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
  • 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
  • C11D3/16—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
  • C11D3/26—Organic compounds containing nitrogen
  • C11D3/30—Amines; Substituted amines ; Quaternized amines
• • 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
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
  • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y10S210/00—Liquid purification or separation
  • Y10S210/902—Materials removed
  • Y10S210/908—Organic
  • Y10S210/91—Nonbiodegradable surfacant

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
• the present teaching extends the novel application of such PQAV to the extent that improvements are not only in terms of of the washing result on the textile to be cleaned, new possibilities are also shown to be able to use surfactant washing and cleaning agent solutions of the type described more effectively and efficiently.
• the teaching according to the invention in particular creates the possibility of reuse, possibly a multiple reuse of the aqueous phase of soiled cleaning liquors, by treating these liquors with the insoluble or immobilized PQAV described in the earlier application mentioned, soiling the solubilized dirt in the liquor at least partly on the undissolved PQAV depressed and thus the contaminated cleaning liquor is at least partially freed from its contamination. All or part of the aqueous liquor treated in this way can be reused for new cleaning operations.
• the present invention accordingly relates to the use of PQAV in aqueous washing and cleaning solutions are at least largely insoluble and / or are immobilized on solids correspondingly insoluble in these aqueous solutions for the at least partial cleaning of dirt-laden aqueous surfactant cleaning liquors, this procedure being intended in particular for subsequent reuse of at least a portion of the cleaned washing liquor.
• the procedure according to the invention is particularly suitable for aqueous alkaline detergent-containing cleaning liquors such as are known, for example, as washing liquors from textile washing.
• Such soiled washing liquors from textile washing are treated according to the invention with the insoluble or insoluble immobilized PQAV and thus regenerated by removing at least a portion of the suspended dirt from the used washing solution.
• the PQAV are present in the form of insoluble solids or immobilized on insoluble solids and, moreover, are used in such a form that a manual and / or mechanical separation between the dirt-laden PQAV solid phase and the treated washing liquor is possible after the cleaning treatment
• the washing liquor can be recycled in subsequent washing cycles.
• the dirt-collecting PQAV in the heterogeneous solid phase of the washing liquor are already used during their use as washing or. Cleaning solution added.
• This embodiment is already the subject of the earlier application P 35 45 990 (D7478 / 7495).
• a separation between the wash liquor and dirt-collecting PQAV component is also provided, which enables the reusability of the surfactant-containing liquid phase.
• a washing or cleaning process - for example a textile wash - is first carried out in the usual manner. Subsequently, the soiled wash liquor is then subjected to regeneration in the sense of the invention, whereupon the wash liquor, which has been at least partially cleaned, can be reused in whole or in part.
• any combination of these two basic principles can be set.
• the following combinations may be mentioned here by way of example:
• the washing liquor is mixed with PQAV components in the sense of the invention; after the washed goods have been separated off, the washing liquor used is fed to an additional cleaning step by means of PQAV.
• a partial stream of the wash liquor is withdrawn from the washing process batchwise or continuously during the washing process and passed through a process stage in which the dirt discharge takes place by means of heterogeneous PQAV components within the meaning of the invention, whereupon this partial stream is returned to the washing process in whole or in part can be.
• the principle of concomitant use of heterogeneous PQAV components can be used in the main washing process, but this principle can also only be implemented in the partial lye stream withdrawn.
• the washing and cleaning process for example in the context of a textile wash, can be divided into two areas.
• the first area covers that Breaking up and detaching the dirt from the soiled textile material
• the second working area of the detergent solution used ensures that the detached dirt is suspended in the washing liquid so that the detached dirt is rinsed out as completely as possible without repositioning on the textile.
• chemical auxiliaries for example surfactants, co-surfactants, dirt-carrying agents and the like - has hitherto been necessary.
• the PQAV components present according to the invention as a heterogeneous solid phase absorb, in particular, negatively charged portions, for example corresponding particle dirt, from the dirt-laden liquor.
• the PQAV solid material can have a cleaning or cleaning-enhancing effect due to other surface forces. In the important others described below Embodiments are 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 high absorption capacity for oleophilic soiling.
