CH620003A5 - Process for producing an aqueous emulsion usable for sizing cellulosic matter - Google Patents

Abstract

Dicyandiamide or cyanamide is condensed with a polyalkylenepolyamine, the product of this condensation is reacted with an epihalohydrin and an aqueous emulsion is prepared containing the reaction product thus obtained and also containing a hydrophobic sizing agent endowed with reactivity for cellulose, for example a ketene dimer, an acid anhydride or an organic isocyanate. The emulsion thus obtained is employed for sizing paper and cardboard. The reaction product acts as a sizing accelerator.

Description

The invention relates to a process for the preparation of an aqueous emulsion which can be used in particular for the production of sized paper and sized cardboard, the emulsion thus obtained essentially comprising a hydrophobic sizing agent, having reactivity with cellulose and such as a ketene dimer, in combination with a new sizing accelerator leading to a higher sizing rate outside the machine than 40 when the sizing agent is used, which is reactive with cellulose, only.

GB Patent No. 1,373,788 describes the use of a condensation product of the dicyandiamide-formaldehyde type in combination with a sizing agent of the ketene dimer type for obtaining a sized paper and '' a glued cardboard whose sizing degree is higher than that which can be obtained by using the same quantity of the sizing agent of the ketene dimer type alone.

The condensation product used according to the teaching 50 of the aforementioned patent has however practically no accelerating effect on the sizing carried out outside the machine, unlike the condensation product contained in the aqueous emulsion obtained by the process according to the claim 1 of this patent. <5

The preferred sizing compositions are aqueous emulsions essentially comprising the sizing agent reactive with cellulose, an emulsifier, and the nitrogen-containing condensation product. The term "emulsion" as used herein is to be understood to mean, in common fashion in the art, either a dispersion of a liquid in a liquid, or a dispersion of the solid type in a liquid.

Aqueous emulsions of hydrophobic sizing agents, which are reactive with cellulose, are well known to 1.5 specialists and are commercially available. To prepare the new sizing compositions according to the present invention, a proportion of sizing accelerator sufficient to increase the sizing action of the sizing agent is incorporated into the emulsion. It has been determined that the incorporation of 0.25 part (abbreviated: p.) To 8 p. by weight (p. by p.) of said accelerator for each part by weight of the hydrophobic sizing agent, endowed with reactivity with the cellulose, present in the emulsion makes it possible to obtain good results.

Consequently, the new sizing compositions included in the scope of the present invention are aqueous emulsions which essentially comprise a hydrophobic sizing agent, reactive with cellulose, such as a ketene dimer, the condensation product. containing nitrogen, used in a sufficient proportion to increase the sizing action of the sizing agent, and an emulsifier. A sufficient proportion of emulsifier should be used to obtain and maintain an emulsion which is stable for an extended period of time; the use of such emulsifiers for such purposes is well known to specialists.

The emulsifier used can be chosen from those conventionally used for the production of sizing agent emulsions which are reactive with cellulose. Such emulsifiers are well known in the art, and among them are in particular cationic starches which are water-soluble starches and the molecule of which contains a sufficient number of cationic amino radicals, quaternary ammonium radicals, or other cationic radicals to make the starch generally substantive with respect to cellulose. An example of such a cationic starch is the cationic starch, modified with an amine, described in GB Patent No. 903,416.

Another emulsifier which can be used is a water-soluble, thermosetting cationic resin obtained by reacting epichlorohydrin with a water-soluble aminopolyamide formed from a dicarboxylic acid and a polyalcoylene-polyamine. . Resins of this type are described in GB Patent No. 865,727.

The nitrogen-containing condensation products obtained, used during the implementation of the present invention, are obtained by reacting an epihalohydrin with a “polyconden-sat”, or condensation polymer, formed by condensing dicyandiamide or cyanamide. with a polyalkylene polyamine, the two reactions being carried out at elevated temperatures.

Condensation products containing nitrogen, suitable for their use for implementing the present invention, are described in GB patent No. 1,125,486.

The epihalohydrin can be epibromohydrin, epichlorohydrin; the latter is preferred. The epihalohydrin can be prepared in situ, if desired, using a glycerol dihalohydrin such as glycerol dichlorohydrin.

