PROCEDURE FOR THE PRODUCTION OF A RESIN AND/OR ITS WASSERIGEN PASSWORDS

The invention concerns in-muddled to production of a resin and/or its aqueous solutions. InderUSA-PatentschrißNr.2, 926,116istein resin for water resistant papers descriptive, soft in the warmth hardening and kationisch is not; it consists of a water-soluble polymere Heaktionsprodul of epichlorohydrin and a PP, which from a Polyalkylenpolyamfn and a satisfied aliphatic bivalent Carboneäure with 3 to 10 Eehlenstoffatomen are derived. The USA Patentschriß No. 2.926.154 differs from the USA patent specification No. 2.926.116 thereby that the Polyalkylenpelyamine contains two primary groups of amines and at least a secondary amino group; preferential satisfied aliphatic bivalent carbonic acids are such with 3 to 8 Kehlensteffatomen, furthermore Diglykelsäure. In the USA Patentschriß Nr.3, a resin for water resistant paper is descriptive 125.552, which from a wasserl8slichenpolymerenHeaktionsprodul (epichlorohydrin and a Polyamfd ven exist, soft from a PoIyalkyfenpolyamin with at least two primary amino groups and at least sekundären&minogruppe as well as one-insatiated Polycarboneäure with at least a Piohlenstoff EohlenetoffDoppelbindung are derived. IuderUSA PatentschrißNr. 3,353,288 is a resin for water resistant papers besehrieben, consisting of a PP, which is the 1Reaktionsprodukt of a Aminocarboxylats and a Pelyalkylenpelyamins and was converted then with epichlorohydrin. In the USA Patentschriß No. 3.645.954 a resin for water resistant papers is descriptive, which one receives following conversion of the received PP with a lactam as well as conversion of the received block Copoiyamids with epichlorohydrin by conversion of an aliphatic Dicarhoneäure with a Polyalkylenamin. In franz. the Patentschrfft No. 884. 271 and/or in the appropriate Belgian patent-ear-eat No. 446,643 is among other things a resin for the improvement of paper descriptive, which of the Heaktionsprodul (t von Epichlorhydrin with an amine consists, which was converted afterwards with a connection, which contains a reactive landing on water EFF atom, like certain carbonic acids, alcohols or amines; furthermore the Epoxydierung of a PP from a polyamine and an acid-resistant is descriptive. According to invention manufactured the kationischen Pelyamide has very desired water resistant-making characteristics and prays higher concentrations an excellent stability. The general procedure for the synthesis of these resins is as follows: 1. An acid is converted with a backbone polyamine, so that a PP basic molecule with finalconstant Carboxylgrappen develops; 2. the PP basic molecule is converted with a polyamine forming the Endgruppen, whereby a finalgroup-final basic molecule (PP) with finalconstant secondary and/or terGären amino groups develops; 3. the finalgroup-final basic molecule is converted with a Eettenverlängerungsmittel, whereby an extended basic molecule develops "; 4. the extended Grundmolekü! with a Epoxl dierungsmittei under education of a epoxydierten basic molecule one converts, which presents the finished water resistant resin. One gives this resin to paper pulp or preformed paper, whereby the water firmness of the final paper is improved. One receives water resistant paper, if one during the production of the paper about 0.1 to 5, 0Gew. - % according to invention manufactured of the resins (related to the dry weight of the mash existing in the paper) adds and the resins then in the paper up to the water-insoluble condition hardens. The resin in the paper is hardened, by heating the harzhaltige paper up about 0, 5 to 30 min long on approximately 80 to 1200C. In such a way treated paper has an improved water firmness. Further ones desirable characteristic those find in accordance with manufactured resins and/or the anmit treated paper are the fast hardening, the good miscibility with the mash, the inclination, not to foam small tackness, good Befeuchtbarkeit, fast mash drainage and excellent Maschinengangigkeit. In addition the resins are very stable and have a long Lagerf'ähigkeit. As useful according to invention acids or SRurederivate one can use separately or in the mixture the following acids or derivatives: a) Satisfied dicarbonic acids with 4 to 12 carbon atoms; b) nichtdecarboxylierende insatiated dicarbonic acids with 5 to 12 carbon atoms; c) satisfied and nichtdecarboxylierende insatiated tri carbonic acids with 6 to 10Kohlenstoffatomen; d) C1 _1 z-alkyl-Monound Di-ester of satisfied and insatiated dicarbonic acids with 2 to 12 gehlenstoffatomen; e) C1 _1 z. - Alkyl-Monound Di-ester of satisfied and insatiated Tricarhonsäuren with 6 to 10 KohIenstoffatemen; I of anhydrides of satisfied and insatiated dicarbonic acids with 4 or 5 carbon atoms. Preferential acids and/or derivatives are among other things: 1. Acids with 2 E ohlenstoffatomen: 2. Acids with 3 E ohlenstoffatomen: 3. Acids with 4 carbon atoms: 4. Acids with 5 carbon atoms: Acids with 6 carbon atoms: 6. Acids with 7 E ohlenstoffatomen: 7. Acids with 8 carbon atoms: 8. Acids with 9 carbon atoms: 9. Acids with 10 I ohlenstoffatomen: Diäthyloxalat Diäthylmalon t succinic acid, amber SAE reanhydrid, Diäthylsuceinat, Monomethylsucclnat, Malelnsäureanhydrid, D, L-Äpfelsäure Glutursäure, Glutarsäureanhydrid, Dimethylglutarat, Itaconsäure A dipinsäure, Monomethyl A dipat Pimelinsäure cork acid A zelainsäure Sebaeinsäure. As far preferential acid is mentioned the Diglykolsäure. A less preferential acid is citric acid (see example 43), in addition is mentioned following acids and/or derivatives: Methyl maleic acid, Dibutyl A ketoglutarat, Diäthyl - ketoglußrat, tri work allyl acid, 3,4-Hexadien-dicarbonsäure, Hexylpimelat, Dldeeylsuberat, methyl octyl azelat, Didodecyl sebaeat, Undeeandiearbonsäure, Dodecandiearbonsäure, 4-Oeten-diearbonsäure etc. One can use the preferential acids and/or derivatives either alone or in combination with other acids. One can use Nichtbevorzugte acids alone only if the received resin exhibits a water firmness of at least 14%. If the resin received using a certain acid has one water firmness of more as 10% however less than 14%, then the used acid should be used only in combination with a preferential acid, so that the resin received with the I ombinatiou the acids possesses a water firmness of at least 14%. Acids, which supply a resin with a Wasserfestlgkeit under 10%, are not to be covered by the invention (s, under testing the Wasserfestlgkeit). As l ückgrat l olyamine one uses according to invention any geradkettiges or branched polyamine and/or a mixture the same; A condition is only that they somewhere contain at least two primary Amlngruppen and at least a secondary or tertiary