• selected plastics for example polyethylene or polypropylene or polyurethane or also superficially highly hydrophobic finished insoluble solids of any origin, have the ability to pull the oleophilic dirt from a wash liquor which has been hydrophilized under the action of surfactants and to hold on to its surface.
• this working principle is used in one embodiment of the invention.
• the collectors for such oleophilic dirt can be used, for example, in the form of flakes, fibers or fibrous structures such as cloths, random fiber fleece, poromer skins and the like. What is essential for this component is only the condition previously specified for the PQAV cleaner that a manual and / or mechanical separation between the liquid phase and the dirt collector present in the solid phase is ensured.
• the oleophilic dirt-collecting auxiliaries can be used simultaneously 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. The embodiment of the invention concerned here goes beyond this prior art:
• insoluble polyanionic components which, like the previously discussed dirt-collecting auxiliaries, can also be used in a manually and / or mechanically separable form - enables the additional removal of such dirt or load components from the used washing solution which are positively charged.
• Such components can arise, for example, in the course of dye transfer or as decomposition products from bleaching processes.
• PQAV polycationic auxiliaries
• Both collectors are so spatially separated from each other in the solid phase that each of these auxiliaries can develop its cleaning effect without being substantially impaired by the auxiliary agent equipped with the opposite polarity.
• the teaching according to the invention covers the joint use of the PQAV auxiliary substances and the polyanionic insoluble auxiliary substances in the presence or in the absence of those previously discussed th third collector component, which is particularly suitable for the absorption of 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 residues, phosphonic acid groups and the like. It is known that components of this type are attributed to a strong increase in washing power in the primary washing process. The use of compounds of this type as water-soluble components in laundry detergents is widespread today, although there are certain reservations about their use. In the embodiment discussed here, the teaching of the invention provides for the use of such components in a heterogeneous solid phase and at the same time in such a way that it is possible to separate these solids with functional groups from the washing solution, so that the uncontrolled release of corresponding compounds into the waste water from the outset is excluded.
• the dirt collector used according to the invention can be used in any physical configuration that allows loading with dirt particles and nevertheless allows the possibility of manual and / or mechanical separation of the undissolved material from the washed goods and from the cleaning liquor.
• two physical forms of state come into consideration, namely use the PQAV or the correspondingly insoluble solid materials impregnated with PQAV in the form of larger, space-filling shaped bodies, for example as sheet-like structures, in particular as sheets, foils or as a cloth or in the form of filter bodies and, on the other hand, as finely divided solid, which is found, for example, in the wash liquor during the washing process can be dispersed, but after the washing process is removed with the wash liquor and thus separated from the washed goods and ultimately also from the cleaned wash liquor.
• the separate treatment of the dirt-laden washing liquor in a cleaning step in the sense of the invention provides, for example, the single or multiple passage of the liquid phase to be cleaned through a solid filter which contains the insoluble or immobilized PQAV on insoluble solids. Simultaneously with this or in separate cleaning steps, the aforementioned further insoluble auxiliary substances based on strongly oleophilic materials or based on polyanionic solids can be used.
• 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.
• Suitable organic mate rialien are, for example, those of plant origin that can be more or less finely divided. Sawdust may be mentioned as an example of a particularly finely divided material; an example of suitable carrier materials of vegetable origin of a coarser nature are plant remains such as straw, wood shavings and the like. These carriers may have been subjected to a pretreatment to remove those portions which could give rise to problems in the subsequent treatment in detergent solutions.
• Suitable inorganic carriers are in particular insoluble and in particular finely divided salts, oxides, silicates and the like. These can be substances of natural and / or synthetic origin. Particularly suitable are, for example, aluminosilicates of the type of zeolites or zeolite-like compounds, in particular sodium zeolite A, which is widely used in detergents today. In its place, however, zeolite A can also be used in an exchanged form, for. B. 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 leads to a considerable activation of the cleaning effect of the PQAV used.
• the outer surface of detergent-quality crystalline zeolite A is usually in the range of 3-4 m2 / g.
• This material can be a useful basis.
• those materials which are particularly suitable can also be have a much larger surface, as is the case, for example, in the case of smectite clays, in particular montmorillorite, hectorite and / or saponite. Specific surfaces of these materials can range up to or even exceed 700 m2 / g. In this case, particularly effective auxiliary substances for the absorption of the detached dirt are then given.
