DE2446449A1 - HYDROPHILIC MIXED POLYMERIZED SALT - Google Patents

Description

Dr.-lng. E. BERKENFELD · Dipl.-ltig. H. BERKCNFELD, patent attorneys, Cologne

24464A9

Attachment file number

for input from 23 September 197 ^ vA / Named.Nm. Hydrophilics International,

" ^: " ■ '■ -. "Ine.

Hydrophilic copolymer salt

The invention relates to a copolymer comprising the acid salt of a copolymer of a hydrophobic monomer, including methyl methacrylate, and a potentially hydrophilic monomer, in particular an amine-substituted acrylate or methacrylate. The hydrophobic monomer is in amounts from 60 to 90 percent and the amine substituted potentially hydrophilic monomer; in amounts of 10 to 40 % . The mixed polymer salt is particularly suitable for the permanent approval of agricultural fine chemicals and as a volatile adhesive for dentures.

Hydrophilic mixed polymer salts, which are required for a permanent release of Agricultural chemicals used are in on August 11th Application No. 279,888 filed by Izhak Blank in 1972 and claimed B; Copolymers of acrylic or methacrylic acid with different acrylates or methacrylates, which with Alkylenimine have been treated are described in the application filed on April 24, 1972 under the file number 246,831 and claimed.

Hydrophilic copolymers are known. Hydrophilic copolymers, which are made by a block copolymerization of methyl methacrylate and acrylic acid are in the US patents 3,728,314 and 3,728,317 to Izhak Blank. Hydrophilic Hydrogel copolymers are in the US patents

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H 120/1

2 976 576 and 3 220 9βΟ described by Wichterle.

Wichterle describes hydrophilic materials that result from interpolymerization in the presence of water from monofunctional as well as difunctional materials. According to these patents used monofunctional materials that are mass polymerized includes dimethylaminoethyl methacrylate. Wichterle's patents relate to the formation of dimensionally stable Bodies; In particular because of the difunctional material present, films cannot be formed according to these patents will.

Films formed from hydrophilic interpolymer material are very valuable for a number of uses. You can for example for the application of agricultural chemicals are used in such a way that the release of these materials is delayed and for a smaller amount of chemicals is required for a given purpose. The use of a hydrophilic film is particularly useful in combination with a chemically similar hydrophobic material is valuable, especially when the hydrophobic material is in contact with one Body part, which part is subject to friction, irritation or some other discomfort or pain.

For such applications it is often important that the material be adhesive Has properties or is useful over a pH ranging from the alkaline to the acidic range. The known Materials cannot be used without reservation for these applications, especially for spray-on films with the desired ones

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Properties and for purposes in which the film is not only the aqueous., but also with the organic solvent carrier must be compatible.

In accordance with the present invention, a material useful for forming hydrophilic films has been developed. This material is made by interpolymerizing one monomer which, if polymerized alone, would be hydrophobic with a second monomer that is potentially hydrophilic. The first groups of mixed polymers include methyl methacrylate, styrene, acrylonitrile, vinyl acetate and other acrylate and methacrylate esters. Methyl methacrylate is the preferred material. The second group of monomers are those which contain an amine group. Of the d first group of monomers should be 60 to 90 wt.? and from the second group 10 to ¹ IO weight? are present. The preferred amounts within these ranges depend to some extent on the particular end use for which the product is intended. If the mixed polymer salt is intended for an adhesive to be sprayed on, should the content of the amine material be less than 20% by weight? turn off; but if a use for a permanent release is intended, should the content of amine material be greater than 20% by weight? be.

After the interpolymerization of the two monomeric groups some or all of the amino groups neutralized with an acid. Organic acids such as citric or acetic acid, or inorganic acids such as hydrochloric or phosphoric acid can be used. The amount of acid used, which determines the degree of neutralization, influences the hydrophilic properties

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Compatibility of the copolymer with aqueous and organic Solvent solutions. In this way the special properties of the material can be modified to suit a wide variety of uses of uses to make usable.

