DE2806450C3 - Starch-based detergents and absorbents - Google Patents

Description

60

The invention relates to a starch-based cleaning agent.

A variety of starch derivatives with different substituents and different degrees of substitution has already been described in the literature, and among those in which the starch grain is preserved has remained and which are referred to below as starches with a starch grain structure, as well as those in which the starch grain was gelatinized and then dried, and the usually swelling starches to be named.

In the last decade, for example, cationic hydrophilic starch derivatives have become increasingly important Such cationic hydrophilic starch derivatives and processes for their preparation are for example in U.S. Patents 28 13 039, 29 17 506, 29 70 140, 29 95 513, 33 20118 and 33 46 563. These Starch derivatives are mainly used as flocculants, as an aid in the paper industry for improvement the retention and also used as an anion exchanger.

Hydrophobic starch ethers and starch esters are also known. These derivatives are notable in that they usually no longer gelatinize or swell in water at boiling temperatures. she are therefore particularly suitable for the production of stable aqueous starch dispersions for coating and Impregnation purposes. Such products and processes for their manufacture are, for example, in U.S. Patents 2,740,724 and 2,858,305.

Normal starch has also been used as an absorbent component in certain cleaning sprays. However, since starch only has a very low dirt absorption capacity, which is only up to approx. 2% their own weight is, in practice the much more active silica, e.g. B. Aerosil used.

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

This object is achieved by the invention according to the patent claim.

The US-PS 34 62 283 relates to an iFilm-forming suspension of non-gelatinized hydrophobic starch granules, those for coating purposes for the production of coatings with good water resistance and low tack is used. It is stated that the known dispersions formed glossy films with reduced stickiness at high levels of humidity, for example in floor polishes as well as wall or floor cleaning agents can be used. The starch granules effect thereby a polishing effect, d. H. a purely mechanical dirt-wiping effect, while according to the invention the hydrophobic starch particles in the detergent for cleaning textiles, especially carpets, absorb the ever-present oily contaminants while maintaining their solid form and after cleaning, for example by means of a vacuum cleaner, of the cleaned surface can be removed.

Since all textile fibers, including synthetic fibers, have an electrically negative or surface on the surface Build up anion-active surface potential, it was feared that the electrically positive or cation-active hydrophilic starch sticks firmly to the textile fibers and can no longer be removed, which takes place dirt removal leads to increased dirt attraction. This has been proven through experiments. Just

thanks to the trick of using a cation-active hydrophilic starch with a grain structure, it is in Surprisingly, it has become possible, on the one hand, for the cationic hydrophilic starch to adhere to it to prevent the fibers and, on the other hand, to adsorb hydrophilic contaminants cause.

In the cleaning agent according to the invention, the remainder of the dry substance can or also extenders already be known as dirt absorbent fillers, however, because they are surprisingly inferior Capacity than the starches used according to the invention, in the present case also to Extenders must be counted. The total mixture can contain up to 50% native starch, in particular contain rice starch, but also potassium carbonate, barium sulfate, magnesium carbonate or amorphous silica. However, the latter, although it would have quite good absorption capacity in itself, has the Disadvantage that it gets stuck on synthetic fibers and thus promotes re-soiling. This However, the disadvantage also applies to a considerable part of the other known absorbents.

As numerous experiments have shown, the cleaning agent according to the invention has a surprising one high cleaning power and capable of anion-active hydrophilic and / or hydrophobic substances such as To spontaneously bind dust, dirt, oleophilic aerosols, oleophilic or oily or fatty substances etc. has a particularly strong affinity for carbon black, iron oxide, kaolin and silicon dioxide as well as for fats and oil up. It was also found that this detergent was excellent in detergency even when dry, d. H. without a liquid carrier, especially without water, what offers particular advantages for the application.

In known carpet cleaners, the presence of water has the disadvantage that the carpet underlay warps and curls that long drying times are required and that the residue of the dried up Carpet shampoos, consisting of detergent substances and / or plastic dispersions, from Vacuum cleaner can no longer be removed. These remaining sticky residues cause a increased soiling and often lead to color shifts. Even with upholstered furniture aqueous cleaners result in excessive penetration of the textile layers, which in particular leads to impairments of down fillings.