• the application and at the same time the activation of PQAV compounds can be promoted in particular by the fact that anion-surfactant components are also used here.
• the anionic surfactant can be applied to the carrier to be coated in a mixture with the PQAV, but it is also possible to first load the carrier with PQAV and then to treat the carrier prepared in this way with the anionic surfactant compound. It is also possible first to form an anionic-surfactant coating on the carrier and to deposit PQAV on it. In all cases it can be seen that the effectiveness of dirt traps prepared in this way is substantially increased.
• the anionic surfactant component is used at least in such an amount that a substantial proportion of the quaternary ammonium groups - for example at least about 50 mole percent - can react with the anionic surfactant. It may be preferred to use at least approximately equimolar amounts of anionic surfactant and PQAV, and in one embodiment of the invention it is possible to use the anionic surfactant in a stoichiometric excess in addition to the available quaternary ammonium groups.
• Particularly suitable anionic surfactants for this purpose are, for example, corresponding alcohol sulfates and / or alcohol ether sulfates, e.g. B.
• fatty alcohol sulfates and / or fatty alcohol ether sulfates which are derived from natural and / or synthetic fatty alcohols with in particular 10 - 22 C atoms, in particular 12 - 18 C atoms and have corresponding residues of ethylene glycol or ring-opened ethylene oxide as ether or polyether intermediate group.
• 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.
• 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 the PQAV under the influence of aqueous surfactant baths, however, the interaction with especially anionic surfactant components are of crucial importance.
• anionic surfactant salts 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.
• anionic surfactant salts from PQAV have been proposed as antistatic agents for application to fibers. In this context, however, it is also known that excesses, in particular considerable excesses of the anionic surfactant, can lead to a redissolution of the primarily precipitated PQAV / anionic surfactant salts, cf.
• 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, in particular 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 draw towards this washing textile goods and bind there additional amounts of pigment dirt in an undesirable manner.
• Suitable originally water-soluble or also 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, 10 million or even at far higher values. 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 immobilized on an insoluble carrier is suitable for all polymers which carry quaternary ammonium groups either in the polymer chain or bound to the polymer chain.
• 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.
• 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 the published European patent application 0 153 146, which, in addition to at least 50 mol% of acrylamide units, contain up to 50 mol% of a quaternized amino alkyl ester of acrylic acid or meth contain acrylic acid. These 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 inconsiderable 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 individual polygalactomannans differ mainly in 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.
• guar-hydroxypropyl-trimethylammonium chloride which is linked to the oxygen atoms of the hydroxyl groups of the polysaccharide cationic groups of the formula wearing.
• Such cationic guar derivatives are e.g. B. under the trade name "Cosmedia Guar C 261" on the market.
• the degree of substitution (DS) of Cosmedia Guar C 261 is about 0.07.
• the PQAV used are insoluble in the wash liquor under the conditions of use, so that the surface of the arbitrarily shaped agent can be loaded with dirt particles and hold it until the process is complete.
• 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.
• the surface of insoluble or insolubilized, shaped natural products and / or corresponding synthesis products can be removed by processes known per se chemical reaction with quaternary ammonium groups. Process steps are used for this, as are known in principle for the production of water-soluble and / or water-swellable PQAV from the literature cited at the beginning. This is exemplified as follows: 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 basic nitrogen compound with subsequent quaternization to the desired dirt-collecting liquor cleaner.
• Other suitable reactive quaternizing agents are the quaternary ammonium compounds with a reactive epoxy group described in connection with the aforementioned British Pat. No. 1 136 842, 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 degrees of substitution in the surface of the natural product or natural product derivative lead 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, which can be introduced into the surface of the base body, for example by carboxymethylation, 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.
• carboxyl-bearing compounds into the viscose is e.g. achieved by admixing alkali metal salts of acrylic acid homopolymers, acrylic acid-methacrylic acid copolymers, methyl vinyl ether-maleic anhydride copolymers, alginic acid or carboxymethyl cellulose to the viscose solution and subsequent spinning in a conventional manner in a precipitation bath.
