FI58783B - CATIONIC POLYURETANER SAERSKILT ANVAENDBARA I LIMNINGSMEDEL FOER PAPPER - Google Patents

Description

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Patent claims (51) Kv.lk.Vci.3 c 08 G 18/32, D 21 H 3Λ8 (21) Pttanttlhakamu * - PataMamMuilnf 3TÖT / T ^ (22) HdwnltpUvi - Amaiailnpdag 30.12.71 * (Fl) (23) Alkuptlvft-Glttlgh «ad» | 30.12.7 ^ (41) Tullut iulklMkai - Blivlc offwtlig θβ.07-75

Patents and registries (44) Date of printing and printing. -

Patent and registration authorities Ansakin uttagd och utUkriftin pubikand 31 · 12. oO

(32) (33) (31) Requested atuelkau · —eagifd prlorltat O5.Ol.7U

Federal Republic of Germany-Förbundsrepubliken Tjrskland (DE) P 2UOOU9O.8 Proof-Styrkt (71) Akzo nv, IJssellaan 82, Amhem, Netherlands-Holland (NL) (72) Horst Schiirmann, Diiren, Josef Bung, Duren, Federal Republic of Germany Tyskland (DE), Hendrikus AA van Aalten, Zeve-naar, Holland-Holland (NL) (7 * 0 Oy Kolster Ab (5M Cationic polyurethanes specially used for paper sizing agents - Cationic polyurethanes, anchored in a limiting medium for paper)

The invention relates in particular to cationic polyurethanes for use in paper sizing agents.

Cationic polyurethanes have long been known. They refer to polyurethanes having one or more positively charged atoms in a polymer molecule. Such compounds can be prepared, for example, by using polyurethanes having groups suitable for the formation of onium as starting materials.

The preparation of such polyurethanes is described, for example, in German Patent DE 880 h85. The compounds mentioned in this publication are prepared as follows: starting material is e.g. a glycol having a group suitable for onium formation, such as tertiary nitrogen or ether oxygen, by reacting this glycol with an equivalent amount of diisocyanate and the products thus obtained are treated with polyfunctional and possibly also monofunctional alkylating agents.

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It is further known to prepare a prepolymer having NCO groups from polyesters (DE 891 T * + 2) containing terminal hydroxyl groups and to further react this prepolymer with dihydroxy compounds having groups suitable for the formation of onium.

Other cationic polyurethanes are described, for example, in German application DE 1 595 602 and in D. Dieterich et al. in Angewandte Chemie 82 (1970) Volume 2, 53-63- It is known to use such compounds as textile auxiliaries, dyeing aids, for the formation of thickeners, for the production of plastics of a rubbery nature, for the production of shape-retaining plastic coatings, for the production of soft adhesive plastics or even thermoplastics. Furthermore, they are well suited for coating and impregnating woven and non-woven textiles, leather, paper, wood, metals, ceramics, stone materials, concrete, bitumen, hard fibers, straw, glass, porcelain, a wide variety of plastics, antistatic and non-squeaky products, as binders for adhesives, adhesion promoters, coating materials, hydrophobizing agents, plasticizers, further e.g. as laminating agents and for the treatment of leather as well as for gluing paper.

Although numerous cationic polyurethanes have already been described in the literature, there is still a need for the preparation of such compounds due to some difficulties in the preparation of known substances and unsatisfactory properties of known cationic polyurethanes for certain uses.

The cationic polyurethanes of the invention are prepared by reacting a substituted monomeric aliphatic dihydroxy compound with a polyisocyanate to give a prodrug having NCO end groups, extending the chain of the prodrug of the resulting prodrug with an alkylate with a tertiary nitrogen-containing aliphatic monomeric diol, , or by extending the chain of the pre-adduct with a corresponding monomeric aliphatic diol already present as an ammonium compound.

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The present invention is characterized in that in a monomeric aliphatic dihydroxy compound, both hydroxy groups are connected to each other via up to 7 atoms of the aliphatic chain, and that the monomeric aliphatic dihydroxy compound is substituted with an aliphatic substituent of at least 10-22, preferably 16-22. As the ammonium compound is meant herein those compounds which, for example, salts of tertiary amines or quaternary ammonium salts contain positively charged nitrogen. For the purposes of the present invention, a monomeric aliphatic dihydroxy compound means non-polymeric aliphatic glycols, i.e. organic compounds which contain two hydroxyl groups in the 1,2- or 1,3- or at some other position, e.g.

