DE2229972A1 - PROCESS FOR PRODUCING LIQUID RESIN COMPOUNDS - Google Patents

Description

Process for the production of liquid resin compositions

The invention relates to a method for producing liquid resin compositions. In particular, "relates to the invention to a process for the production of homogeneous, stable solutions or aqueous emulsions of anionic resins.

Aqueous emulsions of polyurethane are widely available as a coating and adhesive as well as for sealing in use. However, high molecular weight polyurethanes are generally hydrophobic and it is therefore difficult to immediately disperse them uniformly in water in order to obtain such homogeneous, to obtain stable emulsions. For the production of polyurethane emulsions, a process is known in which a Auxiliary emulsifying agents, such as a cationic, an anionic or a nonionic surfactant, are used will. There is also a method in which a polyurethane containing a tertiary amino nitrogen is mixed with an aqueous, acidic solution is mixed, as well as a method in which

209882/1026 _{/ o}

a tertiary amino group is converted to a quaternary one.

However, these earlier processes using an emulsifier require a significant amount of emulsifier, so that the cost of the final product is high. In addition, the emulsifier sometimes causes the Emulsion at the time of use or it has an adverse effect on the properties of the product after this has dried. Therefore, the use of such emulsified products is restricted to an extremely narrow range. In the latter process, in which a tertiary amino group is built into a polyurethane chain in order to then transform it into an acidic salt, or in which one Quaternization is effected, the persistence is emerging Solution low if the molecular weight of the polyurethane is too high. If, on the other hand, the molecular weight of the polyurethane is decreased in order to obtain stable emulsions, the physical properties of the material made from such emulsions are reduced Films bad. Measures that have been taken to improve the stability of the emulsion affect in disadvantageously the physical properties of the resulting polyurethane films. So it is difficult to be stable To obtain polyurethane emulsions with excellent physical properties by the known processes.

The purpose of the invention is to provide new, flüadge polyurethane resin compositions high stability and with excellent physical

209882/1026

see. Properties to produce.

On the basis of extensive research, it was found that one stabil® resin solution or an aqueous dispersion can be produced by 1.) a urethane prepolymer, which has terminal isocyanate groups and consists of a polyhydroxyl compound made with an excess of polyisocyanate is, with 2.) an excess of a polyalkylene polyamine lets react so as to win polyurethaneurea polyamines. Then the product is left with an anhydride cyclic dicarboxylic acid react and finally mixes the reaction product obtained with an aqueous solution of a basic substance. The present invention has been accomplished on the basis of these discoveries.

After the. The method of the present invention is by reaction between a polyurethane urea polyamine and an anhydride a cyclic dicarboxylic acid formed a half amide. Thus, carboxylic acid groups become in the molecule of this reaction product formed and an anionic, liquid resin composition is obtained by neutralizing these carboxylic acid groups with an aqueous solution of a basic substance. The resin composition obtained according to the invention contains within the resin body various urethane groups, urea groups and amide groups, which have a binding force, and due to the presence of such groups, the composition according to the invention is able to have a to form tough foil or a corresponding coating, yourself

209882/102 6 '

if it is dried without further special measures. However, the drying is preferably carried out at a higher temperature. Furthermore, the resin composition according to FIG Invention can be crosslinked by the action of a polyvalent heavy metal. The cross-linking can also be done by a polyfunctional connection made which the ability £ ur Has cross-linking, such as formaldehyde, or a formaldehyde-supplying substance, or a compound that has a similar Has activity such as formaldehyde, such as hexamethylene melamine, or an carbamide resin, or with the help of a masked Polyisocyanate or a polyepoxide. Furthermore, if a compound that has an active double bond is considered a cyclic Dicarboxylic anhydride is used, the resulting anionic Resin mass are crosslinked in the presence of a peroxide. Such processes can be used to produce cross-linked coatings, impregnated products and adhesive layers from the resin composition form according to the invention.

