EP1123378B1 - Shaped detergent bodies with a dry-granulated effervescent system - Google Patents
Shaped detergent bodies with a dry-granulated effervescent system Download PDFInfo
- Publication number
- EP1123378B1 EP1123378B1 EP99947459A EP99947459A EP1123378B1 EP 1123378 B1 EP1123378 B1 EP 1123378B1 EP 99947459 A EP99947459 A EP 99947459A EP 99947459 A EP99947459 A EP 99947459A EP 1123378 B1 EP1123378 B1 EP 1123378B1
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- European Patent Office
- Prior art keywords
- weight
- acid
- process according
- effervescent system
- granulated
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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
- C11D3/10—Carbonates ; Bicarbonates
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/0047—Detergents in the form of bars or tablets
- C11D17/0065—Solid detergents containing builders
- C11D17/0073—Tablets
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- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/0005—Other compounding ingredients characterised by their effect
- C11D3/0052—Gas evolving or heat producing compositions
-
- C—CHEMISTRY; METALLURGY
- C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
- C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
- C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/2075—Carboxylic acids-salts thereof
Definitions
- the present invention is in the field of compact molded articles that are washable have cleaning-active properties.
- Such detergent tablets include for example detergent tablets for washing textiles, Molded detergent for machine dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets.
- the invention relates Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.
- Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage.
- Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to handle and because of their compact structure Advantages in storage and transport. Also in the patent literature detergent tablets are therefore comprehensively described.
- the delayed Disintegration of the moldings also has the disadvantage that they are customary Detergent tablets not through the induction chamber of household washing machines Allow to be flushed in, as the tablets do not get in quickly enough Secondary particles disintegrate, which are small enough to enter the induction chamber Washing drum to be washed in.
- US 5, 114, 647 discloses cleaning particles which contain about 38% by weight of an effervescent system composed of Na 2 CO 3 and organic acid and more than 5% by weight of anionic surfactant.
- the unpublished EP 881 282 A1 discloses tablets which also contain effervescent systems made of Na 2 CO 3 and organic acid as well as anionic surfactants. No information is given in these documents on water-free production or particle sizes of the shower system.
- a method for producing a cogranulate which can be used in detergent tablets is described in WO98 / 14548 (Schmitz).
- a citric acid solution is placed on a solid bed of soda moved in the mixer in order to produce granules which contain sodium bicarbonate, sodium citrate and a portion of residual soda.
- the process disclosed in this document neither provides an effervescent system, nor is the granulation carried out without water.
- the surfactant (s), builder and optionally contain further detergent and cleaning agent components are disclosed, the surfactant (s), builder and optionally contain further detergent and cleaning agent components.
- the moldings disclosed here contain 1 to 10% by weight of one or more swellable, water-insoluble disintegration aid and 3 to 60 wt .-% of a gas-generating shower system, the swellable agent or the components of the shower systems compounded with other ingredients of the detergent and cleaning agent can also be mixed separately.
- Information on a co-granulated shower system or for the water-free production of shower granules are this document not to be removed.
- the present invention was based on the object of providing moldings which are characterized by short disintegration times with a given hardness and thus also dispense via the induction chamber of household washing machines. there should also be a simple and inexpensive method for producing such advantageous Shaped bodies are provided.
- the invention relates to detergent tablets made of compressed, Particulate detergents and cleaning agents containing 5 to 50% by weight of anionic (s) Surfactant (s), which is an anhydrous granulated spray system in amounts of 1 to 20% by weight, each based on the molded article, containing at least 80 wt .-% of the particles of the water-free granulated shower system have particle sizes above 600 ⁇ m.
- anionic (s) Surfactant (s) which is an anhydrous granulated spray system in amounts of 1 to 20% by weight, each based on the molded article, containing at least 80 wt .-% of the particles of the water-free granulated shower system have particle sizes above 600 ⁇ m.
- a shower system generally consists of two components that are exposed to water can react with one another to release one or more gases. Although it is here shower systems are based on a multitude of technical possibilities Carbonates or bicarbonates mixed with acidic components (so-called acidifiers) most widespread. As part of the In the present invention, the ingredients of the effervescent system become a cogranulate processed, using an anhydrous granulation process. The effervescent granules obtained give the washing and Detergent tablets advantageous compared to the use of raw materials alone Characteristics.
- the washing and Detergent tablets the water-free granulated shower system in quantities from 1 to 20% by weight, preferably from 2 to 18% by weight, particularly preferably from 3 to 15% by weight and in particular from 5 to 10% by weight, in each case based on the shaped body.
- the contained in the detergent tablets according to the invention water-free granulated shower system is used in a coarser form. Although one could assume that a fine incorporation due to the more homogeneous distribution and the higher reaction surface leads to better results, it has been shown that exceeding a certain particle size the decay times at the desired Hardness further minimized.
- Particularly preferred detergent tablets are characterized in that at least 90% by weight and in particular that Total amount of particles in the water-free granulated shower system have above 600 ⁇ m.
- shower systems mostly consist of carbonates and / or Hydrogen carbonates and acidic components (acidifying agents) which are suitable To release carbon dioxide from them.
- carbonates and / or hydrogen carbonates in the context of the present invention are the alkali metal salts and among them the sodium salts particularly preferred.
- the relevant ones do not have to be pure Alkali metal carbonates or bicarbonates are used; rather mixtures different carbonates and hydrogen carbonates from washing technology interest or be preferred for economic reasons.
- acidifying agents that release carbon dioxide from the alkali salts in aqueous solution are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used.
- organic acidifiers are used, with citric acid being a particularly preferred Acidifier is.
- the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. From this group tartaric acid is preferred, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid.
- Organic sulfonic acids such as amidosulfonic acid can also be used.
- Sokalan® DCS Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
- detergent tablets which as a water-free granulated shower system is a granulate made of carbonate (s) and / or hydrogen carbonate (s) with acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1.
- the components of the shower system carbonate (s) and / or granulate hydrogen carbonate (s) and acidifying agent
- the components of the shower system carbonate (s) and / or granulate hydrogen carbonate (s) and acidifying agent
- the above usable shower system compounds with at least 60 wt .-% shower system the above as the preferred particle size distribution.
- water-free contain granulated, shower system-containing compounds which have at least 60% by weight shower system (carbonate (s) and / or hydrogen carbonate (s) and acidifying agent), each based on the weight of the compound, preferably at least 80% by weight, preferably at least 90% by weight and in particular the total amount of the compounds have particle sizes above 600 ⁇ m.
- shower system carbonate (s) and / or hydrogen carbonate (s) and acidifying agent
- Disintegrants based on cellulose are used as preferred additional disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 wt .-% included.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, is a ⁇ -1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions.
- Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses.
- the cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose.
- the content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
- the cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed.
- Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants.
- the particle sizes of such disintegrants are usually above 200 ⁇ m, preferably at least 90% by weight between 300 and 1600 ⁇ m and in particular at least 90% by weight between 400 and 1200 ⁇ m.
- the above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
- Particularly preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.
- a disintegration aid preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.
- microcrystalline cellulose As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used.
- This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged.
- a subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, the primary particle sizes of approx. 5 ⁇ m have and for example to granules with an average particle size of 200 microns are compactable.
- Such coated washing and Detergent tablets can by spraying a melt or solution of the Coating material on the molded body or immersing the molded body in the melt or solution can be prepared.
- the laundry detergent and cleaning product tablets are not one Coating, which covers the entire molded body, coated.
- detergent tablets can be produced according to the invention, which disintegrate into their constituents extremely quickly in water. Washing and washing are particularly preferred in the context of the present invention Detergent tablets that are in water at 30 ° C in less than 60 seconds completely disintegrate into their secondary particles, which are so small that they overlap Have the washing-in chamber of a household washing machine wash in.
- Disintegration aids to be used optionally contain the Detergent tablets according to the invention further detergents and Detergent ingredients, especially from the groups of surfactants, builders, Bleaches, bleach activators, optical brighteners, dyes and fragrances etc. These Substances are described below.
- the first process step is the production of a water-free granulated shower system, its presence in the detergent tablets according to the invention gives the beneficial properties.
- granulation aids so-called Granulating liquids
- the granulating liquid being liquid bridges forms between the individual particles and thus to form agglomerates with a "raspberry structure" contributes.
- Water or aqueous solutions are often used as the granulation liquid used, which is to be expressly avoided in the process according to the invention in order to to avoid a premature reaction of the components of the shower system.
- the components of the shower system to mix dry together and a press agglomeration submit.
- the press agglomeration process which is the mixture of the components the shower system is subjected to, can be realized in various devices become. Depending on the type of agglomerator used, different press agglomeration processes are used distinguished. The three most common and within the scope of the present The preferred press agglomeration process is extrusion Roller pressing or compacting and hole pressing (pelleting), so that in the frame preferred press agglomeration operations of the present invention extrusion, roll compacting and pelleting processes.
- the The method according to the invention is carried out by means of roller compaction.
- the mixture of the components of the shower system is targeted between two smooth or metered rollers provided with depressions of a defined shape and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out.
- the rollers exert a high line pressure on the premix and can be additionally heated or cooled as required.
- smooth rollers one obtains smooth, unstructured sash bands, while through the Structured slugs are generated using structured rollers can, in which, for example, certain forms of the later effervescent granules are specified can be.
- the cuff belt is subsequently subjected to a knock-off and crushing process broken into smaller pieces and can thus become granules are processed by further known surface treatment processes can be refined.
- the method according to the invention is carried out by means of pelleting.
- the mixture of the components of the shower system is applied to a perforated surface and pressed through the holes by means of a pressure-generating body.
- the premix is compressed under pressure, pressed through a perforated surface by means of a rotating roller in the form of fine strands, and finally comminuted into granules using a knock-off device.
- the most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers.
- the press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation.
- An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH).
- the ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge.
- the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved.
- the granulation capacity of the shower system can be adjusted or improved by auxiliary substances become. All raw materials common in detergents and cleaning agents can be used for this are used, whereby fatty alcohol ethoxylates with different degrees of ethoxylation, Polyethylene glycols or paraffins are preferred.
- one or more are / are carried out in process step a) Carbonate (s) and / or bicarbonate (s) with one or more acidifying agent (s) dry mixed together and a press agglomeration, preferably one Roll compaction, subjected.
- the detergent tablets according to the invention are also certain weight ratios in the method according to the invention particularly advantageous between the individual components of the shower system. So are Preferred processes in which the carbonate (s) and / or hydrogen carbonate (s) with the acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1, mixed and press agglomerated.
- the alkali metal salts preferably the Sodium salts used, with sodium hydrogen carbonate and sodium carbonate especially are preferred.
- One or more substances are preferably used as acidifying agents from the group of solid organic di-, tri- and Oligocarboxylic acids are used, with citric acid being particularly preferred. In terms of Further applicable acidifying agents are referred to the above statements.
- the particle sizes of the water-free granulated shower system and the amounts in which the water-free granulated shower system in the process according to the invention is used, are completely analogous to the above information.
- Step a) So point in preferred method at least 90 wt .-% and in particular the total amount of in Step a) produced shower system particle sizes above 600 microns.
- Further preferred processes are characterized in that the one produced in step a) Effervescent granules 1 to 20% by weight, preferably 2 to 18% by weight, particularly preferably 3 up to 15% by weight and in particular 5 to 10% by weight of the premix to be pressed accounts.
- the washing and Detergent tablets in addition to the water-free granulated shower system Detergent and cleaning agent ingredients.
- the effervescent granules produced in step a) are processed in step b) with at least a surfactant-containing granulate to a premix to be pressed with a Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l combined.
- the production of the surfactant-containing granules can be done by conventional technical means Granulation processes such as compacting, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is there for later washing and Detergent tablets are advantageous if the premix to be pressed is a Has bulk density that comes close to the usual compact detergent. In particular it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
- the granules containing surfactant also suffice in certain preferred process variants
- sectionchen relienkriterien Methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 ⁇ m, particularly preferably between 400 and 1600 ⁇ m and in particular between 600 and 1400 ⁇ m.
- the surfactant granules preferably also contain carriers, which particularly preferably come from the group of builders.
- Particularly advantageous Processes are characterized in that the surfactant-containing granules are anionic and / or non-ionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
- the surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic Surfactants, anionic surfactants for economic reasons and because of their Range of services are clearly preferred.
- Anionic surfactants used are, for example, those of the sulfonate and sulfate type.
- the surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products.
- alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- the esters of ⁇ -sulfofatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
- Suitable anionic surfactants are sulfonated fatty acid glycerol esters.
- fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol.
- preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
- alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology.
- 2,3-Alkyl sulfates which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
- the sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO; are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
- Suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- alcohols preferably fatty alcohols and in particular ethoxylated fatty alcohols.
- Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below).
- sulfosuccinates the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- Soaps are particularly suitable as further anionic surfactants.
- saturated fatty acid soaps such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
- the anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine.
- the anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
- the detergent tablets contain 5 to 50% by weight anionic surfactant (s).
- anionic surfactant s
- washing and Preferred detergent tablets the 7.5 to 40 wt .-% and in particular 10 to 20 % By weight of anionic surfactant (s), based in each case on the molding weight.
- anionic surfactants When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, freedom of formulation no framework conditions to be observed in the way.
- Preferred washing and However, detergent tablets have a soap content of 0.2% by weight, based on the total weight of the molded body.
- Preferred to use Anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates preferred detergent tablets 2 to 20 wt .-%, preferably 2.5 up to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the molded body 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 (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals.
- EO ethylene oxide
- alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO.
- the degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
- alkyl polyglycosides Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG).
- Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose.
- the degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
- Linear alkyl polyglucosides ie alkyl polyglycosides, are preferably used in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
- the detergent tablets according to the invention can preferably alkyl polyglycosides included, with APG contents of the molded articles being above 0.2% by weight on the entire molded body, are preferred.
- Particularly preferred washing and Detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
- nonionic surfactants of the amine oxide type for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable.
- the amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
- Suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
- R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 represents a linear, branched or cyclic alkyl radical or an aryl
- [Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar for example glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
- builders are the most important ingredients of Detergents and cleaning agents.
- Detergent tablets can all be used in washing and cleaning agents
- Builders may be included, in particular thus zeolites, which according to the invention are within a certain particle size range used silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also the Phosphates.
- the builders mentioned can also be used in surfactant-free moldings are, so that it is possible according to the invention to produce moldings which for Water softening or as bleach tablets can be used.
- processes use surfactant granules which, in addition to surfactant (s) as a carrier, builders (e) contain.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 ⁇ H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x 2, 3 or 4.
- M sodium or hydrogen
- x is a number from 1.9 to 4
- y is a number from 0 to 20, preferred values for x 2, 3 or 4.
- Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514.
- Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 ⁇ yH 2 O are preferred, with ⁇ -sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
- the delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying.
- the term “amorphous” is also understood to mean “X-ray amorphous”.
- silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle.
- it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray amorphous silicates which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
- Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
- the finely crystalline, synthetic and bound water-containing zeolite used is preferably zeolite A and / or P.
- zeolite P zeolite MAP® (commercial product from Crosfield) is particularly preferred.
- zeolite X and mixtures of A, X and / or P are also suitable.
- zeolite X and zeolite A (about 80% by weight of zeolite X)
- VEGOBOND AX® sold by CONDEA Augusta SpA under the brand name VEGOBOND AX® and by the formula nNa 2 O ⁇ (1-n) K 2 O ⁇ Al 2 O 3 ⁇ (2 - 2.5) SiO 2 ⁇ (3.5 - 5.5) H 2 O
- the zeolite can be used both as a builder in a granular compound, and can also be used for a kind of "purging" of the entire mixture to be pressed, usually using both ways of incorporating the zeolite into the premix.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution; measurement method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be.
- alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.
- Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
- Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
- NaH 2 PO 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
- Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
- Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
- Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH.
- Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction.
- Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
- the decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water.
- Potassium diphosphate potassium pyrophosphate
- K 4 P 2 O 7 exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
- Sodium and potassium phosphates in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
- pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
- sodium tripolyphosphate sodium tripolyphosphate
- n 3
- Approx. 17 g of the salt free from water of crystallization dissolve in 100 g of water at room temperature, approx. 20 g at 60 ° and around 32 g at 100 °; After heating the solution at 100 ° for two hours, hydrolysis produces about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the production of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dewatered by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentapotassium triphosphate, K 5 P 3 O 10 (potassium tripolyphosphate), is commercially available, for example, in the form of a 50% strength by weight solution (> 23% P 2 O 5 , 25% K 2 O). The potassium polyphosphates are widely used in the detergent and cleaning agent industry.
- sodium potassium tripolyphosphates which can also be used in the context of the present invention. These occur, for example, when hydrolyzing sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
- these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
- Organic cobuilders can be used in the laundry detergent tablets 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 builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function.
- these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these.
- Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
- the acids themselves can also be used.
- the acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents.
- citric acid succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
- Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mol.
- the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used.
- GPC gel permeation chromatography
- the measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard.
- the molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
- Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
- copolymeric polycarboxylates especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid.
- Your relative molecular mass, based on free acids is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
- the (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution be used.
- the content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
- the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
- allylsulfonic acids such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid
- biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
- copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
- polymeric aminodicarboxylic acids their salts or their precursor substances.
- Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
- polyacetals which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained.
- Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
- Suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
- the hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol.
- DE dextrose equivalent
- Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
- 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.
- oxidizing agents capable of oxidizing at least one alcohol function of the saccharide ring to the carboxylic acid function.
- Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 .
- An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable.
- a product oxidized at C 6 of the saccharide ring can be
- oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
- ethylenediamine-N, N'disuccinate (EDDS) 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 those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups.
- Such cobuilders are used, for example, in the international Patent application WO 95/20029 described.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- HEDP 1-hydroxyethane-1,1-diphosphonate
- Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z. B.
- HEDP is preferably used as the builder from the class of the phosphonates.
- the aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
- the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight.
- the amount of builders used depends on the intended use, so that Bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
- premix in addition to the surfactant granulate and the water-free granulated shower system, this can also be done Compressing premix in the process according to the invention contain further ingredients.
- the premix additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the premix.
- the premix additionally contains one or more Substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, Perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below.
- 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, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced.
- bleaching agents from the group of organic bleaching agents can also be used.
- Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide.
- Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxyaloacidoperoxycaproic acid (P ⁇ ) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diper
- Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing
- Bromine-releasing substances are used.
- appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered.
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
- bleach activators can be used as the sole component or be incorporated as an ingredient of component b).
- Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups.
- Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
- TAED Tetraacetylethylenediamine
- bleaching catalysts can be incorporated into the moldings.
- these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes.
- Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
- Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question.
- Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents.
- Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are 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 mixtures containing cellulase of special interest.
- Peroxidases or oxidases have also been found in some Cases proved to be suitable.
- the enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition.
- the Proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive Shaped bodies can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.
- the detergent tablets can also contain components which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed.
- nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
- the moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their 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, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g.
- Dyes and fragrances become the detergent tablets according to the invention added to improve the aesthetic impression of the products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product.
- Individual as perfume oils or fragrances Fragrance compounds e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used.
- fragrance compounds of the ester type are e.g.
- the ethers include, for example, benzyl ethyl ether, to aldehydes e.g.
- the linear alkanals with 8-18 C atoms citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ⁇ -isomethyl ionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol,
- the hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together.
- perfume oils can also be natural Fragrance mixtures contain, as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- Muscatel sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
- the content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the total Can make up wording.
- the fragrances can be incorporated directly into the agents according to the invention but it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles.
- Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
- the detergent tablets according to the invention can be colored with suitable dyes.
- suitable dyes preferred Dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers, um not to stain them.
- the moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used.
- the premix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, compression (elastic Deformation), plastic deformation and ejection.
- the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined.
- the constant dosage even with high throughputs of shaped bodies, a volumetric flow rate is preferably used Dosage of the premix reached.
- the Upper stamp the premix and continues to lower towards the lower stamp. at this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches is continuous decreases. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation at which the particles flow together and the molded body is formed.
- the phase of elastic Deformation is shortened further and further, so that the resulting shaped body more or may have smaller cavities.
- the Finished moldings are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.
- Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down.
- eccentric tablet presses which the stamp or stamps are attached to an eccentric disc, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works.
- the pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly.
- the throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
- Matrix table For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle.
- the number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available.
- Each die on the die table is an upper and lower stamp assigned, with the pressure again being active only through the upper or lower stamp, but can also be built using both stamps.
- the matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought.
- Rotary presses can also be equipped with two filling shoes to increase the throughput be, whereby only a semicircle is run through to produce a tablet got to.
- Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected.
- By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion-shell-like structure have, in the case of the point tablets the top of the core or core layers is not covered and therefore remains visible.
- Rotary tablet presses are also included Single or multiple tools can be equipped so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing.
- the throughputs of modern rotary tablet presses are over a million tablets per hour.
- Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMAmaschinessysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms.
- Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
- the hydraulic double-pressure press is particularly suitable HPF 630 from LAEIS, D.
- Tableting tools are for example from the company Adams Tablettierwerkmaschinen, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
- Other providers are e.g. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
- the moldings can be made in a predetermined spatial shape and size become. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.
- the portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is.
- the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
- Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
- the spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process.
- a metering aid where it dissolves during the induction process.
- the detergent tablets are easily possible via a dosing aid and within the present invention preferred.
- Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine.
- This The principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles that only on one of their Pages are connected alongside each other, can be realized.
- the layer structure of the moldings can be done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete covering of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
- a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Moldings, the outermost layers, however, are free of peroxy bleach.
- the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
- multiphase molded articles can also be in the form of ring core tablets, Core coated tablets or so-called "bulleye” tablets are produced.
- An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group).
- This document discloses blocks of toilet detergent, which is a molded body made from a slowly soluble detergent composition include in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multiphase molded bodies from from simple multi-phase tablets to complicated multi-layer systems Insoles.
- ⁇ stands for diametral fracture stress (DFS) in Pa
- P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the molded body causes
- D is the molded body diameter in meters
- t is the Height of the molded body.
- Granulation in a 50-liter ploughshare mixer from Lödige resulted in a surfactant-containing Granules (composition see Table 1), which is the basis for a particulate premix was used.
- composition see Table 1 which is the basis for a particulate premix was used.
- a tablettable premix was produced.
- a shower system was incorporated into the premix as a further treatment component, that in the case of the shaped bodies E1 and E2 according to the invention in the form of a homogeneous Co-granules and in the comparative examples V1 and V2 in the form of a mixture of the two finely divided powders.
- effervescent granules to be used according to the invention sodium bicarbonate, sodium carbonate and citric acid were mixed dry (see Table 3) and compacted on a Alexanderwerk compacting roller to form a slug. Then the slugs were ground on a sieve granulator. The ground slug was sieved between 0.6 and 1.6 mm. The effervescent system was added at 5% by weight to the premix to be pressed, after which the premixes were compressed into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g) in a Korsch eccentric press.
- the pressure was adjusted so that two series of molded bodies were obtained (E1, E1 ', E2, E2' or V1, V1 'and V2, V2'), which differ in their hardness.
- the composition of the premixes to be pressed (and thus the shaped body) is shown in Table 2, the composition and particle size distribution of the added spray systems is given in Table 3, and the particle size distribution of the other treatment components is shown in Table 4.
- composition of the surfactant granules [% by weight] C 9-13 alkyl benzene sulfonate 18.4 C 12-18 fatty alcohol with 7 EO 4.9 C 12-18 fatty alcohol sulfate 4.9 Soap 1.6 optical brightener 0.3 sodium 18.8 sodium silicate 5.5 Acrylic acid-maleic acid copolymer 5.5 Zeolite A (anhydrous active substance) 31.3 Na-hydroxyethane-1,1-diphosphonate 0.8 Water, salts rest Composition of the premixes [% by weight]: Granular surfactant (Table 1) 62.5 Shower system (Table 3) 5.0 Sodium perborate monohydrate 15.0 TAED 5.0 foam inhibitor 3.0 polyacrylate 1.0 enzymes 2.0 Perfume 0.5 Wessalith® P (Zeolite A) 1.0 Disintegration aid (cellulose) 5.0 Composition and particle size of the shower systems [% by weight, mm] citric acid Na-bicarbonate sieve fraction Granules (G) / powder mixture
- the hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.