In contrast, the agents according to the invention can and can be used without further ado After picking up dirt, easily remove it from the products to be cleaned without leaving any residue. The resoiling ability is surprisingly low. They are therefore suitable for a wide variety of cleaning purposes. 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 of such Products as well as for removing stains therefrom, as well as for dry washing and care of Hair.

In addition, the hydrophobic starches have a surprisingly high absorption capacity for oils, Have fats and waxes and also develop this effect when dry. The invention relates to hence the use of the hydrophobic starches solely for the absorption of oils, fats and waxes.

Compared to the known cleaning and care products for the purposes mentioned above, the products according to the invention have numerous advantages. This occurs, for example, when cleaning carpets with the cleaning agents according to the invention no warping or buckling of 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, which are incorporated into the carpet through shampooing, due to their high Water content when drying out caused subfloor damage is also the case Use of the products according to the invention for cleaning and caring for textiles, in particular Products made of natural and / or man-made fibers, possible after absorption of the dirt Brushes or a vacuum cleaner to remove residue-free, while with the known by Shampooing applied surfactants a not inconsiderable part of the same on the products remains, fine fibers stick together and thus leads to faster re-soiling when using the inventive r. Cleaning agent d> e antistatic and bactericidal equipment of the Fibers are not removed, as is the case with previous cleaning agents that have been used wet or damp is the case, with such a removal then 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.

Compared to the known cleaning agents based on solvents such as ketones, esters and halogenated hydrocarbons, optionally as Prepared paste, the agents according to the invention have the advantage of no formation of edges, no damage to the Fiber and no color changes and compared to the stain remover prepared as a paste easier to brush or vacuum from the products.

The hydrophobic starch also preferably has a grain structure.

The starches used according to the invention can be a mixture of cationic hydrophilic starch and hydrophobic starch, both types of starch preferably having a grain structure.

The cation-active hydrophilic starch preferably has a degree of substitution of at least 0.05, in particular from 0.08 to 0.3, very particularly from 0.1 to 0.2, and the hydrophobic starch a degree of substitution of at least 0.05, in particular one of 0.1 to 0.5. Preferably highly substituted, cationic, hydrophilic starches are hardened by crosslinking. In more expedient Way, epichlorohydrin is used as a crosslinking agent. It is proceeded in such a way that strength with Epichlorohydrin is reacted in an alkaline medium at temperatures of about 45 to 55 ° C A sufficient hardening of the starch granules is achieved. The cation-active one is then made by cationization Get strength. The mixing ratio of cationic hydrophilic starch to hydrophobic starch Although starch is independent of the amount of dirt, it can be advantageous, depending on the type of

the dirt can be varied. The relationship can very generally advantageously 75 to 25 parts by weight to 25 to 75 parts by weight of hydrophilic to hydrophobic starch be. The ratio of hydrophilic to hydrophobic starch can be used to remove low-fat dirt preferably 60 to 80 to 40 to 20% by weight and preferably 40 to remove oleophilic soil up 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 turned into one Weight ratio of 2: 1 when used as a detergent for most types of dirt than Proven to be particularly beneficial and excellent at removing normal, mostly greasy dirt.

The starch used according to the invention can also be both a cation-active substituent starch having hydrophobic substituents, preferably with a starch grain structure. Such, mixed molecule starch derivatives mentioned have not yet been described and form a special subject of the invention, their production is explained in the following

With such substituents having both cationic and hydrophobic substituents In strengths, the degree of substitution of cationic substituents is preferably at least 0.05, in particular 0.1 to 0.5 and very particularly 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 one another can be preferred can be varied between 3: 1 to 1: 3. The preferred degrees of substitution are based on the total starch content to achieve a particularly high cleaning and care effect higher than with the starch mixtures, which may be due to the fact that here in one and the same starch molecule both Cation-active hydrophilic substituents as well as hydrophobic substituents are present, which differ in their Effect can mutually influence something.

