DE2710061A1 - METHOD OF MANUFACTURING SIZED PAPER AND Means for carrying it out - Google Patents

Description

DR. A. VAN DERWERTH DR. FRANZ LEDERER REINER F. MEYER DlPL-ING. (1934-1974) DIPL-CHEM. DIPL-ING.

8000 MUNICH 80 LUCILE-GRAHN-STRASSE

TELEPHONE: (089) 47 2947 TELEX: 524624 LEOER D TELEGR .: LEATHER PATENT

March 1, 1977 Dumas No. 6

HERCULES INCORPORATED, 910 Market Street, Wilmington, Delaware, 19899, V.St.A.

Process for making sized paper and means too

its implementation

The invention relates to a method for producing sized paper and sized cardboard and to a means to carry out this process, in particular in the case of using a hydrophobic, cellulose-reactive glue, like a ketene dimer glue, and in combination with it a new accelerator for higher glueing outside the machine than when using the cellulose-reactive sizing agent alone.

GB-PS 1 37 3 788 discloses the use of a dicyandiamide-formaldehyde condensate in combination with a ketendimer as glue, to glued paper and glued cardboard with a higher To obtain the same degree of sizing as when using the same amount

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of the ketene dimer as glue alone.

According to the invention, a method for gluing paper and cardboard with a hydrophobic, cellulose-reactive fiber is specified, a new sizing accelerator, which is a nitrogenous one, is used in combination with the cotton fabric Represents condensation product obtained by reacting an epihalohydrin with a condensate which is derived by condensing dicyandiamide or cyanamide with a polyalkylene polyamine.

The invention also relates to a new sizing agent for use in the sizing of paper and cardboard made from cellulose material. The new sizing agent comprises (A) a hydrophobic, cellulose-reactive sizing agent, such as a ketene dimer, an acid anhydride, an organic isocyanate and mixtures of 2 or more of these substances and (B) a nitrogen-containing condensation product, obtained by reacting an epihalohydrin with a condensate obtained by condensing dicyandiamide or cyanamide with a polyalkylene polyamine.

The preferred sizing agents are aqueous emulsions of the cellulose-reactive sizing agent, an emulsifier and the nitrogen-containing one Condensation product. As used herein, the term "emulsion" is common in the art and means either a liquid / liquid type dispersion or of the solid / liquid type.

Aqueous emulsions of hydrophobic cellulose-reactive sizes are known in the art and are commercially available. To the Preparation of the new sizing agents according to the invention is thoroughly mixed with the emulsion with a quantity of a sizing accelerator mixed, which is sufficient to increase the sizing effect of the glue. It was found to be 0.25 to 8 parts by weight lead to good results per part by weight of the hydrophobic, cellulose-reactive glue in the emulsion.

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Thus, the new sizing agents according to the invention are aqueous Emulsions which essentially consist of a hydrophobic, cellulose-reactive sizing agent, such as a ketene dimer, the nitrogen-containing condensation product in an amount sufficient to increase the sizing effect of the sizing agent, and an emulsifier. The amount of emulsifier used is that which is sufficient to produce an emulsion that is stable for a long time and is in the field of experience in the field.

The emulsifier used can be among those conventionally used in the preparation of emulsions of cellulose-reactive sizing agents emulsifiers used can be selected. Such emulsifiers are well known in the art and include cationic ones Starches that represent water-soluble starches that have enough cationic amino groups, quaternary ammonium groups or carry other cationic groups to make the total starch on cellulose noun. An example for one such cationic starch is the cationically amino-modified starch described in GB-PS 903,416.

Another emulsifier which can be used is a water-soluble, cationic, thermosetting resin obtained by reacting Epichlorohydrin with a water-soluble aminopolyamide, a dicarboxylic acid and a polyalkylene polyamine. Resins of this type are described in GB-PS 865 727.

The nitrogen-containing condensation products used according to the invention are produced by reacting an epihalohydrine with a polycondensate obtained by condensing dicyandiamide or cyanamide with a polyalkylene polyamine is formed, both reactions being carried out at elevated temperatures.

