SE429137B - APPLICATION OF CURABLE ART HEART MIXTURES FOR SURFACE TREATMENTS AND FOR PRESSURIZERS FOR DEPTH, FLEXO AND DUST PRINTING - Google Patents

Description

7sos1z7e9d also adduct of a solid polyaminoamide of dimer fatty acid and a diamine and of an excess of a solid epoxy resin and C) solvents and any pigments for use as paints, inks, binders for laminating all types of foils and papers. ii "The object according to German Offenlegungsschrift 1 6.94 958 is a process for the production of synthetic resins by reacting polyamides with epoxide compounds, characterized in that the proportion of diamine for the production of the polyamide, which is prepared in a known manner, consists of 20-100 amino-š-aminomethyl-š, 5,5-trimethylcyclohexane and the proportion of this polyamide in admixture with the epoxide compound is 10-993%.

In this process, the polyamide and the epoxy resin are directly mixed without pre-deduction according to the present invention. Such mixtures are not yet satisfactory with regard to film formation at room temperature or at a slightly elevated temperature, and the field of application of this procedure is correspondingly limited. '“' Printed material on. basis of German Offenlegungsschrift I 494 '523 has a sufficient resistance to chemicals and good mechanical and thermal properties. However, in order to obtain clear solutions, the solvent must contain a relatively large proportion of aromatics. I Due to the consideration for workplace and environmental protection, which has recently come to the fore more and more strongly, in practice binders are required for coatings and printing inks, which constitute clear solutions in aromatic-free solvents. The use of aromatics is also undesirable for technological reasons. Thus, for example, when using aromatic solvents, swelling of the pressure rollers may occur.

The object of the present invention was to provide curable, aroma-free solvents clearly soluble binder systems which, after evaporation of the solvent, give physically dry and clear films and which cure at: room temperature or at a slightly elevated temperature, the coatings and pressure films corresponding to requirements of practice with regard to chemical stresses. This object has, according to the invention, been solved by the use of curable resin mixtures for coatings and for inks for gravure, fleece and cloth printing, consisting of resin mixtures as binders, namely of A) a solid resin component with free amino groups. consisting of an adduct of an epoxy resin and an excess of polyaminoamides, namely of I. solid polyaminoamides having an amine number of 50-200, in particular 50-150, prepared from a 1) a 2) aö) optionally ia 4) aliphatic dicarboxylic acids with 6 to 15 carbon atoms or their mixtures and optionally of aromatic and / or araliphatic and / or hydroaromatic carboxylic acids, which are optionally alkyl-substituted, or their mixtures in amounts of 0.95 - 0.05, in particular 0.8 - 0.2, equivalents, assigned to total carbozcyl groups, and aliphatic, hydroaromatic and aromatic monocarboxylic acids or monofunctional acids or anhydrides mixed with dimeric fatty acids and / or add ition products of acrylic acid to unsaturated fatty acids and / or heptadecandicarboxylic acids and of an excess of, inter alia, one or more diamines of the general formula I 1 R N52 1 R R 1 I R 1 RE in which H 1 = H or one; and 32 = -cna-Nnz or -CKCl2 -a2-NH2 and optionally of -, - sos1s7é9Ai b 2) amines of the general formula II man - - - - cHmX-NH -qbT-H II in which R represents an alkyl group with. 1-4 carbon atoms or hydrogen and x 2-6 and y are 2-4, and of II aminoamide compounds and / or aminoimidazoline compounds and / or imidazoline group-containing aminoamide compounds having amine hydrogen equivalent weights of 90-500 based on polyalkylene polyaners of general formula II (see b 2) i and / or of .III.a) amines of the general formula II or gb) amines of the general formula III I 'in 112m - (cHmx-1vnz' 'III in which R represents an alkyl group having 1 -4- carbon atoms or in particular hydrogen and x are 2-6, in particular 2, and / or of IV. Mannich bases suitable for curing epoxy resins having at least 2 reaction-prone amine hydrogen atoms and consisting of B) a synthetic resin component with free epoxide groups consisting of an adduct of solid polyaminoamides as in AI) and an excess of an epoxy resin and content G) aromatics-free solvents and any pigments.

A further object of the invention is the use of curable synthetic resin mixtures for coatings and for printing inks for gravure, flexo and canvas printing, characterized in that in a variation of claim 1 for the adducts A) the use of the amino compounds II-IV is omitted. A further object of the invention is the use of synthetic resin mixtures for coatings and for inks for low-pressure printing machines, characterized in that instead of the adducts AI, A II, AIII and A IV, one or more of the corresponding non-pre-deducted amine compounds are optionally used. I, II, III and IV, wherein the amine compounds I are preferably used together with one or more of the components II - IV.

For the aliphatic dicarboxylic acids used according to the invention, mention should be made, for example, of: adipic acid, pimelic acid, cork acid, azelaic acid, sebacic acid, decamethylene dicarboxylic acid and brassylic acid.

For the aliphatic, araliphatic and aromatic dicarboxylic acids used simultaneously according to the invention, mention should be made, for example, of: terephthalic acid, isophthalic acid, tetramethylterephthalic acid, cyclohexanedicarboxylic acid-1,4, xylylenediacetic acid, phenylenediacetic acid, fluorenedicarboxylic acid, addition products of higher carbonic acid which is prepared by carboxylation of unsaturated higher monomeric fatty acids having 16-22 carbon atoms. .

According to the invention, difunctionally acting polycarboxylic acids can be used, e.g. cyclopentane tetracarboxylic dianhydride, bicyclo [2.2.2] oct-7-ene tetracarboxylic dianhydride, bicyclo [2.2.2} oct-7-en-tricarboxylic acid, trimellitic anhydride and pyromellitic dianhydride. According to the invention, isophthalic acid and terephthalic acid are preferred. Optionally present alkyl substituents may have 1-4, preferably 1-2, carbon atoms.

For setting or regulating the required or desired degree of polymerization and the melt viscosity of the condensation products, anhydrides of dicarboxylic acids according to the invention can be used simultaneously, which under the given reaction conditions with amines predominantly form imides, and monocarboxylic acids. The possible proportion of the monofunctional or monofunctional compounds may be 0.01 to 0.5 equivalents, in particular 0.1 to 0.5 equivalents, based on total acid equivalents.

Typical representatives of these compounds are: Aromatic series: phthalic acid, phthalic anhydride, dimethylphthalic acid, dimethylphthalic anhydride, benzoic acid, naphthalene carboxylic acid.

Hydroaromatic series: tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, endomethylenetetrahydrophthalic anhydride, hexahydrophthalic anhydride.

Aliphatic series: straight or branched, possibly unsaturated acids with 2-22 carbon atoms, e.g. acetic acid, propionic acid, butyric acid, stearic acid, palmitic acid, oleic acid, tall oil fatty acid.

It is preferred according to the invention to use tetrahydrophthalic acid, hexahydrophthalic acid, acetic acid and o-phthalic acid. Predominantly difunctionally active compounds, for example aromatic tetracarboxylic dianhydrides, can likewise be used in small amounts under the given reaction conditions. amine-forming proportions of the present dianhydride, as these, due to their tri- or tetra-functionality, have a bridging effect, whereby a strong increase in the viscosity takes place, which can lead to gel formation.

The quantities introduced must in each case be chosen in such a way that these harmful effects are reduced to a defensible degree.

