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
  • C11D17/046—Insoluble free body dispenser
• • 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
  • C11D17/0039—Coated compositions or coated components in the compositions, (micro)capsules
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/0005—Other compounding ingredients characterised by their effect
  • C11D3/0036—Soil deposition preventing compositions; Antiredeposition agents
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/1253—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite
  • C11D3/126—Layer silicates, e.g. talcum, kaolin, clay, bentonite, smectite, montmorillonite, hectorite or attapulgite in 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
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
  • C11D3/1286—Stabilised aqueous aluminosilicate suspensions
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/02—Inorganic compounds ; Elemental compounds
  • C11D3/12—Water-insoluble compounds
  • C11D3/124—Silicon containing, e.g. silica, silex, quartz or glass beads
  • C11D3/1246—Silicates, e.g. diatomaceous earth
  • C11D3/128—Aluminium silicates, e.g. zeolites
  • C11D3/1293—Feldspar; Perlite; Pumice or Portland cement
• • 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
  • C11D3/227—Natural or synthetic polysaccharides, e.g. cellulose, starch, gum, alginic acid or cyclodextrin with nitrogen-containing groups
• • C—CHEMISTRY; METALLURGY
  • C11—ANIMAL OR VEGETABLE OILS, FATS, FATTY SUBSTANCES OR WAXES; FATTY ACIDS THEREFROM; DETERGENTS; CANDLES
  • C11D—DETERGENT COMPOSITIONS; USE OF SINGLE SUBSTANCES AS DETERGENTS; SOAP OR SOAP-MAKING; RESIN SOAPS; RECOVERY OF GLYCEROL
  • C11D3/00—Other compounding ingredients of detergent compositions covered in group C11D1/00
  • C11D3/16—Organic compounds
  • C11D3/37—Polymers
  • C11D3/3746—Macromolecular compounds obtained by reactions only involving carbon-to-carbon unsaturated bonds
  • C11D3/3769—(Co)polymerised monomers containing nitrogen, e.g. carbonamides, nitriles or amines
• • D—TEXTILES; PAPER
  • D06—TREATMENT OF TEXTILES OR THE LIKE; LAUNDERING; FLEXIBLE MATERIALS NOT OTHERWISE PROVIDED FOR
  • D06L—DRY-CLEANING, WASHING OR BLEACHING FIBRES, FILAMENTS, THREADS, YARNS, FABRICS, FEATHERS OR MADE-UP FIBROUS GOODS; BLEACHING LEATHER OR FURS
  • D06L1/00—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods
  • D06L1/12—Dry-cleaning or washing fibres, filaments, threads, yarns, fabrics, feathers or made-up fibrous goods using aqueous solvents
  • D06L1/16—Multi-step processes
• • 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
  • C11D2111/00—Cleaning compositions characterised by the objects to be cleaned; Cleaning compositions characterised by non-standard cleaning or washing processes
  • C11D2111/40—Specific cleaning or washing processes
  • C11D2111/46—Specific cleaning or washing processes applying energy, e.g. irradiation

Definitions

• P 35 45 990.5 (D 7478/7495) relates to the use of polyfunctional quaternary ammonium compounds (PQAV) which are insoluble in aqueous-surfactant washing or cleaning solutions, even under the temperature loads of the washing process, and / or on aqueous ones Solutions corresponding to insoluble solids are not washable, immobilized, as a particle-dirt-collecting cleaning booster in aqueous surfactant washing or cleaning solutions, which can be manually and / or mechanically separated from the goods to be cleaned after washing or cleaning.
• PQAV polyfunctional quaternary ammonium compounds
• aqueous alkaline cleaning liquors if desired containing surfactants, in particular washing solutions from textile washing, can be subjected to regeneration in such a way that either during washing and / or afterwards the soiled cleaning liquor with the insoluble or immobilized PQAV treated and thereby at least partially freed from solubilized dirt, in particular pigment dirt.
• the washing solution treated in this way can be reused - for example in the context of textile washing.
• the present teaching is based on the knowledge that the washing result in textile washing can be shown to be particularly effective in enhancing the detergency when using the PQAV in the sense of the invention by increasing the reflectance values of the washed goods when underdosing on one or more detergent components .
