EP1123381B1 - Wasch- und reinigungsmittelformkörper/verpackung-kombination - Google Patents
Wasch- und reinigungsmittelformkörper/verpackung-kombination Download PDFInfo
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- EP1123381B1 EP1123381B1 EP99950709A EP99950709A EP1123381B1 EP 1123381 B1 EP1123381 B1 EP 1123381B1 EP 99950709 A EP99950709 A EP 99950709A EP 99950709 A EP99950709 A EP 99950709A EP 1123381 B1 EP1123381 B1 EP 1123381B1
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- Prior art keywords
- weight
- tablet
- combination according
- acid
- laundry detergent
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Classifications
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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
- C11D1/00—Detergent compositions based essentially on surface-active compounds; Use of these compounds as a detergent
- C11D1/02—Anionic compounds
- C11D1/12—Sulfonic acids or sulfuric acid esters; Salts thereof
- C11D1/22—Sulfonic acids or sulfuric acid esters; Salts thereof derived from aromatic compounds
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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
- C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
- C11D17/04—Detergent materials or soaps characterised by their shape or physical properties combined with or containing other objects
- C11D17/041—Compositions releasably affixed on a substrate or incorporated into a dispensing means
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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
- C11D3/16—Organic compounds
- C11D3/20—Organic compounds containing oxygen
- C11D3/22—Carbohydrates or derivatives thereof
- C11D3/222—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin
Definitions
- the present invention relates to tablets containing alkylbenzenesulfonate (s) and disintegration aids based on cellulose and to ensure better disintegration times combined with a special packaging system at the same time high hardness become.
- the invention relates to such specially packaged tablets as Detergent tablets, detergent tablets, bleach tablets or water softener tablets with alkylbenzenesulfonate (s) and disintegration aid (s) based on cellulose.
- the delayed disintegration of the tablet also has the disadvantage that usual detergent tablets are not on the Ein Stammier of household washing machines Rinse, as the tablets are not in a sufficiently fast time in Secondary particles, which are small enough to disintegrate from the dispenser compartment, decay Wash tub to be washed.
- the international patent application WO98 / 40464 (Unilever) describes a combination of at least one tablet of compressed particulate detergent, which is stored at least 24 hours h in a packaging system having a moisture permeability rate of less than 20 g / m 2/24 h. According to this document, this combination increases the hardness of the tablets during storage, while the dissolution times are reduced. Although the disintegration time of the tablets according to the information in this document under mechanical action (stirring) is measured, all disintegration times are well over 2 minutes. Such high disintegration times make the tablets disclosed in this document unusable for metering via the dispensing chamber of household washing machines, since they do not disintegrate sufficiently quickly and thus can not be flushed. The use of disintegration aids based on cellulose is also not mentioned in this document.
- Phosphate and chlorine-free detergent tablets are the subject of WO95 / 04804 (La Marina).
- the tablets disclosed in this document likewise contain no cellulose-based disintegration aids such as the detergent tablets based on effervescent systems described in WO 97/35955 (Kärcher).
- tablets in which microcrystalline to fibrous cellulose is used are disclosed in DE 2321693 (Henkel).
- the fibrous cellulose acts as a binder depending on the fiber length, for example, and is used in the tablets without prior granulation.
- the present invention was based on the object, the advantages of the use of alkylbenzenesulfonates also to use in detergent tablets, which Contain cellulosic disintegration aids while providing tablets, which are characterized by high hardness with short decay times.
- the tablets should be so Have short disintegration times that a dosage on the dispenser usually household Washing machines easily and residue-free is possible.
- the subject of the present invention is a combination of a detergent tablet (s); containing alkylbenzenesulfonate (s) and cellulose-based disintegration aids in granular, cogranulated or compacted form, in amounts of from 0.5 to 10% by weight, and a packaging system containing the detergent tablet (s), characterized in that the packaging system has a moisture vapor transmission rate from 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is stored at 23 ° C and a relative equilibrium moisture content of 85%.
- the packaging system of the detergent tablet (s) combination and packaging system according to the invention has a moisture vapor transmission rate of 0.1 g / m 2 / day to less than 20 g / m 2 / day when the packaging system is at 23 ° C and a relative equilibrium moisture content of 85 % is stored.
- the temperature and humidity conditions mentioned are the test conditions specified in DIN standard 53122, with minimum deviations permissible according to DIN 53122 (23 ⁇ 1 ° C, 85 ⁇ 2% relative humidity).
- the moisture vapor transmission rate of a given packaging system or material can be determined by other standard methods and is also, for example, in the ASTM standard E-96-53T (test for measuring water vapor transmission of material in sheet form) and TAPPI standard T464 m-45 ("Water Vapor Permeability of Sheet Materials at High Temperature Humidity").
- the measuring principle of common methods is based on the water absorption of anhydrous calcium chloride, which is stored in a container in the appropriate atmosphere, the container is sealed at the top with the material to be tested.
- the relative equilibrium moisture in the measurement of moisture vapor transmission rate in the present invention is 85% at 23 ° C.
- the absorption capacity of air for water vapor increases with the temperature up to a respective maximum content, the so-called saturation content, and is expressed in g / m 3 .
- saturation content For example, 1 m 3 of air is saturated by 17 ° with 14.4 g of water vapor, at a temperature of 11 ° saturation is already present with 10 g of water vapor.
- the relative humidity is the percentage expressed ratio of the actually existing water vapor content to the saturation content corresponding to the prevailing temperature.
- the relative equilibrium humidity of 85% at 23 ° C can be, for example, in laboratory chambers with humidity control to +/- 2% r.L. depending on the device type. set exactly. Also over saturated solutions of certain salts form in closed systems at a given temperature constant and well-defined relative humidities, the on the phase equilibrium between partial pressure of the water, saturated solution and soil body based.
- Packaging systems preferred in the present invention have a moisture vapor transmission rate of from 0.5 g / m 2 / day to less than 15 g / m 2 / day.
- the packaging system of the combination according to the invention encloses depending on the embodiment the invention one or more detergent tablets. It is according to the invention preferred to make either a tablet such that it is an application unit of the washing and cleaning agent, and to pack this tablet individually, or to pack the number of tablets in a single packaging unit Application unit includes. At a nominal dosage of 80 g washing and cleaning agent So it is possible according to the invention to produce a tablet weighing 80 g and individually pack, but it is also possible according to the invention, two each 40 g heavy Pack detergent tablets in a package to form a present invention Combination to arrive. Of course, this principle can be extended so that According to the invention combinations also three, four, five or more detergent tablets contained in a packaging unit. Of course, two or three more tablets in a package have different compositions. On this way it is possible to spatially separate certain components from one another For example, to avoid stability problems.
- the packaging system of the combination according to the invention can be made of the most diverse Materials exist and assume any external forms. For economic reasons however, for reasons of ease of processing, packaging systems are preferred in which the packaging material has a low weight, easy to process and is inexpensive. In preferred combinations according to the invention the packaging system from a bag or sack. single layer or laminated Paper and / or plastic film.
- the detergent tablet may be unsorted, i. as loose bulk, in one Pouch can be filled from the mentioned materials. It is for aesthetic reasons and preferred for sorting the combinations in secondary packaging, the detergent tablet one by one or several sorted into sacks or bags to fill.
- the term "flow pack” has become common in the art. Such "flow packs” can then - optionally again sorted - optionally packed in outer packaging become what the compact offering form of the tablet underlines.
- the preferably used as packaging system bags or bags of single-layer or laminated paper or plastic film can be designed in a variety of ways, such as inflated bag without center seam or bags with center seam, which closed by heat (heat fusion), adhesives or adhesive tapes become.
- Single-layer bag or bag materials are the known papers, which may optionally be impregnated, as well as plastic films, which may optionally be coextruded.
- Plastic films which can be used in the context of the present invention as a packaging system, for example, in Hans Domining House "The Plastics and their properties", 3rd edition, VDI Verlag, Dusseldorf, 1988, page 193 indicated.
- the figure 111 shown there also provides clues to the water vapor permeability of the materials mentioned.
- a bag or bags of single-layer or laminated Plastic film with a thickness of 10 to 200 .mu.m, preferably from 20 to 100 .mu.m and in particular from 25 to 50 microns.
- packaging system indicates in the context of the present invention always the primary packaging of the tablets, i. the packaging, which on its inside directly with the tablet surface is in contact. At an optional secondary packaging are no requirements so that all the usual materials and systems are used here can.
- the detergent tablets of the invention Combination depending on their intended use further ingredients of washing and Detergents in varying amounts. Regardless of the purpose of the According to the invention, tablets are preferred in that the detergent tablets have a relative Equilibrium moisture content of less than 30% at 35 ° C / exhibit.
