DE2806450A1 - Cleansing compsn. absorbing oil, fat and wax - contains grain-structured water-repellent and/or cation-active hydrophilic starch - Google Patents

Abstract

Cleansing- and absorbent compsn. contains >=50 wt.%, w.r.t. solids, of grain-structured water-repellant starch (I) and/or cation-active hydrophilic starch, (II), opt. as a suspension or paste with a liq. carrier. Compsns. contg. (I) are used esp. for absorbing oils, fats or waxes. (I), opt. together with (II), or a starch mol. contg. hydrophobic and cation-active hydrophilic substits., are used for the cleaning and care of natural- and/or chemical fibre textile articles, esp. carpets and upholstery, as well as in dry-cleaning and dry hair-shampoos. The starches, in dry or wet compsns., have high cleansing power and affinity to C black, Fe oxide, kaolin, SiO2, as well as to fats and oils. Carpet-shape is retained. The starches are easily removed, e.g. by vacuum-cleaning, without removing antistatic or bacteridical finishes.

Description

description

The present invention relates to a cleaning and absorbing agent based on starch.

A variety of starch derivatives with different substituents and various degrees of substitution has already been described in the literature, namely those in which the starch grain has been retained and those in the following with starches with starch grain structure, as well as those with which the starch grain was gelatinized and then dried, and the usually swelling starches to be named.

So have cationic hydrophilic starch derivatives in the past decade is becoming increasingly important. Such cationic hydrophilic starch derivatives and methods of making them are described, for example, in US patents 2 813 039, 2 917 506, 2 97O 140, 2 995 513, 3 320 118 and 3 346 563 described. These starch derivatives are mainly used as flocculants, as an aid in the paper industry to improve retention and also as Anion exchanger used.

Furthermore, hydrophobic starch ethers and starch esters are also known. These Derivatives are characterized by the fact that they are usually at boiling temperatures in Water no longer gelatinize or swell. They are therefore particularly suitable for Production of stable aqueous starch dispersions for coating and impregnation purposes. Such products and processes for their manufacture are for example in the U.S. Patents 2,740,724, 2,858,305 and 3,462,283.

In certain cleaning sprays, normal starch was used as an absorbent Component used. However, since strength only has a very low dirt absorption capacity possesses, which is only up to approx. 2% of its own weight, is in practice the much more active silica, e.g. Aerosil, is used.

The object of the invention is now to provide a cleaning agent based on starch with extremely high absorption capacity for hydrophilic and / or oleophilic dirt, which is also related to the absorption of oil in significant quantities on starch weight, can be adjusted.

This task is carried out by a cleaning and absorbing agent Starch base dissolved, which is characterized by a content of at least 50% by weight, based on Xdry weight9 of hydrophobic starch and / or of cation-active, hydrophilic starch with a Xorn structure, optionally suspended in or made into a paste with a liquid carrier, the remainder of the dry substance can be extender or also be fillers already known as dirt absorbents, which, however, there they surprisingly poorer absorption capacity than those used according to the invention Has starches, in the present case they are also counted among extenders have to. So the total mixture can be up to 50% native any starch, in particular Contain rice starch, but also calcium carbonate, barium sulfate, magnesium carbonate or amorphous silica. However, the latter, although quite good in itself, has Absorption would have the disadvantage that it sticks to synthetic fibers and thus the re-soiling is very beneficial. However, this disadvantage also applies to a significant part of the other known absorbents.

It has been found that hydrophobic and / or cationic hydrophilic Starch with a Xorn structure have a surprisingly high cleaning power and are anion-active hydrophilic and / or hydrophobic substances such as dust, dirt, oleophilic aerosols, spontaneously bind oleophilic or oil or fat-containing substance etc. and one special strong affinity for both carbon black, iron oxide, kaolin and silicon dioxide as well as Show fats and oils. It has also been found that these strengths are excellent Have cleaning effect even when dry, i.e. without a liquid carrier, especially without water, which offers great advantages for the application.

With known carpet cleaners, the presence of water has the disadvantage that the carpet underlay warps and that long drying times are required and that the residue of the dried carpet shampoos, existing from washing-active substances and / or plastic dispersions, not from vacuum cleaners more can be removed. This remaining sticky residue causes a Increased - re-soiling and - often lead to color shifts.

Also at. Water-based cleaners have too much penetration into upholstered furniture of the textile layers, which in particular adversely affects down fillings leads.

In contrast, the means according to the invention can be used without further ado and can be removed easily and residue-free after dirt has been picked up remove the products to be cleaned. The resoiling ability is surprising small amount. They are therefore suitable for a wide variety of cleaning purposes. So suitable They are particularly suitable for cleaning and caring for textile products, in particular those made of natural and / or man-made fibers and especially carpets and carpeting, Upholstered furniture covers and the like, both for overall cleaning and care such products and for removing stains therefrom and for dry washing and hair care.

