equilibrium value of monomeric alkali silicate compounds can be obtained, but in particular the additional removal of water with simultaneous condensation of the silica residues to form oligomer and / or polymer compounds is possible.
  • the primary dry material of the process according to the invention is obtained in the form of a free-flowing granular material of considerable bulk weights, which are desirable today for a variety of reasons. Nevertheless, this dry material has suitable BET surfaces for covering with other valuable and / or auxiliary substances, which go far beyond the outer shells of the grain structure to be calculated.
  • the primary dry material is a material with a microporous, absorbent internal structure, which can be filled with sufficiently flowable components in a subsequent work step.
  • This microporous inner structure is also of decisive importance for the dissolving behavior of the dry material according to the invention.
  • the water glasses in admixture with other auxiliary and / or valuable materials from preferably homogeneous solution - but possibly also from appropriate dispersions - processing leads to Recyclable materials, in which those in practical use interact kicking components from the start in an intimate mixture available. Interactions from, for example, builder and Cobuilder components possible in practical use that optimize are.
  • the availability of the internal structure of the primary Dry goods with other detergent components are more advanced Advantages.
  • the dispersibility can be comparatively more water soluble or miscible Detergent components are facilitated in that these components in a flowable state in the inventive microporous solid bodies are absorbed and distributed therein.
  • the alkali metal silicates of the specified module range from 0.8 to 4 in homogeneous mixture with at least 10 wt .-% - based on compound dry weight - further inorganic and / or contains organic valuable and / or auxiliary substances and from a finely divided sprayed aqueous preparation of mixtures of Alkali metal silicates and the other valuable and / or auxiliary substances has been dried using superheated steam.
  • the preferred Alkali metal silicates are those of sodium and potassium. Corresponding comes especially in the field of detergent builders Sodium silicates become paramount while for example, potassium silicate compounds in technical fields may be the preferred compounds.
  • the alkali metal silicates are preferably present in the primary dry material in amounts of at least 25% by weight and in particular in amounts of at least 30% by weight,% by weight here based on the weight of the primary dry good.
  • Particularly important embodiments of the invention contain the alkali metal silicate in quantities of at least 40% by weight and in particular in quantities of at least 50% by weight. Quantity ranges from 45 to 80% by weight, in particular 50 to 75% by weight of alkali metal silicate in the dry product can be particularly useful be important.
  • the recyclable or auxiliary materials used are used in amounts of at least 10% by weight.
  • these second components can at least 15, make up at least 20 or at least 25% by weight, frequently 20 to 50% by weight and in particular 30 to 45% by weight of these second components relate to practically important embodiments.
  • the numerical value of the% by weight is determined on the Weight of the primary dry material.
  • Second components can be used from a specific selected second component exist, but can also also - taking into account the knowledge of possible interactions and in particular for the intended technical purpose - any combination of two or more auxiliary and / or Recyclable materials mixed with the silicate compounds for Come into play.
  • target bulk weights is 150 g / l respectively at 200 g / l.
  • target bulk weights are often as high as possible desired, which - based on primary dry goods - at at least 250g / l or even higher at at least 300 g / l.
  • Particularly preferred values are at least 350 g / l and especially at least 400 g / l.
  • the Bulk densities are, for example, in the range from 50 to 100 g / l. It is known and described to carry out such a hollow spherical structure to destroy mechanical force and thus to a certain Increase in bulk density in the "secondary" dry material come. Work carried out in parallel by the applicant has shown that even when using superheated steam as Drying gas aqueous alkali silicate solutions without the addition of second components to such a hollow spherical light dry powder dry up.
  • the teaching according to the invention envisages practically complete exclusion of access or in-situ formation of CO 2 to or in the drying zone.
  • the circulation flow of the superheated steam is reheated by indirect energy input, as is described in the literature cited for hot steam drying.
  • the selection of the starting materials also ensures that no or no significant amounts of CO 2 can be formed by in-situ conversion, as is possible, for example, if alkali metal bicarbonates are used. In any case, it can be ensured that no or no significant amounts of water-insoluble or sparingly soluble material are formed even in the modification of the formation of an "over-dried" water glass, which is discussed below.
  • the proportion of insoluble material in the product dried according to the invention is preferably ⁇ 3% by weight and in particular ⁇ 1% by weight.
  • the solubility of the dry material formed in its entirety is of course also determined by the solubility parameters of the second and third components, the nature of which will be discussed in detail.