Since the physical properties of the composition according to the invention can be easily improved by the cross-linking reaction Performs as described above, it is not necessary to have an extremely high molecular weight of the polymer in the original aqueous polymer solution or emulsion to provide the improved physical properties to ensure. According to the process of the present invention, stable, liquid polyurethane resin compositions can be easily produced

209882/1026

of excellent physical properties.

Those to be used for the preparation of the compositions according to the invention Polyurethane Ti arnstoffpolyamines can be produced by that a polyalkylenepolyamine, preferably in a ketone solvent, for example acetone or methyl ethyl ketone, can react with a urethane prepolymer which contains isocyanate groups at the end. Such a connection is through Reacting a polyhydroxyl compound with an excess of a polyfunctional isocyanate obtained. Examples of these suitable Polyfunctional isocyanates are aromatic, aliphatic and cycloaliphatic isocyanates, such as 1,5-napthylene diisocyanate, 4,4'-diphenylmethane diisocyanate, 4,4'-diphenyldimethylmethane diisocyanate, Di- and tetraalkyldiphenylmethane diisocyanates, 4,4'-dibenzyl isocyanate, 1,4-phenylene diisocyanate, tolylene diisocyanate, chlorinated isocyanates, brominated isocyanates, phosphorus-containing isocyanates, butane-1,4-diisocyanate, hexane-1,6-diisocyanate, Dicyclohexylmethane diisocyanate, cyclohexane-1,4-diisocyanate and xylylene diisocyanate.

The polyhydroxyl compounds to be used for the preparation of the urethane prepolymer in the process according to the invention are those having molecular weights on the order of 2oo to 10,000. Any polyhydroxyl compounds can be used which are usually used for the production of polyurethanes, for example polyethers, polyesters, polyesteramides, Polyacetals, polythioethers and polybutadiene glycols. As polyethers, for example, homopolymers, mixed polymers and Graft copolymers of tetrahydrofuran, ethylene oxide, propylene

209882/1026

oxide and butylene oxide are used. Homopolyethers can also be added and mixed polyethers obtained by condensation, for example of hexanediol, methylhexanediol, heptanediol and Octanediol, are obtained. Propoxylated and ethoxylated glycols can also be used. The polyethers are thioglycol alone or condensation products of thioglycol with others Glycols are particularly preferable. As polyacetals, for example, water-insoluble polyacetals can be used, which e.g. of hexanediol and formaldehyde or of 4-, 4'Dioxyäthoxydiphenyldimethylmethan and formaldehyde. If necessary, these polyols can be combined with commonly used glycols, such as ethylene glycol, di- and triethylene glycols, butanediol, Propanediol, 1,6-hexanediol, neopentyl glycol and N-alkyl diethanolamines, which contain alkyl groups having 1 to 22 carbon atoms can be used.

As the polyalkylene polyamines used in the process of the invention, various polyalkylene polyamines can be used including polyethylene polyamine, polypropylene polyamine, polybutylene polyamine. The particular polyalkylene enpolyamines to be used in the process of the invention are those polyamines in which the nitrogen atoms are linked by groups represented by the formula - ^ γβ-οη " , in which η is an integer greater than 1, where the number of these groups in the molecule is 2 to about 8. The nitrogen atoms are in the group -G _n ^H 2n "" ⁸ ^ ^ ^e ^ n & Gbba.Tten carbon atoms

209882/1028

2228972

bonded, but not two or more nitrogen atoms are bonded to one carbon atom at the same time. Specific examples of such polyamines are diethylenetriamine, triethyl ent et ramine, tetraethyl enep ent amine and dipropylenetriamine. In addition, these amines can zii mixtures or Eohprodukte these polyamines are used. Hydroxyalkyl-substituted polyamines can also be used together with the above-mentioned polyamine compounds. In some cases, in order to modify the carboxylic acid density in the final anionic resin composition according to the invention or to improve the feel or feel of the resulting end products, it is desirable to increase the distance between the active, hydrogen-containing amino groups in the polyurethaneurea polyamine molecules. This can be achieved by replacing some of the polyalkylenepolyamines with piamines, for example ethylenediamine, propylenediamine and hexamethylenediamine, or those diamines which are substituted with alkyl groups, for example a straight-chain, saturated alkyl group with 1 to 22 carbon atoms, or with the aid of a Addition product of these amines with an alkylene oxide, with acrylonitrile or with an acrylic acid ester. For this purpose, up to about 80% of the polyalkylene polyamine can be replaced with one molar equivalent of such diamine. In general, the desired effect will be achieved by substituting about 50 % or less, calculated on the molecular equivalent, of the polyalgrene polyamine by the diamine.