The dicarboxylic acids according to the invention can also be used in the form of their amide-forming derivatives, i.e .: c. estrar. The dimeric fatty acids which may be used at the same time refer to polymerized acids which can be produced from unsaturated, natural and synthetic, monobasic aliphatic fatty acids having 16 to 22 carbon atoms, preferably 18 carbon atoms, by known methods (cf. German Offenlegungsschriften 1 445 938 and 1,445,968, German Pat. No. 2,118,702 and German Explanatory Memorandum No. 280,852). Typical commercially available dimerized fatty acids have approximately the following composition: monomeric acids 5 - 15% by weight of dimeric acids 60 - 80 "trimeric and higher functional acids 10 - 55" However, dimeric fatty acids may also be used, which hydrated by known methods and / or whose dimer content has been enriched by a. suitable distillation procedure to> 80% by weight.

As an example. an adduct of acrylic acid and an unsaturated fatty acid may be mentioned as a commercially available one. adduct of alcrylic acid and a conjugated Glß monocarboxylic acid. Products of this type can also be hydrogenated. The optionally co-used heptadecandicarboxylic acid can also be prepared according to German Patent Specification 1 006 84-9. -1 7808137-9 These possibly used acids can be introduced in amounts of 0.05 - 0.8 equivalents, attributed to total equivalents.

Within these limits, these values must be varied with respect to the acid component present and the type and quantity of other components in order to obtain the products used according to the invention. Such variations are a matter of course for those skilled in the art and are clear in terms of tendency and effect.

Examples of diamines according to the invention which may be mentioned are: β-aminomethyl-β, 5,5-trimethyloyclohexylamine (isophorone diamine) and 1-methyl-4- (1-amino-1-methylethyl) -oyclohexylylamine (mentandiamine ). The diamines according to the invention can also be introduced in mixtures with themselves and with other amines.

The amines which may be used at the same time can be used simultaneously in amounts of 0.01 - 0.5, in particular 0.1 - 0.25, equivalents, attributed to the total amount of amine. Within these limits, these values must be varied with respect to. the acid component present and the type and quantity of other components in order to obtain the products used according to the invention. Dylilca variations are a matter of course for those skilled in the art and are clear in terms of tendency and effect.

The optionally simultaneously useful amines fall under the general formula II noN-E- (cnlnx-Nn-qïr-æx II in which x is 2-6 and y is 2-4 and R represents an alkyl group having 1-4 carbon atoms or hydrogen and däIf / id y> the value of x within the molecule can be equal or different.

Examples which may be mentioned are diethylenetriamine, triethylenetetramine, tetraethylenepentamine, dihexamethylenetriamine, hydrogenated cyanethylation products of polyvalent amines, e.g. N-aminopropylethylenediamine and N, N'-bis (aminopropylethylenediamine).

These anines are commercially available epoxy resin hardeners and can also be used together with a harder hardener according to the invention.

The carboxylic acids and amines are condensed in such amounts that the polyaminoamides formed have amine numbers between 50 and 200, 7sos1z7-9 in particular between 50 and 150. Examples of the preparation are shown in Table 1. As aminoamides, aminoimidazolines and imidazoline group-containing aminoamides are suitable as harder for epoxide compounds to the prior art and put into practice the compounds known from, for example, German Pat. Nos. 972,757 and 1,074 ass, to German Laid-Open Publications 1,041,246, 11,089,544, 10,06 4-95, 1,295,869. and 1,250,918, British Patents 805 '517, 810 548, 875 224, 865 656 and 956 709, Belgian Patent 595 299, French Patent 264-244 and U.S. Patents 2,705,225, 2,712,001. 2,881,194, 2,966,478, 5,002,941, 5,062,775 and 5,886,566. As advantageous for use in accordance with the invention, aminoamides, aminoimidazolines and imidazoline group-containing aminoamides have been found which are prepared by by reaction of II.a l) monocarboxylic acids, such as: straight or branched alkyl carboxylic acids having 2-22 carbon atoms, in particular having 2-4 'and 16-22 carbon atoms, preferably having 18 carbon atoms, e.g. acetic acid, propionic acid, butyric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid and in particular the natural fatty acids such as stearic, oily, quinolic, linolenic and tall oil fatty acids or a 2) - those by polymerization of unsaturated natural and synthetic tetrabasic aliphatic fatty acids having 16-22 carbon atoms, preferably 18 carbon atoms, by known methods prepared so-called diJnera fatty acids (cf., for example, German Offenlegungsschriften l 4-45 958 and l 44-5 968, German patent specification 2 118 702 and German utläggningsskriften l 280 852).

Typical commercially available polymerized fatty acids have approximately the following composition: g monomeric acids 5 - 15% dimeric acids 60 - 80 "trimeric and higher functional acids 10 - 55" However, it is also possible to use fatty acids whose trimer and higher functional content or which dimer content -enriched by suitable distillation processes, or fatty acids, -hydrogenated by known procedures, or -I 7 ana1z7ë9 a 5) carboxylic acids obtained from unsaturated higher fatty acids with 16-22, in particular 18, carbon atoms or their esters with aromatic vinyl compounds by copolymerization (see for example British Patent Specification so; 517) or a 4) acids, which are prepared by adding phenol or its substitution products to unsaturated monocarboxylic acids, e.g. hydroxyphenylstearic acid (see, for example, German Offenlegungsschriften 1,545,754) or 2,2-bis- (hydroxyphenylvaleric acid, or addition products of phenol to polycarboxylic acids, eg dimeric fatty acid (see, for example, U.S. Pat. No. 3,468,920), or with polyamines in a ratio of amine group carboxyl groups> l.

In general, the acids in the above-mentioned groups are introduced separately for the condensation with the polyamines. However, you can also use mixtures. Of particular importance in the art are polyaminoamides and polyaminoimidazolines of the monomeric and polymeric fatty acids mentioned in II a 1) and II a 2), which are thus preferred to be introduced according to the invention.

As amine components used according to the invention for the production of polyaminoamides, polyamines such as III a l) polyallylene polyamines of the general formula II are used, for example polyethylene polyamines, e.g. diethylenetriamine, triethylenetetramine, tetraethylenepentamine or polypropylene polyamine, and the polyamines produced by cyanethylation of polyamines, in particular ethylenediamine, and subsequent hydrogenation (company prospectus from BASF AG, 1976) or a 2) optionally substituted the alkylene polyamine , for example ethylenediamine, propylenediamine, butylenediaxzine, hexylenediamine and in particular ethylenediamine, or mixtures of two or more of the amines listed under A II and A III. It is preferred according to the invention to introduce the polyamines listed under III a l).

The preferred aminoamides and imidazoline group-containing aminoamides of the invention have amine hydrogen equivalent weights of from about 90 to about 500. Mannich bases of the present invention refer to reaction products of phenols, formaldehyde and secondary amines. Monophenols can be used as phenols, e.g. phenol, ortho-, meta- and paracresol, isomeric xylenols, para-tertiary-butylphenol, para-nonylphenol, d-naphthol, p-naphthol, and di- and polyphenols, e.g. resorcinol, hydroquinone, ÅI-JV-dioxydiphenyl, L1-JV-dioxydiphenyl ether, èf-dioxydiphenylsulfone, 4,4'-dioxydiphenylmethane, bisphenol no., and the novolaks referred to as the condensation products of phenol and formaldehyde.

As secondary amides can be introduced: dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, pyrrolidine, morpholine and methylpiperazine.

A comprehensive list of useful phenols and amines can be found in M. Tramontini, Syntheses 1975, page 705. For the preparation of Mannich bases, reference is also made to this reference. The islet amounts of formaldehyde and amine per mole of phenol refer to the number of groups prone to substitution. In phenol these are 5, in bisphenol A 4 and in para-tertiary-butylphenol 2.