The aliphatic substituent in the aliphatic dihydroxy compound may be attached to a carbon atom to which one of the two hydroxy groups is also attached, but may also be attached to a carbon atom located between the carbon atoms to which both hydroxy functions are attached. This substituent preferably contains 10 to 22 carbon atoms.

It is also not absolutely necessary that the aliphatic chain of the glycol, through which the two hydroxy groups are linked, contains only carbon atoms, but a heteroatom such as oxygen or nitrogen may also be present instead of a carbon atom. In the case where the heteroatom in the aliphatic chain is nitrogen, an aliphatic substituent having at least 10 and preferably 16 carbon atoms may also be attached to the heteroatom.

In the case of a heteroatom present in an aliphatic chain, the preparation according to the invention requires that the dihydroxy compound reacts with polyisocyanates without a group attached to the heteroatom which can react with isocyanate groups, i.e. in the presence of nitrogen the substituent must be substituted with a third valence. no active hydrogen atom.

The aliphatic substituent of the dihydroxy compound must have at least 10, preferably at least 16 carbon atoms. It is not absolutely necessary that the substituent be a corresponding hydrocarbon group. The aliphatic substituent for the purposes of the present invention may also be the group RC00-, in which R is an aliphatic group having at least 9 »preferably at least 15 carbon atoms. Particularly suitable are glycerol fatty acid monoesters, e.g. glycerol monostearate or glycerolibehenic acid monoester.

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Among the compounds having a heteroatom instead of a carbon atom of the aliphatic chain, mention may be made of N-substituted dialkanolamines, in particular N-stearyl-diethanolamine.

Of the other dihydroxy compounds having a substituent having the corresponding number of carbon atoms, 1,2-dihydroxyoctadecane and 1,1'-dihydroxyoctadecane have proved to be quite suitable for the purposes of the invention.

The reaction of the substituted monomeric aliphatic dihydroxy compound with the polyisocyanate is best carried out in an anhydrous solvent, preferably acetone. Other solvents which are inert to the isocyanate groups or which have only a lower reactivity compared with the reaction components are also suitable as reaction media. In this connection, mention may be made of: tetrahydrofuran, dimethylformamide, chloroform, perchlorethylene, methylene chloride, methyl ethyl ketone, ethyl acetate, dimethyl sulfoxide.

However, the reaction of the aliphatic substituted dihydroxy compound with the polyisocyanate can also be carried out without a solvent in the melt itself.

Catalysts can be used in the reaction of the dihydroxy compound and the polyisocyanate. As the catalyst, for example, diacetoxybutyltin has proved to be particularly advantageous. Other catalysts include: dibutyltin laurate, cobalt naphthenate, zinc octoate, and tertiary amines, e.g. triethylamine or 1,1 + -diaza- [2,2,2] -bicyclooctane. Diols used for chain extension with tertiary nitrogen can also be used as catalysts.

The polyisocyanates used to form the pre-adduct can be both aliphatic and aromatic in nature. Mixtures of aliphatic and aromatic compounds can also be used. Diisocyanates are suitably used. Toluene diisocyanate, diphenylmethane +, 1 + J diisocyanate, hexamethylene diisocyanate have proved to be particularly suitable. Can also be used so-called. closed diisocyanates, e.g. the reaction product between diphenylmethane-1 +, U'-diisocyanate and 2 moles of phenol.

Preferred triisocyanates for the purposes of the invention are a 3 mol adduct of glycerol and toluene diisocyanate, as well as tri- (h-isocyanatophenyl) monothiophosphate. When polyisocyanates having more than two large cyanate groups in the molecule are used, relatively more diisocyanates are also preferably used, since uncontrollable crosslinks can be formed quite easily when polyisocyanates having three or more molecules in the molecule are used exclusively or to a large extent. isocyanate functional group.

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Aromatic diisocyanates are particularly preferred within the scope of the invention.

The ratio of the reaction components, namely the molar ratio of dihydroxy compound to polyisocyanate, can be varied within quite wide limits. Thus, it is possible to use molar ratios of dihydroxy compound to diisocyanate of 1: 1.1 to 1.3. A molar ratio of 1: 1.5 to 1: 2.5 is particularly suitable, especially a molar ratio of exactly 1: 2.