- the relative equilibrium moisture content of the detergent tablet can be standardized Be determined in the context of the present investigations
- a water-impermeable 1-liter jar with a lid, which has a closable opening for the introduction of samples has been filled with a total of 300 g detergent tablets and kept at a constant 23 ° C for 24 h to ensure a uniform temperature of vessel and substance -
- the water vapor pressure in the room above the tablets can then with a hygrometer (Hygrotest 6100, Testoterm Ltd., England).
- the water vapor pressure is now every 10th Minutes until two consecutive values show no deviation (Equilibrium moisture).
- the o.g. Hygrometer allows a direct display of the recorded Values in% relative humidity.
- these contain a disintegration aid based on cellulose.
- Pure cellulose has the formal gross composition (C 6 H 10 O 5 ) n and is formally a ⁇ -1,4-polyacetal of cellobiose, which in turn is composed of two molecules of glucose.
- Suitable celluloses consist of about 500 to 5000 glucose units and therefore have average molecular weights of 50,000 to 500,000.
- Cellulose-based disintegrating agents which can be used in the context of the present invention are also cellulose derivatives obtainable by polymer-analogous reactions of cellulose.
- Such chemically modified celluloses include, for example, products of esterifications or etherifications in which hydroxy hydrogen atoms have been substituted.
- Celluloses in which the hydroxy groups have been replaced by functional groups which are not bonded via an oxygen atom can also be used as cellulose derivatives.
- the group of cellulose derivatives includes, for example, alkali metal celluloses, carboxymethylcellulose (CMC), cellulose esters and ethers, and aminocelluloses.
- the cellulose derivatives mentioned are preferably not used alone as disintegrating agents based on cellulose, but used in admixture with cellulose.
- the content of these mixtures of cellulose derivatives is preferably below 50% by weight, particularly preferably below 20% by weight, based on the cellulose-based disintegrating agent. It is particularly preferred to use cellulose-based disintegrating agent which is free of cellulose derivatives.
- the cellulose used as a disintegration aid is preferably not used in finely divided form, but converted into a coarser form, for example granulated or compacted, before it is added to the premixes to be tabletted. Detergent tablets containing disintegrating agents in granular or optionally cogranulated form are described in German Patent Application DE 197 10 254 (Henkel).
- the detergent tablet (s) comprises the disintegration aid based on cellulose in granular, cogranulated or compacted form, in amounts of from 3 to 7% by weight and in particular from 4 to 6% by weight, in each case on tablet weight, contains / contains.
- Microcrystalline cellulose can be used. This microcrystalline cellulose is obtained by partial hydrolysis of celluloses under conditions which only the amorphous regions (about 30% of the total cellulose mass) attack the celluloses and completely dissolve, leaving the crystalline areas (about 70%) undamaged. A subsequent deaggregation of the microfine celluloses resulting from the hydrolysis provides the microcrystalline celluloses having primary particle sizes of about 5 microns and, for example, compactable into granules with an average particle size of 200 microns are.
- Disintegration-promoting systems are often also called “detergent tablets” "Showering systems” used.
- oligomeric oligocarboxylic acids such as succinic acid, maleic acid and especially citric acid in combination used with carbonates or bicarbonates.
- the detergent tablet is not a "effervescent tablet", i.e. preferred detergent tablets are free of oligomeric oligocarboxylic acids, especially citric acid.
- Such coated detergent tablets can be sprayed on a melt or solution of the coating material on the tablet body or Immerse the tablet body in the melt or solution are prepared.
- disintegration aid based on cellulose and the alkylbenzenesulfonate in combination with the packaging system and optionally supported by the use of further disintegration aids (see above)
- detergent tablets are produced which at high hardnesses in water extremely quickly disintegrate into their components.
- Alkylbenzenesulfonates as powerful anionic Surfactants have been known since the thirties of this century. At that time were by monochlorination of kogasin fractions and subsequent Friedel-Crafts alkylation Alkylbenzenes prepared that sulfonated with oleum and neutralized with sodium hydroxide solution were.
- Linear alkylbenzenesulfonates are prepared from linear alkylbenzenes, which in turn are accessible from linear olefins.
- petroleum fractions are industrially separated with molecular sieves into the n-paraffins of the desired purity and dehydrogenated to the n-olefins, resulting in both ⁇ - and i-olefins.
- the resulting Olefins are then in the presence of acidic catalysts with benzene to the alkylbenzenes implemented, with the choice of Friedel-Crafts catalyst influence the isomer distribution of the resulting linear alkylbenzenes has:
- Aluminum trichloride the content of the 2-phenyl isomers in the mixture with the 3-, 4-, 5 and other isomers at about 30 wt .-%, however, is hydrogen fluoride as a catalyst used, the content of 2-phenyl isomer can be reduced to about 20 wt .-%.
- the neutralizing agent By choosing the neutralizing agent, a wide variety of salts, ie alkylbenzenesulfonates, can be obtained from the ABSS. For reasons of economy, it is preferred in this case to prepare and use the alkali metal salts and, among these, preferably the sodium salts of ABSS. These can be described by the general formula I: in which the sum of x and y is usually between 5 and 13. In the present invention combinations are preferred in which the detergent tablets of the alkali metal, preferably sodium salts, of C 8-16 - containing, preferably C 9-13 -alkylbenzenesulfonic acids derived from alkylbenzenes having a tetralin content below 5 wt %, based on the alkylbenzene.
- alkylbenzenesulfonates whose alkylbenzenes were prepared by the HF process, so that combinations are preferred in which the alkylbenzenesulfonate compounds, the alkali metal, preferably sodium, of C 8-16 -, preferably C 9-13 -Alkybenzolsulfonklaren containing a content of 2-phenyl isomer below 22 wt .-%, based on the alkylbenzenesulfonic acid.
- the alkali metal preferably sodium
- the detergent tablet (s) contains / Alkylbenzenesulfonates in amounts preferably from 0.5 to 30 wt .-%, very preferably from 1 to 25 wt .-%, particularly preferably from 2 to 20% by weight and in particular from 5 to 15% by weight, respectively based on the weight of the tablet.
- the detergent tablets in the inventive Combination other surfactants (surfactants) containing preferably come from the groups of anionic and / or nonionic surfactants.
- the total surfactant content of the tablets is from 5 to 60% by weight, based on the tablet weight, wherein surfactant contents above 15 wt .-% are preferred.
- anionic surfactants for example, those of the sulfonate type and sulfates are used.
- surfactants of the sulfonate type are olefin sulfonates, ie mixtures of alkene and hydroxyalkanesulfonates and disulfonates, as are obtained, for example, from C 12-18 monoolefins having terminal or internal double bonds by sulfonation with gaseous sulfur trioxide and subsequent alkaline or acidic hydrolysis the sulfonation obtained.
- alkanesulfonates which are obtained from C 12-18 alkanes, for example by sulfochlorination or sulfoxidation with subsequent hydrolysis or neutralization.
- esters of ⁇ -sulfo fatty acids for example the ⁇ -sulfonated methyl esters of hydrogenated coconut, palm kernel or tallow fatty acids are suitable.
- sulfated fatty acid glycerol esters are sulfated fatty acid glycerol esters.
- fatty acid glycerine esters are the mono-, di- and triesters and their mixtures to understand, as with the preparation by esterification of a monoglycerol with 1 to 3 mol fatty acid or obtained in the transesterification of triglycerides with 0.3 to 2 moles 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) ylsulfates are the alkali metal salts and in particular the sodium salts of the sulfuric monoesters of C 12 -C 18 fatty alcohols, for example 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 these chain lengths are preferred. Also preferred are alk (en) ylsulfates of said chain length, which contain a synthetic, produced on a petrochemical basis straight-chain alkyl radical, which have an analogous degradation behavior as the adequate compounds based on oleochemical raw materials.
- C 12 -C 16 alkyl sulfates and C 12 -C 15 alkyl sulfates and C 14 -C 15 alkyl sulfates are preferred.
- 2,3-alkyl sulfates prepared, for example, according to U.S. Patents 3,234,258 or 5,075,041, which can be obtained as commercial products of the Shell Oil Company under the name DAN®, are suitable anionic surfactants.
- EO ethylene oxide
- Fatty alcohols with 1 to 4 EO are suitable. Due to their high foaming behavior, they are only used in detergents in relatively small amounts, for example in amounts of from 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 the 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 of these.
- Particularly preferred sulfosuccinates contain a fatty alcohol residue derived from ethoxylated fatty alcohols, which in themselves constitute nonionic surfactants (see description below).
- Sulfosuccinates whose fatty alcohol residues are derived from ethoxylated fatty alcohols with a narrow homolog distribution, are again particularly preferred.
- alk (en) ylsuccinic acid having preferably 8 to 18 carbon atoms in the alk (en) yl chain or salts thereof.
- anionic surfactants are particularly soaps into consideration.
- 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.
- the anionic surfactants including the soaps may 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 in the form of their Sodium or potassium salts, especially in the form of the sodium salts.