The production of the urethane prepolymer, the terminal Isocyanate groups ecbhalt, and which according to the invention Yer-

209882/1026

Is to find a turn in the presence or absence of one Solvent such as benzene performed. If an aromatic diisocyanate reacts with the polyhydroxyl compound, a reaction temperature of 60 to 100 ° C is selected. If an aliphatic diisocyanate is used, is a reaction temperature suitable from 109 to 13o ° 0.

In making this prepolymer, it is preferable to use the diisocyanate in an amount such that all of them are functional Groups present in the polyhydroxyl compound actually react with these isocyanate groups. Accordingly, an excess of diisocyanate should be used. The preferred ratio of the total number of moles of NGO groups to the total amount of active hydrogen atoms within a range of 1.4: 1 to 2.4: 1.

Preferably, the Eeaktion between the urethane prepolymer is, which contains terminal isocyanate groups, and the polyalkylenepolyamine carried out under atmospheric pressure in a ketone solvent at a temperature of -2O ° C to +60 ⁰ O. The ketone solvent which can be used in this reaction consists, for example, of aoetone, methyl ethyl ketone, diethyl ketone, methyl isobutyl ketone and methyl isopropyl ketone. Acetone and methyl ethyl ketone are preferably used. It is possible to use a solvent mixture made by mixing a ketone solvent with a relatively

Mencce
nismäßig low νση benzene, tetrahydrofuran, dioxane, an acetate ester, dimethylformamide or chlorine-containing solvents is produced. The duration of the reaction varies depending on the reaction temperature and the reactivity of the

... / 9 20 9882/1026

Polyoxyanate compounds used. You reaction can be accomplished within shorter or longer times of what of Depending on the reaction conditions, you reaction will anyway continued until in the infrared spectrum that was found on the samples taken from the reaction mixture during the reaction is measured, no absorption of -tfCO radicals at a

-1
Wavelength of 228o cm can be determined. The acidity of the reaction is usually 1/2 to 2 hours.

In the reaction of the isocyanate groups at both ends of the prepolymer molecule made of urethane with polyalkylene polyamine are present, a conversion with the secondary 1min takes place first. As a result, the total number of hols should be primary and secondary amine groups in the polyalkylene polyamine can be larger than the total number of moles of isoyanate groups in the diisooyanate compound. To the extent that the total number of moles of amino groups As the total number of isocyanate groups approaches, polyurethaneurea polyamines of higher molecular weight can be formed but the product obtained is gel-like and has a high tendency to gel. the Amino groups are greatly increased, sioh forms a polyurethane urea polyamine of low molecular weight · Such products are unable to produce resins with excellent physical Provide properties when reacted with a cyclic sicarboxylic acid anhydride · Sas Molar ratio of the urethane prepolymer, which terminal Isooyanatgruppen contains ^ to the polyalkylenepolyamine varies, depending according to the type of Polyalkylenpolyaains used. Sas Molver-

• · ./1ο

209882/1026

- 1ο -

ratio is based on physical properties and the stability of the "in the reaction of the resulting polyurethane urea polyamine selected with the cyclic dicarboxylic anhydride to be achieved end product. In general is it is preferable that the polyalkylenepolyamine is used in a sufficient amount as compared with the urethane prepolymer. Bas ratio of the number of moles A of the isocyanate groups in the urethane prepolymer, which contains terminal isocyanate groups, to the number of moles B of amino groups which contain active hydrogen atoms, is on the order of 1 / B ^ $, preferably

1 <B <J. The molecular weight of the polyurethaneurea polyamine is preferably on the order of 6,000 to 30,000.