- the tablet was placed in a beaker with water placed (600ml water, temperature 30 ° C) and the time to complete tablet disintegration measured.
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Abstract
Description
Die vorliegende Erfindung liegt auf dem Gebiet der kompakten Formkörper, die waschund reinigungsaktive Eigenschaften aufweisen. Solche Wasch- und Reinigungsmittelformkörper umfassen beispielsweise Waschmittelformkörper für das Waschen von Textilien, Reinigungsmittelformkörper für das maschinelle Geschirrspülen oder die Reinigung harter Oberflächen, Bleichmittelformkörper zum Einsatz in Wasch- oder Geschirrspülmaschinen, Wasserenthärtungsformkörper oder Fleckensalztabletten. Insbesondere betrifft die Erfindung Wasch- und Reinigungsmittelformkörper, die zum Waschen von Textilien in einer Haushaltswaschmaschine eingesetzt und kurz als Waschmitteltabletten bezeichnet werden.The present invention is in the field of compact molded articles that are washable have cleaning-active properties. Such detergent tablets include for example detergent tablets for washing textiles, Molded detergent for machine dishwashing or hard cleaning Surfaces, bleach tablets for use in washing machines or dishwashers, Water softening tablets or stain tablets. In particular, the invention relates Detergent tablets that are used to wash textiles in one Household washing machine used and briefly referred to as detergent tablets.
Wasch- und Reinigungsmittelformkörper sind im Stand der Technik breit beschrieben und erfreuen sich beim Verbraucher wegen der einfachen Dosierung zunehmender Beliebtheit. Tablettierte Wasch- und Reinigungsmittel haben gegenüber pulverförmigen eine Reihe von Vorteilen: Sie sind einfacher zu dosieren und zu handhaben und haben aufgrund ihrer kompakten Struktur Vorteile bei der Lagerung und beim Transport. Auch in der Patentliteratur sind Wasch- und Reinigungsmittelformkörper folglich umfassend beschrieben. Ein Problem, das bei der Anwendung von wasch- und reinigungsaktiven Formkörpern immer wieder auftritt, ist die zu geringe Zerfalls- und Lösegeschwindigkeit der Formkörper unter Anwendungsbedingungen. Da hinreichend stabile, d.h. form- und bruchbeständige Formkörper nur durch verhältnismäßig hohe Preßdrücke hergestellt werden können, kommt es zu einer starken Verdichtung der Formkörperbestandteile und zu einer daraus folgenden verzögerten Desintegration des Formkörpers in der wäßrigen Flotte und damit zu einer zu langsamen Freisetzung der Aktivsubstanzen im Wasch- bzw. Reinigungsvorgang. Die verzögerte Desintegration der Formkörper hat weiterhin den Nachteil, daß sich übliche Wasch- und Reinigungsmittelformkörper nicht über die Einspülkammer von Haushaltswaschmaschinen einspülen lassen, da die Tabletten nicht in hinreichend schneller Zeit in Sekundärpartikel zerfallen, die klein genug sind, um aus Einspülkammer in die Waschtrommel eingespült zu werden.Detergent tablets are widely described in the prior art are becoming increasingly popular with consumers because of the simple dosage. Tableted detergents and cleaning agents have a number of powdered detergents Advantages: They are easier to dose and to handle and because of their compact structure Advantages in storage and transport. Also in the patent literature detergent tablets are therefore comprehensively described. On Problem that always occurs when using washing and cleaning active moldings occurs again, the decay and dissolving speed of the moldings is too low Conditions of use. Since sufficiently stable, i.e. shape and break resistant molded body can only be produced by relatively high compression pressures to a strong compression of the molded parts and to a consequent delayed disintegration of the shaped body in the aqueous liquor and thus to one slow release of the active substances in the washing or cleaning process. The delayed Disintegration of the moldings also has the disadvantage that they are customary Detergent tablets not through the induction chamber of household washing machines Allow to be flushed in, as the tablets do not get in quickly enough Secondary particles disintegrate, which are small enough to enter the induction chamber Washing drum to be washed in.
Zur Überwindung der Dichotomie zwischen Härte, d.h. Transport- und Handhabungsstabilität, und leichtem Zerfall der Formkörper sind im Stand der Technik viele Lösungsansätze entwickelt worden. Ein insbesondere aus der Pharmazie bekannter und auf das Gebiet der Wasch- und Reinigungsmittelformkörper ausgedehnter Ansatz ist die Inkorporation bestimmter Desintegrationshilfsmittel, die den Zutritt von Wasser erleichtern oder bei Zutritt von Wasser quellen bzw. gasentwickelnd oder in anderer Form desintegrierend wirken. Andere Lösungsvorschläge aus der Patentliteratur beschreiben die Verpressung von Vorgemischen bestimmter Teilchengrößen, die Trennung einzelner Inhaltsstoffe von bestimmten anderen Inhaltsstoffen sowie die Beschichtung einzelner Inhaltsstoffe oder des gesamten Formkörpers mit Bindemitteln.To overcome the dichotomy between hardness, i.e. Transport and Handling stability and easy disintegration of the moldings are state of the art many solutions have been developed. A well-known in particular from pharmacy and is an extensive approach in the field of detergent tablets the incorporation of certain disintegration aids that prevent the entry of water facilitate or swell upon entry of water or gas evolving or in another form act disintegrating. Other proposed solutions from the patent literature describe the Compression of premixes of certain particle sizes, the separation of individual ones Ingredients of certain other ingredients as well as the coating of individual Ingredients or the entire molded body with binders.
Der Einsatz von Brausesystemen - auch in Kombination mit anderen Desintegrationshilfsmitteln - ist dabei ein Ansatz, der auch für das Gebiet der Wasch- und Reinigungsmittelformkörper beschrieben wurde. So offenbaren die DE 35 35 516 (Bucher) und die aus derselben Patentfamilie stammende WO87/02052 (Ockhuizen et al) Waschund Reinigungsmittel-Brausetabletten, die 2 bis 6 Gew.-% eines Tensids, 40 bis 60 Gew.-% Hydrogencarbonat und 33 bis 53 Gew.-% einer festen organischen Säure enthalten. Diese Tabletten stellen allerdings keine Textilwaschmittel dar, sondern weisen als bevorzugte Anwendungsgebiete die Scheibenwaschanlage von Kraftfahrzeugen bzw. die Bodenwischpflege auf.The use of shower systems - also in combination with other disintegration aids - is an approach that has also been described in the area of detergent tablets. DE 35 35 516 (Bucher) and WO87 / 02052 (Ockhuizen et al) from the same patent family disclose detergent and cleaning agent effervescent tablets containing 2 to 6% by weight of a surfactant, 40 to 60% by weight of hydrogen carbonate and 33 contain up to 53 wt .-% of a solid organic acid. However, these tablets are not textile detergents, but have preferred windshield washer systems for motor vehicles and floor wiping care.
Die US 5, 114, 647 offenbart Reinigungsteilchen, welche etwa 38 Gew.-% eines Brausesystems aus Na2CO3 und organischer Säure sowie über 5 Gew.-% Aniontensid enthalten. Die nicht vorveröffentlichte EP 881 282 A1 (Procter&Gamble) offenbart Tabletten, welche ebenfalls Brausesysteme aus Na2CO3 und organischer Säure sowie Aniontenside enthalten. Angaben zur wasserfreien Herstellung oder zu Partikelgrößen des Brausesystems werden in diesen Schriften nicht gemacht. US 5, 114, 647 discloses cleaning particles which contain about 38% by weight of an effervescent system composed of Na 2 CO 3 and organic acid and more than 5% by weight of anionic surfactant. The unpublished EP 881 282 A1 (Procter & Gamble) discloses tablets which also contain effervescent systems made of Na 2 CO 3 and organic acid as well as anionic surfactants. No information is given in these documents on water-free production or particle sizes of the shower system.
Ein Verfahren zur Herstellung eines Cogranulats, das in Reinigungsmitteltabletten eingesetzt werden kann, wird in der WO98/14548 (Schmitz) beschrieben. Hierbei wird eine Citronensäurelösung auf ein im Mischer bewegtes Feststoffbett aus Soda gegeben, um so Granulate zu erzeugen, die Natriumhydrogencarbonat, Natriumcitrat und einen Anteil Restsoda enthalten. Das in dieser Schrift offenbarte Verfahren liefert weder ein Brausesystem, noch wird die Granulation wasserfrei durchgeführt.A method for producing a cogranulate which can be used in detergent tablets is described in WO98 / 14548 (Schmitz). Here, a citric acid solution is placed on a solid bed of soda moved in the mixer in order to produce granules which contain sodium bicarbonate, sodium citrate and a portion of residual soda. The process disclosed in this document neither provides an effervescent system, nor is the granulation carried out without water.
In der älteren deutschen Patentanmeldung DE 197 22 832 (Henkel KGaA) werden Wasch- und Reinigungsmittelformkörper offenbart, die Tensid(e), Builder sowie gegebenenfalls weitere Wasch- und Reinigungsmittelbestandteile enthalten. Als Desintegrationshilfsmittel enthalten die hier offenbarten Formkörper 1 bis 10 Gew.-% eines oder mehrerer quellfähiger, wasserunlöslicher Desintegrationshilfsmittel und 3 bis 60 Gew.-% eines gasentwickelnden Brausesystems, wobei das quellfähige Mittel bzw. die Komponenten des Brausesystems sowohl mit anderen Inhaltsstoffen des Wasch- und Reinigungsmittels compoundiert als auch separat zugemischt sein können. Angaben zu einem cogranulierten Brausesystem oder zur wasserfreien Herstellung von Brausegranulaten sind dieser Schrift nicht zu entnehmen.In the older German patent application DE 197 22 832 (Henkel KGaA) Detergent tablets are disclosed, the surfactant (s), builder and optionally contain further detergent and cleaning agent components. As a disintegration aid the moldings disclosed here contain 1 to 10% by weight of one or more swellable, water-insoluble disintegration aid and 3 to 60 wt .-% of a gas-generating Shower system, the swellable agent or the components of the Shower systems compounded with other ingredients of the detergent and cleaning agent can also be mixed separately. Information on a co-granulated Shower system or for the water-free production of shower granules are this document not to be removed.
Der vorliegenden Erfindung lag nun die Aufgabe zugrunde, Formkörper bereitzustellen, die sich bei vorgegebener Härte durch kurze Zerfallszeiten auszeichnen und sich somit auch über die Einspülkammer haushaltsüblicher Waschmaschinen dosieren lassen. Dabei sollte zusätzlich ein einfaches und kostengünstiges Verfahren zur Herstellung solcher vorteilhaften Formkörper bereitgestellt werden.The present invention was based on the object of providing moldings which are characterized by short disintegration times with a given hardness and thus also dispense via the induction chamber of household washing machines. there should also be a simple and inexpensive method for producing such advantageous Shaped bodies are provided.
Beim Einsatz von Brausesystemen ist man geneigt zu glauben, daß insbesondere ein feinteiliges Brausesystem zu besonders guten Ergebnissen führt, weil einerseits eine homogene Verteilung über den gesamten Formkörper erreicht wird und andererseits eine große Reaktionsoberfläche zur Verfügung steht. Überraschenderweise wurde nun aber gefunden, daß ein gröberteiliges Granulat, das durch wasserfreie Granulation aus den Inhaltsstoffen des Brausesystems erhalten werden kann, Wasch- und Reinigungsmittelformkörpern deutlich bessere Tablettenzerfallszeiten verleiht. When using shower systems, one is inclined to believe that in particular a finely divided one Shower system leads to particularly good results because, on the one hand, it is homogeneous Distribution over the entire molded body is achieved and on the other hand a large reaction surface is available. Surprisingly, it has now been found that a coarser granulate, which is made from the ingredients of the Shower systems can be obtained, detergent tablets clearly gives better tablet disintegration times.
Gegenstand der Erfindung sind Wasch- und Reinigungsmittelformkörper aus verdichtetem, teilchenförmigen Wasch- und Reinigungsmittel, enthaltend 5 bis 50 Gew.-% anionische(s) Tensid(e), die ein wasserfrei granuliertes Brausesystem in Mengen von 1 bis 20 Gew.-%, jeweils bezogen auf den Formkörper, enthalten, wobei mindestens 80 Gew.-% der Teilchen des wasserfrei granulierten Brausesystems Teilchengrößen oberhalb 600 µm aufweisen.The invention relates to detergent tablets made of compressed, Particulate detergents and cleaning agents containing 5 to 50% by weight of anionic (s) Surfactant (s), which is an anhydrous granulated spray system in amounts of 1 to 20% by weight, each based on the molded article, containing at least 80 wt .-% of the particles of the water-free granulated shower system have particle sizes above 600 µm.
Ein Brausesystem besteht generell aus zwei Komponenten, die bei Zutritt von Wasser miteinander unter Freisetzung eines oder mehrerer Gase reagieren können. Obwohl es hier eine Vielzahl technischer Möglichkeiten gibt, sind Brausesysteme auf der Basis von Carbonaten bzw. Hydrogencarbonaten in Mischung mit sauren Komponenten (sogenannten Acidifizierungsmitteln) am weitesten verbreitet. Im Rahmen der vorliegenden Erfindung werden die Inhaltsstoffe des Brausesystems zu einem Cogranulat verarbeitet, wobei auf ein wasserfreies Granulationsverfahren zurückgegriffen wird. Die erhaltenen Brausegranulate verleihen den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern im Vergleich zum Einsatz der Rohstoffe alleine vorteilhafte Eigenschaften. Je nach Verwendungszweck enthalten die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper das wasserfrei granulierte Brausesystem in Mengen von 1 bis 20 Gew.-%, vorzugsweise von 2 bis 18 Gew.-%, besonders bevorzugt von 3 bis 15 Gew.-% und insbesondere von 5 bis 10 Gew.-%, jeweils bezogen auf den Formkörper.A shower system generally consists of two components that are exposed to water can react with one another to release one or more gases. Although it is here shower systems are based on a multitude of technical possibilities Carbonates or bicarbonates mixed with acidic components (so-called acidifiers) most widespread. As part of the In the present invention, the ingredients of the effervescent system become a cogranulate processed, using an anhydrous granulation process. The effervescent granules obtained give the washing and Detergent tablets advantageous compared to the use of raw materials alone Characteristics. Depending on the intended use, the washing and Detergent tablets the water-free granulated shower system in quantities from 1 to 20% by weight, preferably from 2 to 18% by weight, particularly preferably from 3 to 15% by weight and in particular from 5 to 10% by weight, in each case based on the shaped body.
Das erfindungsgemäß in den Wasch- und Reinigungsmittelformkörpern enthaltene wasserfrei granulierte Brausesystem wird in gröberer Form eingesetzt. Obwohl man vermuten könnte, daß eine staubfeine Einarbeitung wegen der homogeneren Verteilung und der höheren Reaktionsoberfläche zu besseren Ergebnissen führt, hat es sich gezeigt, daß das Überschreiten einer bestimmten Partikelgröße die Zerfallszeiten bei gewünschter Härte weiter minimiert. Besonders bevorzugte Wasch- und Reinigungsmittelformkörper sind dabei dadurch gekennzeichnet, daß mindestens 90 Gew.-% und insbesondere die Gesamtmenge der Teilchen des wasserfrei granulierten Brausesystems Teilchengrößen oberhalb 600 µm aufweisen.The contained in the detergent tablets according to the invention water-free granulated shower system is used in a coarser form. Although one could assume that a fine incorporation due to the more homogeneous distribution and the higher reaction surface leads to better results, it has been shown that exceeding a certain particle size the decay times at the desired Hardness further minimized. Particularly preferred detergent tablets are characterized in that at least 90% by weight and in particular that Total amount of particles in the water-free granulated shower system have above 600 µm.
Wie oben bereits erwähnt bestehen Brausesysteme zumeist aus Carbonaten und/oder Hydrogencarbonaten und sauren Komponenten (Acidifizierungsmitteln), die geeignet sind, Kohlendioxid aus ihnen freizusetzen. Bei den Carbonaten und/oder Hydrogencarbonaten sind im Rahmen der vorliegenden Erfindung die Alkalimetallsalze und unter ihnen die Natriumsalze besonders bevorzugt. Selbstverständlich müssen nicht die betreffenden reinen Alkalimetallcarbonate bzw. -hydrogencarbonate eingesetzt werden; vielmehr können Gemische unterschiedlicher Carbonate und Hydrogencarbonate aus waschtechnischem Interesse oder aus ökonomischen bevorzugt sein.As already mentioned above, shower systems mostly consist of carbonates and / or Hydrogen carbonates and acidic components (acidifying agents) which are suitable To release carbon dioxide from them. For the carbonates and / or hydrogen carbonates in the context of the present invention are the alkali metal salts and among them the sodium salts particularly preferred. Of course, the relevant ones do not have to be pure Alkali metal carbonates or bicarbonates are used; rather mixtures different carbonates and hydrogen carbonates from washing technology interest or be preferred for economic reasons.
Als Acidifizierungsmittel, die aus den Alkalisalzen in wäßriger Lösung Kohlendioxid freisetzen, sind beispielsweise Borsäure sowie Alkalimetallhydrogensulfate, Alkalimetalldihydrogenphosphate und andere anorganische Salze einsetzbar. Bevorzugt werden allerdings organische Acidifizierungsmittel verwendet, wobei die Citronensäure ein besonders bevorzugtes Acidifizierungsmittel ist. Einsetzbar sind aber auch insbesondere die anderen festen Mono-, Oligo- und Polycarbonsäuren. Aus dieser Gruppe wiederum bevorzugt sind Weinsäure, Bernsteinsäure, Malonsäure, Adipinsäure, Maleinsäure, Fumarsäure, Oxalsäure sowie Polyacrylsäure. Organische Sulfonsäuren wie Amidosulfonsäure sind ebenfalls einsetzbar. Kommerziell erhältlich und als Acidifizierungsmittel im Rahmen der vorliegenden Erfindung ebenfalls bevorzugt einsetzbar ist Sokalan® DCS (Warenzeichen der BASF), ein Gemisch aus Bernsteinsäure (max. 31 Gew.-%), Glutarsäure (max. 50 Gew.-%) und Adipinsäure (max. 33 Gew.-%).As acidifying agents that release carbon dioxide from the alkali salts in aqueous solution, are, for example, boric acid and alkali metal bisulfates, alkali metal dihydrogen phosphates and other inorganic salts can be used. However, are preferred organic acidifiers are used, with citric acid being a particularly preferred Acidifier is. However, the other fixed ones can also be used in particular Mono-, oligo- and polycarboxylic acids. From this group tartaric acid is preferred, Succinic acid, malonic acid, adipic acid, maleic acid, fumaric acid, oxalic acid as well Polyacrylic acid. Organic sulfonic acids such as amidosulfonic acid can also be used. Commercially available and as an acidifying agent in the context of the present Sokalan® DCS (trademark of BASF) is also preferably used according to the invention Mixture of succinic acid (max. 31% by weight), glutaric acid (max. 50% by weight) and adipic acid (max. 33% by weight).
Bevorzugt sind im Rahmen der vorliegenden Erfindung Wasch- und Reinigungsmittelformkörper, die als wasserfrei granuliertes Brausesystem ein Granulat aus Carbonat(en) und/oder Hydrogencarbonat(en) mit Acidifizierungsmittel(n) im Gewichtsverhältnis 1:20 bis 20:1, vorzugsweise 1:9 bis 9:1, enthalten.In the context of the present invention, preference is given to detergent tablets, which as a water-free granulated shower system is a granulate made of carbonate (s) and / or hydrogen carbonate (s) with acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1.
Es ist erfindungsgemäß auch möglich, die Bestandteile des Brausesystems (Carbonat(e) und/oder Hydrogencarbonat(e) und Acidifizierungsmittel) mit anderen Rohstoffen zu granulieren und durch Mahl- und Sieboperationen auf das erforderliche Partikelspektrum einzustellen. Erfindungsgemäß sind demnach auch Compounds einsetzbar, die zu mindestens 60 Gew.-%, bezogen auf das Compound, aus den Bestandteilen des Brausesystems bestehen, wobei diese Compounds dann ebenfalls dem erfindungsgemäßen Kriterium entsprechen, d.h. wasserfrei granuliert sein müssen. Vorzugsweise gilt auch für die genannten einsetzbaren Brausesystem-Compounds mit mindestens 60 Gew.-% Brausesystem die oben als bevorzugt genannte Teilchengrößenverteilung. Es sind also auch bei Einsatz der genannten Compounds Wasch- und Reinigungsmittelformkörper bevorzugt, die wasserfrei granulierte, Brausesystem-haltige Compounds enthalten, welche mindestens 60 Gew.-% Brausesystem (Carbonat(e) und/oder Hydrogencarbonat(e) und Acidifizierungsmittel), jeweils bezogen auf das Gewicht des Compounds, enthalten, wobei vorzugsweise mindestens 80 Gew.-%, vorzugsweise mindestens 90 Gew.-% und insbesondere die Gesamtmenge der Compounds Teilchengrößen oberhalb 600 µm aufweisen.According to the invention, it is also possible to combine the components of the shower system (carbonate (s) and / or granulate hydrogen carbonate (s) and acidifying agent) with other raw materials and adjust to the required particle spectrum by grinding and sieving operations. According to the invention, it is therefore also possible to use compounds which have at least one 60% by weight, based on the compound, consist of the components of the shower system, these compounds then also meeting the criterion according to the invention, i.e. must be granulated anhydrous. Preferably also applies to the above usable shower system compounds with at least 60 wt .-% shower system the above as the preferred particle size distribution. So it is also when using the above Compounds detergent tablets preferred that are water-free contain granulated, shower system-containing compounds which have at least 60% by weight Shower system (carbonate (s) and / or hydrogen carbonate (s) and acidifying agent), each based on the weight of the compound, preferably at least 80% by weight, preferably at least 90% by weight and in particular the total amount of the compounds have particle sizes above 600 µm.
Um den Zerfall der erfindungsgemäßen Wasch- und Reinigungsmittelformkörper noch weiter zu erleichtern, ist es möglich, weitere Desintegrationshilfsmittel in diese einzuarbeiten, um die Zerfallszeiten noch weiter zu verkürzen.About the disintegration of the detergent tablets according to the invention to further facilitate, it is possible to incorporate further disintegration aids into these, to further reduce the decay times.
