FI80312B - HYDROFOBERINGSMEDEL FOER CELLULOSAFIBRER, SAETT ATT FRAMSTAELLA DETTA MEDEL SAMT ANVAENDNINGEN AV MEDLET FOER MAELDHYDROFOBERING. - Google Patents

Description

8031 2 1 Water-repellent medium for cellulosic fibers, process for the preparation of this medium and its use for water-repellent treatment of fibrous pulp Hydrofoberingsmedel för cellulosafibrer in the manufacture, and in particular in the associated water-repellent treatment (gluing) of the pulp. Paper gluing or water-repellent treatment has long been a well-known technique originating in China. With the advent of the Pa-15 manufacturing technology in Europe, it was found that water-absorbent paper was not very suitable for the pens and papers used at that time. As early as the 14th century, this led to the addition of gelatin to the paper to provide a hard, dense and non-absorbent paper surface. The Gluing Technology using gelatin and starch has since been continuously improved.

In the early 19th century, the gluing technology experienced a revolution when resin glue was invented. In resin sizing, the resin is mixed with alum into the cultured pulp before forming the sheets. The resulting pulp mixture is cationic and is joined by negatively charged fibers. The aluminum resinate formed during the reaction is highly water-repellent (hydrophobic) and imparts water-repellent properties to the paper. The pulp gluing technique with resin glue and alum remained relatively unchanged for the first 150 years. Since then, the composition of the rosin acid has been modified by reacting it with, for example, maleic anhydride and fumaric acid (so-called reinforced resin adhesive). To make the adhesive water-soluble, the rosin acid was saponified with sodium hydroxide solution and diluted before dosing.

35 An improvement in the latter technique was made in the 1960s and 1970s, when the so-called dispersion adhesive. According to this technique, the rosin acid is decomposed into small anlonic constituents (0.2-0.5 μm) in an aqueous solution of 2,80312 l. The dispersion thus obtained is stable and is mixed into the fibrous mass by means of alum.

However, despite certain new developments at various stages of manufacture, the resin gluing technique has remained essentially the same as the technique used in the 19th century, which requires two components to glue, a resin glue and an alumina-based alloy chemical.

GB-A1-2010352 discloses another method of gluing gold pulp, in which a resin adhesive comprising saponified rosin acid is added to the pulp and then mixed with the fibers by adding a substantially sulphate-free aluminum polyhydroxide chloride to the resin pulp. The advantage of this particular mixing method is considered to be less corrosion problems than those which occur when alum is used as an alloying agent. However, in this gluing method, a two-component system is used, in which the alum used as a common alloying agent is replaced by another alloying agent in the form of a special aluminum salt.

20

German Patent Publication No. 363,668 also describes a two-component system in which a resin adhesive is mixed with neutral or basic aluminum chloride.

In addition to the resin dyeing technique, a similar gluing technique has been used with the saponified fatty acids of tall oil (see, for example, Swedish Patent 7507128-2 under publication number 416 831), which are also mixed with an external alloying agent, such as alum.

A major disadvantage of the known sizing methods is that the water-repellent effect is significantly reduced when the paper systems are neutral or alkaline. This poses a particular problem when it is desired to use calcium carbonate instead of clay as a filler, as calcium carbonate dissolves at low pH. This disadvantage of conventional sizing is due to the fact that aluminum cations are required to mix the negatively charged resin acid or fatty acid. In neutral or basic systems, the aluminum ions are present in the form of alumina 3,80312 l, which is a poor alloying agent for resin glue, in this case resulting in a poor degree of sizing. This limiting factor poses a very serious problem in the gluing of neutral or basic fibrous pulp systems, because for both qualitative and cost reasons it is preferable to use calcium carbonate instead of clay as a filler for fine paper, for example.

In addition to conventional resin sizing systems, new synthetic adhesives have also been developed, the use of which has gained ground in papermaking at neutral or basic pH values. Examples of these types of adhesives are alkyl succinic anhydride and alkyl ketenimides. However, these adhesives are significantly more expensive than natural adhesives, such as rosin and fatty acids. Another disadvantage of using these known artificial adhesives is that they require a longer time to achieve the desired sizing effect compared to the curing time of resin or fatty acid based adhesives. The longer time required by the artificial adhesives means that the paper does not have completely water-repellent properties immediately after it has passed through the drying section of the paper machine.