  • the inventive step of drying the aqueous Water glass-based active ingredient mixtures looks important Embodiment the so-called "overdrying" of the alkali silicate material in front.
  • sodium silicates of the usual in detergents Module range from about 1.3 to 4, this means that the Residual water content in the sodium silicate portion below 18 % By weight and in particular below 15% by weight.
  • These dry products with water contents are suitable according to the invention of the silicate content of at most 15% by weight, the Range of about 1 to 13 wt .-%, and again the range from about 3 to 10 wt .-% water in sodium silicate, special importance can come.
  • "Over-dried" X-ray amorphous alkali silicates and especially sodium silicates of the specified module range with water content in the primary dry goods in the range of about 6 to 13% by weight into consideration.
  • the setting of these drying results is in the expert known way through the process parameters of the drying stage with the superheated steam and here in particular the temperature level of the supplied water vapor, its amount and / or the dwell time of the goods in contact with the superheated Determined water vapor.
  • the process parameter in this context is the temperature of the superheated steam flow, determined at its inlet temperature and its outlet temperature.
  • the inlet temperature of the superheated steam within a wide temperature range can be selected. For example in Range of 120 to 450 ° C, preferably in the range of about 150 to 380 ° C.
  • outlet temperature of the evaporated amount of water loaded superheated steam is then correspondingly lower, preferred outlet temperatures can range, for example from about 115 to 220 ° C and in particular in the range from 130 to 200 ° C.
  • the selection and adjustment of the respective working conditions is - as already mentioned - especially determined by the temperature sensitivity, especially that with the alkali silicates sprayed further auxiliary and / or recyclable materials as well through the desired drying result in the dry process product.
  • the maximum temperature of the goods under the drying conditions come, for example in the range of 100 to 200 ° C and in particular can be in the range of about 110 to 150 ° C.
  • temperature-sensitive components can also be used.
  • concerns are ruled out from the outset, if as mixed components for example temperature stable inorganic salts of the type of sodium sulfate or sodium carbonate for use come.
  • Products as detergent builder compounds are important embodiments here in front.
  • the temperature load can be harmless of the purely inorganic material in the drying zone towards an optimized "overdrying" of the alkali silicate can be set.
  • oligomer or polymer structures of the silica residues form in the "overdried” material. Due to the good water solubility of the dry products according to the invention, it can be assumed that these oligomeric or polymeric silica residues essentially correspond to the so-called Q 2 and / or the Q 3 structure, that is to say they have a chain-like or ring-shaped or sheet-like structure, but are not three-dimensionally cross-linked (Q 4 state).
  • the solid material of the teaching according to the invention contains at least 50% by weight, preferably at least 80% by weight, of the alkali metal silicate component as such an “over-dried” material with an oligomer or polymer structure of the silica residues.
  • the term “Q structure” is also explained in EP-A-0488 868.
  • mixture components in the sense of the teaching according to the invention dried together with the water glasses are such Preferred components that are at least partially water-soluble are so that the drying process really homogeneous mixtures accumulate with the microporous dry goods structure. Understandably can at least partially but also finely divided insoluble mixing components in the resulting dry material be incorporated.
  • inorganic mixture components can be found under Consideration of the respective application water-soluble inorganic Salts are used, in particular corresponding ones Carbonates, bicarbonates, sulfates, halides, borates, Phosphates and / or polyphosphates are to be mentioned, in particular in Form of the corresponding sodium and / or potassium salts are.
  • organic, preferably at least partly water-soluble, blend components will be in adjustment determined to the purpose.
  • Usable organic builders are, for example, preferred in the form of their sodium salts used polycarboxylic acids such as citric acid, Adipic acid, succinic acid, glutaric acid, tartaric acid, sugar acids, Aminocarboxylic acids, nitrilotriacetic acid (NTA), if such Use is not objectionable for ecological reasons, and mixtures of these. Salts are preferred Polycarboxylic acids such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids and mixtures of these.
  • Polymeric polycarboxylates are also suitable, for example the sodium salts of polyacrylic acid or methacrylic acid, in particular those with a molecular weight of 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are especially those of acrylic acid with methacrylic acid and Acrylic acid or methacrylic acid with maleic acid.
  • acrylic acid with maleic acid have proven to be the 50 to 90% by weight acrylic acid and 50 to 10% by weight Contain maleic acid.
