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EP1095131B1 - Composition de lavage et detergente utilisable par portions - Google Patents

Composition de lavage et detergente utilisable par portions Download PDF

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Publication number
EP1095131B1
EP1095131B1 EP99934575A EP99934575A EP1095131B1 EP 1095131 B1 EP1095131 B1 EP 1095131B1 EP 99934575 A EP99934575 A EP 99934575A EP 99934575 A EP99934575 A EP 99934575A EP 1095131 B1 EP1095131 B1 EP 1095131B1
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EP
European Patent Office
Prior art keywords
detergent
acid
cleaner composition
portioned
water
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
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EP99934575A
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German (de)
English (en)
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EP1095131A1 (fr
Inventor
Dieter Jung
Bernd Larson
Wilfried Rähse
Peter Sandkühler
Hans-Peter Siegers
Hermann-Josef Welling
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Henkel AG and Co KGaA
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Henkel AG and Co KGaA
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Classifications

    • C—CHEMISTRY; METALLURGY
    • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
    • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
    • 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
    • C11D17/042—Water soluble or water disintegrable containers or substrates containing cleaning compositions or additives for cleaning compositions
    • C11D17/044—Solid 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
    • C11D17/00—Detergent materials or soaps characterised by their shape or physical properties
    • C11D17/06—Powder; Flakes; Free-flowing mixtures; Sheets

