DE2806450B2 - Starch-based detergents and absorbents - Google Patents

Description

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, namely 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 auxiliaries in the paper industry to improve retention and also as anion exchangers used.

Furthermore, hydrophobic stains and Starch esters known These derivatives are notable for the fact that they are usually used at cooking temperatures No longer gelatinize or swell in water. They are therefore particularly suitable for producing more stable ones 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 and 2,858,305.

Normal starch has also been used as an absorbent component in certain cleaning sprays. However, since strength is only a very small one Has dirt absorption capacity, which is only up to approx. 2% of its own weight, becomes very in practice 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 extraordinary high absorption capacity for hydrophilic and / or oleophilic protection, also for the absorption of oil can be adjusted in a considerable amount based on the weight of starch.

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

The US-PS 34 62 283 relates to a film-forming suspension of non-gelatinized hydrophobic starch granules which are used 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 and wall or foot bocuin cleaning agents, can be used. The starch grains cause a polishing effect, el. H. a purely mechanical one dirt-wiping effect, while according to the invention the hydrophobic starch particles in the cleaning agent for cleaning textiles, in particular carpets, absorb the oil-like soiling that is always present, while retaining 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 Build up anion-active surface potential was closed fear that the electrically positive or cationic hydrophilic starch will adhere firmly to the textile fibers remains and can no longer be removed, which instead of removing dirt 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 pastes and on the other hand to adsorb hydrophilic soiling 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., Den Disadvantage that it gets stuck on synthetic fibers and thus greatly favors Wieosran soiling 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 Dust, dirt, oleophilic aerosols, oleophilic or oil or fatty substances etc. to bind spontaneously and has a particularly strong affinity for soot, Iron oxide, kaolin and silicon dioxide as well as fats and oils. It was also found that this Cleaning agent its excellent cleaning effect even when dry, d. H. without liquid Has carrier, in particular pure water, which offers particular advantages for the application.

In known carpet cleaners, the presence of water has the disadvantage that the carpet underlay warps and waves that long drying times are required and that the residue of the dried carpet shampoos, consisting of active washing Substances and / or plastic dispersions that can no longer be removed by the vacuum cleaner. These remaining sticky residues cause increased resoiling and often lead to Color shifts. Even with upholstered furniture, aqueous cleaners have too much of a penetration effect Textile layers result, which in particular leads to impairment of down fillings.

In contrast, the agents according to the invention can be used without further ado and are burdensome 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. So they are particularly suitable for Cleaning and care of textile products, in particular those made of natural and / or man-made fibers and especially of carpets and carpeting, upholstery and the like, namely both for the overall cleaning and care of such products and for removing stains made from it, as well as for dry washing and hair care.

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. For example, when carpet flooring is cleaned with the cleaning agents according to the invention, there is no warping or buckling of the carpet, as is the case with those previously known for this purpose Agents based on alkyl sulfonates, alkyl aryl sulfonates and alkyl sulfates and condensation products of alkylene oxides with aliphatic alcohols or amines, which by shampooing in the carpet due to the damage to the floor caused by their high water content when they dry out 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 cleaning agent according to the invention, the antistatic and bactericidal finish of the Fiber is not removed, as is the case with the previous cleaning agents used on wet or damp routes, whereby by such a Removal of an increased static charge and thus increased re-soiling occurs. When using the agents according to the invention, however, the resoiling ability is reduced.

Compared to the known cleaning agents based on solvents such as ketones, esters and The agents according to the invention have halogenated hydrocarbons, optionally prepared as a paste the advantage of no edge formation, no damage to the fiber and no color changes, and in the It is easier to brush out of the products compared to the stain remover prepared as a paste or to have it aspirated.

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 has a degree of substitution of at least 0.05, in particular from 0.1 to 0.5. Highly substituted, cationic, hydrophilic starches are preferably hardened by crosslinking. Expediently, epichlorohydrin is used as the crosslinking agent. The procedure here is that starch is reacted with epichlorohydrin in an alkaline medium at temperatures of about 45 to 55 ^{° C.} Sufficient hardening of the starch grain is achieved. The cationic starch is then obtained by cationization. The mixing ratio of cation-active hydrophilic starch to hydrophobic starch is independent of the amount of dirt, but can be advantageous depending on the type of

the dirt can be varied. The ratio can generally advantageously be 75 to 25 parts by weight to 25 to 75 parts by weight of hydrophilic to hydrophobic starch. For the removal of low-fat dirt the ratio of hydrophilic to hydrophobic starch can preferably be 60 to 80 to 40 to 20% by weight and to Removal of oleophilic soil is preferably from 40 to 60 to 60 to 40 percent by weight. A mixture of Cation-active hydrophilic starch with a degree of substitution of about 0.1 and hydrophobic starch with ι ο A degree of substitution of about 0.2 has been found in a weight ratio of 2: 1 when used as a Detergents have been found to be particularly beneficial for most types of dirt, and are excellent at eliminating 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 the invention. Their production is explained below.