  • Their relative molecular mass, based on free acids is generally 5,000 to 200,000, preferably 10,000 to 120,000 and especially 50,000 to 100,000.
  • biodegradable terpolymers are also preferred, for example those which are salts of acrylic acid and monomers of maleic acid and vinyl alcohol or vinyl alcohol derivatives (not before published international application WO-A-9415978 (DE-A-4300772)) or the as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well Sugar derivatives (German patent DE-C-42 21 381) contain.
  • Suitable builder systems are oxidation products from carboxyl-containing polyglucosans and / or their water-soluble salts, such as those found in international Patent application WO-A-93/08251 can be described or their Manufacturing, for example, in the international patent application WO-A-93/16110.
  • crystalline ones Layered silicates or limited quantities of the water-insoluble ones Zeolites in detergent quality, especially zeolite NaA.
  • Alkali carbonates can be used according to the teaching of the older international patent application WO-A-9429419 (DE-A-43 19 578) also describes sulfur-free 2 to 11 Carbon atoms and optionally a further carboxyl and / or Amino acids and / or their amino groups replaced become. So, for example, an at least partial exchange of alkali carbonates by glycine or glycinate be made.
  • nonionic cellulose ethers such as methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and Hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as those from the prior art known polymers of phthalic acid and / or terephthalic acid or from their derivatives, in particular polymers Ethylene terephthalates and / or polyethylene glycol terephthalates.
  • the alkali silicate-based components which are dried and in particular “overdried” according to the invention, are generally characterized as dry products by their X-ray amorphous nature.
  • Amorphous alkali silicates have been used in detergents for a long time, their function is essentially to provide the alkalinity necessary for the washing process.
  • amorphous sodium silicates are used as spray-dried water glasses with the module (SiO 2 / Na 2 O molar ratio) of approx. 2 to 3.5.
  • These solid powders usually contain about 18 to 20% by weight of water and are distinguished, inter alia, by the fact that they have only a very small specific surface area according to BET (DIN 66131), which is significantly less than 5 m 2 / g. Their cumulative volume, which can be determined using mercury porosimetry measurements (based on DIN 66133), is also very low and usually reaches values of up to 50 mm 3 / g.
  • the absorption capacity of these spray-dried water glasses compared to liquid components, for example nonionic surfactants is extremely low. Even when 5% by weight of the nonionic surfactant is added, the solids lose their powder properties and stick to one another.
  • the microporous solid builders that are now used according to the invention can overlap in a number of material parameters with the corresponding values of the commercially available water glasses in solid form, but they differ fundamentally in the sum of their properties.
  • the builder components according to the invention are X-ray amorphous sodium silicates usually in the area mentioned here Coming module range from 1 to 4, especially within in the range from 1.3 to 3.7. Module values are of particular importance of at least 1.5 and in particular the range of 1.5 to 3.3 too. Preferred further lower limit values for the module range are at 1.7 and especially at 1.9 while still preferred upper limits for module values of 3.0 and in particular 2.7 lie. In previous practice of use amorphous water glasses in solid form in detergents can have module values around 2 - the disilicate compounds - a special meaning get. According to the invention, water glasses are also these Suitable module value.
  • sodium silicate builders or builder mixtures used which differ at least partially from this module value and otherwise lie in the specified number range.
  • preferred embodiments are characterized in that at least 5% by weight and in particular at least 10 to 20% by weight of the X-ray amorphous sodium silicate builders differ from module value 2.
  • the form of supply of the microporous valuable material grain with its alkali silicate content according to the invention is characterized by high BET surfaces (DIN 66131) and by high numerical values for the cumulative volume (DIN 66133).
  • the BET surface area of the solid material according to the invention (primary dry material) is at least 5 m 2 / g, lower limit values for this BET surface area of at least 7.5 m 2 / g and in particular of at least 10 m 2 / g being of particular importance.
  • the cumulative volume of the primary dry material is generally at least 50 mm 3 / g, preferably at least 100 m 3 / g, and in special cases can also reach higher values, for example 150 mm 3 / g.
  • the rate of dissolution of the primary dry good is admittedly the second and third components used as mixture components co-determined, but it is usually in the higher range Dissolution rates. So the primary release rates Items to be dried for a maximum of about 2 minutes Standard conditions, preferably at most about 1 minute below Standard conditions - 95% by weight / 40 ° C in each case.