On top of that, and this is another aspect of the invention that the hydrophobic starches have a surprisingly high absorption capacity for oils, fats and Possess waxes and also develop this effect in a dry state. the Swelling. therefore also relates to the use of the hydrophobic starches alone for Absorption of oils, fats and waxes.

Compared to the known cleaning and care products for the above The products according to the invention have the stated purposes numerous Advantages. For example, comes with the cleaning of carpets the cleaning agents according to the invention do not warp or buckle the carpet on, as is the case with the previously known agents based on alkyl sulfonates, Alkyl aryl sulfonates and alkyl sulfates and condensation products of alkylene oxides with aliphatic alcohols or amines obtained by shampooing the carpet due to their high water content when they dry out caused underbody damage is the case. Furthermore, when using the Products according to the invention for cleaning and caring for textiles, in particular Products made of natural and / or man-made fibers, possible to remove them after absorption of the Clean up dirt by brushing or using a vacuum cleaner without leaving any residue remove, while with the known surfactants applied by shampooing a not inconsiderable part of it remains on the products, fine Fibers stick together and thus lead to faster re-soiling. Also will when using the products according to the invention the antistatic and bactericidal Finishing the fiber is not removed, as with the previous on wet or Detergents applied to wet ways is the case, with such a Then remove an increased static charge and thus increased re-soiling occurs. When using the agents according to the invention, on the other hand, the resoiling ability is reduced degraded.

Compared to the known stain removers based on Solvents such as ketones, esters and halogenated hydrocarbons, optionally Prepared as a paste, the stain removal compositions according to the invention have the Advantage, no edge formation, no damage to the fiber and no color changes to and compared to the stain removers prepared as a paste easier to brush or vacuum out of the products.

Compared to the well-known dry hair detergents, which are mostly based on the Based on rice or corn starch powder, talc, kaolin or diatomaceous earth, own the inventive dry hair detergents have the advantage of being easier to brush out and not to give the hair a dull look.

The starches used according to the invention can be a mixture of cation-active, be hydrophilic starch and hydrophobic starch, preferably both types of starch Have grain structure.

The cation-active hydrophilic starch then preferably has a Degree of substitution of at least 0.05, in particular 0.08 to 0.3, especially from 0.1 to 0.2, and the hydrophobic starch has a degree of substitution of at least 0.05, in particular from 0. t to 0.5. Preferably highly substituted, cationic, hydrophilic starches are hardened by crosslinking. Appropriately, epichlorohydrin is used as the crosslinking agent. Included the procedure is so that starch with epichlorohydrin in an alkaline medium at temperatures from about 45 to 550C is implemented. This ensures sufficient hardening of the starch granules achieved. The cationic starch is then obtained by cationization. The mixing ratio of cationic hydrophilic starch to hydrophobic starch is independent of the amount of dirt, but can be beneficial, depending on the type the dirt to be removed can be varied. The relationship can be quite general advantageously 75 to 25 parts by weight to 25 to 75 parts by weight more hydrophilic to more hydrophobic Strength. For the removal of low-fat dirt, the ratio can be more hydrophilic for hydrophobic starch preferably 60 to 80 to 40 to 20% by weight and for removal of oleophilic soil are preferably 40 to 60 to 60 to 40% by weight.

A mixture of cationic, hydrophilic starch with a degree of substitution of about 0.1. and hydrophobic starch with a degree of substitution of about 0.2 Has in a weight ratio of 2: 1 when used as a care and cleaning agent Proven to be particularly beneficial for most types of dirt, and excellent at eliminating normal, mostly greasy dirt.

The starch used according to the invention can also be both cationic Starch having substituents and hydrophobic substituents, preferably with starch grain structure.

Such starch derivatives, called egg molecules, have not yet been used described and form a particular object of the invention. Your manufacture will be explained in the following.

With such substituents both cationic and hydrophobic Substituent strengths are preferably the degree of substitution cation-active substituents at least 0.05, in particular 0.1 to 0.5 and completely especially 0.1 to 0.3, and the degree of substitution of hydrophobic substituents at least 0.05, especially 0.1 to 0.5. The ratio of the degrees of substitution to each other can preferably be varied between 3: 1 to 1: 3. Based on the total starch content here are the preferred degrees of substitution to achieve particularly high cleaning and care effect higher than with the starch mixtures, which can be attributed to it It is likely that here in one and the same starch molecule both cationic hydrophilic Substituents as well as hydrophobic substituents are present, which differ in their effect can influence each other.