Nitrogen-containing condensation products suitable for the use according to the invention are described in GB-PS 1,125,486.

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The epihalohydrin can be epibromohydrin, epichlorohydrin but is preferred. The epihalohydrin can, if desired, in situ using a glycerol dihalohydrin such as e.g. glycerol dichlorohydrin.

The polyalkylene polyamine used to make the polycondensate is represented by the formula

B.
^H 2 ^NC n ^H 2n ^(IIc n ^H 2n ⁾ x ^NH 2

where R is hydrogen or Cj-C ^ -alkyl, η is an integer from 2 to 6 and χ is an integer from 1 to 4. Examples of Cj-C.-alkyl are methyl, xthyl, propyl, isopropyl, η-butyl, isobutyl and t-butyl.

Specific examples of the polyalkylenepolyamines of the above formula are diethylenetriamine, triethylenetetramine, tetraethylene pentamine, dipropyltriamine, dihexamethylene triamine, pentaethylene hexamine and methyl bis (3-aminopropydamine.

The nitrogen-containing condensation products are obtained by first adding dicyandiamide or cyanamide at an elevated temperature is condensed with a polyalkylene polyamine, as described above, to form a polycondensate. For each primary amino group of the polyalkylenepolyamine are 0.1 to 1 hol, preferably 0.4 up to 0.6 moles of dicyandiamide are used. If cyanamide is used, then in an amount of 0.2 to 2 moles, preferably 0.8 to 1.2 moles, for each primary amino group of the polyalkylene polyamine. The polycondensate obtained in this way is, preferably at elevated temperature, with an epihalohydrin using 0.3 mol to 5.5 moles, preferably 1 to 1.5 moles, of the epihalohydrin for each secondary or tertiary amino group of the preparation of the polycondensate implemented polyalkylenepolyamine.

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In the preparation of the polycondensates dicyandiamide or cyanamide is reacted with the polyalkylene polyamine at a temperature of about 100 to about 200 ⁰ C, preferably about 150 to about 170 ⁰ C, heated. In the course of the reaction, 2 moles of ammonia are formed for every mole of dicyandiamide and one mole of ammonia for every mole of cyanamide.

As a rule, it is not necessary to carry out this condensation in the presence of a solvent, as the reaction takes place components at the applied reaction temperatures into one another to solve; however, if desired, an inert solvent such as ethylene glycol monoalkyl ethers or dialkyl ethers can be used or diethylene glycol monoalkyl or dialkyl ethers are used will.

The reaction of the polycondensate with epihalohydrin is preferably carried out in an aqueous solution or dispersion. If desired, another medium, for example acetone or an alcohol such as methanol or ethanol, or mixtures thereof with water can be used. The reaction with epihalohydrin is carried out at elevated temperature, preferably at 60 to 100 ⁰ C is performed. As soon as the reaction mixture shows signs of impending gel formation, the reaction is interrupted by adding an acid or by diluting with water or by both measures.

Depending on the polyalkylenepolyamine used and the one chosen The ratio of polyalkylenepolyamine to dicyandiamide or cyanamide and epichlorohydrin are the nitrogen-containing condensation products Easily soluble or only dispersible in water.

The stability of the aqueous solutions can be increased considerably by adjusting the pH to an acidic value. Will continue improved stability can also be achieved by diluting the aqueous solutions, so that, for example, with a 20% solution at stability at pH 4.8 to 5 at room temperature

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3 to 4 months is guaranteed.

Percentages in the following examples are based on weight.

example 1

252 g (3 mol) of dicyandiamide are added to 3O9 g (3 mol) of diethylenetriamide in a reaction flask equipped with a thermometer, stirrer and reflux condenser. The mixture obtained is ^{heated to 120 to 140 °} C. and ammonia, a reaction product, is released. The reaction takes an exothermic course, the temperature rising to about 160.degree. This temperature is maintained for about 1 hour. The amount of ammonia released during the reaction is 5 to 6 moles. The reaction mass is then cooled by adding an amount of water sufficient to give a solids content of about 25%. Then, 358.8 g (3.9 mol) of epichlorohydrin is added slowly so that the temperature of the reaction mass rises to 55 to 60 ⁰ C. This temperature is maintained until the viscosity of the reaction mass reaches the value H on the Gardner-Holdt scale. The reaction is terminated by adding water in an amount giving a solids content of 20%. The resulting solution is adjusted to a pH of 5 by adding formic acid.