- the nonionic surfactants used are preferably alkoxylated, advantageously ethoxylated, in particular primary, alcohols having preferably 8 to 18 carbon atoms and on average 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 linear and methyl-branched radicals in the mixture can contain, as they are usually present in Oxoalkoholresten.
- alcohol ethoxylates with linear radicals of alcohols of natural origin having 12 to 18 carbon atoms, for example of coconut, palm, tallow or oleyl alcohol, and on average 2 to 8 EO per mole of alcohol are preferred.
- the preferred ethoxylated alcohols include, for example, C 12-14 alcohols with 3 EO or 4 EO, C 9-11 alcohols 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 C12-18 alcohol containing 5 EO.
- the degrees of ethoxylation given represent statistical means which, for a particular product, may be an integer or a fractional number.
- Preferred alcohol ethoxylates have a narrow homolog distribution (narrow range ethoxylates, NRE).
- fatty alcohols with more than 12 EO can also be used. Examples include tallow fatty alcohol with 14 EO, 25 EO, 30 EO or 40 EO.
- nonionic surfactants and alkyl glycosides of the general formula RO (G) x can be used in which R is a primary straight-chain or methyl-branched, especially in the 2-position methyl-branched aliphatic radical having 8 to 22, preferably 12 to 18 carbon atoms and G is the symbol which represents a glycose unit having 5 or 6 C atoms, preferably glucose.
- the degree of oligomerization x which indicates the distribution of monoglycosides and oligoglycosides, is any number between 1 and 10; preferably x is 1.2 to 1.4.
- nonionic surfactants used either as the sole nonionic surfactant or in combination with other nonionic surfactants are alkoxylated, preferably ethoxylated or ethoxylated and propoxylated fatty acid alkyl esters, preferably having from 1 to 4 carbon atoms in the alkyl chain, especially fatty acid methyl esters, as they are for example, in Japanese Patent Application JP 58/217598 , or which are preferably prepared according to the method described in International Patent Application WO-A-90/13533 .
- 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 alkanolamide may be suitable.
- the amount of these nonionic surfactants is preferably not more than that of ethoxylated fatty alcohols, in particular not more than half of it.
- polyhydroxy fatty acid amides of the formula (II) wherein RCO is an aliphatic acyl group having 6 to 22 carbon atoms, R 1 is hydrogen, an alkyl or hydroxyalkyl group having 1 to 4 carbon atoms and [Z] is a linear or branched polyhydroxyalkyl group having 3 to 10 carbon atoms and 3 to 10 hydroxyl groups.
- the polyhydroxy fatty acid amides are known substances which can usually be obtained by reductive amination of a reducing sugar with ammonia, an alkylamine or an alkanolamine and subsequent acylation with a fatty acid, a fatty acid alkyl ester or a fatty acid chloride.
- the group of polyhydroxy fatty acid amides also includes compounds of the formula (III) in the R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms, R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having 2 to 8 carbon atoms and R 2 is a linear, branched or cyclic alkyl radical or an aryl radical or an oxyalkyl radical having 1 to 8 carbon atoms, with C 1-4 alkyl or phenyl radicals being preferred and [Z] being a linear polyhydroxyalkyl radical whose alkyl chain is substituted by at least two hydroxyl groups, or alkoxylated, preferably ethoxylated or propoxylated Derivatives of this residue.
- R is a linear or branched alkyl or alkenyl radical having 7 to 12 carbon atoms
- R 1 is a linear, branched or cyclic alkyl radical or an aryl radical having
- [Z] is preferably obtained by reductive amination of a reduced sugar, For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- a reduced sugar For example, glucose, fructose, maltose, lactose, galactose, mannose or xylose.
- the N-alkoxy- or N-aryloxy-substituted compounds may then be used, for example the teaching of 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.
- combinations are particularly preferred in which in the detergent tablets the ratio of anionic surfactant (s) to nonionic surfactant (s) between 10: 1 and 1:10, preferably between 7.5: 1 and 1: 5 and in particular between 5: 1 and 1: 2.
- the invention therefore provides that at least one phase of the tablet is free of nonionic Is surfactants.
- nonionic surfactants can also be removed from the omission of anionic Surfactants resulting from single or all phases of detergent tablets, resulting better suited for certain applications. It is therefore within the scope of the present Detergent tablets also conceivable in which at least one phase of Tablet is free of anionic surfactants.
- detergent tablets of the combination according to the invention all can usually Be contained in detergents and cleaning agents builders, in particular So zeolites, silicates, carbonates, organic cobuilders and -where no ecological Prejudices against their use exist - also the phosphates.
- Suitable crystalline layered sodium silicates have the general formula NaMSi x O 2x + 1 .H 2 O, where M is sodium or hydrogen, x is a number from 1.9 to 4 and y is a number from 0 to 20 and preferred values for x 2, 3 or 4 are.
- Such crystalline sheet 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 is sodium and x assumes the values 2 or 3.
- both ⁇ - and ⁇ -sodium disilicates Na 2 Si 2 O 5 .yH 2 O are preferred, whereby ⁇ -sodium disilicate can be obtained, for example, by the process described in international patent application WO-A-91/08171 .
- amorphous sodium silicates with a Na 2 O: SiO 2 modulus of from 1: 2 to 1: 3.3, preferably from 1: 2 to 1: 2.8 and in particular from 1: 2 to 1: 2.6, which Delayed and have secondary washing properties.
- the dissolution delay compared with conventional amorphous sodium silicates may have been caused in various ways, for example by surface treatment, compounding, compaction / densification or by overdrying.
- the term "amorphous” is also understood to mean "X-ray amorphous”.
- the silicates do not yield sharp X-ray reflections typical of crystalline substances in X-ray diffraction experiments, but at most one or more maxima of the scattered X-rays having a width of several degrees of diffraction angle. However, it may well even lead to particularly good builder properties if the silicate particles provide blurred or even sharp diffraction maxima in electron diffraction experiments. This is to be interpreted as meaning that the products have microcrystalline regions of size 10 to a few hundred nm, values of up to max. 50 nm and in particular up to max. 20 nm are preferred.
- Such so-called X-ray-amorphous silicates which likewise have a dissolution delay compared to the conventional water glasses, are described, for example, in German patent application DE-A-44 00 024 .
- Particularly preferred are compacted / compacted amorphous silicates, compounded amorphous silicates and overdried X-ray amorphous silicates.
- 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 particularly preferred.
- zeolite X and zeolite A are cocrystal of zeolite X and zeolite A (about 80% by weight of zeolite X) ), which is sold by the company 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 can be described.
- the zeolite can be used both as a builder in a granular compound, as well as to a kind of "powdering" of the entire mixture to be pressed, wherein usually both ways for incorporating the zeolite are used in the premix.
- Suitable zeolites have an average particle size of less than 10 ⁇ m (volume distribution, measuring method: Coulter Counter) and preferably contain 18 to 22% by weight, in particular 20 to 22% by weight, of bound water.
- Alkali metal phosphates is the summary term for the alkali metal (especially sodium and potassium) salts of various phosphoric acids, in which one can distinguish metaphosphoric acids (HPO 3 ) n and orthophosphoric H 3 PO 4 in addition to higher molecular weight representatives.
- the phosphates combine several advantages: they act as alkali carriers, prevent lime deposits on machine parts or lime incrustations in fabrics and also contribute to the cleaning performance.
- Sodium dihydrogen phosphate, NaH 2 PO 4 exists as a dihydrate (density 1.91 gcm -3 , melting point 60 °) and as a monohydrate (density 2.04 gcm -3 ). Both salts are white powders which are very soluble in water and which lose their water of crystallization when heated and at 200 ° C into the weak acid diphosphate (disodium hydrogen diphosphate, Na 2 H 2 P 2 O 7 ), at higher temperature in sodium trimetaphosphate (Na 3 P 3 O 9 ) and Maddrell's salt (see below).
- NaH 2 PO 4 is acidic; It arises when phosphoric acid is adjusted to a pH of 4.5 with sodium hydroxide solution and the mash is sprayed.
- Potassium dihydrogen phosphate potassium phosphate primary or monobasic potassium phosphate, KDP
- KH 2 PO 4 is a white salt of 2.33 gcm -3 density, has a melting point of 253 ° [decomposition to form potassium polyphosphate (KPO 3 ) x ] and is light soluble in water.
- Disodium hydrogen phosphate (secondary sodium phosphate), Na 2 HPO 4 , is a colorless, very slightly water-soluble crystalline salt. It exists anhydrous and with 2 moles (density 2.066 gcm -3 , loss of water at 95 °), 7 moles (density 1.68 gcm -3 , melting point 48 ° with loss of 5 H 2 O) and 12 moles water ( Density 1.52 gcm -3 , melting point 35 ° with loss of 5 H 2 O) becomes anhydrous at 100 ° C and, upon increased heating, passes into the diphosphate Na 4 P 2 O 7 .
- Disodium hydrogen phosphate is prepared by neutralization of phosphoric acid with soda solution using phenolphthalein as an indicator.
