DE2537653A1 - PAPER SIZE - Google Patents

Description

The invention relates to new cationic sizing agents for paper.

The sizing of papers can be done with anionic or cationic sizing agents. The latter have the advantage that they are generally also effective with papers free of aluminum sulfate.

Cationic polymers and copolymers are used for sizing paper both in bulk and by treatment of the finished paper instead of natural resin glue used (see Belgian patent specification 654 889). The sizing with cationic synthetic resins also has compared to that with natural resin glue has the advantage that it is resistant to alkali, which, among other things, in the aftertreatment of sized paper with alkaline-reacting coating slips is required.

The cationic sizing agents used are polymers (eg DT-AS 1 621 688) which have a basic character, ie are soluble in an acidic aqueous medium. To obtain a good sizing effect, such a polymer must, however, have so strong hydrophobic character that it is in dissolved form at the quasi immediate limit of solubility and almost completely during the drying of the paper at 80-11O ⁰ C in a

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water-insoluble state passes over, which is then responsible for the low water absorption of the finished product caused by the sizing process Paper should be decisive.

In the GDR patent 5 381 cationic polyurethanes are also described, which in the heat in connection with Formic or acetic acid are soluble and, in addition to the production of films, coatings and threads, are also used as paper sizing agents should be useful. As already from the first-mentioned preferred areas of application for these compounds and also from the equivalent ratios of the starting materials used in their manufacture, mentioned in the GDR patent can be seen, the compounds are high molecular weight polyurethanes from which, already due to Due to their high molecular weight, no clear aqueous solutions that can be further diluted with water at room temperature can be produced, they rather tend to gel.

Due to their high molecular weight, these polyurethanes can only be made from them at relatively low concentrations Produce manageable, easy wexter-thinnable solutions that precipitate at pH values of around 5.5 and are therefore due to The often acidic character of alum-containing papers cannot be used as a sizing agent adapted to the state of the art are. When quartering with e.g. epichlorohydrin takes place the formation of cross-linked products unsuitable for gluing purposes, whose low-concentration solutions, e.g. 5% solids, still have gel character, as the underlying Polymers are too high in molecular weight.

The transport of sizing agent solutions with a relatively low concentration From the manufacturing to the consuming operation, however, there is a considerable technical disadvantage, especially in relation to on transport space, transport costs and storage costs.

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The present invention was therefore based on the object of providing easily accessible cationic sizing agents with the prior art to find the technology comparable or better effectiveness, which also in the concentration range above 20 wt .-% Form sufficiently low-viscosity solutions that can be easily diluted with water to the application concentration.

As has now surprisingly been found, it is possible to achieve this object by using the following sizing agents cationic olegourethanes described in more detail are used, which because of their comparatively low Molecular weight still in a concentration of 25-50% by weight in water or mixtures of water and with water Miscible organic solvents form clear, water-dilutable solutions, and the rest with respect to their effectiveness as sizing agents surpass the known products of the prior art.

The present invention therefore relates to paper sizing agents consisting of a solution of an oligourethane having protonated and / or quaternized ammonium groups and having a molecular weight of 500-5000 in water or mixtures of water and water-miscible organic solvents.
The present invention also relates to a method for sizing paper or cardboard, which is characterized in that the above-mentioned sizing agents are used.
Finally, the present invention also relates to

the sized papers obtainable by this process.

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Under "sizing of paper" in the context of the present invention, both the sizing in the mass and in the Surface can be understood.

The oligourethanes present in the sizing agents according to the invention have an osmotically determinable molecular weight from 500 to 5000, preferably 600 to 3000 and represent reaction products from organic polyisocyanates, tert. Polyhydric alcohols containing amino nitrogen atoms and optionally monofunctional compounds acting as chain terminators in the sense of the isocyanate addition reaction shows which conversion products before or after their preparation by Reaktic-n with a suitable acid and / or a suitable quaternizing agent in protonated and / or oligourethanes containing quaternized ammonium ions were transferred. The type and proportions of the Production of the starting materials to be used for oligourethanes or the degree of protonation and / or quaternization dimensioned so that the molecular weight of the oligourethanes is within the above range and that the oligourethanes at room temperature in a concentration of 20-50% by weight, preferably 20-40% by weight in water or mixtures of water with up to 50 wt .-% based on the solvent mixture of water-miscible organic solvents clear solutions are able to form, which can be diluted as required by adding more water. This latter, the solubility of the The prerequisite relating to oligourethanes is generally always met if the preferred ones mentioned below Polyisocyanates with the preferred alkanolamines mentioned below and optionally those mentioned below Chain terminators in such a quantitative ratio and below

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such reaction conditions listed below are implemented that the resulting oligourethane has a molecular weight of 500-5000 and if at the same time for a protonation and / or quaternization of the present tert. Nitrogen atoms Care is taken.

