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
  • C11D17/0034—Fixed on a solid conventional detergent ingredient
• • 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
  • C11D3/37—Polymers
• • 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
  • C11D3/3703—Macromolecular compounds obtained otherwise than by reactions only involving carbon-to-carbon unsaturated bonds
• • 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

Definitions

• the invention relates to new agents and methods which can be used in the cleaning of objects, in particular objects which are contaminated with pigment dirt. This particularly affects the washing or cleaning of all articles in a water-based surfactant liquor. The most important area of application for such cleaning processes is textile washing.
• the washing process of textiles with conventional detergents comprises breaking up and removing the soiling on or from the fiber.
• Considerable parts of the soiling are components that are insoluble in the wash liquor and pass into the wash liquor in the form of small undissolved particles. A sufficient suspension of the loosened dirt particles is then a prerequisite for effective washing in order to prevent their redeposition and at the same time graying of the washed items.
• Conventional detergents contain additives that serve this task in particular. Adequate dirt-carrying capacity is also seen as an important function of the builder components of conventional detergent mixtures, which are known to be synthetic surfactants components in admixture with such builder components.
• the detergent literature contains numerous suggestions for reducing the tendency to graying and thus improving the secondary washing power. Almost exclusively, all of these suggestions aim at the improved suspension, solubilization and stabilization of the particle dirt in the wash liquor, and especially in the rinsing phases of the washing process, in which the tendency to redeposition of detached particle dirt is increased by diluting the washing chemicals.
• US Pat. No. 3,694,364 describes a different approach in principle: Here it is proposed to use a so-called "dirt-trap" material to take up the undissolved particle dirt from the wash liquor, if appropriate together with the prevention of anionic dye transfer. This dirt trap material consists of a water-insoluble cellulose cloth with a modified surface.
• This surface is equipped with secondary and / or tertiary polyamine compounds which are to be retained on this surface by first giving the cellulose surface an anionic character. This is done by introducing acidic groups, for example by phosphorylation, carboxymethylation and the like.
• Polyethyleneimines which contain a degree of polymerization of 2 to 50,000, in particular 20 to 10,000, monomer units per molecule are designated as particularly suitable for the subsequent coating with polymeric amines and in which about 10 to 50% of the imino groups are occupied by stearic acid residues.
• Cloths equipped in this way are put into the washing process together with conventional textile detergents. Dirt is to be separated from the wash liquor on the surface of the cloth. These parts of the dirt can be separated from the washed goods after washing and discarded with the dirt trap cloth.
• the cited publication describes the manufacture and nature of the finished flat cellulose substrate structures. However, no further statements are made regarding the wash result that can be set.
• European Patent Specification 0 044 003 describes a liquid detergent which consists of selected nonionic surfactants in admixture with textile-softening quaternary ammonium salts, to which a cationic starch ether containing ammonium groups has been added.
• a liquid detergent which consists of selected nonionic surfactants in admixture with textile-softening quaternary ammonium salts, to which a cationic starch ether containing ammonium groups has been added.
• the invention is based on the object of creating improvements in the washing and cleaning of, for example, textiles, in particular with aqueous surfactant detergent liquors, which were previously not accessible in this form.
• the technical solution according to the invention provides for the use or the concomitant use of such components in the cleaning process - in particular in the case of textile washing - that are specifically suitable for the deposition of undissolved dirt particles and absorbed into the washing liquor and thus in particular for the collection of pigment dirt in the liquor during the washing process are suitable without negatively affecting the washing process itself.
• the use of these dirt traps should take place in such a physical form that after the cleaning or washing process has been completed, the manual and / or mechanical separation of the now contaminated auxiliaries from the washed items is possible.
• the invention thus aims to transfer the dirt from the items to be cleaned to auxiliary materials used in the cleaning process, which can then be separated from the cleaned items and discarded together with the dirt constituents collected by them, or - insofar as their capacity for loading the dirt is not yet full is used - can be returned to a washing process.
