NO812902L - APPLICATION OF HARDWARE ARTIFICIAL RESISTANT MIXTURES IN SURFACE COATING AND PRINT - Google Patents

Description

The invention relates to the use of curable synthetic resin mixtures for surface coatings and for printing inks for gravure printing, flexo printing and screen printing, consisting of epoxy resin/hardener mixtures and cellulose derivatives.

Especially in recent years, the strongly increasing need for packaging materials, especially in the consumer goods and food industry, has necessitated changes in packaging engineering. Due to these changes in packaging technology, the requirements for the coatings and printing inks used have also increased rapidly in practice. The necessary high temperature resistance for the increasingly shorter sealing times used, and the resistance to water, acids, bases and especially fats and oils required due to the stricter food laws, are no longer demonstrated sufficiently.

suitable degree of the hitherto used thermoplastic binders.

When using two-component pressure hosts on the basis

of epoxy resin/hardener systems, the chemical resistance of the coatings was indeed improved, but still the printing speed is not always sufficiently great for practical use. Systems of this type are described in DE-AS 1 494 525. In order to obtain clear solutions, the solvent must also contain a relatively large proportion of aromatics.

However, due to the considerations that have to be increasingly taken into account in recent times for the protection of workplaces and surroundings, binders for coating materials and printing inks that dissolve well are required in practice.

even in aromatic-free solvents. The use of aromatics is also undesirable for technological reasons, as this can lead to swelling of the wood. flexo printing used rubber and polymer clichés.

In DE-AS 2 733 597 and DE-OS 2 811 700, epoxy resin/hardener mixtures are used which are clearly soluble in aromatic-free solvents, and which to a large extent also satisfy the practical requirements with regard to film properties and chemical resistance. With regard to press-

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speed and with respect to the sealing strength of the printed film, however, improvements are still desirable.

The known technique also includes printing inks that contain a greater proportion of cellulose derivatives as binders. In order to achieve sufficient adhesion to the substrate being printed, however, it is necessary at the same time to use thermoplastic resins and/or binders as adhesion-promoting agents. With these systems, however, it is not possible to achieve sufficiently high sealing strength and, above all, not sufficiently high chemical resistance. Two-component printing hosts based on cellulose derivatives and isocyanates do indeed produce good films in practice, but the application of

these systems are not completely problem-free, as on the one hand they are sensitive to moisture and on the other hand do not allow the use of the hydroxyl group-containing solvents mainly used in this area, especially the lower alcohols, such as methanol, ethanol and isopropanol.

US Patent No. 2,865,870 describes coating agents based on epoxy resin/hardener mixtures and cellulose acetobutyrates. In this system, a solution of a solid epoxy resin and a polyaminoamide with an amine hydrogen equivalent weight of 237 is used, which does not produce clear films and must also be heat-cured.

The task that formed the basis of the present invention was to provide hardenable, in aromatic-free solvents well-dissolvable binder systerns which, after draining off the solvent, give physically dry and clear films, which harden at room temperature or slightly elevated temperature, which exhibit great strength <g>ling strength, and which can be used in fast-working printing machines, forming coatings or printed films that satisfy the requirements of the time. requirements with regard to chemical resistance.

This task is solved according to the invention by using curable synthetic resin mixtures as a binder in surface coatings and in printing inks for gravure printing, flexo printing and screen printing, which synthetic resin mixtures consist of: A. Glycidyl compounds with more than one epoxy group per

molecule and epoxy values from 0.35' to 0.70, and

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B. cellulose ethers and/or cellulose esters, and

C. one or more amine compounds with at least two reactive amine hydrogen atoms, selected from

a) aliphatic polyamines of the general formula

where R is an alkyl group with 1-4 carbon atoms or hydrogen, R' is hydrogen or the group -Cr^-CI^-CN, and x is a number from 2 to 6, b) polyalkylene polyamines of the general formula

where R is an alkyl group with 1-4 carbon atoms

or hydrogen, while x is a number from 2 to 6 and y is a number from 2 to 4, and

c) polyetheramines of the general formula

where n is a number from 3 to 5, z is 0, 1, 2

or 3, and R is an alkylene group with 1-12 carbon atoms, which may optionally be substituted with an alkyl group with 1-4 carbon atoms,