group of amines in the chain. Examples of preferential polyamine are: primely., sec. Diäthylentriamin; primely., sec. Tetraäthylenpentamtn; primely., save. Until (aminopropyl) - methylamin; primely., sec. Penteäthylenhexamin; ., sec. Triäthylentetramin.Wettore useful polyamine are prime: primely., sec. Imino to propylamia; primely., sec. Dibutylentriamin; primely., sec. Tetrapropylenpentamin; primely., sec. Imino to hexylamin as well as primely., peat. Until (amlnoäthyl) - propylamin. When the Endgruppen bfldende polyamine one can use according to invention any geradkettiges or branched polyamine and/or mixtures the same, provided, since they somewhere contain only a primary group of offices and at least a secondary or tertiary group of amines in the chain. Examples of preferential, the Endgruppen screen end of amine are: primely., tert. Dlmethylamlnopropylamin and primely., sec. N-Aminoäthyläthanolamin. Further useful, the Endgruppen screen end of amines are: primely., tert. Diäthylaminoäthylamin; primely., tert. methyl butylaminopropylamin and primely., sec. A mtnoäthyl isopropanolamin. AlsEettenverlängerungsmittel use-one-according to invention any Alkylenhalogentd, alkyl ether - dihalogenid, benzene until (alkyl halide) or Pheuyl alkylenhalogenid ohlenstoffatomen with 1 to 12 I, or mixtures the same. Attachment plays for preferential I eating extension means are bromidebromide bromide, ethylen bromide, Meüaylenjodid, Dichloräthyläther, Dichlorisopropyläther and Triglykoldiehlorid. Further useful Eettenverlängerungsmittel is benzene until (mefhylchlorid), Phenyl butyl dibromid etc. Iml the invention by the term “Epoxydierungsmittel” a Epoxyverbindung are understood, which serves amino groups of the extended basic molecule for Blockierungder. Useful according to invention Epoxydierungsmittel is all epihalogenohydrins and alkylsubstituterten Eplhalogenhydrine and/or M1sehungen the same. Examples for-useful Epoxydierungsmittel are epichlorohydrin, epibromhydrin, Epijodhydrin, Epifluorhydrin, Bromepoxybutan, Chlorepoxyhexan, Jodepoxyisobutan etc. preferential Epoxydierungsmittel are Epiehlorhydrin and epibromhydrin. In the following the Mengeuverhältnisse of the components used with the synthesis according to invention of the water resistant resins is indicated. With the formation of the PP basic molecule the molar ratio of jerk burr amine/acid must ever smaller than 1: 1 its. The maximum range of the molar ratio is about 0.66 to 0, 99: 1, preferably about 0, 75 to 0, 95: 1. It is critical that fewer mols of the backbone Polyamtns are present than from the acid, so that the PP basic molecule possesses remaining free groups of carboxyls and with the amine forming the Endgruppen reacts lmnn. The PP basic molecule is converted with at least so many outer Endgruppen forming polyamine that all free groups of carboxyls are blocked. Preferably one uses a small surplus the Endgruppen of forming polyamine, so that the complete blocking of the PP GrundmoIeküls is ensured. The finalgroup-final Grundmolokül is converted with that Ke% enverlKugerungsmit%el in approximately äquimolekularen quantities. The extended basic molecule is converted 5 Mel of the Epoxydierungsmit with approximately 0, 6 to 1, els (verzugsweise about 1, 0 to 1.4 mol) per not-converted secondary or tertiary amine in the extended basic molecule, provided that the quantity of the Epoxydierungsmittels is not so large that the pH value of the Reakt [onsmedinms due to a hydrolysis below approximately 5 sinks. Regarding the length or the molecular weight finished polymers exists no restriction; however the water resistant resin must to be in water solubly or a colloidal dispersion to form be able. By presence of a large number of epoxydierten amino groups one receives very large l olymeren (e.g. a polymere with a molar weight from 40,000, whereby the amino groups of the backbone are separate by no more than six following each other carbon atoms). One the largest distributes the invention exists therein that one can manufacture a high proportional concentration of the active material. This takes place via reduction of the caused quantity of water, if one endgruppenabgeschlossens the basic molecule extended or the extended basic molecule epoxydiert. Wlrd the quantity of water decreases, then also the Reakt must be decreased onstemperaü r, and which are extended ReakbionsT.eitlmnn. Since according to invention manufactured polymers still reactive and in the V ärme are hardening, it is not possible to increase the proportional quantity of the active material through ü liche drying methods. Therefore the water added during the synthesis and the pH attitude remains in the resin; it places at least 30Gew. - Teile/70 Gvw. - Parts resin in the final product forwards. A high proportional quantity of the active material is very desirable, since hiedarch the transport costs is decreased and the handling is improved. Normal temperature parameters are as follows: Etwa120 to 240°C with the formation of the PP basic molecule; about 120 to 280oc with the education of the finalgroup-final basic molecule; about 100 to 120°C with the formation extended basic molecule; about 40 to 90oC with the education of the epoxydierten G rundmcleküls. Exceptions of the normal temperature parameters are necessary, if one uses acids with 5 carbon flavours, this, ester of deearboxylierenden acids and Hydroxysäuren. If in the following no exceptions are indicated regarding the temperature parameters, so verläuf the reaction sequence at normal temperatures. If the used acid makes contradicting exceptions necessary, then the lower temperature range should be used. Acid with carbon atoms for the formation of the PP basic molecule with approximately 120 to 175oC are converted, while the education of the endgruppenabgescklnssenen basic molecule with these acids with approximately 12 O to 1700C ring off. The further reactions of the reaction sequence run at normal temperature temperatures. The reduction of the upper temperature parameter is dictated by the inclination of the acids with 5 Kohlenetoffatomen to the education by unsolvable cyclischen polymers. For the formation of the PP basic molecule one sets for this at normal minimum temperatures of for instance 80OCum; the maximum temperature is either the Rücldluß temperature Alkchol/Harzgemi or the temperature, at which decomposes the resin polymers - depending on, which is lower. These temperatures are valid also for h n ichtlich the education of the finalgroup-final and the extended basic molecule. The alcohol mentioned above develops as by-product with the education of the PP Grundmolekü'[s (S. under " production of the resin "); A blank of this alcohol depends