DE2400058A1 - METHOD OF SIZING PAPER - Google Patents

Description

DIPL-PHYS. F. FINALLY PATENT ADVERTISER

DIPU-PHYS. F. FINALLY. 8O34 UNTERPFAFFENHOFEN. P.O. BOX

UNTERPFAFFENHOFEN POST BOX

Jan. 2, 1974

PHONE
PHONE

(MUNICH) 84 36

TELEGRAM ADDRESS: CABLE ADDRESS:

TELEX 5 212 3O8

PATENDLY MUNICH

N-3400
Kr / ma

NATIONAL STARCH AND CHEMICAL CORPORATION 750 Third Avenue, "New York, N.Y. 10017, U.St.A.

Method for gluing paper

The invention relates to a method according to the preamble of the main claim. The invention relates in particular to a method for sizing paper and to a method for the same Wise Made Improved Paper. Furthermore, the invention relates to new glue means for gluing of paper and adhesive products.

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The object of the invention is to provide better glue that enable the production of paper by reducing the absorption of water and ink and is characterized by resistance to aqueous, acidic and alkaline solutions. Furthermore, glue should be used according to the invention, which in all types of paper pulp over the complete Range of pH conditions normally encountered in papermaking is used can be. Finally, the invention is intended to provide glue that contains alum and rosin as well as the various fillers, pigments and other chemicals added to the paper are compatible.

The terms "paper and paperboard" used herein are intended to mean sheet-like masses and molded products made of fibrous materials Designate cellulosic materials that are derived from both natural and synthetic sources. Sheet-like masses and molded products are also to be included; those made up of combinations of Cellulosic and non-cellulosic materials that differ from Synthetic fibers such as polyamide, polyester and polyacrylic resin fibers are derived, as well as from mineral fibers such as from Asbestos and glass are made.

Paper and cardboard are often glued together with different materials to make them water resistant as well other types of aqueous solutions to increase. These materials are known as glue. You can be fed during the papermaking process, in which case one is from an internal or machine sizing speaks. On the other hand, they can also be applied to the surface of the finished fabric or sheet

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be applied, in which case one from an outside or surface gluing speaks.

Various water-repellent materials have been used as glue agents. Examples for this are: Rosin, mixtures of rosin with waxes, wax emulsions, Emulsions of dimeric ketenes, fluorocarbons, fatty acid complexes of chromium and aluminum chlorides, long chain thermoplastic copolymers, as well as some thermosetting condensation type resins. Although While all of these materials are effective under certain conditions, their use is still subject to certain restrictions subject.

For example, rosin possesses, although this substance is relative is cheap and readily available, has poor resistance to alkaline solutions and can therefore cannot be used for sizing neutral or alkaline pulps. Rosin is with the latter Pulp not applicable as it is normally used in combination with alum or an acidic aluminum ion donor which is present to precipitate the sodium rosinate, i.e. the rosin soap, on the fibers and harden. However, the use of alum for this purpose is in neutral or alkaline conditions, locked out. This is a distinct disadvantage since paper is made from neutral and alkaline pulps has been, a higher strength, a greater stability and a better aging behavior Papers made from acidic pulps. Also the internal use of alkaline pigments, e.g. excluded from calcium carbonate. the

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the same restriction applies to use of most wax emulsions that can be used on the alkaline side, as they are usually with small amounts of alum are combined to break the emulsions. On the other hand, certain tolerate Means no appreciable amounts of alum or highly acidic conditions. In some cases it can be useful or it may be necessary to use alum to hold back the filler, increase leaf drainage or retain or cure the condensation resin additives. Certain glues can be in the sheet while the foliage, however, cannot be adequately retained, so that their application to external or superficial Applications is limited.

In addition to the pH restrictions described above, water resistance is achieved by many of the conventional ones Glue is obtained for many uses that require paper or cardboard, which one has an exceptionally high degree of water resistance, often not sufficient. In addition, many have this Sizing agents as incompatible with pigments, fillers or other ingredients, which are often added to the paper proven. Another disadvantage of some glue is that a significant amount of a Heat curing is required to develop full effectiveness. When using these materials you can therefore, immediately after the formation and drying of the paper web, neither full effectiveness nor full Sizing value can be obtained.