The polyalkylene polyamine used to prepare the above polycondensate can be represented by the following formula:

R

H2NC „H2n (NCnH2n) xNH2

wherein R is hydrogen or an alkyl radical having from 1 to 4 carbon atoms; n is an integer from 2 to 6, and x is an integer from 1 to 4. Examples of alkyl radicals having from 1 to 4 carbon atoms are methyl, ethyl, propyl, isopropyl, n-butyl, isobu radicals -tyle and tert.-butyl.

As particular examples of the polyalkylene polyamines included in the scope of the above formula, there may be mentioned in particular: diethylenetriamine; triethylenetetramine; tetraethylenepentamine; dipropyltriamine; dihexamethylene triamine; pentaethylenehexamine; and methyl-bis (3-amino-propyl) amine.

3

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Nitrogen-containing condensation products are obtained by first condensing, at an elevated temperature, dicyandiamide or cyanamide with a polyalkylene polyamine, as specified above, to produce a polycondensate. For each primary amino radical of the polyalkylene polyamine, 0.1 to 1 mole, and preferably 0.4 to 0.6 mole, of dicyandiamide should be used. When cyanamide is used, it should be used in an amount of 0.2 to 2 moles, and preferably in an amount of 0.8 to 1.2 moles, for each primary amino radical of the polyalkylene polyamine. The poiycondensate thus obtained is allowed to react, preferably at an elevated temperature, with an epihalohydrin using 0.3 to 5.5 moles, and preferably 1 to 1.5 moles, of epihalogenohydrin for each radical. secondary or tertiary amino of the polyalkylene polyamine which was used to prepare the polycondensate

During the preparation of the polycondensates, the dicyandiamide or the cyanamide is heated with the polyalkylene polyamine to a temperature of between approximately 100 ° C. and approximately 200 ° C., and preferably between approximately 150 ° C. and approximately 170 ° C. During from the reaction, 2 moles of ammonia are found for each mole of dicyandiamide, and one mole of ammonia is found for each mole of cyanamide.

As a general rule, it is not necessary to carry out this condensation in the presence of a solvent, since the reagents dissolve in one another at the reaction temperatures used; but it is however possible, if desired, to use an inert solvent such as a monoalkyl or dialkyl ether of ethylene glycol, or a monoalkyl or dialkyl ether of diethylene glycol.

The reaction of the poiycondensate with an epihalohydrin is preferably carried out in an aqueous dispersion or solution. It is possible, if desired, to use another medium, for example acetone or an alcohol such as methanol or ethanol, or mixtures of such substances with water. The reaction is carried out with an epihalohydrin at an elevated temperature, preferably between 60 ° C and 100 ° C. As soon as the reaction mixture shows signs of taking a gel, the reaction is stopped by adding an acid or by dilution with water, or by using both of these means simultaneously.

Depending on the polyalkylene polyamine used and according to the chosen ratio of polyalkylene polyamine to dicyandiamide or cyanamide, the nitrogen-containing condensation products obtained are either easily soluble in water or else only dispersible in water. .

The stability of aqueous solutions can be significantly increased by adjusting their pH to a value in the acid range. On the other hand, an improved stability is also obtained by diluting the aqueous solutions in such a way that, for example with a 20% solution whose pH is between 4.8 and 5, it is ensured at ordinary room temperature a stability period of 3 to 4 months.

Below are given various examples, serving to illustrate the methods of implementing the present invention. In these examples, the quantities expressed in "parts" (abbreviated: p.) And the proportions expressed in percentages (%) must be understood by weight, unless otherwise indicated.

Example 1

252 grams (3 moles) of dicyandiamide are added to 309 g (3 moles) of diethylenetriamine contained in a reaction vessel equipped with a thermometer, an agitator and a reflux-condenser-reflux condenser. The resulting mixture is heated to a temperature of 120 ° C to 140 ° C and ammonia is evolved as a reaction product. The reaction takes an exothermic form, the temperature rising to about 160 ° C. This temperature is maintained for about one hour. The amount of ammonia which is eliminated during the reaction is between 5 and 6 moles. The reaction mass is then cooled by adding water to it in a sufficient proportion to result in a solids content of approximately 25%. 358.8 g (3.9 moles) of epichlorohydrin are then added slowly so that the temperature of this reaction mass rises to 55-60 ° C. This temperature is maintained until the viscosity of the reaction mass reaches the H value on the Gardner-Holdt scale. The reaction is terminated by adding water in an amount sufficient to result in a solids content of 20%. The pH of the resulting solution is adjusted to a value of 5 by addition of formic acid.