• the invention accordingly relates to the use of polyfunctional quaternary ammonium compounds - hereinafter referred to simply as 'PQAV' - which are insoluble in aqueous-surfactant washing and cleaning liquors, even under the temperature loads of the washing process, and / or in these aqueous-surfactant liquors Correspondingly insoluble solids cannot be washed off and are immobilized and present as cleaning dirt collecting particle dirt in aqueous-surfactant washing and cleaning liquors, which can be manually and / or mechanically separated from the items to be cleaned after washing or cleaning.
• the invention relates to textile detergents based on customary mixtures of surfactants, associated builders and, if desired, further customary washing aids such as bleaching agents, corrosion inhibitors, brighteners, foam inhibitors, graying inhibitors, enzymes, adjusting agents, fragrances and the like, these textile detergents being characterized in that they are used for Collection of particle dirt from the wash liquor additionally contain PQAV in finely divided and / or flat form, which are insoluble in aqueous-surfactant washing and cleaning liquors even under the temperature loads of the washing process and / or immobilized in these aqueous-surfactant liquors and are not washable immobilized are available.
• these insoluble, finely divided and / or flat PQAV serve as a cleaning amplifier which collects particle dirt and which can be manually and / or mechanically separated from the material to be cleaned after washing or cleaning.
• the invention relates to a method for cleaning enhancement of aqueous surfactant washing and cleaning liquors Using flat and / or finely divided undissolved solids entered into the fleets in the washing process, which bind suspended particle dirt from the aqueous surfactant liquor on their surface, hold there until the washing process is completed and in this form of the items to be cleaned manually and / or mechanically can be separated.
• the new process is characterized by the fact that PQAV are used as cleaning-enhancing solids which are insoluble even under the temperature loads of the washing process in the aqueous surfactant liquors and / or are immobilized in a washable manner on solids which are insoluble in these liquors.
• 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 precipitation forms compare for example 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 the PQAV according to the invention demands the insolubility of the PQAV-based cleaning boosters 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 actually particularly for the field of textile washing indispensable requirement. 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.
• the washing result is then almost reversed.
• an at least spotty, if necessary even completely flat gray textile is obtained.
• 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.
• all polymers are PQAVs which are initially water-soluble but then immobilized on an insoluble carrier suitable 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.
• 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.
• 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 through 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 dirt-collecting cleaning booster used according to the invention can be used in any physical configuration that allows loading of this cleaning booster with dirt particles and nevertheless allows the possibility of a manual and / or mechanical separation of the undissolved cleaning booster from the washed goods.
• two physical forms of state come into consideration, namely the use of PQAV or the insoluble solid materials correspondingly impregnated with PQAV in the form of sheet-like structures, in particular as a sheet, film or cloth and on the other hand as a finely divided solid which, for example, disperses in the wash liquor during the washing process can be, however, after the washing process is removed with the wash liquor and thus separated from the washed goods.
• the invention is described below in particular with reference to these two embodiments, which have as their object the use of the PQAV during the washing process in the washing liquor loaded with textile goods, for example, but it is not restricted to this. Other forms of use are also possible and fall within the scope of the invention.
• An example here is pumping over a washing liquor over a PQAV solid bed and recycling the washing liquor cleaned in this way, for example into the textile washing process.
• the new cleaning booster according to the invention for the field of textile washing, especially for machine textile washing, e.g. B. with household washing machines, two specific forms of application of the new cleaning booster according to the invention can be described: the incorporation of the cleaning booster according to the invention, preferably in the form of fine powders, into the usual textile detergents, e.g. Coarse detergent, on the one hand, and on the other hand the separate addition of the new cleaning booster to the wash liquor, i.e. separate from the usual washing-in of the washing powder.
• the usual textile detergents e.g. Coarse detergent
• both fine and coarser-grained solid formulations are suitable as the condition for the new dirt-collecting amplifiers, but in particular also the preparation of the material in the form of a flat structure, for example as a sheet, film or cloth.