The Mannich bases which are preferred according to the invention are reaction products of phenol or bisphenol A, formaldehyde and dimethylamine with 1-L1 tertiary amine groups.

When using novolaoker as a phenol component, so. Mannich bases with up to 10 and more secondary amine groups are obtained. When Mannich bases are reacted with taminoamides, all tertiary amino groups in the Mannich base can be replaced.

The amine exchange reaction occurs then. Mannich base and aminoamide, optionally together with inert solvents, are heated with stirring to wemperamer> 100 ° o, preferably 150-150 ° o.

The secondary amine released within 1/2 hour to 3 hours is distilled in a chilled publisher. According to gas chromatographic analysis, the distilled amine is so pure that it can be used again for the preparation of the starting base without further reprocessing.

The epoxy resins used simultaneously according to the invention are glycidyl ethers with more than one epoxy group per molecule. They are derived from polyhydric phenols, in particular bisphenols, and novolaks and their epoxide values are between 0.100 and 0.600, but between 7200 and 0.550.

Depending on the amine number and epoxide value, the following mixing ratios are preferably used.

Polyaminoamide hardener Epoxy resin Amintal Epoxide value 50-85 785-115 115-150 O, 200-O, 225 O, 590-O, 44O O, 520-0.550 100 s - - 85-144 s 45-72 e 54-57 s - 100 s - 144-195 s 72-98 s 57-77 s - - 1oo g 195-254 g 98-127 g 77-101 g These mixing ratios can in practice be exceeded and undershot. However, they must be selected so that the printing films thus produced still have good chemical and thermal resistance.

In general, the following requirements are placed on the individual components and on the end product.

The aminoamide must be soluble in aroma-free solvents, the aminoamide must be compatible with the co-used epoxide compounds, adduct A). must be compatible with the adduct B) and the mixture of adducts must be clear both as a physically dried film and as a cured film.

Since the curable synthetic resin systems according to the invention are to be used as binders for printing inks, the individual components are best introduced in the form of their adducts, as the film is physically dry very quickly and the curing also takes place quickly.

For the modern printing process with high printing speeds, this is an important factor.

When only one of the components is introduced as an adduct or adduct is completely excluded - which is generally possible with the simultaneous use of aromatic acid anhydrides - films with the same physical and chemical final properties are obtained.

However, since it takes longer to obtain a physically dry or cured film, this type of insertion is usually preferred for coatings and for printing processes with lower working speeds.

For the synthetic resins used according to the invention, solvents are also selected taking into account the printing process which is used.

.J 'veosßv-a i 12 Thus, for high pressure velocity (rotary pressure) printing processes, rapidly evaporating solvents are used, e.g. mixtures of lower aliphatic alcohols having 2-4 carbon atoms, esters, e.g. acetic acid ethyl ester, -propyl paste -isopropyl ester -butyl ester and -isobutyl ester ketones, e.g. acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone and petrol mixtures with boiling limits between 60 and 160 ° C, but in particular mixtures of ethanol and ethyl acetate.

For printing processes with smaller printing speeds, e.g. solvent printing process, or also for surface coatings, solvents with relatively long evaporation times can also be used, such as the glycol ethers and acetate customary in this field, optionally in admixture with other solvents suitable for the printing processes in question.

With the process according to the invention, inorganic and organic substrates can be printed and coated. Here, the foils customary in the printing industry come into question, e.g. polyamides, polyesters or polyesteramides, heat-sensitive films of e.g. polyethylene and polypropylene, co-spraying films of polyethylene and polypropylene, untreated parts with polymers coated or with nitrocellulose lacquered cellular glass foils, paper, cardboard and possibly polyvinyl chloride or its copolymer, and metal foils, e.g. aluminum foil. Combinations of these materials may also be possible. The coatings can be applied to the materials common in the construction sector, e.g. on concrete, metal, wood and synthetic resins.

Preparation of adducts 1. Hardener adducts a) The polyamine amide hardeners which are used are preferably dissolved as EO% in a solvent or mixture and mixed well with a part of the amount of epoxy resin required for complete curing - likewise preferred - dissolved as äO% in a solvent or mixture.

After the mixture has been allowed to stand for about 2 days at room temperature or the corresponding shorter residence times at elevated temperatures (eg 16 hours at 40%), the pre-reaction is completed and the adduct is ready for use. b) The polyaminoamide hardener to be used is dissolved together with some of the material required for complete curing! 7808137-9 the amount of epoxy resin, preferably 50%, in a solvent or mixture with stirring at room temperature.

After the mixture has been allowed to stand for about 2 days at room temperature or the corresponding shorter residence time at higher temperatures (eg 16 hours at 40 ° C), the pre-reaction is complete and the adduct is ready for use. 2. Epoxy resin adducts a) The epoxy resin to be inserted is preferably dissolved 50% in a solvent or mixture and mixed well with a portion of the amount of polyaminoamide hardener required for complete curing - likewise preferably dissolved 50% in a solvent or mixture. After the mixture has been allowed to stand for about 2 days at room temperature or the corresponding shorter residence time at elevated temperatures (eg about 15 hours at 40 ° C), the pre-reaction is complete and the adduct is ready for use. b) The epoxy resin which is used is dissolved with stirring together with a part of the amount of polyaminoamide / hardener required for complete curing, preferably 50%, in a solvent or mixture at room temperature.

After the mixture has been allowed to stand for about 2 days or the correspondingly shorter residence times at higher temperatures (eg about 15 hours at 4000), the pre-reaction is completed and the adduct is ready for use. e) The epoxy resin which is used is preferably dissolved 50% in a solvent or solvent mixture and mixed well with a part of the amount of hardener adduct required for complete curing according to 1 a) and / or 1 b).

After allowing the mixture to stand for about 2 days at room temperature or correspondingly shorter residence times at elevated temperatures (eg 16 hours at 40 ° C), the reaction is complete and the adduct is ready for use.

The degree of pre-addition is at the individual adducts between 24 parts by weight of polyaminoamide, 24 parts by weight of epoxide resin resp. 1 part by weight of epoxy resin 1 part by weight of polyaminoamide and 78o8137_9 ... W.-11 ..- Uy 15 parts by weight of polyaminoamide 15 parts by weight of epoxy resin resp. 10 parts by weight of epoxy resin 10 parts by weight of polyaminoamide, in particular, however, between 22/5 and 17/8.

This range of pre-reduction for the adduct solutions should suitably not be exceeded, otherwise gelation phenomena can be taken into account for too short a time.

The ideas .the following tables 2 and. The polyaminoamide and epoxy resin components need not be identical in the two adducts but may also vary arbitrarily.

Thus, for the preparation of synthetic resin mixtures, which are ready for use, the individual adduct solutions can be mixed in the following manner; e A) hardener wadduktligt l a) + epo fi dhartsaddukt according to 2 a) B) e "" 'l a) + "" 2 b) c). _ 'nn Ia) + nn "2 c) D) n' nlb) + nn 2 a) E) nn 'lb) + n. n' 2 b) F) nnlb) + nn fa c) .It is preferred on production technology bases .in practice the execution according to G) pretreatment of the synthetic resin mixtures.

Example 1 244 g of polyamine amlanar according to No. 1, Table 1, are dissolved with stirring and slight heating in a mixture of 22 g of ethanol and 22 g of ethyl acetate. To this solution is added and mixed well 12 g of an EO percent solution. a solid bisphenol-A epond resin having an epoxide value of 0.210 in ethanol / ethyl acetate (Izl).