Example 2

252 g (3 moles) of dicyandiamide are added to 438 g (3 moles) of triethylenetetramine contained in a flask equipped with a thermometer, an agitator and a condenser-reflux condenser. The resulting mixture is heated to 120-140 ° C, and ammonia is evolved as the reaction product. The reaction takes an exothermic form, the temperature rising to about 160 ° C. This temperature is maintained for about one hour. The amount of ammonia removed during the reaction is between 4 and 5 moles. The reaction mass is then diluted by adding 400 g of water to it. The resulting solution has a solids content of 59.5%. 336 g of this solution are diluted to a solids content of 25% by adding 464 g of water. 110 g (1.2 mole) of epichlorohydrin are then added slowly (over 15 minutes), and during this addition the temperature of the reaction mass rises to 70 ° C. This temperature is maintained for 44 minutes during which the viscosity of the reaction mass rises to the value of N on the Gardner-Holdt scale. The reaction is terminated by immediately adding 680 g of water and the pH of the solution is adjusted to 4.5 by the addition of 22 g of concentrated formic acid. The resulting solution has a solids content of 21.1%.

Example 3

168 g (2 moles) of dicyandiamide are added to 290 g (2 moles) of methyl-bis (3-aminopropyl) amine contained in a flask equipped with a thermometer, an agitator and a refrigerant-condenser at reflux. The resulting mixture is heated to 220 ° C and maintained at this temperature for one hour. 350 g of water are then added, so as to obtain a solution whose solids content is equal to 44.9%. 768 g of this solution are diluted (therefore containing 345 g, or 2 equivalents, of solids) to a solids content of 20% by adding 957 g of water to it. Then 966 g (10.5 moles) of epichlorohydrin are added slowly. The temperature of the reaction mass is maintained at 80 ° C. until the viscosity of this mass reaches the value of N on the Gardner-Holdt scale. The reaction is terminated by the addition of 3862 g of water, and the pH of the solution is adjusted to a value equal to 5 by the addition of 61 g of concentrated formic acid. The resulting solution has a solids content of 17%.

Acid anhydrides which can be used as sizing agents, with reactivity with cellulose, for paper are well known to specialists; among such anhydrides, there may be mentioned in particular: (A) rosin anhydride as described in US Pat. No. 3,582,464; (B) anhydrides having the structure:

Rl "Q ^ ^ O

5

1 (1

tS

20

2s

M)

35

40

45

50

55

61)

ft5

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4

where R] is a saturated or unsaturated hydrocarbon radical which can be a straight chain or branched chain alkyl radical, an aromatico-substituted alkyl radical, or an alkyl-substituted aromatic radical as long as said hydrocarburo radical comprises in total approximately from 14 to 36 carbon atoms; and (C) cyclic dicarboxylic acid anhydrides having the structure:

VS")

O

R "-R ^

O

where R 'represents a dimethylene or trimethylene radical; and R ″ is a hydrocarbon radical containing more than 7 carbon atoms and which is chosen from the group consisting of alkyl, alkenyl, aralkyl, aralkenyl radicals. Anhydrides of substituted cyclic dicarboxylic acids included in the scope of the above formula ( II) are substituted succinic and glutaric anhydrides In the formula (I) above, each substituent R 1 may be the same hydrocarbon radical or may be a different hydrocarbon radical.

As particular examples of anhydrides which can be represented by formula (I), mention may in particular be made of: myris-toylic anhydride; palmitoyl anhydride; oleoyl anhydride; stearoyl anhydride.

As particular examples of anhydrides which can be represented by formula (II), mention may in particular be made of: isooctadecenyl succinic acid anhydride; n-hexa-decenyl-succinic acid anhydride; dodecyl succinic acid anhydride; decenyl succinic acid anhydride; octenyl succinic acid anhydride; heptylglutaric acid anhydride.