on the used Diester. If one e.g. uses a Dimethylester, then NIethylalkohol develops, on use of a Äthylhexylesters develops for Ä hylalkchol and for Hexylalkchol, while on use of a Didodecylestsrs Dodecylalkchol develops. IstderAlkohol from the PP basic molecule removes, then the temperature restrictions are not valid naturally any longer for the further Reak%ionsfolgen. One converts ester vondeoarboxylierenden acids at lower temperatures, since they are less stable than the esters of nichtdeoarboxylierenden acids. With the formation of the PP basic molecule oxalic acid esters are converted with approximately 15 to 25°C, with the formation of the finalgroup-final basicmolecule with approximately 70 to. 90oC, with the education of the extended Gruùdmolek [üs with approximately 70 to 90oc and with the education epoxydiertenGrundmoleküls with approximately 40 to 700C. The appropriate temperature specifications for malonic acid esters are: etwaS0b [s 160oC with the education of the PP basic molecule, about 80 to 100°C with the education finalgroup lock narrow of the round molecule and about 80 to I00oc with the formation verl switches of the basic molecule. One converts Hydroxysäuren usually at lower temperatures, since they are usually less stable than the appropriate not Hydroxysäuren. D, L-Äpfelsänre (Hydroxybernsteinsäure) is converted for the formation of the PP basic molecule with for instance 120bis 155°C, dle formation endgruppengeschlossehen basic molecule effected in this case with approximately 100 to 120°C. DieReaktionszeitensindwie follows: for instance i to 6 h for the formation of the PP basic molecule; about 15 min to 6 h for the education of the finalgroup-final Grundmolektils; about 1 to 3 h for the education of the veriängerten basic molecule and about 15 min to 3 h to. Epoxydierung under education of the water resistant resin. A remarkable exception of these parameters is valid regarding the oxalic acid esters, which need for the formation of the PP basic molecule about 5 to 20 h. The response time necessary in a certain case depends on the temperature, at which the Beaktion is accomplished. At higher temperature temperature one needs a shorter response time. Furthermore it is pointed out that these time parameters are valid only so for a long time, until the desired reaction temperature is reached. Invention in accordance with if produced resins with a functional component or a procedure parameter are manufactured outside of indicated the above, then a unl0sliches gel can develop. One receives manufacture-water resistant the according to invention resins using the parameters indicated in the examples in the following procedure - if not differently indicated. I5 1, production of the Polyamld Grundmolektlls a) is used an acid or an anhydride, then one gives this first to a Reakttonskessel and mixes with at least as much water, to da6 an even mixing into a paste with develops. Then will-will that Hückgrat polyamine admitted and the mixture agitated, until she is even, it develops exotherms a reaction. Now under agitating one heats up, until an even solution entetandenist. Heating up is continued, until the highest desired temperature is reached, whereby most water is removed by distillation. It concerns sees here both caused water and the water developed with the reaction. One continues to heat up on the same temperature and puts on vacuum, until all remaining water is distant. b) If a liquid ester is used, then one does not fligt water too. The ester is given to a reaction boiler and the backbone polyamine under agitating is added, until an even solution developed. Exotherms or endotherms a reaction develops, depending upon the selected ester. Generally erhältman with insatiated acid esters exotherms a reaction, while a satisfied acid-resistant a reaction supplies endotherms. An exception are oxalic acid esters, which lead to exotherms a reaction. The Beaktionskessel is heated up now on the desired temperature and the desired time under continuous agitating is held on this temperature. If the ester is a Diester, then an alcohol develops as by-product. If the ester is a Mcaoester, then alcohol and water develop. From this alcohol developed can remain in the reaction mixture or by distillation remove. The alcohol/water mixture from the mono ester must be removed, since water cannot remain in it. c) If a firm ester is used, then one gives these in the Beaktionskessel and heats up, until the ester melted. The melted ester is then treated in such a way, as if it would be liquid, whereby the procedure b) is used. d) An exception are the esters of oxalic acid. One gives and shifts these in an l eaktionsgefäß her under agitating with an alcohol misohbaren with water, so that an alcoholic solution develops. Then under agitating the backbone polyamine is given for alcoholic solution. Since exotherms a reaction takes place, the boiler is cooled, so that the desired temperature is not exceeded (S. example 1, table la). 2. One gives the Endgruppen of screen end Amln to production of the finalgroup-final basic molecule into the boiler with the PP Grandmolekül, whereby during the whole reaction one agitates. One heated up on the desired temperature and puts on a vacuum, until surplus quantities of not-converted, which Endgrappen is removed for bfldendem polyamine. 3. One gives mindestensso much water to production of the extended basic molecule IndenKessel with the finalgroup-final basic molecule that a homogeneous solution develops. The quantity of the water depends on the desired proportional quantity of the active material in the final product. In the case of use of a smaller quantity water one receives more active final product. V ährend this reaction is agitated. One adds the chain extension means and heats the mixture up then on the desired temperature. 