Example 2

252 g (3 mol) of dicyandiamide are added to 438 g (3 mol) of triethylenetetramine in a reaction flask equipped with a thermometer, stirrer and reflux condenser. The resulting mixture is ^{heated to 120 to 140 °} C. and ammonia is released as a reaction product. The reaction takes an exothermic course, with the temperature rising to about 160 ° C. This temperature is maintained for about 1 hour. The amount of ammonia evolved during the reaction is 4 to 5 mol. The reaction mass is then diluted by adding 400 g of water. Which he-

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The solution held 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 mol) of epichlorohydrin are then added slowly over 15 min, the temperature of the reaction mass while at 70 ⁰ C increases. This temperature is maintained for 44 minutes, the viscosity of the reaction mass increasing to the value 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 adding 22 g of concentrated formic acid. The solution obtained has a solids content of 21.1%.

Example 3

168 g (2 mol) of dicyandiamide are added to 290 g (2 mol) of methylrbis (3-aminopropyl) amine in a reaction flask equipped with a thermometer, stirrer and reflux condenser. The mixture obtained is ^{heated to 220 °} C. and kept at this temperature for 1 h. Then 350 g of water are added to provide a solution with a solids content of 44.9%. 768 g (345 g solids, 2 equivalents) of this solution are diluted with 957 g water to a solids content of 20%. 966 g (10.5 moles) of epichlorohydrin are then slowly added. The temperature of the reaction mass is kept at 80 ^° C. until its viscosity reaches the value N on the Gardner-Holdt scale. The reaction is ended by adding 3862 g of water and the solution is adjusted to a pH of 5 by adding 61 g of concentrated formic acid. The resulting solution has a solids content of 17%.

Acid anhydrides useful as cellulose-reactive sizes for paper are well known in the art and include (A) Rosin anhydride, see U.S. Patent 3,582,464; (B) anhydrides of the structure _

R ₁ -C ^

^ O (I)

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wherein R-j is a saturated or unsaturated hydrocarbon radical which is a straight-chain or branched-chain alkyl radical, an aromatically substituted alkyl radical or an alkyl-substituted one is an aromatic radical if the hydrocarbon radical contains a total of about 14 to 36 carbon atoms; and (C) cyclic dicarboxylic anhydrides of the formula

O
II

R ¹ '-R' O (II)

Il
O

where R ^{1 is} a dimethylene or trimethylene radical and R ^{1 is} a hydrocarbon radical with more than 7 carbon atoms from the group consisting of alkyl, alkenyl, aralkyl or aralkenyl. Substituted cyclic dicarboxylic anhydrides falling under the above formula (II) are substituted succinic and glutaric anhydrides. In the above formula (I) each group R .. can be the same hydrocarbon radical or a different hydrocarbon radical.

Specific examples of anhydrides of the formula (I) are myristoyl anhydride, Palmitoyl anhydride, oleoyl anhydride and stearoyl anhydride.

Specific examples of anhydrides of the formula (II) are isooctadeceny! Succinic anhydride, n-hexadeceny! succinic anhydride, dodecy! succinic anhydride, deceny! succinic anhydride, Octenysuccinic anhydride and heptylglutaric anhydride.

Hydrophobic organic isocyanates used as sizes for paper are well known in the art. Best results are obtained when the hydrocarbon chains of the isocyanates at least 12 carbon atoms, preferably 14 to 36 carbon

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contain atoms. Such isocyanates include rosin isocyanate, dodecyl isocyanate, octadecyl isocyanate, tetradecyl isocyanate, Hexadecyl isocyanate, eicosyl isocyanate, docosyl isocyanate, 6-ethyl decyl isocyanate, 6-phenyl decyl isocyanate and Polyisocyanates such as 1,18-octadecyl diisocyanate and 1,12-dodecyl diisocyanate, where a long-chain alkyl group serves two isocyanate groups and the molecule has overall hydrophobic properties confers.