• the new cleaning booster can be made available and used as a sheet-like material in roll form, a predetermined amount of the sheet-like material being separated from the roll for each washing process and additionally being added to the washing machine with the textile material to be washed.
• the simple manual and / or mechanical separability of the dirt collector from the washed items must be ensured. If the material is in the form of a sheet, its insolubility ensures that it is separated when the washed textile goods are removed. If the cleaning booster is used as a more or less fine-grained material, there are various forms of Ab - especially depending on the size of the grained material given separation. If the cleaning booster is metered into the wash liquor as an extremely finely divided and insoluble material, then it is drawn off and rinsed out together with the wash liquor in the usual way today together with other insoluble, finely divided components of the detergent mixture, for example with insoluble builder components based on zeolite. However, if the cleaning or washing power booster is used in coarser-grained form, manual separation can be achieved, for example, by shaking out the washed textile goods.
• Sheet-like or sheet-like configurations of the new dirt collector can be designed according to known manufacturing processes as random fiber fleece, fiber fabric or knitted fabric, preferably as an open-pore foam sheet, as a closed film or in any other form. The only requirement is that the surface washed by the wash liquor has the PQAV in insoluble form and in sufficient quantity.
• the PQAV used are insoluble in the wash liquor under the conditions of use, so that the surface of the arbitrarily shaped washing power booster can be loaded with dirt particles and holds them until the washing 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.
• 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 detergent booster.
• a coupling component e.g. B. epichlorohydrin
• a basic nitrogen compound with subsequent quaternization to the desired dirt-collecting detergent booster.
• 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 ammonium groups included Tender residues run 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 cleaning boosters 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.
• an average degree of substitution can be particularly suitable for cleaning reinforcement in the context of textile washing up to about 0.12 and preferably below 0.1.
• the lower limit will generally be the average degree of substitution in the range of approximately 0.01, with particularly good results being able to be obtained in the range from approximately 0.015 to 0.08 and in particular in the range from approximately 0.02 to 0.07. It is astonishing that fine cellulose powders of such a low degree of substitution bring about a substantial increase in washing power, particularly in textile washing.
• washing power enhancement includes the terms “primary washing power enhancement” and also “secondary washing power enhancement”.
• the improvement in the secondary detergency enhancement - that is to say the reduction in the graying tendency - is still understandable from the concept of the action according to the invention.
• suitable cleaning enhancers within the meaning of the invention, significant increases in the washing power of the primary washing result are also obtained, which can be measured as improvements in the degrees of lightening to be recorded in the course of a textile washing process on test sample contaminated with pigment. Details of this can be found in the following examples which explain 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.
• the cationic PQAV coating then binds salt-like to these counterions of the matrix, so that in this way the solidified bond between the insoluble solid and the worn PQAV layer is created.
• 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 group-bearing compounds into the viscose is achieved, for example, by admixing alkali salts of acrylic acid homopolymers, acrylic acid-methacrylic acid copolymers, methyl vinyl ether-maleic anhydride copolymers, alginic acid or carboxymethyl cellulose for 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, 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 under washing conditions, the inseparable union between the inert carrier core and the enveloping PQAV layer is also achieved 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.
• water-insoluble organic materials are suitable as a carrier for the dirt-collecting PQAV layer.
• Inorganic carriers are also of particular importance.
• water-insoluble inorganic carriers are to be considered in particular, which have already been used in the course of washing processes, in particular in the context of textile washing.
• Classic examples of this are natural or synthetic fine-particle aluminosilicates of the bentonite type or synthetic crystalline zeolites, in particular the detergent-grade phosphate substitute Zeolite A, which is widely used today.
• Suitable materials are silica, in particular colloidal silica of the Aerosil type, finely divided, swellable or non-swellable sheet silicates, in particular the montmorillonite group, water-insoluble, finely divided metal oxides and / or hydroxides or corresponding metal salts.