Then let the mixture stand. about 15 hours at 40 ° C, the pre-reaction is complete and the hardener adduct is ready for use. Example 2, 1-10 g of a solid bisphenol-A epoxide resin having an epoxide value of 0.210 is dissolved with stirring and light dripping in a mixture of 20 g of ethanol and 20 g of ethyl acetate. To. this solution is added and mixed well with 20 g of hardener-adduct solution. according to Example 1. After allowing the mixture to stand for about 2 days at room temperature, the pre-reaction is complete and the epoxy resin adduct is ready for use. _! 78Uö10l'7 15 Preparation of tgpk paints After the harder adduct solution and the epoxy resin solution have been prepared, both the one and the other - possibly also both - can be pigmented with the dispersing devices customary in the ink industry. Organic and inorganic pigments and soluble dyes can be used. After the hardener and epoxy resin adducts have been mixed in the correct proportions (see Table 4), the finished inks are diluted according to the requirements of the printing process in question to the correct print viscosity.

A selection of inks thus produced are printed with a commercially available printing machine from roll to roll on polyethylene. Immediately after the evaporation of the solvent, the pressures were physically dry, so that no sticking or copying of the paint could be observed on the back of the rolled-up foil. After the foil was stored for 7 days at room temperature, the prints were subjected to a detailed test, customary in the printing ink industry. The values for the mechanical, chemical and thermal resistance properties are given in Table 5.

Description of the test methods used l. Adhesion The test of the adhesion of the printing films to a printing substrate is performed with Tesafilm strips. 10 glued strips are torn off quickly or slowly. 2. Resistance to scraping The printing films are scraped more or less strongly with the fingernail. 3. Chemical resistance Before the pressure films are stored for 24 hours in the chemicals in question, the mechanical properties of the pressure films were tested and evaluated, such as adhesion, scratch and abrasion resistance immediately after removal from the test medium and after a recovery time of 10 minutes in air. 4. Blookpunkt Folded pressure films are stored under a load of 60 g / cm? with a daily increase in temperature of 10 ° C. The assessment criterion is the temperature at which the films, after development, show the first slight damage. 7a0e.1e37-9i til; Evaluation of the test methods 1-5 very good (objection-free film) good (single, punctate damage) satisfactory (visible damage) sufficient (etor-peeling film skeaer) unsatisfactory (damaged film) mkwruw Evaluation of the test method 4 Indication of the critical temperature. As the determined values show, when using the synthetic resin mixtures according to the invention, better chemical resistance and, above all, a clearly higher thermal resistance (bieek point) were obtained as printing ink binder than via ae in aeg the usual one-component inks (eg based on polyamide resins and / or nitrocellulose). It was also found that the chemical resistance can be further improved when percentage amounts * of the polyaminoamide hardeners according to the invention are replaced by commercially available, at room temperature hardening epoxy resin hardeners (on an amine basis) (see Table 10). i The ratio of the described polyaminoamide hardener Å. I to the commercially available epoxy resin hardeners A II, - IV should be between 10: 1 to 0.5: 1, but preferably between 6: 1 to 2: 1. i Da ae: via ae in henaein the hands occur practically exclusively in liquid products .lämparesig not higher proportions in inks for fast rotary printing machines, otherwise the printing speed - on the basis of the surface tack formed thereby - must be lowered to a level., which. cannot be defended for economic reasons.

On the other hand, in slow-working printing processes, e.g. cloth pressure, and at usual surface coatings the mixing width is increased as given requirements. From the group of typical commercially available epoxy resin hardeners, the products listed in Table 7 a have been tested.

Nan cannot combine all the polyaminoamide hardeners specified according to the invention with the commercially available epoxide resin hardeners. Thus, it has been found that epoxy resin hardeners of type 1-4, Table 7 a, are only compatible with such polyaminoamide hardeners, i.e. gives clear, non-gram / ly solutions, f] i 17 i i ii fi aosdizv-sii which commercially available dimerized fatty acid has been condensed. Hardeners of type 5 - II, table 7 a, can, on the other hand, be combined without difficulty with all the described polyaminoamide hardeners (see table e).

Preparation of hardener adducts (Table 7) c) The polyaminoamide hardener which is used is dissolved together with the commercially available hardener preferably 50% in a solvent or solvent mixture and mixed well with a part of it for complete curing the required amount of epoxy resin - likewise dissolved preferably 50% in a solvent or solvent mixture. After the mixture has been allowed to stand for about 2 days at room temperature or correspondingly shorter residence times at elevated temperatures (eg 16 hours at 4000), the pre-reaction is practically complete and the adduct is ready for use. d) Bone polyaminoamide hardener to be introduced is dissolved by stirring at room temperature together with the commercially available hardener and a part of the amount of epoxy resin required for complete curing, preferably 50% in a solvent or solvent mixture. After the mixture has been allowed to stand for about 2 days at room temperature or correspondingly shorter residence times at higher temperatures (eg 16 hours at 40 ° C), the pre-reaction is practically complete and the adduct is ready for use.

Preparation of epoxy resin adducts (Table 8) Preparation of storage stable epoxide resin adducts can only be accomplished using polyaminoamide hardeners of the invention, as indicated under "Preparation of epoxy resin adducts a + b", since when co-using percentages of commercially available harder an early gel formation the epoxy resin adduct would occur. It is for this reason that the preparation of epoxy resin adducts according to the described "Process e" is not suitable.

The degree of pre-addition in the case of the individual adducts is also between 24 parts by weight of polyaminoamide, 24 parts by weight of epoxide resin resp. 1 part by weight 1 part by weight and J epoxide resin polyaminoamide 15 parts by weight polyaminoamide 15 parts by weight epoxide resin _ resp. g 10 parts by weight of epoxy resin 10 parts by weight of polyaminoamide, however, especially between 22/5 and 17/8.

This area for pre-addition of adduct solutions should not be exceeded, otherwise gel phenomena can be expected in too short a time.

The polyaminoamide and eposd resin components listed in Tables 7 and 8 do not have to be identical in both adducts, but can be varied arbitrarily. ï For the preparation of nenschartsbiananingarnräraigafför use, the individual adduct solutions can then be mixed as follows: A hardener addi fl ct according to lc) + epoxy resin adduct according to 2 a) B nulc) + un 2 b) C unl å) __, un 2 a) DV nnl à ) + uu 2 (b) In the production of synthetic resin mixtures, in practice, for process technical reasons, the embodiment according to L. In particular cases is preferred, it is also possible to prepare mixtures ready for use by combining the epoxy resin adduct with non-fadducted hardener mixture; In these cases, however, one has to reckon with partly significantly lower printing speeds. For normal coatings, however, the delayed surface tack is not of such a decisive importance that a use in this area is always given. This also applies to slow-working printing processes, such as canvas printing.

Example gel of 55 gg polyaminoamide hardener No. 55 (Table 1) and 11 gg of commercially available epochardic hardener No. 6 (Tables) are dissolved with stirring and slight heating together in a mixture of 22 g of ethanol and 22 g of ethyl acetate. To this solution is added and mixed well 12 g of a * 50% solution of a solid bisphenol A epoxide resin with an epoxy value of 0.20 in ethanol / ethyl acetate (121). After allowing the mixture to stand for about 15 hours at 40 DEG C., the pre-reaction is practically complete and the hardener adduct is ready for use. Example 7 42 g of a solid bisphenol A epoxide resin having an epoxide value of 0.210 are dissolved with stirring and slight heating in a mixture of 21 g of ethanol and 21 g of ethyl acetate. To this solution is added and mixed well 16 g of a 50% solution of polyaminoamide hardener No. 55 (Table 1) in ethanol / ethyl acetate (1: 1).