A particular advantage of the copolymer of the present invention is its non-toxicity. It can consequently be used for many purposes, including those relating to the human Bodies stand, are used. Solutions of the copolymer salt of the present invention are particularly useful as spray-applied adhesive films for dentures and applications of agricultural fine chemicals suitable for delayed release. In a corresponding way, the material according to the invention is also for appropriate applications of medical, cosmetic or other materials.

Because of the combination of hydrophilic and hydrophobic properties of the Copolymer salt a film cast from the material can be used Absorb water and yet remain insoluble and have good adhesion to hydrophobic surfaces.

As already explained, the material of the present invention is a Salt formed by neutralization of an interpolymer, the interpolymer being composed of a hydrophobic and a potentially

makes hydrophilic part is formed. The hydrophilic part fea% - about 60 to 90% by weight - of the copolymer. The hydrophobic part is preferably methyl methacrylate. However, up to about 30% by weight of the methyl methacrylate can be replaced by other hydrophobic materials

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This includes styrene, vinyl acetate, acrylonitrile, the appropriate Acrylate and related materials, including other acrylate and methacrylate esters.

The potentially hydrophilic part of the copolymer is an amino-substituted one Acrylate of the general formula:

R 0

CH ₂ = CCO

where R denotes hydrogen or methyl, R 'and R "are independently hydrogen or alkyl groups with 1 to 4 carbon atoms., and η denotes 2 to β. The lower alkyl groups denoted by R' and R" include straight-chain as well as isomeric alkyl groups, for example methyl, ethyl, propyl, isopropyl, butyl and t-butyl. The potentially hydrophilic part makes es- about 10 to 40 wt -.% Of the copolymer of.

The interpolymerization of the various monomeric materials, such as one or more hydrophobic monomers and one or more potentially hydrophilic monomer occurs either in solution or in emulsion. The potentially hydrophilic comonomer can in situ are formed. In such a case, acrylic or methacrylic acid is used copolymerized with the hydrophobic comonomer with a subsequent reaction of the copolymer with a material, such as ethyleneimine to produce the desired copolymer.

In the case of solution polymerization, a solvent is selected that

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is useful for the application of the finished formed material. Examples of solvents are acetone, which is preferred, acetone mixed with methanol, methyl ethyl ketone, mixtures of methyl ethyl ketone and methanol, mixtures of acetone and ethanol and mixtures of methyl ethyl ketone with ethanol. The solvent used can be particularly useful when the material is to be used, for example, as an adhesive for a denture plate. The solvent polymerization is carried out in a known manner, generally with about 40 to 60 % solvent with the remainder being the copolymeric materials.

In addition to the required hydrophobic monomer and potentially hydrophilic monomer, other monomers can be copolymerized to achieve the properties desired in each case. All monomers used are usually monoethylenically unsaturated, so that the copolymers obtained are predominantly linear and not crosslinked. This enables them to be used as films rather than the formation of gels that are not useful for the same purposes.

For the interpolymerization is generally the use of one Free-radical polymerisation-initiating catalyst required; in particular, azo-isobutyronitrile can be used as a catalyst will; however, other known catalysts are also available to the person skilled in the art. The amount of catalyst can, based on the total mixture of monomers to be polymerized in the range of about 0.1 to 0.5 weight percent; preferably the catalyst in an amount of about 0.2 to about 0.3 wt .- ^, based on the

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Weight of monomers used.

The copolymer obtained in this way is hydrophobic; it can, however, be made hydrophilic by partially or completely neutralizing its amino groups. The degree of hydrophilicity is determined by the content of amine groups and the degree of neutralization of the amine groups present. In particular, a higher content of amine group-containing parts of the Copolymer or a neutralization that comes closer to a complete neutralization, the copolymer salt more hydrophilic. As the copolymer becomes more hydrophilic, it is less compatible with non-polar solvents such as organic solvents. Compatibility with non-polar, organic Solvents can be increased by lowering the amine content or by lowering the neutralization. It can accordingly, the properties of the copolymer can be adjusted to very specific uses.