The resulting precursor is then reacted with an approximately equivalent amount of a tertiary nitrogen-containing aliphatic diol. Equivalent amounts herein mean that the same number of hydroxy groups of diols are used per isocyanate group present. N-methyldiethanolamine and 1,2-propanediol-3-dimethylamine have proven to be particularly suitable as aliphatic diols containing tertiary nitrogen. Of course, other compounds containing tertiary nitrogen can be used, e.g. N-n-butyldiethanolamine, N-t-butyldiethanolamine, N-methyldipropanolamine, N, N-bis-2-hydroxyethyl-p-toluidine and 1,1'-bis-hydroxyethylpiperazine. The diol suitably contains only 1 or 2 tertiary nitrogen atoms and generally has a molecular weight of less than 300 and suitably less than 200. The reaction of the pre-adduct with the diol is generally said to extend the chain.

The reaction of the precursor with the chain extender preferably takes place in an anhydrous solvent, in which case acetone has proved to be particularly suitable. Chain extension is generally performed at the boiling point of the solvent. The progress of the reaction can be monitored by a corresponding isocyanate assay method. At the end of the reaction, the NCO content must be less than 1%. The extended chain product is then converted to the ammonium compound. In this case, the still free electron pair of the tertiary nitrogen becomes bound so that the nitrogen receives a positive charge. In this reaction, hydrogen may be attached to the tertiary nitrogen via a suitable acid or alkyl group. This chain extension reaction can be avoided by using the glycol corresponding to the chain extension, which is already present as an ammonium compound, e.g. a salt obtained by the reaction between an acid and a glycol containing tertiary nitrogen, e.g. N-methyldiethanolamine hydrochloride.

The resulting product with an extended chain is converted to the ammonium compound, preferably with hydrogen chloride. This can be done using an aqueous solution of HCl, but HCl can also be introduced as a gas into the solution. A particularly suitable solution of HCl can also be used. The conversion to the ammonium compound can also be carried out by means of a conventional alkylating agent. In this case, dime-style sulfate is suitably used. Particularly advantageous results are obtained in the case where, in the reaction with hydrogen chloride, part of the hydrogen chloride is replaced by dimethyl sulfate. Thus, the advantage is obtained that a part of the tertiary nitrogen atom is not bound to hydrogen but to a methyl group.

It is particularly advantageous when only so much acid or alkylating agent is used in the conversion to the ammonium compound that 45 to 200 milliequivalents of tertiary nitrogen atoms are converted into the ammonium compound per 100 g of polymer. The amount of acid or alkylating agent required to set the value in this range can be quite easily calculated from the amounts of starting materials used.

It is particularly preferred that the extended chain product be occasionally dried before being converted to an ammonium compound. Intermediate drying refers to suitable treatment methods to remove any solvents or residues of other liquids that may have been used. In this case, spray-drying of the product or treatment in a rotary evaporator are particularly possible.

The intermediate dried product can then be suspended at a suitable time in e.g. water and converted into an ammonium compound by adding hydrochloric acid. When acids such as hydrochloric acid are used, the acid is preferably added slowly to the extended chain product.

The cationic polyurethanes according to the invention can also consist of structural units of the general formula ABAD, the members of this structure having the following meanings:

Il M

A = -C-NH-R-NH-C-, where R = a divalent aliphatic, aromatic or araliphatic group ch2orj B = -OCH2-CHOR'-CH2O- or -O-CH-CH2-O-, where 0 R '= -CR ", R" = CH2n + 1, n = 9-21 © D = / HD- (CH) NHR'm- (CH_) -O-f7 X or

"-OCHg-CHO-J X", where R '"= C, H2n, + 1 and n' = 1-4 I © CH

CH J R = 2-6, s = 2-6 HXCH3 58783 X is an acid residue, suitably Cl Member B may also mean: -OCH-CH2O-

CmH2m + 1 m = 10-22, preferably 16-22 or -O-CH-CHp-CH -CH-O- m '= 10-22 preferably 16-22 or -o-ch2-ch2-n-ch2-ch2 ~ o-

CmH2m + 1 m = 10-22, preferably 16-22.

Member A is derived from the diisocyanate formula and is explained by this formula, which shows the structure as it appears in the polymer chain. One skilled in the art will recognize that member A has an isocyanate function at the terminal position when that member A is in the terminal, i.e., the -N = C = O group. Similarly, it is true for member D, which is schematically derived from a diol, and in this connection it is also shown schematically as a member inside the polymer chain that at that end position there is a hydroxyl group at the end position. The groups at the terminal position may also be altered by secondary reactions.

