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 that can be used in the cleaning of items contaminated in particular with pestle dirt. This particularly affects the washing or cleaning of all articles in a water-borne fleet. The most important area of application for such cleaning processes is textile washing.
• the washing process of textiles with conventional washing agents comprises breaking up and detaching 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 detached dirt particles is then a prerequisite for effective washing in order to prevent their deposition and at the same time graying of the washed goods.
• Conventional detergents contain additives that serve this task in particular. Adequate dirt-carrying capacity is also seen as an important function of the Bu ⁇ lder components of conventional detergent mixtures, which are known to contain synthetic surfactant Components in admixture with such Bu ⁇ lder components.
• the detergent dosage contains numerous suggestions for reducing the graying tendency 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 dilution of the washing chemicals.
• US Pat. No. 3,694,364 describes a different approach in principle: Here it is proposed to use a so-called "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 im ⁇ no groups are occupied by stearyl 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 dirt can be separated from the washed goods after washing and discarded with the dirt trap cloth.
• the cited publication describes the production 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 non-ionic surfactants in admixture with quaternary ammonium salts, which have been added to it, and to which an ammonium group-containing starch ether has been added.
• quaternary ammonium salts which have been added to it, and to which an ammonium group-containing starch ether 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 water-based detergent liquors, which were previously not accessible in this form.
• the technical solution according to the invention provides for the use or the use of such components in the cleaning process - in particular in the case of textile washing - which 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 this strainer should be done in such a physical form that after the cleaning or. Washing process, the manual and / or mechanical separation of the now dirty aids from the washed goods is possible.
• the invention thus aims to transfer the dirt from the items to be cleaned to auxiliary means used in the cleaning process, which can finally be separated from the cleaned items and discarded together with the dirt-containing oils they have collected, or - insofar as their capacity for loading 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 accordingly in these aqueous-surfactant liquors
• 'PQAV' 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 accordingly in these aqueous-surfactant liquors
• Insoluble solids that cannot be washed off are immobilized and present as particle cleansing cleaning agents 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 conventional mixtures of surfactants, associated builders and, if desired, further conventional detergents, such as bleaches, 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 wash 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 available.
• PQAV insoluble finely distributed and / or flat PQAV serve in the sense of the invention as a particle repellent cleaning amplifier which, after washing or cleaning, can be separated from the material to be cleaned manually and / or mechanically.
• the invention relates to a method for strengthening the cleaning of aqueous-surfactant washing and cleaning liquors
• a method for strengthening the cleaning of aqueous-surfactant washing and cleaning liquors Use of flat and / or dampened oil in the fleets of undissolved solids in the washing process, which bind suspended particle dirt from the water-surfactant liquor on their surface, hold there until the washing process is complete and ⁇ n this form of the goods to be cleaned manually and / or mechanically can be separated.
• the new method is characterized in that PQAV are used as cleaning-strengthening 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 well-known characteristic of 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 absorption capacity and the adhesive strength of the PQAV on the solid base are differently pronounced. The individual constitution of the PQAV plays a decisive 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.
• the corresponding anionic salt In the case of stoichiometric or approximately stoichiometric amounts of the anionic surfactant components, the corresponding anionic salt generally forms on the quaternary ammonium group.
• Such 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 calls for 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.
• Soluble PQAV components sliding into the wash bath are absorbed onto the textile material to be washed and bind additional pigment stains in an undesirable manner there.
• 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 PQAVs within the meaning 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 PQAV's insolubility 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 either quaternary ammonium groups bonded to 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 Morphol ⁇ n-, P ⁇ per ⁇ d ⁇ n-, P ⁇ perazin- or Indazol-R ⁇ ngen.
• Numerous examples of such water-soluble PQAV are e.g. B. ⁇ n described in more detail in US Pat. No. 4,240,450.
• Homopolymers or copolymers with cyclic units can be particularly suitable.
• Commercial products of this structure are e.g. B. Merquat (R) 100 and Marquart (R) 550 (Quatern ⁇ um 41).
• suitable PQAVs are, for example, cellulose ethers whose anhydroglucose units carry substituents with quaternary ammonium groups which are bonded via ether oxygen.
• Such polymers are e.g. B. known from US-PS 3,472,840.
• a commercial product with this structure is e.g. B. the PoIymer-JR (R) 400.
• Kat ⁇ on ⁇ sche polymers are z. B. those known from US Pat. No. 3,910,862 and, for example. under the trade name Gafquat (R) 734 and 755 available quaternary polyvinylpyroIidone copolymer and the known from US Pat. No. 4,157,388 and z. B. Quaternary polymeric urea derivatives available under the trade name M ⁇ rapol f R) A15.
• Suitable copolymers with a polycat ⁇ onic character are also the polyacrylamide copolymers described in the open European patent application 0 153 146, which in particular contain up to 50 mol% of a quaternized amino alkyl ester of acrylic acid or methacrylic acid in addition to at least 50 mol% of acrylamide units. These copolymers are water soluble. she are applied to cloths based on cellulose fibers and draw on there due to their natural pulling 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 cloths described in the publication are unsuitable for the use according to the invention in the usual tenside washing and cleaning liquors, which can also be exposed to temperature loads of up to about 95 ° C.