In general, it can be stated that the amounts in the presence of a mixture and the ratio of the degrees of substitution to one another in the presence of a strength containing both types of substituents, as well as the type of substituents and the degrees of substitution which give the best results when used for cleaning and care of various products, " In the case of soot-containing types of soil, for example, higher amounts of cation-active substituents that are particularly active for soot are selected, while higher amounts of hydrophobic substituents that are particularly active for such soiling are selected for soiling that is rich in oil or grease In practice, the most suitable substituents, degrees of substitution, ratios of degrees of substitution of hydrophobic and hydrophilic cation-active substituents can be found with a strength or mixing ratio of cations having these two substituents naktiver hydrophilic starch to hydrophobic ·, ^{'o <ärke} determined by simple routine experiments, mostly uereus different by purely visual assessment dirt. Practically all normally occurring soiling can be easily removed with two standard types, namely & 5 for non-greasy soiling with a mixture of 70% by weight of cation-active to 30% by weight of hydrophobic starch with a degree of substitution of 0.2 or the corresponding mixed molecule and for greasy dirt with a ratio of 1: 1 of hydrophilic to hydrophobic starch or the corresponding mixed oil

The cation-active in the products according to the invention as a mixture with hydrophobic starches Hydrophilic starch derivatives can be known cation-active hydrophilic starches with a starch grain structure his and according to the usual methods of making such starches by reacting Starch with reactive tertiary or quaternary ammonium compounds, such as

Chloroethyl diethylammonium hydrochloride, Chlorpropyl diethylammonium hydrochloride, N- (3-chloro-2-hydroxypropyI) -trimethyl-

ammonium chloride and
2,3-epoxypropyltrimethylammonium chloride,

can be obtained.

Cation-active hydrophilic starch derivatives with a starch grain structure are preferred according to the invention Starch ether with quaternary ammonium groups of the general formula

Strength - O - R ₁ - N - R ₃

CV

where Ri is a lower (preferably Ci-Ce) alkylene, in particular a propylene or hydroxypropylene radical, and R2, R3 and R4 represent a lower alkyl radical, preferably Ci- C3, or a cycloalkyl radical, in particular methyl, ethyl or Cyclohexyl radicals are to be mentioned. Any two of the radicals R2, R3 and Rt can also be linked to one another to form a ring. The sum of the carbon atoms of the radicals R ₂ , R3 and R ₄ is 3 to 10.

The starch ethers, those of glycidyl trialkylammonium chloride, are preferred and 1,2-epoxyalkyltrialkylammonium chloride, respectively have derived residues. The starch ethers, those of glycidyltrimethylammonium chloride, are very particularly preferred have derived residues, d. H. Products of the above formula for which Ri has a rest

HHH

I I I —C — c — c—

OH

and R2, R3 and R4 are lower alkyl radicals, in particular represent methyl radicals.

These products are preferably made in the usual way, namely by reacting 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 temperatures below the gelatinization point of the starch , in particular at temperatures between 40 and 50 ⁰ C, produced.

Those present in the products according to the invention together with the cation-active hydrophilic starches Hydrophobic starches can be known hydrophobic starch derivatives with a starch grain structure, which according to the usual methods of making such products can be made. Such products can be achieved by reacting starch with monofunctional aliphatic araliphatic, alicyclic or aromatic compounds that contain an active group and with starch an ether or Form ester bond obtained. As active groups are epoxy, halogen and acid anhydride groups and Double bonds are preferred, with aralkyl epoxy compounds, in particular phenyl glycidyl ethers or Styrene oxide, derived hydrophobic groups

Examples of etherifying agents are propyl chloride, isopropyl chloride, butyl chloride, amyl chloride, allyl chloride, Methallyl chloride, 3-cyclohexenyl chloride, benzyl chloride, p-halobenzyl chloride, o-halobenzyl chloride, Dodecylbenzyl chloride or the corresponding bromides or iodides; Tributyl phosphate, butadiene monoxide, Epoxydecane, styrene oxide, cyclohexene oxide, phenyl glycidyl ether, allyl glycidyl ether, 2-ethylhexyl glycidyl ether or the glycidyl ester of a synthetic mixture of branched, predominantly tertiary monocarboxylic acids with more than 9 carbon atoms, acrylonitrile.

Esterifying agents that can be used to make hydrophobic starch esters are also known. They are, for example, monofunctional aliphatic, alicyclic or aromatic Compounds that contain an active group that can form an ester linkage with starch, such as Acid halides, acid anhydrides, vinyl esters and isocyanates and their mixtures. Examples of 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-halophenyiisocyanate or tosyl isocyanal.