As already mentioned, it can generally be said that the amounts at Presence of a mixture and the ratio of Degrees of substitution with one another in the presence of a strength having both types of substituents and the nature of the substituents and the degrees of substitution which, when used, for Cleaning and care. deliver the best results from different products, depend on the type of dirt to be removed. So with predominantly Soot-containing types of dirt contain higher amounts of cation-active substances that are particularly active for soot Substituents selected, while higher amounts in the case of soiling that is rich in oil or grease chosen for such impurities particularly active hydrophobic substituents will. In practice, the most suitable substituents, degrees of substitution, Ratios of the degrees of substitution of hydrophobic and hydrophilic cation-active Substituents in the case of a strength or mixing ratio having these two substituents from cation-active hydrophilic starch to hydrophobic starch through simple routine tests, can usually be determined by a purely visual assessment of various types of soiling.

With two standard types you can practically all of the normally occurring ones Easily remove soiling, for non-greasy soiling with a Mixture of 70 wt .-% o cationic to 30 wt .-% hydrophobic starch in one Degree of substitution of 0.2 in each case or the corresponding niche molecule and in the case of fatty ones Dirt with a ratio of 1: 1 of hydrophilic to hydrophobic starch or the corresponding mixed molecule.

Those in the products according to the invention in admixture with hydrophobic Cation-active hydrophilic starch derivatives present in starches can be known be cation-active hydrophilic starches with starch grain structure and according to the usual Process for the production of such starches by reacting starch-with reactive tertiary or quaternary ammonium compounds, such as chloroethyl diethylammonium hydrochloride, Chloropropyl diethylammonium hydrochloride, N- (3-chloro-2-hydroxypropyl) trimethylammonium chloride and 2,3-EpoXypropyltrimethylammonium chloride.

Cation-active hydrophilic starch derivatives with a starch granule structure preferred according to the invention are starch ethers with quaternary ammonium groups of the general formula starch where R1 is a lower (preferably C1-C6) alkylene, in particular a propylene or hydroxypropylene radical, and R2, R3 and R4 are a lower alk: yl radical, preferably C1-C3, or a cycloalkyl radical, where in particular methyl, Mention should be made of ethyl or cyclohexyl radicals. Any two of the radicals R2, R3 and R4 can also be linked to one another to form a ring. The sum of the carbon atoms of the radicals R2, R3 and R4 is 3 to 10.

The starch ethers which contain radicals derived from glycidyl trialkylammonium chloride or 1,2-epoxyalkyltrialkylammonium chloride are preferred. The starch ethers which have radicals derived from glycidyltrimethylammonium chloride, ie products of the above formula for which R1 is a radical, are very particularly preferred and R2, R3 and R4 represent lower alkyl radicals, in particular methyl radicals.

These products are preferably used in the usual way, namely by Conversion of starch with glycidyltrialkylammonium chloride and especially glycidyltrimethylammonium chloride in an aqueous medium in the presence of 0.5 to 0.6% of an alkaline catalyst, such as sodium hydroxide, potassium hydroxide and calcium hydroxide at below the gelatinization point the strength lying temperatures, especially at temperatures between 40 and 50 ° C.

Those in the products according to the invention together with the cation-active Hydrophilic starches present hydrophobic starches can be known hydrophobic Be starch derivatives with starch grain structure, which are produced by the usual methods Manufacture of such products can be made. Such products can be by reacting starch with monofunctional aliphatic araliphatic, alicyclisone or aromatic compounds that contain an active group and form an Xther or ester bond with starch. As active groups are Epoxy, halogen and acid anhydride groups and double bonds are preferred, with from Aralkylepoxyverbindungen, in particular phenylglycidäthern or styrene oxide, derived hydrophobic groups are particularly preferred.

Examples of etherifying agents are propyl chloride, isopropyl chloride, Butyl chloride, amyl chloride, allyl chloride, methallyl chloride, 3-cyclohexenyl chloride, Benzyl chloride, p-llalogenbenzyl chloride, o-halobenzyl chloride1 dodecylbenzyl chloride or the corresponding bromides or iodides; Tributyl phosphate, butadiene monoxide, Epoxydecane, styrene oxide, cyclohexene oxide, phenylglycidyl ether, Allyl glycidyl ether, 2-ethylhexylglycidyl ether or the glycidyl ester of a synthetic mixture of branched, predominantly tertiary monocarboxylic acids with more than 9 carbon atoms, acrylonitrile.

Esterifying agents used in the manufacture of hydrophobic starch esters are also known. It is for example to monofunctional aliphatic, alicyclic or aromatic compounds, the contain an active group capable of forming an ester linkage with starch, such as Acid halides, acid anhydrides, vinyl esters and isocyanates and their mixtures. Examples such esterifying agents are lauroyl chloride, benzoyl chloride, benzenesulfonyl chloride, Butyric anhydride, caproic anhydride, benzoic anhydride, vinyl butyrate, vinyl 2-ethylhexoate, Vinyl stearate, vinyl benzoate, isopropyl isocyanate, stearyl isocyanate, phenyl isocyanate, o-, m- or p-tolyl isocyanate, naphthyl isocyanate or o-, m- or p-halogenophenyl isocyanate or mosyl isocyanate.