In US-PS 3 1o2 o64 the use of glue is described, the substituted cyclic dicarboxylic acid anhydrides are. These glue means there is the following

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Structural formula attributed:

Il

0 RR ¹

Il

Here, R denotes a dimethylene or methylene group and R ¹ denotes a hydrophobic group which contains more than 5 carbon atoms and which is selected from the class of alkyl, alkenyl, aralkyl or aralkenyl groups. Substituted cyclic dicarboxylic acid anhydrides which fall under the above formula are, for example, substituted succinic acid and glutaric acid anhydrides.

The use of these known agents as sizes for paper and cardboard results in products which have an unusually high Have water resistance level.

The successful use of these sizing agents is not restricted to a particular pH range, so that the Use for neutral and alkaline pulps as well as acidic pulps is enabled.

The sizing agents described in US Pat. No. 3,102,064 are mainly produced from linear olefins in which the double bond is in the 1,2 or 3-position, or from short-chain branched olefins such as triisobutylene. The use of the above class of olefins results in sizing agents in which the R ¹ group is either linear or linear with

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multiple methyl or ethyl groups attached to the linear chain. Alternatively, R ^{1 is} linear with a pendant methyl, ethyl, or propyl group (which group may be saturated or unsaturated) attached to the carbon atom which in turn is attached to the cyclic anhydride moiety. Examples of sizing agents in this publication are iso-octadecenyl-succinic anhydride, n-hexydecenyl-succinic anhydride, dodecenyl-succinic anhydride, triisobutenyl-succinic anhydride and the like.

It has now been found that in the production of cyclic dicarboxylic anhydride sizing agents from internal Olefins of the general formula

R -CH ₀ -CH = CH-CH ₀ -R

wherein R is an alkyl group having at least 4 carbon atoms and R is an alkyl group having at least 4 carbon atoms mean that the glue obtained is far more effective (that is, the desired glue properties can be obtained even at considerably lower concentrations) than the prior art glue using olefins which have the double bond in the 1,2 or 3-position or of short-chain branched ones Olefins are produced.

The glue agents according to the invention have the following general formula:

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2A00058

R.
χ

H CH ₀

C-C-CH-CH = CH-R

where R is an alkyl group with at least 4 carbon

Ji

atoms and R 'is an alkyl group with at least 4 carbon atoms mean and R and R are interchangeable. Also mixtures of any of the glue agents described above can be used for the procedure.

Examples of typical sizing agents according to the present invention are sizing agents obtained by reacting Maleic anhydride is made with internal olefins such as octadecene-9, tetradecene-7, hexadecene-7 and eicodecene-11 will. Mixtures of 2 or more olefins can also be reacted with the acid anhydride to form a mixture of Manufacture glue agents according to the invention. Although 01efine, with a chain length of about 24 carbon atoms or more may be used in some cases, the preferred olefins contain 14 to 22 carbon atoms.

It will be apparent to those skilled in the art that if symmetrical Olefins used to react with maleic anhydride, the resulting reaction product is a "mixture." of glue, because the olefin with the

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Maleic anhydride moiety can connect through one of the two unsaturated carbon atoms. When using Technical olefins are such olefins, often mixtures of related olefins, one or the other Type prevails. These olefin mixtures result in Implementation with the anhydride mixtures of glue. For these reasons, the new glue compositions according to the invention not defined below by their chemical structures, but rather as the reaction product of Maleic anhydride named and identified with a specific olefin. Implementation of maleic anhydride with the olefins given herein is known to those skilled in the art and requires no special precautions.

The glue agents according to the invention have all the features and Advantages of the cited known glue. In addition, the new glue according to this invention give the glued paper has particularly good resistance to acidic liquids such as acidic inks, citric acid, Lactic acid etc. compared to papers that have been glued with prior art glue. In addition to the properties already mentioned, the glue agents according to the invention can also be used in combination with Alum as well as any pigments, fillers and other ingredients that can be added to the paper are used will. The glue agents according to the invention can also be used in conjunction with other glue agents to get additional gluing effects. Another advantage is that it increases the strength of the paper do not decrease when used with certain excipients will. In fact, they increase the strength of the

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finished sheets. Only mild drying or hardening conditions are required to develop the full glue value necessary.