Definitions

  • the present invention relates to portioned detergent and cleaning agent compositions, the consumer the dosage of detergents and cleaning agents facilitate.
  • the invention relates to portioned detergent and cleaning agent compositions, which is packaged in a bag made of water-soluble film are and are briefly referred to as "portion bags".
  • German Auslegeschrift 11 30 547 (Procter & Gamble) discloses packages made of water-soluble films of polyvinyl alcohol which are filled with non-liquid synthetic detergents. This document does not comment on the particle sizes of the packaged detergents.
  • European patent application EP 158 464 (Clorox) describes low-temperature detergents which can be packaged in a bag made of water-soluble film. Information on particle sizes of the packaged detergents can be found in this document only with regard to the builder used (sodium tripolyphosphate), the particle sizes being between 75 and 400 ⁇ m.
  • the invention therefore relates to a portioned detergent and cleaning agent composition in a bag made of water-soluble film, in which at least 70% by weight the particles of the detergent and cleaning agent composition particle sizes in the range of Have 800 ⁇ m to 3000 ⁇ m.
  • Detergent and cleaning agent compositions have at least 80% by weight, preferably at least 85% by weight, particularly preferably at least 90% by weight and in particular at least 95% by weight of the particles of the detergent and cleaning composition Particle sizes above 800 microns, preferably above 900 microns, particularly preferred above 1000 ⁇ m and in particular above 1200 ⁇ m.
  • Another advantage of the present invention is that existing or emerging Fine particles within the tightly sealed bag and thus within a portion of the Detergents and cleaning agents remain. With usual packaging it happens during of transport to segregation, since the fine particles through the particle pile of the coarse particles fall through.
  • the portioned detergent and cleaning agent compositions according to the invention are packed in bags made of water-soluble film.
  • bag materials or foils are known from the prior art and originate, for example, from the group (acetalized) Polyvinyl alcohol, polyvinyl pyrrolidone, polyethylene oxide, gelatin and mixtures thereof.
  • Polyvinyl alcohols are polymers of the general structure [-CH 2 -CH (OH) -] n which in small proportions also structural units of the type [-CH 2 -CH (OH) -CH (OH) -CH 2 ] contain. Since the corresponding monomer, the vinyl alcohol, is not stable in free form, polyvinyl alcohols are prepared in solution via polymer-analogous reactions by hydrolysis, but technically in particular by alkaline-catalyzed transesterification of polyvinyl acetates with alcohols (preferably methanol). These technical processes also make PVAL accessible which contain a predeterminable residual proportion of acetate groups.
  • PVAL e.g. Mowiol® grades from Hoechst
  • PVAL come as white-yellow Powder or granules with degrees of polymerization in the range of approx. 500-2500 (corresponding to molar masses of approx. 20,000-100,000 g / mol) in the trade and have different Degrees of hydrolysis of 98-99 and 87-89 mol%. So they are partially saponified polyvinyl acetates with a residual acetyl group content of approx. 1-2 or 11-13 mol%.
  • the water solubility of PVAL can be improved by post-treatment with aldehydes (acetalization), by complexing with Ni or Cu salts or by treatment with dichromates, Reduce boric acid, borax and adjust them to the desired values.
  • films made of PVAL are largely impenetrable for gases such as oxygen, nitrogen, helium, Hydrogen, carbon dioxide, however, allow water vapor to pass through.
  • Polyvinylpyrrolidones abbreviated as PVP, can be identified by the general formula describe.
  • PVPs are made by radical polymerization of 1-vinyl pyrrolidone. Commercial PVP have molar masses in the range of approx. 2500-750,000 g / mol offered as white, hygroscopic powder or as aqueous solutions.
  • Polyethylene oxides are polyalkylene glycols of the general formula H- [O-CH 2 -CH 2 ] n -OH which are produced industrially by base-catalyzed polyaddition of ethylene oxide (oxirane) in systems containing mostly small amounts of water with ethylene glycol as the starting molecule. They have molar masses in the range of approx. 200-5,000,000 g / mol, corresponding to degrees of polymerization n of approx. 5 to> 100,000. Polyethylene oxides have an extremely low concentration of reactive hydroxy end groups and show only weak glycol properties.
  • Gelatin is a polypeptide (molecular weight: approx.15,000-> 250,000 g / mol), which is primarily by hydrolysis of the collagen contained in the skin and bones of animals under acid or alkaline conditions.
  • the amino acid composition of the Gelatin largely corresponds to that of the collagen from which it was obtained and varies depending on its provenance.
  • the use of gelatin as a water soluble Envelope material is particularly in the pharmaceutical industry in the form of hard or soft gelatin capsules extremely widespread. Gelatin is found in the form of foils because of their comparison only little use for the above-mentioned high-cost polymers.
  • Portioned detergent and cleaning agent compositions are also preferred in the context of the present invention, whose bags made of water-soluble film from at least a polymer from the group starch and starch derivatives, cellulose and cellulose derivatives, in particular methyl cellulose and mixtures thereof.
  • Starch is a homoglycan, with the glucose units linked ⁇ -glycosidically. Starch is made up of two components of different molecular weights: approx. 20-30% straight-chain amylose (MW.approx. 50,000-150,000) and 70-80% branched-chain Amylopectin (MG. Approx. 300,000-2,000,000), in addition there are still small amounts of lipids, Contain phosphoric acid and cations.