• alkali metal salts of acrylic acid homopolymers, acrylic acid-methacrylic acid copolymers, methyl vinyl ether-maleic anhydride copolymers, alginic acid or carboxymethyl cellulose to the viscose solution and subsequent spinning in a conventional manner in a precipitation bath.
• Commercial products based on such cellulose fibers and on the basis of fibers modified with carboxymethyl groups are available for many applications.
• such fibers or carrier materials produced therefrom are coated with an insoluble PQAV layer and are therefore inextricably bonded for the intended use.
• 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 shape-shaped inert insoluble carrier with a PQAV layer - ideally covering the entire area - and then converting this PQAV layer to the required state of insolubility, the inseparable union between the inert support core and the enveloping PQAV layer is also realized here, even 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 counterion are chloride and / or sulfate, which, however, convert to the corresponding anionic salt group in the presence of anionic surfactants, see the references DE-OS 22 42 914 and "SF ⁇ W" 1985, 530.
• Such PQAV / anionic surfactant salt groups may have been formed in the cleaning booster according to the invention even before it was introduced into the liquor.
• insoluble and / or PQAV immobilized on insoluble solids are used as dirt-collecting cleaning boosters, in which the quaternary ammonium groups characteristic of this substance class are at least partly replaced by non-quaternized basic amino groups and in particular by tertiary amino groups.
• All other information on the Er Description of the invention apply here analogously.
• the basis for this modification is the finding on which this embodiment of the invention is based that those polycationic components and in particular those cationic polymer compounds are also suitable for the purposes of the invention which do not derive their functionality or only partially from quaternary ammonium groups, but otherwise from basic amino groups.
• the preferred non-quaternary basic amino group is the tertiary amino group.
• polycationic compounds of this type are also capable of loading themselves with suspended dirt particles from the wash liquor.
• Polycationic tertiary amino compounds of the type concerned here are then either to be used either as at least largely insoluble solids or as components which are soluble or swellable per se and which in turn are immobilized or insolubly fixed on sufficiently insoluble support materials.
• the content of quaternary ammonium groups here preferably bears at least about 5% based on the sum of quaternary and non-quaternary base groups.
• polycationic compounds of this type is the GAF "Copolymer 937" (R) , which is a PVP-dimethylaminoethyl methacrylate copolymer with an average molecular weight of approximately 1,000,000.
• the respective amount of dirt-collecting PQAV used in the narrower or broader sense of the description of the invention is given by the given and determinable in the individual case units or conditions. They can be determined by the expert by simple experiments.
• the amount of PQAV collecting dirt used in a washing cycle is preferably selected such that at least a substantial proportion, for example at least about 50, preferably at least about 75%, of the loading of the washing liquor with suspended dirt particles can be absorbed by the dirt collector. It is generally advisable to provide formulations that provide such an amount of PQAV that excess capacity of the PQAV is available.
• the dirt collector's ability to absorb dirt is in turn determined in particular by the amount of the functional quaternary ammonium groups or the basic amino groups having the same effect, in particular tertiary amino groups, which are available in individual cases.
• the respective degree of substitution of the PQAV used must therefore be taken into account here.
• the surface of the cleaning or washing power booster, which is insoluble in the wash liquor is another important variable which is considered in the considerations concerned here. Understandably, it can accordingly be preferred according to the invention to select state forms of the dirt-collecting cleaning amplifier which are distinguished by a particularly large surface area.
• highly disperse distribution states come into consideration here - for example solid particles with an individual particle size of up to approximately 1 mm and preferably below 100 ⁇ , in particular below 40 ⁇ and very particularly below approximately 10 ⁇ , as are known for the known detergent builders based on zeolite A or are known for finely dispersed silica.
• high surfaces are also provided by fabrics made from fibers or fiber bundles. From knowledge of the characteristic parameters present here in the respective individual case for the ones according to the invention set work equipment and the expected pollution load can then easily determine the minimum need for dirt-collecting cleaning or cleaning power for the individual case.
• 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, NJ USA.
• 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.