The use of the sizing agents in the manufacture of papers is of a number of variations in the technique subject, which is familiar to the person skilled in the art. It should be noted, however, that in all of these working methods It is extremely important that the sizing agent be uniformly dispersed throughout the slurry of the Fibers through which it is necessary that the addition to the pulp by an extended and vigorous stirring is accompanied. Uniform dispersion can also be obtained in such a way that the Sizing agent is added in completely dispersed form, e.g. as an emulsion, or that a joint addition from chemical dispersants to the fiber slurry he follows.

Another important factor for the effective utilization of the glue compositions according to the invention comprises their use in connection with a material that is either cationic in nature or that is otherwise capable of being in a such a way to ionize or dissociate that one or more cations or other positively charged parts be generated. These cationic agents have been found to be useful, as will be explained below Means proven to support the retention of the glue agents according to the invention and the latter in close proximity with to bring the pulp fibers. Examples of materials that are used in the process according to the invention as cationic Agents that can be used are alum, aluminum chloride, long-chain Fe: ctamine, sodium aluminate, substituted polyacrylamides, Chromium sulfate, animal glues, cationic thermosetting resins and polyamide polymers. Of special

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Various cationic starch derivatives including primary, secondary, tertiary or quaternary amine starch derivatives and other cationic nitrogen-substituted starch derivatives, as well as cationic sulfonium and phosphonium starch derivatives. Such derivatives can be made from all types of starch, e.g. from starches derived from Grain or maize, cassava, potatoes, waxy maize, wheat and rice. In addition, these strengths exist in their original grain form or they can be converted into pregelatinized, cold-water-soluble products have been.

All of these cationic agents listed above can, too the mass, i.e. to the pulp slurry either before, together with, or after adding the glue. To achieve maximum distribution however, it is preferable that the cationic agent is added either after or in direct combination with the sizing agent. The actual addition to the crowd either the cationic agent or the sizing agent, can be used at any point in the papermaking process before the final conversion of the wet pulp into a dry fabric or sheet. So can e.g. this glue is added to the pulp, while the latter is in the head box, the beater, the hydropulping device or in the mass device.

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In order to achieve good gluing, it is advisable to that the conducting agents in the fiber slurry are uniform dispersed in as small a particle size as possible. One method of achieving This aim is that the glue before adding to the mass either by using mechanical devices, e.g. high-speed stirrers, mechanical homogenizers or by adding to emulsify a suitable emulsifying agent. If it is possible then it is very hard to strive for that to use cationic agents as an emulsifier. This method is particularly advantageous when cationic Starch derivatives used v / ground. Examples of suitable non-cationic emulsifiers that act as emulsifiers Hydrocolloids such as common starches can be used for the sizing agents according to the invention, non-cationic starch derivatives, dextrins, carboxymethyl cellulose, gum arabic. Gelatin and polyvinyl alcohol, as well as various wetting agents. Examples of such wetting agents are polyoxyethylene sorbitol trioleate, polyoxyethylene sorbitol hexaoleate, Polyoxyethylene sorbitol laurate and polyoxyethylene sorbitoleate laurate. When using such non-cationic emulsifiers, it is often useful separately adding a cationic agent to the pulp slurry after adding the emulsified sizing agent. In preparing these emulsions using an emulsifier, the latter is usually first in water dispersed whereupon the glue then under vigorous Stirring is added.

Further improvements in the water resistance of the papers produced with the sizing agent according to the invention, can be obtained by cutting the resulting tissues,

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Hardens sheets or molded products. This hardening process provides for the paper to be heated to temperatures in the range from 80 to 150 ° C. for periods of from 1 to 60 minutes. It however, it should be noted that post-curing is essential for the successful implementation of the method according to the invention is not required.