- Dipotassium hydrogen phosphate (secondary or dibasic potassium phosphate), K 2 HPO 4 , is an amorphous, white salt that is readily soluble in water.
- Trisodium phosphate, tertiary sodium phosphate, Na 3 PO 4 are colorless crystals which have a density of 1.62 gcm -3 as dodecahydrate and a melting point of 73-76 ° C (decomposition), as decahydrate (corresponding to 19-20% P 2 O 5 ) have a melting point of 100 ° C and in anhydrous form (corresponding to 39-40% P 2 O 5 ) have a density of 2.536 gcm -3 .
- Trisodium phosphate is readily soluble in water under alkaline reaction and is prepared by evaporating a solution of exactly 1 mole of disodium phosphate and 1 mole of NaOH.
- Tripotassium phosphate (tertiary or tribasic potassium phosphate), K 3 PO 4 , is a white, deliquescent, granular powder of density 2.56 gcm -3 , has a melting point of 1340 ° and is readily soluble in water with an alkaline reaction. It arises, for example, when heating Thomasschlacke with coal and potassium sulfate. Despite the higher price, the more soluble, therefore highly effective, potassium phosphates are often preferred over the corresponding sodium compounds in the detergent industry.
- Tetrasodium diphosphate (sodium pyrophosphate), Na 4 P 2 O 7 , exists in anhydrous form (density 2.534 gcm -3 , melting point 988 °, also indicated 880 °) and as decahydrate (density 1.815-1.836 gcm -3 , melting point 94 ° with loss of water) , For substances are colorless, in water with alkaline reaction soluble crystals.
- Na 4 P 2 O 7 is formed on heating of disodium phosphate to> 200 ° or by reacting phosphoric acid with soda in a stoichiometric ratio and dewatering the solution by spraying.
- the decahydrate complexes heavy metal salts and hardness agents and therefore reduces the hardness of the water.
- Potassium diphosphate (potassium pyrophosphate), K 4 P 2 O 7 , exists in the form of the trihydrate and is a colorless, hygroscopic powder with a density of 2.33 gcm -3 , which is soluble in water, the pH being 1% Solution at 25 ° 10.4.
- Sodium and potassium phosphates in which one can distinguish cyclic representatives, the sodium or Kaliummetaphosphate and chain types, the sodium or potassium polyphosphates. In particular, for the latter are a variety of names in use: hot or cold phosphates, Graham's salt, Kurrolsches and Maddrell's salt. All higher sodium and potassium phosphates are collectively referred to as condensed phosphates.
- pentasodium triphosphate Na 5 P 3 O 10 (sodium tripolyphosphate)
- sodium tripolyphosphate sodium tripolyphosphate
- n 3
- 100 g of water dissolve at room temperature about 17 g, at 60 ° about 20 g, at 100 ° around 32 g of the salt water-free salt; after two hours of heating the solution to 100 ° caused by hydrolysis about 8% orthophosphate and 15% diphosphate.
- pentasodium triphosphate In the preparation of pentasodium triphosphate, phosphoric acid is reacted with sodium carbonate solution or sodium hydroxide solution in a stoichiometric ratio and the solution is dehydrated by spraying. Similar to Graham's salt and sodium diphosphate, pentasodium triphosphate dissolves many insoluble metal compounds (including lime soaps, etc.). Pentakaliumtriphosphat, K 5 P 3 O 10 (potassium tripolyphosphate), for example, in the form of a 50 wt .-% solution (> 23% P 2 O 5 , 25% K 2 O) in the trade. The potassium polyphosphates are widely used in the washing and cleaning industry. There are also sodium potassium tripolyphosphates which can also be used in the context of the present invention. These arise, for example, when hydrolyzed sodium trimetaphosphate with KOH: (NaPO 3 ) 3 + 2 KOH ⁇ Na 3 K 2 P 3 O 10 + H 2 O
- 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 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 used become. These classes of substances are described below.
- Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, wherein among polycarboxylic acids such carboxylic acids 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 environmental 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 thereof.
- the acids themselves can also be used.
- the acids have besides their builder effect typically also the property of an acidifying component and serve thus also for setting a lower and milder pH of washing or Detergents.
- polymeric polycarboxylates are suitable, these are for example the Alkali metal salts of polyacrylic acid or polymethacrylic acid, for example those with a molecular weight of 500 to 70000 g / mol.
- the molecular weights stated for polymeric polycarboxylates are weight-average molar masses M w of the particular acid form, which were determined in principle by means of gel permeation chromatography (GPC), a UV detector being used. The measurement was carried out against an external polyacrylic acid standard, which provides realistic molecular weight values due to its structural relationship with the polymers investigated. These data differ significantly from the molecular weight data, in which polystyrene sulfonic acids are used as standard. The molar masses measured against polystyrenesulfonic acids are generally significantly higher than the molecular weights specified in this document.
- Suitable polymers are, in particular, polyacrylates which preferably have a molecular mass of 2000 to 20,000 g / mol. Because of their superior solubility, this can be Group again the short-chain polyacrylates, the molar masses from 2000 to 10000 g / mol, and more preferably from 3000 to 5000 g / mol, are preferred be.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- copolymeric polycarboxylates in particular those of acrylic acid with methacrylic acid and acrylic acid or methacrylic acid with maleic acid.
- Your molecular weight, based on free acids, is generally from 2000 to 70000 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 be used either as a powder or as an aqueous solution be used.
- the content of the (co) polymeric polycarboxylates is preferably 0.5 to 20 wt .-%, in particular 3 to 10 wt .-%.
- the polymers may also be allyl sulfonic acids, such as For example, allyloxybenzenesulfonic acid and methallylsulfonic acid, as a monomer.
- biodegradable polymers of more than two different Monomer units for example those containing as monomers salts of acrylic acid and the maleic acid and vinyl alcohol or vinyl alcohol derivatives or as Monomeric salts of acrylic acid and 2-alkylallylsulfonic acid and sugar derivatives contain.
- copolymers are those which are described in the German patent applications DE-A-43 03 320 and DE-A-44 17 734 and preferably have as monomers acrolein and acrylic acid / acrylic acid salts or acrolein and vinyl acetate.
- polymeric aminodicarboxylic acids their salts or their precursors.
- polyaspartic acids or their salts and derivatives of which German Patent Application DE-A-195 40 086 discloses that they also have a bleach-stabilizing effect in addition to cobuilder properties.
- polyacetals which are prepared by reaction of dialdehydes with polyol carboxylic acids having 5 to 7 C 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 Polyolcarboxylic acids such as gluconic acid and / or glucoheptonic acid.
- dextrins for example oligomers or polymers of carbohydrates obtained by partial hydrolysis of starches can be.
- the hydrolysis can be carried out by conventional, for example acid or enzyme catalyzed Procedures are performed.
- they are hydrolysis products with average molecular weights in the range of 400 to 500,000 g / mol.
- This is a polysaccharide with a dextrose equivalent (DE) in the range of 0.5 to 40, in particular from 2 to 30, where DE is a common measure of the reducing effect of a polysaccharide compared to dextrose which has a DE of 100.
- DE dextrose equivalent
- Useful are both maltodextrins with a DE between 3 and 20 and dry glucose syrups with a DE between 20 and 37 as well as so-called yellow dextrins and White dextrins with higher molecular weights in the range from 2000 to 30,000 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 described, for example, in 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 the German patent application DE-A-196 00 018.
- a product oxidized to C 6 of the saccharide ring may be particularly advantageous
- oxydisuccinates and other derivatives of disuccinates are other suitable cobuilders.
- This is ethylenediamine-N, N'disuccinat (EDDS) preferably used in the form of its sodium or magnesium salts.
- EDDS ethylenediamine-N, N'disuccinat
- glycerol disuccinates and glycerol trisuccinates are also preferred. Suitable amounts are zeolithissen and / or silicate-containing Formulations at 3 to 15 wt .-%.
- organic cobuilders are, for example, acetylated hydroxycarboxylic acids or their salts, which may optionally also be present in lactone form and which contain at least 4 carbon atoms and at least one hydroxyl group and a maximum of two acid groups.
- Such co-builders are described, for example, in International Patent Application WO 95/20029 .
- phosphonates are in particular hydroxyalkane or aminoalkanephosphonates.
- HEDP 1-hydroxyethane-1,1-diphosphonate
- It is preferably used as the sodium salt, wherein the disodium salt neutral and the tetrasodium salt alkaline (pH 9).
- Aminoalkane phosphonates are preferably ethylenediamine tetramethylene phosphonate (EDTMP), Diethylentriaminpentamethylenphosphonat (DTPMP) and their higher homologues in question. They are preferably in the form of neutral sodium salts, z.
- the builder used here is preferably HEDP from the class of phosphonates.
- the Aminoalkanphosphonate also have a pronounced Schwerinetallbindeabmögen. Accordingly, especially if the agents also contain bleach, be preferred to use Aminoalkanphosphonate, in particular DTPMP, or Use mixtures of the above phosphonates.