  • the absorption capacity of the primary dry goods for liquid components is surprisingly high.
  • liquid components such as corresponding nonionic surfactants.
  • Characteristic of the X-ray amorphous dry products in the sense is that with the help of electron diffraction usually found microcrystalline fractions can be. This applies in particular to comparatively strong "over-dried" products, for example in the temperature range up to maximum 500 ° C, preferably in the temperature range from 120 to 450 ° C have been dried.
  • microcrystallinity means that short-range orders of the individual There are building blocks, but comprehensive long-range orders are absent, so that no reflections occur in the X-ray diffraction spectrum and the silicates can thus be characterized as X-ray amorphous.
  • Embodiments designed according to the invention fall within the scope of the invention
  • the microporous can be of particular importance Builders in the binding and absorption of liquid components to the mentioned area. Examples here are at room temperature or moderately elevated liquid non-surfactant temperatures
  • the intimate mixing of the flowable components with the inorganic carrier component with a large surface area and the Possibility of this given mixture state also in the frame maintain the full packaging of detergents and cleaning agents, not only ensures the initially desired consolidation of the mixture of recyclables, in particular the functional protection the respective recyclable component when mixed into the aqueous wash liquor with a large surface area and high water solubility present builder component instead.
  • the invention consistently used builder components high calcium and magnesium binding capacity, usually of at least 4 meq / g product (calculated on anhydrous alkali silicate substance). The functionality is thus optimized and ensured also of active substances sensitive to water hardness upon first contact with the surrounding aqueous phase in the wash liquor.
  • the mixing of the builder components according to the invention on the basis of the microporous and highly absorbent multicomponent mixtures in the form of the primary dry material enables the loadable finished product which is ultimately obtained to be largely freely adjustable.
  • the bulk weight of the combined material can be varied largely freely.
  • the builder components can thus also be used in modern detergents with bulk densities of at least about 0.7 g / cm 3 .
  • Suitable surfactants of the sulfonate type are preferably the known C 9 -C 13 alkylbenzenesulfonates, olefin sulfonates and alkanesulfonates. Esters of ⁇ -sulfofatty acids or the disalts of ⁇ -sulfofatty acids are also suitable.
  • Other suitable anionic surfactants are sulfonated fatty acid glycerol esters, which are mono-, di- and triesters as well as their mixtures, such as those produced by esterification by a monoglycerol with 1 to 3 moles of fatty acid or in the transesterification of triglycerides with 0.3 to 2 moles of glycerol be preserved.
  • Suitable surfactants of the sulfate type are the sulfuric acid monoesters from primary alcohols of natural and synthetic origin, in particular from fatty alcohols, for example from coconut oil alcohol, tallow fatty alcohol, oleyl alcohol, lauryl, myristyl, cetyl or stearyl alcohol, or the C 10 -C 20 oxo alcohols, and those secondary alcohols of this chain length.
  • Preferred anionic surfactant mixtures contain combinations of Alk (en) yl sulfates, especially mixtures of saturated and unsaturated Fatty alcohol sulfates, and alkylbenzenesulfonates, sulfated fatty acid glycerol esters and / or ⁇ -sulfofatty acid esters and / or alkyl sulfosuccinates.
  • Mixtures in particular are here preferred, the anionic surfactants alk (en) yl sulfates and Alkylbenzenesulfonates and optionally methyl ⁇ -sulfofatty acid and / or contain sulfated fatty acid glycerol esters.
  • Soaps are particularly preferred as further anionic surfactants in amounts below 5% by weight.
  • saturated fatty acid soaps such as the salts of lauric acid, myristic acid, Palmitic acid or stearic acid, and in particular from natural fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
  • Unsaturated fatty acid soaps that are deriving from oleic acid, for example, may also be present However, their proportion of soaps should not be 50% by weight exceed.
  • the anionic surfactants and soaps can be in the form of their sodium, Potassium or ammonium salts as well as organic organic salts Bases, such as mono-, di- or triethanolamine, are present.
  • the anionic surfactants in the form of their sodium or potassium salts, especially in the form of the sodium salts.
  • the salary of the The average of anionic surfactants is between 5 and 40% by weight.
  • the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (E0) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or may contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
  • alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 E0 per mole of alcohol are particularly preferred.
