FI72337B - ANVAENDNING AV HAERDBARA KONSTHARTSBLANDNINGAR SOM BINDEMEDEL FOER TRYCKFAERGER FOER ANVAENDNING VID DJUP- FLEXO- OCH DUKTRYCK - Google Patents

Description

1 72337

Use of curable synthetic resin mixtures as binders for printing inks used in deep, flexographic and silk screen printing

The invention relates to the use of curable synthetic resin compositions as binders for printing inks used in gravure, flexographic and screen printing. The blends consist of epoxy resin / hardener blends and cellulose derivatives.

Especially in recent years, the rapidly increasing demand for packaging materials, especially in the consumer goods and food-10 industries, has made new packaging technology necessary. As a result of this change in packaging technology, the practical requirements for the surface treatments and inks used have also risen rapidly. The thermoplastic binders used so far no longer have the required high temperature resistance for ever shorter closure times or the resistance to water, acids, bases and especially fats and oils required by stricter food laws.

Although the use of two-component paints based on epoxy resin / hardener systems has improved the chemical resistance of coatings, the weight rate is not always high enough in practice. Such systems are described in DE 1 494 525. In order to obtain clear solutions, a relatively large amount of aromatics must be present in addition to solvent 25. However, due to the increasing emphasis on workplace and environmental protection in the foreground recently, the practice requires binders for surface treatments and inks that are highly soluble in aroma-free solvents. The use of aromatics is also not desirable for technological reasons, as this causes the rubber and polymeric image plate used in flexographic printing to swell.

DE-A-2 733 597 and DE-A-2 811 700 describe epoxy resin / hardener mixtures which are soluble in clear aromatic-free solvents and which also largely meet the practical requirements in terms of film properties and chemical resistance.

However, further improvements are desired in terms of printing speed and sealing strength of printing films.

Inks are also known which use large amounts of cellulose derivatives as binders. However, in order to achieve sufficient adhesion to the printable substrate, it is necessary to use thermoplastic resins and / or plasticizers as adhesive media. However, when using these systems, a sufficiently high barrier strength and, above all, chemical resistance are not achieved. Although the use of two-component inks based on cellulose derivatives and isocyanates results in practically good films, the use of these systems is not entirely unproblematic, since they are sensitive to moisture on the one hand and cannot contain hydroxyl groups mainly used in this field. solvents, especially lower alcohols such as methanol, ethanol and isopropanol.

U.S. Patent 2,865,870 describes coatings based on epoxy resin / hardener blends and cellulose aceto-butyrates. This system uses a solution of solid epoxy resin and polyaminoamide (amine hydrogen equivalent weight 237), resulting in no clear films and curing in heat.

It is an object of the present invention to provide hardenable, aromatically-free solvent-soluble binder systems which, after evaporation of the solvents, result in physically dry and clear films which cure at room temperature or at a slightly elevated temperature and have high closures. which can be machined in high-speed printing machines, so that the printing films meet the practical requirements in terms of chemical resistance.

This is done by the present invention. The invention relates to the use of curable synthetic resin compositions as binders for printing inks used in deep, flexographic and screen printing, which, after evaporation of the solvent, form physically dry and clear films, and cure at room temperature or at slightly elevated temperature, the synthetic resin compositions consisting of than one epoxy group per molecule and having an epoxy value of 0.35 to 0.70, and B) cellulose ethers and / or cellulose esters in an amount of 0.5: 1 to 5: 1, expressed as a ratio of epoxy resin / hardener mixture (A + C): cellulose derivatives, and C) one or more amine compounds having at least two reactive amine hydrogen atoms selected from the group consisting of: a) aliphatic polyamines of the formula

15 R '- ^ HN- (CHR) -NH7-R' I

wherein R is alkyl of 1 to 4 carbon atoms, or H, R 'is H or -CH 2 -CH 2 -CN and x is 2-6, b) polyalkylene polyamines of formula 20

H2N4 - (CHR) xNH7y-H II

wherein R is alkyl of 1 to 4 carbon atoms, or H, x is 2 to 6 and y is 2 to 4, c) polyetheramines of the formula