After the mixture has been allowed to stand for about 5 days at room temperature, the pre-reaction is practically complete and the epoxy resin adduct is ready for use.

The combinations listed in Table 9 have been prepared in accordance with Examples 5 and 4 above.

In the following example, the abbreviations listed in Table 1 have the following meanings.

IFD = isophoronediamine AT = amine mp = melting microscope TEVA = tetrahydrophthalic Hhfa = PA = phthalic anhydride hexahydrophthalic BMT = dimethyl terephthalate IFA = isophthalic CPTD = cyklopentantetrakarbonsyradianhydrid DTHEA = dimetyltetrahydroftalsyraanhydrid BTDA = bicyclo [2.2.2] oct-7-en-tetracarboxylic acid dianhydride ETHFA = endometylentetrabydroftalsyraanhydríd DFS = dimeric fatty acid DKMB = 2,6-dimethyl-4-carboxymethylbenzene diacid 1550 = addition product of acrylic acid to unsaturated C18- -monocarboxylic acid ¶ Amines DTA = diethylenetriamine DPTA = dipropylenetriamine DHTA = dihexamethylenetriamine N4-amine-N -l, 2-diaminoethane QNH 7808137 ~ 9 wo wwv w ow.Nvv = w oo. # rv ov wnßmq fi o fl o fl d w oo.oov mo SME I flfl w o lim ». mnhm fl oßnmxaw mm ßmv l fl m fl m oO.wmv O r u fl m flfi ßwsmämø m o0.wßr iv v _ o. . u. ommv No ovv = w om vom mm o mo o ouom fi o w ow, mo onhmq fi o fi owm w oo.oov mv vv w ßowwmm m ~ .o "mo.o onhmqop om o = oæx fl oqox _ rwømnmmn m wo.ow wnhm fl wm fl mwm w oo O o .m mo u mwo m fl hmppwo mnßwqoonoß fi o oov o om = w owwmom mo N mo mnhmpooo Ia fi- Ü _ oonoooho w ow.ovm = m mN.wm ov w. om mo N mo onomopoo mov oo = om mo .a fi o w wm.ov ~ = w mm.om owm .omm mo n mo onhm mov wmv = ä _ l flfi m fl oum w ßN.Orv = w OO.mw wwv _ om mo n mo mnom mvv vmv _ = om w nnonumx | fi onmHhp oxoaoxoo w oo.mNv moßmn fl ooow m oo.ow B oo oov = w mo.oov o1v mMwMM %% wMwwm w æo.oov ow. \ o. wnhmnon fi ßx flfl Nov Nov = oo Now ov xno fl oooawmwo m oo.omm m oov omv = m oo.vom ov mnowq fi o fl o fl m w oo .ovw o oo omv = w om.oom oo = m oo @ oov ß omv oov = w wo.oom oo = o oo oov N om omv omH w vm.væ ~ ov oo onooo fi ooom o oo.oov v Q nwßso fi o < oo «w fl mmm HH o fl aq H oo: <| m>«> om HH mono H onho fl woaowm nwo fiämo flfi ëmh fi on> m æ flfi cuvmm fl mëamm v H fi mßwa 78-08137-'9 A nav vß mm.o "mß.o mwv" vv mm. .o Ham w ~ v.mw w ov. @ øN mo um, o Han w ß @ .m «v wHHwnHmH wNm w oo.ov «wm ww ww mm.o" mß.ø qgn u @ w, mw w ow.ßw «mo u mo | q @ H>» @ a «M @ wm oo.mvv mw M mw mN. o “mß.ø« HmH w @ ß.om w wv. @ mv mo u mo mm ßw m «.o" mß.o ßov ww mw.o “« ß.o sHam | #zw om.mm m @ « .ßvw mo n ß.o: or fi w mm.o ”mß.o wov vw mw.o" mß.o mw ßw mm.o "mß.o nHaw | #zw wß.om w ß @. @@ v mo u mo Hmmm w mß.w@v = w oo.ow mv: cv ww mm.o "« ß.o HHHH m ww. @ mw ßß.w@v mo N mo HH w vv.mwv = w oo.ow mv ww om mm.o “mß.o HHHH w om.vm w ß @. @ mv mo H mo Hmmw w mß.w@v = w oo.om ßv mov vw mm.o" mß. @ Han m wm. & N w @ m. @ Mv mo U m_o qmma ww#.w@v «HHwøHmH @ mw oo.ow wv Oo HšH fi HHH Hmpcm fl QMH Hønnm fi 1wHmaw HH» «> H> Hm HH QHEH H sHs <| m> H> mm HH mHHm H Mmmm Hwwswxm wøHu »Lmw» HoH r HH @ n «H '7808137-9 22 H mn» NH Hm Hß.www Ho; " m, o | HH »» mw mm.wH mn »wnHv« pww m nøMomH ma @oH Hm m Nw.oß ~ Ho H m, o man w ßw.wm m «» wnH @ Hww w oo, omH: à wahm fl onhæx mmH mm w ß @, mHH oH 1 1 | Hun @ n ° sH «w om.ßmH ß: mnhmppww. H Høä fl m. .mnhmnonnæx fi u mmH mm w wH.mHN No “wo« mo mao aan w Hm.HoH LnmHnp «amx @ ø w øo.o: N: w fi hmppmw mw.on@aHw w ow.ßoH woH mm m Ho.wwH u mm. o H om.o mao aan w mm.wm wH »mqHmH @« w oo.mm H: _ mhhm @: H wm w mw. @ mNH mß.on mm.o aan w oo.omH | »HwH H @ aH @ m Hm.wNH Q: HNH moH w mm. @ HN m, o H mo aan w om.mw mnhwH »mmwn @ wm#.å@H mm mHH mm m @@. Hmm mo n ß.o Hmmam w ~ ß.H @. = w oo.omH mm _ mnhmnonhmm fl ø mmH Hm W ow.mmN mN.o H mß.o, azn w @ w.om Lq @ H »HwsmM @@ w oø.øwH mm HB ww w Hm. mmN mo u mo Hmmm w # w.å fi H = w oo.m @ wm Hm Hm m ßm, o: w mw.ou wß.o q fi ma w @ H.mß «nhwnH ° mß @ ww oo1omH ßm NHH å w Éöä md u m6 Häå w Qodm ._ m ådmH ä mm mm w # w.mmm No u wo Hmman w mH.Hß 1 m no.omH mm mm. "mm m omdwm mwo n mo .Ham m mmåö fl mnßwq fl m fl ømm m oo fl o fi mm mmH Hm H w wm.oæw wo n wo Hama w mm.om = w oo1o # H Hm mmH moH m # om @ m mm.o N mß.o. MmH NoH w wm1HßmH mmmo n mßño <@H w Hß. @ M = w oo.mw am QNH ßw w @@. @ m ~ mm.ø n mß.o aan m oø.m @ «H» wqH @ H @ «w oo.o # H <mm F oo.» Hq§n = Hs «H @ _ V | nHms fl 94 n fl omowoww fi mPQo⁇> m> fl> MH HH mnhn Hmmamxm ønhw wnHø »» wwpn0H H HHQQQH 78081374 25 GMBMHU Hm mm I w fl m %%% m oA mnhmppww o, »~ qøm 1 nws fl w w os: må H4 onv fl m fi m HH flfl s fl H nhm M nHH H H fl øpßa “? E0s151- .- 24 Table 2 Häraara-'adaukkar a see example Example Polyaminoamide hardener Epoxy resin Aådulfb- weight-x Type-rr. fold-lx map type Egokia- bsmngens parts (Table 1) parts varde appearance 1 22 1 5 biafaaal A 0.210 clear 2 20 1 5 e "5 0.210 clear 5 17 1 s _" 0.210 clear 4 20 1 5 "" - 0.150 - clear 5 22 2 5 "0.210 clear 6 22 5 5" 0.210 clear 7 '20 5 5 "0.150 clear e 22 4 5" 0.210 clear 9 22 2 5 5 e "0.210 clear 10 20 5 5" 0.210 clear 11 22 e 5 "0.210 clear 12 221 7 _ 5" 0.210 clear 15 22 s 5 "0.210 clear 14 22 9 5" 0.210 clear 15 2-2 10 5 "0.210 clear 16 20 10 5" 0.210 clear 17 22 11 5 "0.210 clear 18 22 11 5" 0.150 clear 19 22 12 5 "0.210 clear 20 22 15 5" 0.210 clear 21 22 14 25 "0.210 clear 22 .22 15 5" 0.210 clear 25 22 'll 5 novolack 0.510 clear 21! - 22 'l 5 bisphenol A 0.210 clear 25 20 4 5 "0.210 clear 20 22 16 5" "0.210 clear 27 22 17 5" 0.210 clear 28 22 18 5 5 "0.210 clear 29 20- 19 5" 0.210 clear 50 22 19 5 "0.210 clear 51 22 20 5" 0.210 clear 52 22 21 5 5 "0.210 clear 55 22 22 5" 0.150 clear 54 22 25 5 "0.210 clear 78028137'9 25 Table 2 continued Example Polyamino amide hardener Epoxy resin ts 2 Addulct- weight -ï Type-no. weight-x Home-type oxide solutions ”parts (Table 1) parts each appearance 55 22 25 5 bisphenol AO, 210 clear ae 22 21+ 3" 0.210 clear 5? 