- the amount of builder is usually between 10 and 70 wt .-%, preferably between 15 and 60 wt .-% and in particular between 20 and 50 wt .-%.
- the amount of Buildem used depends on the purpose, so that Bleaching agent tablets may have higher amounts of builders (for example between 20 and 70 wt .-%, preferably between 25 and 65 wt .-% and in particular between 30 and 55% by weight), for example detergent tablets (usually 10 to 50 wt .-%, preferably 12.5 to 45 wt .-% us and in particular between 17.5 and 37.5% by weight).
- the detergent tablets in the combinations according to the invention further in washing and Detergents conventional ingredients from the group of bleaches, bleach activators, Dyes, fragrances, optical brighteners, enzymes, foam inhibitors, silicone oils, anti redeposition agents, Graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.
- sodium perborate tetrahydrate and sodium perborate monohydrate are of particular importance.
- Other useful bleaching agents are, for example, sodium percarbonate, peroxypyrophosphates, citrate perhydrates and H 2 O 2 -producing peracidic salts or peracids, such as perbenzoates, peroxophthalates, diperazelaic acid, phthaloiminoperacid or diperdodecanedioic acid.
- Typical organic bleaches are the diacyl peroxides such as dibenzoyl peroxide.
- Other typical organic bleaches are the peroxyacids, examples of which include the alkyl peroxyacids and the aryl peroxyacids.
- Preferred representatives are (a) the peroxybenzoic acid and its ring-substituted derivatives, such as alkylperoxybenzoic acids, but also peroxy- ⁇ -naphthoic acid and magnesium monoperphthalate, (b) the aliphatic or substituted aliphatic peroxyacids, such as peroxylauric acid, peroxystearic acid, ⁇ -phthalimidoperoxycaproic acid [phthaloiminoperoxyhexanoic acid (PAP)] , o-carboxybenzamidoperoxycaproic acid, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinate, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, diperoxysebacic acid, diperoxybrassic acid, the diperoxyphthalic acids, 2-decy
- Chlorine or bromine releasing substances are used.
- chlorine or bromine-releasing materials include, for example, heterocyclic N-bromo and N-chloroamides, for example trichloroisocyanuric acid, tribromoisocyanuric acid, Dibromoisocyanuric acid and / or dichloroisocyanuric acid (DICA) and / or salts thereof with Cations such as potassium and sodium into consideration.
- Hydantoin compounds such as 1,3-dichloro-5,5-dimethylhydanthoin are also suitable.
- Combinations preferred in the context of the present invention are packaged Detergent tablets that are suitable for washing colored textiles and no bleach contain.
- a particularly preferred combination is therefore characterized that the detergent tablet (s) is / are free of bleach (s).
- bleach activators can be incorporated.
- Bleach activators may be compounds which are aliphatic under perhydrolysis conditions
- Peroxycarboxylic acids having preferably 1 to 10 C atoms, in particular 2 to 4 C atoms, and / or optionally substituted perbenzoic acid, can be used.
- Suitable substances are the O- and / or N-acyl groups of said C atom number and / or optionally substituted benzoyl groups.
- acylated alkylenediamines in particular tetraacetylethylenediamine (TAED), acylated triazine derivatives, in particular 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine (DADHT), acylated Glycolurils, in particular tetraacetylglycoluril (TAGU), N-acylimides, in particular N-nonanoylsuccinimide (NOSI), acylated phenolsulfonates, especially n-nonanoyl or Isononanoyloxybenzenesulfonate (n- or iso-NOBS), carboxylic anhydrides, in particular Phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
- TAED tetraacetyl
- bleach catalysts are incorporated. These substances are to bleach-enhancing transition metal salts or transition metal complexes such as Mn, Fe, Co, Ru or Mo saline complexes or carbonyl complexes. Also Mn, Fe, Co, Ru, Mo, Ti, V and Cu complexes with N-containing tripod ligands and Co, Fe, Cu and Ru ammine complexes are useful as bleach catalysts.
- the detergent tablets can be colored with suitable dyes.
- Preferred dyes the selection of which presents no difficulty to the skilled person, have a high storage stability and insensitivity to the other ingredients of the funds and against Light and no pronounced substantivity to textile fibers, not these to stain.
- Preferred for use in the detergent tablets of the combination according to the invention are all colorants that can be oxidatively destroyed in the washing process and mixtures the same with suitable blue dyes, so-called Blautönem. It turned out to be have proven advantageous to use colorants which are in water or at room temperature in liquid organic substances are soluble. Suitable examples are anionic Colorants, e.g. anionic nitrosofarads.
- a possible colorant is, for example Naphthol green (Color Index (CI) Part 1: Acid Green 1, Part 2: 10020), which is a commercial product for example, as Basacid® Green 970 from BASF, Ludwigshafen, available is, as well as mixtures of these with suitable blue dyes.
- Pigmosol® Blue 6900 (CI 74160), Pigmosol® Green 8730 (CI 74260), Basonyl® Red 545 FL (CI 45170), Sandolan® Rhodamine EB400 (CI 45100), Basacid® Yellow 094 (CI No.
- the colorant When choosing the colorant, it must be taken into account that the colorants do not have too high an affinity for the textile surfaces and, in particular, for synthetic fibers. At the same time, it should also be taken into account when choosing suitable colorants that colorants have different stabilities to the oxidation. In general, water-insoluble colorants are more stable to oxidation than water-soluble colorants. Depending on the solubility and thus also on the sensitivity to oxidation, the concentration of the colorant in the detergents or cleaners varies. In the case of readily water-soluble colorants, for example the abovementioned Basacid® Green or the abovementioned Sandolan® Blue, colorant concentrations in the range from a few 10 -2 to 10 -3 % by weight are typically selected.
- the suitable concentration of the colorant in detergents or cleaners is typically between 10 -3 and 10 -4 % by weight.
- the tablets may be optical brighteners of the diaminostilbene disulfonic acid type 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 similar compounds which, instead of the morpholino group, have a diethanolamino group, a methylamino group, an anilino group or a 2-methoxyethylamino group wear. Furthermore, brighteners of the type of substituted Diphenylstyryle present be, e.g.
- the optical brighteners are in the laundry detergent tablets according to the invention in concentrations between 0.01 and 1 Wt .-%, preferably between 0.05 and 0.5 wt .-% and in particular between 0.1 and 0.25 wt .-%, each based on the total tablet used, if their use desired becomes.
- the packaged detergent tablets however, free of optical brighteners, so that preferred combinations are characterized are that the detergent tablet (s) is / are free of optical brighteners.
- Fragrances are added to the compositions according to the invention to give the aesthetic impression to improve the products and give the consumer a visual and in addition to performance sensory "typical and distinctive" product to provide.
- perfume oils or fragrances may be individual fragrance compounds, e.g. the synthetic one Products of the ester, ether, aldehyde, ketone, alcohol and hydrocarbon type be used. Fragrance compounds of the ester type are known e.g.
- benzyl acetate Phenoxyethyl isobutyrate, p-tert-butylcyclohexyl acetate, linalyl acetate, dimethylbenzylcarbinyl acetate, Phenylethyl acetate, linalyl benzoate, benzyl formate, ethylmethylphenyl glycinate, Allyl cyclohexyl propionate, styrallyl propionate and benzyl salicylate.
- Ethem include, for example, benzyl ethyl ether, to the aldehydes e.g.
- the linear alkanals with 8-18 C-atoms citral, citronellal, citronellyloxyacetaldehyde, cyclamenaldehyde, hydroxycitronellal, Lilial and Bourgeonal
- ketones e.g. the ionone, ⁇ -isomethylionone and methyl cedryl ketone
- the hydrocarbons belong mainly the terpenes like limonene and pinene.
- mixtures of various are preferred Uses fragrances that together create a pleasing fragrance.
- Perfume oils may also contain natural fragrance mixtures, such as those from vegetable Sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- Natural fragrance mixtures such as those from vegetable Sources are accessible, e.g. Pine, citrus, jasmine, patchouly, rose or ylang-ylang oil.
- the content of detergent tablets is usually in the combinations according to the invention perfumes up to 2% by weight of the total formulation.
- the perfumes can be incorporated directly into the compositions of the invention, but it can also be advantageous to apply the fragrances on carriers that the adhesion of the perfume intensify the wash and by a slower release of fragrance for long-lasting Fragrance of the textiles provide.
- carrier materials are cyclodextrins proven, wherein the cyclodextrin-perfume complexes additionally with other Excipients can be coated.
- Enzymes are those from the class of proteases, lipases, amylases, cellulases or mixtures thereof in question. Particularly suitable are from bacterial strains or Fungi such as Bacillus subtilis, Bacillus licheniformis and Streptomyces griseus enzymatic agents. Preferably, subtilisin-type proteases and in particular Proteases derived from Bacillus lentus.