The preparation process according to the invention results in cationic polyurethanes with advantageous properties in a rather simple and advantageous manner. The reactions take place practically quantitatively, no by-products are formed and no harmful crosslinks occur. Any solvent used can be recovered quite simply. The various reactions proceed rapidly so that high production can be achieved in the manner according to the invention. The successive reactions up to the finished cationic polyurethane can be carried out successively in different reactors, but it is also possible to carry out separate reactions in a single reactor. It is also possible to react the starting materials required for the formation of the cationic polyurethanes according to the invention simultaneously. Thus, in particular, a product whose chain is extended can be produced by applying the so-called "One-pot" method. Suitably, however, a pre-adduct is first prepared, and then a chain extension is performed.

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By selecting suitable starting compounds, the properties of cationic polyurethanes can be varied over a wide range. Thus, the use of aromatic diisocyanates generally results in cationic polyurethanes with even better sizing properties. By varying the proportion of nitrogen atoms converted to the ammonium compound, the particle size of the polyurethanes can be influenced, and it is possible to prepare coarse-dispersed, finely-dispersed and even colloidal systems.

The basicity of the polyurethanes according to the invention is generally higher in the case of chain extenders in which tertiary nitrogen or ammonium nitrogen is not located directly in the chain between the two hydroxyl groups. An example of such a compound is 1,2-propanediol-3-dimethylamine.

The resulting cationic polyurethanes are quite stable during storage. They can be treated as solutions or dispersions and can be easily added to conventional additives. They can be used to make moldings, e.g. foils. They are also suitable for coating or coating a wide variety of plastics.

It was particularly surprising to find that the cationic polyurethanes prepared according to the invention are quite valuable sizing agents for paper. These sizing agents according to the invention can be used in a manner known per se for gluing paper. Thus, polyurethanes have proven to be suitable sizing agents for both mass gluing and surface gluing. It is also possible to apply both methods simultaneously with the sizing agents according to the invention. The gluing of the pulp can also be carried out with previously known sizing agents, e.g. resin adhesives, and then surface gluing can be carried out with the cationic polyurethanes according to the invention.

Further details on paper gluing can be found, for example, in the book by Engelhard, Granich and Ritter "Das Leimen von Papier" VEB, Fachbuch-Verlag Leipzig, 1972.

With the polyurethanes according to the invention, gluing can be carried out over a relatively wide pH range, so that the chalk can also be used as a filler. The adaptability of polyurethanes to alum is excellent. They can be treated quite well with products used for surface treatment of paper, such as starches, which can be oxidatively or fermentatively modified or chemically modified, and cellulose derivatives, e.g. carboxymethylcellulose, cellulose ether, polyvinyl alcohol, alginates, etc., can still be used.

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When using cationic polyurethanes prepared according to the invention, the produced paper obtains a rather advantageous sliding friction, so that e.g. further processing, e.g. in paper stacks, does not cause any difficulties due to the lack of sliding friction. The papers glued with the sizing agents according to the invention are furthermore characterized by rather advantageous handling properties, e.g. when winding, cutting, etc.

Cationic polyurethanes achieve a fairly good degree of sizing. It is particularly advantageous that the gluing effect occurs immediately and the degree of gluing achieved once remains constant over very long storage times. This is especially important when it comes to the raw paper to be coated, as a permanent ability to receive brush colors is always desired in subsequent processing.

Both in the production of polyurethane and in the use of polyurethanes for gluing paper, there are practically no wastewater problems. In particular, it should be emphasized that the use of polyurethanes as a sizing agent for both gluing the mass and also for gluing the surface on a large scale avoids the formation of foam.

Particular emphasis must be placed on the good gluing ability of the product, so that gluing can be done with a much smaller amount of material than when using previously known products. The starting materials are readily available so that extensive technical preparation does not cause any difficulties.

The cationic polyurethanes of the invention can be used in full, three-quarter, half and quarter sizing.

The invention is illustrated by the following examples, in which the following methods are noted in connection with the measurement methods set forth therein: 1. The degree of adhesion to ink is tested on a Hercules Sizing Tester according to the instructions of the manufacturer Hercules Incorporated, Wilmington, Delaware, USA.