  • the preferred ethoxylated alcohols include, for example, C 12 -C 14 alcohols with 3 E0 or 4 E0, C 9 -C 11 alcohol with 7 EO, C 13 -C 15 alcohols with 3 E0, 5 E0, 7 E0 or 8 E0, C 12 -C 18 alcohols with 3 E0, 5 E0 or 7 E0 and mixtures thereof, such as mixtures of C 12 -C 14 alcohol with 3 EO and C 12 -C 18 alcohol with 5 E0.
  • the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
  • Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
  • fatty alcohols with more than 12 E0 can also be used. Examples include tallow fatty alcohol with 14 E0, 25 E0, 30 E0 or 40 E0.
  • alkyl glycosides of the general formula R0 (G) x can also be used as further nonionic surfactants, in which R denotes a primary straight-chain or methyl-branched, in particular methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18, C atoms and G is the symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
  • the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; x is preferably 1.2 to 1.4.
  • Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in the R 2 CO for an aliphatic acyl radical having 6 to 22 carbon atoms, R 3 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups stands.
  • the proportion of nonionic surfactants in the agents is in generally 2 to 25% by weight.
  • All previous builders can be used as further inorganic builder substances usually used builder substances are used. To these include in particular zeolites, crystalline layered silicates, even phosphates, if not used for ecological reasons should be avoided. Your salary can vary depending on the salary on the X-ray amorphous and "over-dried" Silicates with body structure vary in a wide range.
  • the sum of customary builder substances and those according to the invention Silicates are usually 10 to 60% by weight.
  • Usable organic builders which are also separated from the Alkali silicates and / or in combination with corresponding ones Compounds that can be used are, for example previously mentioned, preferably used in the form of their sodium salts Polycarboxylic acids, such as citric acid, adipic acid, succinic acid, Glutaric acid, tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA).
  • NTA nitrilotriacetic acid
  • Suitable polymeric polycarboxylates are those already mentioned above Groups of substances, for example the sodium salts of polyacrylic acid or polymethacrylic acid, for example those with a relative Molecular mass from 800 to 150,000 (based on acid).
  • Suitable copolymeric polycarboxylates are, in particular, those of Acrylic acid with methacrylic acid and acrylic acid or Methacrylic acid with maleic acid. In detail, the previous one Reference is made to these classes of substances.
  • bleaching agents which serve as bleaching agents and supply H 2 O 2 in water
  • sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
  • Further bleaching agents which can be used are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid or diperdodecanedioic acid.
  • the bleaching agent content of the agents is preferably 5 to 25% by weight and in particular 10 to 20% by weight, with perborate monohydrate being advantageously used.
  • bleach activators can be incorporated into the preparations.
  • these are N-acyl or 0-acyl compounds which form organic peracids with H 2 0 2 , preferably N, N'-tetra-acylated diamines, furthermore carboxylic acid anhydrides and esters of polyols such as glucose pentaacetate.
  • Other known bleach activators are acetylated mixtures of sorbitol and mannitol, as described, for example, in European patent application EP-A-0 525 239.
  • the bleach activators contain bleach activators in the usual range, preferably between 1 and 10% by weight and in particular between 3 and 8% by weight.
  • bleach activators are N, N, N ', N'-tetraacetylethylene diamine (TAED), 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine (DADHT) and acetylated sorbitol-mannitol mixtures (SORMAN).
  • TAED N, N, N ', N'-tetraacetylethylene diamine
  • DADHT 1,5-diacetyl-2,4-dioxo-hexahydro-1,3,5-triazine
  • SORMAN acetylated sorbitol-mannitol mixtures
  • Suitable foam inhibitors are, for example, soaps of natural or synthetic origin, which have a high proportion of C 18 -C 24 fatty acids.
  • Suitable non-surfactant-like foam inhibitors are, for example, organopolysiloxanes and their mixtures with microfine, optionally silanized silica, and paraffins, waxes, microcrystalline waxes and their mixtures with silanized silica or bistearylethylenediamide. Mixtures of various foam inhibitors are also used with advantages, for example those made of silicones, paraffins or waxes.
  • the foam inhibitors, in particular silicone or paraffin-containing foam inhibitors are preferably bound to a granular, water-soluble or dispersible carrier substance. Mixtures of paraffins and bistearylethylenediamides are particularly preferred.
  • Enzymes come from the class of proteases, lipases, Amylases, cellulases or their mixtures in question. Particularly good are suitable from bacterial strains or fungi, such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases are preferably from Subtilisin type and especially proteases derived from Bacillus lentus won, used.
  • enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or from cellulase and lipase or from protease, Amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of particular Interest.
  • Peroxidases or oxidases have also been found in some Cases proved to be suitable.
  • the enzymes can on carriers adsorbed and / or embedded in enveloping substances to counter them to protect premature decomposition.
  • the proportion of enzymes, enzyme mixtures or enzyme granules can be, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 wt .-%.
  • HEDP 1-hydroxyethane-1,1-diphosphonic acid
  • DETPMP Diethylenetriaminepentamethylenephosphonic acid
  • ETMP Ethylenediaminetetramethylenephosphonic acid
  • Graying inhibitors have the task of keeping the dirt detached from the fibers suspended in the liquor and thus preventing graying.
  • Water-soluble colloids of mostly organic nature are suitable for this, for example the water-soluble salts of polymeric carboxylic acids, glue, gelatin, salts of ether carboxylic acids or ether sulfonic acids of starch or cellulose or salts of acidic sulfuric acid esters of cellulose or starch.
  • Water-soluble polyamides containing acidic groups are also suitable for this purpose. Soluble starch preparations and starch products other than those mentioned above can also be used, for example degraded starch, strong aldehydes, etc.
  • Polyvinylpyrrolidone can also be used.
  • cellulose ethers such as carboxymethyl cellulose (sodium salt), methyl cellulose, hydroxyalkyl cellulose and mixed ethers, such as methyl hydroxyethyl cellulose, methyl hydroxypropyl cellulose, methyl carboxymethyl cellulose and mixtures thereof, and polyvinylpyrrolidone, for example in amounts of 0.1 to 5% by weight, based on the detergent, are preferred used.
  • the agents can be used as optical brighteners Contain 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 similar connections, which instead of the morpholino group is a diethanolamino group, a Methylamino group, an anilino group or a 2-methoxyethylamino group carry. Brighteners of the type of the substituted diphenyl styrenes, e.g.
  • the alkali salts 4,4'-bis (2-sulfostyryl) diphenyl, 4,4'-bis (4-chloro-3-sulfostyryl) diphenyl, or 4- (4-chlorostyryl) -4 '- (2-sulfostyryl) diphenyl.
  • Mixtures of the aforementioned Brighteners can be used.
  • the bulk density of the preferred granular washing or cleaning agents which contain the silicates according to the invention and with the other components of common washing and cleaning agents are applied, is generally 300 to 1200 g / l, preferably however 500 to 1100 g / l.
  • They can be produced by any of the known processes such as mixing, spray drying, granulating and extruding take place, the X-ray amorphous and "over-dried" according to the invention Silicate compounds and preferably those with flowable Recyclable materials from the field of detergents and cleaning agents, in particular with nonionic surfactants, loaded silicate compounds advantageously be added to the other components of the agent.
  • Sub-components for example spray-dried components and granulated and / or extruded components mixed together become.
  • any anionic surfactants present a spray-dried, granulated or extruded compound either as an admixture in the processes mentioned or as Additive additive to other granules.
  • washing and cleaning agents according to the invention the general specialist knowledge.
  • temperature-sensitive components such as enzymes, volatile fragrances or fragrances, but possibly also temperature sensitive Percarbonate compounds mixed in under working conditions that exclude damage to such components.
  • Temperatur-sensitive components such as enzymes, volatile fragrances or fragrances, but possibly also temperature sensitive Percarbonate compounds mixed in under working conditions that exclude damage to such components.
  • Cicumal for the washing and cleaning agents in the sense of the invention Teaching is the use of alkali silicate builders respectively corresponding builder compounds which are used in the sense of the invention Procure definition and have been produced.
  • Niro-Atomizer produces an aqueous solution of water glass and soda spray dried with superheated steam.
  • the aqueous solution of the The mixture of recyclable materials to be dried is added via a 2-component nozzle superheated steam sprayed as a propellant.
  • the sodium carbonate was dissolved in distilled water at about 80 ° C. to give a clear solution and mixed with the water glass present as an aqueous preparation.
  • a mixing ratio of 1: 1 - based on dry substance (TS) - is set for the two components water glass and soda as Na 2 CO 3 x 10H 2 O.