- enzyme mixtures for example from protease and amylase or protease and lipase or Protease and cellulase or cellulase and lipase or protease, amylase and lipase or protease, lipase and cellulase, but especially cellulase-containing mixtures of special interest. Peroxidases or oxidases have also been found in some Cases proved to be suitable.
- the enzymes can be adsorbed to carriers and / or embedded in encapsulants to protect against premature decomposition.
- Proportion of the enzymes enzyme mixtures or enzyme granules in the tablets of the invention Combinations may, for example, be about 0.1 to 5% by weight, preferably 0.1 to about 2 wt .-% amount.
- the detergent tablets may also contain components containing the oil and Soil repellents from textiles positively influence (so-called soil repellents). This effect becomes particularly clear when a textile is soiled before several times with a detergent according to the invention, this oil and fat dissolving Component contains, was washed.
- nonionic cellulose ethers such as methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups of 15 to 30% by weight and at hydroxypropoxyl groups from 1 to 15 wt .-%, each based on the nonionic cellulose ethers, as well as the polymers known from the prior art phthalic acid and / or terephthalic acid or their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionic and / or nonionically modified derivatives of these.
- sulfonated derivatives of phthalic and terephthalic acid polymers are especially preferred of these.
- dye transfer inhibiting agents are preferred in the packaged detergent tablets of the present invention.
- Color transfer inhibitors have the task, possibly from colored textiles dissolved dyes from the wash liquor to keep or suspend them suspended in the fleet and so prevent re-application to the fiber.
- color transfer inhibitors in particular polymers have proven, with the polyvinylpyrrolidone (PVP) plays an outstanding role.
- the detergent tablet (s) additionally comprises color transfer inhibitors, preferably polyvinylpyrrolidone, in amounts of from 0.1 to 2.0% by weight, preferably from 0.2 to 1.5% by weight. and in particular from 0.5 to 1.0 wt .-%, each based on the tablet weight.
- the preparation of washing and cleaning active tablets is done by applying pressure to a mixture to be compressed, which is located in the cavity of a press.
- a mixture to be tableted is compressed directly, ie without prior granulation.
- the advantages of this so-called Maistablett ist are their simple and cost-effective application, since no further process steps and consequently no other systems are needed. However, these advantages are also faced with disadvantages.
- a powder mixture, which is to be tabletted directly have sufficient plastic deformability and have good flow properties, furthermore, it must not show any separation tendencies during storage, transport and filling of the die.
- washing and cleaning agent tablets are based on pulverulent components ("primary particles") which are agglomerated or granulated by suitable processes to form secondary particles having a relatively high particle diameter. These granules or mixtures of different granules are then mixed with individual powdered additives and fed to the tableting.
- detergent tablets are preferred Pressing a particulate premix of at least one surfactant-containing granules and at least one subsequently admixed powdered component.
- the surfactant-containing granules can be processed by conventional granulation processes such as mixing and plate granulation, fluidized bed granulation, extrusion, pelletizing or compaction getting produced. It is advantageous for the later detergent tablets, if the premix to be compressed has a bulk density of at least 500 g / l, preferably at least 600 g / l and in particular above 700 g / l. Another Advantage can be gained from a narrower particle size distribution of the surfactant granules used result.
- Detergent tablets are preferred in the context of the present invention, in which the granules particle sizes between 10 and 4000 microns, preferably between 100 and 2000 microns and in particular between 600 and 1400 microns have.
- the Premix Prior to compression of the particulate premix to detergent tablets, the Premix be "powdered” with finely divided surface treatment agents. This can for the nature and physical properties of both the premix (Storage, compression) and the finished detergent tablets are beneficial. Fine particulate powdering agents are well known in the art, with mostly zeolites, Silicates or other inorganic salts are used. Preference is given to the premix but “powdered” with finely divided zeolite, wherein zeolites of the faujasite type are preferred. In the context of the present invention, the term "zeolite of the faujasite type "all three zeolites containing the faujasite subgroup of the zeolite structure group 4 (Compare Donald W.
- mixtures or cocrystallizates of zeolites of the faujasite type with other zeolites, which do not necessarily belong to the zeolite structure group 4 are as powdering agents can be used, wherein it is advantageous if at least 50 wt .-% of the powdering agent consist of a zeolite of the faujasite type.
- detergent tablets consist of a consist of particulate premix, the granular components and subsequently contains admixed powdery substances, wherein the or one of the subsequently admixed powdery components, a faujasite-type zeolite having particle sizes below 100 ⁇ m, preferably below 10 ⁇ m and especially below 5 ⁇ m and at least 0.2 wt .-%, preferably at least 0.5 wt .-% and in particular more than 1 wt .-% of the premix to be compressed.
- the finely divided treatment components with the above particle sizes can while being dry admixed to the pre-mix to be compressed. It is also possible and preferred, they by adding small amounts of liquid substances to the surface of the coarser particles "stick".
- These Abpud mecanics vide are in the state of Technique widely described and familiar to the expert.
- liquid components the suitable for the adhesion of the powdering agent, for example, nonionic Surfactants or aqueous solutions of surfactants or other detergent and cleaner ingredients be used. It is within the scope of the present invention preferably, as a liquid adhesion promoter between finely divided Abwud fürsstoff and the coarse particle to use perfume.
- the tabletting is carried out in commercial tablet presses, which in principle with single or Double stamping can be equipped. In the latter case, not only the upper punch used for pressure build-up, also the lower punch moves during the Pressing on the upper punch, while the upper punch presses down.
- the one or more stamps are attached to an eccentric disc, which in turn to a Axis is mounted at a certain rotational speed.
- the movement of this Preßstempel is similar to the operation of a conventional four-stroke engine.
- the compression can be done with a top and bottom stamp, but it can also be several Stamp be attached to an eccentric disc, the number of die holes is extended accordingly.
- the throughputs of eccentric presses vary according to type from a few hundred to a maximum of 3000 tablets per hour.
- rotary tablet presses where on a so-called Matrizentisch a larger number of matrices is arranged in a circle.
- the Number of matrices varies depending on the model between 6 and 55, with larger matrices are commercially available.
- Each die on the die table is a top and bottom stamp assigned, in turn, the pressing pressure active only by the upper or lower punch, but can also be built by both stamps.
- the die table and the Stamps move around a common perpendicular axis, with the stamp by means of rail-like cam tracks during circulation in the positions for filling, Compression, plastic deformation and ejection are brought.
- these curved paths are supplemented by Low pressure pieces, Nierderzugschienen and Aushebebahnen supported.
- the filling the die is made via a rigidly arranged supply device, the so-called Fill shoe connected to a pre-mix reservoir.
- the Pressing pressure on the premix is individualized via the pressing paths for upper and lower punches adjustable, wherein the pressure build-up by the Vorbeirollen the stamp shank heads happens on adjustable pressure rollers.
- Concentric presses can also be equipped with two filling shoes to increase throughput be, with the preparation of a tablet only a semicircle are passed through got to.
- To produce two- and multi-layered tablets several filling shoes are used arranged one behind the other without the slightly pressed first layer before the other Filling is ejected.
- suitable process control are in this way too
- Coat and point tablets can be produced, which have an onion-shell-like structure, wherein in the case of the point tablets, the top of the core or the core layers not is covered and thus remains visible.
- Rotary tablet presses are also available with or multiple tools can be equipped, so that, for example, an outer circle with 50 and an inner circle with 35 holes are used simultaneously for crimping. The Throughputs of modern rotary tablet presses amount to over one million tablets per Hour.
- plastic coatings plastic inserts or plastic stamps.
- Even rotating stamps have proven to be beneficial proven, where possible upper and lower punch be made rotatable should. With rotating punches can be dispensed with a plastic insert usually become. Here, the stamp surfaces should be electropolished.
- Tableting machines suitable for the purposes of the present invention are, for example available from 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 Press AG, Berlin, and Romaco GmbH, Worms. Further providers are, for example Dr. Herbert Pete, Vienna (AU), Mapag Maschinenbau AG, Berne (CH), BWI Manesty, Liverpool (GB), I. Holand Ltd., Nottingham (UK), Courtoy N.V., Halle (BE / LU) and Mediopharm Kamnik (SI).
- the hydraulic double pressure press is particularly suitable HPF 630 from LAEIS, D.
- tabletting tools are, for example, from the companies Adams tabletting tools, Dresden, Wilhelm Fett GmbH, Schwarzenbek, Klaus Hammer, Solingen, Herber% Sons GmbH, Hamburg, Hofer GmbH, Weil, Horn & Noack, Pharmatechnik GmbH, Worms, Ritter Pharamatechnik GmbH, Hamburg, Romaco, GmbH, Worms and Notter negligencebau, Tamm available.
- Other providers are e.g. the Senss AG, Reinach (CH) and the Medicopharm, Kamnik (SI).