Als bevorzugte zusätzliche Desintegrationsmittel werden im Rahmen der vorliegenden Erfindung Desintegrationsmittel auf Cellulosebasis eingesetzt, so daß bevorzugte Waschund Reinigungsmittelformkörper ein solches Desintegrationsmittel auf Cellulosebasis in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise 3 bis 7 Gew.-% und insbesondere 4 bis 6 Gew.-% enthalten. Reine Cellulose weist die formale Bruttozusammensetzung (C6H10O5)n auf und stellt formal betrachtet ein β-1,4-Polyacetal von Cellobiose dar, die ihrerseits aus zwei Molekülen Glucose aufgebaut ist. Geeignete Cellulosen bestehen dabei aus ca. 500 bis 5000 Glucose-Einheiten und haben demzufolge durchschnittliche Molmassen von 50.000 bis 500.000. Als Desintegrationsmittel auf Cellulosebasis verwendbar sind im Rahmen der vorliegenden Erfindung auch Cellulose-Derivate, die durch polymeranaloge Reaktionen aus Cellulose erhältlich sind. Solche chemisch modifizierten Cellulosen umfassen dabei beispielsweise Produkte aus Veresterungen bzw. Veretherungen, in denen Hydroxy-Wasserstoffatome substituiert wurden. Aber auch Cellulosen, in denen die HydroxyGruppen gegen funktionelle Gruppen, die nicht über ein Sauerstoffatom gebunden sind, ersetzt wurden, lassen sich als Cellulose-Derivate einsetzen. In die Gruppe der Cellulose-Derivate fallen beispielsweise Alkalicellulosen, Carboxymethylcellulose (CMC), Celluloseester und -ether sowie Aminocellulosen. Die genannten Cellulosederivate werden vorzugsweise nicht allein als Desintegrationsmittel auf Cellulosebasis eingesetzt, sondern in Mischung mit Cellulose verwendet. Der Gehalt dieser Mischungen an Cellulosederivaten beträgt vorzugsweise unterhalb 50 Gew.-%, besonders bevorzugt unterhalb 20 Gew.-%, bezogen auf das Desintegrationsmittel auf Cellulosebasis. Besonders bevorzugt wird als Desintegrationsmittel auf Cellulosebasis reine Cellulose eingesetzt, die frei von Cellulosederivaten ist.Disintegrants based on cellulose are used as preferred additional disintegrants in the context of the present invention, so that preferred detergent tablets have such a disintegrant based on cellulose in amounts of 0.5 to 10% by weight, preferably 3 to 7% by weight and in particular 4 to 6 wt .-% included. Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and, viewed formally, is a β-1,4-polyacetal of cellobiose, which in turn is made up of two molecules of glucose. Suitable celluloses consist of approximately 500 to 5000 glucose units and consequently have average molecular weights of 50,000 to 500,000. Cellulose-based disintegrants which can be used in the context of the present invention are also cellulose derivatives which can be obtained from cellulose by polymer-analogous reactions. Such chemically modified celluloses include, for example, products from esterifications or etherifications in which hydroxy hydrogen atoms have been substituted. However, celluloses in which the hydroxyl groups have been replaced by functional groups which are not bound by an oxygen atom can also be used as cellulose derivatives. The group of cellulose derivatives includes, for example, alkali celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers and aminocelluloses. The cellulose derivatives mentioned are preferably not used alone as a cellulose-based disintegrant, but are used in a mixture with cellulose. The content of cellulose derivatives in these mixtures is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrant. Pure cellulose which is free of cellulose derivatives is particularly preferably used as the cellulose-based disintegrant.
Die als Desintegrationshilfsmittel eingesetzte Cellulose wird vorzugsweise nicht in feinteiliger Form eingesetzt, sondern vor dem Zumischen zu den zu verpressenden Vorgemischen in eine gröbere Form überführt, beispielsweise granuliert oder kompaktiert. Wasch- und Reinigungsmittelformkörper, die Sprengmittel in granularer oder gegebenenfalls cogranulierter Form enthalten, werden in den deutschen Patentanmeldungen DE 197 09 991 (Stefan Herzog) und DE 197 10 254 (Henkel) sowie der internationalen Patentanmeldung WO98/40463 (Henkel) beschrieben. Diesen Schriften sind auch nähere Angaben zur Herstellung granulierter, kompaktierter oder cogranulierter Cellulosesprengmittel zu entnehmen. Die Teilchengrößen solcher Desintegrationsmittel liegen zumeist oberhalb 200 µm, vorzugsweise zu mindestens 90 Gew.-% zwischen 300 und 1600 µm und insbesondere zu mindestens 90 Gew.-% zwischen 400 und 1200 µm. Die vorstehend genannten und in den zitierten Schriften näher beschriebenen gröberen Desintegrationshilfsmittel auf Cellulosebasis sind im Rahmen der vorliegenden Erfindung bevorzugt als Desintegrationshilfsmittel einzusetzen und im Handel beispielsweise unter der Bezeichnung Arbocel® TF-30-HG von der Firma Rettenmaier erhältlich.The cellulose used as disintegration aid is preferably not used in finely divided form, but is converted into a coarser form, for example granulated or compacted, before being added to the premixes to be pressed. Detergent tablets which contain disintegrants in granular or, if appropriate, cogranulated form are described in German patent applications DE 197 09 991 (Stefan Herzog) and DE 197 10 254 (Henkel) and in international patent application WO98 / 40463 (Henkel). These documents can also be found in more detail on the production of granulated, compacted or cogranulated cellulose disintegrants. The particle sizes of such disintegrants are usually above 200 μm, preferably at least 90% by weight between 300 and 1600 μm and in particular at least 90% by weight between 400 and 1200 μm. The above-mentioned coarser disintegration aids based on cellulose and described in more detail in the cited documents are preferably to be used as disintegration aids in the context of the present invention and are commercially available, for example, under the name Arbocel® TF-30-HG from Rettenmaier.
Im Rahmen der vorliegenden Erfindung besonders bevorzugte Wasch- und Reinigungsmittelformkörper enthalten zusätzlich ein Desintegrationshilfsmittel, vorzugsweise ein Desintegrationshilfsmittel auf Cellulosebasis, vorzugsweise in granularer, cogranulierter oder kompaktierter Form, in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise von 3 bis 7 Gew.-% und insbesondere von 4 bis 6 Gew.-%, jeweils bezogen auf das Formkörpergewicht.Particularly preferred detergent tablets in the context of the present invention additionally contain a disintegration aid, preferably a Disintegration aid based on cellulose, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10 wt .-%, preferably from 3 to 7 % By weight and in particular from 4 to 6% by weight, in each case based on the weight of the shaped body.
Als weiteres Desintegrationsmittel auf Cellulosebasis oder als Bestandteil dieser Komponente kann mikrokristalline Cellulose verwendet werden. Diese mikrokristalline Cellulose wird durch partielle Hydrolyse von Cellulosen unter solchen Bedingungen erhalten, die nur die amorphen Bereiche (ca. 30% der Gesamt-Cellulosemasse) der Cellulosen angreifen und vollständig auflösen, die kristallinen Bereiche (ca. 70%) aber unbeschadet lassen. Eine nachfolgende Desaggregation der durch die Hydrolyse entstehenden mikrofeinen Cellulosen liefert die mikrokristallinen Cellulosen, die Primärteilchengrößen von ca. 5 µm aufweisen und beispielsweise zu Granulaten mit einer mittleren Teilchengröße von 200 µm kompaktierbar sind.As another disintegrant based on cellulose or as a component of this component microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions that only attack the amorphous areas (approx. 30% of the total cellulose mass) of the celluloses and dissolve completely, but leave the crystalline areas (approx. 70%) undamaged. A subsequent disaggregation of the microfine celluloses resulting from the hydrolysis delivers the microcrystalline celluloses, the primary particle sizes of approx. 5 µm have and for example to granules with an average particle size of 200 microns are compactable.
Technisch möglich ist auch die Beschichtung des Formkörpers, mit einem Coating, das den gesamten Formkörper überzieht. Solche beschichteten Wasch- und Reinigungsmittelformkörper können durch Aufsprühen einer Schmelze oder Lösung des Coatingmaterials auf den Formkörper oder Eintauchen des Formkörpers in die Schmelze oder Lösung hergestellt werden. In bevorzugten Ausführungsformen der vorliegenden Erfindung sind die Wasch- und Reinigungsmittelformkörper allerdings nicht mit einem Coating, das den gesamten Formkörper überzieht, beschichtet.It is also technically possible to coat the molded body with a coating that covers entire molded body. Such coated washing and Detergent tablets can by spraying a melt or solution of the Coating material on the molded body or immersing the molded body in the melt or solution can be prepared. In preferred embodiments of the present The laundry detergent and cleaning product tablets, however, are not one Coating, which covers the entire molded body, coated.
Durch den erfindungsgemäßen Einsatz des wasserfrei granulierten Brausesystems und optional durch den Einsatz von weiteren Desintegrationshilfsmitteln unterstützt (siehe oben), lassen sich erfindungsgemäß Wasch- und Reinigungsmittelformkörper herstellen, welche bei hohen Härten in Wasser äußerst schnell in ihre Bestandteile zerfallen. Besonders bevorzugt sind im Rahmen der vorliegenden Erfindung Wasch- und Reinigungsmittelformkörper, die in Wasser bei 30°C in weniger als 60 Sekunden vollständig in ihre Sekundärpartikel zerfallen, welche so klein sind, daß sie sich über die Einspülkammer einer haushaltsüblichen Waschmaschine einspülen lassen.By using the water-free granulated shower system and optionally supported by the use of further disintegration aids (see above), detergent tablets can be produced according to the invention, which disintegrate into their constituents extremely quickly in water. Washing and washing are particularly preferred in the context of the present invention Detergent tablets that are in water at 30 ° C in less than 60 seconds completely disintegrate into their secondary particles, which are so small that they overlap Have the washing-in chamber of a household washing machine wash in.
Neben dem erfindungsgemäß eingesetzten wasserfrei granulierten Brausesystem und optional einzusetzenden weiteren Desintegrationshilfsmitteln enthalten die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper weitere Wasch- und Reinigungsmittel-Inhaltsstoffe, insbesondere aus den Gruppen der Tenside, Gerüststoffe, Bleichmittel, Bleichaktivatoren, optischen Aufheller, Farb- und Duftstoffe usw. Diese Stoffe werden weiter unten beschrieben.In addition to the water-free granulated shower system and Other disintegration aids to be used optionally contain the Detergent tablets according to the invention further detergents and Detergent ingredients, especially from the groups of surfactants, builders, Bleaches, bleach activators, optical brighteners, dyes and fragrances etc. These Substances are described below.
Ein weiterer Gegenstand der vorliegenden Erfindung ist ein Verfahren zur Herstellung von
Wasch- und Reinigungsmittelformkörpern, das die Schritte
Der erste Verfahrensschritt ist dabei die Herstellung eines wasserfrei granulierten Brausesystems, dessen Anwesenheit den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern die vorteilhaften Eigenschaften verleiht. Üblicherweise werden in Granulationsverfahren feinteilige Feststoffe unter Zugabe von Granulationshilfsmitteln (sogenannten Granulierflüssigkeiten) und unter Einwirkung der mechanischen Energie der Mischerwerkzeuge in gröbere Partikel überführt, wobei die Granulierflüssigkeit Flüssigkeitsbrücken zwischen den Einzelpartikeln bildet und so zur Bildung von Agglomeraten mit "Himbeerstruktur" beiträgt. Oft werden als Granulationsflüssigkeit Wasser oder wäßrige Lösungen eingesetzt, was im erfindungsgemäßen Verfahren ausdrücklich vermieden werden soll, um eine verfrühte Reaktion der Bestandteile des Brausesystems zu vermeiden.The first process step is the production of a water-free granulated shower system, its presence in the detergent tablets according to the invention gives the beneficial properties. Usually used in granulation processes finely divided solids with the addition of granulation aids (so-called Granulating liquids) and under the influence of the mechanical energy of the mixer tools converted into coarser particles, the granulating liquid being liquid bridges forms between the individual particles and thus to form agglomerates with a "raspberry structure" contributes. Water or aqueous solutions are often used as the granulation liquid used, which is to be expressly avoided in the process according to the invention in order to to avoid a premature reaction of the components of the shower system.
Zur Durchführung von Verfahrensschritt a) eignen sich also herkömmliche Granulationsverfahren, bei denen andere Granulationsflüssigkeiten als Wasser eingesetzt werden. Hierzu sind beispielsweise flüssige Niotenside, Polyethylenglycole oder andere organische Lösungsmittel geeignet. Nachteilig ist an dieser Verfahrensführung, daß das wasserfrei granulierte Brausegranulat neben den Bestandteilen Carbonat bzw. Hydrogencarbonat und Acidifizierungsmittel weitere Inhaltsstoffe enthält, die nichts zur Brausewirkung beitragen bzw. diese gegebenenfalls sogar abschwächen.Conventional granulation processes are therefore suitable for carrying out process step a), where granulation liquids other than water are used. For this are, for example, liquid nonionic surfactants, polyethylene glycols or other organic solvents suitable. The disadvantage of this procedure is that the water-free granulated Shower granules in addition to the components carbonate or hydrogen carbonate and Acidifier contains other ingredients that do not contribute to the effervescent effect or even weaken them if necessary.
Es ist deshalb im Rahmen des erfindungsgemäßen Verfahrens bevorzugt, die Bestandteile des Brausesystems trocken miteinander zu vermischen und einer Preßagglomeration zu unterwerfen. Der Preßagglomerationsvorgang, dem das Gemisch aus den Komponenten des Brausesystems unterworfen wird, kann dabei in verschiedenen Apparaten realisiert werden. Je nach dem Typ des verwendeten Agglomerators werden unterschiedliche Preßagglomerationsverfahren unterschieden. Die drei häufigsten und im Rahmen der vorliegenden Erfindung bevorzugten Preßagglomerationsverfahren sind dabei die Extrusion, das Walzenpressen bzw. -kompaktieren und das Lochpressen (Pelletieren), so daß im Rahmen der vorliegenden Erfindung bevorzugte Preßagglomerationsvorgänge Extrusions-, Walzenkompaktierungs- und Pelletierungsvorgänge sind.It is therefore preferred in the context of the method according to the invention, the components of the shower system to mix dry together and a press agglomeration submit. The press agglomeration process, which is the mixture of the components the shower system is subjected to, can be realized in various devices become. Depending on the type of agglomerator used, different press agglomeration processes are used distinguished. The three most common and within the scope of the present The preferred press agglomeration process is extrusion Roller pressing or compacting and hole pressing (pelleting), so that in the frame preferred press agglomeration operations of the present invention extrusion, roll compacting and pelleting processes.
Allen Verfahren ist gemeinsam, daß das Gemisch aus den Komponenten des Brausesystems unter Druck verdichtet wird und die einzelnen Partikel unter Verringerung der Porosität aneinandergedrückt werden und aneinander haften. Bei allen Verfahren lassen sich die Werkzeuge dabei auf höhere Temperaturen aufheizen oder zur Abführung der durch Scherkräfte entstehenden Wärme kühlen.All processes have in common that the mixture of the components of the shower system is compressed under pressure and the individual particles while reducing the porosity are pressed together and stick together. In all processes, the Heat tools to higher temperatures or to dissipate them Cool shear forces generated heat.
In einer besonders bevorzugten Ausführungsform der vorliegenden Erfindung wird das erfindungsgemäße Verfahren mittels einer Walzenkompaktierung durchgeführt. Hierbei wird das Gemisch aus den Komponenten des Brausesystems gezielt zwischen zwei glatte oder mit Vertiefungen von definierter Form versehene Walzen eindosiert und zwischen den beiden Walzen unter Druck zu einem blattförmigen Kompaktat, der sogenannten Schülpe, ausgewalzt. Die Walzen üben auf das Vorgemisch einen hohen Liniendruck aus und können je nach Bedarf zusätzlich geheizt bzw. gekühlt werden. Bei der Verwendung von Glattwalzen erhält man glatte, unstrukturierte Schülpenbänder, während durch die Verwendung strukturierter Walzen entsprechend strukturierte Schülpen erzeugt werden können, in denen beispielsweise bestimmte Formen der späteren Brausegranulate vorgegeben werden können. Das Schülpenband wird nachfolgend durch eine Abschlag- und Zerkleinerungsvorgang in kleinere Stücke gebrochen und kann auf diese Weise zu Granulatkörnern verarbeitet werden, die durch weitere an sich bekannte Oberflächenbehandlungsverfahren veredelt werden können.In a particularly preferred embodiment of the present invention, the The method according to the invention is carried out by means of roller compaction. in this connection the mixture of the components of the shower system is targeted between two smooth or metered rollers provided with depressions of a defined shape and between the two rollers under pressure to form a leaf-shaped compact, the so-called Schülpe, rolled out. The rollers exert a high line pressure on the premix and can be additionally heated or cooled as required. When using from smooth rollers one obtains smooth, unstructured sash bands, while through the Structured slugs are generated using structured rollers can, in which, for example, certain forms of the later effervescent granules are specified can be. The cuff belt is subsequently subjected to a knock-off and crushing process broken into smaller pieces and can thus become granules are processed by further known surface treatment processes can be refined.
In einer weiteren bevorzugten Ausführungsform der vorliegenden Erfindung wird das erfindungsgemäße Verfahren mittels einer Pelletierung durchgeführt. Hierbei wird das Gemisch aus den Komponenten des Brausesystems auf eine perforierte Fläche aufgebracht und mittels eines druckgebenden Körpers durch die Löcher gedrückt. Bei üblichen Ausführungsformen von Pelletpressen wird das Vorgemisch unter Druck verdichtet, mittels einer rotierenden Walze in Form feiner Stränge durch eine perforierte Fläche gedrückt und schließlich mit einer Abschlagvorrichtung zu Granulatkörnern zerkleinert. Hierbei sind die unterschiedlichsten Ausgestaltungen von Druckwalze und perforierter Matrize denkbar. So finden beispielsweise flache perforierte Teller ebenso Anwendung wie konkave oder konvexe Ringmatrizen, durch die das Material mittels einer oder mehrerer Druckwalzen hindurchgepreßt wird. Die Preßrollen können bei den Tellergeräten auch konisch geformt sein, in den ringförmigen Geräten können Matrizen und Preßrolle(n) gleichläufigen oder gegenläufigen Drehsinn besitzen. Ein zur Durchführung des erfindungsgemäßen Verfahrens geeigneter Apparat wird beispielsweise in der deutschen Offenlegungsschrift DE 38 16 842 (Schlüter GmbH) beschrieben. Die in dieser Schrift offenbarte Ringmatrizenpresse besteht aus einer rotierenden, von Preßkanälen durchsetzten Ringmatrize und wenigstens einer mit deren Innenfläche in Wirkverbindung stehenden Preßrolle, die das dem Matrizenraum zugeführte Material durch die Preßkanäle in einen Materialaustrag preßt. Hierbei sind Ringmatrize und Preßrolle gleichsinnig antreibbar, wodurch eine verringerte Scherbelastung und damit geringere Temperaturerhöhung des Vorgemischs realisierbar ist. Selbstverständlich kann aber auch bei der Pelletierung mit heiz- oder kühlbaren Walzen gearbeitet werden, um eine gewünschte Temperatur des Vorgemischs einzustellen.In a further preferred embodiment of the present invention, the method according to the invention is carried out by means of pelleting. Here, the mixture of the components of the shower system is applied to a perforated surface and pressed through the holes by means of a pressure-generating body. In conventional embodiments of pellet presses, the premix is compressed under pressure, pressed through a perforated surface by means of a rotating roller in the form of fine strands, and finally comminuted into granules using a knock-off device. The most varied configurations of the pressure roller and perforated die are conceivable here. For example, flat perforated plates are used as well as concave or convex ring matrices through which the material is pressed using one or more pressure rollers. The press rolls can also be conical in the plate devices, in the ring-shaped devices dies and press roll (s) can have the same or opposite direction of rotation. An apparatus suitable for carrying out the method according to the invention is described, for example, in German laid-open specification DE 38 16 842 (Schlüter GmbH). The ring die press disclosed in this document consists of a rotating ring die interspersed with press channels and at least one press roller which is operatively connected to its inner surface and which presses the material supplied to the die space through the press channels into a material discharge. Here, the ring die and the press roller can be driven in the same direction, which means that a reduced shear stress and thus a lower temperature increase in the premix can be achieved. Of course, it is also possible to work with heatable or coolable rollers in the pelletizing in order to set a desired temperature of the premix.
Die Granulierfähigkeit des Brausesystems kann durch Hilfsstoffe eingestellt bzw. verbessert werden. Hierzu können sämtliche in Wasch- und Reinigungsmitteln übliche Rohstoffe zum Einsatz kommen, wobei Fettalkoholethoxylate mit unterschiedlichen Ethoxylierungsgraden, Polyethylenglycole oder Paraffine bevorzugt sind.The granulation capacity of the shower system can be adjusted or improved by auxiliary substances become. All raw materials common in detergents and cleaning agents can be used for this are used, whereby fatty alcohol ethoxylates with different degrees of ethoxylation, Polyethylene glycols or paraffins are preferred.
In besonders bevorzugten Verfahren wird/werden in Verfahrensschritt a) ein oder mehrere Carbonat(e) und/oder Hydrogencarbonat(e) mit einem oder mehreren Acidifizierungsmittel(n) trocken miteinander vermischt und einer Preßagglomeration, vorzugsweise einer Walzenkompaktierung, unterworfen.In particularly preferred processes, one or more are / are carried out in process step a) Carbonate (s) and / or bicarbonate (s) with one or more acidifying agent (s) dry mixed together and a press agglomeration, preferably one Roll compaction, subjected.
Wie bereits bei den erfindungsgemäßen Wasch- und Reinigungsmittelformkörper beschrieben, sind auch beim erfindungsgemäßen Verfahren bestimmte Gewichtsverhältnisse zwischen den einzelnen Komponenten des Brausesystems besonders vorteilhaft. So sind Verfahren bevorzugt, bei denen das oder die Carbonat(e) und/oder Hydrogencarbonat(e) mit dem oder den Acidifizierungsmittel(n) im Gewichtsverhältnis 1:20 bis 20:1, vorzugsweise 1:9 bis 9:1, vermischt und preßagglomeriert werden. As already described for the detergent tablets according to the invention, are also certain weight ratios in the method according to the invention particularly advantageous between the individual components of the shower system. So are Preferred processes in which the carbonate (s) and / or hydrogen carbonate (s) with the acidifying agent (s) in a weight ratio of 1:20 to 20: 1, preferably 1: 9 to 9: 1, mixed and press agglomerated.
Analog wie vorstehend ausgeführt werden auch beim erfindungsgemäßen Verfahren als Carbonate und/oder Hydrogencarbonate die Alkalimetallsalze, vorzugsweise die Natriumsalze eingesetzt, wobei Natriumhydrogencarbonat und Natriumcarbonat besonders bevorzugt sind. Als Acidifizierungsmittel werden vorzugsweise ein oder mehrere Stoffe aus der Gruppe der bei Raumtemperatur festen organischen Di-, Tri- und Oligocarbonsäuren eingesetzt, wobei Citronensäure besonders bevorzugt ist. Bezüglich weiterer einsetzbarer Acidifizierungsmittel sei auf die obigen Ausführungen verwiesen. Auch die Teilchengrößen des wasserfrei granulierten Brausesystems sowie die Mengen, in denen das wasserfrei granulierte Brausesystem im erfindungsgemäßen Verfahren eingesetzt wird, sind den oben genannten Angaben völlig analog. So weisen in bevorzugten Verfahren mindestens 90 Gew.-% und insbesondere die Gesamtmenge des in Schritt a) hergestellten Brausesystems Teilchengrößen oberhalb 600 µm auf. Weiter bevorzugte Verfahren sind dadurch gekennzeichnet, daß das in Schritt a) hergestellte Brausegranulat 1 bis 20 Gew.-%, vorzugsweise 2 bis 18 Gew.-%, besonders bevorzugt 3 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% des zu verpressenden Vorgemischs ausmacht.Analogous to the above, in the method according to the invention, as Carbonates and / or hydrogen carbonates, the alkali metal salts, preferably the Sodium salts used, with sodium hydrogen carbonate and sodium carbonate especially are preferred. One or more substances are preferably used as acidifying agents from the group of solid organic di-, tri- and Oligocarboxylic acids are used, with citric acid being particularly preferred. In terms of Further applicable acidifying agents are referred to the above statements. The particle sizes of the water-free granulated shower system and the amounts in which the water-free granulated shower system in the process according to the invention is used, are completely analogous to the above information. So point in preferred method at least 90 wt .-% and in particular the total amount of in Step a) produced shower system particle sizes above 600 microns. Further preferred processes are characterized in that the one produced in step a) Effervescent granules 1 to 20% by weight, preferably 2 to 18% by weight, particularly preferably 3 up to 15% by weight and in particular 5 to 10% by weight of the premix to be pressed accounts.
Wie bereits oben erwähnt, enthalten die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper neben dem wasserfrei granulierten Brausesystem weitere Inhaltsstoffe von Wasch- und Reinigungsmitteln. In bevorzugten erfindungsgemäßen Verfahren wird das in Schritt a) hergestellte Brausegranulat in Schritt b) mit mindestens einem tensidhaltigem Granulat zu einem zu verpressenden Vorgemisch mit einem Schüttgewicht von mindestens 500 g/l, vorzugsweise mindestens 600 g/l und insbesondere mindestens 700 g/l, vereinigt.As already mentioned above, the washing and Detergent tablets in addition to the water-free granulated shower system Detergent and cleaning agent ingredients. In preferred according to the invention The effervescent granules produced in step a) are processed in step b) with at least a surfactant-containing granulate to a premix to be pressed with a Bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l combined.