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Measure in seconds the time it takes for the remission value of the paper to decrease to 80% when the test ink is applied to the paper and penetrates through the paper ·

Test ink: Paper test ink: blue, DIN 53 126 2. Cobb test: (DIN standard 53 / 32-1 min).

2 (a) Absorbency in relation to water is expressed as the amount of water absorbed in g / m after contact with water for 1 minute.

b) The absorbance relative to a 10% solution of Na 2 CO 2 is expressed in g / m after contact for one minute, as in 2a) above.

Further details of the measurement methods can be found in the above-mentioned book by Engelhardt et al.

Example 1

The apparatus is a heated 500 ml three-necked round-bottomed flask equipped with a stirrer, a reflux condenser with drying tubes and a dropping funnel.

19.5 g (0.015 moles) of commercial grade glycerol monostearate are first placed in a flask. Then 15 mg of dibutyltin diacetate, 2b ml of anhydrous acetone and 16.0 ml (19.5 g) of a 80/20 mixture of toluene diisocyanate (2.1) and - (2.6) (0.112 mol) are added. . The reaction vessel is stirred and heated for 30 minutes until slight refluxing of the solvent begins. During this time, the reaction temperature is about 65 ° C.

A solution of 6.5 g (0.0516 mol) of N-methyldiethanolamine in 20 ml of anhydrous acetone is then added dropwise over 10 minutes and heating is continued again with moderate reflux.

60 min. after a reaction time of 1, the NCO content has fallen below 1.5% and a moderately viscous aqueous polyurethane solution has formed, which is diluted by adding 160 ml of technical acetone.

To form the salt, 27.3 ml of 2N hydrochloric acid solution are added over a period of about 5 minutes. The salt then appears as a partly colloidal and partly 11,58783 white precipitate, which is dissolved by adding 140 ml of water over 15 minutes, maintaining the temperature of the contents of the flask at about 50 ° C.

Acetone is removed from the resulting clear solution by vacuum distillation. This gives a 20% by weight, slightly opalescent and slightly yellowish solution of the polyurethane ionomer.

The concentration can be increased by removing water by distillation. The 32% by weight polymer solution is still easily flowable.

Example 2

Proceed as described in Example 1, but using 6.0 g of N-methyldiethanolamine (instead of 6.3 g) and 23.2 ml of 2N hydrochloric acid solution to form the salt. The polyurethane solution is not diluted with acetone before the addition of hydrochloric acid. Water is added as in Example 1.

A bluish-glowing emulsion with an average particle size of 0.5-1 μm is formed.

Example 3

Proceed as in Example 2, except that the product with an extended chain is occasionally dried by spray drying. The intermediate dried product m.p. is about 93 ° C.

This intermediate dried product is converted to the ammonium compound by suspending it in water, followed by the slow addition of hydrochloric acid.

Example 4

The procedure is as in Example 1, but the reaction between glycerol monostearate and toluene diisocyanate is catalyzed by the addition of 3% of N-methyldiethanolamine in its entirety, the catalyst being removed during chain extension. A similar product is formed as in the example. 1.

Example 5

The procedure is as in Example 1, but as soon as the glycerol monostearate and toluene di-diocyanate are dissolved without a prior catalyzed reaction of these components, organotin compounds, tertiary amines or the like are added and N-methyldiethanolamine is added to the acetone solution of acetone. The reaction time is 2 hours. The ionomer dispersion is slightly turbid.

Example 6 19.5 g of glycerol monostearate are added to a flask and heated until melted. 16 ml of toluene di-diocyanate are then added dropwise so that the temperature does not rise above 75 ° C. After completion of the exothermic reaction, stir for an additional 20 minutes at 75 ° C. The melt is then dissolved by adding 50 ml of anhydrous acetone.

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The reaction with N-methyldiethanolamine, salt formation and diapering are carried out as in Example 1.

Example 7

Proceed as in Example 1, but using 8.0 g of N-butyldiethanolamine instead of 6.5 g of N-methyldiethanolamine. A fine opalescent dispersion is formed.

Example Θ

Proceed as in Example 1, but using 29.4 g of bis- (4-isocyanate-cyclohexyl) -methane instead of 19.5 gs of toluene-diisocyanate. A weakly opalescent solution is formed.

Example 9

The procedure is as in Example 1, but the tertiary nitrogen is neutralized only 80% by reducing the amount of hydrochloric acid to 21.9 ml. A stable fine emulsion is formed.