  • TS content of the feed solution 37% by weight pH of the aqueous preparation 12.2
  • the water glass in the aqueous preparation to be sprayed is characterized by the following characteristics: Density kg / m 3 1,690 - 1,710 Water glass module 2.00 - 2.06 Viscosity mPas / 20 ° C > 10,000 % By weight of water 44.6 - 46.2 % By weight SiO 2 36.0 - 37.0 % By weight Na 2 O 17.8-18.4
  • a free-flowing, fine-grained white product is obtained as a process product, which is characterized by the following material parameters: Residual moisture at 140 ° C 1.0% by weight Bulk density 420 g / l Solubility in water (90% / 20 ° C) 30 sec
  • Example 1 In the system of Example 1, an aqueous preparation of water glass, soda and sodium citrate is spray-dried with superheated steam as the drying gas.
  • the following mixing ratio (calculated as TS) is set: 45% by weight water glass, 10% by weight Na 2 CO 3 x 10 H 2 O and 45% by weight C 6 H 5 O 7 Na 3 x 2 H 2 O
  • the Sodium carbonate together with the trisodium citrate in distilled water dissolved at approx. 80 ° C to a clear solution and added to the water glass.

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Claims (14)

  1. Produit solide qui renferme des silicates de métaux alcalins avec un rapport molaire SiO2: M2O (dans lequel M représente un métal alcalin) de 0,8 à 4, en mélange homogène avec d'autres matières de valeur et/ou adjuvantes inorganiques et/ou organiques, caractérisé en ce qu'il contient, comme matières de valeur et/ou adjuvantes inorganiques et/ou organiques, au moins 10 % en poids de sels inorganiques et/ou organiques solubles dans l'eau, présente une densité en vrac d'au moins 150 g/l et une surface BET d'au moins 5 m2/g, la fraction de silicate de métaux alcalins possède une teneur en eau inférieure à 15 % en poids et les silicates de métaux alcalins sont présents à au moins 50 % en poids dans une structure Q2 et/ou Q3.
  2. Produit solide selon la revendication 1, caractérisé en ce que la fraction de silicates de métaux alcalins possède une teneur en eau dans la plage de 1 à 13 %.
  3. Produit solide selon une des revendications 1 et 2, caractérisé en ce que la fraction de silicates de métaux alcalins représente au moins 25 % en poids, de préférence au moins 40 % en poids et en particulier, au moins 50 % en poids, auquel cas il est en outre préférable que les autres matières de valeur et/ou adjuvants présentes en mélange homogène soient contenues en proportions d'au moins 15 % en poids, de préférence d'au moins 20 % en poids et en particulier, en proportions d'au moins 25 % en poids.
  4. Produit solide selon une des revendications 1 à 3, caractérisé en ce qu'il renferme comme silicates de métaux alcalins et, de préférence, également comme sels incorporés par mélangeage homogène, des composés de sodium et/ou de potassium.
  5. Produit solide selon une ou plusieurs des revendications 1 à 4, caractérisé en ce qu'au moins la fraction de silicates de métaux alcalins se distingue par une solubilité dans l'eau, même à température ambiante, telle qu'il présente une fraction de produit insoluble inférieure à 3 % en poids et en particulier, inférieure à 1 % en poids.
  6. Produit solide selon une ou plusieurs des revendications 1 à 5, caractérisé en ce que la fraction de silicates de métaux alcalins est amorphe aux rayons X.
  7. Produit solide selon une ou plusieurs des revendications 1 à 6, caractérisé en ce qu'il renferme en mélange avec les silicates de métaux alcalins, comme matières de valeur et/ou adjuvantes inorganiques solubles dans l'eau, des sels de métaux alcalins, sous la forme des carbonates, sulfates, halogénures, phosphates, polyphosphates et borates correspondants, et/ou des sels d'acides carboxyliques, de préférence polyfonctionnels, et/ou d'acides polycarboxyliques ou des copolymères de ceux-ci.
  8. Utilisation du produit solide selon une ou plusieurs des revendications 1 à 7, comme adjuvants dans des produits de lavage et de nettoyage.
  9. Utilisation selon la revendication 8, caractérisée en ce que le produit solide est chargé d'autres matières de valeur et mélanges de matières de valeur coulantes du domaine des produ de lavage et de nettoyage, en particulier des détersifs pour les textiles.