The amine groups in the copolymers are neutralized with an organic or an inorganic mineral acid. The amount used will of course depend on the degree of neutralization desired. Organic acids, such as acetic and citric acid, or inorganic acids, such as hydrochloric acid or phosphoric acid, can be used as acids. Regardless of the type of acid, a sufficient amount must be used for the film to have a water absorption of at least 20 % ; this amount depends, as indicated, on the amine content. As an example, with an amine content of about 30 %, it should be stated that a partially new

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tralization of about 60 % leads to a water absorption capacity of 2o % . The neutralization can be carried out by adding the required amount of the desired acid to the solution of the copolymer before the copolymer has been cooled to room temperature, or after cooling. It depends in particular on the safety measures to be taken and less on technical requirements when the acid is added.

After the formation of the desired copolymer salt by a Interpolymerization of the monomers and neutralization of a part or all amine groups, the solution is generally useful for the particular intended use. For example Agriculture fine chemicals can be mixed with the solution for spraying, or the solution can be mixed with various materials blended to make the material useful as a fugitive adhesive for application to dentures. In the latter case, the Solution for example with astringents as well as with fuels can be added to make the material suitable for spraying purposes close; it can also be used with known disinfectants, deodorants, Flavors, such as menthol, with colorings and pigments, such as calcium carbonate, or with drugs such as novocaine, or bactericides such as benzalkonium chloride or neomycin sulfate will. If the concentration of the mixed polymer salt in the solution is greater than desired for use, an additional amount of water or solvent can be added as desired.

Exemplary embodiments of the invention are in the following

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-S-

Examples described.
EXAMPLE 1

A copolymer of methyl methacrylate and dimethylaminoethyl methacrylate was prepared in the 'manner that, with stirring, l60 parts of methyl methacrylate, 40 parts of dimethylaminoethyl methacrylate _s 200 parts of acetone and 0.6 part of azo-isobutyronitrile were heated under reflux for seven hours. The resulting solution contained 50.2 % copolymer solids. The solution was admixed with 15.5 parts of glacial acetic acid while stirring, without cooling, in order to neutralize any amino groups present.

EXAMPLE 2

The copolymer solution obtained according to Example 1 was admixed with a fluorocarbon propellant, a further amount of acetone and small amounts of pigments and menthol in order to achieve a content of copolymer salt of 3 % . Methyl methacrylate dentures were rinsed with water and dried with tissue paper. The propellant solution obtained as indicated above was sprayed onto the denture on the rubber side and a film of the copolymer salt obtained, which absorbed about 25% of water. The bits were found to be extremely comfortable when inserted into the mouth.

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EXAMPLE 3

A copolymer salt was prepared from the same materials and in the same manner as described in Example 1, with the difference that the neutralization was carried out with the same amount of hydrochloric acid. The resulting spray-applied film on methyl methacrylate dentures absorbed about 50 % water.

EXAMPLE 4

A copolymer was produced according to Example 1 with the difference that the neutralization was carried out with the same amount of citric acid. A film obtained from the solution obtained by spraying onto dentures absorbed approximately 20 % water.

EXAMPLE - ■. .

A copolymer was formed from 160 parts of methyl methacrylate, 40 parts of t-butylaminoethyl methacrylate, 200 parts of acetone and 0.6 part of azo-isobutyronitrile by refluxing for about eight hours. The resulting solution contained 48.7 % copolymer solids. To neutralize amine groups, the solution was admixed with 12.9 parts of glacial acetic acid and an aerosol, as indicated in Example 2, was prepared. The aerosol was sprayed onto dentures made of methyl methacrylate; the resulting film absorbed approximately 20 % water.

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EXAMPLE 6

423 parts of methyl methacrylate, 2 parts of ethylhexyl acrylate, 90 parts of acrylic acid, 320 parts of acetone, 80 parts of methanol and 1.8 parts of azo-isobutyronitrile were refluxed for 4.5 hours. The resulting solution contained 56 % copolymer solids. 100 parts of the solution of the copolymer were mixed with 145 parts of ethanol and the solution obtained was heated in order to distill off all of the acetone present; 95 parts of acetone were recovered at / a final distillation temperature of 79 ° C. 4 parts of ethyleneimine in 20 parts of ethyl alcohol were added to the solution over the course of one hour while maintaining a temperature of 75.degree. Heating and stirring were continued for a further 30 minutes and 5.6 parts of acetic acid were added to neutralize the amine groups obtained. A film was cast from the solution of the polymer which absorbed 25% water.