Example 10

Proceed as in Example 1, but using 19.5 g of N, N-di-α-hydroxyethyl stearylamine instead of glycerol monostearate.

Example 11

The procedure is as in Example 1, but 15.6 g of 1,2-dihydroxyoctadecane are used instead of glycerol monostearate. A slightly opalescent, slightly yellowish dispersion is formed.

Example 12

The procedure is as in Example 1, including the reaction with N-methyldiethanolamine.

By adding 0.86 g of dimethyl sulfate and continuing the reaction at reflux for a further 30 minutes, tertiary nitrogen is quaternized.

Dilute with 160 ml of technical acetone, then dropwise add 20.4 ml of 2N hydrochloric acid solution and then disperse as described in Example 1.

The final product is a stable fine emulsion with strongly cationic centers.

Example 13

HolanterisBa is glued in a manner known per se to cellulose fibers to produce paper. In this case, 70 l of bleached spruce cellulose and 30 l of bleached beech cellulose are used. Further, 1 i of the sizing agent prepared according to Example 2 is added. The gluing of the pulp is first performed without the addition of a retention aid, and then 0.3 l of a commercially available retention aid (polyamideamine) is added. The paper thus produced has a basis weight of 70 g / m 2. For comparison, 13,58783 are otherwise made under the same conditions using a commercially available cationic sizing agent based on modified maleic anhydride-styrene copolymers.

Measure the degree of sizing, the Cobb water value, and the Cobb value of the papers to be produced using a 10% soda solution. The results are shown in the following table.

table 1

According to Pearl 2, a commercially produced poly product is urethane

Bonding degree (sec): 458 140 without retention agent C, J ^ retention agent 855 190

Cobb (water): without retention aid 27 28 0.5 retention aid 25 27

Cobb (10 in soda solution): without retention aid 20 22 0.5 / ¾ retention aid 19 20

Example 14 2

The non-adhesive raw paper having a basis weight of 80 g / m 2 is treated in an adhesive press with an adhesive solution containing 10 l of oxidatively modified potato starch and 0.25 $ atrol sizing agent prepared as in Example 2. The paper absorbs 1.85 / ¾ dry matter, based on the weight of the paper, in the gluing press.

Otherwise, surface sizing is performed under the same conditions using a commercially available cationic sizing agent based on modified maleic anhydride-styrene copolymers. The values measured from the paper are shown in Table 2.

Table 2

Commercial The product of Example 2 is a polyurethane dispersion

Degree of gluing (Hercules-sec) 510 1590

Cobb value (water) 1 min. 26 19

Example 15

Otherwise, under the same conditions as in Example 14, the surface sizing is performed with the difference that the sizing solution contains only $ 5 of starch and $ 0.3 of Atro sizing agent. In an adhesive press, the paper absorbs $ 1.8 in dry matter. The properties measured from the paper are shown in Table 3!

Table 3

Commercial poly product of Example 2 urethane dispersion

Glue saw (sec): 120 4290

Cobb value (water) 1 min. 37 19

Cobb value (10 i soda solution) 1 min. 27 15

Example 16

Otherwise, under the same conditions as in Example 15, surface sizing is performed with the difference that 0.2 and 0.3 $ of the Atro sizing agent of Example 1 are used. The properties measured from the paper are shown in Table 4.

Table 4 0.2 i »atro- $ 0.2 Commercial Atro poly product of Example 1 urethane dispersion

Glue saw (sec) 218 2136

Cobb value (water) 1 min. 47 21

Cobb value (10 # soda solution) 1 min. 40 17 0.3 i »atro-0.3 i of the commercial Atro-polyure product of Example 1 in a dane dispersion

Glue saw (sec.) 312 2602

Cobb value (water) 1 min. 33 19

Cobb value (10 and soda solution) 1 min. 30 16

Example 17

The cholera is glued in a manner known per se from the cellulosic fibrous material to produce paper in the pulp using gluing. 75 l of bleached spruce sulphite cellulose, 15 l of birch sulphate cellulose and 10 l of bleached pine sulphate cellulose, ground to a degree of grinding of 40 ° S.R. A further 10 Atro sizing agent prepared according to Example 1 is added. The basis weight of paper made from this pulp was 45 g / m · The test results are shown in Table 5 · λ * 58783

Table 5

Cobb value (water) 1 min. 14

Cobb value 10 ^ soda solution, 1 min. 13 Example 18 2

The non-glued raw paper with a basis weight of 80 g / m 2 is treated in a gluing press with an glue solution containing only 0.5 ° $ of Atro sizing agent prepared according to Example 1. The values measured from the paper are shown in Table 6.