20

The longer curing time causes disadvantages in surface sizing and / or coating of the paper immediately after drying. In the case of a low degree of sizing (when alkyl ketene sizing is used), the paper is often rewetted too vigorously, which can cause the material web 25 to break and reduce productivity. In addition, gluing with such neutral gluing systems can lead to low paper friction as well as coating problems in various parts of the paper machine equipment. These production problems have thus been one of the reasons why resin sizing has consistently remained the predominant water-repellent concept technology in acidic fiber pulp systems using clay as a filler. Another reason is the significantly higher cost of synthetic adhesives compared to resin or fatty acid based adhesives.

British Patent Publication No. 1,107,717 also proposes a sizing-35 system comprising a paraffin wax emulsion as a dispersed phase and a basic aluminum chloride solution as a continuous phase, said emulsion being stabilized by nonionic emulsifiers and / or nonionic thickening agents. Examples of other water-repellent substances in addition to paraffin include microcrystalline waxes, polyethylene and the like, and high molecular weight fatty alcohols and fatty amides, the use of which, however, has not yet been exemplified.

5 However, it has been shown that such gluing systems have not had the desired effect. The same is true of the gluing system described in British Patent Specification 1,274,654, which is also based on a combination of the same substances. What the gluing system according to both these patents has in common is that Ίq there is staining in the glued paper, which is an indication of the uneven distribution of the glue.

One disadvantage of known sizing systems is also that they are suitable for use in either acidic or neutral and basic fibrous Ί5 pulp systems. This causes difficulties for the paper mill, which wants to move from, for example, acidic pulp systems to neutral or alkaline systems. Namely, the exchange involves changing a number of interrelated factors, so that the transition from one gluing system to another causes considerable implementation difficulties. There is thus a need for a sizing system that can be used in both acidic and neutral or basic pulp systems, as the problems associated with moving from one system to another are substantially reduced.

The main object of the present invention is thus to provide a water-repellent treatment agent for the pulp, which avoids the limitations of the conventional technique. Another object of the invention is to provide a water-repellent agent which can be used as a one-component agent without the need for additional mixing. It is a further object of the invention to provide a process for the preparation of such a novel water repellent. Another further object of the invention is to provide an aeration system that can be used in both acidic and neutral and basic gold pulp systems.

The invention is based on the surprising finding that a stable one-component substance which can be used as an adhesive and which requires the use of any mixed mixture (which is required by conventional resin or fatty acid-based adhesives) can be prepared by combining certain polyaluminum salts , one or more rosin acids and / or fatty acids, optionally mixed with a melting point lowering additive such as paraffin or other water repellent, a melting point lowering agent and preferably also a low pH (less than 4) cationic organic substance. Such an adhesive contains small emulsifying (dispersing), highly cationic solvents that are directly absorbed into the negatively charged fibers upon dosing into the papermaking system or upon contact with other organic Ί0 fibers.

The water-repellent agent according to the invention thus comprises a water-emulsifiable / dispersible resin and / or fatty acid, a water-soluble polyaluminum salt and, most preferably, a cationic organic compound.

Ί5 This water-repellent substance is prepared by decomposing the resin and / or fatty acid as fine constituents in water together with a polyaluminium salt and possibly also a cationic organic compound. The invention also relates to the use of this water-repellent agent for the water-repellent treatment of cellulosic fibrous pulp in the papermaking industry.

One advantage of the invention is that the polyaluminum salt and the rosin and / or fatty acid are mixed together at a low pH (below 4), with immediate activation upon addition of this water repellent to the pulp, a mixture of aluminum and rosin and / or fatty acid. formed when the emulsion droplets reach pH 4-6. The invention provides close contact between the resin and / or fatty acid and the polyaluminum salt, so that, despite the high pH present in papermaking, aluminum hydroxide cannot precipitate before the formation of the active resin / fatty acid resinate. Another advantage of the water-repellent agent according to the invention is that the small emulsifying / dispersing ingredients, due to their small size, cover the surface to be coated with the water-repellent agent as effectively as possible.

A very great advantage of the invention is that no external precipitant is required when using the water-repellent agent according to the invention.

This means a considerable simplification of the water-repellent treatment 6 80312 1, especially in papermaking, not only because only one substance has to be used, but also because a more secure and even gluing is achieved, as it is easier to optimize the amount of additive when using the one-component glue according to the invention. g in the case of the use of two-component adhesives.