These reagents are mostly used in an alkaline medium with unglued, granular starch reacted. The reaction can be done in the dry state or in suitable liquids such as water, alcohols and ketones.

The reaction temperature is mostly from 40 to 650 ° C., in particular 50 to 600C.

According to the invention are hydrophobic starch derivatives with a starch grain structure of the general formula starch - 0 - R1 O O - R2 preferred, in which R1 is a lower one (preferably C1 - C6) alkylene, especially propylene or hydroxypropylene radical, means and R2 means one Alkyl, aralkyl, cycloalkyl or aryl radical represents, wherein the number of carbon atoms of the radical R2 is at least 5 and can go up to around C20. The upper practical limit is the natural one Fatty acid mixtures or their hydrogenation products and aralkyl or aryl it is preferably naphthyl or, in particular, phenyl as the aryl group. Examples the radicals R2 are thus phenyl, hexyl, decanyl, stearyl, cetyl and the C16-C18 mixtures natural fatty acids and their hydrogenation products.

Starch derivatives which contain groups derived from phenylglcidyl ether, ie products of the above formula for which R1 is a radical, are particularly preferred and R2 is a radical -C6H5.

These particularly preferred derivatives are preferably made by reaction of granular starch with phenyl glycidyl ether in an alkaline aqueous medium at temperatures from 50 to 55 ° C.

Depending on the degree of substituents and substitution, hydrophobic starches are capable of the general formula given above from an oil / water system over 50 to to bind over 90% by weight of oil, based on the weight of starch used. According to the invention Hydrophobic starches can be used with advantage for removing oils, e.g. B.

be used in garages, on streets, or on or in water.

Both cationic hydrophilic substituents according to the invention as well as starch derivatives having hydrophobic substituents, which are New connections can be made by implementing strength with both the above mentioned hydrophobic reactants as well as the above-mentioned cation-active reactants among the starch derivatives containing only one type of substituent there specified conditions can be obtained. The preferred embodiment for manufacture of these starch derivatives, the starch is first with the hydrophobic reactant and then to react with the cationic reactants. The reaction conditions are the per se for the production of the starch derivatives having only one function known conditions. If the order is reversed, there is a tendency to form of only slightly substituted, swollen and dark colored products.

So the order is important.

The strength that makes up the cationic and hydrophobic, as well as the only cation-active or only hydrophobic derivatives can be obtained, either be native starch, such as corn, rice, potato, sago, wheat or tapioca starch. Due to the grain structure, corn starch and especially cracked starch are preferred. Instead of native starch, acidic or oxidizing agents can also be used Strengths are used.

The cleaning and care products according to the invention are supplied as a powder or applied in a liquid carrier to the products to be cleaned, and can be easily removed again after taking up the dirt, for example after brushing into a floor with a vacuum cleaner.

Since dry starch powders tend to dust easily, this can be done Effortlessly prevent dust according to the invention if the dry Powder just as much of a volatile organic solvent as, for example Ethanol or isopropanol, is added to transform the fine starch granules into larger ones Agglomerate structures. For this purpose, 1 to 5% addition of solvent is sufficient, in particular 2%, completely off. The means are then in the form of non-dusting, scattering or free-flowing powders. The solvent evaporates during use and the powder can be easily removed without leaving any residue.

In principle, however, all customary agglomeration processes can be used as known for starches and the agglomerated starches can be used directly.

For cleaning large areas, it is useful to use an inventive To formulate cleaning and care products on a dry basis that binds dust contains a moisture-saturated cellulose fiber, preferably in an amount from 10 to 20, in particular 15 to 16% by weight. The addition of fibers increases the flowability of the agent as well as the required even distribution on the to be cleaned Surface, for example on a textile floor covering, is not impaired. Such a thing Agent can also be removed without residue using a vacuum cleaner. The addition the cellulose fibers, which preferably have a length of 0.1 to 0.5 mm in addition, an increase in the bulk volume of the agent, thereby causing it can be evenly distributed. In addition, there is a stretching effect through the Cheaper cellulose fiber achieved without affecting the cleaning effect will.

The cleaning and care products according to the invention can also be used as Spray can be applied. In order to avoid clogging of the nozzles this should Type of preparation does not exceed the particle diameter of the products according to the invention 70 Å. Preferred particle sizes are between 30 and 50 Å. When shredding the agglomerates remain on this area the starch grain structure obtain. In such a preparation form, it is to avoid dust formation for certain purposes, for example when cleaning and caring for carpets and carpeting or dry cleaning of windows, expedient, the Add a weighting agent to the spray. Such weighting agents are preferred High vapor pressure compounds such as methylene chloride and isopropanol. By means of such weighting means it is achieved that the products according to the invention reach the surfaces to be cleaned without dust, after which the weighting agent evaporates. It has proven to be particularly special as a carrier and / or propellant Proven beneficial, those with a specific gravity similar to that of starch select or a carrier mixture or propellant mixture with similar specific Insert weight, e.g. B. a mixture of isopropanol and methylene chloride approximately Ratio 50:50 to 30:70, the ratio 30:70 being particularly preferred is.