Die Herstellung der tensidhaltigen Granulate kann dabei durch übliche technische Granulationsverfahren wie Kompaktierung, Extrusion, Mischergranulation, Pelletierung oder Wirbelschichtgranulation erfolgen. Es ist dabei für die späteren Wasch- und Reinigungsmittelformkörper von Vorteil, wenn das zu verpressende Vorgemisch ein Schüttgewicht aufweist, das dem üblicher Kompaktwaschmittel nahe kommt. Insbesondere ist es bevorzugt, daß das zu verpressende Vorgemisch ein Schüttgewicht von mindestens 500 g/l, vorzugsweise mindestens 600 g/l und insbesondere mindestens 700 g/l aufweist. The production of the surfactant-containing granules can be done by conventional technical means Granulation processes such as compacting, extrusion, mixer granulation, pelleting or fluidized bed granulation. It is there for later washing and Detergent tablets are advantageous if the premix to be pressed is a Has bulk density that comes close to the usual compact detergent. In particular it is preferred that the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular at least 700 g / l.
Das tensidhaltige Granulat genügt in bevorzugten Verfahrensvarianten ebenfalls bestimmten Teilchengrößenkriterien. So sind erfindungsgemäße Verfahren bevorzugt, bei denen das tensidhaltige Granulat Teilchengrößen zwischen 100 und 2000 µm, vorzugsweise zwischen 200 und 1800 µm, besonders bevorzugt zwischen 400 und 1600 µm und insbesondere zwischen 600 und 1400µm, aufweist.The granules containing surfactant also suffice in certain preferred process variants Teilchengrößenkriterien. Methods according to the invention are preferred in which the surfactant-containing granules particle sizes between 100 and 2000 microns, preferably between 200 and 1800 µm, particularly preferably between 400 and 1600 µm and in particular between 600 and 1400 µm.
Neben den Aktivsubstanzen (anionische und/oder nichtionische und/oder kationische und/oder amphotere Tenside) enthalten die Tensidgranulate vorzugsweise noch Trägerstoffe, die besonders bevorzugt aus der Gruppe der Gerüststoffe stammen. Besonders vorteilhafte Verfahren sind dadurch gekennzeichnet, daß das tensidhaltige Granulat anionische und/oder nichtionische Tenside sowie Gerüststoffe enthält und Gesamt-Tensidgehalte von mindestens 10 Gew.-%, vorzugsweise mindestens 20 Gew.-% und insbesondere mindestens 25 Gew.-%, aufweist.In addition to the active substances (anionic and / or nonionic and / or cationic and / or amphoteric surfactants) the surfactant granules preferably also contain carriers, which particularly preferably come from the group of builders. Particularly advantageous Processes are characterized in that the surfactant-containing granules are anionic and / or non-ionic surfactants and builders and total surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
Zur Entfaltung der Waschleistung enthalten die Tensidgranulate grenzflächenaktive Substanzen aus der Gruppe der anionischen, nichtionischen, zwitterionischen oder kationischen Tenside, wobei anionische Tenside aus ökonomischen Gründen und aufgrund ihres Leistungsspektrums deutlich bevorzugt sind.To develop washing performance, the surfactant granules contain surface-active substances from the group of anionic, nonionic, zwitterionic or cationic Surfactants, anionic surfactants for economic reasons and because of their Range of services are clearly preferred.
Als anionische Tenside werden beispielsweise solche vom Typ der Sulfonate und Sulfate eingesetzt. Als Tenside vom Sulfonat-Typ kommen dabei vorzugsweise C9-13-Alkylbenzolsulfonate, Olefinsulfonate, d.h. Gemische aus Alken- und Hydroxyalkansulfonaten sowie Disulfonaten, wie man sie beispielsweise aus C12-18-Monoolefinen mit endoder innenständiger Doppelbindung durch Sulfonieren mit gasförmigem Schwefeltrioxid und anschließende alkalische oder saure Hydrolyse der Sulfonierungsprodukte erhält, in Betracht. Geeignet sind auch Alkansulfonate, die aus C12-18-Alkanen beispielsweise durch Sulfochlorierung oder Sulfoxidation mit anschließender Hydrolyse bzw. Neutralisation gewonnen werden. Ebenso sind auch die Ester von α-Sulfofettsäuren (Estersulfonate), z.B. die α-sulfonierten Methylester der hydrierten Kokos-, Palmkem- oder Talgfettsäuren geeignet. Anionic surfactants used are, for example, those of the sulfonate and sulfate type. The surfactants of the sulfonate type are preferably C 9-13- alkylbenzenesulfonates, olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates such as are obtained, for example, from C 12-18 monoolefins with an end or internal double bond by sulfonation with gaseous sulfur trioxide and subsequent receives alkaline or acidic hydrolysis of the sulfonation products. Also suitable are alkanesulfonates obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization. The esters of α-sulfofatty acids (ester sulfonates), for example the α-sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids, are also suitable.
Weitere geeignete Aniontenside sind sulfierte Fettsäureglycerinester. Unter Fettsäureglycerinestern sind die Mono-, Di- und Triester sowie deren Gemische zu verstehen, wie sie bei der Herstellung durch Veresterung von einem Monoglycerin mit 1 bis 3 Mol Fettsäure oder bei der Umesterung von Triglyceriden mit 0,3 bis 2 Mol Glycerin erhalten werden. Bevorzugte sulfierte Fettsäureglycerinester sind dabei die Sulfierprodukte von gesättigten Fettsäuren mit 6 bis 22 Kohlenstoffatomen, beispielsweise der Capronsäure, Caprylsäure, Caprinsäure, Myristinsäure, Laurinsäure, Palmitinsäure, Stearinsäure oder Behensäure.Other suitable anionic surfactants are sulfonated fatty acid glycerol esters. Among fatty acid glycerol esters the mono-, di- and triesters and their mixtures are to be understood as they are the production by esterification of a monoglycerin with 1 to 3 moles of fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 mol of glycerol. preferred sulfated fatty acid glycerol esters are the sulfonation products of saturated fatty acids with 6 to 22 carbon atoms, for example caproic acid, caprylic acid, capric acid, Myristic acid, lauric acid, palmitic acid, stearic acid or behenic acid.
Als Alk(en)ylsulfate werden die Alkali- und insbesondere die Natriumsalze der Schwefelsäurehalbester der C12-C18-Fettalkohole, beispielsweise aus Kokosfettalkohol, Talgfettalkohol, Lauryl-, Myristyl-, Cetyl- oder Stearylalkohol oder der C10-C20-Oxoalkohole und diejenigen Halbester sekundärer Alkohole dieser Kettenlängen bevorzugt. Weiterhin bevorzugt sind Alk(en)ylsulfate der genannten Kettenlänge, welche einen synthetischen, auf petrochemischer Basis hergestellten geradkettigen Alkylrest enthalten, die ein analoges Abbauverhalten besitzen wie die adäquaten Verbindungen auf der Basis von fettchemischen Rohstoffen. Aus waschtechnischem Interesse sind die C12-C16-Alkylsulfate und C12-C15-Alkylsulfate sowie C14-C15-Alkylsulfate bevorzugt. Auch 2,3-Alkylsulfate, welche beispielsweise gemäß den US-Patentschriften 3,234,258 oder 5,075,041 hergestellt werden und als Handelsprodukte der Shell Oil Company unter dem Namen DAN® erhalten werden können, sind geeignete Aniontenside.As alk (en) yl sulfates are the alkali and especially the sodium salts of the sulfuric acid half esters of C 12 -C 18 fatty alcohols, for example from coconut fatty alcohol, tallow fatty alcohol, lauryl, myristyl, cetyl or stearyl alcohol or the C 10 -C 20 oxo alcohols and those half-esters of secondary alcohols of this chain length are preferred. Also preferred are alk (en) yl sulfates of the chain length mentioned, which contain a synthetic, petrochemical-based straight-chain alkyl radical which have a degradation behavior analogous to that of the adequate compounds based on oleochemical raw materials. The C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates as well as C 14 -C 15 alkyl sulfates are preferred from the point of view of washing technology. 2,3-Alkyl sulfates, which are produced, for example, according to US Pat. Nos. 3,234,258 or 5,075,041 and can be obtained as commercial products from the Shell Oil Company under the name DAN®, are also suitable anionic surfactants.
Auch die Schwefelsäuremonoester der mit 1 bis 6 Mol Ethylenoxid ethoxylierten geradkettigen oder verzweigten C7-21-Alkohole, wie 2-Methyl-verzweigte C9-11-Alkohole mit im Durchschnitt 3,5 Mol Ethylenoxid (EO) oder C12-18-Fettalkohole mit 1 bis 4 EO; sind geeignet. Sie werden in Reinigungsmitteln aufgrund ihres hohen Schaumverhaltens nur in relativ geringen Mengen, beispielsweise in Mengen von 1 bis 5 Gew.-%, eingesetzt.The sulfuric acid monoesters of the straight-chain or branched C 7-21 alcohols ethoxylated with 1 to 6 mol of ethylene oxide, such as 2-methyl-branched C 9-11 alcohols with an average of 3.5 mol of ethylene oxide (EO) or C 12-18 - Fatty alcohols with 1 to 4 EO; are suitable. Because of their high foaming behavior, they are used in cleaning agents only in relatively small amounts, for example in amounts of 1 to 5% by weight.
Weitere geeignete Aniontenside sind auch die Salze der Alkylsulfobernsteinsäure, die auch als Sulfosuccinate oder als Sulfobemsteinsäureester bezeichnet werden und die Monoester und/oder Diester der Sulfobernsteinsäure mit Alkoholen, vorzugsweise Fettalkoholen und insbesondere ethoxylierten Fettalkoholen darstellen. Bevorzugte Sulfosuccinate enthalten C8-18-Fettalkoholreste oder Mischungen aus diesen. Insbesondere bevorzugte Sulfosuccinate enthalten einen Fettalkoholrest, der sich von ethoxylierten Fettalkoholen ableitet, die für sich betrachtet nichtionische Tenside darstellen (Beschreibung siehe unten). Dabei sind wiederum Sulfosuccinate, deren Fettalkohol-Reste sich von ethoxylierten Fettalkoholen mit eingeengter Homologenverteilung ableiten, besonders bevorzugt. Ebenso ist es auch möglich, Alk(en)ylbernsteinsäure mit vorzugsweise 8 bis 18 Kohlenstoffatomen in der Alk(en)ylkette oder deren Salze einzusetzen.Other suitable anionic surfactants are also the salts of alkylsulfosuccinic acid, which are also referred to as sulfosuccinates or as sulfosuccinic acid esters and which are monoesters and / or diesters of sulfosuccinic acid with alcohols, preferably fatty alcohols and in particular ethoxylated fatty alcohols. Preferred sulfosuccinates contain C 8-18 fatty alcohol residues or mixtures thereof. Particularly preferred sulfosuccinates contain a fatty alcohol residue, which is derived from ethoxylated fatty alcohols, which in themselves are nonionic surfactants (description see below). Again, sulfosuccinates, the fatty alcohol residues of which are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are particularly preferred. It is also possible to use alk (en) ylsuccinic acid with preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
Als weitere anionische Tenside kommen insbesondere Seifen in Betracht. Geeignet sind gesättigte Fettsäureseifen, wie die Salze der Laurinsäure, Myristinsäure, Palmitinsäure, Stearinsäure, hydrierte Erucasäure und Behensäure sowie insbesondere aus natürlichen Fettsäuren, z.B. Kokos-, Palmkem- oder Talgfettsäuren, abgeleitete Seifengemische.Soaps are particularly suitable as further anionic surfactants. Are suitable saturated fatty acid soaps, such as the salts of lauric acid, myristic acid, palmitic acid, Stearic acid, hydrogenated erucic acid and behenic acid and in particular from natural Fatty acids, e.g. Coconut, palm kernel or tallow fatty acids, derived soap mixtures.
Die anionischen Tenside einschließlich der Seifen können in Form ihrer Natrium-, Kaliumoder Ammoniumsalze sowie als lösliche Salze organischer Basen, wie Mono-, Di- oder Triethanolamin, vorliegen. Vorzugsweise liegen die anionischen Tenside in Form ihrer Natrium- oder Kaliumsalze, insbesondere in Form der Natriumsalze vor.The anionic surfactants including the soaps can be in the form of their sodium, potassium or Ammonium salts and as soluble salts of organic bases, such as mono-, di- or Triethanolamine. The anionic surfactants are preferably in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
Erfindungsgemäß enthalten die Wasch- oder Reinigungsmittelformkörper 5 bis 50 Gew.-% anionische(s) Tensid(e). Im Rahmen der vorliegenden Erfindung sind Wasch- und Reinigungsmittelformkörper bevorzugt, die 7,5 bis 40 Gew.-% uns insbesondere 10 bis 20 Gew.-% anionische(s) Tensid(e), jeweils bezogen auf das Formkörpergewicht, enthalten.According to the invention, the detergent tablets contain 5 to 50% by weight anionic surfactant (s). In the context of the present invention, washing and Preferred detergent tablets, the 7.5 to 40 wt .-% and in particular 10 to 20 % By weight of anionic surfactant (s), based in each case on the molding weight.
Bei der Auswahl der anionischen Tenside, die in den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern zum Einsatz kommen, stehen der Formulierungsfreiheit keine einzuhaltenden Rahmenbedingungen im Weg. Bevorzugte Wasch- und Reinigungsmittelformkörper weisen jedoch einen Gehalt an Seife auf, der 0,2 Gew.-%, bezogen auf das Gesamtgewicht des Formkörpers, übersteigt. Bevorzugt einzusetzende anionische Tenside sind dabei die Alkylbenzolsulfonate und Fettalkoholsulfate, wobei bevorzugte Wasch- und Reinigungsmittelformkörper 2 bis 20 Gew.-%, vorzugsweise 2,5 bis 15 Gew.-% und insbesondere 5 bis 10 Gew.-% Fettalkoholsulfat(e), jeweils bezogen auf das Formkörpergewicht, enthalten. When selecting the anionic surfactants that are used in the washing and Detergent tablets are used, freedom of formulation no framework conditions to be observed in the way. Preferred washing and However, detergent tablets have a soap content of 0.2% by weight, based on the total weight of the molded body. Preferred to use Anionic surfactants are the alkylbenzenesulfonates and fatty alcohol sulfates preferred detergent tablets 2 to 20 wt .-%, preferably 2.5 up to 15% by weight and in particular 5 to 10% by weight of fatty alcohol sulfate (s), in each case based on the molded body weight.
Als nichtionische Tenside werden vorzugsweise alkoxylierte, vorteilhafterweise ethoxylierte, insbesondere primäre Alkohole mit vorzugsweise 8 bis 18 C-Atomen und durchschnittlich 1 bis 12 Mol Ethylenoxid (EO) pro Mol Alkohol eingesetzt, in denen der Alkoholrest linear oder bevorzugt in 2-Stellung methylverzweigt sein kann bzw. lineare und methylverzweigte Reste im Gemisch enthalten kann, so wie sie üblicherweise in Oxoalkoholresten vorliegen. Insbesondere sind jedoch Alkoholethoxylate mit linearen Resten aus Alkoholen nativen Ursprungs mit 12 bis 18 C-Atomen, z.B. aus Kokos-, Palm-, Talgfettoder Oleylalkohol, und durchschnittlich 2 bis 8 EO pro Mol Alkohol bevorzugt. Zu den bevorzugten ethoxylierten Alkoholen gehören beispielsweise C12-14-Alkohole mit 3 EO oder 4 EO, C9-11-Alkohol mit 7 EO, C13-15-Alkohole mit 3 EO, 5 EO, 7 EO oder 8 EO, C12-18-Alkohole mit 3 EO, 5 EO oder 7 EO und Mischungen aus diesen, wie Mischungen aus C12-14-Alkohol mit 3 EO und C12-18-Alkohol mit 5 EO. Die angegebenen Ethoxylierungsgrade stellen statistische Mittelwerte dar, die für ein spezielles Produkt eine ganze oder eine gebrochene Zahl sein können. Bevorzugte Alkoholethoxylate weisen eine eingeengte Homologenverteilung auf (narrow range ethoxylates, NRE). Zusätzlich zu diesen nichtionischen Tensiden können auch Fettalkohole mit mehr als 12 EO eingesetzt werden. Beispiele hierfür sind Talgfettalkohol mit 14 EO, 25 EO, 30 EO oder 40 EO.The nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary alcohols having preferably 8 to 18 carbon atoms and an average of 1 to 12 moles of ethylene oxide (EO) per mole of alcohol, in which the alcohol radical can be linear or preferably methyl-branched in the 2-position or can contain linear and methyl-branched radicals in the mixture, as are usually present in oxo alcohol radicals. However, alcohol ethoxylates with linear residues of alcohols of native origin with 12 to 18 carbon atoms, for example from coconut, palm, tallow fat or oleyl alcohol, and an average of 2 to 8 EO per mole of alcohol are particularly preferred. The preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohol with 7 EO, C 13-15 alcohols with 3 EO, 5 EO, 7 EO or 8 EO, C 12-18 alcohols with 3 EO, 5 EO or 7 EO and mixtures thereof, such as mixtures of C 12-14 alcohol with 3 EO and C 12-18 alcohol with 5 EO. The degrees of ethoxylation given represent statistical averages, which can be an integer or a fraction for a specific product. Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE). In addition to these nonionic surfactants, 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.
Eine weitere Klasse bevorzugt eingesetzter nichtionischer Tenside, die entweder als alleiniges nichtionisches Tensid oder in Kombination mit anderen nichtionischen Tensiden eingesetzt werden, sind alkoxylierte, vorzugsweise ethoxylierte oder ethoxylierte und propoxylierte Fettsäurealkylester, vorzugsweise mit 1 bis 4 Kohlenstoffatomen in der Alkylkette, insbesondere Fettsäuremethylester, wie sie beispielsweise in der japanischen Patentanmeldung JP 58/217598 beschrieben sind oder die vorzugsweise nach dem in der internationalen Patentanmeldung WO-A-90/13533 beschriebenen Verfahren hergestellt werden.Another class of preferably used nonionic surfactants, which are 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 with 1 to 4 carbon atoms in the alkyl chain, in particular fatty acid methyl esters, such as them are described, for example, in Japanese patent application JP 58/217598 or which are preferably produced by the process described in international patent application WO-A-90/13533.
Eine weitere Klasse von nichtionischen Tensiden, die vorteilhaft eingesetzt werden kann, sind die Alkylpolyglycoside (APG). Einsetzbare Alkypolyglycoside genügen der allgemeinen Formel RO(G)z, in der R für einen linearen oder verzweigten, insbesondere in 2-Stellung methylverzweigten, gesättigten oder ungesättigten, aliphatischen Rest mit 8 bis 22, vorzugsweise 12 bis 18 C-Atomen bedeutet und G das Symbol ist, das für eine Glykoseeinheit mit 5 oder 6 C-Atomen, vorzugsweise für Glucose, steht. Der Glycosidierungsgrad z liegt dabei zwischen 1,0 und 4,0, vorzugsweise zwischen 1,0 und 2,0 und insbesondere zwischen 1,1 und 1,4.Another class of nonionic surfactants that can be used advantageously are the alkyl polyglycosides (APG). Alkypolyglycosides that can be used satisfy the general formula RO (G) z , in which R denotes a linear or branched, in particular methyl-branched, saturated or unsaturated, aliphatic radical having 8 to 22, preferably 12 to 18, carbon atoms and G is the Is symbol which stands for a glycose unit with 5 or 6 carbon atoms, preferably for glucose. The degree of glycosidation z is between 1.0 and 4.0, preferably between 1.0 and 2.0 and in particular between 1.1 and 1.4.
Bevorzugt eingesetzt werden lineare Alkylpolyglucoside, also Alkylpolyglycoside, in denen der Polyglycosylrest ein Glucoserest und der Alkylrest ein n-Alkylrest ist.Linear alkyl polyglucosides, ie alkyl polyglycosides, are preferably used in which the polyglycosyl radical is a glucose radical and the alkyl radical is an n-alkyl radical.
Die erfindungsgemäßen Wasch- und Reinigungsmittelformkörper können bevorzugt Alkylpolyglycoside enthalten, wobei Gehalte der Formkörper an APG über 0,2 Gew.-%, bezogen auf den gesamten Formkörper, bevorzugt sind. Besonders bevorzugte Wasch- und Reinigungsmittelformkörper enthalten APG in Mengen von 0,2 bis 10 Gew.-%, vorzugsweise 0,2 bis 5 Gew.-% und insbesondere von 0,5 bis 3 Gew.-%.The detergent tablets according to the invention can preferably alkyl polyglycosides included, with APG contents of the molded articles being above 0.2% by weight on the entire molded body, are preferred. Particularly preferred washing and Detergent tablets contain APG in amounts of 0.2 to 10% by weight, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3 wt .-%.
Auch nichtionische Tenside vom Typ der Aminoxide, beispielsweise N-Kokosalkyl-N,N-dimethylaminoxid und N-Talgalkyl-N,N-dihydroxyethylaminoxid, und der Fettsäurealkanolamide können geeignet sein. Die Menge dieser nichtionischen Tenside beträgt vorzugsweise nicht mehr als die der ethoxylierten Fettalkohole, insbesondere nicht mehr als die Hälfte davon.Also nonionic surfactants of the amine oxide type, for example N-cocoalkyl-N, N-dimethylamine oxide and N-tallow alkyl-N, N-dihydroxyethylamine oxide, and the fatty acid alkanolamides can be suitable. The amount of these nonionic surfactants is preferably not more than that of the ethoxylated fatty alcohols, especially not more than half of it.
Weitere geeignete Tenside sind Polyhydroxyfettsäureamide der Formel (I), in der RCO für einen aliphatischen Acylrest mit 6 bis 22 Kohlenstoffatomen, R1 für Wasserstoff, einen Alkyl- oder Hydroxyalkylrest mit 1 bis 4 Kohlenstoffatomen und [Z] für einen linearen oder verzweigten Polyhydroxyalkylrest mit 3 bis 10 Kohlenstoffatomen und 3 bis 10 Hydroxylgruppen steht. Bei den Polyhydroxyfettsäureamiden handelt es sich um bekannte Stoffe, die üblicherweise durch reduktive Aminierung eines reduzierenden Zukkers mit Ammoniak, einem Alkylamin oder einem Alkanolamin und nachfolgende Acylierung mit einer Fettsäure, einem Fettsäurealkylester oder einem Fettsäurechlorid erhalten werden können.Other suitable surfactants are polyhydroxy fatty acid amides of the formula (I), in which RCO stands for an aliphatic acyl radical with 6 to 22 carbon atoms, R 1 for hydrogen, an alkyl or hydroxyalkyl radical with 1 to 4 carbon atoms and [Z] for a linear or branched polyhydroxyalkyl radical with 3 to 10 carbon atoms and 3 to 10 hydroxyl groups. The polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
Zur Gruppe der Polyhydroxyfettsäureamide gehören auch Verbindungen der Formel (II), in der R für einen linearen oder verzweigten Alkyl- oder Alkenylrest mit 7 bis 12 Kohlenstoffatomen, R1 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest mit 2 bis 8 Kohlenstoffatomen und R2 für einen linearen, verzweigten oder cyclischen Alkylrest oder einen Arylrest oder einen Oxy-Alkylrest mit 1 bis 8 Kohlenstoffatomen steht, wobei C1-4-Alkyl- oder Phenylreste bevorzugt sind und [Z] für einen linearen Polyhydroxyalkylrest steht, dessen Alkylkette mit mindestens zwei Hydroxylgruppen substituiert ist, oder alkoxylierte, vorzugsweise ethoxylierte oder propoxylierte Derivate dieses Restes.The group of polyhydroxy fatty acid amides also includes compounds of the formula (II) in which R represents a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 represents a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 represents a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, C 1-4 -alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this rest.