• the invention accordingly in a first embodiment, the use of in aqueous washing and PQAVs that are insoluble in cleaning liquors or immobilized on correspondingly insoluble solid carriers, in particular of the type described in the earlier applications, in detergent and / or cleaning agent formulations containing surfactants as dirt-absorbing emollients for reducing the need for conventional chemicals in detergents and cleaning agents.
• detergent and / or cleaning agent formulations containing surfactants as dirt-absorbing emollients for reducing the need for conventional chemicals in detergents and cleaning agents.
• it is in particular possible to substantially reduce the need for conventional detergents and cleaning agents for soluble chemical constituents of detergents and cleaning agents customary today, but it is also possible at least in part to dispense with insoluble detergent and cleaning agent components which are known per se , as will be described in the following.
• the effect of the PQAV used according to the invention as a dirt-absorbing weight-loss agent can be adjusted to such an extent that a number of previously indispensable components of classic detergent and cleaning agent formulations can be completely or at least partially dispensed with.
• This surprising state of affairs is at least partially understandable by the following considerations:
• the classic detergent formulations common today meet a number of requirements for effective washing, whereby only the pigment dirt content of the items to be cleaned should be considered in this consideration.
• This pigment dirt must be detached from the detergent under the washing conditions from the substrate to be cleaned and at the same time be so reliably solubilized in the wash liquor that its discharge with the used wash liquor, including the subsequent rinsing steps, is ensured without substantial redeposition of the textile soiling on the wash comes to be cleaned. Understandably, considerable amounts of chemicals are required for this comparatively complex task of the conventional washing process.
• the task to be performed by the washing chemicals is reduced to the detachment of the dirt from the items to be cleaned and the dirt transfer and unloading on the PQAV receiver. It is obvious that the chemical requirement required for this is lower in comparison with conventional detergents and cleaning agents, so that this makes it possible to lower the content of detergent constituents up to the complete elimination of components previously considered indispensable.
• the new detergent formulations derived from these considerations and their use in washing and cleaning processes are further objects of the present invention.
• the invention relates to PQAV aids of the type concerned and described at the outset, which are present in a particularly active form and thus correspond particularly well to the intended purpose of reducing the chemical requirement in detergents and cleaning agents.
• the teaching of the invention provides in a further embodiment the combination of the new technical rule described here in connection with the teaching of the aforementioned older application P 36 05 716.9 (D 7538), according to which the washing liquor cleaned of pigment dirt is intended to be reused. This is understandably an even greater reduction in the amount of chemicals to be discarded, for example with the wastewater.
• auxiliaries for Detachment of the dirt from the material to be cleaned and dirt-absorbing insoluble or insoluble immobilized PQAV in the sense of the invention are suitable as aids for dirt detachment and for transferring the detached dirt to the PQAV dirt trap.
• the nature of the surfactant and its quantity can no longer be based on the fact that - as before - the surfactants are also of decisive importance for the solubilization of the detached pigment dirt.
• the type of surfactants to be selected is also influenced by the new task and its importance in the new washing process. For example, excellent washing results have been obtained using only one class of surfactant, which in itself is of little importance in conventional detergent formulations, but rather is used in the area of cleaning personal care products.
• surfactant components selected in a certain direction which are distinguished, for example, by particular ecological safety and / or by particularly rapid degradability.
• Suitable surfactants in this direction are, for example, the known fatty alcohol sulfates, fatty alcohol ether sulfates, disalts of alpha-sulfofatty acids, alpha-sulfofatty acid methyl ester salts and / or alkyl glycosides.
• the principle of the teaching according to the invention is not restricted to these specific surfactants.
• the classes of surfactants that can be used in practice are: especially subsumed under the terms of anionic surfactants, nonionic surfactants and / or amphoteric surfactants. If one takes into account that effective cleaning does not only require the removal of pigment dirt, it is understandable that the use of surfactant mixtures, for example anionic and nonionic surfactants, can be useful. In principle, however, the amount of surfactants required can be significantly reduced compared to conventional detergent formulations.
• the dirt is not transferred back to the material to be cleaned, so that high remission values can be achieved even in the complete absence of conventional builder components, while known and previously known soluble and / or insoluble builder components, in particular, also counteract unwanted particle dirt redeposition on the textile.