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. 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 is probably due to the fact that here in one and the same starch molecule both cationic and hydrophilic substituents hydrophobic substituents are present, which can mutually influence one another somewhat in terms of their effect.

In general, it can be stated that the quantities in the presence of a mixture and there :; Ratio of Degrees of substitution with one another in the presence of a starch having both types of S-substituents and the type of substituents and the degrees of substitution, which when used for cleaning and care of different products give the best results, depending on the type of product to be removed Hang out the dirt. In the case of types of smut that predominantly contain soot, for example, higher amounts of soot are used particularly active cation-active substituents selected, while with oil or fat-rich soiling selected higher amounts of hydrophobic substituents which are particularly active for such impurities will. In practice, the most suitable substituents, degrees of substitution, and ratios can be used in each case the degree of substitution of hydrophobic and hydrophilic cation-active substituents in a these two substituents having strength or mixing ratios of cationic more hydrophilic Starch to hydrophobic starch through simple routine tests, mostly through purely visual assessment determine various types of soiling. With two standard types you can practically all of the normally occurring ones Remove dirt easily, for non-greasy dirt with a mixture of 70 % By weight of cationic to 30% by weight of hydrophobic starch with a degree of substitution of 0.2 or in each case the corresponding mixed molecule and in the case of greasy dirt with a ratio of 1: 1 of hydrophilic to hydrophobic starch or the corresponding mixed molecule,

The ion-active substances present in the products according to the invention in a mixture with hydrophobic starches Hydrophilic starch derivatives can 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, chloropropyl diethylammonium hydrochloride, N- (3-chloro-2-hydroxypropyl) trimethyl

ammonium chloride and
23-epoxypropyltrimethylammonium chloride,

can be obtained.

According to the invention preferred cation-active hydrophilic Starch derivatives with a starch grain structure are starch ethers with quaternary ammonium groups general formula

Strength —O - R, —N

R,

R4

CV

where Ri is a lower (preferably Ci-Ci) alkylene, in particular a propylene or hydroxypropylene radical, and R2, R3 and R »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 Rj 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

H H H

—C -CC-

I I

H H

OH

and R2, Rj and R4 are lower alkyl radicals, in particular. Represent methyl radicals.

These products are preferably prepared in the usual way, namely by reacting starch with glycidyltrialkylammonium chloride and, in particular, glycidyltrimethylammonium chloride in an aqueous medium in the presence of 0.5 to 0.6% of an alkaline catalyst, ie sodium hydroxide, potassium hydroxide and calcium hydroxide at below the gelatinization point of Strong lying temperatures, in particular at temperatures between 40 and 50 ⁰ C. produced.

Present in the inventive products together with the cationic hydrophilic hydrophobic strengths strengths, known hydrophobins be starch derivatives with starch grain structure be, that can be produced by conventional methods for producing such products. Such products can be obtained by reacting starch with monofunctional aliphatic araliphatic, acyclic or aromatic compounds which contain an active group and form an ether or ester bond with starch. As active groups, epoxy, halogen and acid anhydride groups and double bonds are preferred, aralkyl epoxy compounds, in particular phenyl glycidyl ethers or styrene oxide. derived hydrophobic groups are particularly preferred.

Examples of etherifying agents are propyl chloride. Isopropyl chloride. Butyl chloride. Ammonium chloride. Allyl chloride, methallyl chloride, 3-cyclohexenyl chloride, benzyl chloride, p-halobenzyl chloride. o-halobenzylchlo- _ί> rid, 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.

Esterification agents used for the production of hydrophobic Starch esters are also known. It is, for example, m 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 biityrate, vinyl 2-ethylhexoate, Vinyl stearate. Vinyl benzoal, isopropyl isocyanate. Stearyl isocyanate, phenyl isocyanate, o-, m- or jo p-tolyl isocyanate. Naphthyl isocyanate or o-, m- or p-Halvjgenphenylisocyanat or Tosylisoeyanat.