[Z] wird vorzugsweise durch reduktive Aminierung eines reduzierten Zuckers erhalten, beispielsweise Glucose, Fructose, Maltose, Lactose, Galactose, Mannose oder Xylose. Die N-Alkoxy- oder N-Aryloxy-substituierten Verbindungen können dann beispielsweise nach der Lehre der internationalen Anmeldung WO-A-95/07331 durch Umsetzung mit Fettsäuremethylestern in Gegenwart eines Alkoxids als Katalysator in die gewünschten Polyhydroxyfettsäureamide überführt werden.[Z] is preferably obtained by reductive amination of a reduced sugar, for example glucose, fructose, maltose, lactose, galactose, mannose or xylose. The N-alkoxy- or N-aryloxy-substituted compounds can then, for example, according to the teaching of the international application WO-A-95/07331 by reaction with fatty acid methyl esters in the presence of an alkoxide as a catalyst in the desired polyhydroxy fatty acid amides be transferred.
Neben den waschaktiven Substanzen sind Gerüststoffe die wichtigsten Inhaltsstoffe von Wasch- und Reinigungsmitteln. In den erfindungsgemäßen. Wasch- und Reinigungsmittelformkörper können dabei alle üblicherweise in Wasch- und Reinigungsmitteln eingesetzten Gerüststoffe enthalten sein, insbesondere also Zeolithe, die erfindungsgemäß innerhalb eines bestimmten Teilchengrößenbereichs eingesetzten Silikate, Carbonate, organische Cobuilder und - wo keine ökologischen Vorurteile gegen ihren Einsatz bestehen - auch die Phosphate. Die genannten Gerüststoffe können auch in tensidfreien Formkörpern eingesetzt werden, so daß es erfindungsgemäß möglich ist, Formkörper herzustellen, die zur Wasserenthärtung oder als Bleichmitteltabletten eingesetzt werden können. Bevorzugte Verfahren setzen allerdings Tensidgranulate ein, die neben Tensid(en) als Trägerstoff Gerüststoff(e) enthalten.In addition to the washing-active substances, builders are the most important ingredients of Detergents and cleaning agents. In the invention. Detergent tablets can all be used in washing and cleaning agents Builders may be included, in particular thus zeolites, which according to the invention are within a certain particle size range used silicates, carbonates, organic Cobuilder and - where there are no ecological prejudices against their use - also the Phosphates. The builders mentioned can also be used in surfactant-free moldings are, so that it is possible according to the invention to produce moldings which for Water softening or as bleach tablets can be used. preferred However, processes use surfactant granules which, in addition to surfactant (s) as a carrier, builders (e) contain.
Geeignete kristalline, schichtförmige Natriumsilikate besitzen die allgemeine Formel NaMSixO2x+1 ·H2O, wobei M Natrium oder Wasserstoff bedeutet, x eine Zahl von 1,9 bis 4 und y eine Zahl von 0 bis 20 ist und bevorzugte Werte für x 2, 3 oder 4 sind. Derartige kristalline Schichtsilikate werden beispielsweise in der europäischen Patentanmeldung EP-A-0 164 514 beschrieben. Bevorzugte kristalline Schichtsilikate der angegebenen Formel sind solche, in denen M für Natrium steht und x die Werte 2 oder 3 annimmt. Insbesondere sind sowohl β- als auch δ-Natriumdisilikate Na2Si2O5 · yH2O bevorzugt, wobei β-Natriumdisilikat beispielsweise nach dem Verfahren erhalten werden kann, das in der internationalen Patentanmeldung WO-A-91/08171 beschrieben ist.Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 · H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20, preferred values for x 2, 3 or 4. Such crystalline layered silicates are described, for example, in European patent application EP-A-0 164 514. Preferred crystalline layered silicates of the formula given are those in which M represents sodium and x assumes the values 2 or 3. In particular both β- and δ-sodium disilicates Na 2 Si 2 O 5 · yH 2 O are preferred, with β-sodium disilicate being obtainable for example by the method / described in the international patent application WO-A-91 08,171th
Einsetzbar sind auch amorphe Natriumsilikate mit einem Modul Na2O : SiO2 von 1:2 bis 1:3,3, vorzugsweise von 1:2 bis 1:2,8 und insbesondere von 1:2 bis 1:2,6, welche löseverzögert sind und Sekundärwascheigenschaften aufweisen. Die Löseverzögerung gegenüber herkömmlichen amorphen Natriumsilikaten kann dabei auf verschiedene Weise, beispielsweise durch Oberflächenbehandlung, Compoundierung, Kompaktierung/ Verdichtung oder durch Übertrocknung hervorgerufen worden sein. Im Rahmen dieser Erfindung wird unter dem Begriff "amorph" auch "röntgenamorph" verstanden. Dies heißt, daß die Silikate bei Röntgenbeugungsexperimenten keine scharfen Röntgenreflexe liefern, wie sie für kristalline Substanzen typisch sind, sondern allenfalls ein oder mehrere Maxima der gestreuten Röntgenstrahlung, die eine Breite von mehreren Gradeinheiten des Beugungswinkels aufweisen. Es kann jedoch sehr wohl sogar zu besonders guten Buildereigenschaften führen, wenn die Silikatpartikel bei Elektronenbeugungsexperimenten verwaschene oder sogar scharfe Beugungsmaxima liefern. Dies ist so zu interpretieren, daß die Produkte mikrokristalline Bereiche der Größe 10 bis einige Hundert nm aufweisen, wobei Werte bis max. 50 nm und insbesondere bis max. 20 nm bevorzugt sind. Derartige sogenannte röntgenamorphe Silikate, welche ebenfalls eine Löseverzögerung gegenüber den herkömmlichen Wassergläsern aufweisen, werden beispielsweise in der deutschen Patentanmeldung DE-A- 44 00 024 beschrieben. Insbesondere bevorzugt sind verdichtete/kompaktierte amorphe Silikate, compoundierte amorphe Silikate und übertrocknete röntgenamorphe Silikate.Amorphous sodium silicates with a modulus Na 2 O: SiO 2 of 1: 2 to 1: 3.3, preferably 1: 2 to 1: 2.8 and in particular 1: 2 to 1: 2.6, can also be used are delayed in dissolving and have secondary washing properties. The delay in dissolution compared to conventional amorphous sodium silicates can be caused in various ways, for example by surface treatment, compounding, compacting / compression or by overdrying. In the context of this invention, the term “amorphous” is also understood to mean “X-ray amorphous”. This means that the silicates in X-ray diffraction experiments do not provide sharp X-ray reflections, as are typical for crystalline substances, but at most one or more maxima of the scattered X-rays, which have a width of several degree units of the diffraction angle. However, it can very well lead to particularly good builder properties if the silicate particles provide washed-out or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline areas of size 10 to a few hundred nm, values up to max. 50 nm and in particular up to max. 20 nm are preferred. Such so-called X-ray amorphous silicates, which also have a delay in dissolution compared to conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 . Compacted / compacted amorphous silicates, compounded amorphous silicates and over-dried X-ray amorphous silicates are particularly preferred.
Der eingesetzte feinkristalline, synthetische und gebundenes Wasser enthaltende Zeolith ist
vorzugsweise Zeolith A und/oder P. Als Zeolith P wird Zeolith MAP® (Handelsprodukt
der Firma Crosfield) besonders bevorzugt. Geeignet sind jedoch auch Zeolith X sowie Mischungen
aus A, X und/oder P. Kommerziell erhältlich und im Rahmen der vorliegenden
Erfindung bevorzugt einsetzbar ist beispielsweise auch ein Co-Kristallisat aus Zeolith X
und Zeolith A (ca. 80 Gew.-% Zeolith X), das von der Firma CONDEA Augusta S.p.A.
unter dem Markennamen VEGOBOND AX® vertrieben wird und durch die Formel
Selbstverständlich ist auch ein Einsatz der allgemein bekannten Phosphate als Buildersubstanzen möglich, sofern ein derartiger Einsatz nicht aus ökologischen Gründen vermieden werden sollte. Unter der Vielzahl der kommerziell erhältlichen Phosphate haben die Alkalimetallphosphate unter besonderer Bevorzugung von Pentanatrium- bzw. Pentakaliumtriphosphat (Natrium- bzw. Kaliumtripolyphosphat) in der Wasch- und Reinigungsmittel-Industrie die größte Bedeutung.It goes without saying that the generally known phosphates are also used as builder substances possible, provided that such use is not avoided for ecological reasons should be. Among the variety of commercially available phosphates are the alkali metal phosphates with particular preference for pentasodium or pentapotassium triphosphate (Sodium or potassium tripolyphosphate) in the detergent and cleaning agent industry the greatest importance.
Alkalimetallphosphate ist dabei die summarische Bezeichnung für die Alkalimetall- (insbesondere Natrium- und Kalium-) -Salze der verschiedenen Phosphorsäuren, bei denen man Metaphosphorsäuren (HPO3)n und Orthophosphorsäure H3PO4 neben höhermolekularen Vertretern unterscheiden kann. Die Phosphate vereinen dabei mehrere Vorteile in sich: Sie wirken als Alkaliträger, verhindern Kalkbeläge auf Maschinenteilen bzw. Kalkinkrustationen in Geweben und tragen überdies zur Reinigungsleistung bei.Alkali metal phosphates is the general term for the alkali metal (especially sodium and potassium) salts of the various phosphoric acids, in which one can differentiate between metaphosphoric acids (HPO 3 ) n and orthophosphoric acid H 3 PO 4 in addition to higher molecular weight representatives. The phosphates combine several advantages: They act as alkali carriers, prevent limescale deposits on machine parts and lime incrustations in fabrics and also contribute to cleaning performance.
Natriumdihydrogenphosphat, NaH2PO4, existiert als Dihydrat (Dichte 1,91 gcm-3, Schmelzpunkt 60°) und als Monohydrat (Dichte 2,04 gcm-3). Beide Salze sind weiße, in Wasser sehr leicht lösliche Pulver, die beim Erhitzen das Kristallwasser verlieren und bei 200°C in das schwach saure Diphosphat (Dinatriumhydrogendiphosphat, Na2H2P2O7), bei höherer Temperatur in Natiumtrimetaphosphat (Na3P3O9) und Maddrellsches Salz (siehe unten), übergehen. NaH2PO4 reagiert sauer; es entsteht, wenn Phosphorsäure mit Natronlauge auf einen pH-Wert von 4,5 eingestellt und die Maische versprüht wird. Kaliumdihydrogenphosphat (primäres oder einbasiges Kaliumphosphat, Kaliumbiphosphat, KDP), KH2PO4, ist ein weißes Salz der Dichte 2,33 gcm-3, hat einen Schmelzpunkt 253° [Zersetzung unter Bildung von Kaliumpolyphosphat (KPO3)x] und ist leicht löslich in Wasser.Sodium dihydrogen phosphate, NaH 2 PO 4 , exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white, water-soluble powders that lose water of crystallization when heated and at 200 ° C into the weakly acidic diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below). NaH 2 PO 4 is acidic; it arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed. Potassium dihydrogen phosphate (primary or monobasic potassium phosphate, potassium biphosphate, KDP), KH 2 PO 4 , is a white salt with a density of 2.33 gcm -3 , has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
Dinatriumhydrogenphosphat (sekundäres Natriumphosphat), Na2HPO4, ist ein farbloses, sehr leicht wasserlösliches kristallines Salz. Es existiert wasserfrei und mit 2 Mol. (Dichte 2,066 gcm-3, Wasserverlust bei 95°), 7 Mol. (Dichte 1,68 gcm-3, Schmelzpunkt 48° unter Verlust von 5 H2O) und 12 Mol. Wasser (Dichte 1,52 gcm-3, Schmelzpunkt 35° unter Verlust von 5 H2O), wird bei 100° wasserfrei und geht bei stärkerem Erhitzen in das Diphosphat Na4P2O7 über. Dinatriumhydrogenphosphat wird durch Neutralisation von Phosphorsäure mit Sodalösung unter Verwendung von Phenolphthalein als Indikator hergestellt. Dikaliumhydrogenphosphat (sekundäres od. zweibasiges Kaliumphosphat), K2HPO4, ist ein amorphes, weißes Salz, das in Wasser leicht löslich ist.Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very easily water-soluble crystalline salt. It exists anhydrous and with 2 mol. (Density 2.066 gcm -3 , water loss at 95 °), 7 mol. (Density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 mol. Water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O), becomes anhydrous at 100 ° and changes to diphosphate Na 4 P 2 O 7 when heated more strongly. Disodium hydrogen phosphate is prepared by neutralizing phosphoric acid with soda solution using phenolphthalein as an indicator. Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is easily soluble in water.
Trinatriumphosphat, tertiäres Natriumphosphat, Na3PO4, sind farblose Kristalle, die als Dodecahydrat eine Dichte von 1,62 gcm-3 und einen Schmelzpunkt von 73-76°C (Zersetzung), als Decahydrat (entsprechend 19-20% P2O5) einen Schmelzpunkt von 100°C und in wasserfreier Form (entsprechend 39-40% P2O5) eine Dichte von 2,536 gcm-3 aufweisen. Trinatriumphosphat ist in Wasser unter alkalischer Reaktion leicht löslich und wird durch Eindampfen einer Lösung aus genau 1 Mol Dinatriumphosphat und 1 Mol NaOH hergestellt. Trikaliumphosphat (tertiäres oder dreibasiges Kaliumphosphat), K3PO4, ist ein weißes, zerfließliches, körniges Pulver der Dichte 2,56 gcm-3, hat einen Schmelzpunkt von 1340° und ist in Wasser mit alkalischer Reaktion leicht löslich. Es entsteht z.B. beim Erhitzen von Thomasschlacke mit Kohle und Kaliumsulfat. Trotz des höheren Preises werden in der Reinigungsmittel-Industrie die leichter löslichen, daher hochwirksamen, Kaliumphosphate gegenüber entsprechenden Natrium-Verbindungen vielfach bevorzugt.Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 , are colorless crystals which, as dodecahydrate, have a density of 1.62 gcm -3 and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 . Trisodium phosphate is readily soluble in water with an alkaline reaction and is produced by evaporating a solution of exactly 1 mol of disodium phosphate and 1 mol of NaOH. Tripotassium phosphate (tertiary or triphase potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder with a density of 2.56 gcm -3 , has a melting point of 1340 ° and is easily soluble in water with an alkaline reaction. It arises, for example, when Thomas slag is heated with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over corresponding sodium compounds in the cleaning agent industry.
Tetranatriumdiphosphat (Natriumpyrophosphat), Na4P2O7, existiert in wasserfreier Form (Dichte 2,534 gcm-3, Schmelzpunkt 988°, auch 880° angegeben) und als Decahydrat (Dichte 1,815-1,836 gcm-3, Schmelzpunkt 94° unter Wasserverlust). Bei Substanzen sind farblose, in Wasser mit alkalischer Reaktion lösliche Kristalle. Na4P2O7 entsteht beim Erhitzen von Dinatriumphosphat auf >200° oder indem man Phosphorsäure mit Soda im stöchiometrischem Verhältnis umsetzt und die Lösung durch Versprühen entwässert. Das Decahydrat komplexiert Schwermetall-Salze und Härtebildner und verringert daher die Härte des Wassers. Kaliumdiphosphat (Kaliumpyrophosphat), K4P2O7, existiert in Form des Trihydrats und stellt ein farbloses, hygroskopisches Pulver mit der Dichte 2,33 gcm-3 dar, das in Wasser löslich ist, wobei der pH-Wert der 1%igen Lösung bei 25° 10,4 beträgt.Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also stated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , Substances are colorless crystals that are soluble in water with an alkaline reaction. Na 4 P 2 O 7 is formed by heating disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying. The decahydrate complexes heavy metal salts and hardness formers and therefore reduces the hardness of the water. Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH value being 1% Solution at 25 ° is 10.4.
Durch Kondensation des NaH2PO4 bzw. des KH2PO4 entstehen höhermol. Natrium- und Kaliumphosphate, bei denen man cyclische Vertreter, die Natrium- bzw. Kaliummetaphosphate und kettenförmige Typen, die Natrium- bzw. Kaliumpolyphosphate, unterscheiden kann. Insbesondere für letztere sind eine Vielzahl von Bezeichnungen in Gebrauch: Schmelz- oder Glühphosphate, Grahamsches Salz, Kurrolsches und Maddrellsches Salz. Alle höheren Natrium- und Kaliumphosphate werden gemeinsam als kondensierte Phosphate bezeichnet.Condensation of the NaH 2 PO 4 or the KH 2 PO 4 produces higher moles. Sodium and potassium phosphates, in which one can differentiate cyclic representatives, the sodium or potassium metaphosphates and chain-like types, the sodium or potassium polyphosphates. A large number of terms are used in particular for the latter: melt or glow phosphates, Graham's salt, Kurrol's and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
Das technisch wichtige Pentanatriumtriphosphat, Na5P3O10 (Natriumtripolyphosphat), ist
ein wasserfrei oder mit 6 H2O kristallisierendes, nicht hygroskopisches, weißes, wasserlösliches
Salz der allgemeinen Formel NaO-[P(O)(ONa)-O]n-Na mit n=3. In 100 g Wasser
lösen sich bei Zimmertemperatur etwa 17 g, bei 60° ca. 20 g, bei 100° rund 32 g des
kristallwasserfreien Salzes; nach zweistündigem Erhitzen der Lösung auf 100° entstehen
durch Hydrolyse etwa 8% Orthophosphat und 15% Diphosphat. Bei der Herstellung von
Pentanatriumtriphosphat wird Phosphorsäure mit Sodalösung oder Natronlauge im
stöchiometrischen Verhältnis zur Reaktion gebracht und die Lsg. durch Versprühen entwässert.
Ähnlich wie Grahamsches Salz und Natriumdiphosphat löst Pentanatriumtriphosphat
viele unlösliche Metall-Verbindungen (auch Kalkseifen usw.). Pentakaliumtriphosphat,
K5P3O10 (Kaliumtripolyphosphat), kommt beispielsweise in Form einer 50 Gew.-%igen
Lösung (> 23% P2O5, 25% K2O) in den Handel. Die Kaliumpolyphosphate finden in
der Wasch- und Reinigungsmittel-Industrie breite Verwendung. Weiter existieren auch
Natriumkaliumtripolyphosphate, welche ebenfalls im Rahmen der vorliegenden Erfindung
einsetzbar sind. Diese entstehen beispielsweise, wenn man Natriumtrimetaphosphat mit
KOH hydrolysiert:
Diese sind erfindungsgemäß genau wie Natriumtripolyphosphat, Kaliumtripolyphosphat oder Mischungen aus diesen beiden einsetzbar; auch Mischungen aus Natriumtripolyphosphat und Natriumkaliumtripolyphosphat oder Mischungen aus Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat oder Gemische aus Natriumtripolyphosphat und Kaliumtripolyphosphat und Natriumkaliumtripolyphosphat sind erfindungsgemäß einsetzbar.According to the invention, these are exactly like sodium tripolyphosphate, potassium tripolyphosphate or mixtures of these two can be used; also mixtures of sodium tripolyphosphate and sodium potassium tripolyphosphate or mixtures of potassium tripolyphosphate and Sodium potassium tripolyphosphate or mixtures of sodium tripolyphosphate and potassium tripolyphosphate and sodium potassium tripolyphosphate can be used according to the invention.
Als organische Cobuilder können in den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpern insbesondere Polycarboxylate / Polycarbonsäuren, polymere Polycarboxylate, Asparaginsäure, Polyacetale, Dextrine, weitere organische Cobuilder (siehe unten) sowie Phosphonate eingesetzt werden. Diese Stoffklassen werden nachfolgend beschrieben.Organic cobuilders can be used in the laundry detergent tablets 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.
Brauchbare organische Gerüstsubstanzen sind beispielsweise die in Form ihrer Natriumsalze einsetzbaren Polycarbonsäuren, wobei unter Polycarbonsäuren solche Carbonsäuren verstanden werden, die mehr als eine Säurefunktion tragen. Beispielsweise sind dies Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Äpfelsäure, Weinsäure, Maleinsäure, Fumarsäure, Zuckersäuren, Aminocarbonsäuren, Nitrilotriessigsäure (NTA), sofern ein derartiger Einsatz aus ökologischen Gründen nicht zu beanstanden ist, sowie Mischungen aus diesen. Bevorzugte Salze sind die Salze der Polycarbonsäuren wie Citronensäure, Adipinsäure, Bernsteinsäure, Glutarsäure, Weinsäure, Zuckersäuren und Mischungen aus diesen. Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such polycarboxylic acids being among polycarboxylic acids can be understood that carry more than one acid function. For example, these are citric acid, Adipic acid, succinic acid, glutaric acid, malic acid, tartaric acid, maleic acid, Fumaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if one such use is not objectionable for ecological reasons, as well as mixtures from these. Preferred salts are the salts of polycarboxylic acids such as citric acid, adipic acid, Succinic acid, glutaric acid, tartaric acid, sugar acids and mixtures of these.
Auch die Säuren an sich können eingesetzt werden. Die Säuren besitzen neben ihrer Builderwirkung typischerweise auch die Eigenschaft einer Säuerungskomponente und dienen somit auch zur Einstellung eines niedrigeren und milderen pH-Wertes von Wasch- oder Reinigungsmitteln. Insbesondere sind hierbei Citronensäure, Bernsteinsäure, Glutarsäure, Adipinsäure, Gluconsäure und beliebige Mischungen aus diesen zu nennen.The acids themselves can also be used. The acids have a builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH value of washing or Detergents. In particular, citric acid, succinic acid, glutaric acid, Adipic acid, gluconic acid and any mixtures of these.
Als Builder sind weiter polymere Polycarboxylate geeignet, dies sind beispielsweise die Alkalimetallsalze der Polyacrylsäure oder der Polymethacrylsäure, beispielsweise solche mit einer relativen Molekülmasse von 500 bis 70000 g/mol.Polymeric polycarboxylates are also suitable as builders, for example those Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a relative molecular mass of 500 to 70,000 g / mol.
Bei den für polymere Polycarboxylate angegebenen Molmassen handelt es sich im Sinne dieser Schrift um gewichtsmittlere Molmassen Mw der jeweiligen Säureform, die grundsätzlich mittels Gelpermeationschromatographie (GPC) bestimmt wurden, wobei ein UV-Detektor eingesetzt wurde. Die Messung erfolgte dabei gegen einen externen Polyacrylsäure-Standard, der aufgrund seiner strukturellen Verwandtschaft mit den untersuchten Polymeren realistische Molgewichtswerte liefert. Diese Angaben weichen deutlich von den Molgewichtsangaben ab, bei denen Polystyrolsulfonsäuren als Standard eingesetzt werden. Die gegen Polystyrolsulfonsäuren gemessenen Molmassen sind in der Regel deutlich höher als die in dieser Schrift angegebenen Molmassen.In the context of this document, the molecular weights given for polymeric polycarboxylates are weight-average molecular weights M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), 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 to the polymers investigated. This information differs significantly from the molecular weight information for which polystyrene sulfonic acids are used as standard. The molecular weights measured against polystyrene sulfonic acids are generally significantly higher than the molecular weights given in this document.
Geeignete Polymere sind insbesondere Polyacrylate, die bevorzugt eine Molekülmasse von 2000 bis 20000 g/mol aufweisen. Aufgrund ihrer überlegenen Löslichkeit können aus dieser Gruppe wiederum die kurzkettigen Polyacrylate, die Molmassen von 2000 bis 10000 g/mol, und besonders bevorzugt von 3000 bis 5000 g/mol, aufweisen, bevorzugt sein.Suitable polymers are in particular polyacrylates, which preferably have a molecular weight of Have 2000 to 20,000 g / mol. Because of their superior solubility, this can Group in turn the short-chain polyacrylates, the molecular weights from 2000 to 10000 g / mol, and particularly preferably from 3000 to 5000 g / mol, preferably his.