• the suspension of solubilized dirt particles is usually supported in conventional detergent formulations in that so-called dirt-carrying agents of the carboxymethyl cellulose type or corresponding polymeric soluble components are also used. According to the invention, the use of these conventional dirt-carrying agents can be dispensed with in whole or in part
• washing alkalis Conventional detergents and cleaning agents often work at comparatively strongly alkaline pH values, whereby the corresponding pH range is ensured by using these soluble washing alkalis.
• Typical washing alkalis are, for example, water glass, soda and the like.
• the setting of strongly alkaline pH values is possible, but not necessary.
• suitable surfactant components known per se it is possible to work in the neutral to weakly alkaline range.
• buffer systems can be used in a manner known per se, which, for example, keep the pH of the washing and / or cleaning liquor in the neutral range to weakly alkaline range. In terms of numbers, this means, for example, that washing can also take place in the range from about 7 to 8.5.
• the insoluble PQAV can - as described in detail in the older applications - be used in sheet or film form or in the form of a wipe that is also used.
• these essential auxiliaries in the form of finely divided solids, which enable their disperse fine distribution in the washing or cleaning liquors, and thus ensure that, with the most homogeneous possible distribution of the dirt-adsorbing PQAV, every contaminated area of the items to be cleaned is of the PQAV is ready for adsorption.
• the transport path of a detached dirt particle from its original location to the desired landfill location on the PQAV surface is kept as short as possible in this way, and the movement and mixing of the material to be cleaned means that new PQAV surfaces of the surface that are ready for adsorption are constantly created of the goods to be unloaded from dirt.
• the limitation of the surfactant performance now required and the resulting considerations for the selection and / or reduction of the surfactants or amount of surfactant and / or the other conventional detergent constituents can be understood from this.
• the PQAV components present as a heterogeneous solid phase according to the invention absorb particularly negatively from the dirt-laden liquor charged portions, for example, corresponding particle dirt.
• the PQAV solid material can have a cleaning or cleaning-enhancing effect due to other surface forces. In the important further embodiments described below, it is consciously assumed that not only negatively charged dirt can be removed from soiled washing liquors.
• an auxiliary is also used in the heterogeneous solid phase, which is characterized by a high absorption capacity for oleophilic soiling.
• selected plastics for example polyethylene or polypropylene or polyurethane or surface-insoluble solids of any origin which have a highly hydrophobic finish, have the ability to pull the oleophilic dirt content which has been hydrophilized under the action of surfactants from a wash liquor and to hold on to its surface. This working principle is also used in this embodiment for the effective cleaning of soiled washing liquors.
• the collectors for such oleophilic dirt can be used, for example, in the form of flakes, fibers or fiber structures such as cloths, random fiber fleeces, poromer skins and the like. What is essential for this component is only the condition previously stated for the PQAV cleaners that a manual and / or mechanical separation between the liquid phase and / or textile material and the dirt collector present in the solid phase is ensured. A particularly important embodiment will be discussed below.
• the use of the oleophilic dirt-collecting auxiliaries can coincide with the treatment of the wash liquor by PQAV and / or separately therefrom.
• the working conditions in detail are determined by the nature of the pollution in the wash liquor and the expected load of the dirt-collecting auxiliary substances in the solid phase.
• polyanionic cleaning aids present in a separate solid phase are also used.
• Polyanionic components in dissolved and / or undissolved form play a considerable role in today's washing and cleaning agents. They are used, for example, as builders or cobuilders for the surfactants. They have a wide range of tasks, the binding of calcium and / or magnesium ions from the present water hardness being mentioned as an example.
• insoluble polyanionic components which, like the previously discussed dirt-collecting auxiliaries, are also used in a manually and / or mechanically separable form - the polycationic components used can be negatively influenced Avoid auxiliary substances (PQAV) and the polyanionic auxiliary substances discussed here. Both components are provided in such a way that they are spatially separated from one another in the solid phase, such that each of these auxiliaries can develop its effect without being substantially impaired by the auxiliary material which has the opposite polarity.
• PQAV auxiliary substances
• the teaching according to the invention covers the joint use of the PQAV auxiliaries and the polyanionic insoluble auxiliaries in the presence or in the absence of the previously discussed third collector component, which is particularly suitable for taking up the oleophilic dirt from the washing solution.
• Natural and / or synthetic solids with a plurality of anionic acid residues are particularly suitable as the insoluble polyanionic solid phase.
• examples include insoluble components containing carboxyl groups, sulfonic acid esters, phosphonic acid groups and the like.