At present, the main advantage of the water-repellent agent of the invention over conventional resin adhesives appears to be that the agent of the invention is much more effective even at high pH values when used in paper types containing large amounts of calcium carbonate as a filler.

A further advantage of the invention is that the water-repellent agent according to it requires the use of considerably cheaper raw materials than the synthetic adhesives available on the market. Resin and fatty acids are available in almost unlimited quantities. From a technical point of view, the new water-repellent is also superior to synthetic adhesives (e.g. alkyl alkyl enders) when used in neutral or basic paper production systems, since the water-repellent according to the invention hardens rapidly and thus makes the paper water-repellent already in the paper machine. Thus, there are no production disturbances that can be caused by other synthetic adhesives.

The invention generally comprises mixing a polyaluminum salt, an elaptic resin and / or a fatty acid optionally with a melting point lowering additive such as paraffin, and optionally also a cationic organic substance with vigorous stirring in water to give an emulsion or dispersion comprising 3Q small cationic droplets on the order of 0.05-50 μm, preferably 0.05-25 μm.

The best possible efficiency and stability of the adhesive is achieved if the cationic organic substance in question is contained in the adhesive itself. However, in certain applications, it is possible to combine the one-component adhesive (i.e. the resin or fatty acid and the special polyaluminum salt) with the cationic organic substance only when mixed with the organic 7 80312 l fibers. In papermaking, therefore, the cationic substance can be mixed separately into its paper pulp, either for sizing or for some other purpose. Thus, the sizing process according to the invention can be combined with known papermaking processes by adding a cationic organic substance to the pulp in accordance with e.g. European Patent Publication EP-B1-41056 and European Published Patent Application EP-A1-80986.

The dispersion or emulsion prepared in this way is, in particular if it contains a cationic organic substance, stable and of such high concentration that it can be distributed very advantageously to consumers by means of conventional transport methods.

Basic polyaluminum salts, such as polyaluminum sulfate or polyaluminum chloride, have proven to be the most suitable polyaluminum salts for the purposes of the invention. These salts are characterized by a high molar ratio between aluminum and counterion (> 1) and the fact that they generate high-charged polyaluminum ions, such as α113o4 (oh) 26 (h2o) io5 +, in aqueous solution.

2 °

The raw materials for the water-repellent agent according to the invention can be pure resin or fatty acids or combinations thereof, in which case melting point-lowering additives, such as paraffins, can also be added.

25

When resin acid is used, its typical composition is as follows:

abletic acid 40 Z

neoabletllnihapo 4 Z

30 pimaric acid 3 Z

isopimeric acid 6%

palustric acid 7 Z

other acids 40% 35 When fatty acid from tall oil is used, the following composition is common: 8 80312 1 oleic acid 30%

linolenic acid 65 Z

other acids 5% g In the context of the invention, it is possible to use a modified rosin or fatty acid which has been fortified by the reactions of substances customarily used in this context, such as maleic anhydride, fumaric acid, etc.

In the context of the invention, it is important that the resin and / or fatty acids it contains are in an uncharged form (non-saponified) so that the pH can be kept low, preferably below 5. At higher pH values, negatively charged carboxylate groups are obtained. , which reduce the cationic nature of the emulsion or dispersion droplets (thereby dispersing the emulsion or dispersion).

A suitable amount of the various components is 0.5-90 Z of resin or fatty acid and 10-99.5 Z of water.

A suitable weight ratio between the resin or fatty acids contained in the dispersion and aluminum is 100: 1 to 1: 4, preferably 10: 1 and 1: 2.

The cationic organic compounds contained in the aqueous phase may be surfactants, starch, guar gum, carboxymethylcellulose, polyacrylic amide, polylmillin, polyamine, polyamidamine, polyethyleneimine or polyacrylate. A suitable weight ratio between resin or fatty acids and the cationic organic compound is 100: 0.01 to 100:30.

The invention is described in more detail below with the aid of a few practical 3Q examples.