Geeignet sind weiterhin copolymere Polycarboxylate, insbesondere solche der Acrylsäure mit Methacrylsäure und der Acrylsäure oder Methacrylsäure mit Maleinsäure. Als besonders geeignet haben sich Copolymere der Acrylsäure mit Maleinsäure erwiesen, die 50 bis 90 Gew.-% Acrylsäure und 50 bis 10 Gew.-% Maleinsäure enthalten. Ihre relative Molekülmasse, bezogen auf freie Säuren, beträgt im allgemeinen 2000 bis 70000 g/mol, vorzugsweise 20000 bis 50000 g/mol und insbesondere 30000 bis 40000 g/mol. Also suitable are copolymeric polycarboxylates, especially those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid. As special copolymers of acrylic acid with maleic acid have proven suitable, the 50 to Contain 90 wt .-% acrylic acid and 50 to 10 wt .-% maleic acid. Your relative molecular mass, based on free acids, is generally from 2000 to 70,000 g / mol, preferably 20,000 to 50,000 g / mol and in particular 30,000 to 40,000 g / mol.
Die (co-)polymeren Polycarboxylate können entweder als Pulver oder als wäßrige Lösung eingesetzt werden. Der Gehalt der Mittel an (co-)polymeren Polycarboxylaten beträgt vorzugsweise 0,5 bis 20 Gew.-%, insbesondere 3 bis 10 Gew.-%.The (co) polymeric polycarboxylates can either be as a powder or as an aqueous solution be used. The content of (co) polymeric polycarboxylates in the agents is preferably 0.5 to 20% by weight, in particular 3 to 10% by weight.
Zur Verbesserung der Wasserlöslichkeit können die Polymere auch Allylsulfonsäuren, wie beispielsweise Allyloxybenzolsulfonsäure und Methallylsulfonsäure, als Monomer enthalten.To improve water solubility, the polymers can also allylsulfonic acids, such as for example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
Insbesondere bevorzugt sind auch biologisch abbaubare Polymere aus mehr als zwei verschiedenen Monomereinheiten, beispielsweise solche, die als Monomere Salze der Acrylsäure und der Maleinsäure sowie Vinylalkohol bzw. Vinylalkohol-Derivate oder die als Monomere Salze der Acrylsäure und der 2-Alkylallylsulfonsäure sowie Zucker-Derivate enthalten.Also particularly preferred are biodegradable polymers made from more than two different ones Monomer units, for example those which are salts of acrylic acid as monomers and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid as well as sugar derivatives contain.
Weitere bevorzugte Copolymere sind solche, die in den deutschen Patentanmeldungen DE-A-43 03 320 und DE-A-44 17 734 beschrieben werden und als Monomere vorzugsweise Acrolein und Acrylsäure/Acrylsäuresalze bzw. Acrolein und Vinylacetat aufweisen.Further preferred copolymers are those which are described in German patent applications DE-A-43 03 320 and DE-A-44 17 734 and which preferably contain acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate as monomers.
Ebenso sind als weitere bevorzugte Buildersubstanzen polymere Aminodicarbonsäuren, deren Salze oder deren Vorläufersubstanzen zu nennen. Besonders bevorzugt sind Polyasparaginsäuren bzw. deren Salze und Derivate, von denen in der deutschen Patentanmeldung DE-A-195 40 086 offenbart wird, daß sie neben Cobuilder-Eigenschaften auch eine bleichstabilisierende Wirkung aufweisen.Also to be mentioned as further preferred builder substances are polymeric aminodicarboxylic acids, their salts or their precursor substances. Particularly preferred are polyaspartic acids or their salts and derivatives, of which it is disclosed in German patent application DE-A-195 40 086 that, in addition to cobuilder properties, they also have a bleach-stabilizing effect.
Weitere geeignete Buildersubstanzen sind Polyacetale, welche durch Umsetzung von Dialdehyden mit Polyolcarbonsäuren, welche 5 bis 7 C-Atome und mindestens 3 Hydroxylgruppen aufweisen, erhalten werden können. Bevorzugte Polyacetale werden aus Dialdehyden wie Glyoxal, Glutaraldehyd, Terephthalaldehyd sowie deren Gemischen und aus Polyolcarbonsäuren wie Gluconsäure und/oder Glucoheptonsäure erhalten.Other suitable builder substances are polyacetals, which are obtained by reacting dialdehydes with polyol carboxylic acids, which have 5 to 7 carbon atoms and at least 3 hydroxyl groups can be obtained. Preferred polyacetals are made from dialdehydes such as glyoxal, glutaraldehyde, terephthalaldehyde and mixtures thereof and from Obtained polyol carboxylic acids such as gluconic acid and / or glucoheptonic acid.
Weitere geeignete organische Buildersubstanzen sind Dextrine, beispielsweise Oligomere bzw. Polymere von Kohlenhydraten, die durch partielle Hydrolyse von Stärken erhalten werden können. Die Hydrolyse kann nach üblichen, beispielsweise säure- oder enzymkatalysierten Verfahren durchgeführt werden. Vorzugsweise handelt es sich um Hydrolyseprodukte mit mittleren Molmassen im Bereich von 400 bis 500000 g/mol. Dabei ist ein Polysaccharid mit einem Dextrose-Äquivalent (DE) im Bereich von 0,5 bis 40, insbesondere von 2 bis 30 bevorzugt, wobei DE ein gebräuchliches Maß für die reduzierende Wirkung eines Polysaccharids im Vergleich zu Dextrose, welche ein DE von 100 besitzt, ist. Brauchbar sind sowohl Maltodextrine mit einem DE zwischen 3 und 20 und Trockenglucosesirupe mit einem DE zwischen 20 und 37 als auch sogenannte Gelbdextrine und Weißdextrine mit höheren Molmassen im Bereich von 2000 bis 30000 g/mol.Other suitable organic builder substances are dextrins, for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be. The hydrolysis can be carried out according to customary methods, for example acid-catalyzed or enzyme-catalyzed Procedures are carried out. They are preferably hydrolysis products with average molecular weights in the range of 400 to 500000 g / mol. There is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30 preferred, DE being a common measure of the reducing effect of a polysaccharide compared to dextrose, which has a DE of 100. Both maltodextrins with a DE between 3 and 20 and dry glucose syrups can be used with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molar masses in the range from 2000 to 30000 g / mol.
Bei den oxidierten Derivaten derartiger Dextrine handelt es sich um deren Umsetzungsprodukte mit Oxidationsmitteln, welche in der Lage sind, mindestens eine Alkoholfunktion des Saccharidrings zur Carbonsäurefunktion zu oxidieren. Derartige oxidierte Dextrine und Verfahren ihrer Herstellung sind beispielsweise aus den europäischen Patentanmeldungen EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 und EP-A-0 542 496 sowie den internationalen Patentanmeldungen WO 92/18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 und WO 95/20608 bekannt. Ebenfalls geeignet ist ein oxidiertes Oligosaccharid gemäß der deutschen Patentanmeldung DE-A-196 00 018. Ein an C6 des Saccharidrings oxidiertes Produkt kann besonders vorteilhaft sein.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. Such oxidized dextrins and processes for their preparation are known, for example, from European patent applications EP-A-0 232 202, EP-A-0 427 349, EP-A-0 472 042 and EP-A-0 542 496 and international patent applications WO 92 / 18542, WO 93/08251, WO 93/16110, WO 94/28030, WO 95/07303, WO 95/12619 and WO 95/20608 . An oxidized oligosaccharide according to German patent application DE-A-196 00 018 is also suitable. A product oxidized at C 6 of the saccharide ring can be particularly advantageous.
Auch Oxydisuccinate und andere Derivate von Disuccinaten, vorzugsweise Ethylendiamindisuccinat, sind weitere geeignete Cobuilder. Dabei wird Ethylendiamin-N,N'disuccinat (EDDS) bevorzugt in Form seiner Natrium- oder Magnesiumsalze verwendet. Weiterhin bevorzugt sind in diesem Zusammenhang auch Glycerindisuccinate und Glycerintrisuccinate. Geeignete Einsatzmengen liegen in zeolithhaltigen und/oder silicathaltigen Formulierungen bei 3 bis 15 Gew.-%.Also oxydisuccinates and other derivatives of disuccinates, preferably ethylenediamine disuccinate, are other suitable cobuilders. Here, ethylenediamine-N, N'disuccinate (EDDS) 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 those containing zeolite and / or silicate Formulations at 3 to 15% by weight.
Weitere brauchbare organische Cobuilder sind beispielsweise acetylierte Hydroxycarbonsäuren bzw. deren Salze, welche gegebenenfalls auch in Lactonform vorliegen können und welche mindestens 4 Kohlenstoffatome und mindestens eine Hydroxygruppe sowie maximal zwei Säuregruppen enthalten. Derartige Cobuilder werden beispielsweise in der internationalen Patentanmeldung WO 95/20029 beschrieben. Other useful organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may also be present in lactone form, and which have at least 4 carbon atoms and at least one hydroxyl group and at most contain two acid groups. Such cobuilders are used, for example, in the international Patent application WO 95/20029 described.
Eine weitere Substanzklasse mit Cobuildereigenschaften stellen die Phosphonate dar. Dabei handelt es sich insbesondere um Hydroxyalkan- bzw. Aminoalkanphosphonate. Unter den Hydroxyalkanphosphonaten ist das 1-Hydroxyethan-1,1-diphosphonat (HEDP) von besonderer Bedeutung als Cobuilder. Es wird vorzugsweise als Natriumsalz eingesetzt, wobei das Dinatriumsalz neutral und das Tetranatriumsalz alkalisch (pH 9) reagiert. Als Aminoalkanphosphonate kommen vorzugsweise Ethylendiamintetramethylenphosphonat (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) sowie deren höhere Homologe in Frage. Sie werden vorzugsweise in Form der neutral reagierenden Natriumsalze, z. B. als Hexanatriumsalz der EDTMP bzw. als Hepta- und Octa-Natriumsalz der DTPMP, eingesetzt. Als Builder wird dabei aus der Klasse der Phosphonate bevorzugt HEDP verwendet. Die Aminoalkanphosphonate besitzen zudem ein ausgeprägtes Schwermetallbindevermögen. Dementsprechend kann es, insbesondere wenn die Mittel auch Bleiche enthalten, bevorzugt sein, Aminoalkanphosphonate, insbesondere DTPMP, einzusetzen, oder Mischungen aus den genannten Phosphonaten zu verwenden.Another class of substances with cobuilder properties are the phosphonates it is especially hydroxyalkane or aminoalkanephosphonates. Under the hydroxyalkane phosphonates is 1-hydroxyethane-1,1-diphosphonate (HEDP) from of particular importance as a cobuilder. It is preferably used as the sodium salt the disodium salt being neutral and the tetrasodium salt being alkaline (pH 9). As Aminoalkane phosphonates preferably come from ethylenediaminetetramethylenephosphonate (EDTMP), diethylenetriaminepentamethylenephosphonate (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z. B. as the hexasodium salt of EDTMP or as the hepta- and octa-sodium salt of DTPMP, used. HEDP is preferably used as the builder from the class of the phosphonates. The aminoalkanephosphonates also have a pronounced ability to bind heavy metals. Accordingly, especially if the agents also contain bleach, be preferred to use aminoalkanephosphonates, in particular DTPMP, or To use mixtures of the phosphonates mentioned.
Darüber hinaus können alle Verbindungen, die in der Lage sind, Komplexe mit Erdalkaliionen auszubilden, als Cobuilder eingesetzt werden.In addition, all compounds that are capable of complexing with alkaline earth ions train as cobuilders.
Die Menge an Gerüststoff beträgt üblicherweise zwischen 10 und 70 Gew.-%, vorzugsweise zwischen 15 und 60 Gew.-% und insbesondere zwischen 20 und 50 Gew.-%. Wiederum ist die Menge an eingesetzten Buildem abhängig vom Verwendungszweck, so daß Bleichmitteltabletten höhere Mengen an Gerüststoffen aufweisen können (beispielsweise zwischen 20 und 70 Gew.-%, vorzugsweise zwischen 25 und 65 Gew.-% und insbesondere zwischen 30 und 55 Gew.-%), als beispielsweise Waschmitteltabletten (üblicherweise 10 bis 50 Gew.-%, vorzugsweise 12,5 bis 45 Gew.-% uns insbesondere zwischen17,5 und 37,5 Gew.-%).The amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60% by weight and in particular between 20 and 50% by weight. In turn the amount of builders used depends on the intended use, so that Bleach tablets can have higher amounts of builders (for example between 20 and 70% by weight, preferably between 25 and 65% by weight and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50% by weight, preferably 12.5 to 45% by weight and in particular between 17.5 and 37.5% by weight).
Zusätzlich zum Tensidgranulat und dem wasserfrei granulierten Brausesystem kann das zu verpressende Vorgemisch im erfindungsgemäßen Verfahren weitere Inhaltsstoffe enthalten. In bevorzugten Verfahren enthält das Vorgemisch zusätzlich ein Desintegrationshilfsmittel, vorzugsweise ein Desintegrationshilfsmittel auf Cellulosebasis, vorzugsweise in granularer, cogranulierter oder kompaktierter Form, in Mengen von 0,5 bis 10 Gew.-%, vorzugsweise von 3 bis 7 Gew.-% und insbesondere von 4 bis 6 Gew.-%, jeweils bezogen auf das Gewicht des Vorgemischs.In addition to the surfactant granulate and the water-free granulated shower system, this can also be done Compressing premix in the process according to the invention contain further ingredients. In preferred processes, the premix additionally contains a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case based on the weight of the premix.
In weiter bevorzugten Verfahren enthält das Vorgemisch zusätzlich einen oder mehrere Stoffe aus der Gruppe der Bleichmittel, Bleichaktivatoren, Enzyme, pH-Stellmittel, Duftstoffe, Parfümträger, Fluoreszenzmittel, Farbstoffe, Schauminhibitoren, Silikonöle, Antiredepositionsmittel, optischen Aufheller, Vergrauungsinhibitoren, Farbübertragungsinhibitoren und Korrosionsinhibitoren. Diese Stoffe werden nachfolgend beschrieben.In more preferred processes, the premix additionally contains one or more Substances from the group of bleaching agents, bleach activators, enzymes, pH regulators, fragrances, Perfume carriers, fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors. These substances are described below.
Unter den als Bleichmittel dienenden, in Wasser H2O2 liefernden Verbindungen haben das Natriumperborattetrahydrat und das Natriumperboratmonohydrat besondere Bedeutung. Weitere brauchbare Bleichmittel sind beispielsweise Natriumpercarbonat, Peroxypyrophosphate, Citratperhydrate sowie H2O2 liefernde persaure Salze oder Persäuren, wie Perbenzoate, Peroxophthalate, Diperazelainsäure, Phthaloiminopersäure oder Diperdodecandisäure. Auch beim Einsatz der Bleichmittel ist es möglich, auf den Einsatz von Tensiden und/oder Gerüststoffen zu verzichten, so daß reine Bleichmitteltabletten herstellbar sind. Sollen solche Bleichmitteltabletten zur Textilwäsche eingesetzt werden, ist eine Kombination von Natriumpercarbonat mit Natriumsesquicarbonat bevorzugt, unabhängig davon, welche weiteren Inhaltsstoffe in den Formkörpern enthalten sind. Werden Reinigungsoder Bleichmitteltabletten für das maschinelle Geschirrspülen hergestellt, so können auch Bleichmittel aus der Gruppe der organischen Bleichmittel eingesetzt werden. Typische organische Bleichmittel sind die Diacylperoxide, wie z.B. Dibenzoylperoxid. Weitere typische organische Bleichmittel sind die Peroxysäuren, wobei als Beispiele besonders die Alkylperoxysäuren und die Arylperoxysäuren genannt werden. Bevorzugte Vertreter sind (a) die Peroxybenzoesäure und ihre ringsubstituierten Derivate, wie Alkylperoxybenzoesäuren, aber auch Peroxy-α-Naphtoesäure und Magnesium-monoperphthalat, (b) die aliphatischen oder substituiert aliphatischen Peroxysäuren, wie Peroxylaurinsäure, Peroxystearinsäure, ε-Phthalimidoperoxycapronsäure [Phthaloiminoperoxyhexansäure (PAP)], o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipinsäure und N-nonenylamidopersuccinate, und (c) aliphatische und araliphatische Peroxydicarbonsäuren, wie 1,12-Diperoxycarbonsäure, 1,9-Diperoxyazelainsäure, Diperocysebacinsäure, Diperoxybrassylsäure, die Diperoxyphthalsäuren, 2-Decyldiperoxybutan-1,4-disäure, N,N-Terephthaloyl-di(6-aminopercapronsäue) können eingesetzt werden.Among the compounds 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, phthaloiminoperic acid or diperdodecanedioic acid. Even when using the bleaching agents, it is possible to dispense with the use of surfactants and / or builders, so that pure bleach tablets can be produced. If such bleach tablets are to be used for textile washing, a combination of sodium percarbonate with sodium sesquicarbonate is preferred, regardless of which other ingredients are contained in the shaped bodies. If cleaning tablets or bleach tablets are produced for machine dishwashing, bleaching agents from the group of organic bleaching agents can also be used. Typical organic bleaching agents are the diacyl peroxides, such as dibenzoyl peroxide. Other typical organic bleaching agents are peroxy acids, examples of which include alkyl peroxy acids and aryl peroxy acids. Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy-α-naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ε-phthalimidoperoxyaloacidoperoxycaproic acid (Pε) )], o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipinic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperocysebacic acid, diperoxydiperoxybiperyldoxybiperyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutyldiacyldiperoxy-diperoxybutanoic acid, 4-diacid, N, N-terephthaloyl-di (6-aminopercapronic acid) can be used.
Als Bleichmittel in Formkörpern für das maschinelle Geschirrspülen können auch Chlor oder Brom freisetzende Substanzen eingesetzt werden. Unter den geeigneten Chlor oder Brom freisetzenden Materialien kommen beispielsweise heterocyclische N-Brom- und N-Chloramide, beispielsweise Trichlorisocyanursäure, Tribromisocyanursäure, Dibromisocyanursäure und/oder Dichlorisocyanursäure (DICA) und/oder deren Salze mit Kationen wie Kalium und Natrium in Betracht. Hydantoinverbindungen, wie 1,3-Dichlor-5,5-dimethylhydanthoin sind ebenfalls geeignet.Chlorine or. Can also be used as bleaching agents in moldings for automatic dishwashing Bromine-releasing substances are used. Among the appropriate chlorine or bromine releasing materials come, for example, heterocyclic N-bromo- and N-chloramides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromo isocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or their salts with Cations such as potassium and sodium are considered. Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
Um beim Waschen oder Reinigen bei Temperaturen von 60 °C und darunter eine verbesserte Bleichwirkung zu erreichen, können Bleichaktivatoren als alleiniger Bestandteil oder als Inhaltsstoff der Komponente b) eingearbeitet werden. Als Bleichaktivatoren können Verbindungen, die unter Perhydrolysebedingungen aliphatische Peroxocarbonsäuren mit vorzugsweise 1 bis 10 C-Atomen, insbesondere 2 bis 4 C-Atomen, und/oder gegebenenfalls substituierte Perbenzoesäure ergeben, eingesetzt werden. Geeignet sind Substanzen, die O- und/oder N-Acylgruppen der genannten C-Atomzahl und/oder gegebenenfalls substituierte Benzoylgruppen tragen. Bevorzugt sind mehrfach acylierte Alkylendiamine, insbesondere Tetraacetylethylendiamin (TAED), acylierte Triazinderivate, insbesondere 1,5-Diacetyl-2,4-dioxohexahydro-1,3,5-triazin (DADHT), acylierte Glykolurile, insbesondere Tetraacetylglykoluril (TAGU), N-Acylimide, insbesondere N-Nonanoylsuccinimid (NOSI), acylierte Phenolsulfonate, insbesondere n-Nonanoyl- oder Isononanoyloxybenzolsulfonat (n- bzw. iso-NOBS), Carbonsäureanhydride, insbesondere Phthalsäureanhydrid, acylierte mehrwertige Alkohole, insbesondere Triacetin, Ethylenglykoldiacetat und 2,5-Diacetoxy-2,5-dihydrofuran.To improve when washing or cleaning at temperatures of 60 ° C and below To achieve bleaching effect, bleach activators can be used as the sole component or be incorporated as an ingredient of component b). Can be used as bleach activators Compounds containing aliphatic peroxocarboxylic acids under perhydrolysis conditions preferably 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used. Suitable substances are the O- and / or N-acyl groups of the number of carbon atoms mentioned and / or optionally substituted Wear benzoyl groups. Multi-acylated alkylenediamines are preferred, in particular Tetraacetylethylenediamine (TAED), acylated triazine derivatives, especially 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated glycolurils, in particular Tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated phenol sulfonates, especially n-nonanoyl or isononanoyloxybenzene sulfonate (n- or iso-NOBS), carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
Zusätzlich zu den konventionellen Bleichaktivatoren oder an deren Stelle können auch sogenannte Bleichkatalysatoren in die Formkörper eingearbeitet werden. Bei diesen Stoffen handelt es sich um bleichverstärkende Übergangsmetallsalze bzw. Übergangsmetallkomplexe wie beispielsweise Mn-, Fe-, Co-, Ru - oder Mo-Salenkomplexe oder -carbonylkomplexe. Auch Mn-, Fe-, Co-, Ru-, Mo-, Ti-, V- und Cu-Komplexe mit N-haltigen Tripod-Liganden sowie Co-, Fe-, Cu- und Ru-Amminkomplexe sind als Bleichkatalysatoren verwendbar.In addition to the conventional bleach activators or in their place, too so-called bleaching catalysts can be incorporated into the moldings. With these fabrics are bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo salt complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing ones Tripod ligands as well as Co, Fe, Cu and Ru amine complexes are used as bleaching catalysts usable.
Als Enzyme kommen solche aus der Klasse der Proteasen, Lipasen, Amylasen, Cellulasen bzw. deren Gemische in Frage. Besonders gut geeignet sind aus Bakterienstämmen oder Pilzen, wie Bacillus subtilis, Bacillus licheniformis und Streptomyces griseus gewonnene enzymatische Wirkstoffe. Vorzugsweise werden Proteasen vom Subtilisin-Typ und insbesondere Proteasen, die aus Bacillus lentus gewonnen werden, eingesetzt. Dabei sind Enzymmischungen, beispielsweise aus Protease und Amylase oder Protease und Lipase oder Protease und Cellulase oder aus Cellulase und Lipase oder aus Protease, Amylase und Lipase oder Protease, Lipase und Cellulase, insbesondere jedoch Cellulase-haltige Mischungen von besonderem Interesse. Auch Peroxidasen oder Oxidasen haben sich in einigen Fällen als geeignet erwiesen. Die Enzyme können an Trägerstoffen adsorbiert und/oder in Hüllsubstanzen eingebettet sein, um sie gegen vorzeitige Zersetzung zu schützen. Der Anteil der Enzyme, Enzymmischungen oder Enzymgranulate in den erfindungsgemäßen Formkörpern kann beispielsweise etwa 0,1 bis 5 Gew.-%, vorzugsweise 0,1 bis etwa 2 Gew.-% betragen.Enzymes come from the class of proteases, lipases, amylases, cellulases or their mixtures in question. Bacterial strains or are particularly well suited Mushrooms such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Proteases of the subtilisin type and in particular are preferred Proteases obtained from Bacillus lentus are used. Here are 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 mixtures containing cellulase of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable. The enzymes can be adsorbed on carriers and / or be embedded in coating substances to protect them against premature decomposition. The Proportion of the enzymes, enzyme mixtures or enzyme granules in the inventive Shaped bodies can, for example, about 0.1 to 5 wt .-%, preferably 0.1 to about 2 % By weight.