• Not inconsiderable portions of the numerous PQAV copolymers described in the publication slide into the wash bath, pull onto the items to be cleaned and lead to increased pollution. Only the conversion of such PQAV to the physical state required according to the invention, as described below, makes them cleaning boosters 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 cat ⁇ onic polymers are especially the cationic polygalactomannan derivatives known for example from GB-PS 1 136 842.
• Galactomannans are polysaccharides that are found in the endosperm cells of many legume seeds, but which are produced on an industrial scale only from Joha ⁇ nesbrotker ⁇ meh! (locust bean gurrt), guar gum (guar gum) and tara gum (tara gum). They are made up of a linear mannan main chain consisting of beta- (1 .4) -g! Ycosidically linked mannopyranose building blocks, to which individual galactopyranose residues are fixed as branches in an alpha- (1 .6) -glycoside bond. The individual polygalactomannans differ mainly through the mannose-lactose ratio.
• the cationic derivatives of the polygalactomannans are prepared 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
• R 5 is an alkyl group with 1 - 3 carbon atoms
• X chlorine or bromine
• Z an An ⁇ on such as.
• a particularly suitable quaternary ammoniumdervate of a polygalactomannan is e.g. B.
• Such canonical guar derivatives are e.g. B. on the market under the trade name "Cosmedia Guar C 261".
• the degree of substitution (DS) of Cosmedia Guar C 261 is around 0.07.
• the dirt-collecting cleaning booster used according to the invention can be used in any physical configuration that allows this cleaning booster to be loaded with dirt particles and nevertheless allows the manual and / or mechanical separation of the undissolved cleaning booster from the washed items.
• two physical forms of state come into consideration, namely the use of the 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, 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.
• the invention is described in the following 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 oil washing process.
• both fine and coarser-grained solids preparations are suitable as the condition for the new dirt-collecting amplifiers, but in particular 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, with a predetermined amount of the sheet-like material being separated from the roll for each washing process and additionally given to the washing machine with the textile goods to be washed.
• the simple manual and / or mechanical separability of the dirt collector from the washed items must be ensured.
• the material is in the form of a sheet, the fact that it is indispensable means that it can be separated when the washed textiles are removed.
• the cleaning booster is used as a more or less fine-grained material, there are various forms of absorption, especially depending on the size of the grained material. given separation. If the cleaning booster is dosed into the wash liquor as an extremely fine and insoluble material, then it is removed and rinsed out together with the wash liquor together with other insoluble, finely divided components of the detergent mixture - for example with insoluble Zeolite-based Bu ⁇ lder components. However, if the cleaning or washing power booster is used in coarser-grained form, manual separation is possible, for example, by shaking out the washed textile goods.
• Sheet-like or sheet-like designs of the new dirt collector can be designed according to known manufacturing processes as random fiber fleece, fiber fabric or knitted fabric, as a preferably open-cell foam sheet, as a closed film or in any other shape.
• 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 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 sufficient water insolubility is achieved for the purposes of the invention.
• 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 knowledge into account.
• the surface of insoluble or insolubilized, shaped natural products and / or corresponding synthesis products can be equipped with quaternary ammonium groups by chemical reaction using methods known per se. Process steps are used for this, as are known in the Priz ⁇ p 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 building, e.g. B.
• 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, for.
• granular or powdery material made from natural and / or synthetic water-insoluble materials are suitable reactive quaternizing agents.
• 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.
• Natural materials of the cellulose type, insoluble cellulose derivatives and other insoluble or insolubilized poly-saccharide-like natural substances or their derivatives are particularly easily accessible and inexpensive starting materials for such reactive surface modification that are insoluble in washing or cleaning liquors of the type mentioned.
• the introduction of quaternary ammonium groups 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 enhancers with an insoluble polycathonic surface can also be of particular importance for practical use in the washing process.
• even very low average degrees of substitution on 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 used up to about 0, 12 and preferably below 0, 1.
• the lower limit will generally be the average degree of substitution ⁇ m in the range of approximately 0.01, whereby particularly good results in the range of approximately 0.015 to 0.08 and in particular ⁇ m in the range of approximately 0.02 to 0.07 can be obtained. It is astonishing that fine cellulose powders of such a low degree of substitution bring about a substantial increase in washing power, in particular in textile washing.
• washing power boost includes the terms “primary washing power boost” as well as “secondary washing power boost”.
• 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 obtained, which can be measured as improvements to be recorded in numerical terms den in the degrees of lightening an in the context of a textile washing process on test material contaminated with pigment. Details of this can be found in the following examples which explain the invention.
• the embodiments which provide a water-insoluble support in flat or granular form, on whose surface PQAV, preferably a thin layer, are immobilized 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 ah ⁇ onic groups on or on the surface of the base body.
• anionic groups are carboxy 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 catonic PQAV coating then binds salt-like to these counter-ions of the matrix, so that in this way the solidified bond between the insoluble Solid and applied PQAV layer is created.