  • amylose due to the binding in the 1,4-position long, helical, intertwined chains with about 300-1200 glucose molecules forms, the chain branches in amylopectin after an average of 25 Glucose building blocks through 1,6-binding to a knot-like structure with about 1500-12000 Molecules of glucose.
  • they are more water-soluble for production Bags within the scope of the present invention also contain starch derivatives polymer-analogous reactions from starch are available.
  • Such chemically modified Starches include, for example, products from esterifications or etherifications, in which have substituted hydroxy hydrogen atoms.
  • Starch derivatives include, for example, alkali starches, carboxymethyl starch (CMS), Starch esters and ethers as well as amino starches.
  • 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 derivatives made by polymer-analogous reactions from cellulose are available.
  • Such chemically modified celluloses include, for example Products from esterifications or etherifications, in which hydroxy hydrogen atoms were substituted.
  • celluloses, in which the hydroxyl groups against functional Groups that are not linked via an oxygen atom have been replaced are used as cellulose derivatives.
  • the group of cellulose derivatives Alkaline celluloses, carboxymethyl cellulose (CMC), cellulose esters and ethers as well as aminocelluloses.
  • Preferred bags made of water-soluble film consist of a polymer with a molecular weight between 5000 and 500,000 daltons, preferably between 7500 and 250,000 Daltons and especially between 10,000 and 100,000 Daltons.
  • the water-soluble film, which forms the bag preferably has a thickness of 1 to 150 microns, preferably of 2 to 100 ⁇ m, particularly preferably from 5 to 75 ⁇ m and in particular from 10 to 50 ⁇ m, on.
  • the washing and packaging packed in the bags made of water-soluble film in the form of a single dose Detergent composition is preferred in the required particle size by Granulation produced.
  • Granulation denotes in the context of the present Registration of any shaping process that can be predetermined into particles Greatness leads.
  • press agglomeration processes can also be used.
  • Granulation can be found in a wide variety of industries in the laundry and home care industries usually used apparatus are carried out. For example, it is possible to use the rounders commonly used in pharmacy. In such turntable devices the residence time of the granules is usually less than 5 minutes. Also conventional mixers and mixing granulators are suitable for granulation. As a mixer can both high-intensity mixers (“high-shear mixer”) and normal Mixers with lower circulation speeds and especially combinations used by both.
  • high-shear mixer high-intensity mixers
  • normal Mixers with lower circulation speeds and especially combinations used by both.
  • Suitable mixers are, for example, Eirich® mixers Series R or RV (trademark of Maschinenfabrik Gustav Eirich, Hardheim), the Schugi® Flexomix, the Fukae® FS-G mixer (trademark of Fukae Powtech, Kogyo Co., Japan), the Lödige® FM, KM and CB mixers (trademarks of Lödige Maschinenbau GmbH, Paderbom) or the Drais® series T or K-T (trademark of Drais-Werke GmbH, Mannheim).
  • the residence times of the granules in the mixer combination are in the range of less than 60 seconds in the high-speed mixer and less than 7 minutes in the slow-running mixer, the residence time also depending on the circulation speed depends on the mixer. The dwell times are reduced accordingly, the faster the mixer runs.
  • the detergent and cleaning agent composition in the plastic solidification area of the casing under pressure and under The action of shear forces is compressed and homogenized, and then gives shape discharged from the apparatus.
  • the most technically significant press agglomeration processes are extrusion, roller compaction, pelleting and tableting.
  • preferably for the production of washing and Press agglomeration processes used in detergent compositions are Extrusion, roller compaction and pelletizing.
  • the detergent and cleaning agent composition preferably continuously a planetary roller extruder or a 2-shaft extruder or 2-screw extruder with co-rotating or counter-rotating Screw guide fed, its housing and its extruder pelletizing head can be heated to the predetermined extrusion temperature.
  • the premixing is sheared by the extruder under pressure, which is preferred is at least 10 bar, with extremely high throughputs depending on the used machine but can also be below, compressed, plasticized, in shape fine strands extruded through the perforated die plate in the extruder head and finally that Extrudate by means of a rotating knock-off knife, preferably to approximately spherical down to cylindrical granules.
  • the hole diameter of the hole nozzle plate and the strand cut length are matched to the selected granule dimension.
  • the production of granules essentially succeeds uniformly predeterminable particle size, with the absolute particle sizes in detail can be adapted to the intended purpose.
  • Important embodiments see the production of uniform granules in the millimeter range, for example in the range of 0.8 to 5 mm and in particular in the range of approximately 1.0 to 3 mm in front.
  • the length / diameter ratio of the chipped primary granules In an important embodiment, it is in the range from about 0.7: 1 to about 3: 1.
  • the still plastic primary granules give a further shape
  • the raw extrudate is present Rounded edges so that ultimately spherical to approximately spherical extrudate grains can be obtained.
  • extrusions / pressings can also be carried out in low pressure in the Kahl press, in the extruder, or in the plastic agglomerator (company Pallmann).