Hydrophobic organic isocyanates used as sizing agents are well known to specialists. The best results are obtained when the hydrocarbon chains of -isocyanates contain at least 12 carbon atoms, and preferably contain from 14 to 36 carbon atoms. Among such isocyanates, mention may in particular be made of: rosin isocyanate; dodecyl isocyanate; octadecyl isocyanate; tetradecyl isocyanate; hexadecyl isocyanate; eicosyl isocyanate; docosyl isocyanate; 6-ethylIdecyl isocyanate; 6-phenyldecyl isocyanate; and polyisocyanates such as 1,18-octadecyl diisocyanate and 1,12-dodecyl diisocyanate in which a long-chain alkyl radical is linked to two isocyanato radicals and imparts hydropho-! bes to the whole molecule.

Ketene dimers used as sizing agents which are reactive with cellulose are ketene dimers which can be represented by the following formula:

& V

CH = C = 0

and the benzyl ketene dimer is:

CH2-CH = C = 0

however, the decyl ketene dimer is [C10H21-CH-1 = C = 0] 2. As examples of ketene dimers, mention may especially be made of octyl-, decyl-, dodecyl-, tetraded-cyl-, hexadecyl-, octadecyl-, eicosyl-, docosyl-, tetracosyl-, phe-nyl-, benzyl- dimers , ß-naphthyl- and cyclohexyl-ketene, as well as dimers of ketenes prepared from montanic acid, 'naphthenic acid, A9,10-decylenic acid, A9,10-dodecylenic acid, d palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid and eleostearic acid, as well as ketene dimers prepared from natural mixtures of fatty acids such as those of mixtures which are found naturally in coconut oil, in Babassu oil, in palm almond oil, in palm oil, in olive oil, in oil peanut, rapeseed or rapeseed oil, beef tallow, lard, and whale bacon. Mixtures of any of the aforementioned fatty acids may also be used with each of the others.

Example 4

An emulsion of a ketene dimer is prepared, itself prepared from a mixture of palmitic and stearic acids, by mixing together 880 p. water, 60 percent cationic corn starch and 10 percent sodium lignin sulfonate. The pH of the resulting mixture is adjusted to a value of approximately 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90-95 ° C for about an hour. To the mixture thus obtained, water is then added in a sufficient proportion to result in a total weight of the mixture of 1750 p. Then add about 240 percent to the mixture while stirring. of the above-mentioned ketene dimer together with 2.4 p. of thiadiazine. Thiadiazine is used as an antiseptic (or antiputrid). The resulting premix (at 65 ° C) is homogenized by passing it once through a homogenizer operating at a pressure of 280 kg / cm2. The product, thus homogenized, is diluted with water i to a solid content (ketene dimer) equal to about 6%.

[R "'CH = C = 0] 2

in which R "′ is a hydrocarbon radical such as an alkyl radical comprising at least 8 carbon atoms, a cycloalkyl radical comprising at least 6 carbon atoms, an aryl, aralkyl or alkaryl radical. To denote such dimers of ketenes, first specify that it is a dimer, then precede with the indication of the radical R "'substituting the term" ketene "which is generic. Thus, the phenyl ketene dimer is:

Example 5

Example 4 is repeated, except that the ketene dimer of oleic acid is used in place of the ketene dimer prepared from a mixture of palmitic and stearic acids.

As specialists are well aware, agents are used

() 0 hydrophobic bonding, with reactivity with cellulose, to achieve internal bonding of paper and external bonding of paper. The accelerator according to the invention can be used with the bonding agent during the implementation of either of these two methods.

65

Example 6

The product of Example 4 is diluted with water to a ketene dimer content of 0.10%.

5

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Table I

Hercules sizing test Composition Outside the machine Natural aging of sizing up to one up to a reflectance s of the ex, n "reflectance of 80% of 85%

Example 7

The product of Example 5 is diluted with water to a ketene dimer content of 0.10%.

Example 8

The products of Example 4 and of Example 1 are combined, with the addition of water as necessary, so as to obtain an aqueous sizing composition containing 0.10% of ketene dimer from Example 4 and 0.20% of the condensation product 1 containing nitrogen from Example 1.

Example 9

The products of Example 4 and of Example 1 are combined, with the addition of water as necessary, so as to obtain an aqueous sizing composition containing 0.10% of ketene dimer from Example 4 and 0.10% of the nitrogen-containing condensation product of Example 1.