Ketene dimers used as cellulose-reactive adhesives are dimers of the formula / R ¹¹ ^ CH = C = QZ ₂ / in which R ^{111 is} a hydrocarbon radical, such as an alkyl radical with at least 8 carbon atoms, a cycloalkyl radical with at least 6 carbon atoms, an aryl, aralkyl and Is alkaryl. When naming ketene dimers, the radical R ^{111 is} named, followed by "ketene dimer". So is phenyl ketene dimer

CH = C = O

Benzyl ketene dimer

VcH ₂ -CH = C = O

and decyl ketene dimer / C ₁₀ H ₂₁ -CH = C = QZ ₂ - examples of ketene dimers are octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, docosyl, tetracosyl, phenyl, benzyl β -Naphthyl and cyclohexyl ketene dimers, so / ie the ketene dimers, which are derived from montanic acid, naphthenic acid, A9,10-decylenic acid, Δ9,10-dodecylenic acid, palmitoleic acid, oleic acid, ricinoleic acid, linoleic acid, linolenic acid and elaostearic acid, as well as ketene

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dimers made from naturally occurring mixtures of fatty acids, e.g. such mixtures as are described in Coconut oil, babassu oil, palm kernel oil, palm oil, olive oil, peanut oil, rapeseed oil, beef tallow, bacon (slices) and whale bacon or - be encountered drenched. Mixtures of any of the above-mentioned fatty acids with one another can also be used.

Example 4

An emulsion of a ketene dimer made from a mixture of palmitic and stearic acids was prepared by mixing together 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignin sulfonate. The mixture was adjusted to a pH of about 3.5 with 98% sulfuric acid. The mixture obtained was ^{heated to 90 to 95 °} C. for one hour. Water was then added to the mixture in an amount sufficient to provide a mixture of 1750 parts (total weight). About 240 parts of ketene dimer were stirred into the mixture along with 2.4 parts of thiadiazine. The thiadiazine was used as a preservative. The premix obtained

(at 65 ⁰ C) was in one pass through a homogenizer

ο
homogenized at 281 kp / cm (400 psi). The homogenized product was diluted with water to a ketene dimer solids content of about 6%.

Example 5

Example 4 was repeated except that the ketene dimer of oleic acid was used instead of that of a mixture of palmitic acid and ketene dimer made from stearic acid was used.

As is well known in the art, hydrophobic cellulose-reactive cells become Sizing agents used in substance sizing and external sizing of paper. The inventive loading

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Schleuniger can be used in combination with the sizing agent by any of these methods.

Example 6

The product of Example 4 is adjusted to a ketene dimer content with water diluted by 0.1O%.

Example 7

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

Example 8

The products of Examples 4 and 1 are combined, mixed with water as required, to form an aqueous sizing agent from 0.10% of the ketene dimer of Example 4 and 0.20% of the nitrogen-containing condensation product of Example 1 result.

Example 9

The products prepared according to Examples 4 and 1 were combined with the addition of water, as required, an aqueous sizing agent composed of 0.10% ketene dimer from Example 4 and 0.10% of the nitrogen-containing condensation product of Example 1 to result.

Example 10

The products prepared according to Examples 4 and 2 were combined with the addition of water, as required, to an aqueous sizing agent with 0.1O% ketene dimer of Example 4 and 0.1O% of the nitrogen-containing condensation product of example 2 to deliver.

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2VUJÜ61

Example 11

The products prepared according to Examples 4 and 3 were combined with the addition of water, as required, to an aqueous sizing agent with 0.10% ketene dimer of Example 4 and 0.10% of the nitrogen-containing condensation product of example 3 to deliver.

Example 12

The products prepared according to Examples 5 and 1 were combined with the addition of water, as required, to an aqueous sizing agent with 0.10% ketene dimer of Example 5 and 0.10% of the nitrogen-containing condensation product of example 1 to deliver.