These reactants are mostly used in an alkaline medium with unglossed. granular starch reacted. The reaction can be carried out in the dry state or in suitable liquids such as water, alcohols and ketones. The reaction temperature is mostly from 40 to 65.degree. especially 50 to m C.

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

Strength — O —R ₁ -OR,

preferably wherein Ri is a lower (preferably Cj-Ο,) Aikyien-, xypropylenrest particular propylene or hydraulic means and R2 represents an alkyl, aralkyl, cycloalkyl or aryl group, 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, the natural fatty acid mixtures or their hydrogenation products, and aralkyl or aryl it is preferably naphthyl or especially phenyl, as aryl group. Examples of the radicals R ₂ are thus phenyl. Hexyl, decanyl, stearyl, cetyl and the C ₁₆ -Cia 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

11 H.
C "C

Il

OH

and Rj represents a radical - (VH;

These particularly preferred derivatives are preferably obtained by reacting granular starch with phenyl glycidyl ether in an alkaline aqueous medium at temperatures from 50 to 55.degree .

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 oil. z. 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 services listed there for the starch services 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 are preferred. Instead of native starch, starches modified by acids or oxidizing agents can also be used.

The cleaning agents according to the invention are applied to the products to be cleaned as a powder or in a liquid carrier and can be easily removed again after the dirt has been absorbed, for example after brushing into a carpet by means of a vacuum cleaner. Since dry starch powder has a tendency to dust, dusting can be easily prevented according to the invention if just enough of a volatile organic solvent, such as ethanol or isopropanol, is added to the dry powder for the fine starch granules to agglomerate to form larger structures. For this purpose, 1 to 5% addition of solvent, in particular 2%, is completely sufficient. The agents are then in the form of non-dusting, scatterable or free-flowing powders. The solvent evaporates during use 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 tc \ tilem 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, also has an increase in the bulk volume of the agent, which makes it can be evenly distributed. In addition, there will be a back cover for the cheaper Zcüüioscfsscr 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 weighting agents are preferred 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, it has proven particularly advantageous in particular, 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 30:70 being particularly preferred

As already mentioned, the agents can contain up to 50% other common additives, such as extenders, but of course also, for example, fragrances, bactericides or, in particular, bacteriostats and antistatic agents Middle. Such additives can be added after simple mixing, or they can be added in be introduced in a known manner in the agglomeration, z. B. by being in the agglomeration solvents used are dissolved or suspended in these.

In particular with cleaning agents for products made from natural and / or man-made fibers, antistatic and bactericidal or bacteriostatic substances are used with advantage, since these are low molecular weight Compounds remain on the fiber surface and an additional desirable antistatic and result in bacteriocidal or bacteriostatic finishing of these products.

The following examples illustrate the invention.

ίο

example 1

Manufacture of a both cationic hydrophilic

Substituents as well as hydrophobic substituents
exhibiting starch (mixed molecule)

/ u A solution of 182 g of sodium sulfate decahydrate in 1900 ml of water becomes a solution of 11.2 g Sodium hydroxide was added to 36 ml of water. In addition

ίο slowly pour 720 g while stirring vigorously 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 glycidyltrimethylammoni-

II added chloride. The reaction mixture is allowed to continue stirring for 22 hours at 43 ⁰ C. After cooling, the pH is adjusted to 5 with 10% strength sulfuric acid. The starch is sucked off and

rns! s Γϊΐϊί

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
i>

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 substitution! "'Ad 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 into a drum and dirt mixture A is added in excess. By Balls in the rotating drum, the dirt mixture is then worked intensively into the carpet the excess dirt is removed with a vacuum cleaner in addition to this pollution the dirt mixtures B and C were applied with a cloth.

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" dirt on the carpet, the following dirt was collected

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

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 they were vacuumed to remove excess dirt. The results were visual judged. 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.

In a corresponding manner, pieces of carpet measuring 35 × 14 cm were soiled with shoe polish, namely

"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 was able to regain its original appearance

ίο be.