25 H, N- (CH-) -O- (R1-O) (CH) -NH9 III

2 2 nz 2 n 2 wherein n is 3-5, z is 0, 1, 2 or 3 and R is alkylene having 1 to 12 carbon atoms optionally substituted by an alkyl group having 1 to 4 carbon atoms, 30 d) cycloaliphatic polyamines, having the formula 4 72337 _3 R3 4 i_. R · - ° -1 3 4 5 wherein R is H or CH 2 -, R is -CH 2 'and R is alkylene which is the same or different and occurs 0, 1 or 2 times and contains 1 to 3 carbon atoms, e) aminoamide compounds and / or aminoamide compounds containing imidazoline groups having an amine hydrogen equivalent weight of 90 to 175, f) phenol-formaldehyde amine condensation products (Mannich bases) having at least two reactive amine hydrogen atoms, 15 g) of Ca) to Cf ) adducts of the amine compounds according to A) prepared by reacting the excess amine with the glycidyl compounds according to A), D) aromatic-free solvents and optionally E) pigments, dyes, accelerators, reactive thinners, extenders and fluxes.

The invention also relates to a method for printing surfaces. The process is characterized in that the synthetic resin mixtures described above are used as binders.

The invention furthermore relates to a material for printing surfaces, which is characterized in that the synthetic resin mixtures described above are used as binders.

The epoxy resins used according to the invention, which can be used alone or in admixture, are liquid semi-solid aromatic glycidyl ethers containing more than one epoxy group per molecule, derived from polyvalent phenols, in particular bisphenols and Novolakic aliphatic aliphatic aliphatics. derived from aliphatic polyhydric alcohols, in particular ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, tripropylene glycol, glyceryl glycol, tetra-propylene glycol, neon-glycol, nonapropylene glycol, 0.7, especially 0.50-0.6.

In addition to said lower alcohols, commercially available higher molecular weight polyalkylene polyether polyols based in particular on ethylene glycol and propylene glycol can optionally be used to elasticize the epoxy resin. The proportion of these alcohols used is determined by their molecular weight and the desired degree of elasticization of the epoxy resin.

The cellulose derivatives used according to the invention are commercial cellulose ethers and cellulose esters obtained by the reaction of cellulose with alkyl halides (ethers or lower monocarboxylic acids (ester)). Cellulose derivatives with different degrees of substitution are always obtained according to the reaction components.

According to the invention, products soluble in low-boiling organic solvents are preferred, such as, in particular, cellulose ethers such as ethylcellulose having a degree of substitution of 2.15-2.60, in particular 2.42-2.60, cellulose esters such as cellulose acetate having a degree of substitution of 2.2 -2.7, 25 cellulose acetobutyrate with an acetyl content of 2-30.5%, a butyryl content of 15-54% and a hydroxyl group content of 0.45-4.7%, in particular cellulose acetopropionate with an acetyl content of 1.8 -3.6%, propionyl content 40-46.5% and hydroxyl-30 group content 1.6-5.5%.

These cellulose derivatives are used according to the invention in binders for inks in amounts of: epoxy-resin / hardener mixtures (A + C): cellulose derivatives (B) = 0.5: 1-5: 1, in particular 1: 1-3: 1.

The high proportions of cellulose derivatives advantageously affect the fast-drying, non-adherent surfaces, which are absolutely required in high-speed printing machines 6 72337 when printed from one roll to another. However, excessive proportions impair the adhesion of the film to the substrate.

The amount of cellulose derivatives used in printing inks from one roll to another is very limited due to the speed of the printing machine required, while when using the Seri printing method, the range is less critical.

Ethylcellulose and cellulose acetate are not compatible with other cellulose derivatives, but cellulose acetobutyrate and cellulose acetopropionate may also be mixed with each other.