  • the manufacturing process for the detergent and cleaning agent composition by means of roller compaction carried out.
  • the detergent and cleaning agent composition in the plastic solidification area of the coating between two smooth or dosed rollers of defined shape are metered in 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 Use of structured rollers with correspondingly structured slugs or individual pellets can be generated in which, for example, certain forms of the later granules or moldings can be specified.
  • the cuff band is below broken down into smaller pieces by a knock-off and crushing process and can processed in this way to Granulatkömem, known by others Surface treatment process further remunerated, especially in approximately spherical Can be brought into shape.
  • the washing and cleaning agent composition to be packaged is produced by means of pelleting.
  • the detergent and cleaning agent composition is applied to a perforated surface in the plastic solidification area of the casing and pressed through the holes by means of a pressure-generating body.
  • the detergent and cleaning agent composition is compressed under pressure, plasticized, pressed by means of a rotating roller in the form of fine strands through a perforated surface and finally comminuted into granules with a knock-off device.
  • the most varied configurations of the pressure roller and perforated die are conceivable here.
  • 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.
  • Another press agglomeration process used to manufacture the detergent and cleaning composition Tableting can be used.
  • the process of shaping the detergent and cleaning agent composition in a die pressed, with the design of the upper or lower punch of the tablet press coated solid particles can be produced in a wide variety of forms.
  • Preferred portioned detergent and cleaning agent compositions are by a granulation or press agglomeration process, in particular by extrusion.
  • the portioned detergent and cleaning agent compositions according to the invention contain one or more substances from the group of surfactants, surfactant compounds, builders, Bleaching agents, bleach activators, enzymes, foam inhibitors, colors and fragrances as well as binding and disintegration aids. These classes of substances are as follows described.
  • compositions from the group containing anionic, nonionic, zwitterionic or cationic surfactants, taking 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 glycerin 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 especially ethoxylated fatty alcohols.
  • alcohols preferably fatty alcohols and especially 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 non-ionic 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.
  • Portioned detergent and cleaning agent compositions are within the scope of the present invention preferably, the 5 to 50 wt .-%, preferably 7.5 to 40 wt .-% us in particular 15 to 25 wt .-% anionic surfactant (s), based in each case on the washing and Detergent composition included.
  • detergent and cleaning agent compositions When choosing the anionic surfactants that are portioned in the invention Detergent and cleaning agent compositions are used, the freedom of formulation no framework conditions to be observed in the way. Preferred portioned However, detergent and cleaning agent compositions have a content Soap, which is 0.2% by weight, based on the total weight of the detergent and cleaning agent composition, exceeds.
  • 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 for example, are described 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 and cleaning agent compositions according to the invention can be preferred Contain alkylpolyglycosides, contents of detergent and cleaning compositions of APG over 0.2% by weight, based on the total molded body, is preferred are.
  • Particularly preferred detergent and cleaning agent compositions contain APG in amounts of 0.2 to 10 wt .-%, preferably 0.2 to 5 wt .-% and in particular from 0.5 to 3% by weight.
  • 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 propylated Derivatives of this remainder.
  • 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 international application WO-A-95/ 07331, be converted into the desired polyhydroxy fatty acid amides by reaction with fatty acid methyl esters in the presence of an alkoxide as catalyst.
  • builders are the most important ingredients of Detergents and cleaning agents.
  • detergent and cleaning agent compositions according to the invention can usually all in detergents and cleaning agents builders used, in particular thus zeolites, silicates, carbonates, organic cobuilders and - where there are no ecological prejudices against their use - 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.
  • M sodium or hydrogen
  • x is a number from 1.9 to 4
  • y is a number from 0 to 20 and 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 disilicate Na 2 Si 2 O 5 .yH 2 O are preferred, wherein ⁇ -sodium disilicate can be obtained, for example, by the method described in international patent application WO-A-91/08171 .
  • 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
  • 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.
  • the sodium salts of orthophosphates, pyrophosphates, are particularly suitable and especially the tripolyphosphates.
  • Useful organic builders are, for example, those in the form of their sodium salts usable polycarboxylic acids, such as citric acid, adipic acid, succinic acid, glutaric acid, Tartaric acid, sugar acids, aminocarboxylic acids, nitrilotriacetic acid (NTA), if provided 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 this.