Zusätzlich können die Wasch- und Reinigungsmittelformkörper auch Komponenten enthalten, welche die Öl- und Fettauswaschbarkeit aus Textilien positiv beeinflussen (sogenannte soil repellents). Dieser Effekt wird besonders deutlich, wenn ein Textil verschmutzt wird, das bereits vorher mehrfach mit einem erfindungsgemäßen Waschmittel, das diese öl- und fettlösende Komponente enthält, gewaschen wurde. Zu den bevorzugten öl- und fettlösenden Komponenten zählen beispielsweise nichtionische Celluloseether wie Methylcellulose und Methylhydroxy-propylcellulose mit einem Anteil an Methoxyl-Gruppen von 15 bis 30 Gew.-% und an Hydroxypropoxyl-Gruppen von 1 bis 15 Gew.-%, jeweils bezogen auf den nichtionischen Celluloseether, sowie die aus dem Stand der Technik bekannten Polymere der Phthalsäure und/oder der Terephthalsäure bzw. von deren Derivaten, insbesondere Polymere aus Ethylenterephthalaten und/oder Polyethylenglykolterephthalaten oder anionisch und/oder nichtionisch modifizierten Derivaten von diesen. Besonders bevorzugt von diesen sind die sulfonierten Derivate der Phthalsäure- und der Terephthalsäure-Polymere. In addition, the detergent tablets can also contain components which positively influence the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is dirty is already several times with a detergent according to the invention, this contains oil and fat-dissolving component, was washed. Among the preferred oil and fat-dissolving components include, for example, nonionic cellulose ethers such as methyl cellulose and methylhydroxy-propyl cellulose with a proportion of methoxyl groups of 15 to 30 wt .-% and of hydroxypropoxyl groups of 1 to 15 wt .-%, each based on the nonionic cellulose ether, as well as those known from the prior art Polymers of phthalic acid and / or terephthalic acid or their derivatives, in particular Polymers made from ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these. Particularly preferred of these are the sulfonated derivatives of phthalic acid and terephthalic acid polymers.
Die Formkörper können als optische Aufheller Derivate der Diaminostilbendisulfonsäure bzw. deren Alkalimetallsalze enthalten. Geeignet sind z.B. Salze der 4,4'-Bis(2-anilino-4-morpholino-1,3,5-triazinyl-6-amino)stilben-2,2'-disulfonsäure oder gleichartig aufgebaute Verbindungen, die anstelle der Morpholino-Gruppe eine Diethanolaminogruppe, eine Methylaminogruppe, eine Anilinogruppe oder eine 2-Methoxyethylaminogruppe tragen. Weiterhin können Aufheller vom Typ der substituierten Diphenylstyryle anwesend sein, z.B. die Alkalisalze des 4,4'-Bis(2-sulfostyryl)-diphenyls, 4,4'-Bis(4-chlor-3-sulfostyryl)-diphenyls, oder 4-(4-Chlorstyryl)-4'-(2-sulfostyryl)-diphenyls. Auch Gemische der vorgenannten Aufheller können verwendet werden.The moldings can, as optical brighteners, derivatives of diaminostilbenedisulfonic acid or their 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, have a diethanolamino group, a methylamino group, carry an anilino group or a 2-methoxyethylamino group. Brighteners of the substituted diphenylstyryl type may also be present, e.g. the alkali salts of 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.
Farb- und Duftstoffe werden den erfindungsgemäßen Wasch- und Reinigungsmittelformkörpem zugesetzt, um den ästhetischen Eindruck der Produkte zu verbessern und dem Verbraucher neben der Leistung ein visuell und sensorisch "typisches und unverwechselbares" Produkt zur Verfügung zu stellen. Als Parfümöle bzw. Duftstoffe können einzelne Riechstoffverbindungen, z.B. die synthetischen Produkte vom Typ der Ester, Ether, Aldehyde, Ketone, Alkohole und Kohlenwasserstoffe verwendet werden. Riechstoffverbindungen vom Typ der Ester sind z.B. Benzylacetat, Phenoxyethylisobutyrat, p-tert.-Butylcyclohexylacetat, Linalylacetat, Dimethylbenzyl-carbinylacetat, Phenylethylacetat, Linalylbenzoat, Benzylformiat, Ethylmethylphenyl-glycinat, Allylcyclohexylpropionat, Styrallylpropionat und Benzylsalicylat. Zu den Ethern zählen beispielsweise Benzylethylether, zu den Aldehyden z.B. die linearen Alkanale mit 8-18 C-Atomen, Citral, Citronellal, Citronellyloxyacetaldehyd, Cyclamenaldehyd, Hydroxycitronellal, Lilial und Bourgeonal, zu den Ketonen z.B. die Jonone, ∝-Isomethylionon und Methyl-cedrylketon, zu den Alkoholen Anethol, Citronellol, Eugenol, Geraniol, Linalool, Phenylethylalkohol und Terpineol, zu den Kohlenwasserstoffen gehören hauptsächlich die Terpene wie Limonen und Pinen. Bevorzugt werden jedoch Mischungen verschiedener Riechstoffe verwendet, die gemeinsam eine ansprechende Duftnote erzeugen. Solche Parfümöle können auch natürliche Riechstoffgemische enthalten, wie sie aus pflanzlichen Quellen zugänglich sind, z.B. Pine-, Citrus-, Jasmin-, Patchouly-, Rosen- oder Ylang-Ylang-Öl. Ebenfalls geeignet sind Muskateller, Salbeiöl, Kamillenöl, Nelkenöl, Melissenöl, Minzöl, Zimtblätteröl, Lindenblütenöl, Wacholderbeeröl, Vetiveröl, Olibanumöl, Galbanumöl und Labdanumöl sowie Orangenblütenöl, Neroliol, Orangenschalenöl und Sandelholzöl. Dyes and fragrances become the detergent tablets according to the invention added to improve the aesthetic impression of the products and the Consumers in addition to performance a visually and sensory "typical and distinctive" To provide product. Individual as perfume oils or fragrances Fragrance compounds, e.g. synthetic products of the ester, ether, aldehyde type, Ketones, alcohols and hydrocarbons can be used. fragrance compounds of the ester type are e.g. Benzyl acetate, phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, Linalyl acetate, dimethylbenzylcarbinylacetate, phenylethyl acetate, Linalyl benzoate, benzyl formate, ethyl methylphenyl glycinate, allyl cyclohexyl propionate, Styrallyl propionate and benzyl salicylate. The ethers include, for example, benzyl ethyl ether, to aldehydes e.g. the linear alkanals with 8-18 C atoms, citral, citronellal, Citronellyloxyacetaldehyde, Cyclamenaldehyde, Hydroxycitronellal, Lilial and Bourgeonal, to the ketones e.g. the Jonone, ∝-isomethyl ionone and methyl cedryl ketone, to the Alcohols anethole, citronellol, eugenol, geraniol, linalool, phenylethyl alcohol and terpineol, The hydrocarbons mainly include terpenes such as limonene and Pinene. However, mixtures of different odoriferous substances are preferably used create an appealing fragrance together. Such perfume oils can also be natural Fragrance mixtures contain, as are available from vegetable sources, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil. Are also suitable Muscatel, sage oil, chamomile oil, clove oil, lemon balm oil, mint oil, cinnamon leaf oil, linden blossom oil, Juniper berry oil, vetiver oil, olibanum oil, galbanum oil and labdanum oil as well Orange blossom oil, neroliol, orange peel oil and sandalwood oil.
Üblicherweise liegt der Gehalt der erfindungsgemäßen Wasch- und Reinigungsmittelformkörper an Farbstoffen unter 0,01 Gew.-%, während Duftstoffe bis zu 2 Gew.-% der gesamten Formulierung ausmachen können.The content of the detergent tablets according to the invention is usually in the range of dyes below 0.01% by weight, while fragrances up to 2% by weight of the total Can make up wording.
Die Duftstoffe können direkt in die erfindungsgemäßen Mittel eingearbeitet werden, es kann aber auch vorteilhaft sein, die Duftstoffe auf Träger aufzubringen, die die Haftung des Parfüms auf der Wäsche verstärken und durch eine langsamere Duftfreisetzung für langanhaltenden Duft der Textilien sorgen. Als solche Trägermaterialien haben sich beispielsweise Cyclodextrine bewährt, wobei die Cyclodextrin-Parfüm-Komplexe zusätzlich noch mit weiteren Hilfsstoffen beschichtet werden können.The fragrances can be incorporated directly into the agents according to the invention But it can also be advantageous to apply the fragrances to the carrier, which have the liability of the perfume on the laundry and by a slower fragrance release for long-lasting fragrance of the textiles. Such carrier materials have, for example Cyclodextrins have proven themselves, with the cyclodextrin-perfume complexes additionally can be coated with other auxiliaries.
Um den ästhetischen Eindruck der erfindungsgemäßen Wasch- und Reinigungsmittelformkörper zu verbessern, können sie mit geeigneten Farbstoffen eingefärbt werden. Bevorzugte Farbstoffe, deren Auswahl dem Fachmann keinerlei Schwierigkeit bereitet, besitzen eine hohe Lagerstabilität und Unempfindlichkeit gegenüber den übrigen Inhaltsstoffen der Mittel und gegen Licht sowie keine ausgeprägte Substantivität gegenüber Textilfasem, um diese nicht anzufärben.For the aesthetic impression of the detergent tablets according to the invention To improve, they can be colored with suitable dyes. preferred Dyes, the selection of which is not difficult for the person skilled in the art a high storage stability and insensitivity to the other ingredients of the Medium and against light and no pronounced substantivity towards textile fibers, um not to stain them.
Die Herstellung der erfindungsgemäßen Formkörper erfolgt zunächst durch das trockene Vermischen der Bestandteile, die ganz oder teilweise vorgranuliert sein können, und anschließendes Informbringen, insbesondere Verpressen zu Tabletten, wobei auf herkömmliche Verfahren zurückgegriffen werden kann. Zur Herstellung der erfindungsgemäßen Formkörper wird das Vorgemisch in einer sogenannten Matrize zwischen zwei Stempeln zu einem festen Komprimat verdichtet. Dieser Vorgang, der im folgenden kurz als Tablettierung bezeichnet wird, gliedert sich in vier Abschnitte: Dosierung, Verdichtung (elastische Verformung), plastische Verformung und Ausstoßen.The moldings according to the invention are first produced by dry Mixing the components, which can be partially or completely pre-granulated, and then Inform, in particular pressing into tablets, whereby conventional Procedure can be used. For the production of the invention The premix is molded in a so-called die between two stamps compacted into a solid compressed. This process, hereinafter briefly referred to as tableting is divided into four sections: dosage, compression (elastic Deformation), plastic deformation and ejection.
Zunächst wird das Vorgemisch in die Matrize eingebracht, wobei die Füllmenge und damit das Gewicht und die Form des entstehenden Formkörpers durch die Stellung des unteren Stempels und die Form des Preßwerkzeugs bestimmt werden. Die gleichbleibende Dosierung auch bei hohen Formkörperdurchsätzen wird vorzugsweise über eine volumetrische Dosierung des Vorgemischs erreicht. Im weiteren Verlauf der Tablettierung berührt der Oberstempel das Vorgemisch und senkt sich weiter in Richtung des Unterstempels ab. Bei dieser Verdichtung werden die Partikel des Vorgemisches näher aneinander gedrückt, wobei das Hohlraumvolumen innerhalb der Füllung zwischen den Stempeln kontinuierlich abnimmt. Ab einer bestimmten Position des Oberstempels (und damit ab einem bestimmten Druck auf das Vorgemisch) beginnt die plastische Verformung, bei der die Partikel zusammenfließen und es zur Ausbildung des Formkörpers kommt. Je nach den physikalischen Eigenschaften des Vorgemisches wird auch ein Teil der Vorgemischpartikel zerdrückt und es kommt bei noch höheren Drücken zu einer Sinterung des Vorgemischs. Bei steigender Preßgeschwindigkeit, also hohen Durchsatzmengen, wird die Phase der elastischen Verformung immer weiter verkürzt, so daß die entstehenden Formkörper mehr oder minder große Hohlräume aufweisen können. Im letzten Schritt der Tablettierung wird der fertige Formkörper durch den Unterstempel aus der Matrize herausgedrückt und durch nachfolgende Transporteinrichtungen wegbefördert. Zu diesem Zeitpunkt ist lediglich das Gewicht des Formkörpers endgültig festgelegt, da die Preßlinge aufgrund physikalischer Prozesse (Rückdehnung, kristallographische Effekte, Abkühlung etc.) ihre Form und Größe noch ändern können.First, the premix is introduced into the die, the filling quantity and thus the weight and shape of the resulting molded body by the position of the lower one Stamp and the shape of the press tool can be determined. The constant dosage even with high throughputs of shaped bodies, a volumetric flow rate is preferably used Dosage of the premix reached. In the further course of tableting, the Upper stamp the premix and continues to lower towards the lower stamp. at this compression, the particles of the premix are pressed closer together, whereby the void volume within the filling between the punches is continuous decreases. From a certain position of the upper stamp (and thus from a certain Pressure on the premix) begins the plastic deformation at which the particles flow together and the molded body is formed. Depending on the physical Properties of the premix are also crushed some of the premix particles and sintering of the premix occurs at even higher pressures. at increasing press speed, i.e. high throughput, the phase of elastic Deformation is shortened further and further, so that the resulting shaped body more or may have smaller cavities. In the last step of tableting the Finished moldings are pressed out of the die by the lower punch and through subsequent transport devices transported away. At this point, it's just that Weight of the molded body finally determined, because the compacts due to physical Processes (stretching, crystallographic effects, cooling etc.) their shape and size can still change.
Die Tablettierung erfolgt in handelsüblichen Tablettenpressen, die prinzipiell mit Einfachoder Zweifachstempeln ausgerüstet sein können. Im letzteren Fall wird nicht nur der Oberstempel zum Druckaufbau verwendet, auch der Unterstempel bewegt sich während des Preßvorgangs auf den Oberstempel zu, während der Oberstempel nach unten drückt. Für kleine Produktionsmengen werden vorzugsweise Exzentertablettenpressen verwendet, bei denen der oder die Stempel an einer Exzenterscheibe befestigt sind, die ihrerseits an einer Achse mit einer bestimmten Umlaufgeschwindigkeit montiert ist. Die Bewegung dieser Preßstempel ist mit der Arbeitsweise eines üblichen Viertaktmotors vergleichbar. Die Verpressung kann mit je einem Ober- und Unterstempel erfolgen, es können aber auch mehrere Stempel an einer Exzenterscheibe befestigt sein, wobei die Anzahl der Matrizenbohrungen entsprechend erweitert ist. Die Durchsätze von Exzenterpressen variieren ja nach Typ von einigen hundert bis maximal 3000 Tabletten pro Stunde.Tableting takes place in commercially available tablet presses, which are basically single or Double stamps can be equipped. In the latter case, it is not only the upper stamp used to build up pressure, also the lower stamp moves during the Pressing process towards the upper punch, while the upper punch presses down. For Small production quantities are preferably used with eccentric tablet presses which the stamp or stamps are attached to an eccentric disc, which in turn on one Axis is mounted with a certain rotational speed. The movement of this Press ram is comparable to the way a conventional four-stroke engine works. The pressing can be done with one upper and one lower stamp, but several can also be used Stamp be attached to an eccentric disc, the number of die holes is expanded accordingly. The throughputs of eccentric presses vary depending on the type from a few hundred to a maximum of 3000 tablets per hour.
Für größere Durchsätze wählt man Rundlauftablettenpressen, bei denen auf einem sogenannten Matrizentisch eine größere Anzahl von Matrizen kreisförmig angeordnet ist. Die Zahl der Matrizen variiert je nach Modell zwischen 6 und 55, wobei auch größere Matrizen im Handel erhältlich sind. Jeder Matrize auf dem Matrizentisch ist ein Ober- und Unterstempel zugeordnet, wobei wiederum der Preßdruck aktiv nur durch den Ober- bzw. Unterstempel, aber auch durch beide Stempel aufgebaut werden kann. Der Matrizentisch und die Stempel bewegen sich um eine gemeinsame senkrecht stehende Achse, wobei die Stempel mit Hilfe schienenartiger Kurvenbahnen während des Umlaufs in die Positionen für Befüllung, Verdichtung, plastische Verformung und Ausstoß gebracht werden. An den Stellen, an denen eine besonders gravierende Anhebung bzw. Absenkung der Stempel erforderlich ist (Befüllen, Verdichten, Ausstoßen), werden diese Kurvenbahnen durch zusätzliche Niederdruckstücke, Nierderzugschienen und Aushebebahnen unterstützt. Die Befüllung der Matrize erfolgt über eine starr angeordnete Zufuhreinrichtung, den sogenannten Füllschuh, der mit einem Vorratsbehälter für das Vorgemisch verbunden ist. Der Preßdruck auf das Vorgemisch ist über die Preßwege für Ober- und Unterstempel individuell einstellbar, wobei der Druckaufbau durch das Vorbeirollen der Stempelschaftköpfe an verstellbaren Druckrollen geschieht.For larger throughputs, rotary tablet presses are selected, on which a so-called Matrix table a larger number of matrices is arranged in a circle. The The number of matrices varies between 6 and 55, depending on the model, with larger matrices also are commercially available. Each die on the die table is an upper and lower stamp assigned, with the pressure again being active only through the upper or lower stamp, but can also be built using both stamps. The matrix table and the Stamps move around a common vertical axis, the stamp with the help of rail-like cam tracks during the circulation in the positions for filling, Compression, plastic deformation and discharge are brought. In the places where a particularly serious raising or lowering of the stamp is required (filling, compacting, ejecting), these cam tracks are replaced by additional ones Low-pressure pieces, low-tension rails and lifting tracks supported. The filling the matrix is carried out via a rigidly arranged feed device, the so-called Filling shoe, which is connected to a reservoir for the premix. The pressure the pre-mix is individual via the press paths for upper and lower punches adjustable, the pressure build-up by rolling the stamp shaft heads past adjustable Print rolls happen.
Rundlaufpressen können zur Erhöhung des Durchsatzes auch mit zwei Füllschuhen versehen werden, wobei zur Herstellung einer Tablette nur noch ein Halbkreis durchlaufen werden muß. Zur Herstellung zwei- und mehrschichtiger Formkörper werden mehrere Füllschuhe hintereinander angeordnet, ohne daß die leicht angepreßte erste Schicht vor der weiteren Befüllung ausgestoßen wird. Durch geeignete Prozeßführung sind auf diese Weise auch Mantel- und Punkttabletten herstellbar, die einen zwiebelschalenartigen Aufbau haben, wobei im Falle der Punkttabletten die Oberseite des Kerns bzw. der Kernschichten nicht überdeckt wird und somit sichtbar bleibt. Auch Rundlauftablettenpressen sind mit Einfach- oder Mehrfachwerkzeugen ausrüstbar, so daß beispielsweise ein äußerer Kreis mit 50 und ein innerer Kreis mit 35 Bohrungen gleichzeitig zum Verpressen benutzt werden. Die Durchsätze moderner Rundlauftablettenpressen betragen über eine Million Formkörper pro Stunde.Rotary presses can also be equipped with two filling shoes to increase the throughput be, whereby only a semicircle is run through to produce a tablet got to. Several filling shoes are used to produce two- and multi-layer molded articles arranged one behind the other without the slightly pressed first layer in front of the further filling is ejected. By appropriate process control are in this way also coated and dot tablets can be produced, which have an onion-shell-like structure have, in the case of the point tablets the top of the core or core layers is not covered and therefore remains visible. Rotary tablet presses are also included Single or multiple tools can be equipped so that, for example, an outer circle with 50 and an inner circle with 35 holes can be used simultaneously for pressing. The throughputs of modern rotary tablet presses are over a million tablets per hour.
Bei der Tablettierung mit Rundläuferpressen hat es sich als vorteilhaft erwiesen, die Tablettierung mit möglichst geringen Gewichtschwankungen der Tablette durchzuführen. When tableting with rotary presses, tableting has proven to be advantageous with the smallest possible fluctuations in weight of the tablet.
Auf diese Weise lassen sich auch die Härteschwankungen der Tablette reduzieren. Geringe Gewichtschwankungen können auf folgende Weise erzielt werden:
- Verwendung von Kunststoffeinlagen mit geringen Dickentoleranzen
- Geringe Umdrehungszahl des Rotors
- Große Füllschuhe
- Abstimmung des Füllschuhflügeldrehzahl auf die Drehzahl des Rotors
- Füllschuh mit konstanter Pulverhöhe
- Entkopplung von Füllschuh und Pulvervorlage
- Use of plastic inserts with small thickness tolerances
- Low number of revolutions of the rotor
- Big filling shoes
- Matching the filler paddle speed to the speed of the rotor
- Filling shoe with constant powder height
- Decoupling of filling shoe and powder supply
Zur Verminderung von Stempelanbackungen bieten sich sämtliche aus der Technik bekannte Antihaftbeschichtungen an. Besonders vorteilhaft sind Kunststoffbeschichtungen, Kunststoffeinlagen oder Kunststoffstempel. Auch drehende Stempel haben sich als vorteilhaft erwiesen, wobei nach Möglichkeit Ober- und Unterstempel drehbar ausgeführt sein sollten. Bei drehenden Stempeln kann auf eine Kunststoffeinlage in der Regel verzichtet werden. Hier sollten die Stempeloberflächen elektropoliert sein.All known from the art can be used to reduce stamp caking Non-stick coatings. Plastic coatings are particularly advantageous, Plastic inlays or plastic stamps. Rotating stamps have also proven to be advantageous proven, where possible, upper and lower punches are rotatable should. In the case of rotating stamps, a plastic insert is generally not required become. The stamp surfaces should be electropolished here.
Es zeigte sich weiterhin, daß lange Preßzeiten vorteilhaft sind. Diese können mit Druckschienen, mehreren Druckrollen oder geringen Rotordrehzahlen eingestellt werden. Da die Härteschwankungen der Tablette durch die Schwankungen der Preßkräfte verursacht werden, sollten Systeme angewendet werden, die die Preßkraft begrenzen. Hier können elastische Stempel, pneumatische Kompensatoren oder federnde Elemente im Kraftweg eingesetzt werden. Auch kann die Druckrolle federnd ausgeführt werden.It was also shown that long pressing times are advantageous. This can be done with pressure rails, several pressure rollers or low rotor speeds. Since the Fluctuations in the hardness of the tablet are caused by the fluctuations in the pressing forces systems should be used that limit the pressing force. Here elastic Stamp, pneumatic compensators or spring elements used in the force path become. The pressure roller can also be designed to be resilient.
Im Rahmen der vorliegenden Erfindung geeignete Tablettiermaschinen sind beispielsweise erhältlich bei den Firmen Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Köln, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, sowie Romaco GmbH, Worms. Weitere Anbieter sind beispielsweise Dr. Herbert Pete, Wien (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE/LU) sowie Mediopharm Kamnik (SI). Besonders geeignet ist beispielsweise die Hydraulische Doppeldruckpresse HPF 630 der Firma LAEIS, D. Tablettierwerkzeuge sind beispielsweise von den Firmen Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber % Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms und Notter Werkzeugbau, Tamm erhältlich. Weitere Anbieter sind z.B. die Senss AG, Reinach (CH) und die Medicopharm, Kamnik (SI).Tableting machines suitable for the purposes of the present invention are, for example available from the companies Apparatebau Holzwarth GbR, Asperg, Wilhelm Fette GmbH, Schwarzenbek, Hofer GmbH, Weil, Horn & Noack Pharmatechnik GmbH, Worms, IMA Verpackungssysteme GmbH Viersen, KILIAN, Cologne, KOMAGE, Kell am See, KORSCH Pressen AG, Berlin, and Romaco GmbH, Worms. Other providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Bern (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (GB), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI). The hydraulic double-pressure press, for example, is particularly suitable HPF 630 from LAEIS, D. Tableting tools are for example from the company Adams Tablettierwerkzeuge, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Söhne GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter Werkzeugbau, Tamm available. Other providers are e.g. the Senss AG, Reinach (CH) and Medicopharm, Kamnik (SI).