22 25 5 "0, 210 clear 58 20 25 5 “0, 210 clear 59 22 26 5" 0, 210 a clear 40 22 27 5 "O, 210 kl ar 41 22 28 5" O, 210 clear 42 22 29 5 "0, 210 clear 14-5 22 50 5 "0, 150 clear lll! - 22 51 5" 0, 210 clear 45 22 52 5 "0, 210 clear 46 22 55 5" 0, 210 clear 47 22 54 5 f '»0, 210 clear 48 22 55 5 "O, 210 clear 14-9 ^ 20 56 5" 0, 210 clear 50 22 56 5 "O, 210 clear 51 22 56 5" 0, 150 clear 52 22 57 5 "O, 210 clear 5 * 22 38 5" 0, 210 clear 54 22 59 5 "0, 210 clear 55 22 40 5" 0, 210 clear see 22 41 5 "0.210 clear 57 22 4-2 5" 0, 210 clear ss 22 45 3 "0.210 clear 59 22 44 5 "0. 210 clear 60 22 45 5" 0, 210 clear 61 25.4 41 1.6 "0.420 clear 52 25.7 4-1 1.5" 0.550 clear Comparative Example G5 22 46 5 "0, 210 not loose - lig strong erumlis a: All quantity indications relate; to the following solutions containing 50 "70 resin: Solution; i ag Example 1-22, 26-60 = ethanol / ethyl acetate = 1: 1 b Example 25 = ethanol / ethyl acetate / methyl ethyl ketone l-zlzl c) Example 24-25 = ethyl glycol / ethyl glycol acetate = 1: 1 * 1280012137- «29 26 Table 2 Egoxide resin adducts (as 'described in' example 2) Example Epoxy resin. Hardener adduct Adduct solution Yilct-K resin Egoxide weight type component (n) see 1st appearance be11 2) 1 20 bísfe- 0,210 5 l clear 'nol Yes. 2 20 "0, 210 5 2 clear 5" 0, 210 1 5 clear 4 20 "0,150 5 14- clear 5 20" 0 , 210 5 5 clear 6 2 '"0.210 5 6 clear 7 2" 0, 150 5 7 1:12; - 8 20 "0.210 5 8 clear 9 2-" 0.210 5 9 more 10 20 "0, 210 5 10 clear 11 .'20 "0, 210 5 11 clear 12 20" 0, 210 5 12 clear 15 '0 "0.210 5 15 clear 11+ 2" 0.210 5 14 clear 5 _ 20 "0, 210 5 15 clear 16 2 20" 0, 210 5 16 clear l? 20 "0, 210 5 l? clear 12 "0, 150 5 18 Mar 19 2" 0, 210 5 17 clear 20 20 0 f '0, 210 5 20 years 21 20 f' 0.210 5 21 more 22 20 "0.210 5 22 'clear 25 20 novolack O, 510 5 25 clear 2 20 0 Risphenol 0.210 5 21+ more 25 2 20 "0, 210 5 25 clear 26 2“ 0.210 5 26 clear 2? 20 "2 0,210 5 27 aklal '28 20" 0, 210 5 28' clear '29 _ 20 "0.210 5 29 .clear 50 A 2" 0, 210 5 50 clear' 51 20 "0.210 5 31 clear 52 20" ' 0.210 5 52 clear 55 20 "0.150 5 55 clear 54 20" 0, 210 5 54 clear 55 20 "_ 0, 210 5 55 clear -J '7808137-9 Table 5 continued 27 Exem- Epoxide resin Hair adduct Adduct ladle weight resin - Epoxide- weight-x adductnr ningens parts type verde parts (see ta- appearance bell 2) 56 20 bisfe- 0.210 5 56 clear zero A 5? 20 “0.210 5 57 clear 58 20" 0.210 5 58 clear 59 20 "0, 210 5 59 clear 40 2" 0.210 5 40 clear 41 20 "0.210 5 41 clear 42 20 f '0.210 5 42 clear 45 20" 0, 150 5 14-5 clear 44 20 "0.210 5 44 clear 45 20" 0.210 5 45 clear 4-6 20 "0, 210 5 46 clear 47 20" 0.210 5 47 clear 48 20 "0.210 5 48 clear 49 20" 0.210 5 49 clear 50 20 "0.210 5 50 clear 51 20" 0.150 5 51 clear 52 2 "0.210 5 52 clear 55 20" 0.210 5 55 clear 54 20 "0.210 5 54 clear 55 20" 0.210 5 55 clear 56 20 "0.210 5 56 clear 5? 20 "0, 210 5 57 clear 58 20" 0.210 5 58 clear 59 20 "0.210 5 59 clear 60 20" 0.210 5 60 clear 61 19 "0.420 6 61 clear '62 17" 0.550 8 62 clear Comparative example 65 20 bisphen- 0.210 strongly cloudy can not be set before zero A is not useful, as the hardener adduct is not useful All quantity indications refer to the following solutions containing 50% resin: Solution in ag example l-22, 26-62 b example 25 0) Example 24-25 μl II II ethanol / ethyl acetate = 1: 1 / ethyl ethyl ketoacetyl ethyl glycol / ethyl glycol acetate = 1: 1 ethanol / ethyl acetate 7sos21s7- «9 2, Table 47 Mixture ratio of adducts Examples- Hardener- Epoxide- Mixture-, The mixed Non-pigmented adduct resin- ratio of adducts terad pressure- enrite- 6 eaaum: ) 111-27 (Table 2) 1 1 1 2 1 ~ = 1.75 clear “clear 2 2 2 -1 = 1.5" "5 5 5» le = 0.77 "" 4 4 u, 1 = 2 , 1 fl ß 5 å 5 z II I! 6 '6 6 141,5 "" "7 7 7 * 1 = 2,1' H '- ssa 1 - =; 1,75" "9 9 9 l2 = 1,75" "_ 10 .10 10 1 = 1.5 'f' f 11 11 11 1: 1,75 "7" 12 12 12 1: 1,75 fl "15 15 15 1 .: 1,75" fl 14 14+ 14 21 = 1,75 f ' "15 15 15 1: 1,75" "16 16 16 1 = 1,5 e" -fl 17 17 17 1 = 1,75 fl '- 18 16 1s' 1 z 2,4 f' ß 19 19 19 11 = 1,75 "- e" 20 20 20 1 = 1,75 fl 'ff 21 21 21 1 .: 1,5 * - "22 22 22' 1 z 1,5" fl 25 25 25 .1 = 0, 76 * HH 24 24 24 1 = 1,75 ß f- 25 25 25 1: 1,5 "" 26 26 26 1 = 1,5 f '' fl 27 27 'l: 1,75 nn 26 28 28 1 = 1,5 "e" 29 29 29 1 = 1,5 "I '50 50 50 15: 1,75 f' ß 51 51 51 1 = 1,5 ß f '52 V52 52 lz 1,5 uu 55 55 55 "11: 2,4" ß 51+ 54 54, 1 = 1,5 fl °° 55 55 55 1 = 1,5 "fl J 52,7 vsfas fl w-s Table 4 (continued) Eczema- Hardener- Epoxide- Blanänings - The mixed Non-pigmented adduct resin ratio aadduktemas terad pressure- no (ta- adukt appearance film bell 2) m »27 (table 2) 56 56 56 l: 1.5 clear clear 5? 57 '57 1 = 1,75 "" 58 58 58 l: 1,5 "" 59 59 59 l = 1,75 "" 4o 4o 4o 1 = 1,5 "" i 41 41 41 1: 1,75 " "42 42 42 1 = 1,75" fl 45 45 45 l = 2,4 "" 44 44 44 l: 1,5 "" 45 45 45 l = 1,75 "" 46 46 46 lz 1,75 "" '4-7 47 47 1 = 1,75 "" 48 48 48 l = 1,5 "" 49 49 49 1: 1,5 "" 50 50 50 l = 1,75 "" 51 51 51 1: 2, 4 "" 52 52 52 l = 1,75 "" 55 55 55 1: 1,75 "" 54 54 54 1 = 1,75 "" 5 55 55 l 2 1,75 "" 56 56 56 1: 1, 75 "" 57 57 57 l = 1,75 "" 58 58 58 l: 1,75 "" 59 59 59 1 = 1,75 "" 60 60 60 l: 1,75 "" 61 61 62 l: 1, 5 "" 62 61 62 1: 1,5 "" Comparative example 65 does not apply does not occur occurs reversible, does not represent non-grumlifz. lai The mixing ratios can be exceeded and undershot. The mixing conditions must be set so that pressure films with good mechanical, chemical and thermal resistance are obtained. 