As already mentioned, the funds can be up to 50% more usual Contain additives, such as extenders, but of course also, for example, fragrances, Bactericidal or in particular bacterial and antistatic agents. The addition such additives can be made after simple Durduic, or they can be in be introduced in a known manner in the agglomeration, z. B. by entering the solvents used in agglomeration are dissolved or suspended in them will.

In particular for cleaning and care products for products from natural and / or man-made fibers can be antistatic and bactericidal or bacteriostatic Active substances can be used with advantage, since these low molecular weight compounds remain on the fiber surface and an additional desirable antistatic and give bacteriocidal or bacteriostatic finishing of these products.

The following examples illustrate the invention.

Example 1 Production of a hydrophobic, oleophilic starch a) To a solution of 1.4 kg of sodium sulfate decahydrate in 7 liters of water becomes a solution of 100 g of sodium hydroxide in 550 ml of water. Then be under intense Stir gradually suspended 5.5 kg of native corn starch and the mash obtained mixed with 0v9 kg of phenyl glycidyl ether. The reaction mixture is then intensified Stirring heated to 60 to 65 ° C for 6 hours.

After cooling, with 10 a hydrochloric acid to a pH of 6-adjusted the starch derivative centrifuged, once with water and then with methanol washed to remove unreacted phenyl glycidyl ether and dried. the Starch shows neither a maximum viscosity nor a final viscosity in the Brabender viscograph, d. i.e., it does not gelatinize.

Oil absorption: 50% b) In a solution of 140 g of sodium sulfate and 10 g of sodium hydroxide in 950 ml of water become 580 g of native with vigorous stirring Entered rice starch and the mash is then mixed with 100 g of hexyl glycidyl ether offset. After stirring for 44 hours at 50-52 ° C., 10% hydrochloric acid is added adjusted to a pH of 6. The starch is then suctioned off, twice with water washed, slurried in acetone and again suctioned off. After evaporation of the Acetone extract could in this 25% of the hexyl glycidyl ether used with a Spoxide content of 81% can be isolated again.

The starch showed a maximum viscosity in the Brabender viscograph (ElV) of 95 and an ultimate viscosity (EV) of 240.

c) 250 g of native corn starch are in a solution of 61 g of sodium sulfate suspended in 300 ml of water and slowly mixed with 17 g of a 30% sodium hydroxide solution. Then 62.5 g of allyl glycidyl ether are added and the reaction mixture 24 Heated to 45 ° C for hours. Analogously after working up the substituted starch Example 1b was able to find 4.5% of the initial viscosity in the acetone solution will.

The starch showed neither a maximum viscosity in the Brabender viscograph another final viscosity.

d) 500 g of native corn starch are suspended in 52% ml of isopropyl alcohol and 15 g of sodium hydroxide dissolved in 3O ml of water are added. After adding 167 g of epoxystyrene, the reaction mixture is stirred at 45 ° C. for 18 hours. Thereafter is neutralized with dilute hydrochloric acid and the derivatized starch with water Washed free of chloride.

The Brabender had a maximum viscosity of 790 and a final viscosity of 1170 found.

Example 2 Preparation of 3-hexyloxy-2-hydroxypropyl starch ether In a solution of 140 g of sodium sulfate and 10 g of sodium hydroxide in 950 ml of water 585 g of native corn starch are entered with vigorous stirring. Then will 100 g of hexyl glycidyl ether are added to the mash up to 520C the pH is adjusted to 5 with 10% hydrochloric acid. The strenght is then filtered off with suction, washed twice with water, slurried in acetone and again sucked off. After evaporation of the acetone extract, a residue could be left in it isolated from 10 g of the hydrolyzed hexyl glycidyl ether.

The starch showed a maximum viscosity in the Brabender viscograph bS = 0 and an end viscosity EV = 0.

Degree of substitution: 0.17 DS; Oil absorption: 55% Example 3 Preparation of starch benzoate A suspension of 180 g of corn starch in a mixed solution of 180 ml of water and 180 ml of acetone are brought to a pH value with a 3% sodium hydroxide solution brought by 10. This suspension is added dropwise with 28.2 g of benzoyl chloride and the simultaneous addition of 3% sodium hydroxide solution. The pH should be stay constant. The reaction has ended after 1.5 hours. After short Post-reaction time resulting from the completion of the addition of sodium hydroxide solution is the suspension is adjusted to pH 5 with 10% hydrochloric acid. Then the starch benzoate Sucked off, washed twice with water intensively and then dried.