• alkaline earth metal salts such as calcium carbonate, calcium sulfate and the like or aluminum oxide and the like may be mentioned.
• a particular advantage can be the use of acidic or polyanionically formed inorganic carrier materials, such as are given, for example, in the case of aluminosilicates, layered silicates or silica gel.
• the possibility of additional ionic influencing between the PQAV coating composition and the inorganic base body with its opposite charge ensures that the dirt-collecting PQAV layer is firmly anchored.
• 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 description of the invention applies here analogously.
• Basis for this A 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 determined by the particular circumstances or conditions that are present and determinable in the individual case. They are done by a specialist to determine simple attempts.
• the amount of PQAV collecting dirt used in a wash cycle is preferably selected such that at least a substantial proportion, for example at least about 50, preferably at least about 75%, of the expected loading of the washing liquor with suspended dirt particles can be taken up by the dirt-collecting cleaning booster. It is generally expedient to provide formulations which provide such an amount of PQAV in the washing process that excess capacity of the PQAV is available in order to be able to intercept occasionally occurring peaks in the dirt load during different washing processes.
• the amounts of the cleaning enhancer to be added to the detergent formulation are nevertheless small and are, for example, below 10 g / l of washing liquor, preferably below 5 g / l of washing liquor, for example in the range from about 0.5 to 3 g / l of washing liquor .
• the ability of the cleaning boosters to collect dirt to collect dirt is itself 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.
• 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 - for example solid particles with an individual particle size up to about 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 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 work equipment used according to the invention and the expected pollution load, the minimum requirement for dirt-collecting cleaning or washing power booster can then easily be determined for the individual case.
• the cleaning or washing power intensifiers collecting dirt according to the invention can be used in particular together with conventional heavy-duty detergents or also with mild detergents. It goes without saying that both the carrier and the PQAV coating must be selected in such a way that the temperature loads to be expected in this application are withstood at least slightly elevated temperatures of up to approximately 95 ° C. without damage.
• Anionic and / or nonionic surfactants are particularly suitable as surfactant components.
• cationic surfactants with their special effects are not excluded.
• the usual builders and co-builders as well as the other usual detergent components can be used together with this. May be mentioned in this connection: washing alkalis, bleaching agents, corrosion inhibitors, brighteners, foam inhibitors, graying inhibitors, enzymes, adjusting agents, fragrances and the like.
• Typical basic recipes for today's textile detergent mixtures correspond, for example, to the following information:
• 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.
• Launderometer washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV test fabric, wash for 30 minutes, rinse 4 ⁇ 30 seconds.
• test rags are used in the launderometer pot.
• the number of soiled test fabric flaps is gradually increased from 1 to 6 and the number of non-soiled filler fabrics used is reduced accordingly from 5 to 0.
• Launderometer washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV fabric, wash for 120 minutes, rinse 4 ⁇ 30 seconds
• washing tests are carried out with increasing contamination at 30 ° C. In a first test series, a washing period of 30 minutes is observed. In a second series of tests, to test the long-term behavior of the PQAV additives according to the invention, washing is carried out with a period of time extended to 4 hours per washing process.
• a series of washing tests is carried out in the launderometer, which, in the event of gradually increasing dirt levels, first provides a commercially available heavy-duty textile detergent without the addition of PQAV compounds and then - with the same dosage of the commercially available heavy-duty textile detergent - the addition of the chemically modified cellulose powder according to the invention.
• Washing temperature 30 ° C, water hardness 16 ° dH, liquor ratio 1:20, 10 steel balls, H-SH-PBV fabric as soiled test material, wash for 30 minutes, rinse 4 ⁇ 30 seconds.
• washing tests are now carried out with a washing time of 4 hours each.
• the experimental setup and the results obtained are summarized below.
• the swellable layered silicate from the Montmorillonite group is used as the mineral carrier, which is sold under the protected trade name "Dis-Thix-Extra”.