The above sizing agents were applied to the surface of a

2 2

A sheet of unsized paper of 65 g / m (40 lb / 300 ft) was applied. The sheet is made from a 50:50 hardwood / softwood pulp mixture on a pilot paper machine. Each sizing agent was adjusted to pH 7 in the nip or line of contact of a horizontal size press prior to application to the sheet. The size press was running at 12.2 m / min (40 ft / min) and the wet pick-up was 70%. The retention of the ketene dimer size was the same in all of these runs. The sized sheets were 20 see on a laboratory drum drier to 4% moisture at 93 ⁰ C (200 ⁰ F) dried. The size was measured according to the Hercules size test with test solution No. 2 for the specified reflection. The data outside the machine were obtained within 2 minutes of drying and the data on natural aging after at least 3 days of storage at room temperature. It is known in the art that ketene dimer size develops essentially all of its sizing properties in paper in 3 days. After this time, the sizing properties of the paper remain essentially the same.

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Gluing results are listed in Table I below:

Table I.

Hercules glue test lake door 1. aged in lake Linen of the Outside the machine to 85% reflection na- 330 Example 80% reflection, 450 6th 0 300 7th 0 500 8th 180 536 9 (1st attempt) 335 600 9 (2nd attempt) 200 455 9 (3rd attempt) 160 460 10 202 500 11 125 12th 250 Example 13

An emulsion of stearic anhydride is prepared by first mixing together 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignosulfonate. The mixture is then adjusted to a pH of about 3.5 with 98% strength sulfuric acid. The resulting mixture is heated to 90 to 95 ° C for about 1 hour. Water is then added to the mixture in an amount sufficient to provide a mixture of 1750 parts (total weight). The temperature of the mixture is adjusted to 70 ⁰ C. About 240 parts of stearic anhydride are stirred into the mixture together with 2.4 parts of thiadiazine. The thiadiazine is used as a preservative. The premix obtained (at 70 ° C.) is homogenized in one pass through a homogenizer at 281 kp / cm (4000 psi). The homogenized product is diluted with water to a stearic anhydride solid content of about 6%.

Example 14 An emulsion of i-octadecenyl succinic anhydride is produced

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by first mixing 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignosulfonate. The mixture is adjusted to a pH of about 3.5 with 98% strength sulfuric acid. The resulting mixture is about 1 hour heated to 90 to 95 C. Water is then added to the mixture in an amount sufficient to make a mixture of 1750 parts (Total weight) to be delivered. About 240 parts of i-octadecenyl succinic anhydride are stirred into the mixture together with 2.4 parts of thiadiazine. The thiadiazine is used as a preservative used. The premix obtained is at room temperature in one pass through a homogenizer

281 kp / cm (400 psi) homogenized. The homogenized product is diluted with water to an anhydride solids content of about 6%.

Example 15

An emulsion of octadecyl isocyanate is prepared by first mixing together 880 parts of water, 60 parts of cationic corn starch and 10 parts of sodium lignosulfonate. The mixture is adjusted to a pH of about 3.5 with 98% strength sulfuric acid. The mixture obtained is heated ^{to 90 to 95 ° C. for about 1 hour.} Water is then added to the mixture in an amount sufficient to provide a mixture of 1750 parts (total weight). About 240 parts of octadecyl isocyanate are stirred into the mixture together with 2.4 parts of thiadiazine. The thiadiazine is used as a preservative. The resulting premix is homogenized at room temperature in one pass in a homogenizer at 281 kp / cm (4000 psi). The homogenized product is diluted with water to an octadecyl isocyanate solids content of about 6%.

Example 16

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

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- ys -

Example 17

The product of Example 14 is diluted with water to an i-octadecenylsuccinic anhydride content diluted by 0.20%.

Example 18

The product of Example 15 is adjusted to an octadecyl isocyanate content with water diluted by 0.20%.

Example 19

The product of Example 13 and a nitrogen-containing condensation product, prepared according to Example 1, are combined with the addition of water, as required, to form an aqueous To supply sizing agents with 0.20% stearic anhydride and 0.20% of the nitrogen-containing condensation product.