7808137'9 50 .fi oqmpma fi w fifi WWN .ßmm Hmpmwhm .N.m H «» q «a« .then f O fl O fi hmonm noo flfifl ø flflfl w fl HVW .wnhmm fi pum .mnhmøpow .wmnmw fi NWA fl o> m mum, Mm wuamnø flfi MH fi if umm f PMM al moänm »mw al maaoxmnwm flfi wu al ms .w on the was .Twmamxmmm fi wnmwsmb w O If. OåH Om fl Oå fi Oå fi Om fl OO fl mOH 0 .: Oå fl OOH Oå fl Om fl Oà fl ONH 0 amnw fi unmpmwpuoo fl m ßm mm mm H * 0% åm Hm BN om ß fi à fl m fl QH ^ # H fl mp mm nu nu H H AH H fi wpßpv _ ¶. ... E w fi øu fi mm mad. : A ma w fl HH OH mm ß ¶ @ m å m N ¶ H Hwmawwa dw fl mawwm Pm fi nw vømobwp mon .Hmmmnwnwmw ¶ m .fi wmaøunw 11 780813729 lo 51 Tabêll 6 šïâm ': åâšlïåââšarde epn nrn - \ Ö .. = tolerable - = non-tolerable + 41 Legend: 2/6780 / ll 12 14 15 17 18 7808137-9 52 HHH H »dumowHoM% HwHhvw \ HoMhHwHhpm HHH n» wnwømHhuo \ Hoqmvm æH fl mmñmwM Hß om » MH | H Hwmamxw Ma H wnHnmMH umpnmg M OM @ øn «HHMHunnH HMMHHQWMH @@ n« HHMH HHHH wHm Hwwqmn H @ wH @> Hwn «@wqma wHH = NH oMM.o = HHM MM HM, wH. MH omàfo ._ H n M NuM H MM.wH H: mH = M oHm.o = HHM MM M M.wH MM wH = M oHN.o = H n M MM w M.mH MN MH = M oHm.o = H n M MM w M.MH MM MH = M oHm.o = HHM #. # W w.MH NM MH = M oHw.o = H u M «. # M w.MH MN: H = M oHm. ø = H n M MM M M.wH ww MH = M oHN.o = HHM MM HH M.wH Mm NH = M oHN.o = HHM MM oH M.wH Mm HH = M oHm.o = H n M MM M M.mH M oH = WM oHN.ø = HHM MM M M.wH MH MMM oHN.o = HHM MM M M. @ HMM = M øHw.o = H n M HM M M.wH w .M = M oHN.o = HMM HM M M.MH HM = M oHm.o = H "M MM HM, wH N: M = M oHm.o = H" M .: o. @ M o.wH H: à = M oHm, o = HHM MM N M.wH oi M: M OHNMO: HHNH BHÉH HH N 4 Hon HMHH M oHm.o | @HmHp H "M. @ o. & H o.wH MH HQ. wMnM> Map gMH @ M »MH> Hmm HHMQMMV HMHHH HHMMMMV M Mo al mmmuä mämHoø nuwxomm umunmm wønmH WHmuHmQm @ nmnøH% iff mwcma | wmpMH> HQ one Hmm mnwwQHQmmH @ Mo ©© <| UMH> mvnmnuHRomH x fl wnnmm lsomwnmm GHW flfl ms H MHM © Hws © HsmoqHSmhHom namx al TAC HOQÉQKQ wwg HWSS f ß f ñ al lüäß flfi mm N AHWQÉB a; 7808137-9 Table fza Harder Amine hydrogen equivalent weight l Condensation n product on. base of dimerized fatty acids (DES) and cietethylenetriamine 275 (ratio of amine group carboxyl groups = 1) 2 As il but as amine component triethylenetetramine 257 As il but as amine component a mixture of hydrogenated mono- and dicyanethylated ethylene product 25 of triethylenetetramine and the addition product of acrylic acid 237 to oleic acid 5 As in 2 with increased content of imidazoline 95 6 Condensation product based on monomeric fatty acid and triethylenetetramine 93 7 Tougher based on dipropylenetriamine 28 8 isolated aminaddulct based on an excess of an ethylene and an ethylene 166 bisphenol A epoxy resin having an epoxide value of 0.21 9 Phenol-formaldehyde-trimethylhexamethylenediamine condensation product 74-110 Amine adduct based on an excess of polyalkylene polyamine (Formula I) with simultaneous use of accelerator containing hydroxyl groups and aromatic nuclei ll Hardener based on an aromatic amine lll vslosís fi fíelàw "ä» Epoxide resin adduklaise example 11)] Eczema- Epoxy resin 9 fold? Polyaminoamide hardener Adâukt sluice Resin-Egoxld painter: Type no. Weight of the weight (table 1) parts parts 1 bisfe- O, 210 21 9 4 clear nol1A E "0.210 21 ll 4" 5 "'0.210 21 40 4 "4" 0.210 21 41 4 "¶5" 0.210 21 42 ~ 4 "6" 0.210 21 1 4 "7" 0.210 21 4 4 "s lf" - 0.210 21 5 4 ß 9 "0.210 21 .18 ~ 4 "10" O, 1 210 21 9 44 * "11" 0.210 21 25 4 "12" 10, 210 121 '27 4 "15" 1 0, 210 21 28 4 e "14" 0.210 21 29 4 "15" 0.210 -21; 52 4 "16" 0.210 221 55 4 "17" 0.210 21 2? 4 "18-" 0.210 21 59 4 “19" o, 42o 10, 5 1 -4 * f 20 "0,550 8, š 'l 4 '* A11a ~ Quantity Reference refers to the following solutions containing 50% resin: Solution ia) Examples 1-17 and 19-20 = -ethanol / ethyl acetate =' 1: lb) Example 18 ~ = ethyl glycol / ethyl glycol acetate 1 : 1 1 ,, 1 vaosm-s Table 2 Mixture ratio in the adduct Eczema- Hardener- Epoxide- Mixture- Appearance of pile adduct resin ratio mixed non-pigment- no adduct no adduct terated pressure- (Table 7) (fabeu a) film 1 1 1 l : 1,87 klar klar f 2 2 1: 1,76 "" š 5 5 lz II II 4 4 4 1: 2,13 "" 5 5 5 1: 2,12 "" 6 6 6 1: 2,72 "" 7? 7 l = 5,14 "" 8 8 8 1: 2,90 "" 9 9 9 l = 1,85 "" 10 10 10 l: 5,22 "" ll ll ll 1: 2,69 "" 12 1 "2 1: 2,20" "15 15 1] l: 5,74" "14 14 14 1: 3,05" "15 15 15 1: 5,06" "16 16 16 1: 2,89" " 17 17 1? 1: 2.41 "" 18 13 18 1: 2.98 "" 19 19 19 1: 1.16 "" 20 2: o 1 = 1 "" The landing conditions can be exceeded and undershot. The mixing conditions however, must be inhaled to obtain pressure films with good mechanical, chemical and thermal resistance.56 NIH oN mH oN mH mH HN m | NN | H QNH H “H ON oN oH N | H oN o, N HN mH oN wH m | NN | H omH @ H, H u H NH NH NN | H NH oN NH NN oN NH m | NN | H QNH mN.H u HNNNN | H @ .HN, H NH H, N ß.H NH N NIH QNH H # .N n H BH NH NN | H ß.H ß.H ß, H wH ß.H wH NN | H ONH # ß.mu H MH MH w N | H HN NH o, N: .N HN oN NN | H oHH NN.mu H oH oH m N | H wH ß.H oN oN wH ß.HNN | H QMH Nß.N "H ww NN | H oN @ .H oN oN @ .H w, H m: NN | H QNH mH.N n HNH m N | H m, H mH wH NH NH @ .HNN | H ø: H NH.NNH m MNN | H w, H oN HN NN oN @ .H m | NN | H QNH @ ß. Hmm | N fi Ho | HN> @ | HHmH @ H «HHwaH | NH» »H 1n0N» Ho 1pw> INHNQNHWNN «@ fl @ H. | H @ øHm | wNaHn @ qNHm | @HxoNw nw fi wwumm | s @ »m 7808137-9 F QQMOMHP WOQ Hw fi ñåm fl ww fi OH HHODMÉ