• zeolite NaA in detergent quality is used as the mineral carrier.
• washing is first carried out with a commercial heavy-duty detergent on its own and then with the addition of the non-coated mineral carrier materials to this aqueous washing liquor. Finally, under the same test conditions, 3 PQAV-coated minerals of the specified type are used, which can be identified as follows.
• PQAV Quaternized galactomannan type polysaccharide with an average degree of substitution of about 0.05.
• Use of a surfactant of the FAES type commercial product "Texapon N 25" / 28% active substance C 12/14 fatty alcohol-2EO sulfate Na salt).
• a preservative commercial product "Bronidox" is used in the coating of the mineral carrier substance.
• composition of the PQAV components used according to the invention is shown in Table 5 below.
• the PQAV additives based on swellable layered silicate are labeled DTE 1 to 3
• the corresponding additives based on zeolite NaA are labeled SAS 1 to 3.
• H-SH-PBV Mixed fabric soiled with dust / skin fat is used again as the soiled test fabric.
• the commercial heavy-duty laundry detergent already delivers a high-quality cleaning result in the dosage of 5 g / l used. Nevertheless, the addition of the PQAV components in the sense of the invention once again achieves a significant improvement in the reflectance values. The addition of the non-coated mineral carriers does not bring any corresponding improvements.
• a second PQAV-coated mineral material is produced in a corresponding manner, with a comparable synthetic layered silicate with hardly any swelling capacity now being used as the mineral base body instead of the swellable layered silicate of natural origin.
• the aqueous surfactant liquor is mixed with PQAV-1 or PQAV-2, but the FAES surfactant content in the aqueous washing liquor is reduced by the amount that is entered into the system via the respective PQAV component.
• the washing conditions used are as follows:
• washing tests are carried out in a liquor containing 0.5 g (AS) / l FAES surfactant, the washing performance of the pure surfactant liquor being determined once and then in each case with the addition of 0.5 g / l of said PQAV Components is worked.
• Unfitted cotton rags are impregnated with the following active ingredient formulation and then dried by storage at room temperature for 2 days: 0.5 percent by weight "Cosmedia Guar C 261", 53.6 percent by weight “Texapon N 25" (28% AS), 0.2 percent by weight Preservative, 45.7 weight percent water.
• washing tests are carried out under the following conditions:
• Launderometer wash wash temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV fabric, wash duration 30 minutes, rinse 4 times 30 seconds
• the washing result of the surfactant liquor without the use of the PQAV-coated cotton fabric (2 dirty rags, 2 filling rags) - determined as a% remission - is 59.7.
• the PQAV-coated cotton flaps as such are first subjected to washing under the specified standard conditions.
• the coated cotton flaps separated from this laundry and freed from soluble PQAV components are washed together with the test fabric in a further washing test under the specified standard conditions.
• the washing result now determined shows the significantly increased% remission value of 66.4.
• the importance of the process condition required according to the invention that the PQAV compounds as such are insoluble even under the temperature loads of the washing process and / or are immobilized in a washable manner on solids which are insoluble in these aqueous surfactant liquors is evident from these comparative washing tests.

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• 1985
  • 1985-12-23 DE DE19853545990 patent/DE3545990A1/de not_active Withdrawn
• 1986
  • 1986-12-16 JP JP62500473A patent/JPS63501963A/ja active Pending
  • 1986-12-16 WO PCT/EP1986/000753 patent/WO1987003900A1/fr not_active Ceased
  • 1986-12-16 EP EP87900129A patent/EP0250510A1/fr active Pending
  • 1986-12-16 EP EP86117501A patent/EP0230606A1/fr not_active Withdrawn
  • 1986-12-22 ZA ZA869641A patent/ZA869641B/xx unknown
  • 1986-12-22 CA CA000526081A patent/CA1272933A/fr not_active Expired - Fee Related
  • 1986-12-23 US US06/945,610 patent/US4761249A/en not_active Expired - Fee Related

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