d) cycloaliphatic polyamines of the general formula

2 where R is a group 3 4 where R is hydrogen or CH_-, R is -CH - and R 5 is an alkylene group, as this may or may not be the same for the two substituents R^, and may be 0 , 1 or 2 times and may contain 1-3 carbon atoms, e) aminoamide compounds and/or imidazoline group-containing aminoamide compounds with amine hydrogen equivalent weights from 90 to 175, f) phenol-formaldehyde-amine condensation products (Mannich bases) with at least two reactive amine hydrogen atoms,

g) adducts of amine compounds according to Ca) - Cf), produced by reacting an excess of

amine with glycidyl compounds according to A),

D) aromatic-free solvents and possibly

E) pigments, dyes, accelerators, reactive diluents, fillers and flow agents.

The invention further relates to a method for coating or printing surfaces, which method is distinguished by the fact that synthetic resin mixtures are used as binders in accordance with the requirements.-

Furthermore, the invention relates to an agent for use in the method of coating or printing surfaces, which agent is distinguished by the fact that it contains synthetic resin mixtures as a binder in accordance with the requirements.

The epoxy resins used according to the invention, and which can be used individually or in mixture with each other, are liquid to semi-solid aromatic glycidyl ethers, with more than one epoxy group per molecule, which is derived from polyhydric phenols, especially bisphenols, such as novolaks, or liquid aliphatic glycidyl ethers derived from aliphatic polyhydric alkanols, especially ethylene glycol, propylene glycol, butylene glycol, dipropylene glycol, tripropylene glycol, tetrapropylene glycol, nonapropylene glycol, tetraethylene glycol, neopentyl glycol, glycerol, pentaerythritol and whose epoxide values lie between 0.30 and 0.7, especially between 0.50 and 0.6.

For softening the epoxy resin, commercial higher molecular weight polyalkylene polyether polyols based on ethylene glycol and propylene glycol in particular can be used in addition to the aforementioned short-chain alkanols. The proportion of these simultaneously used alkanols depends on their molecular weight and the desired degree. of softening of the epoxy resin.

The cellulose derivatives used according to the invention are commercial cellulose ethers and cellulose esters obtained by reacting cellulose with alkyl halides (ethers) or lower monocarboxylic acids (esters). The cellulose derivative's degree of substitution will vary with the ratio between the reaction components.

Particularly preferred according to the invention are the products which are soluble in lower-boiling organic solvents, such as in particular: Cellulose ethers, such as ethyl cellulose with a degree of substitution of 2.15 - 2.60, preferably 2.42 - 2.60, cellulose esters, such as cellulose acetate, with a degree of substitution of 2.2 - 2.7,

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%, but especially

cellulose acetopropionate with an acrylic content of 1.8 -

3.6%, a propionyl content of 40 - 46.5% and a hydroxyl group content of 1.6-5.5%.

In the preferred application according to the invention, these cellulose derivatives are used in printing ink binders in quantities corresponding to a quantity ratio epoxy resin/hardener mixture (A+C): cellulose derivative (B) of from 0.5:1 to 5:1, especially from 1: 1 to 3:1.

Large proportions of cellulose derivatives have a beneficial effect in the direction of fast-drying, stick-free surfaces, as is absolutely necessary when using fast-running printing machines1 when the pressure is from roll to roll. Too large a proportion, however, impairs the film's ability to adhere to the substrate.

The amount of cellulose derivatives used in printing inks in roll-to-roll printing is limited within narrow limits due to the 'printing speed required,

while the area is less critical with the screen printing method..^j .

In the case of the equally possible use according to the invention as coating agents and surface coating agents, which can be applied either mechanically or manually, a spontaneous freedom from surface adhesion is not always necessary or desired, so that the proportion of cellulose derivatives can be adapted to the requirements required by the application, which means that proportions from 10:1 to 15:1 are fully applicable.

While ethylene cellulose and cellulose acetate are not compatible with other cellulose derivatives, cellulose acetobutyrate and cellulose acetopropionate can also be mixed with each other.