  10. Utilisation selon la revendication 9, caractérisée en ce que le produit solide est chargé de matières de valeur et de mélanges de matières de valeurs coulantes, qui sont sélectionnées parmi les tensioactifs non ioniques, les préparations liquides de surfactifs anioniques, les tensioactifs anioniques à haute concentration plastifiés, les formulations coulantes d'assouplissants pour les textiles et/ou les inhibiteurs de mousse, appartenant en l'espèce de préférence à la classe des silicones et/ou des paraffines.
  11. Produits de lavage et de nettoyage sous forme solide, en particulier détersifs pour les textiles à base d'un mélange de tensioactifs, de composants adjuvants et d'autres matières de valeur et/ou adjuvantes usuelles, caractérisés en ce qu'ils renferment un produit solide selon les revendications 1 à 7.
  12. Procédé de production d'un produit solide, qui renferme des silicates de métaux alcalins avec un rapport molaire SiO2:M2O (dans lequel M représente un métal alcalin) de 0,8 à 4, en mélange homogène avec d'autres matières de valeur et/ou adjuvantes inorganiques et/ou organiques, et qui contient au moins 10 % en poids de sels inorganiques et/ou organiques solubles dans l'eau, présente une densité en vrac d'au moins 150 g/l, la fraction de silicate de métaux alcalins possède une teneur en eau inférieure à 15 % en poids, les silicates de métaux alcalins sont présents à au moins 50 % en poids dans une structure Q2 et/ou Q3 et le produit solide présente une surface BET d'au moins 5 m2/g, par séchage par pulvérisation et/ou en lit fluidisé d'une préparation aqueuse finement pulvérisée de mélanges des silicates de métaux alcalins et des matières de valeur et/ou adjuvantes inorganiques et/ou organiques, à l'aide de vapeur d'eau surchauffée.
  13. Procédé selon la revendication 12, caractérisé en ce que le séchage par pulvérisation ou en lit fluidisé est opéré, en excluant l'accès de CO2 à la zone de séchage, en utilisant comme flux de gaz de séchage, un flux partiel, acheminé en circuit et réchauffé à nouveau par apport indirect d'énergie, de la vapeur d'eau surchauffée prélevée de la zone de séchage.
  14. Procédé selon une des revendications 12 et 13 ou selon les deux, caractérisé en ce que la vapeur d'eau surchauffée présente une température d'entrée dans la zone de séchage comprise dans l'intervalle de 280 à 380 °C et une température de sortie de la zone de séchage, dans la plage de 180 à 240 °C.
EP95911243A 1994-03-01 1995-02-20 Melanges complexes a base de composes de silicate alcalin hydrosolubles et leur utilisation Expired - Lifetime EP0748369B1 (fr)

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DE4406592 1994-03-01
DE4406592A DE4406592A1 (de) 1994-03-01 1994-03-01 Verbesserte Mehrstoffgemische auf Basis wasserlöslicher Alkalisilikatverbindungen und ihre Verwendung, insbesondere zum Einsatz als Builder in Wasch- und Reinigungsmitteln
PCT/EP1995/000604 WO1995023841A1 (fr) 1994-03-01 1995-02-20 Melanges complexes a base de composes de silicate alcalin hydrosolubles et leur utilisation

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FR2688798B1 (fr) * 1992-03-20 1994-10-14 Rhobb Poulenc Chimie Agent "builder" a base de silicate et d'un produit mineral.
DE4300772C2 (de) * 1993-01-14 1997-03-27 Stockhausen Chem Fab Gmbh Wasserlösliche, biologisch abbaubare Copolymere auf Basis von ungesättigten Mono- und Dicarbonsäuren, Verfahren zu ihrer Herstellung und ihre Verwendung
DE4319578A1 (de) * 1993-06-14 1994-12-15 Henkel Kgaa Waschmittel, enthaltend Aminosäuren und/oder deren Salze
DE4330393C2 (de) * 1993-09-08 1999-08-26 Heidelberger Druckmasch Ag Bogenführung im Ausleger einer Bogendruckmaschine

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ES2138192T3 (es) 2000-01-01
DE4406592A1 (de) 1995-09-07
JPH09509641A (ja) 1997-09-30
ATE185164T1 (de) 1999-10-15
CN1140466A (zh) 1997-01-15
WO1995023841A1 (fr) 1995-09-08
EP0748369A1 (fr) 1996-12-18
US5814597A (en) 1998-09-29
DE59506956D1 (de) 1999-11-04

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