  • inventive Detergents and cleaning agents further ingredients common in detergents and cleaning agents from the group of bleaching agents, bleach activators, enzymes, fragrances, perfume carriers, Fluorescent agents, dyes, foam inhibitors, silicone oils, anti-redeposition agents, optical brighteners, graying inhibitors, color transfer inhibitors and corrosion inhibitors contain.
  • 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. If cleaning or bleaching agent compositions for machine dishwashing are 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.
  • 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, ⁇ -phthalimidthanoic acid paproacidaproacidoxyhexanoic acid , o-Carboxybenzamidoperoxycapronsäure, N-nonenylamidoperadipic acid and N-nonenylamidopersuccinates, and (c) aliphatic and araliphatic peroxydicarboxylic acids, such as 1,12-diperoxycarboxylic acid, 1,9-diperoxyazelaic acid, Diperocysebac
  • Chlorine or bromine releasing substances are used.
  • suitable chlorine or bromine-releasing materials come, for example, heterocyclic N-bromine 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 in the detergent and cleaning agent composition be incorporated.
  • bleach activators compounds which are preferred under perhydrolysis conditions with aliphatic peroxocarboxylic acids 1 to 10 carbon atoms, in particular 2 to 4 carbon atoms, and / or optionally result in substituted perbenzoic acid can be used.
  • 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, especially tetraacetylglycoluril (TAGU), N-acylimides, especially N-nonanoylsuccinimide (NOSI), acylated Phenolsulfonates, especially n-nonanoyl or isononanoyloxybenzenesulfonate (n- or.
  • TAED Tetraacetylethylenediamine
  • DADHT 1,5-diacetyl-2,4-dioxohexahydro-1,3,5-triazine
  • TAGU acylated glycolurils
  • TAGU tetraacetyl
  • iso-NOBS carboxylic anhydrides, especially phthalic anhydride, acylated polyhydric alcohols, especially triacetin, ethylene glycol diacetate and 2,5-diacetoxy-2,5-dihydrofuran.
  • bleach catalysts in the detergent and cleaning agent composition 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 tripod ligands as well as Co, Fe, Cu and Ru amine complexes can be used as bleaching catalysts.
  • 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 Compositions can be, for example, about 0.1 to 5% by weight, preferably 0.1 to be about 2% by weight.
  • the detergent and cleaning agent compositions can also contain components contain, which have a positive influence on the oil and fat washability from textiles (so-called soil repellents). This effect is particularly evident when a textile is soiled, which has previously been repeatedly washed with a detergent according to the invention, that contains this oil and fat-dissolving component has been washed.
  • Oil- and fat-dissolving components include, for example, nonionic cellulose ethers such as Methyl cellulose and methyl hydroxypropyl cellulose with a proportion of methoxyl groups from 15 to 30% by weight and from 1 to 15% by weight of hydroxypropoxyl groups, each based on the nonionic cellulose ether, as well as those from the prior art known polymers of phthalic acid and / or terephthalic acid or of their derivatives, in particular polymers of ethylene terephthalates and / or polyethylene glycol terephthalates or anionically and / or nonionically modified derivatives of these.
  • the sulfonated derivatives of phthalic and are particularly preferred Terephthalic acid polymers.
  • the detergent and cleaning agent compositions can be used as optical brighteners contain the diaminostilbenedisulfonic acid or its alkali metal salts. Suitable are e.g. Salts of 4,4'-bis (2-anilino-4-morpholino-1,3,5-triazinyl-6-amino) stilbene-2,2'disulfonic acid or similarly structured compounds that replace the morpholino group a diethanolamino group, a methylamino group, an anilino group or carry a 2-methoxyethylamino group. Brighteners of the substituted type can also be used Diphenyl styrenes are present, e.g.
  • Dyes and fragrances are added to the washing and cleaning agents according to the invention, to improve the aesthetic impression of the products and the consumer alongside the softness performance a visually and sensory "typical and unmistakable" To provide product.
  • perfume oils or fragrances individual olfactory joints, 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 dye content of the compositions according to the invention is usually less than 0.01% by weight, while fragrances can make up up to 2% by weight of the total formulation.
  • the fragrances can be incorporated directly into the agents according to the invention, but it can also be advantageous to apply the fragrances to carriers which increase the adhesion of the perfume to the laundry and ensure a long-lasting fragrance of the textiles due to a slower fragrance release.
  • Cyclodextrins for example, have proven useful as such carrier materials, and the cyclodextrin-perfume complexes can additionally be coated with further auxiliaries.
  • the agents can be dyed with suitable dyes.
  • Preferred dyes the selection of which Specialist poses no difficulty, have a high storage stability and insensitivity compared to the other ingredients of the agents and against light and none pronounced substantivity towards textile fibers so as not to stain them.
  • Portion bags were made from a 25 ⁇ m thick polyvinyl alcohol film from Aquafilm Ltd., which is made up of various Mowiol® types (trademark of HOECHST AG), into each of which 40 g of a detergent composition were filled. The bags were sealed thermally using permanently heated sealing strips.
  • the detergent composition was produced by means of a granulation process
  • example E according to the invention the identically composed detergent and cleaning agent composition was produced by extrusion and had a significantly narrower particle size distribution.
  • the following table shows the sieve analyzes of the two compositions: Siebfresh e V > 1.6 mm 2.5 27.0 > 0.8 mm 93.2 26.0 > 0.4 mm 4.2 30.0 ⁇ 0.4 mm 0.1 17.0