4. One gives further quantities water to production of the epoxydierten basic molecule IndenKessel with the extended basic molecule - depending upon gewünschtenKonzentrationim the final products. During the reaction one agitates. One gives a epoxydierendes means up in the desired quantity to and 10st it, the reading wird'dann on the desired temperature heated up, and zw. sports club is enough, until the reaction is terminated. The completion of the reaction can be determined by the rise of the Viskositä't, which determines, becomes 5 with a usual Viscometer. A registering Viscometer is preferential, if one wants to supervise the reaction continuously. The preferential viscosity is straight below the Gelierpunktss. One gives so much water that the concentration of the active material in the desired extent is reduced, in such a way to Hersteilung of the final product indenKesselmitdem epoxydierten basic molecule furthermore vlel acid (e.g. Sälzsäure, sulfuric acid, nitric acid, phosphoric acid, formic acid or acetic acid) that the pH value sinks on approximately 1, 0 to 5, 5. Hiebei is continuously agitated. The expressions “desired quantity”, “desired temperature”, “desired Zei etc. refer to the reaction parameters indicated above or the values in the examples. Producible the according to invention resins are used in the paper trade for the improvement of the water firmness, one apply the resins on paper or other feltlike cellulose products according to arbitrary methods. A preferential method to the Elnarbeitung of the resins in paper consists of that one adds the resin before sheet forming to the paper pulp, whereby one uses the Substantivität of the resins for hydratisieße cellulose fibers. Given with the Durch£ührung this kind of application an aqueous solution of the resin in not-hardened and hydrophilic condition to an aqueous suspension of the paper pulp in the material mill, in the mash tank, Jordan, in vane-type pump, main housing or another suitable steers, before sheet forming takes place. One gives about 0.1 to 5, 0 thread - parts of the dry resin (preferably about 0, 5 to i, 5 thread - parts), related to 100 thread - parts of the dry mash, for the aqueous suspension of the paper pulp. The quantity of the caused resin depends on the desired extent of the water firmness in the finished paper and of the quantity of the resin held back by the paper fibers. Then one forms paper sheets from the harzhalfigen Papisrbrei and heats about 0 up, 5 to 30 min on approximately 80 to iZ0°C, in order to harden the resin contained in the paper to a polymerized water-insoluble condition, whereby the paper sheet becomes water resistant. Mankanndie of resins also preformed, partially or completely dried paper apply, and zw. by spraying, impregnating, immersing, covering or other suitable methods for the creation of aqueous solutions of these resins during the paper trade. The application and hardening are then accomplished in the same Mengenverhällmissen and in the same way, as if the resins would have been brought into the mash. The hardening according to invention manufactured of the resins takes place under sour, neutralenoderalkaHschen conditions, e.g. at a pH value from ehva 4.0 to I0,0, preferably about 7.0 to 9.0 (s.Tabelle 3). One receives optimal results with these resins under neutral or alkaline Applikationsund hardening conditions, which predominate during the paper trade frequently. Since under conditions drink an expanded corrosion of the equipment take place, one uses no satires conditions favourably. The paper manufactured with these resins has a strongly improved water firmness. By the term “paper” in the context of the invention Papiertücher, absorbing fabrics, filter papers, are understood papers for resin saturation etc. furthermore heavier materials, like impact paper, bag paper, pasteboard, cardboard container etc. To testing the water firmness a standard method used, those in the paper industry is usual ind of K.W. Britt in “The PAPER Industry and PAPER World” was described, 1944, P. 37. 0 Hienach understands one by a water resistant paper a paper, whose ultimate tensile strength in the wet condition of at least 15 those of the drying condition amounts to. Considering the fact that to more erfindangsgemäßenHerstellungder water resistant resins can be the used Heaktionskomponenten mixtures, and regarding experimental errors a resin with 14% and more water firmness than is adequately regarded. One ability resins with small Wasserfestigkeft as well as resins use, which have more than 14% water firmness, provided that the total mixture exhibits a water firmness of at least 14%. Also it is possible to use resins which from mixtures of preferential and not-preferential acids were synthesized, provided that resul the isrende resin possesses a water firmness of at least 14% (see the above Ansführungen under “Reaktionskomponenteff'). Such mixtures can be desired because of the costs of the basis chemicals or the easier fabrication. The resin is tested as follows: One manufactures paper towels in usual way after the groping iv-experiencing, whereby one uses 100 ml an unbleached sulfate cellulose of 2% consistency (2 g dry weight) and in each case 1, 2, or 6 ml 1 thread - own solution of the resins in accordance with example 1 to 68 adds, i.e. (5, 1,0,2; 0 or 3,0Gew. - % of the dry resin, related to the weight of the dry mash. Samples like of the towels manufactured above are then hardened and subjected to the TAP PE test procedures T456 m-49 and T404 ts-66. The Wasserfesüigkeit is indicated in each case in the column to “% water firmness of the tables i and 2. IndenfolgendenTabellensind the production and the results of the water firmness tests of 49 Hatzen arranged. These become after the methods indicated above manufactured, l arze with a Wasserfesiigkeit of at least 10% with an E onzentration of 0,5, 1, o, 2, 0 or 3, 0% fall under the E rfindung. Resins with a water firmness of at least 14 o with a concentration of 0,5, 1, O, 2, 0 or 3 WHETHER are preferentially. In table la the temperature parameters for the examples of table 1 are indicated, both those to the real synthesis, and the acceptable ranges. Table lb contains the quantitative proportions (g) that reaction components and the response time for all examples of table 1. the ußnoten to table 1 and table lb to find see according to the table 2b. Example NR, 11 12 Ith acid Diäthyloxalat oxalic acid () malonic acid () malonic acid () Diäthylmalonate B-Propiolacton () succinic acid succinic acid anhydride mark in äureanhydrid ® the Diä hylsuccinat mono Methylsucoinat Djh Äpfelsäure (IL. Backbone polyamine (prime., sec., save.) Triäthylen tetramin (1,2) Diäthylen triamin (1, 2) DiäUlylen triamin (1, 2) Tetraäthylen - pentamin (1, 2) Diäthylen triamin (1,2) Dläthylen triamin Diäthylen triamin (1,2) Diäthylen triamin (1, 2) Tetraäthylen - pentamin (1, 2) until (aminopropyl) - - methylamin (1, 3) Diäthylen triamin (1,2) Diäthylen triamin (1,2) molar ratio nn 0.9 O, 95 0, 95 0, 95 0.94 0.92 0, 95 0.94 0.94 0, O, 95 0, 95 table 1 REAR ONE the Endgruppen of screen end polyamine (prime., sec., save.) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamiù (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - - propylamiu (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1, 3) Dlmethylamino - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylam! uo - propylamin (1,3) 1V. Chain-longer Dichloräthyläther Dichloräthyläther Triglycoldichlorid Triglykoldichlorid Dichloräthyläther Dichloräthyläther Dichloräthyläther Dichloräthyläther DiohlorÄthyläther Diehloräthyläther Dichloräthyläther Dichloräthyläther Vth Epoxydierungsmittel epichlorohydrin epichlorohydrin epichlorohydrin Epiehlorhydrin Epiohlorhydrin epichlorohydrin epichlorohydrin epichlorohydrin epichlorohydrin Eplchlorhydrin epichlorohydrin Epiehlorhydrin molar ratio V./äktive NH 1.26 1.16 1.14 0, 84 1.15 1.14 1.14 1.14 1.14 1.15 i, 14 1.14 active ones 39.5 30.0 25.0 21.5 25, 0 22.2 28.0 22.0 26.0 14.0 21.7 25.0% water firmness with addition of 0,5% 1, o% 16.0 21.1 2.1,2.3,1.9,1.9,3.3,4.4 18.1 22.3 2.8,4.3 15.1 17.0 13.2 16.5 10.2 14.0 15.5 17.5 15.0 16.0 13.2 15.5 example No. 13 14 16 17 18 19 21 22 23 24 Ith acid Sueeinylehlorid Fumarsäu Glutarsäure, glow rsäureII. Backbone polyamine (prime., sec., save.) Diäthylen triBmin (l, 2) Diäthylen trianain (1,2) anhydride Dimethylglutarat Itacons ure (7-Vale - laeton 7-Valerolaeton (&) adipic acid A dipinsäure adipic acid Adipins äure Diäthylen triamin (1,2) Diäthylen triMolverhältnis well O, 93 0, 95 0, 95 O, 95 0, 95 0, 95 0, 95 0.95 0.95 0.95 0.95 table 1 M. the Endgruppen of screen end polyamine (prime., sec., terL) continuation) IVTH chain-longer Vth Epoxydierungsmittel Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin epibromhydrin molar ratio V./al VE NH 1.14 1.09 1.05 1.05 1.31 1.14 1.14 2.28 1.14 1.34 1.15 active ones 32, 8 16,0 25,0 25, 0 60.0 18.8 33.3 40.2 i0,0 41, 7 30.0 0, 5% % water firmness with addition of 1,0% 1.8,1.0 18.6 18, 0 21.2 18.4, 1.7,2.6 21.2 18.7 19.3 amine (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1, 2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Pentaäthylen - min (1,2) 0.95 Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - p opylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) A minoäthyl äthanolamin (1,2) Dieh! oräthyläther bromidebromide bromide Diehloräthyläther Diehloräthyläther Dichloräthyläther Triglykoldiehlorid Diehloräthyläther Diehloräthyläther Diehloräthyläther DiehlorÄthyläther Diehloräthyläther Diehlorätäyläther epibromhydrin 0.91 29.8 15.2 1.9,1.0 21.6 21.8 22.6 22, 8,1.8,3.1 24.1 22.9 23.1 17.5 l I O table i (continuation) example No. 26 27 28 29 31 32 33 34 36 I, acid adipic acid A dipinsäure adipic acid adipic acid adipic acid adipic acid A dipins äure adipic acid adipic acid adipic acid A dipins äure adipic acid II, R ückgrat polyamine (prime., sec., save.) Diäthylen trichloroethylene - amine (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Triäthyleu tetramin (1,2) mol-holds back is 0, 95 0, 95 0, 95 0, 95 M. the Endgruppeu of screen end polyamine (prime., sec., tert.) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) IVTH Kettsnverlängerer Triglykoldichlorid Äthylendibromid Dijodmethan Diehloräthyläther Vth Epoxydierungsmittel epichlorohydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin molar ratio V, /aktive NH 1.14 1.14 1.14 1, 02 active ones 34.5 34, 7 34.5 28.0 Penf ethylen - hexadecimal min (1,2) until (aminopropyl) - - methylamin (1, 3) until (aminopropyl) - - methylamin (1,3) Diäthylen triamin (l, 2) tri ethylen - tetram ù (1,2) Pentaäth len - hexadecimal min (1,2) Diäthyleu - tri amine (1,2) Diäthylen - tri amine (1,2) 0.95 0.95 0, 95 0,95 0.95 O, 95 0.85 0.9 Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1,3) A minoäthyl äthanolamin (1,2) Aminoäthyl äthanolamin (1,2) Aminoäthyl äthanolamin (1,2) Aminoäthyl äthanolamin (1,2) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dichloräthyläther Triglykoldichlorid Dichloräthyläther Diehloräthyläther Dichloräthyläther Dichloräthyläther Tri#ykoldiehlorid Triglykoldichlorid Epiehlorhydrin epichlorohydrin epichlorohydrin epichlorohydrin Epiehlorhydrin epichlorohydrin epichlorohydrin epichlorohydrin 1, 02 1.27 1.27 1.05 1.05 1.05 1.27 1.20 24.0 15.8 16.5 19.1 24.0 33.3 18.0 18.0% water firmness with addition of o, 5% 1, 0% 19, 9 24.4 20.2 23.8 19, 6 24, 6 15.4 18.1 15.2 16.6 16.4 20.0 14.1 16, 6 16.9 19.5 13, 9 16, 7 14.8 17.4 21, 0 24, 7 21.4 23.6 example NR, 37 38 39 41 42 43 44 46 47 48 49 Ith acid adipic acid adipic acid Adip%nsäure adipic acid A dipinsäure Monomethyladipat Z err detection acid (£) adipic acid Pimelinsäure K orks äure A zelainsäure A zelainsäure sebacic acid H. 1 ückgrat polyamine primely., sec., tert.) Diäthyleu triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (l, 2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamiu (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Tetraäthylen - pentamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) molar ratio n/i O, 95 O, 95 0.95 0.95 0, 95 0.95 0.9 0, 95 O, 95 0, 95 0.95 0, 95,0.9 table 112. the Endgruppen of screen end polyamine (prime., sec., tert.) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamiu (1,3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dimethylamino - - propylamin (1, 3) Dimethylamino - propylamin (1,3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) Dimethylamino - propylamin (1, 3) I (Fortsetzun IVTH chain-longer Dichloräthyläther Dichloräthyläther Dichloräthyläther Dichloräthyläther Dichloräthyläther Dichloräthyläther Triglykoldichlorid Dichloräthyläther Diehloräthyläther Dichleräthyläther Dichloräthyläthe r Dichloräthylä%her Dichleräthyläther Vth Epoxydierungsmittel Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin Epiehlorhydrin epichlorohydrin epichlorohydrin Epiehlorhyäriù epichlorohydrin E piehlorhydrin Epichlorohydrin Epiehlorhydrin Epiehlorhydrin epichlorohydrin 1V [olverhältnis v./active NH 0, 84 i, 05 1.57 1.89 1.34 1.14 1.14 1.14 1.05 1.14 0, 1.0 1.14 active ones 23.4 15.1 16.4 34.7 41.7 18.5 22, 0 10.0 14.5 11.0 20, 0 24.0 20.0% water firmness with addition of O, 5% 18, 0 21.0 20.1 19.2 16.1 18.0 14.1 19.9 14, 21.5 23.5 23.4 18.1 27.2 () 22.8 19.9 21, 8 17.6 24.0 15.4 table la No. 339050 example No. 1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 26 27 28 29 31 32 33 34 36 37 38 39 41 42 43 44 46 47 48 49 PP basic molecule WirM. Temp. Temp. Range 22 15160 120-160 200 120-200 200 120-240 of endgruppenabges ehlossenes Grundm olekül work!. Temp. Temp. Range extended basic molecule resin (Epoxydation) WirM. Temp. 84-144 80-160 120100-150 " 200 120-240 202 120-240 200 120-240 200 80-200 200 120-240 150 120-155 10-15 0160 120-170 174 120-175 162 120-165 80-150 80-170 200 120-240 240 120-240 240 120-240 200 120-240 200 120-240 210 120-240 200 120-240 210 120-240 210 120-240 210 120-240 210 120-240 200 120-240 200 120-240 200 120-240 200 120-240 200 120-240 200 120-240 200 120-240 200 120-240 210 120-240 200 120-240 200 120-240 210 120-240 200 120-240 201 120-240 200 120-240 200 120-240 200 120-240 200 120-240 202 120-240 200 120-240 180 120-240 7090 150 120-160 165 120-180 165 120-180 80-100 100-150 120-180 120-180 120-180 80-160 120-180 100-120 20120-160 120-170 