The paper sizes according to the invention are solutions represents, either in water or in mixtures of water with up to 60 wt .-% based on the total solvent mixture organic, water-miscible solvents. Such water-miscible organic compounds suitable according to the invention Solvents are e.g. methanol, ethanol, propanol, isopropanol, t-butanol, ethylene glycol, diethylene glycol, Propylene glycol, dipropylene glycol, acetone, methyl ethy! Ketone, Dioxane, dimethylformamide, dimethyl sulfoxide. The preference is given in the case of the use of organic solvents but given methanol, ethanol or, in particular, isopropanol.

For storage and transport, 20-50% by weight solutions of the oligourethanes are generally prepared, which are then converted to a content of 0.02-10% by weight by further addition of water or a water / solvent mixture before use. %, preferably 0.03 - 5 wt -.% oligourethane be diluted.

In principle, any polyisocyanates known from polyurethane chemistry can be used to produce the oligourethanes suitable, as for example in "Kunststoff-Handbuch, Volume VII, Polyurethane, Carl Hanser Verlag Munich (1966)" or by W. Siefken in Justus Liebigs's Annalen der Chemie, 562, pages 75-136 are mentioned by way of example. Examples

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Suitable polyisocyanates are hexamethylene diisocyanate, dodikanmethylene diisocyanate, cyclohexane-1,3-diisocyanate, Cyclohexane-1,4-diisocyanate, 1-isocyanate-3,3,5-trimethyl-5-isocyanatomethyl-cyclohexane, 2,4- and 2,6-hexahydrotoluene diisocyanate and any mixtures of these isomers, 2,4- and 2,6-toluene diisocyanate and any Mixtures of these isomers, diphenylmethane-2,4'- and / or -4,4'-diisocyanate, triphenylmethane-4,4 ', 4, 2' trisocyanate, Polyphenyl-polymethylene-polyisocyanates, as obtained by aniline-formaldehyde condensation and subsequent phosgenation and e.g. in the British patents 874 430 and 848 671, polyisocyanates containing carbodiimide groups as described in German Patent 1,09,2007 (US Pat. No. 3,152,162), containing alophanate groups Polyisocyanates, such as those described in British patent specification 994 890, isocyanorate groups containing polyisocyanates, such as those in US Pat. No. 3,001,973 in German patents 1,022,789, 1,222,067 and 1,027,394, polyisocyanates containing urethane groups, such as are e.g. in Belgian patent 752 261 or in US patent 3,394,164 or biurit groups containing polyisocyanates, as for example in the German patent 1 101 394 (US patents 3 124 605 and 3 201 372).

Preferred for the production of the paper sizing agents according to the invention Polyisocyanates to be used are 4,4'-diisocyanatodiphenylmethane and especially those per se known phosgenation products of aniline / formaldehyde

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Condensates which, in addition to a content of isomeric diisocyanato-diphenylmethanes of at least 50% tri-, tetra- and having higher functional 3,4 and more aromatic nuclei Contain homologues of these isomers. A typical such technical polyisocyanate mixture contains, for example, 50-60 % By weight of bifunctional two-ring polyisocyanates, 33-38% by weight of trifunctional three-ring polyisocyanates and 2-7% by weight of higher functionality 4- and multinuclear polyisocyanates as main components. These polyisocyanates are preferred to be used generally and also hereinafter referred to as "MDI".

In addition to the polyisocyanates mentioned, the sizing agents according to the invention can also be used as chain terminators active monoisocyanates such as phenyl isocyanate can also be used, although the use of monohydric, especially secondary alcohols such as isopropanol is preferred for this purpose.