The amine compounds used as curing agents according to the invention are: ethylenediamine, propylenediamine, hexamethylenediamine, trimethylhexamethylenediamine, nonamethylenediamine, 1,12-diaminododecane, as well as N- and N,N'-cyanoethylation products of these diamines, diethylenetriamine, dipropylenetriamine, triethylenetetramine, tetraethylenepentamine, 3-(2-aminoethyl)-aminopropyleneamine, bis-(3-aminopropyl)-ethylenediamine; 1,7-diamino-4-oxa-heptane, 1,7-diamino-3,5-dioxa-heptane, 1,10-diamino-4,7-dioxa-decane, 1,10-diamino-4,7- dioxa-5-methyl-decane, 1,ll-diamino-6-oxa-undecane, 1,ll-diamino-4,8-dioxa-undecane, 1,ll-diamino-4,8-dioxa-5-methyl- undecane, • 1,12-diamino-4,8-dioxa-5,6-dimethyl-7-propionyl-undecane, 1,12-diamino-4,9-dioxa-dodecane, 1,13-diamino-4,1O -dioxa-tridecane, 1,13-diamino-4,7-trioxa-5,8-dimethyl-tridecane, 1,14-diamino-4,11-dioxa-tetradecane, .1,14-diamino-4,7, 10-trioxa-tetradecane, 1,16-diamino-4,7,10,13-tetra-oxa-hexadecane, 1,20-diamino-4,17-dioxa-eicosane; 1-amino-4 (γ-aminopropyl)-cyclohexane, 3-aminomethyl-3,.5,5-tri-methyl-cyclohexylamine, 4,4'-diaminodicyciohexy 1-methane, 3,3'-"dimethyl-4, 4<1->diaminodicyclohexy1-methane, bis-(aminomethy1)-cyclohexane, 1,4-diamino-cyclohexane; polyamides and polyaminoamides containing imidazoline groups based on monofatty acids and polymeric fatty acids and an excess of amines with amine hydrogen equivalent weights of 90 - 175. Suitable aminoamides and Aminoamides containing imidazoline groups are the compounds which are used in practice according to the known technique as curing agents for epoxy compounds, and which are known, for example, from German patent documents no. 972-757 and 1,074,856, German explanatory documents no. 1,041,246, 1,089,544, 1,106,495, 1,295,869 and 1,250,918, British Patent Nos. 803,517, 810,248, 873,224, 865,656 and 956,709, Belgian Patent No. 593,299, French Patent No. 1,264,244 and US patent documents no. 2,705-223, 2,712,001, 2,881,194, 2,966,478, 3,002,941, 3,062,773 and 3,188,566.

The amino amides and imidazoline group-containing amino amides which are produced by reacting: e (1) monocarboxylic acids, such as straight-chain or for- branched alkylcarboxylic acids with 16 - 22 carbon atoms, preferably with 18 carbon atoms, such as in particular the naturally occurring fatty acids such as palmitic acid, stearic acid, oleic acid, linoleic acid, linolenic acid and tall oil fatty acid, or

e (2) those by polymerization of unsaturated naturally occurring and synthetic monobasic aliphatic fatty acids with 16 - 22 carbon atoms, preferably 18

carbon atoms, so-called dimeric fatty acids that can be produced by known methods (cf. e.g. German publication documents no. 1 443 938

and 1,443,968, German Patent Document No. 2,118,702

and German interpretation document no. 1 280 852). Typical commercially available polymerized fatty acids have approximately the following composition: monomeric acids 5-15% by weight dimer acids 60-80% by weight trimers and higher functional

functional acids 10-35% by weight However, other fatty acids can also be used, whose content of trimers and higher functional

acids or whose content of dimers has been enriched through suitable distillation methods, or fatty acids which have been hydrogenated according to known methods, or

e (3) carboxylic acids obtained by copolymerization of unsaturated higher fatty acids with 16 - 22 carbon atoms, especially 18 carbon atoms, or of their esters with aromatic vinyl compounds (see e.g. British Patent Document No. 803 517) or of d.ijuy carboxylic acids obtained from from the addition products of acrylic acid with higher monomeric fatty acids with

16 - 22 carbon atoms, which are obtained by carboxylation of unsaturated monomeric fatty acids with 16 - 22 carbon atoms, or

e (4) acids produced by the addition of phenol or substitution products of phenol to unsaturated monocarboxylic acids such as hydroxyphenylstearic acid (see e.g. German publication no. 1 54 3 754) or 2,2-bis-(hydroxyphenyl)- valeric acid, or addition products of phenol

• and polycarboxylic acids, such as dimeric fatty acids

(see e.g. US Patent No. 3,468,920)

with polyamines in a quantity ratio between amine groups and carboxyl groups that is greater than 1.