• PQAV Polyfunctional quaternary ammonium compounds
• An important area of use for such compounds is in the field of cosmetic preparations, in particular for the treatment or conditioning of hair. It is a known characteristic of the PQAV that they are capable of being coated on solid surfaces, this capability being possible in particular in the presence of customary surfactant components. Depending on the constitution, the absorbency and the adhesive strength of the PQAV on the solid base are different. The individual constitution of the PQAV plays a crucial role here. For the behavior of PQAV under the influence of aqueous surfactant baths, however, interaction with anionic surfactant components in particular can also be of crucial importance.
• anionic surfactant salt With stoichiometric or approximately stoichiometric amounts of the anionic surfactant components, the corresponding anionic surfactant salt generally forms on the quaternary ammonium group.
• PQAV anionic surfactant salts generally show a greatly reduced water solubility. Corresponding precipitates form, see for example the German Offenlegungsschrift 22 42 914.
• Such anionic surfactant salts from PQAV have been proposed as antistatic agents for application to fibers.
• these previously known PQAV are oligomers and / or polymers which have a plurality or a plurality of quaternary ammonium groups on their oligomeric or polymeric matrix. Adequate water solubility of the PQAV is generally required for use in the field of cosmetics.
• the use of PQAV according to the invention calls for the insolubility of the PQAV-based auxiliaries used as dirt collectors in the aqueous surfactant washing or cleaning solutions.
• the insolubility of the PQAV components used as dirt collectors in the sense of the invention is in fact an indispensable prerequisite, particularly for the field of textile washing. If this critical precondition according to the invention is not met, the washing result is reversed to the contrary. Soluble PQAV components sliding into the wash bath are absorbed onto the textile goods to be washed and there bind undesirably additional amounts of pigment dirt.
• Suitable originally water-soluble or water-insoluble PQAV in the sense of the invention preferably have an average molecular weight of at least about 200, preferably at least about 300 and in particular at least about 1000.
• the upper limit of the PQAV is basically meaningless and is, for example, 50 million, e.g. 10 million. This is understandable from the requirement of the insolubility of the PQAV required according to the invention. If this is ensured, there are no upper limits to the molecular weight.
• PQAV polymers which carry quaternary ammonium groups either in the polymer chain or bound to the polymer chain
• PQAV polymers which carry quaternary ammonium groups either in the polymer chain or bound to the polymer chain
• Such quaternary ammonium groups can also be derived from cyclically bound nitrogen.
• Examples of such quaternary ammonium groups are corresponding members of 5- or 6-membered ring systems, for example of morpholine, piperidine, piperazine or indazole rings. Numerous examples of such water-soluble PQAV are described in more detail, for example, in US Pat. No. 4,240,450.
• Homopolymers or copolymers with cyclic units can be particularly suitable.
• Commercial products with this structure include Merquat (R) 100 and Marquart (R) 550 (Quaternium 41).
• PQAV poly(vinyl)-styrene resin
• cellulose ethers the anhydroglucose units of which bear substituents with quaternary ammonium groups which are bonded via ether oxygen.
• Such polymers are known, for example, from US Pat. No. 3,472,840.
• a commercial product with this structure is, for example, the Polymer-JR (R) 400.
• Suitable cationic polymers are, for example, the quaternary polyvinylpyrolidone copolymers known from US Pat. No. 3,910,862 and available, for example, under the trade name Gafquat (R) 734 and 755, and those known from US Pat. No. 4,157,388 and, for example, under the trade name Mirapol (R) A15 available quaternary polymeric urea derivatives.
• Suitable copolymers with a polycationic character are also the polyacrylamide copolymers described in published European patent application 0 153 146, which in particular contain up to 50 mol% of a quaternized aminoalkyl ester of acrylic acid or methacrylic acid in addition to at least 50 mol% of acrylamide units.
• copolymers are water soluble. There they are applied to cloths based on cellulose fibers and are drawn up there due to their natural drawing power. Cloths of this type can be washed out and should then be used together with anionic surfactant-free surfactant systems for cleaning hard surfaces, in particular for cleaning glass. Under these conditions, they are characterized by an increased dirt absorption capacity.
• the cleaning wipes described in the publication are unsuitable for the use according to the invention in customary surfactant washing and cleaning liquors, which can also be exposed to temperature loads of up to about 95 ° C. Not insignificant proportions of the numerous PQAV copolymers described in the publication slip into the wash bath, pull onto the items to be cleaned and lead to increased pigment contamination. Only the conversion of such PQAVs to the physical state required according to the invention, as described below, makes them tools in the sense of the invention.