Reactants for the polyisocyanates for the preparation of the sizing agents according to the invention are in particular at least an alcoholic hydroxyl group and at least one tert. Alkanolamines containing nitrogen atoms. As alkanolamines are understood alone or as a mixture with one another, above all, those amines as they are obtained by reacting aromatic, araliphatic and, in particular, aliphatic mono- or polyfunctional amines with alkylene oxides such as e.g., styrene epoxide, cyclohexene epoxide, butylene oxides, in particular Propylene oxide or especially ethylene oxide are easily accessible by known methods.

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Although the addition of more than one mole of alkylene oxide per NH function of the amine is also useful in accordance with the process Alkanolamines, preference is given to those alkanolamines which are formed by the addition of 0.8-1.1, in particular of about 1 mole of alkylene oxide, especially ethylene oxide, per amine hydrogen can be obtained.

Accordingly, according to the process, mono- and, above all, di-, tri- or polyalkanolamines, as can be derived from, for example, the following amines: ammonia, methylamine, dimethylamine, ethylamine, diethylamine, propylamine, butylamine, dodecylamine, oleylamine, abietylamine, cyclohexylamine, Aniline, methyl-cyclohexylamine, ethylenediamine, propylenediamine, hexamethylenediamine, N-methyl-diethylenetriamine, N-methyl-dipropylenetriamine, N-methylethylenediamine, N-dimethylethylenediamine, N-dimethylpropylenediamine, N, N ¹ -dimethylethylenediamine, morpholine, piperazine, etc. A large number of the alkanolamines to be considered are particularly suitable di- and trialkanolamines, for example triethanolamine, N-methyldiethanolamine, N-ethyldiethanolamine, N-benzyldiethanolamine, N-cyclohexyldiethanolamine, tetra-hydroxyäthy1-ethylenediamine, N-dimethylamino-propylene diamine . Particularly preferred alkanolamines are N-alkyl-dialkanolamines with a total of 5-12 carbon atoms of the formula

R.
ι

HO-R'-N-R'-0H

in which

R stands for an alkyl radical with 1-6 carbon atoms and

R ¹ stand for alkylene radicals with 2-4 carbon atoms.

The additional use of non-basic di- and multifunctional ones Alcohol is possible, but is due to the resulting reduction in the basic character of the resulting oligourethanes are less taken into account.

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The reaction between polyisocyanate and alkanolamine _f, which ultimately leads to the sizing agents, can be carried out without solvents; However, due to the considerable heat of reaction and the risk of uncontrollable crosslinking reactions, it should preferably be carried out in the presence of solvents. So that these solvents can possibly remain in the ready-made sizing agent, the solvents already listed at the beginning should expediently be used here. Isopropanol is preferably used as the solvent. The presence of small amounts of water does not interfere with the implementation. Of course, other solvents which are not miscible with water or which are not very volatile, such as chlorinated hydrocarbons, aromatics or esters, can also be used, but since these would have to be removed in an additional operation, their use is less favorable.

The solvent is generally used in amounts of 5-100, preferably 20-80% by weight, based on the total weight Polyisocyanate plus alkanolamine used.

The reaction between polyisocyanate and alkanolamine can be accelerated with the usual diisocyanate polyaddition reactions Catalysts are catalyzed, although such catalysis is generally superfluous in view of the high reactivity of the reaction components.

The reaction between polyisocyanate and alkanolamine is particularly preferred in the presence of monohydric, with water miscible secondary or tertiary alcohols e.g. isopropanol. The hydroxyl groups of such alcohols face opposite Isocyanate groups have a lower reactivity than the hydroxyl groups of the alkanolamines, with the result that

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on the one hand, the reaction between polyisocyanate and alkanolamine is hardly disturbed by the presence of these monohydric alcohols is, on the other hand, however, due to the slower addition reaction between polyisocyanate and monovalent Alcohol breaks the chain, especially when using an excess of isocyanate based on hydroxyl groups of the alkanolamine is guaranteed, so that in the presence of these monohydric alcohols largely independent of the NCO / OH equivalent ratio (based on hydroxyl groups of the alkanolamine) always olegourethanes of the molecular weight range 500 - 5000 can be obtained. This aspect of the molecular weight regulation through the use of unreactive monovalent Alcohols are of course not required in the case of using an NCO deficiency, based on the hydroxyl groups of the Alkanolamine, as in this case also with the exclusive use of di- and higher-functional structural components the structure of high molecular weight polyurethanes is impossible. In principle, the molecular weight of the olegourethane even without using the monohydric alcohols mentioned by using others in the sense of the isocyanate polyaddition reaction monofunctional structural components are kept under control. Such other monofunctional Build-up components are e.g. the already mentioned monofunctional isocyanates or also monofunctional alkanolamines such as Ν, Ν-dimethyl-ampholnoethanol. When implementing between Polyisocyanate and alkanolamine, the proportions of the reactants are generally chosen so that per hydroxyl group of the alkanolamine 0.15-2.9, preferably 0.2 to 2.0 isocyanate groups of the polyisocyanate are present.