EXAMPLE 7

A mixed polymer was prepared according to Example 1 with the difference that 140 parts of methyl methacrylate and 20 parts of styrene were used instead of 160 parts of methyl methacrylate. A film cast from the solution of the obtained polymer absorbed 25 % water.

EXAMPLE 8

0.1 part of tannic acid was added to 100 parts of the propellant solution of Example 2. The film was sprayed in the same way

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and found j that he besides the desirable properties the copolymer salt film had astringent properties,

EXAMPLE 9

A copolymer was prepared from 140 parts of methyl methacrylate, 60 parts of t-butylaminoethyl methacrylate, 200 parts of acetone and 0.6 part of azo-isobutyronitrile by heating under reflux for eight hours. The mixed polymer content was 51 %. 50 g of this material were treated with 2.4 parts of acetic acid to neutralize the amine groups, and a film was cast from the solution thus obtained, which film absorbed 60% of water.

The use of copolymer salts according to the invention for the application of agricultural chemicals is described in the following examples. In some cases ± it desirable to keep ready a chemical compound for agricultural purposes in one place for an extended period. If, however, the compound is used on site in pure form or in the presence of one or more of the usual carriers, it is usually only available for a short period of time before it is spread by the environmental conditions. If, however, a lasting effect is to be achieved, the material, based on the amount actually required, must be present in such large amounts that undesired pollution of the environment occurs.

For example, fine chemicals in agriculture are currently

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gel by spraying an aqueous solution, emulsion or dispersion or by dusting on plants or those surrounding the plants Soil applied. Such materials, especially pestic

little
de, are generally only / soluble or practically insoluble in water, although they are soluble in organic solvents. These materials therefore generally become emulsifiable in the form

To the

Concentrates applied, salts suitable as agricultural pain chemicals are described in the pending application Izhak Blank, Serial No. 279,888. The salts described in this application are useful for the stated purpose, but they can only be used for alkaline or neutral media. On the other hand, the salts of the present invention can be used to 9 ₃ over a wide pH range, in particular from about 5. .

The agricultural compounds that are present with the copolymer salts Invention can be used, for example, pesticides, such as insecticides, and other animal pesticides, fungicides and herbicides as they are commonly known. The invention Salts are particularly useful with the insecticides methyl and ethyl parathion. Since the solubility properties of the salts of the Copolymers can be so largely changed, there is a great deal of leeway with regard to the formulation of the desired agricultural mixtures. Such mixtures can, for example, be wettable Be powder or aqueous solutions if the pesticide is water soluble. Optionally, the salts can also be produced in such a way that that they form surfactant-containing solutions in organic solvents, such that emulsifiable or water-

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dispersible concentrates are formed prior to their application just need to be mixed with water. The finished agriculture mix is applied in one place in each case; where a controllable release of the agricultural chemical contained in the mix or chemicals is desired.

EXAMPLE 10

A copolymer was made from a mixture of 9 & 0 parts of methyl methacrylate, 420 parts of dimethylaminoethyl methacrylate, 1400 parts of acetone and 4.2 parts of azo-isobutyronitrile by heating prepared under reflux for eight hours. The resulting solution of the polymer was cooled; the solution had a content in copolymer solids of $ 48.5 · The chilled solution 162 parts of acetic acid was added, sufficient to neutralize all of the amine groups; the solution was during further Stirred for thirty minutes. The polymer solution obtained was complete with many solvents such as xylene, toluene, ethanol and methyl ethyl ketone and water miscible. The polymer solution was mixed with such an amount of water that ten percent Polymer solution was obtained, which could be handled in a simple manner.

EXAMPLE 11

In the same way and with the same amounts as in Example IC was described with the difference that instead of dimethylaminoethyl methacrylate t-butylaminoethyl methacrylate was used,

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a copolymer produced. 137 parts of acetic acid were used and the resulting solution of the copolymer was Miscible with the solvents given in Example 10.

EXAMPLE 12

According to Example 1, a copolymer solution composed of 700 parts was obtained Methyl methacrylate, 280 parts of styrene, 420 parts of dimethylaminoethyl methacrylate, 1400 parts of acetone and 4.2 parts of azo-isobutyronitrile prepared. The amine groups were added with 137 parts of acetic acid neutralized; the resulting solution of the polymer was miscible with xylene, toluene, ethanol and water.