EXAMPLE 1 In this example, an adhesive emulsion was prepared using 500 g of pine fatty acid (BEVACID 2, Bergvik Kemi, Söderhamn, Sweden), fortified with 5% fumaric acid and mixed with 2.49 g of cationic surfactant (hexadesyltrimethyllampmonium chloride, Riedel-de-Ha .9 80312 1 West Germany) and 69.9 g of ethanol. This mixture was then added under vigorous stirring (mixer ULTRA-TURRAX, ΙΚΑ-Werk, Stuten) to a mixture of 5.61 g of cationic starch at a nitrogen content of 0.4 Z (starch S-195, Raisio-SLR AB, Gothenburg, Sweden) and 967.5 g of polyalu-5 mine chloride Α ^ ίΟΗί, ΧΙ H ^ O, Albright & Wilson, London, Al content 25% by weight in 4454 grams of water. The temperature during the mixing operation was 25 ° C in both the fatty acid and aqueous phases.

The mixture was then homogenized in a valve homogenizer (Gualin 10 Lab 60, APV Schröder, Liibeck, West Germany) at an overpressure of 350 bar. The pH of the resulting emulsion was measured at room temperature and was 3.7. In connection with microscopic examinations, it was found that the size of the emulsion droplets of the prepared adhesive was 1-2 pn.

The resulting emulsion was stable to phase separation for more than two months.

EXAMPLE 2 20 25 g 22% pine fatty acid and 45% pine resin acid (special mixture

From the distillery of Bergvik Kemi AB - the mixture was fortified with 10% fumaric acid) was added in the same way as in Example 1 to a mixture of 24 g of polyaluminum chloride (same as in Example 1) and 0.063 g of cationic polyacrylamide ("PERCOL" 181, COM, Västra 25 Frölunda, Gothenburg) and 250 ml of water. Otherwise, the mixture was prepared as in Example 1 to give a stable dispersion with a small ingredient size and a pH of about 2.5.

EXAMPLE 3 In this example, a stable dispersion was prepared by adding 1.7 g of unreinforced rosin acid ("BEVIR0S SG", Bergvik Kemi AB, Söderhamn) to 16.7 grams of water containing 0.02 g of cationic surfactant (hexadecyltrimethylammonium bromide, Riedel de Ha AG, Seelze-Hannover, West-35 Germany) and 1.6 g of polyaluminum chloride (same as in Example 1).

The mixture was transferred to a 100 mL pressure vessel and heated to 148 ° C with a magnetic stirrer under magnetic stirring. Heating was stopped after 30 minutes and the dispersion was allowed to slowly cool to room temperature. The pH of the resulting product was 2.8.

EXAMPLE 4 To 50 grams of a fatty / rosin acid mixture (same mixture as in Example 2) was added 0.13 g of a cationic surfactant (dissolved in 3.5 grams of ethanol). The cationic surfactant was the same as in Example 3.

10

The fatty / rosin acid mixture was added to 148 grams of water containing 48.4 g of polyaluminum chloride (same as in the previous example) and 0.25 g of cationic starch having a nitrogen content of 0.4%. Otherwise, the preparation method was the same as in Examples 1 and 2.

This experiment resulted in a stable dispersion with a pH of 2.5 and a slightly higher viscosity than in the previous example.

EXAMPLE 5 In this example, 25 g of a fatty / rosin acid mixture (same mixture as in Example 2) was added to 250 ml of water containing 0.6 g of cationic guar-Kumla (nitrogen content 1.5 X, "GENDRIVE 162", Henkel Company, USA) and 150 g of polyaluminum sulphate (purchased from Boliden Kemi AB, Helsingborg and containing 15.5% aluminum and 65% sulphate, thus having a molar ratio of A1: SO 2 = 0.9).

The manufacturing method was otherwise the same as in the previous example. The pH of the dispersion was 2.5. The experiment showed that the fatty / resin acid could be combined with other components to give a dispersion. However, the stability of the dispersion against phase separation was lower (one day) than in the previous example.

EXAMPLE 6 1.25 g of cationic starch with a nitrogen content of 0.40% and 4.86 g of polyaluminum chloride (see previous example) were dissolved in 250 g of hydrogen at 95 ° C.

25 g of pine fatty acid (same as in Example 1) was heated to 95 ° C and added continuously to a warm aqueous solution using the method described above.

The resulting emulsion had a pH of 2.5 and an emulsion droplet of the order of 3-4 pn. The emulsion proved to be stable against phase separation for eight days.