In order to convert the polyurethaneurea polyamine thus prepared into an anionic resin solution, it is left with a cyclic Dicarboxylic anhydride react. When this reaction is carried out in the absence of an organic solvent the resulting end product is very viscous. Ss is therefore, it is preferable that the viscosity of the product produced is reduced by having the reaction in the presence of a organic solvents such as acetone, methyl ethyl ketone and tetrahydrofuran. Although the reaction also takes place at room temperature can go on, it is preferable to do it with heating. Generally temperatures are suitable in an area between 5 ° 0 and 70 ° Q. The heaction time varies depending on the reaction temperature, but

.. ./11 20 98 82/1026

the reaction is usually carried out within one-half to about 2 hours.

In the reaction between the polyurethane urea polyamine and the cyclic dicarboxylic anhydride is formed as a result of the reaction of the primary and secondary amino groups Polyamines with the cyclic dicarboxylic acid anhydride form a halide. Therefore, in the above-described reaction, the formation caused by carboxylic acid groups.

As a cyclic dicarboxylic acid anhydride, maleic anhydride, ■ Succinic anhydride, phthalic anhydride, di-, tetra- and Hexahydrophthalic anhydrides, (trimellitic anhydride and Itaconic anhydride can be used.

In general, satisfactory results are obtained when the cyclic dicarboxylic anhydride in an amount of about 0.5 to about 2.0 moles, preferably 0.8 to 1.5 moles, to 1 mole of the primary and secondary amino groups in the polyurethane urea polyamine is applied.

The polyurethane urea polyamine in the above-described reaction and the cyclic dicarboxylic acid anhydride ^ is converted into a stable resin solution, when the reaction product is neutralized with a basic substance dissolved in a small amount of water. the An aqueous emulsion is produced by adding a

■ ... / 12

2 0 9882/1026 '

large amount of water * u the neutralized product with removal of the organic solvent, for example by distilling off the solvent under reduced pressure at 30 to 80 ° C. In this way, an aqueous emulsion of low viscosity is obtained which has a solid component in the order of magnitude of about 10 to 50 % .

As the base used for the neutralization, there may be mentioned Hydroxides, carbonates and bicarbonates of alkalis, such as sodium hydroxide, potassium hydroxide, lithium hydroxide, sodium carbonate, Sodium bicarbonate and potassium carbonate and ammonia. Also lower amines represented by the general formulas NHoE, NKEL · and NE are, where E represents an alkyl group with 1 to 4 carbon atoms or a hydroxyethyl or hydroxypropyl group, can be used.

The liquid, anionic resin compositions prepared according to the process of the invention can be used as coating agents for fabric, paper, leather, wood and metal. They can also be used as an impregnating agent for fibers, paper and fabric to make them antistatic, dirt-repellent and crease-resistant. They can also be used as binders for non-woven search and furs as well as adhesives, as thickeners, as agents that give the finished structure an elasticity in the construction industry, and as agents that allow the product in question to be comminuted during transport Prevent powder. Furthermore, the mass according to the invention as

... / 13

209882/1026

Color binder, as a resin for plastic stone mortar and as a Use binding agent for casting sand. Furthermore, the composition according to the invention can be used for the production of films, fabrics and yarns serve or as an aid or to support in fabric printing and in the paper industry. After all, that can Mass also as an additive for synthetic resin dispersions, such as general sizing agents, as leather finishing agents, as Softeners as well as used to make fibers water-repellent.

The composition according to the invention can also be made with anionic dispersions which are mixed by polymerization or copolymerization of vinyl chloride, vinylidene chloride, ethylene, Styrene, butadiene, vinyl acetate, an acrylic acid ester or acrylonitrile are obtained.

Fillers, plasticizers, dyes, carbon, aluminum, Clay dispersions, asbestos dispersions and tar dispersions can be combined with the masses according to the invention.