• Preferred PQAV as starting material are those compounds which, in solid form, cause difficulties in dissolving in water.
• Such cationic polymers are especially the cationic polygalactomannan derivatives known for example from GB-PS 1 136 842.
• Galactomannans are polysaccharides that occur in the endosperm cells of many legume seeds, but which are obtained on an industrial scale only from locust bean gum, guar gum and tara gum. They are made up of a linear Mannan main chain, consisting of beta- (1.4) -glycosidically linked mannopyranose building blocks, to which individual galactopyranose residues are fixed as branches in an alpha- (1.6) -glycosidic bond. The main difference between the individual polygalactomannans is the mannose-lactose ratio.
• the cationic derivatives of the polygalactomannans are produced by reacting hydroxyl groups of the polysaccharide with reactive quaternary ammonium compounds.
• Suitable reactive quaternary ammonium compounds are, for. B. those of the general formula in the R1, R2 and R3 z.
• B. methyl or ethyl groups and R4 an epoxyalkyl group of the formula or a halohydrin group of the formula mean and in which R5 an alkylene group with 1 - 3 C atoms, X chlorine or bromine and Z an anion such.
• B. is chloride, bromide, iodide or hydrogen sulfate.
• the degree of substitution should be at least 0.01 and preferably at least 0.05 and is typically between 0.05 and 0.5.
• a particularly suitable quaternary ammonium derivative of a polygalactomannan is e.g. B.
• the PQAV used are insoluble in the wash liquor under the conditions of use, so that can load the surface of the arbitrarily shaped means with dirt particles and hold them until the end of the process.
• insoluble PQAV There are several ways to obtain such insoluble PQAV. It is known, for example, to crosslink water-soluble PQAV by reaction with at least bifunctional crosslinking agents in such a way that water-insolubility which is sufficient for the purposes of the invention is achieved.
• the selection of the appropriate crosslinking agent is determined by the structure of the compounds to be crosslinked in the individual case, taking general chemical expertise into account.
• a flat structure for example a random fiber fleece or a woven or knitted cloth based on natural fibers and / or synthetic fibers, can be reacted with a coupling component e.g. B. epichlorohydrin and subsequent reaction with a basic nitrogen compound with subsequent quaternization to the desired dirt-collecting liquor cleaner.
• a coupling component e.g. B. epichlorohydrin
• a basic nitrogen compound with subsequent quaternization to the desired dirt-collecting liquor cleaner.
• suitable reactive quaternizing agents are the quaternary ammonium compounds described in connection with the aforementioned British Patent 1 136 842 reactive epoxy grouping or their reaction products with hydrogen halide to form the associated halohydrin group.
• Particularly easily accessible and inexpensive starting materials for such a reactive surface modification which are insoluble in washing or cleaning liquors of the type mentioned are natural substances of the cellulose type, insoluble cellulose derivatives and other insoluble or insolubilized poly-saccharide-like natural substances or their derivatives.
• the introduction of quaternary residues containing ammonia proceeds without problems here, the polyaccharide components used as carriers are either insoluble from the outset - for example in the case of cellulose - or easily converted to the insoluble state by simple chemical reactions, for example with polyfunctional crosslinking agents.
• a granulate, or powdery solid material based on natural materials is usually easier and therefore cheaper to obtain than a flat structure, for example in the sense of woven or knitted cloths.
• the use of such granular or powdery auxiliaries with an insoluble polycationic surface can also be of particular importance for practical use in the washing process.
• very low average substituents already result Degree of tion in the surface of the natural product or natural product derivative to effective results in the sense of the trade according to the invention.
• the embodiments which provide a water-insoluble carrier in flat or granular form, on the surface of which PQAV are applied by sufficient fixation in a preferably thin layer in such a way that they do not slide off into the wash bath during the washing process can also be of particular practical importance.
• the solidification of a polymeric PQAV coating on a shaped base body can be promoted by forming or having anionic groups in or on the surface of the base body.
• anionic groups are carboxyl groups, for example by carboxymethylation in the surface of the base body can be introduced, or other acid groups such as sulfonic acid residues. Further information can be found, for example, in US Pat. No. 3,694,364.