EXAMPLE 7 In this experiment, a stable adhesive emulsion was prepared by adding 25 g of pine fatty acid ("BEVACID 2") to 250 g of water containing 5.6 g of cationic starch with a nitrogen content of 0.40% and 29.2 g of polyaluminum chloride. experimental conditions as in Example 1. The pH of the resulting emulsion was 2.8.

EXAMPLE 8 20 g of a special mixture of fatty / rosin acid (same product as in Example 2) were added as described in Example 1 to a solution of 58.3 g of polyaluminum chloride (same as in Example 1) and 216.7 ml of water. The preparation was otherwise carried out according to Example 1, resulting in an emulsion / dispersion with a pH of 2.8.

EXAMPLE 9 In this example, 25 g of a fatty / rosin acid mixture (same mixture as in Example 2) was added to a solution of 58.3 g of polyaluminum chloride (same as in Example 1) and 91.7 g of water using the same method as in Example 1. After cooling in a water bath, 125 g of a 1% cationic starch solution (nitrogen content 0.40%) was mixed with the above product. The resulting stable emulsion / dispersion had a pH of 2.8.

i2 8031 2 1 EXAMPLE 10

The following composition was made in paper pulp: g 70 Z fully bleached pulp (60/40 birch sulphate / pine sulphate) 30% calcium carbonate ("Sjöhästen", Malmökrita)

Birch and pine sulfate were ground in a laboratory holster to a grinding degree of 200 ml CSF (Canadian Standard Freeness). Calcium carbonate (1Q (slurried in water)) was added to the pulp and the pulp was diluted to a dry concentration of 0.5 Z. The pH of the pulp was then 8.0.

In the experiment, different amounts of the adhesive according to Example 1 on the one hand and the conventional resin adhesive ("T-adhesive 7635", Herc5 Hercules AB, Gothenburg) on the other hand were applied to different doses of paper pulp.

In experiments with a conventional resin adhesive, 2 Z alum (based on sowing weight) was added as usual before the adhesive was dosed.

20

The adhesives were dispensed as 1% solutions and added to the 0.5% pulp under agitation (45 s). The pulp was then transferred to a labora-torloarkklmuottiln (Finnish mold) equipped with a 100-mesh wire. The sheets were formed according to SCAN C 26:67 25 (basis weight 73 g / m 2). The sheets were dried at 23 ° C and 50% relative humidity overnight, after which they were placed in a heating cabinet at 120 ° C for 30 minutes.

After conditioning (23 ° C, 50 Z relative humidity), their dewatering capacity was determined according to SCAN P 12:64 (Cobb ^ g).

The evaluation results are given in the table. The amounts of adhesive (weight-Z) refer to the added amounts (active content) calculated from the dry fibrous mass. It can be seen from Table 1 that the Hima agent according to the invention gives a completely valid sizing (Cobb ^ g <25) despite the high pH and the high amounts of calcium carbonate.

.3 8031 2 1 TABLE 1 I I 2

Adhesive Dosage amount (%) Cobbgg (g / m) 5 ---

Example 1 0.3 46 "0.5 17" 0.7 14 "1.3 13 10" 2 '° 12 --L- EXAMPLE 11

The paper pulp was prepared in the same manner as in Example 1. The pH of the resulting gold pulp was 7.3. Various adhesives according to the invention were added to the dry mass.

Sheeting and drying of the paper sheets was performed as described in Example 8 2q. Dehydration was determined according to Cobb® (SCAN P 12:64). The results are shown in Table 2.

TABLE 2 2 25 Dewatering according to CobbgQ (g / m)

\ Dosage Z

\ 0 1.0 1.5 2.0

Adhesive according to Example \ 2q \ 2 113 45 38 23 3 113 83 69 40 4 113 21 16 14 35 5 1 13 67 57 42 1 EXAMPLE 12 i4 8031 2 Paper fiber pulp obtained from a newsprint mill was used in this experiment. The pulp had a concentration of 3 Z and was ground to a degree of grinding of g 125 CSF. The composition of the pulp used was: 22 Z fully bleached chemical pulp 15% TMP (thermomechanical pulp) 35% wood chips 10 28 I waste

30% kaolin (C-clay, ECC) based on dry fiber weight was added to the cultured pulp. The pulp was diluted to 0.5% and the pH was adjusted to 5.0.

15

The adhesive prepared according to Example 3 was added in various amounts to the slurry mixture of cults and filler. The sheets were prepared according to SCAN C 26:67 2 (basis weight 73 g / m 2).