The carpet swatches so soiled were then treated with mixtures of cationic and hydrophobic Cleaned starch of varying composition by rubbing the starch preparation with a rotating

n the brush was incorporated and then vacuumed with a vacuum cleaner. The starch mixture was varied from 50% cationic starch to 50% hydrophobic starch to 100% cationic starch unH fl0 / n hvHrnnhnhpr starch p In Hpn fnlcrpnHpn

2 (i tables show the results, the term "road dirt" referring to the dirt mixture of 109 g calcium carbonate, 26 g carbon black and 22 g oil on the soil composition, secondly depending on the soil concentration and thirdly depending on the amount of starch used.
The cleaning ability is calculated according to

ίο the following formula:

WGg-WG
WGna - WGa

j-, RF = cleanability

WG = whiteness

g = cleaned

a = dirty

na = not soiled

Starch blend 3% dirt. 20g starch mix. RF 0.5% dirt, 20g starch mix. RF cat. : hydroph. WGg-WGa Wna-Wa 66.1 Wg-Wa Wna-Wa 66.4 50:50 19.7 29.8 63.4 16.2 24.4 64.0 60:40 19.1 30.1 71.4 14.6 22.8 75.4 70:30 24.5 34.3 63.7 22.1 29.3 75.3 80:20 21.6 33.9 65.4 20.7 27.5 68.9 100: 0 22.5 34.4 19.7 28.6 continuation Starch blend 3% dirt, 10 g starch mixture. RF 0.5% dirt, 10g starch mix. RF kaL: hydroph. Wg-Wa Wna-Wa WG-Wa Wna-Wa

50:50 14.9 60:40 16.7 70:30 19.0 80:20 19.6 100: 0 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

hydroph. 13th 28 06 450 14th Wna-Wa RF 50 28.8 66 40 2Ug starch mixture. lOg starch mix. 28.3 63.9 "Shoe polish" 30th Wg-Wa Wg-Wa 29.1 57.7 Starch mix 20th 20.4 Wna-Wa Theatrical Version 19.0 30.1 62.4 kai. 0 20.9 28.8 70.9 18.1 31.8 59.7 50 19.9 28.3 73.8 16.8 60 21.6 29.1 68.4 18.8 70 20.6 30.1 71.7 10.0 80 31.8 65.4 100

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

The reaction product '; from native starch and Giycidyitrimeihyiammoniumchlorid and as the hydrophobic starch, the reaction product of starch with phenyl glycidyl ether used.

Example 4

oil absorption of hydrophobic starches

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 vigorous stirring with the Tl rax, 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)

O recording

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

50% 60% 76% 60% 55% 49%

21% 0%

Example 5

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

The following table shows the influence of the density of the Solvent on the shaking time depending on the starch mixture.

Starch mix. Strong / 50 "» hydr. 50 strength 30th 50 ⁿ o kai. 60 50 40 70 IPA 70 40 1.064 60 1.17; CH _: C1 _: 30th 1.011 1.118 density 0.951 Shake it up 2.7 approx time (see) 3.3 1.2 1.6 I. after 1 h 7.4 2.2 6.1 approx 3.9 after 15 h 8.1 12.3 5.5 after 46 h 30.6 (Stand)

SlMrkcmiM.il.

4 (1 '. ImIr. St.iikc / Mi kai. Brand

CII-Cl;

density

Shaking time (see)

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

"0
30th

W)
40

40

0.951 1,011 1,064 1.1 IS 1,172

3.6
3.8

18.8

2
2
8.1

approx.

4.2

1 2.1

1 approx.

Starch mix.

30% hydr. Strength / 70% cat. strength

IPA 70 60 50 40 30

CH ₂ CI 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. 1

(Stand) Remarks: IPA = isopropyl alcohol

The shaking times were determined as follows: In a 100 ml spray can 25 g starch mixture, 50 ml solvent mixture and a given small steel ball. After closing the can with a rubber stopper, shake it for so long with the magnetic stirrer, which is equipped with a shaking attachment, until the rattling of the ball can be heard For the individual tests, measurements are made at the same 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 substance 2. Cleaning agent according to claim 1, characterized in that it consists of a starch (mixed molecule) having both cationic hydrophilic substituents and hydrophobic substituents with a starch grain structure 3. Cleaning agent according to claim 1 or 2, characterized in that it is in a liquid Carrier is suspended or made into a paste 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 in the mixed molecule the degree of substitution of cationic hydrophilic substituents at least 0.05, in particular 0.1 to 0.3 and the Degree of substitution of hydrophobic substituents pp. 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 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. 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 nich claim 5, characterized in that the ratio of hydrophilic to the jcsimination of hydrophilic dirt hydrophobic starch is 40 to 60 to 60 to 40 wt .-%. · »> 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. > o 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.