Amine compounds used in the hardeners of the invention include ethylenediamine, propylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, nona-methylenediamine, 1,12-diaminododecane, and the N and N, N'-cyanethylation products of these di-amines; diethylenetriamine, dipropylene triamine, triethylenetetraamine, tetraethylenepentamine, 3- (2-aminoethyl) aminopropylamine, bis- (3-aminopropylethylenediamine; 1,7-diamino-4-oxa-heptane, 1,7-diamino-3,5 -dioxaheptane, 1,10-diamino-4-dioxadecane, 1,10-diamino-4,7-dioxa-5-methyldecane, 1,11-diamino-6-oxaundecane, 1,11-diamino 4,8-dioxa-undecane, 1,11-diamino-4,8-dioxa-5-methyl-undecane, 1,11-diamino-4,8-dioxa-5,6-dimethyl-7-propionyl-undecane, 1,12-diamino-4,8-dioxadodecane, 1,1,3-diamino-4,1O-dioxatridecane, 1,13-diamino-4,7,10-trioxa-5,8-dimethyltridecane, 1,14- diamino-4,11-dioxa-tetradecane, 1,11-diamino-4,7,1O-trioxa-tetradecane, 1,16-diaamino-4,7,10,13-trioxahexadecane, 1, 20-diamino-4,17-dioxa-eicosanane, 1-amino-4- (N-aminopropyl) cyclohexane, 3-aminomethyl-3,5,6-trimethylcyclohexylamine, 4,4'-diaminodicyclohexylamine Methane, 3,3'-dimethyl-4,4'-diaminodicyclohexyl-1-methane-bis- (aminomethyl) cyclo hexane, 1,4-diaminocyclohexane; I! 7,72337 Polyamides and imidazoline-containing polyaminoamides based on mono- and polymeric fatty acids and excess amines with amine hydrogen equivalent weights of 90-175.

Suitable aminoamides containing aminoamides and imidazoline groups are those used in epoxy compounds as hardeners, which are described, for example, in DE patents 972,757 and 1,074,856, DE 1,041,246, 1,089,544, 1,106,495, 1,295,869 and 1,250,918, GB Patent 10 publications 803,517, 810,248, 873,224, 865,656, 956,709, BE Patent 593,299, FR Patent 1,264,244, and U.S. Patent 2,705,223, 2,712,001, 2,881,194, 2,996,478, 3,002,941, 3,062,773 and 3,188,566.

Preferred for use in the invention are proven aminoamides and aminoamides containing imidazoline groups which are prepared by using as component e 1) monocarboxylic acids, such as straight-chain or branched alkylcarboxylic acids having 20 to 22, preferably 18 C atoms, such as especially natural fatty acids, such as palmitic, stearic oil, linoleic, linolenic, tallow fatty acids or e 2) the so-called dimeric fatty acids obtained by polymerizing unsaturated natural and synthetic mono-25 basic aliphatic fatty acids having 16 to 22 carbon atoms, preferably 18 carbon atoms, according to known methods (cf. e.g. DE-A-1 443 938, DE application publication 1 443 968, DE patent publication 2 118 702 and DE-publication publication 1 280 852). The composition of typical commercial poly-30 fatty acids is approximately as follows: 8 72337 monomeric acids 5-15% by weight dimeric acids 60-80% by weight trimeric and higher functional acids 10-35% by weight 5 However, fatty acids may also be used, whose trimeric and higher functional content or their dimer content has been added by suitable distillation methods or fatty acids hydrogenated according to known methods. In addition, 10 e 3) unsaturated higher fatty acids having 16 to 22, in particular 18 carbon atoms or their esters with aromatic vinyl compounds, carboxylic acids obtained by copolymerization (e.g. GB 803 517), or acrylic acid and higher monomeric, 15 16-22 carbon atom-containing fatty acid addition products dicarboxylic acids obtained by carboxylation of unsaturated monomeric fatty acids having 16 to 22 carbon atoms, or e 4) acids prepared by coupling phenol 20 or its substitution products to unsaturated monocarboxylic acids (such as unsaturated monocarboxylic acids, such as DE-A-1,543,754) or to 2,2-bis- (hydroxyphenyl) -valeric acid or addition products consisting of phenol and polycarboxylic acids such as dimeric fatty acids (e.g. U.S. Pat. No. 3,468,920).

The component in question is reacted with polyamines in relation to the amine groups: carboxyl groups => 1.