In this experiment, the sheets were tumble dried at 85 ° C. The sheets were then placed in an oven (120 ° C) for 30 minutes.

After conditioning (23 ° C, 50 Z relative humidity), the dewatering capacity was measured according to Cobbg®. The results of these measurements are given in Table 3 3.

TABLE 3 30% Cobbgg adhesive according to Example 4 2 (g / m) 0 219 35 0.5 193 1.0 93 2.0 19 li 1 EXAMPLE 13 15 8031 2 A pulp with a dry weight of 1.37% and a degree of grinding of 200 was used in this experiment. ml CSF and comprising 60% birch sulphate pulp and g 40% pine sulphate pulp.

To the pulp was added 30% calcium carbonate (Malmokritan "SJÖHÄSTEN") based on dry fiber weight. The pH was then adjusted to 8.5. The adhesive prepared according to Example 1 was added to the pulp in various amounts. The sheets were then prepared according to SCAN C 26:67 2 at a surface pressure of 73 g / m 2. The sheets were dried and evaluated as described in Example 10 to achieve very good sizing. The gluing results are given in Table 4.

15 TABLE 4 2

Dewatering according to Cobbgg (g / m) 2Q Dosage

Adhesive 0% 0.3% 0.5% 1.0% 2.0%

According to Example 1 103 58 27 15 12 --L ---- 25 EXAMPLE 14 The same culturing mass and preparation method as in Example 10 was used in this experiment. However, the adhesive according to Example 3Q 8 was used as the water-repellent medium. It was dosed in various amounts, with 0.6% of cationic starch (based on the dry weight of the pulp) being added to the mixture 15 s after the adhesive was added as an external retention agent. The results of the experiment are shown in Table 5. In this experiment, it was found that the adhesive of Example 1 gave a better result even without the cationic substance, but that the improvement was more pronounced when the cationic substance was added.

1 TABLE 5 16 8031 2

Dewatering according to Cobb ^ Q 5 -----

Adhesive Adhesive dosage Cationic starch Cobb ^ Q

(%) dose of the mixture 00 (g / m2)

For example, according to 8, 0.3 0 83 "0.5 0 65" 1.0 0 50 "2.0 0 46

For example 8 according to 0.3 0.6 76 "0.5 0.6 67" 1.0 0.6 37 "2.0 0.6 18 20 Blank test -0 0 99 EXAMPLE 15 25 In the experiment according to this example, the following example was used. 10. The same procedure as for example 10 was used for gluing, however, in the present example the glue prepared according to Example 9 was used, and a fully valid gluing was also obtained in this experiment, the results of which are shown in Table 6.

35 1 TABLE 6 17 8031 2

Dewatering according to Cobbgg 5 --- j-η

Adhesive Dose of adhesive (%) Cobbgg Cg / m)

Eg 9 according to 0.3 71 "0.5 66 10" 1.0 46 "2.0 17

Blank test 0 99 15 EXAMPLE 16

As a water repellent in this example, a mixture containing 42 g of pine resin (BEVIROS SG, Bergvik Kemi) and 18 g of paraffin wax 2Q (melting point 58 ° C, Malmsten & Bergvall, Gothenburg) was used. This water repellent was added under very vigorous stirring (ULTRA TURRAX, ΙΚΑ-Werk, Staufen) to a mixture of 3 g of cationic starch with a nitrogen content of 0.4%, 144.7 g of a polyaluminum chloride solution (KLORHYDROL, Reheis Chemical Ltd, Dublin, Al content). 12.5% by weight) and 92.3 g of water. During emulsification, the temperature was 95 ° C for all chemicals in the mixture.

The emulsion was further homogenized for three minutes at 10,000 rpm, after which it was cooled in a water bath to room temperature-3Q.

The product prepared in this way had a pH of 3.7 and an ingredient size of about 1-2. Stability was good for more than two months.

35 For the purpose of testing the adhesive thus prepared, paper pulp having the following composition was prepared:

______ - · I

,. 80312 1 80 Z fully bleached chemical pulp (60/40 birch sulphate / pine sulphate) 20 Z calcium carbonate (Malmökritan "Sjöhästen").

g Birch and pine sulphate were ground in a laboratory holester to a degree of grinding of 200 ml CSF (Canadian Standard Freeness). Calcium carbonate (slurried in water) was added to the mixture and the pulp was diluted to 0.5% of dry weight. The pH of the pulp was then 8.0.