These reactants are usually made to react in an alkaline medium with non-gelatinized, granular starch. The reaction can be carried out in the dry state or in suitable liquids such as water, alcohols and ketones. The reaction temperature is usually 40 to 65 ° C, especially 50 to 6O ⁰ C.

According to the invention, hydrophobic starch derivatives with a starch grain structure of the general formula are used

Strength -OR ₁ -O - R ₂

preferred, where Ri is a lower (preferably Ci- Ce) alkylene, in particular propylene or hydroxypropylene radical, and R2 is an alkyl, aralkyl, cycloalkyl or aryl radical, the number of carbon atoms of the radical R2 being at least 5 and up to can go to about C20. The upper practical limit is the natural fatty acid mixtures or their hydrogenation products, and aralkyl or aryl is preferably naphthyl or, in particular, phenyl, as the aryl group. Examples of the radicals R2 are thus phenyl, hexyl, decanyl, stearyl, cetyl and the Qs-cis mixtures of natural fatty acids and their hydrogenation products.
Starch derivatives which contain groups derived from phenylglycidyl ether, ie products of the above formula for which Ri is a radical, are particularly preferred

HHH

I I I —C — c — c—

OH

and R2 is a radical -CeHs.

These particularly preferred derivatives are preferably prepared by reacting granular starch in an alkaline aqueous medium with Phenylglycidäther KGj Xgni ^ eraturen of 50 to 55 ⁰ C obtained

Depending on the substituents and degree of substitution, hydrophobic starches are capable of those given above general formula from an oil / water system over 50 to over 90 wt .-% oil, based on the oil used Starch weight to tie. According to the invention, hydrophobic starches can advantageously be used to remove Oils, e.g. B. in garages, on streets or on or in water.

Both cation-active hydrophilic substituents and hydrophobic substituents according to the invention having starch derivatives, which are new compounds, can by reaction of starch with both the above-mentioned hydrophobic reactants and the above-mentioned cation-active Reactants among the starch derivatives listed there for the starch derivatives containing only one type of substituent Conditions are obtained. The preferred embodiment for making these starch derivatives is the starch first with the hydrophobic reactant and then with the cationic reactant to implement. The reaction conditions are those per se for the production of the only one function Starch derivatives known conditions. If the order is reversed, there is a tendency to form only slightly substituted, swollen and dark colored products. So the order is important.

The starting starch can be any native starch, such as corn, rice, potato, sago, wheat or tapioca starch. Because of the grain structure, corn starch, and especially rice starch, is preferred instead of native starch, starches modified by acids or oxidizing agents can also be used.

The cleaning agents according to the invention are used as a powder or in a liquid carrier cleaning products and can be easily removed after taking up the dirt, for example after brushing into a carpet with a vacuum cleaner. As dry starch powder easily tend to dust, dust can be prevented according to the invention easily if the dry powder just enough of a volatile organic solvent such as ethanol or isopropanol, is added so that the fine starch granules agglomerate to form larger structures. to For this purpose, 1 to 5% addition of solvent, in particular 2%, is completely sufficient. The means lie then in the form of non-dusting, scatterable or free-flowing powders. During use the solvent evaporates and the powder can easily be removed without leaving any residue.

In principle, however, all common agglomerates

ration processes are used as they are known for starches, and the agglomerated starches can be used directly.

For cleaning large areas, it is useful to use a dry-based cleaning agent according to the invention to formulate, which contains a moisture-saturated cellulose fiber for dust formation, preferably in an amount of 10 to 20, in particular 15 to 16% by weight. The addition of fibers increases the flowability of the agent and the required uniform distribution on the surface to be cleaned, for example on textile flooring, not impaired. Such a means can also be used without leaving any residue a vacuum cleaner. The addition of cellulose fibers, which preferably have a length of 0.1 to 0.5 mm have, moreover, result in an increase in the bulk volume of the agent, which makes it can be evenly distributed. In addition, a stretching effect is provided by the cheaper cellulose fiber achieved without the cleaning effect is impaired.