Usually the acids in the above-mentioned groups are used individually in the condensation with the polyamines, but mixtures can also be used. The polyaminoamides and polyaminoimidazolines of the monomeric and polymeric fatty acids mentioned under points e (1) and 2 (2) have gained particular importance in the field, and these are therefore preferred for use according to the invention.

As amine components which, according to the invention, are used for the production of the polyaminoamides, polyamines such as

e (5) polyalkylene polyamines of the general formula II, such as polyethylene polyamines, such as e.g. diethylenetriamine, triethylenetetramine, tetraethylenepentamine, or polypropylene polyamine,

as well as the polyamines obtained by cyanoethylation of polyamines, especially of ethylenediamine, with subsequent hydrogenation (brochure from BASF AG, 1976) or

e (6) optionally substituted alkylene polyamines of

the general formula I, such as ethylenediamine, propylenediamine, -butylendiamine))---hexylendiamine and mixtures of two or more of the amines mentioned under items e(5) and 2(6). It is preferred to use the polyamines mentioned under point e(5).

The amino amides and imidazoline group-containing amino amides preferred according to the invention have amine hydrogen equivalent weights of from 90 to 175.

In connection with the invention, Mannich bases are understood as reaction products of phenols, formaldehyde and polyvalent amines. Monophenols can be used as phenols, such as phenol, ortho-, metha- and para-cresol, the isomeric xylenols, para-tert-butylphenol, para-nonylphenol, α-naphthol. (3-naphthol, as well as di- and polyphenols such as resorcinol, hydroquinone, 4,4<1->dioxy-diphenyl, 4,4'-dioxydiphenylether, 4,4'-dioxydiphenylsulfone, 4,4<1->di- oxyphenylmethane and bisphenol A, as well as the condensation products of phenol and formaldehyde designated as novolaks.

As polyvalent amines, the diamines mentioned under points Ca) and C b) can be used, but in particular hexamethylenediamine, trimethylhexamethylenediamine, diethylenetriamine, triethylenetetramine and xylyenediamine and mixtures of these amines. The Mannich bases produced by amine substitution which are described in German publication no. 2 805 853 are also suitable.

The amine compounds mentioned under points Ca)-Cf) can be pre-adducted with part of the quantity of epoxy resin required for complete curing. For this purpose, the lower-viscosity aliphatic and aromatic glycidyl ethers are preferably used, such as neopentyl glycol diglycidyl ether or bisphenol-A-diglycidyl ether or bisphenol-F-diglycidyl ether. The degree of adduction is determined from the amine and epoxy resin components used in each case and is regulated so that the total mixture produces clear films.

The components mentioned under point C) can be used as

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either individually or in a mixture with each other.

Use of the alcoholic, phenolic and amine accelerators common in this area is preferred according to the invention when using the curing agents according to points Ca) -Cd) and C g) to achieve faster curing at room temperature. Such compounds are e.g. benzyl alcohol, furfuryl alcohol, nonylphenol, para-tert-butylphenol, dimethylaminomethylphenol and tris-(dimethylaminomethyl)phenol.

If necessary, one can also use the common reactive diluents in the field, such as cresyl glycidyl ether, p-tert-butylphenyl glycicyl ether, phenyl glycidyl ether, alkyl hexyl glycidyl ether.

For the mixtures used according to the invention, the solvent is also selected taking into account the printing method to be used.

Thus, in printing methods with a high printing speed (rotational printing), rapidly evaporating solvents are used, such as mixtures of lower aliphatic alcohols with 1-4 carbon atoms, esters, such as acetic acid ethyl ester,

-propyl ester, -isopropyl ester, -butyl ester and -isobutyl ester

and ketones, such as acetone, methyl ethyl ketone, methyl isobutyl ketone and methyl n-butyl ketone.

For printing methods with a low printing speed, such as e.g. with the screen printing method, and likewise with surface coating/ you can also use solvents with a relatively long evaporation time, such as the glycol ethers and -acetates common in this area, possibly in a mixture with other solvents suitable for the chosen printing method.