EXAMPLE 13

A mixed polymer solution was prepared from a mixture of 222 parts of methyl methacrylate, 78 parts of dimethylaminoethyl methacrylate, 300 parts of acetone and 0.9 part of azo-isobutyronitrile by heating under reflux for eight hours. The resulting solution was cooled; it had a solids content of copolymer of 48.5 %. With stirring for thirty minutes, all amine groups were neutralized with 29.7 parts of acetic acid.

The polymer solution obtained in this way was completely miscible with many solvents such as xylene, toluene, ethanol, methyl ethyl ketone and water. While stirring vigorously, the polymer solution was diluted to a concentration of 10% by adding water; the solution thus obtained was convenient to handle. One litre

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the solution prepared according to Example 10 was with one gram
Benomil added while stirring vigorously to dissolve the benomil. A clear film was cast from the resulting solution
and absorbed water.

EXAMPLE 1 * 1

Solutions were prepared in order to determine the effectiveness of copolymers according to the invention with agricultural fine chemicals in comparison with the chemicals in the absence of the inventive copolymer salts for controlling aphids. It
Five different areas were tested and sprayed using a rape sack sprayer as follows:

a) untreated control area;

b) 3> 3 1 of a 50 % effective concentration,
Malathion in 300 liters of water per hectare;

c) 3> 3 1 of a 50 % effective concentration,

Malathion in 300 l of water, which contained 1.25 % of the copolymer salt of Example 10, per hectare;

d) 2 1 of a 35 % effective concentration,

Thionex (endosulphan) in 300 liters of water per hectare; and

e) 1 1 of a 35 % effective concentration,

Thionex (Endosulphan) in 300 1 water, the 1.25 % des
Copolymer salt according to Example 11 contained, each
Hectares.

The treated areas were part of a common location for peppers planted in spring; the different faces were

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Checked during a period of 15 days in April / May. Myzus Persicae (Sc.) Was the predominant aphid. The following results were obtained: '.

a) constant growth of aphid population;

b) a sharp drop in the aphid population to zero during the first six days, followed by a sharp increase followed the original level of infestation;

e) good control of the leafy tau population for fifteen Days;

d) full dosage (2 liters in 300 liters of water) gave good control for the entire period of fifteen days; and ' "

e) half a dosage (1 1 in 300 1 water) of Thionex with the polymer gave good aphid control for fifteen days. - · '

Test results show that the copolymer salts according to the invention the effectiveness of agricultural fine chemicals is increased.

EXAMPLE i $ . · ■

A cotton field infested with Prodenia and sown during the spring was selected _{9 to} test the effectiveness ⁷ of controlling the insect using the copolymer salts of the present invention. Treatment was carried out in August by aerial spraying as follows:

a) there were 3 kg of parathion, 50 % effective concentration, 5 0 9 8 15/1164

applied in 30 liters of water per hectare on a 4 hectare plot ;

b) 3 kg of parathion, 50 % effective concentration,. in 30 l of water containing 3% of the copolymer salt of Example 10, applied per hectare to a separated k hectare parcel ^. . · -. ".-.

A first spray took place on August 8th and the egg masses and larvae were then checked daily. It was found that by August 28, treatment with five sprays (a) was required to achieve adequate control of the insect, while adequate control was achieved with treatment (b) without additional sprays. It follows that the presence of mixed polymer salts according to the invention the effective -he- -

e of an insecticide treatment increased considerably.

EXAMPLE 1?

It has been applying the effectiveness of fly control of mixed polymer salts of the present invention tested. Two cowshed enclosures heavily infested with house flies, approximate

80 m area was treated with a Knapsack sprayer. The spraying took place on 2k. June took place and the treatments were like:

Spray components enclosure B

Copolymer salts of Example .10,

10 % in water 2 liters none

Sugar 800 g 800 g

Dimethoate, SP, HO% effective 500 g 500 g

Water 5 0 9 8 1 5/1 1 6 A on 20 1 on 10 1

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The pliegen concentration was determined in such a way that one wooden sieve with an area of 0.25 m in various places in the enclosure and counted the number of flies that covered the screen after two minutes. Each time it was approximate twelve such readings taken, and the average, multiplied by 4 was used to determine the concentration of flies per square meter. The results are shown in Table I, from which it appears that control of the fly was permanent can be achieved by means of a copolymer of the present invention at the same time with an agricultural chemical and so the Prevents flies from multiplying. Is.