The degree of substitution is determined by saponification of the starch benzoate using potassium hydroxide solution certainly. A degree of substitution of 0.16 was found. The strength showed im Brabender viscograph has a maximum viscosity of 0 and a final viscosity of 170. The oil absorption is 60%.

Example 4 Preparation of a Cation Active Corn Starch In a Solution of 2 kg of sodium sulfate and 50 g of sodium hydroxide in 10 1 of water are under intense Stir 10 kg of an acid-modified corn starch and then slurried mixed with 2 kg of glycidyltrimethylammonium chloride. The reaction mixture is then heated to 430C and left at this temperature for 22 hours with stirring. Thereafter the pH is brought to 5 with 10% sulfuric acid. Then it is suctioned off and the starch cake slurried again in water. For the dried cationic According to Kjedahl, starch was found to have a nitrogen value of 1.04%, which is a degree of substitution of 0.1.

Example 5 Preparation of a Crosslinked Cation Active Starch One Suspension of 10 kg of corn starch in 11.4 1 of water is mixed with 1 1 of 6 strength sodium hydroxide solution offset. After the suspension has been heated to 500 g, 100 g of epichlorohydrin are added and left to react for 2 hours. The suspension is then mixed with 1 kg of sodium sulfate and 1.68 kg of glycidyltrimethylammonium chloride are added and the mixture is stirred at 500 for 6 hours. The temperature is then increased to 60 ° C. and left for 16 hours. To Completion of the reaction is the suspension with 10% sulfuric acid on a pH brought from 5 to 6. Then the cross-linked, cationic starch is sucked off, Washed intensively with water once and then dried.

For the crosslinked, cation-active starch, a nitrogen value of 1.14% found, which corresponds to a degree of substitution of 0.15. In the Brabender discograph became for the starch derivative described here neither a maximum viscosity nor a final viscosity measured. This indicates a hardening of the starch grain.

Example 6 Production of a hydrophobic, cation-active starch Zu a solution of 182 g sodium sulfate decahydrate in 1900 ml water becomes a solution of 11.2 g of sodium hydroxide in 36 ml of water. To do this, pour in slowly vigorous stirring 720 g native corn starch. One adds to the mixture thus obtained Add 120 g of phenyl glycidyl ether and stir vigorously for 30 hours at 50 to 520C. After this reaction time, 122 g of glycidyltrimethylammonium chloride are added. The reaction mixture is allowed to stir for a further 22 hours at 430.degree. After cooling down is adjusted to pH 5 with 10% sulfuric acid. The strength sucks you and rinse again with water and acetone ..

The following were used for the dried, hydrophobic and cationic starches Degree of substitution determined: hydrophobic residue: DS = 0.18 nitrogen: DS = 0.07 # 0.58% NO absorption: 49% The above starch is therefore not a mixture of a cation-active one Starch with a hydrophobic starch but the same starch has been substituted twice.

Application Examples Example 7 To carry out this example an agent used, which is composed as follows: 35% crosslinked cation-active Starch with a degree of substitution of 0.15, 15% hydrophobic starch with a degree of substitution from 0.1, 12% bleached cellulose with a maximum fiber length of 0.5 mm and a water content of 22% and an isopropanol content of 16%.

Ratio of cationic starch to hydrophobic starch = 70:30.

A sand-colored velor carpet made of polyamide (size of the pattern 35 x 14 cm) was artificially soiled with the following dirt mixtures: A 100 g calcium carbonate 5 g furnace black 1 g iron oxide 15 g mineral oil B 10 g mineral oil 0.5 g furnace black C black Shoe polish The carpet is stretched in a drum and the dirt mixture A in Excess added. The dirt mixture is removed by balls in the rotating drum worked intensively into the carpet. Then the excess dirt with removed with a vacuum cleaner. In addition to this pollution, the dirt mixtures B and C applied with a cloth.

Then it became a powdery mixture of the above composition rubbed in intensively, whereupon the powder was sucked off with a vacuum cleaner. It it was found that the carpet fiber was back to its original state State could be reset. No sticking of the fiber was observed. Further there was no change in either the antistatic or the bacteriocidal finish the carpet.

The attempts were made several times with different colored carpet patterns repeated and it was found that no color shifts whatsoever were observed.

Example 8 To get a blacker stain on the carpet, The following soil composition was used: 109 g calcium carbonate 26 g carbon black 22 g of oil Sand-colored velor carpet samples measuring 35 x 14 cm were used again, the better retention of the dirt in a ball mill with 40 small balls (Porcelain), 20 medium balls, 10 medium balls and 10 large balls Soiled with different lengths of dirt (based on the weight of the carpet) for half an hour became. After taking the samples out of the ball mill, they were left for removal vacuumed of excess dirt. The results were assessed visually.

It was found that the amount of dirt in a simple relation to the required amount of cleaning agent is available, i.e. the higher the amount of dirt applied is, the greater the amount of cleaning agent required.