Table 6 0.5 i * Atro commercial 0.2 ^ e.g. 1 mu support lane Atro polyurethane dispersion

Cobb value (water) 1 min. 21 15

Cobb value $ 10 soda solution, 1 min. 21 16

Example 19 2

The non-glued raw paper having a basis weight of 80 g / m 2 is treated in a gluing press with an glue solution containing 5 l of starch and 0.3 l of Atro sizing agent prepared according to Example 11. The values measured from the paper are shown in Table 7 ·

Table 7

Commercial product of Example 11 polyurethane dispersion i

Glue level (sec.) 300 1250

Cobb value (water) 1 min. 24 17

Example 20

The surface sizing is performed under the conditions shown in Example 15, except that 0.1, 0.2 and 0.3 i of the sizing agent of Example 12 are used. The properties measured on the paper are shown in Table 8.

Table 8 $ 0.1 Atro trade 0.1 i e.g. List of Atro polyurethane dispersion

Glue level (sec) 53 420

Cobb value (water) 1 min. 92 90 0.2 i Atro trade- $ 0.2 e.g. 12-product Atro polyurethane diepperation

Degree of gluing (sec.) 260 1840

Cobb value (water) 1 min. 35 24 16 5 8783 0.3 <$> Atro-trade 0.3 $ e.g. List of products according to 12 Atro-polyurethane dispersion

Glue level (sec.) 305 3250

Cobb value (water) 1 min. 30 21

Example 21

Under the same conditions as in Example 14, surface sizing is performed with the difference that the sizing solution contains $ 5 starch and $ 0.3 sizing agent. In this case, the polyurethane dispersion described in Example 1 is compared with a product prepared from the sock of German application 1,595,602. The results are shown in Table 9 *

Table 9

Polyurethane-disodium product according to Example 8 of German Patent Application Laid-Open No. 1 593 602

Degree of gluing (sec.) 229 1850

Cobb value (water) 1 min. 70 19

Claims (12)

17 58783 1. Cationic polyurethanes, especially for paper sizing agents, prepared by reacting a substituted monomeric aliphatic dihydroxy compound with a polyisocyanate to give a prodrug product having NCO end groups by extending the chain of the resulting prodrug product with a tertiary nitrogen-containing, tertiary nitrogen-containing aliphatic , by treating it with an acid or an alkylating agent, or by extending the chain of the prodrug with the corresponding monomeric aliphatic diol already present as an ammonium compound, characterized in that in a monomeric aliphatic dihydroxy substituent having at least 10 to 22, preferably 16 carbon atoms. Cationic polyurethanes according to Claim 1, characterized in that they are prepared using glycerol fatty acid monoester as the monomeric substituted aliphatic dihydroxy compound. Cationic polyurethanes according to Claim 2, characterized in that they are prepared using glycerol monostearate as the substituted dihydroxy compound. Cationic polyurethanes according to Claim 2, characterized in that they are prepared using glycerol behenic acid monoester as a substituted dihydroxy compound. Cationic polyurethanes according to Claim 1, characterized in that they are prepared using N-stearyldiethanolanine as the monomerically substituted aliphatic dihydro compound. Cationic polyurethanes according to Claim 1, characterized in that they are prepared using 1, 2- or 1,1 + -dihydroxyoctadecane as the monomerically substituted aliphatic dihydroxy compound. Cationic polyurethanes according to Claims 1 to 6, characterized in that they are prepared by comprising hydrogen chloride to form an ammonium compound. Cationic polyurethanes according to Claims 1 to 7, characterized in that they are prepared using N-methyldiethanolamine as the tertiary nitrogen-containing aliphatic diol. 58783 18 Cationic polyurethanes according to Claims 1 to 7, characterized in that they are prepared using 1,2-propanediol-3-dimethylamine as the tertiary nitrogen-containing aliphatic diol. Cationic polyurethanes according to Claims 1 to 9, characterized in that they are prepared by using an elongated chain-extended product for conversion to the ammonium compound. Cationic polyurethanes according to Claims 1 to 10, characterized in that they are prepared in a solvent. Cationic polyurethanes according to Claim 11, characterized in that they are prepared using acetone as solvent. 19 5 8 7 8 3