The sizing agents according to the invention can of course be used successfully for sizing papers made from of all types, both of cellulose and combinations of cellulose with non-cellulose fibers. The cellulosic fibers that can be used include those made from bleached and unbleached sulfate (Kraft), bleached and unbleached sulphite, bleached and unbleached soda, neutral sulphite, semi-Jaemisch-semi-ground Wood, ground wood, and combinations of these fibers. These names refer to wood palm fibers that be manufactured by a variety of processes used in the pulp and paper industry. Additionally Synthetic fibers made from viscose rayon or regenerated cellulose can also be used.

All types of pigments and fillers can be added to the paper that is glued with the sizing agent according to the invention added / ground. Such materials include clay, talc, Titanium dioxide, calcium carbonate, calcium sulfate and diatomaceous earth. With this glue you can continue to add other additives including alum as well as other sizing agents can be used.

The sizing agents according to the invention can be used in amounts of about 0.05 to about 3.0% based on the dry weight of the pulp can be used in the finished sheet or fabric. Although quantities in excess of 3% can also be used, the advantages that can be achieved in this way are not economically justified. Within the specified range

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the precise amount of glue that is used depends in large part on the type of pulp that is used will depend on the specific operating conditions as well as the particular end use of the paper. For example, a Paper that's a good one. Water resistance or ink-out must have the use of a higher concentration of sizing agent as a paper that is used in applications is used where too strong gluing is not required. The same factors also apply to that Amount of the cationic agent to go along with the sizing agents is used. The practitioner can use these materials in any concentration that is acceptable to the specific operating conditions is applicable. However, under the usual circumstances, it is a range from 0.5 to 2.0 Weight tie. of the cationic agent each 0.10 Tie. of the glue usually appropriate. The cationic agent can be specified in an amount of at least 0.025% based on the dry weight of the pulp is present in the paper.

The use of the sizing agents according to the invention results in a degree of acidic water resistance for the paper that is considerable higher than when using the well-known glue? medium in particular according to US-PS 3 1o2 o64 is obtained.

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The invention is illustrated in examples. Are in it all parts based on weight.

example 1

This example illustrates the use of a sizing agent that is suitable for the liners according to the invention is representative, in the form of an aqueous emulsion, in which the emulsifier used is a tertiary amine derivative of a cationic starch. The water resistance of the resulting paper will match that compared by paper, as with iso-octadecenyl - succinic anhydride has been glued. This connection is a typical glue according to US Pat. No. 3,102,064.

An aqueous emulsion of a glue made from maleic anhydride and octadecene-9 (hereinafter referred to as MA / OD-9) was prepared, by initially 10 TIe. of beta ethyl aminoethyl chloride hydrochloride ether of corn starch, the preparation of which is described in Example 1 of US Pat. No. 2,813,093, in 90 TIn. Water were boiled. The dispersion of the cationic starch derivative became after boiling for 20 minutes Cooled to room temperature and placed in a high speed stirrer convicted, whereupon 5 Tie. MA / OD-9 was slowly added to the stirred dispersion. The stirring was Continued for about 3 minutes and the resulting emulsion was then made up by adding water 1,000 TIe. diluted (0.5% solids).

Calculated amounts of this stock emulsion (diluted with water) were bleached into aqueous slurries Sulphate pulp with a freedom of 5OO, one consistency

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of 0.5% and a pH of 7.6, so that the glue in a concentration of 0.10, 0.20 and 0.40 % By weight of the dry pulp was present. Leaves were formed and dried according to standard TAPPI methods. The basis weight of these sheets was 24.9 kg / ream (61 cm by 91 cm - 500 sheets). After Comparative sheets containing identical amounts of isooctadecenyl succinic anhydride were prepared in the same manner (abbreviated as I0DSA), emulsified with the cationic starch derivative described above, contained. In hardening the sheets, hardening was carried out for 1 hour using hot air circulating ovens. carried out at 1O5 ° C for a long time.

When comparing the water resistance of these sheets (ie, those made with MA / OD-9 and IODSA), a dye test with crystals of potassium permanganate and a penetration test for acidic inks were used. In the dye test, several crystals of potassium permanganate were applied to the top surface of the test paper, which was then allowed to float in distilled water at room temperature. As the water absorbed into the paper, the crystals were moistened and gave the paper a distinctive deep purple color. The time in seconds required for an end point when three-colored stains first appeared on the paper surface was measured. This period of time is directly related to water resistance, since a more water-resistant paper will delay the wetting of the permanganate crystals lying on the top surface.