In a corresponding manner, pieces of carpet measuring 35 x 14 cm were covered with shoe polish dirty, namely with a mixture of dirt for better penetration of the shoe polish from 4 g black shoe polish 40 ml carbon tetrachloride.

The degree of whiteness after treatment with the detergent was restored assessed visually. The original appearance could be achieved again.

The carpet swatches so soiled were then made more cationic with mixtures and hydrophobic starch of varying composition purified by the starch preparation incorporated by rubbing in with a rotating brush and then with vacuum cleaner. The starch blend became 50% more cationic Starch with 50% hydrophobic starch up to 100 ao cationic starch and 0% hydrophobic Strength varies. The results are given in the following tables, where the expression "street dirt" refers to the dirt mixture of 109 g calcium carbonate, 26 g soot and 22 g oil. The tables show the excellent cleaning effect of starch mixtures used as powder, firstly as a function of the composition of the dirt, and secondly as a function of the dirt concentration and thirdly, depending on the amount of starch used.

The cleaning ability is calculated according to the following formula: WGg - WG RF = x 100% WGna - WGa RF # cleaning ability WG - whiteness g - cleaned a - soiled na = not soiled "street dirt" 3% dirt 0.5% dirt Starch mixture 20 g starch mixture. 20 g starch mixture. cat. : hydroph. WGg-WGa Wna-Wa RF Wg-Wa Wna-Wa RF 50: 50 19.7 29.8 66.1 16.2 24.4 66.4 60: 40 19.1 30.1 63.4 14.6 22.8 64.0 70: 30 24.5 34.3 71.4 22.1 29.3 75.4 80: 20 21.6 33.9 63.7 20.7 27.5 75.3 loo: O 22.5 34.4 65.4 19.7 28.6 68.9 3% dirt o.5 ç dirt Starch mixture 10 g starch mixture. 10 g starch mixture. cat. : hydroph. Wg-Wa Wna-Wa RF WG-Wa Wna-Wa RF 50: 50 14.9 29.8 50.0 13.6 24.4 54.8 60: 40 16.7 30.1 55.5 13.2 22.8 57.9 70: 30 19.0 34.3 55.4 20.5 29.3 69.9 80: 20 19.6 33.9 57.8 18.6 27.5 67.6 loo: 0 17.7 34.4 51.4 16.5 28.6 57.7, "Shoe polish" Starch mixture 20 g starch mixture. lo starch mix. cat. : hydroph. Wg-Wa Wna-Wa RF Wg-Wa Wna-Wa RP 5 °: 5o 20.4 28.8 70.9 l9, o 28.8 66 60: 40 20.9 28.3 73.8 18.1 28.3 63.9 : @ 30 19.9 29.1 68.4 16.8 29.1 57.7 80: 20 21.6 30.1 71.7 18.8 30.1 62.4 100: 0 20.6 31.8 65.4 19.0 31.8 59.7 The tests were all carried out with starch powder, ie the dirt-dissolving effect of a solvent mixture was not involved.

As cation-active starches, the conversion products from native Starch and glycidyltrimethylammonium chloride and, as a hydrophobic starch, the reaction product of starch used with phenyl glycidyl ether.

Example 9 Oil absorption of hydrophobic starches 5 g of special oil become emulsified in 50 ml of water by means of a Turrax and immediately with 5 g of hydrophobic, oleophilic Strength offset. After 30 seconds of intensive stirring with the Turrax, the tertiary Mixture spun in a centrifuge at 2500 rpm for 15 minutes. This sets the oily starch cake settles on the bottom, while the excess oil on the watery surface floats. The oily starch cake is made by decanting isolated and dried in a drying cabinet at 50 ° C. for 48 hours. The anhydrous, Oily starch cake is then extracted with 75 ml dichloromethane for 2 hours in a Soxhlet. The oil absorbed by the hydrophobic starch results after the removal of the Solvent.

The results are summarized in the following table: Starch substituent DS (Substit.grad) Oil absorption Glycidyl phenyl ether 0.1 50% Glycidyl phenyl ether 0.2 60% glycidyl phenyl ether 0.4 76% benzoate 0.1 60% glycidyl hexyl ether 0.2 55% cation-active and hydrophobic starch from Example 4 0.18 hydroxyl 49 * remainder glycidyl allyl ether 0.1 21% unsubstituted, native corn starch 08 Example 10 How Mentioned earlier, when using liquid carriers, especially as a spray, the carrier and / or the propellant have a specific weight or density similar to that that of strength. This counteracts the sedimentation of the starch or favors the re-shaking of the sedimented starch, which is mainly due to convenient use of spray cans is important.