• the cationic PQAV coating then binds salt-like to these counterions of the matrix, so that the solidified bond between the insoluble solid and the applied PQAV layer is created in this way.
• a basic body based on cellulose fibers, in which free carboxyl groups have been introduced into the cellulose molecule, may be mentioned merely as an example of this embodiment.
• a particularly simple, insoluble connection between the inert carrier and the insoluble PQAV layer applied can be achieved by implementing the so-called coating principle. If, for example, a fine-grained, shaped, inert, insoluble carrier is coated with a PQAV layer - ideally covering the entire area - and this PQAV layer is then converted to the required state of insolubility, the inseparable union between the inert carrier core and the enveloping PQAV layer is also realized here, itself if there are no special binding forces between these two materials.
• the conversion of the PQAV layer to the insoluble material can, for example, take place again chemically by crosslinking this enveloping material layer.
• the application of this coating principle is understandably not limited to granular cleaning boosters.
• the quaternary ammonium group in the PQAV components used according to the invention preferably contains 1 to 3 lower alkyl radicals each having 1 to 6, in particular 1 to 3, carbon atoms.
• the quaternary ammonium group which has 1 to 3 alkyl residues and contains, as counterion, residues of such acids, as are usually to be expected in the washing process, can be of particular importance. Examples of this counter ion are chloride and / or sulfate Convert the presence of anionic surfactants to the corresponding anionic surfactant salt group, see the references DE-OS 22 42 914 and "SF ⁇ W" 1985, 530.
• any insoluble materials of an inorganic and / or organic type are suitable as insoluble carrier materials for fixing PQAV and thus for the immobilization of these dirt-collecting active components, provided that they are otherwise inert in the washing solutions.
• Suitable organic materials can be of vegetable origin.
• Preferred inorganic carriers are mineral substances of natural and / or synthetic origin, which are in the form of finely divided solids.
• PQAV-coated carrier substances having a specific surface area of at least about 0.5 m2 / g are preferably used according to the invention, this specific surface area in particular preferably being at least 1 m2 / g.
• the specific surface is understood to be the area that can be covered with PQAV.
• Certain minerals that are particularly suitable here have additional surface areas inside the solid phase - be it due to their pore structure or their ability to swell - which, however, are not or only to a limited extent accessible with PQAV.
• the verifiable outer surface can, however, reach considerable values, which lead to the range of 100 m2 / g or even up to, for example, 300 m2 / g.
• Colloidal silicas may be mentioned as examples of such extreme surfaces which can be covered with PQAV.
• the maximum particle sizes of the PQAV-loaded fine particles are preferably not above about 100 ⁇ , preferably not above about 40 ⁇ - these numerical values are based on the absolute particle diameter and mean that all or at least the vast majority of the fine particles present Framework conditions ent speak. Particles which have an average particle size (volume average) of at most about 10 .mu.m can be particularly useful for textile washing, the absolute particle size also being below this value, at least for the majority of all solid particles.
• Suitable inorganic carriers are in particular insoluble and finely divided salts, oxides, silicates and the like.
• aluminosilicates of the type of zeolites or zeolite-like compounds are particularly suitable, in particular sodium zeolite A which is widely used in detergents today.
• zeolite A can also be used in an exchanged form e.g. find use as calcium salt.
• a particularly suitable mineral carrier class is swellable, finely divided substances of the type of clays and / or swellable layered silicates, in particular from the smectite class.
• Swellable inorganic minerals of this type are characterized by a particularly large surface when swollen. This can be used within the scope of the invention.
• the known smectite clays montmorillonite, hectorite and / or saponite are particularly suitable here.
• comparable synthetic materials with only limited swellability are also suitable, as are described, for example, in the earlier application P 35 26 405.5 (D 7031).
• insoluble and / or PQAVs immobilized on insoluble carriers are used as dirt-absorbing emollients, the counteranions of which - originally present from the quaternization reaction - are at least partially replaced by surface-active agents before use in the washing or cleaning liquor. It may be preferred to use corresponding reaction products between the original PQAV and the surface-active agents, in which at least 50 equivalent percent and ins especially at least about 80 equivalent percent of the quaternary ammonium groups are activated for their counter anion by exchange with the surfactants.
• the activation of the quaternary ammonium groupings is carried out by using at least equivalent amounts of PQAV on the one hand and surface-active agent on the other hand in the preparation stage of the dirt-absorbing emollient.