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The Acid Penetration Test is a comparative test in which a test paper is placed in a tray left to float the acidic tine (pH 1.5) at 37.8 ° C The time (in seconds) required for the ink to pass through the paper is measured penetrates and an end point is reached where about 50% of the paper is colored.

The following table contains values from various paper sheets that were used in the test procedure described were compared with each other.

TABEL

Penetration of the acidic ink

KMnO,

Gluing% by weight (period in seconds) (period in seconds)

Leaf medium dry un- un-

Pulp hardens hardened hardened hardened

1. MA / OD-9 0.10 25th 600 46 53 2. MA / OD-9 0.20 475 600+ 55 74 3. MA / OD-9 0.40 600+ 600+ 61 77 4th IODSA 0.10 3 3 23 18th 5. IODSA 0.20 15th 19th 44 65 6th IODSA 0.40 25th 25th 51 69

The above values clearly show that a paper that was glued with the new MA / OD-9 glue, a significantly increased acid resistance was measured

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after the acid inks penetration test compared to a paper sized with IODSA had been. Approximately a four-fold increase in the concentration of IODSA was required to ensure acid resistance, conferred by MA / OD-9, measured at a 0.10% addition value to the pulp to achieve the described ink penetration test.

Also the results of the dye test using KMnO. show that increased water resistance using MA / OD-9 compared to IODSA at comparable concentration values, the more substantial increases are noted at the lower concentration values.

Example 2

This example illustrates the use of another sizing agent according to the invention in conjunction with alum. The water resistance of the resulting paper is compared with that of a paper that has been glued with IODSA.

Following the procedure of Example 1, an aqueous emulsion of a sizing agent composed of maleic anhydride and tetradecene-7 (hereinafter abbreviated as MA / TD-7) was produced. as In turn, the tertiary amine derivative of the cationic starch, which was described above, was used as an emulsifier. Calculated amounts of the stock emulsion were added to separate batches of bleached sulfate pulp given a freedom of 500 and a consistency of 0.5%, so that a glue concentration of 0.10, 0.25

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and 0.40% by weight based on the dry pulp became. The pH of the pulp slurry was 7.6. According to the TAPPI standard methods, Leaves formed and dried. The basis weight of these sheets was 24.9 kg / ream. The same way of working Comparative sheets were made for comparison purposes, containing comparable concentrations of IODSA contained. As in Example 1, the sheets were cured, curing using Hot air was carried out for 1 hour at 1O5 ° C.

All sheets were subjected to the acidic ink penetration test according to Example 1. The results obtained are compiled in Table 2.

TABLE 2

Penetration of the acidic ink

% By weight of (period in sec.)

Sheet No. Glue means dry urigehärtet hardened

Pulp

1. MA / TD-7 0.10 11 8th 2. MA / TD-7 0.25 131 140 3. MA / TD-7 0.40 189 255 4th IODSA 0.10 5 5 5. IODSA 0.25 25th 34 6th IODSA 0.40 49 80

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Example 3

In this example, the gluing properties of a glue according to the invention are compared with those of a glue according to US-PS 3 1o2 o64. The latter was made using an olefin with an equal number of carbon atoms, but with the double bond in the 1-position.

Following the procedure of Example 1, two parts of a sizing agent, namely a reaction product of Maleic anhydride and tetradecene-7 (MA / TD-7), which is an inventive glue, with a Part of a cationic starch emulsified. Using the emulsified sizing agent, sheets of paper were made produced using unbleached softwood pulp with a pH of 7.6 and 6.0 (the pH was with alum lowered) was used, so that the glue in a concentration of 0.1, 0.12 and 0.4% by weight of the dry pulp was present.

By repeating the procedure of the above paragraph, paper sheets were prepared using tetradecenyl succinic anhydride (TDSA) was used.