• Unfinished white cotton flaps (11 x 13 cm, approx. 2 g in weight) are drizzled with 2 g of the following active ingredient solution and then air-dried for several days: 0.5% by weight PQAV (Cosmedia Guar C 261) 53.6% by weight synthetic surfactant based on fatty alcohol ether (FAES) + (15% WAS, "Texapon N 25") 0.2% by weight preservative based on bromine-5-nitro-1,3-dioxane "Bronidox L”) 45.7 weight percent water
• PQAV contain cleaning enhancers and are used in laundering trials for repeated use of a wash liquor under standard washing conditions with standardized dirt tissue.
• Detergent dosage 5 g of a standard commercial detergent / l Launderometer conditions: 60 ° C, 16 ° ie, 10 steel balls, 30 minutes washing, 4 times 30 seconds rinsing Fleet ratio: 1: 30
• Loading In a first test series, two standardized dirt rags (H-SH-PBV) are washed together with two pieces of non-equipped filler fabric. In a parallel test, two corresponding standardized dirt rags (H-SH-PBV) are washed together with two filler fabrics that are equipped with the PQAV recipe specified above.
• Working and comparison conditions After the first wash cycle, the washed items are separated from the wash liquor, but the wash liquor is not discarded but saved for subsequent washing. The washing or lightening results set for the first wash are determined by determining the reflectance values.
• the two wash liquors separated from the first wash cycle are washed with the addition of new standardized dirty fabrics and the number of non-soiled filler fabrics comparable to the first wash cycle. Then the wash liquor is again separated from the washed goods and the lightening of the washed goods is measured by determining the reflectance values.
• the three washing liquors according to a), b) and c) are compared with regard to their washing action in multiple washing, ie in five successive washing tests, each with the same washing liquor, tested.
• the H-SH-PBV dirty fabrics to be cleaned are freshly used in these five successive washes.
• the PQAV used is fine-grain cellulose with an average degree of substitution (MS) of 0.05.
• a fatty alcohol ether sulfate (“Texapon N 50”) is again used as an additional anionic surfactant component.
• test series a) to g) and h) to n) are subdivided as follows:
• the blank values are determined with the pure detergent fleet a) or h).
• the additives (b to d or i to k) added during the first wash and then no longer renewed in the subsequent washes.
• washing liquors based on the powdered heavy-duty textile detergent "WMP” are used in a first series (1 to 3) and corresponding washing tests based on the liquid heavy-duty detergent "WMF” in a second series. used.
• the washing performance of the pure detergent liquor is compared with a corresponding liquor to which a predetermined amount of surfactant has been added and a second comparative liquor to which PQAV plus surfactant has been added.
• fine-grain cellulose (average particle diameter not larger than 50 ⁇ ) with an average degree of substitution (MS) of about 0.1 is used as PQAV.
• the co-surfactant used in this test series - test series 2/3 or 5/6 - is a fatty alcohol ethoxylate ("Dehydol LT 7").
• the working parameters used in all washing tests are as follows: Launderometer, 30 ° C, 16 ° dH, liquor 1:30, 10 steel balls, H-SH-PBV fabric, 30 minutes washing, 4 times 30 seconds rinsing 6 washes with the used washing liquor, but new test fabrics (on 2 H-SH-PBV / 2 filling fabrics).
• the composition of the washing liquors 1 to 6 is shown in Table 5 below.
• surfactant and PQAV are used together, present: PQAV, drizzle with surfactant (as a 10% solution), shake gently and let stand for approx. 10 minutes, then add the detergent solution.
• washing-active chemicals are inevitably removed from the fleet, so that the depletion of washing-active components that has finally occurred must lead to a breakdown of the washing power.
• 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 dosage of the commercial textile detergent is 3 g / l in both cases.
• the PQAV is added to the wash liquor without prior activation by means of surfactant treatment.

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• 1986
  • 1986-02-22 DE DE19863605716 patent/DE3605716A1/de not_active Withdrawn
• 1987
  • 1987-01-27 WO PCT/EP1987/000034 patent/WO1987005047A1/fr not_active Application Discontinuation
  • 1987-01-27 EP EP87101125A patent/EP0234311A1/fr not_active Withdrawn
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  • 1987-02-19 CA CA000530103A patent/CA1269298A/fr not_active Expired - Fee Related
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