The present invention will be further illustrated by the following examples, but the invention is based on these examples not restricted. The parts and percentages are parts by weight, unless otherwise stated, and percentages by weight.

example 1

34.8 parts (0.2o moles) of a mixture of 8o parts of 2,4-toluene

... / 14

209882/1026

diisooyanate and 2o ropes of 2,6-toluene diisocyanate and 90 parts of benzene are added to 2o2 ropes (0.1o moles) of a polytetramethylene ether glycol with a hydroxyl value of 55.5, which was previously added within 30 minutes at 120 ° G under a reduced pressure of 10 mm Hg had been rendered anhydrous. The mixture is heated to 80 ° for one hour with stirring. The mixture is then allowed to cool by itself at room temperature, a urethane prepolymer being obtained which has terminal isocyanate groups. Benzene is used to reduce the viscosity of the reaction mixture, which facilitates further processing, but this is not always necessary. As a result of the analysis of the resulting prepolymer, it is found that the number of remaining isocyanate groups is 2.5o % .

A four-neck bottle with 25o parts is separated from this Methyl ethyl ketone and 5.83 parts (0.037 moles) of diethylenetriamine loaded. The mixture is kept at a temperature below 10 ° by external cooling with ice. Under Sühren are now 100 parts (0.030 moles) of the above prepolymer solution dropwise gradually over a period of 2 hours added to the mixture present in the flask, a polyurethane urine toffpolyamine solution being obtained. A solution from 5.1o parts (0.052 moles) of maleic anhydride, which is dissolved in 5o parts of methyl ethyl ketone, is now under vigorous stirring Polyurethane urea polyamine solution at a temperature that Does not exceed 10 O, added within the shortest possible time. The reaction takes place almost instantaneously, and the

... / 15

209882/1026

The viscosity of the mixture increases rapidly. The temperature of the reaction mixture is gradually increased to 60 ° 0 over a period of 1 hour in order to make the reaction necessary . complete. The resulting product is a slightly yellowish, viscous, transparent solution. The heating is now interrupted, and about 10 parts of an alkali solution containing about 2.1 parts of dissolved sodium hydroxide are added to the reaction product to bring the pH to 6 To set 5 to 7i5. In this way the finished resin solution is obtained. If an aqueous emulsion is required, 200 parts of water are added to the resin solution set above to the specified pH value, and the solvent is distilled off by distillation at a bath temperature which is regulated to 60 ° C. under reduced pressure . The concentration is then adjusted to the desired value by adding water. In this way, a stable aqueous emulsion is obtained which has a resin content of 25 % and has a low viscosity.

The resin composition obtained in this way is poured into a large, leflon-coated The vessel is poured out and left to stand for 24 hours at room temperature. Hasse is air-dried, taking a transparent film is obtained. When this clear film is Mts-treated, the physical properties the film improved so that the film in iLeißea water remains insoluble at 80 °.

209882/1026

The physical properties of the air-dried and heat-treated film are as follows:

Eeißfestig module (kg / om) extension

XL C? X ν \ XLg) / WAl ^) at at
3oo% in % Air-dried
Movie 71 16.5 2o, o 86o Heat treated
Film (20 minutes
at 12o ° 0) 2o4 19.5 26.2 727 Example 2

The reaction is carried out using the same procedural conditions as in Example 1, with the exception that about 7 parts of a 28% aqueous ammonia solution are used to adjust the pH to 6.5 "to 7.5 instead the sodium hydroxide solution mentioned in Example 1. Then 250 ropes of water are added. A stable aqueous emulsion with a resin content of 25 % and a low viscosity is obtained.

The resulting solution is poured into a large, Seflon-lined She leaves the vessel poured out at room temperature to allow air to dry. This is a get transparent film. The physical properties

... / 17 2098 8 2/1026

of the elm produced in this way and one by heat treatment at 12o ° 0 ι
the following :

are obtained at 120 ° 0 for 20 minutes

ability Ckg / cm * ^:) at
1oo! % at
3oo! ,8th tion in % Air-dried
Ulm 77 17th ,1 19th , 5 84o Heat treated
FiIm 22o 19th , 6 28 71o Example 3

40 parts of benzene are added to 10 2 parts (0.1 moles) of polytetramethylene ether glycol with a hydroxyl value of 11, which has previously been dehydrated by heating to 120 ° for 30 minutes at a reduced pressure of 1 o mm Hg. Subsequently, 34.8 parts (0.2 moles) of a mixture of 80 parts of 2.4 and 20 parts of 2,6-toluene diisocyanate are added. The mixture is then left to rest at 80 ° for 1 hour. The reaction mixture is allowed to cool at room temperature, a solution of a urethane prepolymer having terminal isocyanate groups being obtained. As a result of the analysis, it was found that the number of isocyanate groups remaining is 4.73 % .