120-170 80-100 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180J 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 120-180 WirM. Temp. Temp. Range 7090 100 100-120 100 100-120 i00 100-120 80-100 100-120 110-120 100-120 100-120 80-110 100-120 100-120 100-120 100-120 100-120 100-120 80-100 100-120 I00-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 100-120 75-85 70-75 70-90 120,165,180,180 I00 160,120,130,170,170 90 170,150,150,165,165,180,165,168,168 168,165,165,175,170,165,165,165,154,160,180,165,165,180,165,175,150,165,177,170,175,167,155,110,105,107,105,108,105,102 i00 100,101,102,103,110,110,105,105,106,114,100,101,100 107,118,105,105,109,110,114,107,105,106,106,106,106,105,106,105,105,104,103,103,100,105 75-85 70-76 70-80 65-80 75-80 57 54 60-65 60-68 60-63 60-64 63-70 62-72 62-75 60-75 70-72 70-75 70-73 60-68 70-72 70-85 70-75 60-75 73 70-80 57 51 temp. Range 40-70 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 40-90 example No. 1 2 3 4 6 7 8 9 11 12 13 14 16 17 18 19 21 22 23 24 26 Ith acid 42,104 52 160 72 118 51 49 87 66 134 77.5 58 66 57 384,292,292,146,146,146,146 table lb PP g round molecule H. backbone polyamine 22.5 32.5 97.8 80.0 97.0 95.0 97.8 48.5 89.0 54.4 water ReakGonszeit 84,104 52 0 0 118 51 100 0 Endg uppenabgesohlos sene s 20° 2° 2o, 8, 2055 ' 4045, 2° 2o15' lO40' basic molecule] I [. the Endgruppen l eakbildendes polyamine tions time lO30, lO25, lO40, Verläugertes basic molecule Wassen Reaklions time Epoxydiertes Grundmo [ekül 49.0 97.8 48, 0 49.0 49.0 49.0 234, 8 48.9 49.0 49.0 195, 7,195, 7 97.8 220, 0 97.8 97.8 66 1°30' 134 3° 200) 1°45' 100 2° 66 2030 ' 57 2°15' 0,108 ' 1030 ' 0 3° 0 3° 292 3°10' 292 4°30' 146 2° 146 2° 146 2045, 146 2o45' (prime., sec., save.) IO 30 ' 15 ' 55 ' io14' 55 ' iolO, 1e 2° 2° 2° 2° I'V.K of Elbe-longer 100,100,100,100 2° io30, io30, io16, IO30, 1030, io30, lO35, 2° 4.1,3.3 10.2 5.1 11.0 18.0 10.2 6.0 10.0 25.5 2.5,2.3 10.0 5.0,8.0 12.0 8.0,4.0,5.0 18.0 100,100,100,150,300,100,200,200,100,100,480,480 1° io30, 2° i020, io35, IO22, io30, io30, 1030, I030' lO30' lO30' lO30, 2o30, 2o30' Vth Epoxydie-- Water Reakrungsmittel tions time 5.1 10.2 5.0,5.1,5.1,5.1 24, 5.1,5.1,5.1 25, 0 25.0 12.5 10.4 12.5 12.5 4.0,8.0,4.0,6.0,4.0,4.0 18.0 5.0,4.0,4.0 16.0 16.0 8.0,8.0 10.5 10.5 36 0 84 128,100,800,110,500,100,600,100,900,100,700,500,700,455,500 i00 600,200 48 270 46.2 276 46.2 350 277.0 0 50.0 550 50.0 250 100.0 250 200.0 2400 23 ' 7.0,195 150.0 400 120.0 1200 99.0 0 99.0 0 3° 4o15, 13° 13° 4° 50 ' 14o30' 7o25, 7o37, 6035 ' 8030 ' 9o20, 7040 ' 13o30' 3o30' io16, lO26' 2023, 7030 ' 7030 ' 3045 ' 5o50, i035, lO20' IO50, 2o10, oI C example No. 27 28 29 31 32 33 34 36 37 38 39 41 42 43 44 46 47 48 49 Ith acid 146,146,146,146,146,146,146,146,146,146,146,146,146,146,292 32 105,292 87 94 94 101 I olyamid g ndm olekül IL backbone polyamine 97.8 138.7 220.0 136, 0,136, 0 97.8 138.7 220, 0 87.5 water 146,146,146,146,146,146,146,146,146 table eakBonszeit lb (continuation) Endgruppenabges of chlos senes extended Grundmolek'ül basic molecule 117. the Endgruppen ReakIV. EettenverWasser l eak2o45, lO30' lO30, lO30, lO30, lO30' lO30, lO30' 1° of screen end polyamine (primely., sec., more ter.) tions time 2° lO15' i°i0' IOI0, IOi0, lO20' lO15' io15' lO15' of longer tionszeit 13.5 480 2030 ' 8, 0,125 1°30' 8.0 75 i030' I0, 0 i00 1°30' 8,100 1°30' 8 i00 lO30' 8 i00 lO30' 8,100 1°30' 100 lO30' Epoxydiertes basic molecule rungsmittel 92, 7 97.8 97.8 97.8 97.8 195.7 19.6 70.0 195, 7 24.4 48, 9 90, 0 48, 9 46.6 146,146,146,146,146,292 0 96 292 87 94 94 96 2° 3o10' 3o10, 2° 4030 ' lO15' 1° 3o10, lO45' 2o10' 2045, lO20' 2050 ' 12, 10.2 10.2 10.2 10.4 10.4 10.4 10.4 30.6 ioi0, 2° 2° 2° 2° 2° 2045 ' 2° lO35' lO25' 15 ' io15, lO15' i0 i00 1°30' 8 i00 lO30' 8,100 lO30' 8 i00 1°30' 8,100 lO30' 16,200 lO30' 1.5 20 1°30' i00 lO30' 16,200 l°30' 2.5 30 1037 ' 4 50 lO36' 4,100 1° 4 50 lO30' 8 50 lO30, Vth EpoxydieWasser reaction time 20.4 12.5 12.5 12.5 12.5 25, 0,2.5 10.2 25.0 3.0,5.1,5.1,5.1 10.2 99.0 180, 0 360.0 112, 0,112, 0 92, 0,184, 0,368, 0 i00, 0 i00,0 74.0 92.4 138, 0 166.8 237, 0 20.0 I00,0 200.0 23.2 50.0 92.5 46.2 50, 0 0 930 1940 1000 1000 800 1280 1200 800,800,400 1150 1150 400,195,125 9OO 2 00 445 26O 8OO 366,300 lO45' 6040 ' 7050, lO15' 13030, 13045 ' 7030 ' 55 ' lO50' 2o10, io15, 14o 15o 5o50, 6o10' 5030, 3045 ' 7o10, 2o15' 21 ' 2o15' 4035, o o Q in the following tables are arranged the production and the results of the water firmness tests of 19 resins. These resins manufactured in accordance with the USA patent chriften No. 2.926.116 and No. the 2.926.154, if not differently indicated. In table 2 are indicated the reaction components, their molar ratio as well as the effectiveness and the water firmness of the resins. In table 2the example appropriate with the Synthtse really used temperature as well as the temperature range is indicated. In table 2b the quantities of the reaction components and the response times are arranged. The footnotes to table 2 and 2b are at the end of the table 2b. Example No. 51 52 53 54 56 57 58 59 Ith acid sebacic acid Diäthyloxalat (!) Diäthyloxalat Oxa1säur malonic acid succinic acid Glutarsäure Dimethy glutarat I%aconsäure (adipic acid IITH backbone polyamine (prime., sec., save.) Diäthylen triamin (1,2) Melverhältùis 0, 95 table 2 REAR ONES the Endgruppen of screen end polyamine (prime., sec., save.) Dimethylamino - propylamin (1,3) PT. Chain-longer Dichloräthyläther Vth Epoxydierungsmittel molar ratio V/akfi VE NH Diäthylen triamin (1,2) Diäfhylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen triamen (1,2) Diäthylen triamin (l, 2) Diäthylen triamin (1,2) 1.0,1.0 1.09 1.09 1.06 1.08 i, i 1.1,1.1 Epichlor hydrin epichlorohydrin epichlorohydrin epichlorohydrin Epiehlorhydrin epichlorohydrin epichlorohydrin Epichlorhydrm epichlorohydrin 1.2,1.2 1.08 1.08 1.0 1.08 1.0,1.0,1.0 active ones 42.2 8.5 20.3 19.8 21, 17.4 15, 0 I0,0 RST, O % water firmness with addition of 0, 5% i, 0% water-insolubly 6.1,9, 0 ii, i 13.7 1.3,1.7,1.4,1.5 13.9 20.0 16.0 20.0 15.5 16.5 17.0 21.0 16.5 22.0 O Ith acid example No. II. RäckgzatPolyamin (prime., sec., save.) Diäthylen triamin (1,2) Diäthylen triamin (1,2) Diäthylen tr - amine (1,2) and Äthylenöiamin (relationship 2: 3) ethylen diamine and Diäthylentriamin (relationship 1: 10) ethylen diamine and Diäthylentriamin (relationship 1: 10) ÄthFlendiamin and Diäthylentriamin (relationship 4: 6) molar ratio i, i O, 95 i, i0 i, i0 1.4,1.1,1.1,1.1 table 2 continuation) IV, chain-longer adipic acid 61 A dipinsäure 62 Pimelinsäure 63 cork acid 64 cork acid Eorksäure 66 cork acid 67 cork acid 6 8 of cork äure ethylen diamine and Diäthyle ntriamin (relationship 4: 6) 1.1 III. the Endgruppen of screen end PolFamän (prime., sec., tert.) Dimethylam! - o - propylamin (1,3) Diehleräthyläther Vth Epoxydierungsmittel Epiehlorhydrin Äthylendibromid (epichlorohydrin Epiehlerhydrin epichlorohydrin Epiehlorhydrln Ep ehlorhydrin Epiehlorhydrin Eplehlorhydrin Molverhällmis V/aktive NtI 1.0 1.39 1.0,1.0,0.5,1.0,0.5,0.5,1.0 active ones 10, O 14.0 ii, 0 8.0% Wasserfest2gkeit with addition of o, 5% 1.0% 24, s ® 2s, 3 ® 5.5,7.4 gel gel 3.7,5.1 gel gel gel gel o D O example No. 51 52 53 54 56 57 58 59 61 62 63 64 66 67 68 PolyamidGrundmolek'dl work. Temp. Temp. Range 180 120-240 22 1522 15150 120-160 185 110-250 200 110-250 185 110-250 150 t10-250 165 160-210 185-200 110-250 185-200 i10-250 200 120-240 195 110-250 194 110-250 198 110-250 185-200 110-250 185-200 110-250 185-200 110-250 185-200 110-250 table 2a endgruppenab - ges chlossenes - basic molecule Wirkl. Temp. Temp. Range 155 120-180 165 120-180 extended G olekül works approximately. Temp. Temp. Range 105 100-120 105 100-120 resin (Epoxydafion) Wirkl. Temp. Temp. Range 60-70 50SO 60-70 5075-85 45-100 - 75-85 45-100 66-68 45-100 45-100 45-i00 60-100 60-70 45-100 60-70 45-100 94 50-100 45-100 56 45-100 76 45-100 60-65 45-100 45-100 45-100 45-100 example No. 51 52 53 54 56 57 58 59 61 62 63 64 66 67 68 Ith acid 101 63 52! 18 66! 60 • 292,292,146 87 87 87 87 87 87 PP g round molecule H. backbone water ReakPolyamin 48.9 28.3 40.0 50.0 56.0 109.0 56, 0 113.0 56.0 226, 6 226.6 97.8 28.4 56.3 28.8 + 25, 2 3 + 51.5 3 + 51.5 13.2 + 34 13.2 + 34 table 2b (weight in Gramm% time in hours) tionszeit Endgruppenabges cbloss enes G round molecule III. the Endgruppen Reakbildendes polyamine tionszeit (primely., sec., tert.) Extended basic molecule IVTH chain water l more eaklängerer tions time Epoxydiertes basic molecule Vth EpoxydieWasser Reakrungsmittel tions time 101,160,160,100 0 100,100,146 lO30' 20° 200 2° 1o30' lO30' 2° 3° 2° 2° 2° 3° 3035 ' lO50' 1050 ' lO50' lO50' lO50' 5.1 12.5 1045 ' 2° 100 io40, lO30' 30, 61, 0 50, 0 50, 0 92, 0 50, 0 92, 50, 0,185, 0,185, 0,250, 0 23, 2 46, 4 13, 0 46, 3 23, 1 13, 9 27.8 200,200,500,400 1000 520 1660 450 3800 3800 1800 470,450,920,940,940,940,940 2° 3° 8° 3° 50 ' 45 ' 301 3° 4° 8° 8° 3° 1° 10 ' 38 ' 5040 ' 16 ' 40 ' 16 ' 37 ' 0 C.n o lG footnotes to the tables 1, lb and 2, 2b (hetrachtet outside of the extent manufactured by the USA patent specifications No. 2.926.116 and No. 2.926.154, however in the there procedure () Wirdals mono acid. ) Insatiated acid. () Hydroxysäure. (Manufactured in accordance with the USA Patentschrfft No. 3,125,552. (Results after 19 days aging. C) Tri acid. (2 WHETHER concentration sf H O, 5%. () 3, 0% Eonzentration I, 0% sBtt. A Eettenverlängerungsmi was used el (QuaternisierungsmiHel) in place of a Epoxydlerungsmittels, with which conversion decomposes. In place of water isopropanol is used. In place of water benzene is used. Interpretation of the tables 1, la, lb and 2, 2a, 2b the examples 1 to 49 different reaction components, by which most are useful according to invention, show furthermore different l eaktionsbedingungen. The examples 1 to 21 and 42 his 49 show different acids. With most of these examples the same backbone l becomes olyam n, which Endgruppe of screen end polyamine, Eettenverlängerungsmittel and Epoxydierungsmittel uses, so that one receives an objective basis for the analysis of the relative effects of these acids. As evidently from the examples 2, 3, 4, 6, 13, 14, 19 and 20, are not suitable the acids for the production according to invention of water resistant hearts, used there. The fact is particularly interesting that gesäF the industrial union n acids of the examples 2, 3 and 4 decarboxylieren are useless and therefore, while the appropriate esters (examples lundS) are excellent. Example 13 shows that Säurehalogenide are useless, in the same way Laetone (see examples 19 and 20) and decarboxylierende insatiated acids (example 14). Useful satisfied Diearbonsäuren is in the examples 7, 12, 15, 18, 21 to 41und43 to 49beschrieben. A-useful insatiated Diearbonsäure is descriptive in the example 18, an useful Triearbonsäure in the example 43. Useful CI_I - Alkyl-monound Diester are in the examples 1, 5, 10, 11, 17 and 42 descriptive, useful anhydrides in the examples 8, 9 and 16. Useful according to invention backbone polyamine, which are Endgruppen screen end of polyamine, EettenverlängerungsmiHel and Epoxydierungsmittel in the examples revealed. The Molverhälb eating backbone polyamine/acid vary in accordance with table i of 0, 75 to 0, 95. This molar ratio was kept 95 intentionally very frequent approximately 0, in order to be able to compare the effectiveness Reaktionskomponentenaufeiner objective basis. Mol with restraint is the Epoxydierungsmittel/active Aminogr ppen lies in accordance with table 1 between 0,70 and 1, 89. Special attention should be dedicated to the examples 21 to 41. Hiebei is used in each case adipic acid, and it becomes evident that the other functional components and the molar ratios can be varied to a large extent. The column “%Aktive” is very important for the nben indicated reasons. The activity of the resin is of course in relation to its water firmness of selmndärer meaning. If a resin has a low water firmness, then its effectiveness is completely irrelevant. The examples 50 to 6S concern resins, which lie outside of the invention. Example 50 was manufactured using reaction components, which lay within the range according to invention, whereby however the Molverhälinis of backbone l is too high olyamin/acid (0, 95) hiedurcherhältmaneinwasseruniösllches PP, which cannot be epoxydlert. With Beispiel49 the same Reaktienskomponenten is used, but with a low molar ratio (0, 9). From this it becomes evident that the molar ratio backbone Polyaminosäure should lie in the lower part of the molar ratio range, if a higher acid is used. Example 61 differentiates stands by the examples according to invention thereby, daf a Epoxydierungsmi egg outside of the invention was only used. It is referred to it, there this Epoxydierungsmittel however according to invention as Eettenverlängerungsmittel usefully is this concerns a well-known Quaternisierungsmittel. This shows that the chain extension and Epoxydierung according to invention are different steps and that one cannot exchange the reaction components with one another. The examples 54 to 56, 59, 60 as well as 62 to 68 become of the USA Patentsohriften NR, 2.926! 