• a basic body based on cellulose fibers, in which free carboxyl groups have been introduced into the cellulose molecule, is merely an example of this embodiment. This is possible, for example, in two different ways:
• n can have a value from 1 to 3, modified cellulose fibers.
• carboxyl-bearing compounds into the viscose is described, for. B. achieved by admixing alkali 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 as well as 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 principle of enveloping. If, for example, a fine-grained, shaped, inert, insoluble carrier is coated with a PQAV layer - preferably covering the entire area - and this PQAV layer is then converted into the required state of insolubility under washing conditions, the inseparable union between the inert carrier 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 chemically again 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.
• those water-insoluble inorganic carriers are to be considered that 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 alumositicates of the Benton ⁇ t 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 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 anyway 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-surfactant salt group in the presence of anionic surfactants, see the designated literature 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 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 themselves 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.
• Type is the GAF "Copolymer 937" R , which is a PVP-dimethyla mino ⁇ ethyl methacrylate copolymer with an average molecular weight of about 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 present and determinable in each 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 absorbed 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. B. in the range of about 0.5 to 3 g / l of wash liquor.
• the ability of the cleaning amplifier to collect dirt to collect dirt is in turn in particular determined 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 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 may accordingly be preferred according to the invention to choose the 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 of 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 pollution load to be expected, it is then easy to determine the minimum test requirement for dirt-collecting cleaning or washing power intensifiers for the individual case.
• the cleaning or washing power intensifiers collecting dirt according to the invention can in particular be used together with conventional heavy-duty textile oil detergents or also with mild detergents. It goes without saying that both the carrier and the PQAV coating have to be selected so that the temperature loads to be expected in this application can withstand at least slightly elevated temperatures up to about 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. 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 formulations for today's textile detergent mixtures correspond, for example, to the following information:
• Anionic surfactants alkylbenzenesulfonate 5 to 10 nonionic surfactants fatty alcohol polyglycol 1 to 5 ether
• Graying inhibitor carboxymethyl cellulose, 0, 5 to 2, 0 or other cellulose ethers
• Enzyme proteases 0, 3 to 1, 0
• Optical brighteners St ⁇ lben-disulfonic acid, 0, 1 to 0, 3 bis (styryl) biphenyl
• Anionic surfactants alkylbenzenesulfonate, 9 to 20
• Nonionic surfactants alkyl polyglycol ethers 1 to 2
• Ion exchanger zeolite A 0 to 25 alkalis Na carbonate 5 to 25
• Optical brighteners St ⁇ lben-disulfonic acid, 0, 1 to 0, 3 bis (styryl) - b ⁇ phenyl-Der ⁇ vate
• Anionic surfactants alkylbenzenesulfonate 0 to 8
• Nonionic surfactants alkyl polyglycol ethers 3 to 1 1
• Foam inhibitors soaps silicone oils 0, 1 to 3
• Graying inhibitors carboxylmethyl cellulose 0, 2 to 2
• Enzyme proteases 0, 2 to 1, 0
• Optical brighteners stilbene-disulfonic acid, 0, 1 to 0, 3 bis (styryl) biphenyl derivatives
• Optical brighteners 60 to 70 60 to 80 65 to 75
• 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 currently used in the review and development of
• Detergent formulations are common and some of them are commercially available or manufactured by the detergent industry according to their own pattern.
• 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-Test ⁇ gewebe - 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 wool, with pigments and skin fat soiled (H-SH-PBV).
• the degree of soiling of the untreated starting material and the gev / ash 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).
• Launderometer washing temperature 60 ° C, water hardness 16 ° dH, liquor ratio 1: 30, 10 steel balls, H-SH-PBV test fabric, wash 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 from 5 to 0 accordingly.
• washing process corresponds to those of Example 1, but now the washing process is extended to a total of 120 minutes.
• 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. A wash room of 30 minutes is maintained in a first test series. In a second test series, in order to test the long-term behavior of the PQAV additives according to the invention, washing is carried out with a length of time extended to 4 hours per washing process.
• 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 "D ⁇ s-Thix-Extra".
• zeolite NaA ⁇ n detergent grade is used as the mineral carrier.
• washing is first carried out with a commercially available heavy-duty textile detergent alone 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 12/1 4 fatty acid alcohol 2EO sulfate Na salt).
• a preservative (commercial product "Bronidox") is used in the coating of the mineral carrier substance.
• the composition of the PQAV components used in accordance with 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 at the dosage of 5 g / l, but 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.
• PQAV-2 was introduced into the system.
• 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 associated with the respective PQAV component. ⁇ n the system is entered.
• the washing conditions used are as follows:
• PQAV-3 Merquat 100 (R) PQAV-4 B ⁇ naquat (R) PQAV-5 Cellquat (R) PQAV-6 I R-400 (R) PQAV-7 Mirapot A 15 (R)
• washing tests are carried out in a liquor containing 0.5 g (AS) / I 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 soaked with the following 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:
• the PQAV-coated cotton flaps as such are first subjected to washing under the specified standard conditions.
• the coated cotton flaps separated from this wash and freed from soluble PQAV components are washed together with the test fabric in a further wash test under the specified standard conditions.
• the washing result now determined shows the significantly higher% 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
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