By means of the method according to the invention can

both inorganic and organic substrates are printed or coated. These are foils common in the printing industry

of e.g. polyamides, polyesters or polyester amides, heat-sensitive foils of e.g. polyethylene and polypropylene, coextrusion foils of polyethylene and polypropylene, untreated or coated with polymers or varnished with nitrocellulose cellulose glass foils, paper, cardboard and possibly polyvinyl chloride and its copolymers, as well as metal foils, such as e.g. aluminum foils. Optionally, combinations of these materials can also be used. Coating can be carried out on the materials common in the construction sector, such as e.g. concrete, metal, wood and plastics.

Production of the materials

1. Epoxy resin materials

a) In a mixture consisting of 10.0 g of ethanol, 27.2 g of ethyl acetate and 37.0 g of acetone, 15.0 g of novolak epoxy resin (epoxy value = 0.56) and 10.8 g of cellulose acetopropionate are dissolved under stirring and weak heating.

After cooling, the solution is ready for use

(Example 16, Table 3).

b) In a mixture consisting of 50.0 ethyl acetate and 10.0 g of methyl ethyl ketone, 10.5 g of novolak epoxy resin

(epoxide value = 0.56), 10.5 g bisphenol-A epoxy resin (epoxide value = 0.52) 14.0 g cellulose propionate and 5.0 g ketone resin dissolved under stirring and gentle heating. After cooling, a finished mixture is obtained

for use, and which exhibits a slight haziness, which, however, does not have any influence on the gloss of the finished printed film (Example 28, Table 2).

2. Curing Materials-

a) In a mixture consisting of 7.0 g of ethanol, 6.0 g of ethyl acetate and 5.5 g of acetone, 2.7 g of dipropylene triamine is dissolved while stirring, after which 3.8 g of bisphenol-A epoxy resin is added (epoxy value = 0, 52). After heating for 3 hours at 40 - 50°C, the mixture is cooled to room temperature. The hardener solution is then ready for use (example 16, table 4). b) 7.9 g hardener no. 13 (table 2) is dissolved in 17.1 g of ethanol while stirring. The solution is immediately ready for use

use (Example 28, Table 4).

Ready-to-use mixtures with the correct mixing ratio are obtained when 25 g of the solutions according to respectively 2a) and 2b) are added to 100 g of the solutions according to respectively la) and lb) and mixed well (examples 16 and 28, table 5).

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All of them are produced in a similar way

Tables 3 and 4 listed resin and hardener materials and Table 5 listed mixtures.

Production of printing inks

After the final production, the epoxy resin solutions are pigmented using dispersing devices common to the printing ink industry. For this purpose, organic and inorganic pigments and 'H' f. II can also be used soluble dyes in the usual quantities in this area. After mixing the hardener component and the epoxy resin component in the correct mixing ratio (see table V), the finished printing inks are diluted to the viscosity required by the printing method to be used.

With a selection of the thus produced printing inks, printing was carried out with a commercial printing machine

on polyethylene and aluminum foil from roll to roll. The prints were physically dry as soon as the solvent had evaporated, so that no adhesion or smearing of the printing ink to the back of the rolled foil was observed. After resting for 7 days at room temperature, the prints were subjected to an extensive test, common in the printing ink industry. The values for the mechanical, chemical and thermal resistance properties are listed in tables VI and VII.

Description of the test methods used

1. Adhesion strength

The determination - of the strength of the adhesion of printing films to a substrate was made with "Tesafilm" strips.

In each case, 10 adhered strips were quickly or slowly torn off.

2. Scratch resistance

The printing films were scratched more or less strongly with the fingernail.

3. Chemical resistance

After resting for 24 hours in the chemical in question, the printing film's mechanical properties, such as adhesion and resistance to scratching and scrubbing, are examined directly after removal from the test medium and likewise after a 10-minute residence time in air.

4. Resistance to sealing

About. 4 cm wide strips of print on aluminum foil

are folded pressure side to pressure side and sealed against each other at temperatures rising from 80° to 250°C in a Brugger automatic sealer using a pressure load of 1 kg/cm 2 and a sealing time of 1 second. After cooling<1> unfolding and assessment is carried out.