In general, the acids 30 of the above groups are used separately for condensation with polyamines, but mixtures can also be used. Of particular importance in the art are the polyaminoamides and polyaminoimidazolines of the monomeric or polymeric fatty acids mentioned in e1) and e 2), which can therefore be used as preferred according to the invention.

n 9 72337

The amine components used according to the invention for the preparation of polyaminoamides are polyamines, such as polyalkylene polyamines of the general formula II, such as polyethylene polyamines, such as diethylenetriamine, triethylenetetraamine, polyamethylamine, polyamethylene pentamine, polyamines obtained (Firmenprospekt der BASF AG, 10 1976) or e 6) optionally substituted alkylene polyamines of the general formula I such as ethylenediamine, propylenediamines, butylenediamines, hexylenediamines or two or more of the amines mentioned in e 5) and e 6). According to the invention, the polyamines mentioned in e 5) are preferred.

Preferred aminoamides or aminoamides containing imidazoline groups in accordance with the invention have amine hydrogen equivalent weights of about 90-175.

By Mannich bases in the context of the present invention are meant the reaction products of phenols, formaldehyde and polyvalent amines. Monophenols such as phenol, ortho-, meta-, paracresol, isomeric xylenols, para-tert-butylphenol, para-nonylphenol, β-naphthol, β-naphthol and di- and polyphenols such as resorcinol, hydroquinone, 4,4'-dioxidediphenyl, 4,4'-dioxidediphenyl ether, 4,4'-dioxidediphenylsulfone, 4,4'-dioxidediphenylmethane, bisphenol A, and Novo-30 lakes. condensation products of phenol and formaldehyde.

As the polyvalent amines, the diamines mentioned in C a) and C b) can be used, but in particular hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetraamine and xylylenediamine or mixtures of these amines can also be used. Also suitable are Mannich bases prepared using amine exchange, which are described in DE 2 805 853.

The amine compounds mentioned in C a) to C f) can be formed as a pre-adduct with a part of the epoxy resin required to achieve complete curing. In this case, it is preferred that low-viscous aliphatic and aromatic glycidyl ethers, such as neopentyl glycol glycidyl ether and / or bisphenol-A or F-di-glycidyl ether, are obtained.

Said amine components according to C) can be used both alone and in admixture with each other or with each other.

In this range, the use of conventional alcoholic, phenol-20-containing and amine-containing accelerators is preferred according to the invention when using the hardeners according to C a) to C d) 'and C g) to achieve rapid curing at room temperature. Examples of such compounds are benzyl alcohol, furfuryl alcohol, nonylphenol, para-tertiary butylphenol, dimethylaminomethylphenol and tris- (dimethylaminomethyl) phenol.

If necessary, conventional reactive reactants such as cresyl glycidyl ethers, p-tert-butylphenylglycidyl ethers, phenylglycidyl ethers, alkyl-hexylglycidyl ethers can be further used in the art.

Solvents are also selected for the mixtures used according to the invention, taking into account the printing method used.

tl 11 72337

Thus, for printing processes where the printing press is high (rotational weight), volatile solvents such as mixtures of lower aliphatic alcohols having 1 to 4 carbon atoms, esters such as acetic acid-ethyl, propyl, isopropyl, butyl are used. -, isobutylene ester, ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone.

When using printing methods that require a lower printing speed, such as a batch printing process, solvents with a relatively long evaporation time can also be used, such as glycol ethers and acetates conventional in the art, optionally in admixture with other solvents suitable for the printing process. .

The method according to the invention can be used to print inorganic and organic substrates. Suitable films for the printing industry are those of polyamides, polyesters or polyesteramides, heat-resistant films of polyethylene and polypropylene, co-extrusion films of polyethylene and polypropylene, untreated or polymerised with cellulose, cellulose-treated or nitrocellulose , cardboard products and possibly polyvinyl chloride or its copolymers, as well as metal foils such as e.g. aluminum foils. Combinations of these materials may also be possible. The treatments can also be performed in the construction sector 30 on conventional materials such as concrete, metal, wood, plastics.