When testing in the acid inks penetration test However, if the leaves dry uncured, the following results were obtained

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TABEL

penetration of the sour tine

% By weight of (period in sec.)

dry
Sheet Ur. Sizing agent pulp pH 7.6 pH 6.0

95 135 165

80 115 145

1 . MA / TD-7 0.10 6th 2. MA / TD-7 0.20 20th 3. MA / TD-7 0.40 200 4th TDSA 0.10 3 5 .. TDSA 0.20 7th 6th TDSA 0.40 30th

Example 4

According to the procedure of Example 1, one part MA / OD-9 was mixed with one part of a tertiary amine derivative of a · cationic starch emulsified.

Using the emulsified glue, in Paper sheets made conventionally using a bleached Kraft softwood pulp so that the Sizing agent was present at a concentration of 0.10, 0.20 and 0.40% by weight of the dry pulp. The leaves were cured at 105 ° C. for 1 hour.

When testing the resulting leaves against leaves, those made for comparison using IODSA in the lactic acid test, the results shown in Table 4 were obtained.

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The lactic acid test was carried out in a similar manner to the acid inks penetration test described above, however, the ink was replaced with a 20% aqueous solution of lactic acid and the endpoint is reached when about 5% of the upper surface are penetrated by the acidic solution.

TABEL

Glue % By weight of
dry
Pulp Penetration test for
Lactic acid
(Period in seconds) MA / OD-9 0.10 5 MA / OD-9 0.20 106 MÄ / OD-9 O, 4O 600+ IODSA 0.10 "0 IODSA O, 2O 2 IODSA 0.40 3 Example 5

To further illustrate the invention, a sizing agent according to the invention was prepared by adding maleic anhydride was reacted with a mixture of olefins, which consists of 1 part, tetradecene-7, 2 parts. Hexadecene-7 and 1 part. Octadecene-9 consisted of.

The resulting sizing agent was mixed with the beta-ethylaminoethyl chloride hydrochloride ether emulsified by corn starch and then used for gluing paper sheets the procedure of Example 1 is used. The results when testing with acid inks, those with the glued paper showed that the paper had durability opposite had acidic water) ,, which of those of

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Paper was superior because IODSA was used for gluing. The results according to the invention were comparable to those obtained with papers which with the MA / OD-9 of Example 1 had been glued.

The above existing sizing agents were made by reacting maleic anhydride with selected olefins. However, suitable gluing agents can also be used using homologous anhydrides, glutaconic acid, produced together with the identical olefins. It can be assumed that these are similarly effective Give the paper gluing properties.

The invention thus provides new glue means that can be used under a wide variety of conditions are applicable and which are capable of producing paper products which have an exceptionally high degree of durability compared to acidic water with low levels of glue.

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Claims (6)

PATENT CLAIMS 1. Method for gluing paper, thereby g e k e η η ζ e i c h η e t that one in the wet pulp before the final transformation of the pulp into a dry fabric a · sizing agent disperses the reaction product of Maleic anhydride with an internal olefin of the general formula "R, -CH ₉ -CH = CH-CH ₀ -R where R is an alkyl group with at least 4 carbon atoms and R represents an alkyl group having at least 4 carbon atoms. 2. The method according to claim 1, characterized in that g e k e η η draw t that the glue is used in the form of an aqueous emulsion. 3. The method according to claim 1 or 2, characterized in that one in the wet pulp before the ultimate conversion of the pulp into a dry web, (a) a sizing agent which is the reaction product of Maleic anhydride with an internal olefin of the formula -CH ₂ -CH = CH-CH ₂ -R wherein R is an alkyl group having at least 4 carbon atoms and R is an alkyl group having at least 4 carbon atoms and (b) at least 0.025% based on the weight of the dry pulp of a cationic agent is intimately dispersed. 409833/0665 -24- 4. The method according to claim 3, characterized in that the cationic agents alum, aluminum chloride, long-chain fatty amines, substituted polyacrylamines, animal glues, polyamide polymers,
cationic resins and / or cationic starch derivatives
used. 5. The method according to claim 3, characterized in that the sizing agent with a wetting agent prior to its dispersion in the wet pulp
emulsified. 6. The method according to claim 3, characterized in that selected as the sizing agent, the reaction product of maleic anhydride with an internal olefin is selected from the group consisting of octadecene-9, tetradecene-7,
Hexadecene-7 and eicodecene-11 are used. 409833/0665