Assessment by test methods 1-3

1 very good (film without blemishes)

2 good (isolated, punctate damage)

3 satisfactory (obvious damage)

4 sufficient (large areas of the film damaged)

5 insufficient (film damaged)

Assessment by test method 4

0 the film absolutely flawless

1 crackling, but no damage to the film

2 less than 5% of the film damaged

3 less than 10% of the film damaged

4 less than 25% of the film damaged

5 more than 2 5% of the film damaged

As the indicated values show, when using the new synthetic resin mixtures as printing ink binders, very good chemical resistance was achieved and, above all, clearly better heat resistance (resistance to sealing) than for the previously known two-component printing inks based on epoxy resin..

Claims (10)

1. Use of hardenable synthetic resin mixtures as a binder in surface coatings and in printing inks for gravure printing, flexo printing and screen printing, which synthetic resin mixtures, (jH| • consist of: A. Glycidyl compounds with more than one epoxy group per molecule and epoxy values from 0.35 to 0.70, and B. cellulose ethers and/or cellulose esters, and C. one or more amine compounds with at least two reactive amine hydrogen atoms, chosen among) aliphatic polyamines of the general formula where R is an alkyl group with 1-4 carbons atoms or hydrogen, R' is hydrogen or the group -CH2 -CH2 -CN, and x is a number from 2 to 6, b) polyalkylene polyamines of the general formula where R is an alkyl group with 1-4 carbon atoms or hydrogen, while x is a number from 2 to 6 and y is a number from 2 to 4, and c) polyetheramines of the general formula where n is a number from 3 to 5, z is 0, 1, 2 i or 3, and R''" is an alkylene group of 1 -.12 carbon atoms, which may optionally be substituted with an alkyl group with 1-4 carbon atoms, d) cycloaliphatic polyamines of the general formula where R 2 is a group VI i 3 4 where R is hydrogen or CH^ -, R is ~ CE^~ and R^ is an alkylene group, since this can be the the same or not for the two substituents R, and can be present 0, 1 or 2 times and can in hold 1-3 carbon atoms, e) aminoamide compounds and/or imidazoline group-containing aminoamide compounds with amine hydrogen equivalent weights from 90 to 175, f) phenol-formaldehyde-amine condensation products (Mannich bases) with at least two reactive amine hydrogen atoms, g) adducts of amine compounds according to Ca) - Cf), produced by reacting an excess of amine with glycidyl compounds according to A), D) aromatic-free solvents and possibly E) pigments, dyes, accelerators, reactive diluents, fillers and flow agents. 2. Use of curable synthetic resin mixtures according to claim 1, characterized by the fact that glycidyl ethers based on novolaks with epoxy values from 0.50 to 0.60 are used as glycidyl compounds according to point A). 3. Use of curable synthetic resin mixtures according to claim 1, characterized in that monocyanoethylated trimethylhexamethylenediamine, dipropylenetriamine, 1,12-diamino-4,1-dioxa-dodecane, isophoronediamine, aminoamide based on a C1-g-monocarboxylic acid and tetraethylenepentamine, aminoamide based on of dimerized fatty acids and triethylenetetramine or Mannich bases based on phenol, formaldehyde and trimethylhexamethylenediamine or p-tert-butylphenol, formaldehyde and trimethylhexamethylenediamine and xylylenediamine. 4. Use of curable synthetic resin mixtures according to claim 1, characterized in that as resin/hardener mixtures, mixtures of A) novolak glycidyl ether with an epoxide value of from 0.55 to 0.57 and B) cellulose acetopropionate in an amount of from 1:1 to 3:1, calculated on the basis of epoxy resin/hardener amount, and C) an adduct of • neopentyl glycol glycidyl ether and dipropylene triamine with an amine hydrogen equivalent weight of 71. 5. Use of resin/hardener mixtures according to claim 4, characterized in that a mixture of dipropylenediamine (amine hydrogen equivalent weight 2 8) and the Mannich base of p-tert-butylphenol, formaldehyde and trimethylhexamethylenediamine and xylylenediamine (amine hydrogen equivalent weight 2 4) is used as the curing agent according to point C). in 6. Use of resin/hardener mixtures according to claim 4, characterized in that a mixture of an adduct of isophoronediamine and bisphenol-A-diglycidyl ether (epoxide value 0.52) with benzyl alcohol and nonylphenol as an accelerator is used as the curing agent, with an amine hydrogen equivalent weight for the mixture of 111, and the Mannich base of p-tert-butylphenol, formaldehyde and trimethylhexamethylenediamine and xylylenediamine (amine hydrogen equivalent weight 2 4) . 