16 and/or. No. 2.926.154 covers. As evident, handeltes itself only with the examples 55, 56 as well as 59 and 60 around water resistant resins according to the ü3olichen definition (s.unter testing of the water firmness " b the highest proportional effect is hiebei 21, special attention earns the examples 63 to 68, with which in each case the same reaction components use will. Different cone conditions, temperatures and Reak onskomponenten were received tried, all this within the scope of protection of the Patentechriften specified above llegen however no water resistant resins. Examples 51 to 53 as well as 57 lie outside of the scope of protection of the Patentschrfften specified above, and zw. because of the choice of the acid and/or substituted acid. It is to it referred, there the examples 51 and 52 only by the selection DOS 1Rüokgrat-Polyamins differentiates between themselves example 52 shows water resistant characteristics, however only very small. Example 58 lies in the range of the USA Patentechrfft No. 3,125,552. This concerns a water resistant resin, although the proportional effect amounts to only 10. Dio according to invention hergestelll EN of water resistant resins can both under be drunk and alkali-seen mash conditions be used. The following table shows that two loads of a typical resin (see example 22) for water resistant purposes are useful, if one uses them with pH words of the mash from 4 to. mash pH table 3 water firmness with addition of 0,5% 4, 0 18, 7,5.0 16.2 6, 0 20, 3 7, 0 21.0 8.0 21.4 9, 0 21 2 i0, 0 22.1 * Durchsohnittswerte from tests with 1,07o 2Z, 4 20.0 22, 2 26.5 29, Z 27.4 29.1 load 1 2 2 2 1 two loads. Samples of resins, which lie within and outside of the scope of protection of the invention, are tested hinsiohtlichäer stability and effectiveness after aging. The results are arranged in the following table table 4 sample A° B. C. D. E. F. Resin in accordance with example No. Time temperature water firmness originally after Al%erung o, 5% 1, o% o, 5% 1, o% 0.5% 90.0 90.0 94.4 89.0 137.0 94.5 21 21 22, 41 22% Retentien of the water firmness 1.0% 349 days 182 days 14 days 9 days 19 days 137 days 22Oc 22oc 50Oc 50Oc 22oc 22oc of 21.8 23.8 19.6 24.6 18.5 22.0 16.5 18.1 19.6 24.6 18.5 21.0 17.3 21.2 15.4 18.8 16.2 20.7 22.3 27.2 19.9 22.8 18.8 22.2 103.0 82.4 85.3 88.6 131.0 97.3 means 96, 86.2 89.9 88.8 134, 0 95, 9 * the resin of example 1 that USA lOa%entsehrif%en No. 2.926.116 and No. 2,926,154. fuel element b O1 Viskositätdes of the resin in accordance with example 22 ageing periods in purchase set to the appropriate water firmness, chiedenen after verse, so that one receives a procedure for the rapid determination of the effectiveness of a certain resin, without one must manufacture towels. These data are shown in the following. Ageing time (50°0) 0 3 days days 7 days 9 days % water firmness (o, 5%) 22.8 20.5 19.4 17.5 16.2 table % retention of the original Wasserfcstigkeit 90 77 71 viscosity * 620,500,440,405 266% retention of the urspriingHchen Wasserfestigkclt 81 71 43 * measured in Centipoises with a Brookfield Viskometer with 25°C on basis of the correlation of the numbers of table 5 was durchgefiihrt a ageing test with further erflndungsgemäß manufactured resins, and zw. 42 h with 50PC. The results are shown in the following. Table 6 sample A. B. O. D. E. F. G. H. Resin in accordance with example No. 1 7 17 34 48 49 original viscosity * 16 2, 700 12 final Viskosität* % Retenfion of the original viscosity 2, 000 36 71 100 94 74 120 i00 76 83 estimated retention of the original Wasserfesflgkeit 100 97 87 100 " 100 88 91 * measured in Centipoises with a Brookfield Viskometer with 25oc. I0 most water resistant resins make the treatment of cycles of waste paper and the recovery of break more difficult. By “break” one understands paper, which reject-became during the manufacturing process, e.g. Gewebekanten, incorrect paper etc. constitutes, is role ends there break generally about 10 of production its recovery importantly. The recovery (Überfühbarkeit in mash) of the water resistantly made paper becomes difficult by the presence of the resins, since they are not easy degradable. It is favourable to be used a resin be reduced soft during the break production can, without hiedurch the water firmness suffers Eiabußen. Papierbruch, which was treated mild according to invention manufactured water resistant resins, lets itself easier recovering. h. again in mash) as break of paper, which was treated with other water resistant resins, e.g. in accordance with the USA PatentsehriIten No. 2.926.116 and No. 2,926,154 transfer that. With a mill attempt it was found that paper, which 0, 5 to 0, 6% contain the resin in accordance with example 22 (40% activity), at a temperature from 21 to 32°C easily in a Hydra Pulper " 'again in mash be tibergeführt can. E s is accepted, this primarily on the smaller Polymerisationsges chwinùdigkeitdererfindungsgemäßhergesteUten of resins is based. With according to invention manufactured the resins if treated break is transferred again in mash, then the resins are still incompletely polymerized and more zersetzensichdaherloichter. The polymerization of the resin becomes by mild aging completes; it is terminated, if the paper is used. In contrast hiezu the Polymerlsation of the resins is terminated after the Patenteehriften specified above, as soon as the fabric is produced. With paper, which was treated with a not degradable resin, the machinery can be clogged, whereby a working interruption becomes necessary, because one must remove the paper manually. Small pieces of this paper know the finished paper verunstalten. A further factor, which contributes to the easier recovery of the break, is the small self-tackness-those-find-in accordance with-manufactured resins. That is, these resins lend geringers water-repellent effect to the paper one as those in accordance with the USA patent specifications Nri2,92G, 116 and No. 2,926,154. Therefore the break has a larger water absorbability and more easily again in mash is transferred. In addition it is partly not necessary due to this characteristic to shift the mash with a humidification means in order to increase the water absorbability in the cases, in which this is desired, e.g. with the production of paper towels. Waste paper ability also lighter to be recovered, if it water resistant-resin-contains according to invention the manufactured. Also if they is vollpolymeristert, them with the transfer in mash is more easily reduced than the resins of the state of the art. If one uses e.g. water resistant resins of the MelaminTyp in quantities from I to 3%, then these köuuen during the transfer of the waste paper in mash not to be reduced. 1VIit such resins treated Papfer must be driven manually removed and cannot not in the cycle. The lower self adhesive characteristics of the paper treated with according to invention manufactured the water resistant resins contribute thus even to the easier transfer in mash.