Die Formkörper können dabei in vorbestimmter Raumform und vorbestimmter Größe gefertigt werden. Als Raumform kommen praktisch alle sinnvoll handhabbaren Ausgestaltungen in Betracht, beispielsweise also die Ausbildung als Tafel, die Stab- bzw. Barrenform, Würfel, Quader und entsprechende Raumelemente mit ebenen Seitenflächen sowie insbesondere zylinderförmige Ausgestaltungen mit kreisförmigem oder ovalem Querschnitt. Diese letzte Ausgestaltung erfäßt dabei die Darbietungsform von der Tablette bis zu kompakten Zylinderstücken mit einem Verhältnis von Höhe zu Durchmesser oberhalb 1.The moldings can be made in a predetermined spatial shape and size become. Practically all useful configurations come as a spatial form into consideration, for example the formation as a board, the shape of bars or bars, Cubes, cuboids and corresponding room elements with flat side surfaces as well in particular cylindrical configurations with a circular or oval cross section. This last embodiment covers the presentation form from the tablet to to compact cylinder pieces with a ratio of height to diameter above 1.
Die portionierten Preßlinge können dabei jeweils als voneinander getrennte Einzelelemente ausgebildet sein, die der vorbestimmten Dosiermenge der Wasch- und/oder Reinigungsmittel entspricht. Ebenso ist es aber möglich, Preßlinge auszubilden, die eine Mehrzahl solcher Masseneinheiten in einem Preßling verbinden, wobei insbesondere durch vorgegebene Sollbruchstellen die leichte Abtrennbarkeit portionierter kleinerer Einheiten vorgesehen ist. Für den Einsatz von Textilwaschmitteln in Maschinen des in Europa üblichen Typs mit horizontal angeordneter Mechanik kann die Ausbildung der portionierten Preßlinge als Tabletten, in Zylinder- oder Quaderform zweckmäßig sein, wobei ein Durchmesser/Höhe-Verhältnis im Bereich von etwa 0,5 : 2 bis 2 : 0,5 bevorzugt ist. Handelsübliche Hydraulikpressen, Exzenterpressen oder Rundläuferpressen sind geeignete Vorrichtungen insbesondere zur Herstellung derartiger Preßlinge.The portioned compacts can each be separate individual elements be formed, the predetermined dosage of detergents and / or cleaning agents equivalent. However, it is also possible to form compacts that have a plurality connect such mass units in a compact, in particular by predetermined The easy separation of portioned smaller units is provided for predetermined breaking points is. For the use of laundry detergents in machines of the type common in Europe with horizontally arranged mechanics, the formation of the portioned compacts as Tablets, in the shape of a cylinder or cuboid, are appropriate, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred. Commercial hydraulic presses, Eccentric presses or rotary presses are suitable devices in particular for the production of such compacts.
Die Raumform einer anderen Ausführungsform der Formkörper ist in ihren Dimensionen der Einspülkammer von handelsüblichen Haushaltswaschmaschinen angepaßt, so daß die Formkörper ohne Dosierhilfe direkt in die Einspülkammer eindosiert werden können, wo sie sich während des Einspülvorgangs auflöst. Selbstverständlich ist aber auch ein Einsatz der Waschmittelformkörper über eine Dosierhilfe problemlos möglich und im Rahmen der vorliegenden Erfindung bevorzugt.The spatial shape of another embodiment of the shaped body is in its dimensions the induction chamber of commercial household washing machines adapted so that the Shaped bodies can be metered directly into the induction chamber without a metering aid, where it dissolves during the induction process. Of course, there is also a stake the detergent tablets are easily possible via a dosing aid and within the present invention preferred.
Ein weiterer bevorzugter Formkörper, der hergestellt werden kann, hat eine platten- oder tafelartige Struktur mit abwechselnd dicken langen und dünnen kurzen Segmenten, so daß einzelne Segmente von diesem "Riegel" an den Sollbruchstellen, die die kurzen dünnen Segmente darstellen, abgebrochen und in die Maschine eingegeben werden können. Dieses Prinzip des "riegelförmigen" Formkörperwaschmittels kann auch in anderen geometrischen Formen, beispielsweise senkrecht stehenden Dreiecken, die lediglich an einer ihrer Seiten längsseits miteinander verbunden sind, verwirklicht werden.Another preferred molded body that can be produced has a plate or panel-like structure with alternating thick long and thin short segments, so that individual segments of this "bar" at the predetermined breaking points, the short thin Display segments, can be canceled and entered into the machine. This The principle of the "bar-shaped" shaped body detergent can also be used in other geometric Shapes, for example vertical triangles that only on one of their Pages are connected alongside each other, can be realized.
Möglich ist es aber auch, daß die verschiedenen Komponenten nicht zu einer einheitlichen Tablette verpreßt werden, sondern daß Formkörper erhalten werden, die mehrere Schichten, also mindestens zwei Schichten, aufweisen. Dabei ist es auch möglich, daß diese verschiedenen Schichten unterschiedliche Lösegeschwindigkeiten aufweisen. Hieraus können vorteilhafte anwendungstechnische Eigenschaften der Formkörper resultieren. Falls beispielsweise Komponenten in den Formkörpern enthalten sind, die sich wechselseitig negativ beeinflussen, so ist es möglich, die eine Komponente in der schneller löslichen Schicht zu integrieren und die andere Komponente in eine langsamer lösliche Schicht einzuarbeiten, so daß die erste Komponente bereits abreagiert hat, wenn die zweite in Lösung geht. Der Schichtaufbau der Formkörper kann dabei sowohl stapelartig erfolgen, wobei ein Lösungsvorgang der inneren Schicht(en) an den Kanten des Formkörpers bereits dann erfolgt, wenn die äußeren Schichten noch nicht vollständig gelöst sind, es kann aber auch eine vollständige Umhüllung der inneren Schicht(en) durch die jeweils weiter außen liegende(n) Schicht(en) erreicht werden, was zu einer Verhinderung der frühzeitigen Lösung von Bestandteilen der inneren Schicht(en) führt.But it is also possible that the various components do not become one Tablet are pressed, but that shaped bodies are obtained which have several layers, thus have at least two layers. It is also possible that these different Layers have different dissolving speeds. From this you can advantageous application properties of the molded articles result. If, for example Components contained in the moldings are mutually negative affect, so it is possible to find a component in the more rapidly soluble layer integrate and 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 done in a stack-like manner, with one dissolution process the inner layer (s) on the edges of the molded body already takes place, if the outer layers are not yet completely detached, it can also be one complete covering of the inner layer (s) by the outer layer (s) Layer (s) can be achieved, which prevents the premature dissolution of components the inner layer (s).
In einer weiter bevorzugten Ausführungsform der Erfindung besteht ein Formkörper aus mindestens drei Schichten, also zwei äußeren und mindestens einer inneren Schicht, wobei mindestens in einer der inneren Schichten ein Peroxy-Bleichmittel enthalten ist, während beim stapelförmigen Formkörper die beiden Deckschichten und beim hüllenförmigen Formkörper die äußersten Schichten jedoch frei von Peroxy-Bleichmittel sind. Weiterhin ist es auch möglich, Peroxy-Bleichmittel und gegebenenfalls vorhandene Bleichaktivatoren und/oder Enzyme räumlich in einem Formkörper voneinander zu trennen: Derartige mehrschichtige Formkörper weisen den Vorteil auf, daß sie nicht nur über eine Einspülkammer oder über eine Dosiervorrichtung, welche in die Waschflotte gegeben wird, eingesetzt werden können; vielmehr ist es in solchen Fällen auch möglich, den Formkörper im direkten Kontakt zu den Textilien in die Maschine zu geben, ohne daß Verfleckungen durch Bleichmittel und dergleichen zu befürchten wären.In a further preferred embodiment of the invention, a molded body consists of at least three layers, ie two outer and at least one inner layer, wherein at least one of the inner layers contains a peroxy bleach, while in the case of the stacked shaped body, the two outer layers and in the case of the shell-shaped one Moldings, the outermost layers, however, are free of peroxy bleach. Farther it is also possible to use peroxy bleaching agents and any bleach activators present and / or to separate enzymes spatially from one another in a shaped body: such multilayer Shaped bodies have the advantage that they do not have only one induction chamber or via a metering device which is added to the wash liquor can be; rather, in such cases it is also possible to direct the molded body To give contact to the textiles in the machine without staining Bleach and the like would be feared.
Ähnliche Effekte lassen sich auch durch Beschichtung ("coating") einzelner Bestandteile der zu verpressenden Wasch- und Reinigungsmittelzusammensetzung oder des gesamten Formkörpers erreichen. Hierzu können die zu beschichtenden Körper beispielsweise mit wäßrigen Lösungen oder Emulsionen bedüst werden, oder aber über das Verfahren der Schmelzbeschichtung einen Überzug erhalten.Similar effects can also be achieved by coating individual components of the detergent and cleaning agent composition to be pressed or all of them Reach shaped body. For this purpose, the bodies to be coated can be coated with, for example aqueous solutions or emulsions are sprayed, or via the process of Get a coating on the melt coating.
Neben dem Schichtaufbau können mehrphasige Formkörper auch in Form von Ringkemtabletten, Kernmanteltabletten oder sogenannten "bulleye"-Tabletten hergestellt werden. Eine Übersicht über solche Ausführungsformen mehrphasiger Tabletten ist in der EP 055 100 (Jeyes Group) beschrieben. Diese Schrift offenbart Toilettenreinigungsmittelblöcke, die einen geformten Körper aus einer langsam löslichen Reinigungsmittelzusammensetzung umfassen, in den eine Bleichmitteltablette eingebettet ist. Diese Schrift offenbart gleichzeitig die unterschiedlichsten Ausgestaltungsformen mehrphasiger Formkörper von der einfachen Mehrphasentablette bis hin zu komplizierten mehrschichtigen Systemen mit Einlagen.In addition to the layer structure, multiphase molded articles can also be in the form of ring core tablets, Core coated tablets or so-called "bulleye" tablets are produced. An overview of such embodiments of multi-phase tablets is in EP 055 100 (Jeyes Group). This document discloses blocks of toilet detergent, which is a molded body made from a slowly soluble detergent composition include in which a bleach tablet is embedded. This document reveals at the same time the most diverse designs of multiphase molded bodies from from simple multi-phase tablets to complicated multi-layer systems Insoles.
Nach dem Verpressen weisen die Wasch- und Reinigungsmittelformkörper eine hohe Stabilität
auf. Die Bruchfestigkeit zylinderförmiger Formkörper kann über die Meßgröße der
diametralen Bruchbeanspruchung erfaßt werden. Diese ist bestimmbar nach
Hierin steht σ für die diametrale Bruchbeanspruchung (diametral fracture stress, DFS) in Pa, P ist die Kraft in N, die zu dem auf den Formkörper ausgeübten Druck führt, der den Bruch des Formkörpers verursacht, D ist der Formkörperdurchmesser in Meter und t ist die Höhe der Formkörper. Here σ stands for diametral fracture stress (DFS) in Pa, P is the force in N which leads to the pressure exerted on the molded body, which is the Breakage of the molded body causes, D is the molded body diameter in meters and t is the Height of the molded body.
Durch Granulation in einem 50-Liter-Pflugscharmischer der Firma Lödige wurde ein tensidhaltiges Granulat (Zusammensetzung siehe Tabelle 1) hergestellt, das als Basis für ein teilchenförmiges Vorgemisch verwendet wurde. Im Anschluß an die Granulation wurden die Granulate in einer Wirbelschichtapparatur der Firma Glatt bei einer Zulufttemperatur von 60°C über einen Zeitraum von 30 Minuten getrocknet. Nach der Trocknung wurden Feinanteile < 0,4 mm und Grobkomanteile > 1,6 mm abgesiebt.Granulation in a 50-liter ploughshare mixer from Lödige resulted in a surfactant-containing Granules (composition see Table 1), which is the basis for a particulate premix was used. Following the granulation were the granules in a fluidized bed apparatus from Glatt at an inlet air temperature dried at 60 ° C over a period of 30 minutes. After drying Fine particles <0.4 mm and coarse particles> 1.6 mm sieved.
Durch Abmischung des tensidhaltigen Granulats mit Bleichmittel, Bleichaktivator sowie weiteren Aufbereitungskomponenten wurde ein tablettierfähiges Vorgemisch hergestellt. Als weitere Aufbereitungskomponente wurde ein Brausesystem in das Vorgemisch inkorporiert, das im Falle der erfindungsgemäßen Formkörper E1 und E2 in Form eines homogenen Co-Granulats und bei den Vergleichsbeispielen V1 und V2 in Form eines Gemischs der beiden feinteiligen Pulver vorlag.By mixing the granules containing surfactant with bleach, bleach activator and Further preparation components a tablettable premix was produced. A shower system was incorporated into the premix as a further treatment component, that in the case of the shaped bodies E1 and E2 according to the invention in the form of a homogeneous Co-granules and in the comparative examples V1 and V2 in the form of a mixture of the two finely divided powders.
Zur Herstellung der erfindungsgemäß einzusetzenden Brausegranulate wurden Natriumhydrogencarbonat,
Natriumcarbonat und Citronensäure trocken vermischt (siehe Tabelle 3)
und auf einer Kompaktierwalze vom Typ Alexanderwerk zu einer Schülpe kompaktiert.
Anschließend erfolgte die Vermahlung der Schülpe auf einem Siebgranulator. Die vermahlene
Schülpe wurde zwischen 0,6 und 1,6 mm abgesiebt. Das Brausesystem wurde zu
jeweils zu 5 Gew.-% dem zu verpressenden Vorgemisch zugegeben, wonach in einer
Korsch-Exzenterpresse die Verpressung der Vorgemische zu Tabletten (Durchmesser: 44
mm, Höhe: 22 mm, Gewicht: 37,5 g) erfolgte. Dabei wurde der Preßdruck so eingestellt,
daß jeweils zwei Serien von Formkörpern erhalten wurden (E1, E1', E2, E2' bzw. V1, V1'
und V2, V2'), die sich in ihrer Härte unterscheiden. Die Zusammensetzung der zu verpressenden
Vorgemische (und damit der Formkörper) zeigt Tabelle 2, die Zusammensetzung
und Teilchengrößenverteilung der zugesetzten Brausesysteme ist in Tabelle 3 angegeben,
die Teilchengrößenverteilung der übrigen Aufbereitungskomponenten zeigt Tabelle 4.
Die Härte der Tabletten wurde nach zwei Tagen Lagerung durch Verformung der Tablette bis zum Bruch gemessen, wobei die Kraft auf die Seitenflächen der Tablette einwirkte und die maximale Kraft, der die Tablette standhielt, ermittelt wurde.The hardness of the tablets became after two days of storage by deforming the tablet measured to break, the force acting on the side surfaces of the tablet and the maximum force that the tablet withstood was determined.
Zur Bestimmung des Tablettenzerfalls wurde die Tablette in ein Becherglas mit Wasser gelegt (600ml Wasser, Temperatur 30°C) und die Zeit bis zum vollständigen Tablettenzerfall gemessen. To determine tablet disintegration, the tablet was placed in a beaker with water placed (600ml water, temperature 30 ° C) and the time to complete tablet disintegration measured.
Die experimentellen Daten zeigen die Tabellen 5 und 6:
Claims (19)
- Laundry detergent and cleaning product tablets comprising compacted particulate laundry detergent and cleaning product which comprises from 5 to 50% by weight of anionic surfactant(s), characterized in that they comprise an anhydrously granulated effervescent system in amounts of from 1 to 20% by weight, based in each case on the tablet, at least 80% by weight of the particles of the anhydrously granulated effervescent system having particle sizes above 600 µm.
- Laundry detergent and cleaning product tablets according to Claim 1, characterized in that they comprise the anhydrously granulated effervescent system in amounts of from 2 to 18% by weight, preferably from 3 to 15% by weight and in particular from 5 to 10% by weight, based in each case on the tablet.
- Laundry detergent and cleaning product tablets according to one of Claims 1 or 2, characterized in that at least 90% by weight and in particular the entirety of the particles of the anhydrously granulated effervescent system have particle sizes above 600 µm.
- Laundry detergent and cleaning product tablets according to one of Claims 1 to 3, characterized in that they comprise as anhydrously granulated effervescent system granules of carbonate(s) and/or hydrogen carbonate(s) with acidifier(s) in a weight ratio of from 1:20 to 20:1, preferably from 1:9 to 9:1.
- Laundry detergent and cleaning product tablets according to one of Claims 1 to 4, characterized in that they comprise anhydrously granulated commixtures comprising effervescent system, which comprise at least 60% by weight effervescent system (carbonate(s) and/or hydrogen carbonate(s) and acidifier(s)), based in each case on the weight of the commixture, and preferably at least 80% by weight, preferably at least 90% by weight, and in particular the entirety of the commixtures have particle sizes above 600 µm.
- Laundry detergent and cleaning product tablets according to one of Claims 1 to 5, characterized in that they further comprise a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the tablet weight.
- Process for producing laundry detergent and cleaning product tablets, characterized by the steps ofa) preparing an effervescent system by anhydrous granulation, at least 80% by weight of the particles of the anhydrously granulated effervescent system having particle sizes above 600 µm,b) blending the granules prepared in step a) with further ingredients of laundry detergents and cleaning products, to give a premix intended for compression,c) compressing the premix to tablets which comprise from 5 to 50% by weight of anionic surfactant(s).
- Process according to Claim 7, characterized in that in step a) of the process one or more carbonates and/or hydrogen carbonates are dry-mixed with one or more acidifiers and the mixture is subjected to compressive agglomeration, preferably roll compacting.
- Process according to Claim 8, characterized in that the carbonate(s) and/or hydrogen carbonate(s) are mixed with the acidifier(s) in a weight ratio of from 1:20 to 20:1, preferably from 1:9 or 9:1, and subjected to compressive agglomeration.
- Process according to one of Claims 8 or 9, characterized in that carbonates and/or hydrogen carbonates used comprise the alkali metal salts, preferably the sodium salts, particular preference being given to sodium hydrogen carbonate and sodium carbonate.
- Process according to one of Claims 8 to 10, characterized in that acidifiers used comprise one or more substances from the group consisting of organic dicarboxylic, tricarboxylic and oligocarboxylic acids solid at room temperature, particular preference being given to citric acid.
- Process according to one of Claims 7 to 11, characterized in that at least 90% by weight and in particular the entirety of the effervescent system prepared in step a) have particle sizes above 600 µm.
- Process according to one of Claims 7 to 12, characterized in that the effervescent granules prepared in step a) make up from 1 to 20% by weight, preferably from 2 to 18% by weight, with particular preference from 3 to 15% by weight and in particular from 5 to 10% by weight of the premix intended for compression.
- Process according to one of Claims 7 to 13, characterized in that the effervescent granules prepared in step a) are combined in step b) with at least one type of surfactant granules to give a premix intended for compression and having a bulk density of at least 500 g/l, preferably at least 600 g/l and in particular at least 700 g/l.
- Process according to Claim 14, characterized in that the surfactant granules, have particle sizes of between 100 and 2 000 µm, preferably between 200 and 1 800 µm, with particular preference between 400 and 1 600 µm and in particular between 600 and 1 400 µm.
- Process according to one of Claims 14 or 15, characterized in that the surfactant granules comprise anionic and/or nonionic surfactants and also builders and have overall surfactant contents of at least 10% by weight, preferably at least 20% by weight and in particular at least 25% by weight.
- Process according to Claim 16, characterized in that the surfactant granules have particle sizes of between 100 and 2 000 µm, preferably between 200 and 1 800 µm, with particular preference between 400 and 1 600 µm and in particular between 600 and 1 400 µm.
- Process according to one of Claims 7 to 17, characterized in that premix further comprises a disintegration aid, preferably a cellulose-based disintegration aid, preferably in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, preferably from 3 to 7% by weight and in particular from 4 to 6% by weight, based in each case on the weight of the premix.
- Process according to one of Claims 7 to 18, characterized in that the premix further comprises one or more substances from the group consisting of bleaches, bleach activators, enzymes, pH modifiers, fragrances, perfume carriers, fluorescers, dyes, foam inhibitors, silicone oils, antiredeposition agents, optical brighteners, greying inhibitors, colour transfer inhibitors and corrosion inhibitors.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19847283 | 1998-10-14 | ||
DE19847283A DE19847283A1 (en) | 1998-10-14 | 1998-10-14 | Detergent tablets, especially for use in domestic washing machines, contain anhydrous effervescent granules for rapid disintegration |
PCT/EP1999/007361 WO2000022085A1 (en) | 1998-10-14 | 1999-10-05 | Shaped detergent bodies with a dry-granulated effervescent system |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1123378A1 EP1123378A1 (en) | 2001-08-16 |
EP1123378B1 true EP1123378B1 (en) | 2004-02-11 |
Family
ID=7884397
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99947459A Expired - Lifetime EP1123378B1 (en) | 1998-10-14 | 1999-10-05 | Shaped detergent bodies with a dry-granulated effervescent system |
Country Status (4)
Country | Link |
---|---|
EP (1) | EP1123378B1 (en) |
AT (1) | ATE259414T1 (en) |
DE (2) | DE19847283A1 (en) |
WO (1) | WO2000022085A1 (en) |
Families Citing this family (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
EP1389230A1 (en) * | 2000-11-24 | 2004-02-18 | Unilever N.V. | Cleaning compositions |
DE10123621B4 (en) * | 2001-05-15 | 2006-12-07 | Henkel Kgaa | Process for the preparation of a water softener tablet |
DE102009011928A1 (en) * | 2009-03-10 | 2010-09-23 | Licciardi, Natale, Dipl.-Ing. | Process for the preparation of cleaning tablets |
DE102010051226A1 (en) | 2010-11-12 | 2012-05-31 | Dental Care Innovation Gmbh | Rinse-off tray with abrasive components |
ES2586461B1 (en) * | 2015-03-12 | 2017-12-01 | Lorena MARTÍ COMA | DETERGENT COMPOSITION IN THE FORM OF AN EFFECTIVE PAD |
CA3051863C (en) | 2017-02-02 | 2023-12-19 | Water Pik, Inc. | Dental cleaning tablets comprising glycine as abrasive |
CN108841469B (en) * | 2018-07-19 | 2023-09-01 | 河南城建学院 | Laundry effervescent tablet coating agent, moisture-resistant laundry effervescent tablet and preparation method thereof |
Family Cites Families (9)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
US4217234A (en) * | 1978-02-16 | 1980-08-12 | Werner Krisp | Denture cleansing tablet and method of manufacturing the same |
DE3535516A1 (en) * | 1985-10-04 | 1987-04-09 | Fritz Buchner | TABLET-SHAPED DETERGENT AND CLEANING AGENT, METHOD FOR THE PRODUCTION THEREOF AND ITS USE |
EP0248936A1 (en) * | 1986-06-13 | 1987-12-16 | Richardson GmbH | Cleaning tablet for dentures and method for producing thereof |
AU7538387A (en) * | 1986-07-15 | 1988-01-21 | Warner-Lambert Company | Bleach activator compositions |
US5114647A (en) * | 1991-02-01 | 1992-05-19 | Olin Corporation | Effervescent tablets having increased disintegration rates |
GB9622845D0 (en) * | 1996-11-01 | 1997-01-08 | Procter & Gamble | Effervescent bleaching compositions |
MA24525A1 (en) * | 1997-04-14 | 1998-12-31 | Procter & Gamble | DETERGENT PARTICLE |
EP0881282B2 (en) * | 1997-05-27 | 2009-06-03 | The Procter & Gamble Company | Tablets, and process for making tablets |
DE19722832A1 (en) * | 1997-05-30 | 1998-12-03 | Henkel Kgaa | Detergent tablets with improved dissolving properties |
-
1998
- 1998-10-14 DE DE19847283A patent/DE19847283A1/en not_active Withdrawn
-
1999
- 1999-10-05 EP EP99947459A patent/EP1123378B1/en not_active Expired - Lifetime
- 1999-10-05 DE DE59908529T patent/DE59908529D1/en not_active Expired - Lifetime
- 1999-10-05 WO PCT/EP1999/007361 patent/WO2000022085A1/en active IP Right Grant
- 1999-10-05 AT AT99947459T patent/ATE259414T1/en not_active IP Right Cessation
Also Published As
Publication number | Publication date |
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ATE259414T1 (en) | 2004-02-15 |
EP1123378A1 (en) | 2001-08-16 |
WO2000022085A1 (en) | 2000-04-20 |
DE19847283A1 (en) | 2000-04-20 |
DE59908529D1 (en) | 2004-03-18 |
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