The cleaning agents according to the invention can also be used as a spray. To avoid clogging of the nozzles, the particle diameter according to the invention should in this preparation Products do not exceed 70 μ. Preferred particle sizes are between 30 and 50 μ. At a Shredding the agglomerates in this area preserves the starch grain structure. With such a It is in the form of preparation to avoid dust formation for certain purposes, for example in the cleaning and care of carpets and carpeting or dry cleaning of Windows, it is advisable to add a weighting agent to the spray. Such complaints are preferably Medium high vapor pressure compounds such as methylene chloride and isopropanol. By Such weighting means is achieved that the products according to the invention without dust on the cleaning surfaces arrive, after which the weighting agent evaporates as a carrier and / or Propellant has proven to be particularly advantageous, those with a specific Select a weight similar to that of starch or a carrier mixture or propellant mixture with similar to use specific weight, e.g. B. a mixture of isopropanol and methylene chloride approximately Ratio 50:50 to 30:70, the ratio being 30:70 is particularly preferred

As already mentioned, the agents can contain up to 50% other common additives, such as extenders,

de or in particular bacteriostats and antistatic agents. The addition of such additives can after simple mixing, or they can be introduced in a known manner during the agglomeration be e.g. B. by dissolving them in the solvents used in the agglomeration or in these be suspended.

Especially with cleaning agents for products eo Antistatic and bactericidal or bacteriostatic substances can be made from natural and / or man-made fibers can be used with advantage, since these low molecular weight compounds remain on the fiber surface and an additional desired antistatic and bacteriocidal or bacteriostatic finish of these Products.

The following examples illustrate the invention.

example 1

Manufacture of a both cationic hydrophilic

Substituents as well as hydrophobic substituents

exhibiting starch (mixed molecule)

To a solution of 182 g of sodium sulfate decahydrate in 1900 ml of water a solution of 11.2 g Sodium hydroxide was added to 36 ml of water. To this end, 720 g are poured in slowly with vigorous stirring native corn starch. 120 g of phenyl glycidyl ether are added to the mixture thus obtained and the mixture is left for 30 hours Keep stirring vigorously at 50 to 52 ° C. After this reaction time, 122 g of glycidyltrimethylammonium chloride are obtained added. The reaction mixture is allowed to stir at 43 ° C. for a further 22 hours. After this Cooling is adjusted to pH 5 with 10% sulfuric acid. The starch is sucked off and rinses again with water and acetone.

The following degrees of substitution were determined for the dried, hydrophobic and cation-active starch:

hydrophobic residue:

Nitrogen:

oil absorption:

DS = 0.18

DS = 0.07 = 0.58% N

49%

The above starch is therefore not a mixture of a cationic starch with a hydrophobic starch, but rather the same starch was substituted twice.

The following examples explain the use of the cleaning agents according to the invention:

Application examples
Example 2

To carry out this example, a means is used which is composed as follows:

35% cross-linked cationic starch with a degree of substitution of 0.15,

15% hydrophobic starch with a degree of substitution of 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 carpet made of polyamide (size of the pattern 35 × 14 cm) was made with the following Mixtures of dirt artificially soiled:

A 100 g calcium carbonate

5 g soot

1 g iron oxide

15 g mineral oil

B 10 g mineral oil

0.5 g soot
C black shoe polish

The carpet is stretched in a drum and that Dirt mixture A was added in excess. The dirt mixture is created by balls in the rotating drum The excess dirt is then worked into the carpet intensively with a vacuum cleaner In addition to this soiling, the dirt mixtures B and C were removed by means of a Cloth applied.

Then, a powdery mixture became the above

The specified composition was rubbed in intensively, whereupon the powder was sucked off with a vacuum cleaner became. It was found that the carpet fiber was restored to its original state could be. No sticking of the fiber was observed. Furthermore, there was no change in the antistatic and bacteriocidal properties of the carpets.

The experiments were repeated several times with different colored carpet samples and were able to do so it can be determined that no color shifts whatsoever were observed.

Example 3

In order to get a "blacker" soil on the carpet, the following soil composition was used used:

109 g calcium carbonate
26 g of carbon black
22 g of oil

20th

Sand-colored velor carpet patterns 35 χ 14 cm in size were used again, for the better Compliance with the dirt in a ball mill with 40 small balls (porcelain), 20 medium balls, 10 medium-sized balls and 10 large balls with different dirt lengths (based on carpet weight) half an hour dirty. After removing the samples from the ball mill vacuumed to remove excess dirt. The results were visual It was found that the amount of dirt in a simple relation to the required amount of Detergent stands, d. In other words, the higher the amount of dirt, the greater the amount of detergent are required

Correspondingly, pieces of carpet measuring 35 × 14 cm were soiled with shoe polish

"Street dirt"

for better penetration of the shoe polish with a mixture of dirt

4 g black shoe polish
40 ml carbon tetrachloride.