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  • Chemical & Material Sciences (AREA)
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  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
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  • Wood Science & Technology (AREA)
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Claims (8)

  1. Composition de lavage et de nettoyage portionnée dans une pochette faite d'une feuille soluble dans l'eau, caractérisée en ce qu'au moins 70% en poids des particules de la composition de lavage et de nettoyage présentent une granulométrie comprise entre 800 et 3000 µm.
  2. Composition de lavage et de nettoyage portionnée selon la revendication 1, caractérisée en ce qu'au moins 80% en poids, de préférence au moins 85% en poids, de façon particulièrement préférée au moins 90% en poids et au moins en particulier 95% en poids des particules de composition de lavage et de nettoyage présentent une granulométrie supérieure à 800 µm, de préférence supérieure à 900 µm, de préférence supérieure à 1000 µm, et en particulier supérieure à 1200 µm.
  3. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 ou 2, caractérisée en ce que la pochette se compose d'une feuille soluble dans l'eau faite d'au moins un polymère du groupe de l'alcool polyvinylique éventuellement acétalisé, de la potyvinylpyrrolidone, de l'oxyde de polyéthylène, des gélatines et de leurs mélanges.
  4. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 ou 2, caractérisée en ce que la pochette se compose d'une feuille soluble dans l'eau faite d'au moins un polymère du groupe de l'amidon et des dérivés d'amidon, de la cellulose et des dérivés de cellulose, et particulier la méthylcellulose, et de leurs mélanges.
  5. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 à 4, caractérisée en ce que la pochette se compose d'une feuille soluble dans l'eau faite d'un polymère ayant une masse molaire comprise entre 5000 et 500 000 daltons, de préférence entre 7500 et 250 000 daltons, et en particulier entre 10 000 et 100 000 daltons.
  6. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 à 5, caractérisée en ce que la feuille soluble dans l'eau qui forme la pochette présente une épaisseur de 1 à 150 µm, de préférence de 2 à 100 µm, de façon particulièrement préférée de 5 à 75 µm et en particulier de 10 à 50 µm.
  7. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 à 6, caractérisée en ce que la composition de lavage et de nettoyage a été fabriquée par un procédé de granulation ou d'agglomération sous pression, en particulier par extrusion.
  8. Composition de lavage et de nettoyage portionnée selon l'une des revendications 1 à 7, caractérisée en ce que la composition de lavage et de nettoyage contient un ou plusieurs matériaux du groupe des agents tensioactifs, des combinaisons tensioactives, des matériaux d'ossature, des agents de blanchiment, des activateurs de blanchiment, des enzymes, des anti-mousses, des colorants et des parfums ainsi que des adjuvants de liaison et de désintégration.
EP99934575A 1998-07-15 1999-07-06 Composition de lavage et detergente utilisable par portions Expired - Lifetime EP1095131B1 (fr)

Applications Claiming Priority (3)

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DE19831703A DE19831703A1 (de) 1998-07-15 1998-07-15 Portionierte Wasch- und Reinigungsmittelzusammensetzung
DE19831703 1998-07-15
PCT/EP1999/004672 WO2000004125A1 (fr) 1998-07-15 1999-07-06 Composition de lavage et detergente utilisable par portions

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AT (1) ATE262581T1 (fr)
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HUP0102604A2 (hu) 2001-11-28
EP1095131A1 (fr) 2001-05-02
ATE262581T1 (de) 2004-04-15
DE59908963D1 (de) 2004-04-29
ES2219034T3 (es) 2004-11-16
US6133214A (en) 2000-10-17
WO2000004125A1 (fr) 2000-01-27
DE19831703A1 (de) 2000-01-20

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