... / 18 209882/10 26

Independently of this, a flask is charged with 250 parts of methyl ethyl ketone and 7.3 parts (0.07 moles) of diethylenetriamine. The mixture is kept at a temperature below 10 ° C. from the outside by cooling with ice. 100 parts (0.056 moles) of the above-mentioned prepolymer solution are then gradually added dropwise, with stirring, to the mixture present in the flask over a period of 2 hours. In this way, a polyurethane urea polyamine solution is obtained. A solution of 11.0 parts (0.11 moles) of succinic anhydride, which is dissolved in 50 parts of methyl ethyl ketone, is added to the above-mentioned polyurethane urea polyamine solution with vigorous stirring at a temperature below 10 ° C. within the shortest possible time. The reaction starts almost instantly and the viscosity of the reaction mixture suddenly increases. The temperature of the reaction mixture is gradually increased to 60 ° C. over a period of 1 hour in order to complete the reaction. A transparent, viscous solution is obtained. The heating is then interrupted, and about 300 parts of water, which contain 14 parts of a 28 # strength aqueous ammonia solution, are added to the reaction solution in order to adjust its pH to 6.5 to 7.5. The solvent is removed by distilling off at a bath temperature set at 60 ° 0 under reduced pressure. The concentration of the solution is adjusted to the desired value by adding water. This gives a stable, transparent _y aqueous solution with a resin content of 25% and a low viscosity.

.. «/ 19 209882/1026

In the same manner as in Example 1, a film was prepared from the resin solution. The resulting ulm lasted 20 minutes "Heat-treated at 12o ° C. The physical properties of the heat-treated films are as follows:

Tear strength module (kg / cm) elongation (kg / cm ² ) at 5oo % in%

Heat treated>

Film 112 13.2 '98o

Example 4

A stable aqueous solution with a resin content of 25 % and low viscosity is prepared by carrying out the reaction using the same reaction conditions as in Example 3, with the difference that instead of the succinic anhydride used in Example 3, 16.3 parts (0.11 moles) phthalic anhydride can be used.

A film produced from the aqueous emulsion in the same way as in Example 1 is heat-treated at 120 ° C. for 20 minutes. The physical properties of the heat-treated film are as follows:

Tear strength module (kg / cm) elongation (kg / cm ² ) at 5oo% in %

Heat treated

Film 1o6 12.5 1o5o

.. ./2o 209882/1028

- 2ο -

Example 5

52.2 parts of a mixture of 80 parts of 2,4- and 2o parts of 2,6-toluene diisocyanate are added to 2o2 parts (0.1 moles) of polytetramethylene ether glycol with a hydroxyl value of 55-3 and 98 parts (0.05 moles) of polyethylene glycol added to a hydroxyl value of 57.2. The glycols had previously been rendered anhydrous at 120 ° C. under a pressure of 10 mm Hg for 30 minutes. The mixture was heated to 80 ° and allowed to react with stirring for 1 hour. Then the temperature was lowered to room temperature, whereby a urethane prepolymer having terminal isocyanate groups was obtained. As a result of the analysis, it was found that the amount of isocyanate groups present was 3.55 % .

Independently of this, a four-necked flask with 200 parts of methyl ethyl ketone and 5 * 5 parts (0.053 moles) of diethylenetriamine was added loaded. The contents of the bottle were removed by external cooling kept at a temperature below 10 ° C with ice. With stirring, a solution was now obtained by mixing 100 parts (0.042 moles) of the above-mentioned prepolymer with 50 parts Methyl ethyl ketone was obtained, gradually dropping the in The mixture present was added to the flask over a period of 2 hours. In this way, a polyurethane urea polyamine solution became obtain.