Example 10

The products of Example 4 and of Example 2,, are combined with the addition of water as necessary, so as to obtain an aqueous sizing composition containing 0.10% of the ketene dimer of Example 4 and 0.10% of the nitrogen-containing condensation product of Example 2.

Example 1 /

The products of Example 4 and of Example 3 are combined,

with addition of water as necessary "so as to obtain an aqueous sizing composition containing 0.10% of the dimer i? of ketene from Example 4 and 0.10% uu condensation product containing nitrogen from Example 3.

Example 12 4n

The products of Example 5 and of Example 1 are combined,

with addition of water as necessary, so as to obtain an aqueous sizing composition containing 0.10% of the ketene dimer of Example 5 and 0.10% of the condensation product containing nitrogen from the example 1. 45

The above-specified sizing compositions are applied to the surface of a sheet of unglued paper weighing 65 g / m2. This sheet is prepared from a 50:50 mixture of hardwood pulp: softwood, on a semi-industrial pilot machine. The pH of each sizing composition is adjusted to 7 before 5 (l apply it to the sheet in the nip interval of a horizontal sizing press. This press is operated at a speed of 12.19 meters per minute; the humidity capture rate is 70%. The glue retention rate (ketene dimer) is the same for all these operations. The leaves, dried in this way, are dried at 93.3 ° C. for 20 seconds on a laboratory tumble dryer up to a humidity level of 4% The sizing is measured using the Hercules sizing test method with test solution No. 2 up to at the indicated reflectance. The data "out of the machine" are obtained in a drying of two minutes, and the data "with natural aging" after at least three days of storage at ordinary room temperature. glue to ketene dimer develops almost all of its sizing capacity in paper in three days. As soon as (15) time, the paper sizing properties remain substantially unchanged. The sizing results thus obtained are shown in Table I below:

6 0 330

7 0 450

8,180,300

9 (1st test) 335 500 9 (2 * ™ test) 200 536 9 (3tmc test) 160 600

10 202 455

11 12 ') 460

12,250,500

Example 13

An emulsion of stearic anhydride is prepared by first mixing together 880 p. water, 60 percent cationic corn starch and 10 percent sodium lignin sulfonate. The pH of the mixture is adjusted to a value equal to approximately 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90-95 ° C for about an hour. Water is then added in a sufficient proportion to obtain a total weight of the mixture representing 1750 p. The temperature of this mixture is adjusted to 70 ° C. after which it is incorporated, while stirring, approximately 240%. stearic anhydride together with 2.4 p. of thiadiazine. Thiadiazine is used as an antiseptic, or antiputrid agent. The resulting mixture is homogenized (at 70 ° C) by passing it once through a homogenizer operating at a pressure of 280 kg / cm2. The product, thus homogenized, is diluted with water to a solid content (stearic anhydride) equal to about 6%.

Example 14

An iso-octadecenylsucci-anhydride emulsion is prepared by mixing together 880 p. water, 60 percent cationic corn starch and 10 percent sodium lignin sulfonate. The pH of the mixture is adjusted to a value equal to approximately 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90-95 ° C for about an hour. Water is then added in a sufficient proportion to result in a total weight of the mixture representing 1750 p. About 240 percent is added to the mixture while stirring. iso-octadecenylsuccinic anhydride together with 2.4 p. of thiadiazine. Thiadiazine serves as an antiputrid agent. The resulting premix is homogenized, at ordinary room temperature, by passing it once through a homogenizer operating at a pressure of 280 kg / cm2. The product, thus homogenized, is diluted with water to a solid content (anhydride) equal to about 6%.

Example 15

An octadecyl isocyanate emulsion is prepared by mixing 880% together. water, 60 percent cationic corn starch and 10 percent sodium lignin sulfonate. The pH of the mixture is adjusted to a value equal to approximately 3.5 with 98% sulfuric acid. The resulting mixture is heated to 90-95 ° C for about an hour. Water is then added to the mixture in a sufficient proportion to obtain a total weight of the mixture representing 1750 p. Then add about 240 percent while stirring. octadecyl isocyanate together with 2.4 p. of thiadiazine. Thiadiazine serves as an antiputrid agent. The resulting premix is homogenized, at ordinary room temperature, by passing it once through a homogenizer operating at a pressure of 280 kg / cm2. The product, thus homogenized, is diluted with

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6

water up to a solid content (octadecyl isocyanate) of approximately 6%.