• PQAV surface-active agent
• surfactant components which are capable of such an exchange of the counter anion originally present are used as surface-active agents.
• the counter anion can be replaced by known anionic surfactants with a surfactant character.
• Particularly suitable surfactant surfactants for the formation of the PQAV / surfactant complexes are anionic surfactants of the type of wash-active alcohol sulfates, for example fatty alcohol sulfates of natural and / or synthetic origin, corresponding wash-active alcohol ether sulfates which, for example, from fatty alcohols by alkoxylation, in particular by ethoxylation with up to 5 EO -Groups and subsequent sulfation have been prepared, but also conventional soaps or other carboxylic acid salts, mixed types of the type of alpha-sulfofatty acid disalts or the corresponding ester sulfonates.
• wash-active anionic surfactants can be used, as are listed in numerous detergent chemistry publications.
• Suitable agents for pretreating PQAV are, however, amphoteric surfactants, for example of the amphoteric surface-active agent type of the aminocarboxylic acid type.
• the pretreatment of the insoluble PQAV with surfactants which are not to be addressed as anionic surfactants or amphoteric surfactants is also of particular importance according to the invention.
• Non-ionic surfactants are particularly suitable here as activation components. Details on this known class of substances can be found in the previously cited reference "Ullmann" loc. Cit.
• swellable layered silicates of the smectite group mentioned above and in particular the use of swellable, finely divided montmorillonite, hectorite or saponite can be modified as follows: To create the largest possible surface that is ready for PQAV absorption, it is recommended to pre-swell these swellable materials. This pre-swelling is possible in the purely aqueous phase, but in a special embodiment, the inner regions of the swellable materials can be designed such that they take on an additional function within the scope of the dirt collector according to the invention.
• suitably equipped layered silicates can also be used as a mixture component together with the solids according to the invention which serve as pigment dirt collectors.
• dirt-absorbing slimming agents which contain an impregnation with PQAV or PQAV / surfactant complex on an organic and / or inorganic insoluble carrier, then it may be preferred to determine the amount of this impregnation - based on the total weight of the impregnated solid - To keep in the range of about 0.01 to 20 percent by weight and in particular in the range of about 0.1 to 10 percent by weight.
• the amount of PQAV or PQAV / surfactant complex to be used in the detergent is matched to the expected dirt load. If it is intended to use these dirt absorbers only once, even the smallest amounts of these absorbers are sufficient to bind the pigment dirt that is usually obtained, for example, in textile washing.
• PQAV components of the type concerned here are able to bind the same to pigment dirt up to a multiple of their weight - in particular due to the spreading of the PQAV on the carrier substrate and thus the thickness of the PQAV layer solidified there.
• the finely divided dirt absorber can then be separated from the wash liquor in a separate process step. This is possible, for example, by filtration using so-called precoat filters.
• the principle of pigment dirt collection by PQAV-loaded solid carriers can also be used in this second process step.
• the fine solid particles in the surfactant-containing solution can be regarded as conditioned particle dirt, which can be held on a separately arranged solid with PQAV / surfactant complex loading. It is thus possible, for example, to route the used washing liquor containing the finely divided dirt collector via sacrificial substrates, which in turn are loaded with PQAV / surfactant complexes. In this stage, the primary dirt-laden solids collector is held on the sacrificial substrate so that the cleaned washing liquor can be drawn off and used again, while the now loaded sacrificial substrate can be discarded, for example.
• the core of the teaching according to the invention is the knowledge that by incorporating the insoluble or insoluble immobilized PQAV compounds - and in particular the PQAV / surfactant complexes in the previously described sense - as an integral part of the auxiliaries for textile washing, a reduction in the need for conventional chemicals in the washing - and cleaning agents is possible. This affects in particular the proportion of chemicals that affect the removal of particle dirt. The extent of this reduction is determined by the level of performance required and the working conditions used conditions. Conventional framework formulations for textile detergents of all kinds and requirement profiles are known to the experts and are described in numerous literature references. Reference is also made to the information in the earlier application mentioned for P 35 45 990.5 (D 7478/7495). In each case, the washing and cleaning power of systems according to the invention can be determined by simple preliminary tests and - taking into account the desired cleaning result - the extent of the reduction in conventional chemical components can be determined.