A solution of 7 »4 parts (o, o75 mol) of maleic anhydride in 5 ⁽ > parts of methyl ethyl ketone was the above-mentioned polyurethane urine toi i'pol yaminlö solution with vigorous stirring at a temperature not exceeding 10 ° 0 within a possible

... / 21

209882/1026

added for a short period of time; Immediately after this, the reaction took place, and the viscosity of the reaction mixture suddenly rose. The temperature of the reaction mixture was gradually increased to 60 ° G over a period of 1 hour to complete the reaction. A slightly yellowish, transparent, viscous solution was obtained. About 600 parts of water containing 3 parts of dissolved sodium hydroxide was added to the above-mentioned viscous solution to adjust its pH to 6.5 to 7.5. The solvent is removed by distilling off at a bath temperature maintained at 60 ° C. under reduced pressure, and the concentration is adjusted to the desired value by adding water. A transparent aqueous solution is obtained which has a resin content of 15 ° / ° and has a low viscosity.

The transparent aqueous solution became the same In the same way as in Example 1, a film was produced. The film was heat treated at 120 ° C. for 20 minutes. The physical properties of the heat-treated film are as follows:

Hot strength module (kg / cm) Extension (kg / cm ² ) at 3oo% in %

Heat treated

Film 166 21.8 71o

The surface resistance of the heat-treated film, measured at 25 ° 0 and a relative humidity of -4o%, is 5.4 χ 10 ⁹ ohms.

... / 22

209882/1026

Example 6

17 »4- parts (0.1 moles) of a mixture of 80 parts 2.4 and 20 parts 2,6-toluene diisocyanate are added to 10 8 parts (0.05 moles) of a polypropylene glycol with a hydroxyl value of 54.5, which has previously been freed from water at 12o ° C under a negative pressure of 1ο mm Hg for 20 minutes. The reaction is carried out at 100 ° for 3 hours with stirring, a urethane prepolymer having terminal isocyanate groups being obtained. As a result of the analysis, it was found that the number of isocyanate groups remaining is 3.46 % .

Independently of this, a four-neck bottle with .300 parts was produced Acetone and 5.3 parts (0.051 moles) of methylene triamine were charged. The mixture was kept at a temperature below 10 ° C. by external cooling with ice. 100 parts were then added with stirring (0.041 moles) of the above-mentioned urethane prepolymer dropwise gradually added to the mixture present in the flask over a period of 2 hours. It was a Obtained polyurethane urea polyamine solution. This polyurethane urea polyamine solution was a solution of 7, o parts (o, o71 moles) of maleic anhydride dissolved in 5o parts of acetone were added at a temperature not exceeding 10 ° C. with vigorous stirring within the shortest possible time. the The reaction occurred almost instantaneously and the viscosity of the reaction mixture suddenly increased. The temperature of the mixture is increased to 60 ° 0 in order to complete the reaction. A yellowish, transparent, viscous solution is obtained.

... / 23 209882/1026

About 300 ropes of water containing 9 parts of a 28% aqueous ammonia solution were added to the viscous resin solution thus obtained to adjust its pH to 6.5 to 7.5. The solvent is removed by distillation at a bath temperature of 60 ° 0 under reduced pressure, and the concentration of the solution is adjusted to the desired value by adding water. The result is a stable, transparent, aqueous solution with a resin content of 25 % and low viscosity.