Example 16

The product of Example 13 is diluted with water to a stearic anhydride content equal to 0.20%.

Example 17

The product of Example 14 is diluted with water to a content of isooctadecenylsuccinic anhydride equal to 0.20%.

Example 18

The product of Example 15 is diluted with water to a content of octadecyl isocyanate equal to 0.20%.

Example 19

The product of Example 13 is combined with a condensation product, containing nitrogen, prepared by operating as described in Example 1, with addition of water to the mixture as necessary, so as to establish a aqueous sizing composition containing 0.20% of stearic anhydride and 0.20% of the above-mentioned condensation product containing nitrogen.

The pH of each sizing composition is adjusted to a value of 7 before it is applied to the sheet in the nipping area of a horizontal sizing press which is operated at a speed of 12.19 meters per minute , with a humidity capture rate of 70%. The glue retention rate is the same for all these operations. The sheets, thus glued, are dried at 93.3 ° C for 20 seconds on a laboratory drum dryer to 4% humidity. The sizing is measured by the Hercules sizing test method, „with test solution No. 2, up to the indicated reflectance. The data“ out of the machine ”are obtained in two minutes of drying, and data with natural aging after at least three days of storage at ordinary room temperature.

i * The gluing results indicated in Table II below are thus obtained:

Table II

Hercules in glue test (up to 80% reflectance)

Composition Out of the After aging of natural gluing machine of the ex, n "

Example 20

The product of Example 14 and a condensation product, containing nitrogen, prepared by operating as described in Example 1, are combined with addition of water to the mixture as necessary, so as to establish a aqueous sizing composition containing 0.20% of iso-octadé-cenyl-succinic anhydride and 0.20% of the above-mentioned condensation product containing nitrogen.

Example 21

The product of Example 15 is combined with a condensation product, containing nitrogen, prepared by operating as described in Example 1, with addition of water to the mixture as necessary, so as to establish a aqueous sizing composition containing 0.20% of octadecylisocyanate and 0.20% of the above-mentioned condensation product containing nitrogen.

The above-specified sizing compositions, described in Examples 16 to 21, are applied to the surface of an unglued sheet of paper weighing 65 g / m2. This sheet was prepared from a 50:50 mixture of hardwood pulp and softwood pulp on a semi-industrial pilot paper machine.

16

0

451

17

460

882

18

0

602

19

732

920

20

0

620

.m 21

325

930

Specialists are well aware that hydrophobic sizing agents, which have a reactivity with cellulose, do little or practically no sizing outside the machine, is The above examples, concerning a surface sizing, prove that the compositions sizing according to the present invention very considerably improve sizing outside the machine.

The sizing compositions according to the invention can be used for internal sizing of the paper and give improved sizing results.

Although it is preferred to use the compositions according to the invention for the internal sizing of paper, it should not be forgotten that a hydrophobic sizing agent, having reactivity with is cellulose, and the accelerator d sizing can be added separately, if desired.

4 (1

VS

Claims (9)

620 003 1. Process for the preparation of an aqueous emulsion which can be used for sizing cellulosic materials, characterized in that dicyandiamide or cyanamide is condensed with a polyalkylene polyamine, the product of this condensation is reacted with an epihalohydrin and an aqueous emulsion is prepared containing the reaction product thus obtained and also containing a hydrophobic sizing agent endowed with reactivity with cellulose. 2. Method according to claim 1, characterized in that epichlorohydrin is used as epihalohydrin, and in that the emulsion also contains an emulsifier. 2 3. Method according to claim 1, characterized in that the sizing agent is a ketene dimer. 4. Method according to claim 1, characterized in that i s the sizing agent is an acid anhydride. 5. Method according to claim 1, characterized in that the sizing agent is an organic isocyanate. 6. Method according to claim 1, characterized in that diethylene-2 () triamine is used as the polyalkylene polyamine. 7. Method according to claim 1, characterized in that one uses as polyalkylene-polyamine, triethylenety-tramine. 8. Method according to claim 1, characterized in that _ \ s is used as polyalkylene polyamine, methyl-bis (3-aminopropyl) amine. 9. Use of the aqueous emulsion obtained according to the process according to claim 1 for the production of sized paper or sized cardboard. m