12 72337

Preparation of preparations ♦ Epoxy resin preparations a) In a mixture of 10.0 g of ethanol, 27.2 g of ethyl acetate and 37.0 g of 5 acetone is dissolved 15.0 g of Novolakepox resin (epoxy value = 0 , 56) and 10.8 g of cellulose acetopropionate with stirring and gentle heating.

After cooling, the solution is ready for use 10 (Example 16, Table 3).

(a) In a mixture of 50.0 g of ethyl acetate and 10.0 g of methyl ethyl ketone are dissolved 10.5 g of Novolak epoxy resin (epoxy value = 0.56), 10.5 g of bisphenol A epoxy resin (epoxy value 0 , 52), 14.0 g of cellulose propionate and 5.0 g of ketone resin with stirring and gentle heating. After cooling, a ready-to-use preparation is obtained which is somewhat slightly turbid, but has no effect on the gloss of the printing film obtained later.

20 (Example 28, Table 3).

2. Hardener preparations (a) To a mixture of 7.0 g of ethanol, 6.0 g of ethyl acetate and 5.5 g of acetone is dissolved 2.7 g of dipropylene triamine with stirring and finally 3.8 g of bisphenol- Epoxy resin A (epoxy value = 0.52). After heating for 3 hours at 40-50 ° C, cool to room temperature; the hardener solution is then ready for use (Example 16, Table 4).

B) 7.9 g of hardener no. Are dissolved in 17.1 g of ethanol. 13 (Table 2) with stirring; the solution is immediately ready for use (Example 28, Table 4).

Ready-to-use preparations in the correct mixing ratio are obtained if in each case 100 g of the solutions in 35 1 a) or Ib) are added, 25 g of the solutions in 2 a) or 2 b) are added and mixed well.

13,72337 (Examples 16 and 28, Table 5).

In the same way, all the resin and hardener preparations shown in Tables 3 and 4 and the mixtures shown in Table 5 are prepared.

5 Manufacture of inks

Once the epoxy resin solutions are ready, they are pigmented with conventional dispersing equipment in the ink industry. In this case, organic and inorganic pigments as well as soluble dyes can be used in this range in conventional amounts.

After the hardener and epoxy resin components have been mixed in the correct mixing ratio (see Table V), the finished inks are always diluted to the desired printing viscosity in accordance with the requirements of the printing method used.

A variety of inks thus prepared were printed on a commercial printing machine from roll to second polyethylene and aluminum foil. Immediately after evaporation of the solvents, the prints were physically dry, so no adhesion or reproduction of the colors on the back of the rolled film was observed. After allowing to stand for 17 days at room temperature, the prints were subjected to a thorough, conventional test in the ink industry. The values of mechanical, chemical and thermal resistance properties are shown in Tables VI and VII.

Description of test methods used 1. Adhesion 30 Adhesion testing of printing films on the printing medium is performed on TesafilirM film strips. In each case, the ten glued strips are torn off slowly or quickly.

14 72337 2. Scratch resistance

The printing films are more or less severely scratched with a fingernail.

3. Chemical resistance 5 After storage for 24 hours in each chemical, the mechanical properties of the printing films, such as adhesion, scratch resistance and abrasion resistance, are tested as soon as they are removed from the test medium and after 10 minutes. exposed to air and assessed accordingly.

4. Closure strength

The strips about 4 cm wide printed on the aluminum foil are folded against each other and pressed together at a load of 1 kg / cm and a compression time of 1 second at an elevating temperature of 80-250 ° C in a Brugger sealing machine. After cooling, the fold is opened and evaluated.

Test Methods 1-3. evaluation 20 1 very good (membrane sound) 2 good (single, punctate damage) 3 satisfactory (visible damage) 4 adequate (large film damage) 5 inadequate (film destroyed) 25 Evaluation of test method 4 0 completely good 1 rolls, no film damage 2 < 5% membrane damaged 3 <10% "30 4 <25%" "5> 25%" "

II

15 72337

As the values obtained show, the use of the synthetic resin mixtures according to the invention as binders for inks gave very good chemical resistance and, above all, a clearly higher heat resistance (hart-5 tensile strength) than that obtained with the two-component epoxy resin-based inks known to date.