TABLE I. Number of flies per square meter Enclosure A Enclosure B

65 65

15 55

0 20 '

15 35

The present invention relates to a new and valuable copolymer salt, <. of which the amount of one of its components and the degree to which this constituent can be neutralized after the polymerization is variable in order to ensure compatibility to be determined with water and non-polar organic solvents. The material is extremely useful as a fake pad and adhesive for dentures or other hydrophobic methacrylate plastics, as well as a means of increasing the effective life of agricultural

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date Τε LfCjW it GL wi-A VXw ItX
Spray June 24 O (before spraying) 25th June 1 June 28th -tr ■ July 1st 8th

to extend culture fine chemicals.

Claims

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Claims (17)

Dr.-lng. E, BERKENFElü · Oipl .. 1. Hydrophilic Mischpolymerisatsalz containing 60 to "90 weight -% of a hydrophobic monomer units formed and 10 to 40% by weight of units of a potentially hydrophilic monomer of the general formula: RO
CH ₂ = CCQ ( ^G _n ^H 2n ⁾ NR'R " contains, wherein R is hydrogen or methyl, R 'and R "are independently hydrogen or alkyl groups with 1 to carbon atoms, and η is 2 to 6, and some of the amine groups are neutralized with an acid so that the copolymer salt has a water absorption of has at least 20 % . 2. mixed polymer salt according to claim 1, characterized in that that the hydrophobic comonomer is methyl methacrylate. 3. mixed polymer salt according to claim 2, characterized in that up to 20 % of the methyl methacrylate has been replaced by styrene, acrylonitrile, vinyl acetate or acrylate or methacrylate esters. 4. mixed polymer according to claim 1, characterized in that the hydrophobic comonomer 70 to oO % e and the hydrophi- <xusnr><xch
le copolymer 20 to 30 % -e. 509815/1164 5. mixed polymer salt according to claim.1, characterized in that the hydrophobic comonomer 8Q to 90. % And the hydrophilic comonomer 10 to 20 % -. 6. Mischpolymerisatsalζ according to claim 1, characterized in that the hydrophobic comonomer 60 to 80 % and the hydrophilic comonomer 20 to kO% ^: ·. ^: 7 · mixed polymer salt according to claim. 1, characterized in that that the amine groups have been neutralized by acetic acid, citric acid, hydrochloric acid or phosphoric acid. 8. Use of a hydrophilic copolymer salt according to claims 1 to 7 for coating hydrophobic surfaces. 9. Use of a hydrophilic copolymer salt according to claims 1 to 7 in the form of a solvent solution which comprises 20 to 50 % water and 80 to 50 % of an organic solvent for coating hydrophobic surfaces. 10. Use according to claim 9, characterized in that the organic Solvent acetone ,. Ethanol, methanol ,. Methyl ethyl ketone or a mixture of these. 11. Use according to claim 9, characterized in that the mixture additionally contains flavorings, pigments, medicaments or bactericides. 50S81.5 / 116A 12. Use of a hydrophilic copolymer salt according to the claims 1 to 7 to extend the effective life of Agricultural agony chemicals. 13. Use according to claim 12, characterized in that the hy- • drophobic comonomer 60 to 80 % and the hydrophilic comonomer 20 & us * -> -! eight
up to HO% 14. Use according to claim 12, characterized in that the copolymer salt is present in an amount of about 10 % in water with an effective amount of an agricultural fine chemical. 15. Use according to claim I ¹ I, characterized in that, based on the agent, the agricultural pain chemical is present in an amount of not more than 10 % . 16. Use according to claim 14, characterized in that the Agricultural pain chemical from methyl parathion, ethyl parathion, Dimethoat or Thionex consists. 17. Use of a copolymer salt according to claims 1 to 7 for making a film. 50 9 815 / 116A