- the tablets can be made in a predetermined spatial form and predetermined size are always made up of several phases, i. Layers, inclusions or cores and wrestling exist.
- Layers, inclusions or cores and wrestling exist.
- the training as a blackboard the rod or Barrel shape, cubes, cuboids and corresponding room elements with flat side surfaces and in particular cylindrical configurations with circular or oval Cross-section.
- This last embodiment detects the presentation form of the tablet up to compact cylinder pieces with a ratio of height to diameter above 1.
- the portioned compacts can each as separate individual elements be formed, the predetermined dosage of the detergent and / or detergent equivalent. However, it is also possible to form compacts, a plurality connect such mass units in a compact, in particular by predetermined Predetermined breaking points the easy separability of portioned smaller units provided is.
- the formation of the portioned compacts as Tablets to be useful in cylindrical or cuboidal shape, with a diameter / height ratio in the range of about 0.5: 2 to 2: 0.5 is preferred.
- Commercial hydraulic presses, Eccentric or rotary presses are suitable devices in particular for producing such compacts.
- the spatial form of another embodiment of the tablets is in their dimensions of Ein Titanauer-Teller adapted from commercial household washing machines, so that the Tablets without dosing aid can be metered directly into the dispenser, where they dissolves during the flushing process.
- the Tablets without dosing aid can be metered directly into the dispenser, where they dissolves during the flushing process.
- a dosing aid can be metered directly into the dispenser, where they dissolves during the flushing process.
- Another preferred multiphase tablet which can be prepared has one plate-like or tabular structure with alternately thick long and thin short segments, so that individual segments of this "multiphase bar" at the predetermined breaking points, which represent the short thin segments, canceled and entered into the machine can be.
- This principle of the "bar-shaped" tablet detergent can in other geometric shapes, such as vertical triangles, the are connected together only on one side, be realized.
- a different staining of both phases is in this embodiment especially sexy.
- multiphase tablets can also be produced in the form of ring-core tablets, core-coat tablets or so-called "bulleye" tablets.
- An overview of such embodiments of multiphase tablets is described in EP 055 100 (Jeyes Group).
- This document discloses toilet cleaner blocks comprising a molded body of a slow-dissolving detergent composition in which a bleach tablet is embedded.
- This document simultaneously discloses the most varied embodiments of multiphase tablets from the simple multiphase tablet to complicated multi-layered systems with inserts.
- the detergent tablets After pressing, the detergent tablets have a high stability.
- ⁇ stands for the diametrical fracture stress (DFS) in Pa
- P is the force in N that leads to the pressure exerted on the tablets, which causes the pressure Breakage of the tablet causes
- D is the diameter of the tray in meters
- t is the height the tablet.
- a surfactant granulate was mixed with further treatment components and compressed on an eccentric tablet press into tablets.
- the composition of the surfactant granules is given in the following Table 1, the composition of the premix to be compressed (and thus the composition of the tablets) can be found in Table 2.
- Surfactant granules [% by weight] C 9-13 alkyl benzene sulphonate 19.4 C 12-18 fatty alcohol sulfate 5.2 C 12-18 fatty alcohol with 7 EO 4.8 C 12-16 alkyl-1,4-glycoside 1.0 Soap 1.6 sodium 17.2 sodium silicate 5.6 Zeolite A (anhydrous active substance) 28.5 Na-hydroxyethane-1,1-diphosphonate 0.8 Acrylic acid-maleic acid copolymer 5.6 Water, salts rest Premix [% by weight] Surfactant granules 87.3 foam inhibitor 3.5 enzymes 1.7 Perfume 0.5 Zeolite A (Wessalith® P, Degussa) 1.0 cellulose 5.0
- the tabletting premixes were compressed in a Korsch eccentric press into tablets (diameter: 44 mm, height: 22 mm, weight: 37.5 g). In this case, the pressing pressure was adjusted so that in each case three series of tablets were obtained (E, E ', E "and V, V', V"), which differ in their hardness.
- the detergent tablets E according to the invention were packaged after manufacture for a combination of the invention by two tablets in a flow pack of laminate foil (aluminized film, thickness: 35 microns, the water vapor permeability of 1 g / m 2/24 hr) were packed; Comparative Examples V were stored open. Of all the tablet series, hardness and disintegration time were measured before packaging.
- Both tablets (combination E according to the invention and comparison tablet V were stored for 14 days in a climate cell at 23 ° C. and 85% relative humidity (test conditions according to DIN 53122), after which the hardnesses and disintegration times were determined again the tablet measured to break, with the force acting on the side surfaces of the tablet and determining the maximum force that sustained the tablet.
- the tablet was placed in a beaker with water (600 ml of water, temperature 30 ° C) and measured the time to complete tablet disintegration.
- the Ein Cyprus Kings 3 tablets were placed in the Ein Cyprushunt a household washing machine (AEG ⁇ ko Lavärnat) and started a 40 ° C program without prewash. After completion of the Ein Cyprusvorgangs the residues located in the Ein Cyprushunt were dried and weighed.
- Table 3 shows impressively that the hardness and disintegration times of detergent tablets change only slightly in the combinations according to the invention, while the Tablets of Comparative Example V unacceptably aftercure and very bad or not decay anymore.
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- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Wood Science & Technology (AREA)
- Organic Chemistry (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Emergency Medicine (AREA)
- Detergent Compositions (AREA)
- Wrappers (AREA)
Description
Die Herstellung wasch- und reinigungsaktiver Tabletten geschieht durch Anwendung von Druck auf ein zu verpressendes Gemisch, das sich im Hohlraum einer Presse befindet. Im einfachsten Fall der Tablettenherstellung, die nachfolgend vereinfacht Tablettierung genannt wird, wird die zu tablettierende Mischung direkt, d.h. ohne vorhergehende Granulation verpreßt. Die Vorteile dieser sogenannten Direkttablettierung sind ihre einfache und kostengünstige Anwendung, da keine weiteren Verfahrensschritte und demzufolge auch keine weiteren Anlagen benötigt werden. Diesen Vorteilen stehen aber auch Nachteile gegenüber. So muß eine Pulvermischung, die direkt tablettiert werden soll, eine ausreichende plastische Verformbarkeit besitzen und gute Fließeigenschaften aufweisen, weiterhin darf sie während der Lagerung, des Transports und der Befüllung der Matrize keinerlei Entmischungstendenzen zeigen. Diese drei Voraussetzungen sind bei vielen Substanzgemischen nur außerordentlich schwierig zu beherrschen, so daß die Direkttablettierung insbesondere bei der Herstellung von Wasch- und Reinigungsmittel-tabletten nicht oft angewendet wird. Der übliche Weg zur Herstellung von Wasch- und Reinigungsmitteltabletten geht daher von pulverförmigen Komponenten ("Primärteilchen") aus, die durch geeignete Verfahren zu Sekundärpartikeln mit höherem Teilchendurchmesser agglomeriert bzw. granuliert werden. Diese Granulate oder Gemische unterschiedlicher Granulate werden dann mit einzelnen pulverförmigen Zuschlagstoffen vermischt und der Tablettierung zugeführt.
- 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
Tensidgranulat [Gew.-%] | |
C9-13-Alkylbenzolsulfonat | 19,4 |
C12-18-Fettalkoholsulfat | 5,2 |
C12-18-Fettalkohol mit 7 EO | 4,8 |
C12-16-Alkyl-1,4-glycosid | 1,0 |
Seife | 1,6 |
Natriumcarbonat | 17,2 |
Natriumsilikat | 5,6 |
Zeolith A (wasserfreie Aktivsubstanz) | 28,5 |
Na-Hydroxyethan-1,1-diphosphonat | 0,8 |
Acrylsäure-Maleinsäure-Copolymer | 5,6 |
Wasser, Salze | Rest |
Vorgemisch [Gew.-%] | |
Tensidgranulat | 87,3 |
Schauminhibitor | 3,5 |
Enzyme | 1,7 |
Parfüm | 0,5 |
Zeolith A (Wessalith® P, Degussa) | 1,0 |
Cellulose | 5,0 |
Waschmitteltabletten [physikalische Daten] | |||||||
Tablette | E | E' | E" | V | V' | V" | |
vor Lagerung | Tablettenhärte [N] | 39 | 49 | 62 | 39 | 49 | 62 |
Tablettenzerfall [s] | 14 | 26 | 49 | 14 | 26 | 58 | |
Einspülbarkeit (Rest) [g] | 6 | 4 | 8 | 6 | 4 | 8 | |
nach Lagerung | Tablettenhärte [N] | 45 | 54 | 62 | 35 | 46 | 53 |
Tablettenzerfall [s] | 14 | 30 | 59 | > 60 | > 60 | > 60 | |
Einspülbarkeit (Rest) [g] | 6 | 6 | 5 | 58 | 92 | 105 |
Claims (15)
- Kombination aus (einer) Waschmitteltablette(n); welche Alkylbenzolsulfonat(e) und Desintegrationshilfsmittel auf Cellulosebasis in granularer, cogranulierter oder kompaktierter Form, in Mengen von 0,5 bis 10 Gew.-% enthält/enthalten und einem die Waschmitteltablette(n) enthaltenden Verpackungssystem, dadurch gekennzeichnet, daß das Verpackungssystem eine Feuchtigkeitsdampfdurchlässigkeitsrate von 0,1 g/m2/Tag bis weniger als 20 g/m2/Tag aufweist, wenn das Verpackungssystem bei 23°C und einer relativen Gleichgewichtsfeuchtigkeit von 85% gelagert wird.