table 1

Epoxy resin components 10 no. rust Description of epoxy resins_Epoxy value 1 A Commercial bisphenol A- 0.52-0.55 epoxy resins liquid 2 A commercial bisphenol A- 0.39-0.44 epoxy resins semi-solid 15 3 A commercial bisphenol F- 0.52-0.55 epoxy resins liquid 4 A commercial Novolak 0.55-0.58 epoxy resins semi-solid 5 A Glycemine commercial 0.65-0.70 2 0 glycidyl ester low viscosity 6 A Neopentyl glycol commercial 0.64-0.70 glycyl ether low viscosity 25 7 A Commercial 0.59-0.64 glycidyl ether of pentaerythritol

8 A

72337 BC

Table 2 Hardener components no. group hardener description Amine hydrogen equivalent weight_ 5 1 C a) KK based on trimethylhexamethylenediamine formulated with alkylphenol 2 C a) KK based on N-cyanoethylated diamine 3 C b) KK based on based on dipropyl-28-trienitrileine 4 C b) K based on tetraethylenepentamine formulated with alkylphenol 5 C b) K based on 3- (2-amino-26-ethyl) -aminopropylamine formulated with alkylphenol ^ 6 C b) KK based on Ν, Ν'-bis (3-aminopropyl) ethylenediamine 7 Cc) KK based on butanediol-ether diamine 8 C d) K based on aminopropyl cyclohexylamine formulated with benzyl alcohol-20-alcohol 9 Cd) KK based on diaminodimethyl-65dicyclohexylmethane 10 C e) Commercial polyaminoamide hardener 166 based on dimer fatty acid polyamine and polyamine 12 C e) Commercial polyaminoamide hardener 93 based on monomeric 2Q fatty acid and polyamine 13 C f) KK, in the form of a Mannich base 76 based on xylenediamine 14 C f) KK, in the form of a Mannich base 74 based on hexamethylenediamine 15 Cg) Hardener adduct based on 83 2 moles of ethylenediamine and 1 mole of 35 bisphenol A diglycidyl ether

II

17 72337

Table 2 (continued) no. Group Description of the hardener Amine hydrogen equivalent weight 5 16 C g) Hardener adduct based on 80 2 moles of dipropylene triamine and 1 mole of bisphenol A-diglycidyl ether 17 Cg) Hardener adduct based on 71 2 moles of dipole polyene diglycidyl ether 18 C g) KK, hardener adduct 111 based on isophorone diamine and bisphenol A with diglycidyl ether, benzyl alcohol and alkyl-15 phenol KK = commercial hardener 18 72337 ti tn

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Table 4 (continued)

Hardener preparations 24 72337 no. Hardener Weight! ! ---- nr> parts Solvents Weight parts (Table 2) --- k-- 14 15 7.0 ethanol '6.0 ethyl acetate 6.0 methyl ethyl ketone 6.0 15 16 16.4 ethanol * 6.6 ethyl acetate 6.0 acetone 6.0 16 17 6.5 ethanol 7.0 ethyl acetate 6.0 acetone 5.5 17 9 6.0 ethanol 11.0 acetone 8.0 18 3 2.4 ethanol - 7.0 ethyl acetate 7, o acetone 8.6 19 18 9.3 ethanol 8.0 methyl ethyl ketone 7.7 20 1 7.6 ethanol 7.4 acetone 10.0 21 11 8.0 ethanol 9.0 acetone gj 0 2 2 13 M, 8 ethanol 20.2 2 3 11 9.7 ethanol 8.3 acetone 7.0 2H \ l> 1 ethanol 18.8 13 M, 5 2 5 18 6.5 ethanol 10.0 13 4.5 acetone 4.0 26 18 6.5 ethanol 3 \ l, 7 16 · 8 | 11 25

Table 4 (continued)

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II

Claims (10)