The adhesives were dispensed as a 1% solution and added to the 0.5% pulp with stirring (45 s). The pulp was then transferred to a laboratory sheet mold (Finnish mold) equipped with a 100-mesh wire. The sheets were formed according to SCAN C 26:67 (basis weight was 73 g / m 2). The sheets were dried at 23 ° C and 50 ° C relative humidity overnight, then placed in an oven at 120 ° C for 30 minutes.

After conditioning (23 ° C, 50 Z relative humidity), the dewatering capacity was determined according to SCAN P 12:64 (Cobbgg).

20

Table 7 shows the results of the assays. The dosage amounts (weight-Z) of the adhesives refer to the addition amounts (active concentration) calculated from the dry pulp flake. It can be seen from Table 7 that the adhesive according to the invention gives a perfectly valid adhesive (Cobb <g <25) despite the high pH and the high amount of calcium carbonate.

TABLE 7 - ^ 3Q Adhesive Dosage Amount Cobb ^ g (g / m)

Example 16 0.3 71 f "0.5 64" 0.8 22 35 "i.O 18" 2.0 15 1 EXAMPLE 17 "80312

However, in Example 16, the same ingredients were used in the adhesive emulsion in the following amounts: 5 48 g of pine resin 12 g of paraffin wax 144.7 g of polyaluminum chloride solution 3 g of cationic starch 1Q 92.3 g of water

The resulting emulsion had a pH of 3.7 and an ingredient size of about 1-2 μm and had good stability for more than two months.

The emulsion was then used to glue the paper pulp of Example 16 and the results of this experiment are given in Table 8.

TABLE 8 20 ___ 2

Adhesive Dosage Amount Cobb ^ (g / m)

Example 17 0.3 90 "0.5 82 25" ° * 8 71 "1.0 65" 2.0 18 30 35

Claims (14)

2o 8031 2 Water-repellent agent comprising a finely divided emulsion / spray in the aqueous phase, characterized in that the finely divided material g comprises resin and / or fatty acid and the aqueous phase contains an aluminum salt which is polyaluminum chloride and / or polyaluminum sulphate. 1 Claims Substance according to Claim 1, characterized in that the finely divided material is a soap-free, mainly reinforced resin acid. Substance according to Claim 1, characterized in that the aluminum salt is polyaluminum chloride. Ί g Substance according to Claim 1 or 3, characterized in that the molar ratio between aluminum and counterion in the polyaluminum compound is greater than 1: 1. Substance according to Claim 1, characterized in that it also contains a cationic organic compound. Substance according to Claim 5, characterized in that the cationic organic compound is cationic starch, catholic guar gum, cationic polyacrylamine, polyamine, polyamidoamine or polyethyleneimine. Substance according to Claim 1, characterized in that it contains 30 to 700 g / l of rosin acid and / or fatty acid, 1 to 200 g / l of polyaluminum compound calculated as aluminum and, in particular, also 0.05 to 200 g / l of 3 cationic organic compound. 8. A process for preparing a water-repellent agent, characterized in that an aqueous solution containing an aluminum salt is formed, which aluminum salt is polyaluminium chloride or polyaluminium sulfate, and preferably also includes a cationic organic compound and then emulsifies / disperses . II 2i 80312 Process according to Claim 8, characterized in that the material which is dispersed as a fine phase is an unsaponifiable, predominantly reinforced rosin acid. Process according to Claim 8, characterized in that the aluminum salt is polyaluminum chloride. Process according to Claim 8 or 10, characterized in that the molar ratio between aluminum and counterion in the aluminum salt 10 is y11 1: 1 * Process according to Claim 8, characterized in that the cationic organic compound is cationic starch, cationic guar gum, cationic polyacrylamide, polyamine, polyamidoamine or polyethyleneimine. Process according to one of Claims 8 to 12, characterized in that the dispersion / emulsion contains 30 to 700 g / l of resin and / or fatty acid, 1 to 200 g / l of polyaluminum compound, calculated as aluminum, and preferably also 0.05 to 200 g / l of a cationic organic compound. Use of a water-repellent agent according to any one of claims 1 to 7 for the water-repellent treatment of fibrous pulp in papermaking. 25 30 35 22 80312