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The conversion of the oligourethanes into oligourethanes containing protonated and / or quaternized ammonium groups can take place before, during or after the polyaddition reaction, for example, instead of the alkanolamines their reaction products with quaternizing agents of the type exemplified below in the isocyanate addition reaction can be used. It is also possible to use the quaternizing agent in a mixture with the polyisocyanate use, so that at the same time with the isocyanate addition reaction a quaternization of the tert. Nitrogen atoms takes place. Finally, it is of course also possible, after the isocyanate polyaddition reaction has taken place, to carry out the organic addition Quaternize solution present oligourethane. Also those that come into consideration next to or instead of the quartering Protonation of the oligourethanes with the acids mentioned below by way of example can take place before or after the isocyanate polyaddition reaction take place in such a way that the reaction between alkanolamine and polyisocyanate in the presence of carboxylic acids such as in particular formic acid or Acetic acid made or in such a way that the oligourethane is added to a suitable acid after its preparation will. Especially when converting trialkanolamines such as triethanolamine into sizing agents In addition to accelerating the reaction, the addition of e.g. acetic acid also results in a low viscosity of the reaction products achieved. The acids that may also be used are, based on the total weight of the total batch, in quantities from 0 to 30, preferably 1 to 15% by weight are used.

Of course, following the reaction, further amounts of acid or solvents can be used for formulation purposes can also be used.

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Suitable for the production of the sizing agents according to the invention Quaternizing agents are in principle all quaternizing substances, provided they do not affect the solubility of the quaternizing products Reduce too much in an aqueous medium. It is therefore preferable to use such quaternizing agents which have no more than 10 carbon atoms. In addition to e.g. sulfones or phosphites, ... - -> isp compounds with activated halogen, e.g. benzyl chloride, propyl chloride, allyl chloride, ethyl chloride, methyl iodide, methyl chloride, Dichloropropene, dichlorobutane, dichloroethane, active esters such as dimethyl sulfate or epoxides such as cyclohexene oxide, butene oxides, Propylene oxide, ethylene oxide or epichlorohydrin. The latter is particularly important because of its ease of use and good effectiveness preferred.

Suitable acids for protonating the oligourethanes are in particular medium-strength, highly volatile acids, such as in particular formic acid or acetic acid. Also suitable however, inorganic acids such as hydrochloric acid, sulfuric acid or inorganic acids of phosphorus are less preferred

Paper sizing agents preferred in the context of the present invention are those based on oligourethanes whose tert. Nitrogen atoms to 10 to 100, preferably 30 to 100% in quaternized form. The not completely quaternized oligourethanes show in the sizing agents according to the invention often in addition to the quaternized nitrogen atoms, protonated ammonium nitrogen atoms, since it turns out to be It was found to be useful to adjust the pH of the paper sizing agents by adding formic acid and / or acetic acid

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Set to approx. 4 to 7. The quantities of acid required for this are mostly between 0.1 and 70% by weight, based on (partially) quaternized, solid oligourethane.

The quaternized or quaternized and protonated nitrogen atoms In the form of their solution, oligourethanes containing oligourethanes are those preferred in the context of the present invention Paper sizing agents. Valuable paper sizing agents However, they are also obtained if quartering is completely dispensed with, i.e. if in the paper sizing agents only oligourethanes with (partially) protonated ammonium nitrogen atoms are present, as they are for example by adjusting the pH of their solutions to 4-7 by adding suitable acids in particular Formic and / or acetic acid can be obtained.

The reaction between alkanolamine and polyisocyanate takes place at temperatures between 0 and 150 C, preferably at 20-90 C, if necessary, under reflux of the solvent or cooling or heating.

The quaternization takes place at 25-120 ° C, preferably at 50 - 90 ° C.