Example 20

The product of Example 14 and a nitrogen-containing condensation product, prepared according to Example 1, are combined with the addition of water, as required, to form an aqueous Sizing agent with 0.20% i-octadecenyl succinic anhydride and to provide 0.20% of the nitrogen-containing condensation product.

Example 21

The product of Example 15 and a nitrogen-containing condensation product, prepared according to Example 1, are combined with the addition of water, as required, to form an aqueous Sizing agent with 0.20% octadecyl isocyanate and 0.2O% to deliver nitrogen-containing condensation product.

The above sizing agents of Examples 16-21 were used

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onto the surface of a sheet of unsized paper

2 2

65 g / m (40 lb / 3,000 ft) applied. The sheet is made from a 50:50 hardwood / softwood pulp mixture on a pilot paper machine. Each sizing agent was adjusted to pH 7 in the nip or line of contact of a horizontal size press prior to application to the sheet. The size press was running at 12.2 m / min (40 ft / min) and the wet pick-up was 70%. The retention of the glue was the same in all of these runs. The sized sheets were 20 see on a laboratory drum drier to 4% moisture at 93 ⁰ C (2OO ⁰ F) dried. The size was measured according to the Hercules size test with test solution No. 2 for the specified reflection. The data outside the machine were obtained within 2 minutes of drying and the data on natural aging after at least 3 days of storage at room temperature. ·

Gluing results are shown in Table II below:

Table II 80% reflection Sizing agent des Hercules glue test Aged naturally Example Outside the machine 451 16 0 882 17th 460 6O2 18th 0 92O 19th 732 620 20th 0 930 21 325

It is well known in the art that the hydrophobic, cellulose-reactive sizing agents are low, if any Offer sizing outside the machine. The above examples directed to surface sizing show that the Sizing agents according to the invention lead to a considerable improvement in the sizing outside the machine.

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The sizing agents according to the invention can also be used for interior or substance sizing with improved sizing results of paper to be used.

It goes without saying that the use of the agents according to the invention in the substance sizing of paper is also preferred however, that the hydrophobic, cellulose-reactive sizing agent and the sizing accelerator are added separately, if desired can.

The above description and the examples are only intended to illustrate the invention without limiting it.

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Claims (10)

PATENT CLAIMS . Process for producing sized paper or sized paperboard from cellulosic material using a cellulose-reactive sizing agent, characterized in that a sizing agent in the form of an aqueous emulsion with (A) a hydrophobic, cellulose-reactive sizing agent and (B) a nitrogen-containing condensation product obtained by reaction an epihalohydrin with one from the condensation of dicyandiamide or cyanamide with a polyalkylene polyamine originating condensate is used. 2. The method according to claim 1, characterized in that an additionally (C) emulsifier containing sizing agent is used. 3. Sizing agents for carrying out the method according to claim 1 or 2 in the form of an aqueous emulsion, containing (A) a hydrophobic, cellulose-reactive glue and (B) a nitrogen-containing condensation product by reacting an epihalohydrin with one from the condensation of dicyandiamide or cyanamide with a polyalkylene polyamine originating condensate. 4. Sizing agent according to claim 3, characterized in that it consists essentially of the components (A), (B) and (C) an emulsifier. 5. Sizing agent according to claim 4, characterized in that (A) is a ketene dimer. 6. Sizing agent according to claim 4, characterized in that (A) is an acid anhydride. 709838/0722 ORIGINAL INSPECTED 7. Sizing agent according to claim 4, characterized in that that (A) is an organic isocyanate. 8. Sizing agent according to one of claims 5 to 7, characterized in that the production of the nitrogen-containing Condensation product (B) polyalkylenepolyamine used is diethylenetriamine. 9. sizing agent according to any one of claims 5 to 7, characterized in that the for the production of the nitrogen-containing Condensation product (B) used polyalkylenepolyamine is triethylenetetramine. 10. Sizing agent according to one of claims 5 to 7, characterized in that the polyalkylene polyamine used to prepare the nitrogen-containing condensation product (B) Methyl bis (3-aminopropy is diamine. 709838/0722