7. Use of resin/hardener mixtures according to claim 4, characterized in that a mixture of an adduct of isophoronediamine and bisphenol-A-diglycidyl ether is used (epoxide value 0.52) with benzyl alcohol and nonylphenol as accelerator and an amine hydrogen equivalent weight of the mixture of 111, and dipropylene triamine. 8. Use of resin/hardener mixtures according to claims 1 - 7, characterized in that cellulose acetopropionate is used as the cellulose component according to point B). 9. " Procedure for coating or printing surfaces, characterized in that artificial resin mixtures consisting of: A. Glycidyl compounds with more than one epoxy group per molecule and epoxy values from 0.35 to 0.70, and B. cellulose ethers and/or cellulose esters, and C. one or more amine compounds with at least two reactive amine hydrogen atoms, chosen among) aliphatic polyamines of the general formula where R is an alkyl group with 1-4 carbon atoms or hydrogen, R' is hydrogen or the group -Cr^ -Cr^ -CN, and x is a number from 2 to 6, b) polyalkylene polyarnines of the general formula where R is an alkyl group with 1-4 carbon atoms 'VI or hydrogen, while x is a number from 2 to 6 and y is a number from 2 to 4, and c) polyetheramines of the general formula where n is a number from 3 to 5, z is 0, 1, 2 or 3, and R is an alkylene group with 1-12 carbon atoms, which may optionally be substituted with an alkyl group with 1-4 carbon atoms, d) cycloaliphatic polyamines of the general formula 2 where R is a group 3 4 where R is hydrogen or CH_-, R is -CH - and 5 R J Å R is an alkylene group, as this may or may not be the same for the two substituents R^, and ican be present 0, 1 or 2 times and may contain 1-3 carbon atoms, e) aminoamide compounds and/or imidazoline group-containing aminoamide compounds with .amine hydrogen equivalent weights from 90 to 175, f) phenol-formaldehyde-amine condensation products VI (Mannich bases) with at least two reactive amine hydrogen^ atoms, g) adducts of amine compounds according to Ca) Cf), produced by reacting an excess of amine with glycidyl compounds according to A), D) aromatic-free solvents and possibly E) pigments, dyes, accelerators, reactive diluents, fillers and flow agents. 10. Means for use in the method according to claim 9, characterized in that the binding agent contains synthetic resin mixtures consisting of: A. - Glycidyl compounds with more than one epoxy group per molecule and epoxy values from 0.35 to 0.70, and B. cellulose ethers and/or cellulose esters, and C. one or more amine compounds with at least two reactive amine hydrogen atoms, chosen among) aliphatic polyamines of the general formula where R is an alkyl group with 1-4 carbon atoms. or hydrogen, R' is hydrogen or the group -CH2~ CH2 -CN, and x is a number from 2 to 6, i b) polyalkylene polyamines of the general formula where R is an alkyl group with 1-4 carbon atoms in or hydrogen, while x is a number from 2 to 6 and y is a number from 2 to 4, and. c) polyetheramines of the general formula where n is a number from 3 to 5, z is 0, 1, 2 or 3, and R is an alkylene group with 1-12 carbon atoms, which may optionally be substituted with an alkyl group with 1-4 carbon atoms, d) cycloaliphatic polyamines of the general formula where R^ is a group 3 4 where R is hydrogen or CH_-, R is -CH„- and5 R J . R ^ R is an alkylene group, as this may or may not be the same for the two substituents R^, and can be present 0, 1 or 2 times and can inside-i hold 1-3 carbon atoms, e) aminoamide compounds and/or imidazoline group-containing aminoamide compounds with amine hydrogen equivalent weights from 90 to lhs, f) phenol-formaldehyde-amine condensation product type , (Mannich bases) with at least two reactive amine hydrogen atoms, g) adducts of amine compounds according to Ca) - Cf), produced by reacting an excess of amine with glycidyl compounds according to A), D) aromatic-free solvents and possibly E) pigments, dyes, accelerators, reactive diluents, fillers and flow agents.