It is advisable to stir vigorously to ensure thorough mixing to ensure the reactants. For this purpose, stirred kettles, reaction screws or those for the production of Polyurethane foams often used mixing devices suitable.

The reaction itself can be continuous or discontinuous Procedure to be made.

The conversion to the sizing agent according to the invention takes place in generally in such a way that the polyisocyanate is placed in a generously dimensioned stirred vessel, followed by the alkanolamine possibly in a mixture with the solvent and quaternization

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agent and / or the carboxylic acid added in the appropriate amount. Now, if necessary, stir vigorously with cooling, until the reaction is over. Of course, the Airiin can also and / or quaternizing agents and / or solvents are used as a template.

In the case of continuous operation, for example, the phases to be reacted are mixed with vigorous mixing sent through a reaction zone kept at about 50-150 ° C, residence times of 0.5 to 60 minutes depending on the nature of the reaction components and the degree of dilution have proven themselves.

After the reaction has taken place, the primarily organic solution of the oligourethane can add the desired amount of water, if necessary. with simultaneous or subsequent removal of part or the total amount of organic solvent be added. In this way, water-dilutable solutions of olegourethanes with a solids content of 5-75% by weight, preferably 20-50% by weight, accessible, which are stored and transported in this concentrated form and which can only be diluted with water before processing. In the case of the (partially) quartered Olegourethane, it is also possible to convert the olegourethane into powder form by removing the solvent and only prepare the ready-to-use sizing agent before use by dissolving it in water or aqueous acids. Since the olegourethanes mostly have molecular weights below 3000, the subsequent dissolving prepares them such powder preparations generally do not pose any problems.

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The 0.02-10, preferably 0.03 to 5% by weight solutions of the 01 * gourethane represent the ready-to-use according to the invention Sizing agents. The sizing agents can be used both in the paper pulp and in the paper surface be used according to the known method.

It must be regarded as surprising that the invention Sizing agents develop an excellent sizing effect, although compared to the known ones cationic sizing agents of the prior art (DT-ASS 1 621 688 and 1 621 689) to relatively low molecular weight is hydrophilic compounds.

Since high molecular weight compounds often give rise to adhesions and deposits on the paper-making systems, there is not only the viscosity of the solutions due to the low molecular weight, but also the advantage of giving rise to less disturbing adhesions on the rollers. Another advantage is the ease of accessibility of ^it ~ findungsgemäßanLeimungsmittel, runs the technical by very briefly executable Association bulk products in simple apparatus with high space-time yields.

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The new sizing agents are characterized by a surprising range of applications, both in terms of the character of the
sizing paper type, as well as in relation to the application conditions, e.g. the tolerable pH range of the liquor.

You can use acidic, neutral or even basic fillers with chalk, talc, kaolin or casein, especially starch or also dyes, find common application.

The application can be done by adding to the paper pulp
subsequent soaking or spraying of the sheet and other customary procedures take place, in particular the
Application on the paper surface in the so-called size press.

The following is the production and operation of the new
Sizing agents explained by way of example. The specified parts
and percentages are based on weight, unless otherwise noted.

The production of the sizing agents will be described below by way of example.

A technical MDI of the following specification is used as the polyisocyanate;

2-core isocyanate, bifunctional approx. 60% by weight

3-core isocyanate, trifunctional approx. 33% by weight

Multinuclear isocyanates approx. 5% by weight

other unidentified Components approx. 2% by weight

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Isocyanate content: hydrolyzable chlorine: total chlorine: Viscosity at 25 ° C:

Sediment:

4 density d ₂ c ^:

Viscosity at 20 ° C:

Flash point:

Vapor pressure at room temperature:

30 - 32% max. 0.3% max. 0.8% 130 + 20 mPa.s max. 1% 1.23 g / cm ³

180 + 30 mPa.s 200 ° C

<10 ~ ⁴ mbar

The production of the various quaternized reaction products, which are used as sizing agents in aqueous solution is described below.

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4?

example 1

Production of a sizing agent by quartering after implementation.

A. Production of the reaction product:

180 TIe. of the techn. MDI come in a Submitted a stirred vessel, then a mixture of 191 parts is added. Isopropanol and 71 TIn. N-ethyl diethanolamine. That stirred reaction mixture warms to about 80 ° C., the reaction mixture is then kept for about 1 hour at 60 ° C., then it is the reaction ended.