- Kombination nach Anspruch 1, dadurch gekennzeichnet, daß das Verpackungssystem eine Feuchtigkeitsdampfdurchlässigkeitsrate von 0,5 g/m2/Tag bis weniger als 15 g/m2/Tag aufweist.
- Kombination nach einem der Ansprüche 1 oder 2, dadurch gekennzeichnet, daß die Waschmitteltablette(n) eine relative Gleichgewichtsfeuchtigkeit von weniger als 30% bei 35°C aufweist/aufweisen.
- Kombination nach einem der Ansprüche 1 bis 3, dadurch gekennzeichnet, daß das Verpackungssystem aus einem Sack oder Beutel aus einschichtigem oder laminiertem Papier und/oder Kunststoffolie besteht.
- Kombination nach Anspruch 4, dadurch gekennzeichnet, daß das Verpackungssystem aus einem Sack oder Beutel aus einschichtiger oder laminierter Kunststoffolie mit einer Dicke von 10 bis 200 µm, vorzugsweise von 20 bis 100 µm und insbesondere von 25 bis 50 µm besteht.
- Kombination nach einem der Ansprüche 1 bis 5, dadurch gekennzeichnet, daß das Verpackungssystem keine Kartons aus wachsbeschichtetem Papier umfaßt.
- Kombination nach einem der Ansprüche 1 bis 6, dadurch gekennzeichnet, daß die Waschmitteltablette(n) weitere(s) Tensid(e) und Gerüststoff(e) enthält/enthalten.
- Kombination nach einem der Ansprüche 1 bis 7, dadurch gekennzeichnet, daß die Waschmitteltablette(n) das Desintegrationshilfsmittel auf Cellulosebasis in granularer, cogranulierter oder kompaktierter Form, in Mengen von 3 bis 7 Gew.-% und insbesondere von 4 bis 6 Gew.-%, jeweils bezogen auf das Tablettengewicht enthält/enthalten.
- Kombination nach einem der Ansprüche 1 bis 8, dadurch gekennzeichnet, daß die Waschmitteltablette(n) frei von Bleichmittel(n) ist/sind.
- Kombination nach einem der Ansprüche 1 bis 9, dadurch gekennzeichnet, daß die Waschmitteltablette(n) frei von Bleichaktivator(en) ist/sind.
- Kombination nach einem der Ansprüche 1 bis 10, dadurch gekennzeichnet, daß die Waschmitteltablette(n) frei von optischen Aufhellern ist/sind.
- Kombination nach einem der Ansprüche 1 bis 11, dadurch gekennzeichnet, daß die Waschmitteltablette(n) zusätzlich Farbübetragungsinhibitoren, vorzugsweise Polyvinylpyrrolidon, in Mengen von 0,1 bis 2,0 Gew.-%, vorzugsweise von 0,2 bis 1,5 Gew.-% und insbesondere von 0,5 bis 1,0 Gew.-%, jeweils bezogen auf das Tablettengewicht, enthält/enthalten.
- Kombination nach einem der Ansprüche 1 bis 12, dadurch gekennzeichnet, daß die Waschmitteltablette(n) die Alkalimetall-, vorzugsweise Natriumsalze, von C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren enthält/enthalten, die sich von Alkylbenzolen ableiten, welche einen Tetralingehalt unter 5 Gew.-%, bezogen auf das Alkylbenzol, aufweisen.
- Kombination nach einem der Ansprüche 1 bis 13, dadurch gekennzeichnet, daß die Waschmitteltablette(n) die Alkalimetall-, vorzugsweise Natriumsalze, von C8-16-, vorzugsweise C9-13-Alkybenzolsulfonsäuren enthält/enthalten, welche einen Gehalt an 2-Phenyl-Isomer unter 22 Gew.-%, bezogen auf die Alkylbenzolsulfonsäure, aufweisen.
- Kombination nach einem der Ansprüche 1 bis 14, dadurch gekennzeichnet, daß die Waschmitteltablette(n) die Alkylbenzolsulfonate in Mengen von 0,5 bis 30 Gew.-%, vorzugsweise von 1 bis 25 Gew.-%, besonders bevorzugt von 2 bis 20 Gew.-% und insbesondere von 5 bis 15 Gew.-%, jeweils bezogen auf das Tablettengewicht, enthält/enthalten.
Applications Claiming Priority (3)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
DE19848458 | 1998-10-21 | ||
DE19848458A DE19848458A1 (de) | 1998-10-21 | 1998-10-21 | Wasch- und Reinigungsmittelformkörper/Verpackung-Kombination |
PCT/EP1999/007656 WO2000023559A1 (de) | 1998-10-21 | 1999-10-12 | Wasch- und reinigungsmittelformkörper/verpackung-kombination |
Publications (2)
Publication Number | Publication Date |
---|---|
EP1123381A1 EP1123381A1 (de) | 2001-08-16 |
EP1123381B1 true EP1123381B1 (de) | 2004-02-04 |
Family
ID=7885140
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
EP99950709A Expired - Lifetime EP1123381B1 (de) | 1998-10-21 | 1999-10-12 | Wasch- und reinigungsmittelformkörper/verpackung-kombination |
Country Status (5)
Country | Link |
---|---|
EP (1) | EP1123381B1 (de) |
AT (1) | ATE258977T1 (de) |
DE (2) | DE19848458A1 (de) |
ES (1) | ES2216572T3 (de) |
WO (1) | WO2000023559A1 (de) |
Families Citing this family (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
GB2352725A (en) * | 1999-07-30 | 2001-02-07 | Mcbride Robert Ltd | Detergent packaging |
DE10027672A1 (de) * | 2000-06-03 | 2001-12-13 | Henkel Kgaa | Wasch- und Reinigungsmittelformkörper/Verpackung-Kombination |
ES2530061T3 (es) | 2008-04-15 | 2015-02-26 | Takasago International Corporation | Composición reductora del mal olor y usos de la misma |
CN103383351A (zh) * | 2013-07-22 | 2013-11-06 | 上海嘉麟杰纺织品股份有限公司 | 一种助剂对分散染料增容量的测试方法 |
WO2018030431A1 (en) | 2016-08-09 | 2018-02-15 | Takasago International Corporation | Solid composition comprising free and encapsulated fragrances |
Family Cites Families (7)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
DE2321693C2 (de) * | 1972-12-29 | 1982-07-01 | Henkel KGaA, 4000 Düsseldorf | Zur Anwendung mit Textilwaschmitteln geeignete Aufheller-Tablette |
ZA752732B (en) * | 1974-05-15 | 1976-12-29 | Colgate Palmolive Co | Unitary detergent compositions and washing methods |
US5431841A (en) * | 1993-06-23 | 1995-07-11 | Lockhart; Ronald R. | Golf equipment cleaner formulation |
DK0634484T3 (da) * | 1993-07-14 | 1999-05-10 | Procter & Gamble | Detergentemballeringskombination |
CH686002A5 (de) * | 1993-08-06 | 1995-11-30 | Marina Patent Holding Sa | Phosphatfreies Waschmittel. |
ES2151154T3 (es) * | 1996-03-22 | 2000-12-16 | Kaercher Gmbh & Co Alfred | Concentrado detergente. |
GB9704776D0 (en) * | 1997-03-07 | 1997-04-23 | Unilever Plc | Detergent - packaging combination |
-
1998
- 1998-10-21 DE DE19848458A patent/DE19848458A1/de not_active Ceased
-
1999
- 1999-10-12 ES ES99950709T patent/ES2216572T3/es not_active Expired - Lifetime
- 1999-10-12 EP EP99950709A patent/EP1123381B1/de not_active Expired - Lifetime
- 1999-10-12 WO PCT/EP1999/007656 patent/WO2000023559A1/de active IP Right Grant
- 1999-10-12 AT AT99950709T patent/ATE258977T1/de not_active IP Right Cessation
- 1999-10-12 DE DE59908481T patent/DE59908481D1/de not_active Expired - Lifetime
Also Published As
Publication number | Publication date |
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EP1123381A1 (de) | 2001-08-16 |
WO2000023559A1 (de) | 2000-04-27 |
ES2216572T3 (es) | 2004-10-16 |
DE19848458A1 (de) | 2000-04-27 |
ATE258977T1 (de) | 2004-02-15 |
DE59908481D1 (de) | 2004-03-11 |
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