A film prepared in the same manner as in Example 1 from the above ^Ji ? Z solution was heat-treated at 120 ° G for 20 minutes. The physical properties of the heat-treated 3J ¹ ILDiS were measured, and the following values were found:

Tear strength module (kg / cm) elongation (kg / cm ² ) at 3oo% in%

Heat treated

Film 124 15.6 89o

Example 7

50 parts benzene, 4.5 parts (0.05 moles) 1,4-butanediol and 34.8 parts Parts (0.2o moles) of a mixture of 80 parts of 2,4- and 2o parts of 2,6-toluene diisoeyanate become 1o1 parts (0.05 moles) of one Polytetramethylene ether glycols with a hydroxyl value of 55 »3 added, which had previously been dehydrated at a negative pressure of 10 mm Hg with heating to 120 ° G for 30 minutes was. The reaction was carried out at 80 ° C. for 1 hour with stirring

... / 24 2 0 9 8 8 2/1026

carried out, whereby a urethane prepolymer was obtained which had terminal isocyanate groups. As a result of the analysis, it was found that the number of isocyanate groups still present was 4.4-3 % .

Independently of this, a four-neck bottle was charged with Joo parts of methyl ethyl ketone and 6.8 parts (0.066 moles) of diethylenetriamine. The mixture was kept at a temperature below 10 ° C. by external cooling with ice. With stirring, 100 parts (0.053 moles) of the above-mentioned prepolymer solution were then gradually added to the mixture contained in the flask over a period of 2 hours, a polyurethaneurea polyamine solution being obtained. A solution of 9.0 parts (0.092 moles) of maleic anhydride in 50 parts of methyl ethyl ketone was added to the abovementioned polyurethane urea polyamine solution with vigorous stirring at a temperature below 10 ° within the shortest possible time. The reaction started immediately and the viscosity of the reaction mixture suddenly increased. The temperature of the reaction mixture is gradually increased to -60 ° C. over a period of 1 hour to complete the reaction. In this way a light yellowish, transparent, viscous solution was obtained. The heating was stopped and about 250 parts of water containing 5.7 parts of dissolved sodium hydroxide were added to the viscous solution to adjust its pH to 6.5 to 7.5. The solvent was removed from the solution by distillation at a bath temperature maintained at 60 ° under reduced pressure

209882/102 6

removed, and the concentration of the solution was adjusted to the desired value by adding water. It was a stable aqueous emulsion obtained, with a resin content of 25% and low viscosity.

An IiIm prepared in the same way as described in Example 1 from the solution thus obtained was heated at 120 ° for 20 minutes long heat treated. The physical properties of the heat-treated elm were measured, with the following results were achieved:

Bite resistance module (kg / cm) Extension (kg / om2) at 3oo % in%

Heat treated

PiIm 265 87 54-0

... / 26

209882/1026

Claims (1)

Claims K) Process for the preparation of anionic, liquid resin compositions, characterized in that 1.) a urethane prepolymer which contains free isocyanate groups is reacted in the liquid phase with an excess of polyalkylenepolyamine to form polyurethaneureapolyamine, and that further 2.) this is allowed to react reaction product obtained is reacted with a cyclic dicarboxylic acid and that finally the reaction product obtained in this way is mixed with an aqueous, basic solution in order to neutralize it. 2φ method according to claim 1, characterized in that that the polyalkylene polyamine is up to 80 #, calculated on molecular equivalents, alkylenediamines or alkylene oxide adducts, Contains acrylonitrile adducts or their acrylic ester adducts. A method according to claim 1, characterized in that the first reaction stage is carried out in a ketone solvent at a temperature within a region of -2O to +60 ⁰ G. ... / 27
209882/1026 4. Procedure according to. Claim. 3 »characterized, that the total number of moles of primary and secondary amino groups in the polyalkylenepolyamine is greater than the total number of moles of isocyanate groups in the urethane prepolymer 5. The method according to claim 1, characterized in that that the second reaction stage at a temperature in of the order of 5 to 7 ° C is carried out. 6. The method according to claim 1, characterized in that the cyclic dicarboxylic anhydride in the second Eeaktionsstufe from maleic anhydride, succinic anhydride, phthalic anhydride, di-, tetra- or hexahydrophthalic anhydrides, trimellitic anhydride or itfeconic anhydride. 7. The method according to claim 1, characterized in that in the second level about 0.5 to about 2, ο Moles of cyclic dicarboxylic anhydride per mole of primary and secondary amino groups in the polyurethane urea polyamine are used. 8. Anionic, liquid resin mixture prepared by the method according to claim Λ . 209882/1026