The product produced in this way (osmotically determined molecular weight approx. 1100) is quaternized as follows:

B. Quartering of the conversion product:

The reaction mixture obtained according to A. 49 Tie. Epichlorohydrin is added, then the mixture is stirred for about 8 hours at 70 C. Then a solution of 144 TIn. Acetic acid in 565 TIn. Water diluted, the solution obtained has a Pesticide content of approx. 25% by weight.

Example 2

Production of a sizing agent by quartering parallel to implementation.

For comparison purposes, the approach described under A. is selected, with the difference that at the same time as the amine component 49 tIe left. (Molar ratio approx. 1; 1) Epichlorohydrin can be added to the batch. The reaction temperature rises in a few minutes to about 80 °, allowed to drop to 70 ° C and

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stirs at this temperature for a further 5 h. Then with a Solution of 100 parts of acetic acid in 609 TIn. Water diluted, an approx. 25% strength by weight sizing agent solution is obtained,

Example 3

175 TIe are placed in a stirring pot. of the MDI specified above. The following is then added, with stirring: 27 5 tea. Isopropanol and 100 teas. N-cyclohexyl diethanolamine. When the reaction temperature, which has risen to about 70 ^° C., begins to drop, 37 Ties are still set. Add dimethyl sulfate (molar ratio 1: 0.5) and stir at 70 ° C. for 5 h. It is then diluted to a solids content of approx. 35% by weight with 50% strength formic acid.

Example 4

180 TIe are placed in a stirred vessel. of the above specified MDI and 57 Tie. Benzyl chloride (molar ratio 1: 0.75). Then add, with stirring: 270 tea. Isopropanol, as well 71.5 parts by weight. N-methyl diethanolamine. The mixture is left at 85 ° C. for 8 h stir and then give 144 Tie while cooling. Add acetic acid. An approx. 42% free-flowing solution is obtained, which is further diluted with water according to the intended use can.

Example 5

Here the variant with alkanolamine quaternized before the reaction should be used to be discribed:

60 TIe. Triethanolamine, 160 TIe. Isopropanol and 37.3 TIe. Epichlorohydrin (Molar ratio approx. 1: 1) are heated to 80 ° C. for 8 hours with stirring, then 140 TIe are added. of the above specified MDI, as well as 40 Tie · acetic acid. Will be under good cooling

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the shock is intercepted, then the mixture is stirred for a further 30 minutes at 70 ° C. and then diluted with a solution of 40 parts Acetic acid in 470 parts of water to a solids content of approx. 25% by weight.

Example 6

^{At 50 °} C., the following are placed in a stirred vessel: 170 Tie. 4,4'-Diphenylmethane diisocyanate, then 97 Tie. N-methyldiisopropanolamine (from N-methylamine and 2 mol propylene oxide) and 57 Tie. Benzyl chloride and after 5 min. 135 TIe. Add isopropanol. The mixture is stirred for 8 hours at 85 ° C. and then diluted with 447 TIn. 30% acetic acid to a solids content of 38% by weight.

Example 7

The procedure is completely analogous to Example 1B. Only instead of 49 TIn. Epichlorohydrin are now only 33 TIe. used, i.e. that a product that is about 30% under-quartered is created.

The test for the sizing effect is carried out by means of the so-called floating ink test: For this purpose, an unsized paper is mixed with the Treated sizing agent and then applied to liquid ink. The time that passes before the ink rests on the paper The underside penetrates and becomes visible on the surface, is a measure of the sizing effect of the examined Substance. The method delivers reliable relative assessments, especially when the individual experiment is repeated several times of the various substances examined. It is expedient to leave a state of the art for comparison purposes Sizing agents run along in the experiments.

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For this purpose, the sizing agent 1 of DT-AS 1 621 688, a cationic sizing agent with excellent effectiveness used.

The test was carried out as follows: A

75 g / m paper made from 50 parts needle sulphate pulp, 50 parts of hardwood pulp, 0.12 part of a commercial one White toner, 20 parts of talc, with a low content of alum (pH 5 in the headbox).

2
Pieces about 4 cm in size were punched out of the paper and soaked by immersion at 20 ° C. for 10 seconds with a 0.04% aqueous solution of the comparison or the reaction products to be tested as sizing agents (pH 4.5, acetic acid). It was then squeezed between filter paper in order to remove excess impregnation solution. It was ^{then dried for 4 minutes at 110 °} C. in a circulating air cabinet, then conditioned for 1 hour at room climate and applied to the ink (commercially available fountain pen ink - Pelikan ink 4001 - diluted with distilled water in a ratio of 1: 1). All samples were treated the same and carried out 5 times.