Claims (2)

1. 7808137-'9 37 F 1. Use of hardenable synthetic resin mixtures for coatings and inks for gravure, flexo and canvas printing, consisting of synthetic resin mixtures as binders, characterized by A) a solid synthetic resin component with free amino groups, consisting of an adduct of an epoxy resin and an excess of polyaminoamides, namely of I. solid polyaminoamides having an amine number of 50-200, in particular 50-150, made from aliphatic dicarboxylic acids having 6-15 carbon atoms or their mixtures and optionally of a 2) aromatic and / or araliphatic and / or hydroaromatic dicarboxylic acids, which are optionally alkyl-substituted and their mixtures in amounts of 0.95-0.05 equivalents, assigned to total / carboxyl groups, and optionally of a 5) aliphatic, hydroaromatic and aromatic monocarboxylic acids or monofunctional acids or anhydrides optionally in admixture with a 4) dimeric fatty acids and / or adducts of acrylic acid to In unsaturated fatty acids and / or hepta-decanedicarboxylic acids and in excess of one or more diamines of the general formula I in which R 1 = H or C 35 and H 2 a -CH 2 -NHQ or -C (CH 5) 2 - NH 2, and optionally of b 2) amines of the general formula II HQN-e- (c fl ltx-NH-ay-a in which R represents an alkyl group 'having 1-4 carbon atoms or hydrogen and x is 2-6 and vy is 2 -4, -and of II. aminoamide compounds and / or aminoimidazoline compounds and / or imidazoline group-containing aminoamide compounds having amine hydrogen equivalent weights of 90-500 based on polyallylene polyamines having the general; formula II (see b 2) and / or - of _III. «a) amines of the general formula II or b) amines of the general formulaIII .n. _ (galax-mon ¶ n: in which R represents an alkyl group of 1- 4 carbon atoms or in particular hydrogen and x is 2-6, in particular 2, and / or of IV. For curing epoxy resins. Suitable Mannich bases having at least two reaction-prone amine hydrogen atoms in and consisting of a B) a synthetic resin component with free epoxy groups, consisting of an adduct of the solid polyaminoamides as in A-I) and an excess of an epoxy resin and containing C) aromatics-free solvents and optionally pigments. 2. Use of curable synthetic resin mixtures for coatings and pre-printing inks for gravure, flexo and canvas printing, can be deduced from the fact that in variation of requirement 1 for the adduct A) the use of the amino compounds II - IV is eliminated. 5. Use of curable synthetic resin mixtures for coatings and inks for low-speed printing machines, unless it is indicated that instead of the adducts AI, A. II, A III and A IV optionally use one or more of corresponding to unsupported amine compounds I, II, III and IV, * wherein the amine compounds I are preferably used together with one or more of the components II - IV. 7808137-9 Abstract Use of a two-component binder system for high-speed rotary printing machines as well as slow-moving printing processes and for coatings, which binder system consists of a curable synthetic resin mixture consisting of Component A in the form of a solid synthetic resin component with free amino group which is an adduct of on the one hand an epoxy resin based on polyhydric phenols and / or novolaks and on the other hand an excess of a solid polyaminoamide, prepared from mono- and multifunctional carboxylic acids and diamines as specified in the original claim 1 under A ), I-IV and Component B in the form of a synthetic epoxy component with free epoxy groups, which consists of an adduct of solid polyaminoamides on the one hand, prepared from mono- and multifunctional carboxylic acids and diamines, as stated in the original claim 1 under A) , In and on the other hand an excess of an epoxy resin. The binder system may also contain aroma-free solvents and optionally pigments, thus in the form of a component C.. s ._ «..._.._..__. - ~ «_...__._....-