• the detergency of the detergent formulations used in the following examples is determined on the known artificially soiled test fabrics on the basis of different fibers and soils, which are common today in practice in the review and development of detergent formulations and some of which are commercially available or from the detergent industry own pattern.
• Well-known manufacturers of corresponding commercially available, artificially soiled test fabrics are EMPA, Eidgenössische Material developmentss- und reliesweg, Unterstrasse 11, CH-9001 St. Gallen; Laundry research Krefeld, WFK-Testgewebe - GmbH, Adlerstrasse 44, D-4150 Krefeld; Testfabric Inc., 200 Blackford, Ave. Middlesex, N.J. UNITED STATES.
• the washing tests for determining the primary washing power have been carried out with soiled standard test cloths based on polyester / cotton-refined, soiled with pigments and skin fat (H-SH-PBV).
• the degree of soiling of the untreated starting material and the washed tissue samples is determined by measuring the degree of remission with the Elrephomat DSC 5 (Carl Zeiss, Oberkochen, FRG).
• the degree of soiling of the PBV test tissue used in this way is 30.0 (% remission).
• the washing tests are carried out in the launderometer.
• the respective working conditions are given in connection with the examples.
• Test cloths based on polyester / cotton fabric soiled with standard soiling are used as items to be washed (standard soiling H - SH - PBV).
• test series 1 The approaches of test series 1 are repeated. However, instead of the surfactant additive from test series 1, 5 g of a high-quality powdery textile standard detergent are used per liter of washing liquor.
• Cellulose powder with an average particle size below 50 ⁇ is quaternized to an average degree of substitution (MS) of 0.05 with 3-chloro-2-hydroxypropyltrimethylammonium chloride.
• the quaternized product is drizzled with the aqueous solution of a fatty alcohol ether sulfate (Texaphon NSO) and mixed intimately.
• the weight ratio chosen is 10 parts of the quaternized cellulose to one part (active substance) of the surfactant component.
• the mixing time is at least 15 minutes each.
• the surfactant-treated quaternized cellulose powder is washed intensively several times with distilled water at room temperature before use, in order to remove any excess surfactant from the cellulose powder.
• 4 successive launderometer washes are again carried out under the conditions specified above.
• the washing results - determined as% remission - are as follows: after 1 wash 48.6 after 2 washes 45.8 after 3 washes 40.6 after 4 washes 37.0
• washing result is significantly improved compared to washing in the absence of the PQAV.
• the result of the 3rd wash corresponds approximately to the first wash result with the PQAV-free detergent fleet.
• Powdered quaternized cellulose is quaternized to a mean degree of substitution of about 0.3 with 3-chloro-2-hydroxypropyltrimethylammonium chloride.
• the effect of the addition of increasing amounts of this insoluble PQAV on the washing effect of a purely non-surfactant liquor while increasing Amount of nonionic surfactant is examined.
• the nonionic surfactant used is a fatty alcohol ethoxylate with an average of 7 ethoxy groups in the polyethoxyl radical (Dehydol LT 7).
• the conditions of the washing tests are as follows: Launderometer wash 30 ° C, 16 dH, liquor 1: 30, 10 steel balls H-SH-PBV fabric, 30 min. Wash, rinse 4 ⁇ 30 sec Dosage: 0.1, 0.2, 0.3, 0.4, 0.5 or 1.0 g nonionic surfactant / l + 0, 1.0, 1.5, 2.0 and 3.0 g PQAV / l
• Example 3 The washing tests of Example 3 are repeated. However, a fatty alcohol mixed ether (EO-PO adduct "Dehypon LS 54") is now used as the nonionic surfactant.
• EO-PO adduct "Dehypon LS 54” a fatty alcohol mixed ether
• Washing tests are carried out using a purely non-surfactant wash liquor several times. The following conditions apply in detail. Launderometer wash, 30 ° C, 16 ° dH, liquor 1: 30, 10 steel balls, H-SH-PBV fabric, 30 min. Wash, rinse 4 ⁇ 30 sec
• the quaternized cellulose is first drizzled with the nonionic surfactant component - as a 10% aqueous solution - the mixture is left to stand for about 10 minutes with occasional shaking. The mixture is then diluted with water to the chosen liquor concentration.
• test series A shows the washing results with the purely non-ionic surfactant liquor
• test series B shows the washing results of the PQAV / non-ionic surfactant liquor.

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• 1986
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