The time it took for the first ink stains to penetrate the surface was measured as time I, as time II the time it takes for about 50% penetration of the surface to be achieved. The times measured are in seconds given in tabular form as average values.

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Ink swim test

Sizing agents
according to the example

Time I (sec.)

Time II (sec.)

comparison 2.5 24 1 A 2.8 32 1 B. 4.0 60 2 4.5 51 3 4.9 45 4th 3.5 38 5 3.8 55 6th 3.0 38

The effect as a surface sizing agent was also turned on examined the following papers:

Paper I:

Paper II:

Bleached pulp, 12% talc ash,

1% alum, 75 g / m ² .

Bleached cellulose, 10% calcium carbonate ash (correcteda: CaO value), 80 g / m ² .

The papers were in a laboratory size press from Werner Mathis, Zurich, Type HF equipped with a fleet of the following composition:

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5% starch,

0.125 - 0.25% active substance of the

Sizing agents,

Rest water,

pH about 6.0.

The sizing agent 1 of DT-AS 1 621 688 was again used as a comparison.

After the papers had dried on a drying cylinder at 100 ° C., they were air-conditioned for 2 hours at room temperature and the sizing effect was then tested with the aid of the water absorption. For this purpose, sections were pre-weighed paper de ^s, immersed for 1 minute in water at 20 ° C, pressed between filter paper using a 10 kg rolling weight once and reweighed. The weight difference became the value for

2 Calculates the water absorption on both sides in g / m. The lower

the water absorption, the better the sizing effect. Sizing is good if there is a water absorption of approx. 40 g / m and lower is achieved.

The measured values are compiled in tabular form, the% data referring to the proportion of sizing agent active substance in the fleet.

To test the sizing effect when added to the paper pulp, sheets of paper were bleached on a laboratory sheet former. Sulphite pulp manufactured. In this case, 1% of the sizing agent (active substance) was obtained from the 0.5% pulp suspension on dry pulp) 15 seconds before sheet formation with stirring admitted. No further additions were made. The papers were dried on a drying cylinder at 100.degree. To

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After the papers were air-conditioned for 2 hours at room temperature, the sizing was tested by means of a floating ink test. Was used Test ink Pelikan 4001 (undiluted).

The sizing agent 1 of DT-AS 1 621 688 was again used as a comparison.

Sizing agents according to the example:

No.

Water absorption

Paper I Paper II

0.125% 0.25% 0.125% 0.25%

Comparison 1 B 2 5 7

32 , 9 29.2 55, 4th 37.2 32 30th 44, 4th 32.1 33 29.1 50 33.4 33 ,8th 31.1 50 31.3 33 , 5 31, 6 48 31, 9

comparison

1 B 2 5 7 1 A

Ink swim test after mass sizing (1% additive)

over 20 minutes

over 20 minutes over 20 minutes over 20 minutes over 20 minutes about 18 minutes

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The following examples illustrate the production and use of non-quaternized nitrogen atoms Sizing agents according to the invention described.

The technical MDI already mentioned is used as the polyisocyanate.

The preparation of the various reaction products according to the invention as an acidic aqueous solution as a sizing agent are used is listed in the following table.

Phase I was placed in a stirred vessel, then phase II was added and the mixture was stirred until the reaction temperature reached the in all cases did not exceed 84, began to decline again. The mixture was then stirred for a further 30 minutes and then phase III added.

In all cases, the reaction products resulted in well-flowing solutions, which are further diluted with water to the desired application concentration.

The test for the sizing effect is again carried out using the ink float test. Here, too, the sizing agent 1 the DT-AS 1 621 688 used in a comparative experiment. The paper used and the test procedure correspond to the information already given above.

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_{> Product of} conversion! A! B! C! D! E! F! G! H! I! K! Phase!

MDI (parts by weight)! 270! 270! 300! 300! 175! 175! 40! 160! 460 ί 75! I!

j «Isopropanol! 357! 100! 302! 302! 225 I 245! 50! 180! 450! 70! i

Acetic acid! - Ϊ -! - ί -! 50! -! -! 40 I 50! 20! !