The following table shows the influence of the density of the solvent on the shaking time depending on the starch mixture. Starch mix. 50% cat. Starch / 50% hydr. strength IPA 70 60 50 40 30 CH2Cl2 30 40 50 60 70 Density o, 951 l, oll 1, o64 1.118 1.172 Shaking time (sec) after 1 h 7.4 3.3 2.7 1.6 approx. 1 after 15 h 8.1 2.2 1.2 about l 1 after 46 h 30.6 12.3 6.1 5.5 3.9 (Stand) Starch mix. 40% hydr. Strength / 6o f cat. strength IPA 70 6o 50 40 30 CH2C12 3o 40 5Q 60 7o Density 0.951 1.011 1.064 1.118 1.172 Shaking time (sec) after 1 h 3.6 2 approx. 1 1 1 after 15 h 3.8 2 approx. 1 1 1 after 46 hh 18.8 8.1 4.2 2.1 approx. 1 (Stand) Starch mix. 30 ç hydr. Starch / 70% cat. strength IPA 70 60 50 40 30 CH2C12 30 4o 50 60 70 Density 0.951 1.011 1.064 1.118 1.172 Shaking time (sec) after 1 h 4.4 1.8 approx. 1 1 1 after 15 h 3.2 1.8 approx. 1 1 1 after 46 h 14.5 9.4 3.7 2.3 approx. 1 (Stand) Comments: IPA = isopropyl alcohol. The shaking times were determined as follows: 25 g of starch mixture, 50 ml of solvent mixture and a small steel ball are placed in a 100 ml spray can.

After closing the can with a rubber stopper, shake it so long with the magnetic stirrer, which is equipped with a shaking attachment, until the rattle of the ball can be heard. For the individual experiments measured at the same number of revolutions (approx. 550 rpm).

Claims (15)

Cleaning agents and absorbents based on starch. Patent claims 1. Cleaning and absorbing agents based on starch, characterized by a Content of at least 50% by weight, based on dry substance, of hydrophobic starch and / or of cationic, hydrophilic starch with a grain structure, if appropriate suspended in or made into a paste with a liquid carrier. 2. Cleaning agent according to claim 1, characterized in that it from a mixture of cationic hydrophilic starch with a starch grain structure and hydrophobic starch with starch grain structure. 3. Cleaning agent according to claim 1, characterized in that it from a both cationic hydrophilic substituent and hydrophobic substituent having starch (mixed molecule) with starch grain structure. 4. Cleaning agent according to claim 2 or 3, characterized in that that the cation-active hydrophilic starch has a degree of substitution of at least 0.05, in particular 0.08 to 0.2, and the hydrophobic starch a degree of substitution of at least 0.05, in particular 0.1 to 0.5, or the degree of substitution in the mixed molecule of cationic hydrophilic substituents at least 0.05, in particular 0.1 to 0.3, and the degree of substitution of hydrophobic substituents at least 0.05, in particular 0.1 to 0.5. 5. Cleaning agent according to claim 4, characterized in that the cation-active hydrophilic starch through crosslinking, preferably with epichlorohydrin, is hardened. 6. Cleaning agent according to the response 4 to 5, characterized in that that the mixing ratio of cationic hydrophilic starch to hydrophobic Starch is 75 to 25 parts by weight to 25 to 75 parts by weight or the ratio of hydrophilizing to hydrophobizing substituents is between 3: 1 and 1: 3. 7. Cleaning agent according to claim 6, characterized in that for the removal of hydrophilic or low-fat dirt the ratio of hydrophilic to hydrophobic starch is 60 to 80 to 40 to 20 wt .-%. 8. Cleaning agent according to claim 6, characterized in that for Removal of oleophilic dirt the ratio of hydrophilic to hydrophobic Starch is 40 to 60 to 60 to 40% by weight. 9. Cleaning agent according to one of the preceding claims, characterized characterized in that it is derived from 1,2-epoxyalkyltrialkylammonium chloride, in particular glycidyltrimethylammonium chloride, derived cation-active hydrophilic groups and from aralkyl epoxy compounds, in particular phenyl glycidyl ether or styrene oxide, contains derived hydrophobic groups. 10. Cleaning agent according to one of the preceding claims, characterized characterized in that it is in the form of a non-dusting, agglomerated, litter or free-flowing powder or in the form of a spray in a liquid carrier. 11. Cleaning agent according to claim 10, characterized in that it as a liquid carrier lower alkanols, especially isopropanol, and / or chlorinated Contains hydrocarbons, in particular methylene chloride, the carrier preferably as close as possible to the same density as the starch. 12. Cleaning agent according to claim 10, characterized in that it, if formulated in dry form, is a moisture-saturated cellulose fiber, preferably in an amount of 10 to 20%. 13. Use of hydrophobic starches to absorb oils, fats and waxes, or dirt containing such substances. 14. Use according to claim 13 together with cationic hydrophilic Starch in a mixture or with the presence of the hydrophobic and the cation-active hydrophilic function on the same starch molecule. 15. Use according to claim 13 or 14 for cleaning and care of Textile products made from natural and / or man-made fibers.