The degree of whiteness after treatment with the cleaning agent was again assessed visually. It the original appearance could be achieved again.

The carpet swatches so soiled were then treated with mixtures of cationic and hydrophobic Starch of varying composition cleaned by rubbing the starch preparation with a rotating Brush was incorporated and then vacuumed with a vacuum cleaner. The starch blend went from 50% cationic starch to 50% hydrophobic starch to 100% cationic starch and 0% hydrophobic starch varied. The following tables show the results, with the expression "street dirt" refers to the dirt mixture of 109 g calcium carbonate, 26 g carbon black and 22 g oil relates. The tables show the excellent cleaning effect of starch mixtures used as powder, Firstly as a function of the soil composition, secondly as a function of on the concentration of dirt and, thirdly, on the amount of starch used.

The cleanability is calculated using the following formula:

RF =

RF
Flat share

n / A

WGna - WGa

Cleanability whiteness
cleaned
soiled
not dirty

Starch blend
cat: hydroph.

3% dirt, 20 g starch mixture. WGg-WGa Wna-Wa

RH 0.5% dirt, 20g starch mixed. Wg-Wa Wna-Wa

50:50
60:40
70:30
80:20
100: 0

19.7
19.1
24.5
21.6
22.5

29.8 30.1 34.3 33.9 34.4

66.1 63.4 71.4 63.7 65.4 16.2
14.6
22.1
20.7
19.7

24.4 22.8 29.3 27.5 28.6

66.4 64.0 75.4 75.3 68.9

continuation

Starch blend
cat: hydroph.

3% dirt, 10g starch mixed. Wg-Wa Wna-Wa

RH 0.5% dirt, 10 g starch mixed. WG-Wa Wna-Wa RF

50:50
60:40
70:30
80:20
100: 0

14.9
16.7
19.0
19.6
17.7

29.8 30.1 34.3 33.9 34.4

50.0 55.5 55.4 57.8 51.4 13.6
13.2
20.5
18.6
16.5

24.4 22.8 29.3 27.5 28.6

54.8 '57, 9 69.9 67.6 57.7

"Shoe polish"

Starch blend hydroph. 20 g starch mixture. Wna-Wa RF 10g starch mix. Wna-Wa RF cat. 50 Wg-Wa 28.8 70.9 Wg-Wa 28.8 66 50 40 20.4 28.3 73.8 19.0 28.3 63.9 60 30th 20.9 29.1 68.4 18.1 29.1 57.7 70 20th 19.9 30.1 71.7 16.8 30.1 62.4 80 0 21.6 31.8 65.4 18.8 31.8 59.7 100 20.6 19.0

The experiments were all carried out with powdered starch, i. h, the dirt removing effect of a Solvent mixture was not involved.

The reaction products of native starch and glycidyltrimethylammonium chloride became the cation-active starches and the reaction product became the hydrophobic starch
used.

of starch with phenyl glycidyl ether Example 4

Oil absorption of hydrophobic starches

25th

5 g of special oil are emulsified in 50 ml of water using a Turrax and immediately mixed with 5 g of hydrophobic, added oleophilic starch. After 30 seconds of intensive stirring with the Turrax, the tertiary mixture becomes spun in a centrifuge at 2500 rpm for 15 minutes. The oily starch cake settles here on the bottom while the excess oil floats on the watery surface. The oily one Starch cake is isolated by decanting and dried in a drying cabinet at 50 ° C. for 48 hours. Of the Anhydrous, oil-containing starch cake is then extracted with 75 ml of dichloromethane for 2 hours in a Soxhlet. That Oil absorbed by the hydrophobic starch results after removal of the solvent.