Formic acid! -! 10! -! -! -! 30! -! -! -! -! !

N-methyldiethanolamine! 72! 72! -! -! -! -! -! -! - ί -! II!

^ N-ethyl diethanolamine! -! -! 72! 72 I -! -! -! -! 72! -! !

to triethanolamine! -! -! -! -! -! -! -! 60! 60! -! !

ο N-cyclohexyl diethanolamine! - I - ί -! -! 100! - I -! -! - I -! ! **

ζ N-Benzyl diethanolamine! -! -! -! - ί - ί 100! -! - I -! -! !

° N-dimethylethanolamine! - ί -! -! -! -! -! 10! -! - I -! ■

cd tetrapropoxylated ethylene diam.! -! - i -! -! -! -! -! -! - 115Ϊ ' ro

Addition of acetic acid ί 154! 130! 150! -! 140 I 140! 20! 44! 160! 20! _τι1 ϊ addition of formic acid! -! - ϊ -! 120! —Ϊ -! -! -! -! - I i

Solids content wt%.! 40! 44! 45! 47! 40! 40! 42! 45! 47! 45! !

Viscosity Ford cup nozzle 6 22 ⁰ C

(Sec.)! 79! 105! 98 ί 112! 110! 99! 81! 112! 128! 129 Γ ^!

Molecular weight, osmotic 11170! /! 111Oi / 11210! /! / 11380 11220 1 ι J ^!

Sizing agents Time I (sec.) Time II (sec.) comparison 2.5 24 A. 2.1 29 B. 2.9 25th C. 2.8 32 D. 2.6 32 E. 3.1 30th F. 1.1 22nd G 2.8 30th H 2.5 32 I. 2.0 25th

The tests already described for surface sizing using the papers I and II already mentioned were repeated, all test conditions being kept constant, with the exception that now
the non-quaternized oligourethanes were present as active ingredients in the sizing agents.

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Sizing agents

Paper I.

2
Water absorption g / m

Additive (active substance)

Paper II

for sizing agents from

0125% 81 0.25% 0.125% 83.3 0.25% without - - - - comparison 32.8 29.1 50.5 37.3 A. 29.7 28.5 39.9 36.3 H 28.3 25.9 38.4 30.6 E. 30.5 27.6 38.0 31.7 D. 31.9 28.8 50.0 37.0 I. 31.8 28.7 48.0 32.0

Comparative example;

According to Example 3 of GDR patent 5381, an amine-rich Made of polyurethane. The material dissolves in concentrated acetic acid, the solution can be mixed with water dilute. In the pH range above 5.5 the polyurethane begins to precipitate as a cloudiness and is therefore not suitable for sizing purposes suitable.

According to the present invention, the quaternized reaction products prepared according to the process are then special well suited when epichlorohydrin is used as a quaternizing agent is used. Therefore, a quaternization attempt was made with the polyurethane obtained in accordance with GDR 5381:

36.5 tIe. of the basic polyurethane prepared above at 70 ° C in 146 TIn. Isopropanol dissolved and with 8 TIn. Epichlorohydrin (1 mole of quaternizing agent per mole of amine contained) Stirred for 7 h at this temperature. A precipitate forms. The resulting quarter product is networked and as an approx. 3% slurry in water / acetic acid results in only a gel, but not a processable one Sizing agent solution.

According to the invention, the most suitable sizing agents are obtained under these quaternization conditions.

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Claims (4)

containing oligourethane of the molecular weight range 500-5000 in water or mixtures of water and with Water-miscible organic solvents. 2) sizing agent according to claim 1, characterized in that the protonated and / or quaternized ammonium groups containing oligourethane is a conversion product from polyisocyanates or polyisocyanate mixtures Diphenylmethane series with N-alkyl dialkanolamines with 5-12 carbon atoms and, if appropriate, compounds used as chain terminators with one opposite isocyanate groups reactive group whose tertiary amino nitrogen atoms at least partially protonated by reaction with an acid and / or a quaternizing agent or were quartered. 3) Method of sizing paper or cardboard with cationic Paper sizing agents, characterized in that the paper sizing agents used are those according to Claim 1 or 2 in the form of their 0.02-10% strength by weight solution reach. 4) According to claim 3 available sized papers and cardboard. Le A 16 676 - 28 - 709808/0692