Use of curable synthetic resin mixtures such as printing ink binders for use in deep, flexo and fabric printing, which, after evaporation of the solvent, form physically dry and clear films and cure at room temperature or at elevated temperatures, where artificial blends A) glycidyl compounds having more than 1 epoxide group per molecule and having an epoxide value of 0.35-0.70, and B) cellulose ethers and / or cellulose esters in an amount of 0.5: 1 - 5: 1, expressed as the epoxy resin ratio / curing mixture (A + C): cellulose derivatives, and C) one or more amine compounds having at least two reactive hydrogen atoms and selected from the group a) aliphatic polyamines of the formula r'-Zhn- (chr) x-nh7-r ' In which R is alkyl radical of 1-4 carbon atoms or H, R 'is H or 20 -C 1 -C 2 -CN and x is 2-6, b) polalkylene polyamines of the formula H 2 N / - (CHR) wherein R is an alkyl of 1-4 carbon atoms or H, x is 2-6 and y is 2-4, c ) polyether arrays of the formula HON- (CH2) -O- (R4 -O) (CH-) -NH_ III 2. 2 n z 2 n 2 Use of curable synthetic resin mixtures according to claim 1, characterized in that glycidyl ether based on novolacs having an epoxide value of 0.50-0.60 is used as glycidyl compounds according to point A). Use of curable synthetic resin mixtures according to claim 1, characterized in that monocyanethylated trimethylhexamethylenediamine, dipropylenetriamine, 1,12-diamino-4,1-dioxadodecane, isophorone diamine, aminoamide based on a C are used as amine compounds according to point C) β-monocarboxylic acid and tetraethylene pentamine, aminoamide based on dimerized fatty acid and triethylenetetramine or Mannich bases based on phenol, formaldehyde and trimethylhexamethylenediamine or p-tert-butylphenol, formaldehyde and trimethylhexamethylenediamine and xylenediamine. 3 R3 4 72337 'r50 · r5' Use of curable synthetic resin mixtures according to claim 1, characterized in that, as resin-hardener mixtures, mixtures consisting of 37 7 2 3 37 A) novolac glycidyl ether having an epoxide value of 0.55-0.57 and B) cellulose acetopropionate are used. amount of 1: 1 - 1: 3, calculated on the epoxide resin / hardener amount, and Use of resin-hardener mixtures according to claim 4, characterized in that as a hardening agent according to point C) a mixture of dipropylenetriamine (amine hydrogen equivalent weight 28) and a Mannich base based on p-tert-butylphenol is used. , formaldehyde and trimethylhexamethylenediamine and xylylenediamine (amine hydrogen equivalent weight 76). C) an adduct consisting of neopentyl glycol glycidyl ether and dipropylenetriamine having an amine hydrogen equivalent weight of 71. Wherein R is H or CH 2 -, R is "CH 2 - and R is the alkyl, which is the same or different and occurs Π, 1 or 2 times and contains 1-3 carbon atoms, e) aminoamide compounds and / or aminoamide compounds containing imidatazole groups having an anine hydrogen equivalent weight of 90-175; f) phenol-formaldehyde-amine condensation products (Mannich bases) having at least two reactive amine hydrogen atoms; g) adducts of amine compounds of points Ca) -15 Cf) by reacting amine in excess with glycidyl compounds according to paragraph A), D) aromatically free solvents and optionally E) pigments, dyes, accelerators, reactive diluents, diluents and emulsifiers. Use of resin-hardener mixtures according to claim 4, characterized in that as a hardening agent a mixture consisting of an adduct of isophorone diamine and bisphenol-A-diglycidyl ether (epoxide value 0.52) with benzyl alcohol and nonylphenol is used as accelerator. wherein the amine hydrogen equivalent weight of the mixture is 111, and one The Mannich base is based on p-tert-butylphenol, formaldehyde and trimethylhexamethylenediamine and xylylenediamine (amine hydrogen equivalent weight 76). Use of resin-hardener mixtures according to claim 4, characterized in that a mixture consisting of an adduct of isophorone diamine and bisphenol A-diglycidyl ether (epoxide value 0.52) with benzyl: alcohol and nonylphenol as an accelerator, the amine hydrogen equivalent weight of the mixture being 111 and dipropylenetriamine. Use of resin-hardener mixtures according to claims 1-7, characterized in that cellulose acetopropionate is used as cellulose components according to point B). 9. A method of printing surfaces, characterized in that as an adhesive, an artificial resin mixture is used according to any of claims 1-8.