The results are summarized in the following table:

Starch substituent

DS (substitute degree)

Oil absorption

45

Glycidyl phenyl ether
Glycidyl phenyl ether
Glycidyl phenyl ether
Benzoate

Glycidyl hexyl ether
Cation-active and
hydrophobic starch
from example 4
Glycidyl allyl ether
Unsubstituted, naive
Cornstarch

0.1

0.2

0.4

0.1

0.2

0.18

more hydrophobic

rest

0.1

The following table shows the influence of the density of the solvent on the shaking time as a function from the starch mixture.

Starch mix.

50% kaL starch / 50% hydr. strength

0.951 1.011 1.064 1.118 1.172

IPA 70 60 50 40 30

CH ₂ Cl ₂ 30 40 50 60 70

density

Shaking time (see)

after 1 h 7.4 3.3 2.7 1.6 approx.

after 15 h 8.1 2.2 1.2 approx. 1 1

after 46 h 30.6 12.3 6.1 5.5 3.9 (standing)

Starch mixture.

40% hytlr. Stürkc / 60% kai. Suirke

50%

60%

76%

60%

55%

CH.Cl

density

Shaking time (see)

after 1 h
after 15 h
after 46 h
(Stand)

70 30th

60 40

50 50

40 60

3.6
3.8
18.8

2
2
8.1

approx. 1 approx. 1 4.2

1 1 2.1

Strength crimps.

30% hydr. Starch / 70% kaL surcharge

21% 0%

55

Example 5

60

As mentioned earlier, when using a liquid carrier, especially a spray, the carrier should and / or the propellant has a specific weight or density similar to that of starch. this counteracts the sedimentation of the starch or favors the re-shaking of the sedimented Strength, which is especially important for the convenient use of spray cans.

0.951 1.011 1.064 1.118 1.172

1 approx.

IPA 70 60 50 40 3 ©

CH ₂ Cl ₂ 30 40 50 60 70

Density 0.951 1.011 1.064 1.118 1.172

Shaking time (see)

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. (standing)

Remarks:

IPA = isopropyl alcohol

The shaking times were determined as follows: 25 g are put into a 100 ml spray can Add starch mixture, 50 ml solvent mixture and a small steel ball. After closing the The can with a rubber stopper is shaken with the magnetic stirrer or the shaker attachment is provided, until the rattling of the ball can be heard. For each experiment, the same Measured number of revolutions (approx. 550 rpm).

Claims (9)

Patent claims: 1. Cleaning agent containing a hydrophobic starch, characterized in that it in addition to the hydrophobic starch contains a cation-active hydrophilic starch with a grain structure, wherein the total amount of starch is at least 50% by weight, based on dry matter 2. Cleaning agent according to claim 1, characterized in that it consists of a both cationic hydrophilic substituents as well as hydrophobic substituents having starch (mixed molecule) with starch grain structure 3. Cleaning agent according to claim 1 or 2,! 5 characterized in that it is suspended or made into a paste in a liquid carrier 4. Cleaning agent according to claims 1 to 3, characterized in that the cation-active hydrophilic starch a degree of substitution of at least 0.05, in particular 0.08 to 0.2, and the hydrophobic starch has a degree of substitution of at least 0.05, in particular 0.1 to 0.5 or at least the degree of substitution of cationic hydrophilic substituents in the mixed molecule 0.05, in particular 0.1 to 0.3 and the degree of substitution of hydrophobic substituents is at least 0.05, in particular 0.1 to 0.5. 5. Cleaning agent according to claims 1 and 3 to 4, characterized in that the mixing ratio from cationic hydrophilic starch to hydrophobic starch 75 to 25 parts by weight to 25 to 75 parts by weight is or the ratio of hydrophilizing to hydrophobizing substituents is between 3: 1 and 1: 3. 6. Cleaning agent according to claim 5, characterized in that for the removal of hydrophilic or low-fat dirt the ratio of hydrophilic to hydrophobic starch 60 to 80 is 40 to 20 wt .-%. 7. Cleaning agent according to claim 5, characterized in that the removal of hydrophilic Dirt the ratio of hydrophilic to hydrophobic starch 40 to 60 to 60 to 40 wt .-% amounts to. 8. Cleaning agent according to claim 1, characterized in that it, if it is in dry form is formulated, a moisture-saturated cellulose fiber, preferably in an amount of 10 to 20%, contains. 9. Use of the cleaning agent according to the preceding claims for cleaning and Maintenance of textile products made from natural and / or man-made fibers, in particular carpeting. 55