CA1117234A - Synthetic resin binders for coatings and printing colours - Google Patents

Abstract

ABSTRACT OF THE INVENTION

The invention is concerned with synthetic resin mixtures comprising (A) an adduct of an excess of a solid polyaminoamide and an epoxy resin, and (B) an adduct of an excess of an epoxy resin and a solid polyaminoamide, the polyaminoamides in components (A) and (B) having an amine number of 30 to 200 and being obtained from dicarboxylic acids having 6 to 13 carbon atoms, optionally in admixture with other carboxylic acids, and certain diamines, op-tionally in admixture with other amines.
The synthetic resin mixtures are used as binding agents for surface coatings and printing colours for both rapidly opera-ting rotary printing machines and slowly operating printing pro-cesses. They are soluble in alcohol/ethyl acetate mixtures free from aromatic substances and are therefore environmentally toler-able, are suitable for sensitive printing processes, and immediately after evaporation of solvent they are surface dry so that they can be printed from roll to roll without difficulty.

Description

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, . , Th~s inven-tion is concerned with hardenable synthetic resin systems, comprising adducts of polyaminoamides and epoxides, and their use as binding agents for surface coatings and printing colours for intaglio printing, screen printing and flexo-printing.
Owing -to the changed packing techn.iques in recent years there has been a rapid advance in the modern consumer groups and food industries and also in the practical requirements of the .
coatings and printing colours used. The necessary resistances to water, acids bases and especially fats and oils and also the high temperature resistance necessary for the sealing times that con-tinually become shorter are not provl.ded for to a suff;.cient ex-tent by thermoplastic binding agents.
Applicants German Patent No. 1,494,525 issued 14 November 1977 describes hardenable synthetic resin mixtures of (~) a synthetic resin component containing free amino groups, composed of an adduct of a solid epoxy-resin and an excess of a solid polyaminoamide of a dimeric fatty acid and a di-amine, (B) a synthetic resin component containing free epoxy-groups, composed of an adduct of a solid polyaminoamide of a dimeric fatty acid and a diamine and of an excess of a solid epoxy-resin, and (C) one or more solvents and optionally pigments, which may be ~:
used for the preparation of paints, printing 7'~3~

colours and adhesives for coating foils of all kinds and paper.
German Auslegeschrift 1,694,958 published 3 February 1977 to Veba-Chemie, A~ describes a process for the production of synthetic materials by the reaction of polyamides wi-th epoxy-compounds, wherein the diamine constituent Eor the production of the polyamide, which has been produced in known manner, is com-posed to an extent of 20 to 100% of 1-amino-3-amino-methyl-3,5,5-trimekhylcyclohexane, and the quantity of this polyamide in admix-ture with the epoxy-compounds is 10 to 99.8%.
In the las~-men-tioned process the polyamides and epoxy--resins are mixed directly wi-thou-t using an adduct. Such mixtures are not satisfactory with regard to film formation at room tem-perature or a slightly raised temperature and the range of use of this process is correspondingly limited.
Printed material based on German Pa-tent 1,494,525 has a sufficient resistance to chemicals and good mechanical and also thermal properties. Ilowever, for the production of clear solutions the solvent must contain a relatively large amount of aromatic substances.
Owing to the requirement that has become increasingly in the foreground in recent times for the protection of working premises and the environment, practical experience demands bind-ing agents for coatings and ~1~7Z34 printing colours that are clearly soluble in solven~s free from aromattc substances The use of aromatic substances is also undesirable for technical reasons. Thus, for example, solvents containing arc,natic substances can cause the swelling of print-ing rollers.
An object of the invention is to select hardenable binding agent systems that are soluble in solvents free from aromatic substances to give clear solutions, and which, after -~
evaporation of the solvent, give physically dry and clear films and which harden out at room temperature or a slightly raised temperature, while the coatings and prin-ted films fulfil -the requirements of practice with r~gard to chemical stresses.
The present invention provides a hardenable synthetic resin mixture forl.surface coating compositions and compositions for printing colours for intaglio printing, flexo-printing and screen printing, which comprises: :
(A) a synthetic resin component containing free amino groups, comprising an adduct of an excess of a solid polyaminoamide ~ ~
and an epoxy-resin, ~: ;
(B) a synthetic resin component containing an excess o~ epoxy groups, comprising an adduct of an excess of an epoxy resin . and a solid polyaminoamide, and ~, 7Z3~L

(C) one or more solvents free ~r4m aromatic compounds, the polyaminoam~de used in components (A) and (s) having an amine - number of 30 to 200, especially 50 to 150, and being obtained from one or more aliphatic dicarhoxylic acids containing 6 to 13 carbon a-toms and from an excess of one or more diamines of the general formula I Rl NH2 Rl ~ ~ Rl (I), 10Rl ~ 2 in wh.ich R is H or CH3 and R is a -CH2-NH2 or -C(CH3)2-NH2 group.
The polyaminoamide used in components (A) and (B) is optionally obtained from a mixture of amines comprising in addi-tion to a diamine of the genera~ formula (I), an amine of the general formula (II) H2N [ (CHR)x-NH - ~ H (II), in which R is an alkyl radical containing 1 to 4 carbon atoms or a hydrogen atom, x is an integer of from 2 to 6, and y is an inte-ger of from 1 to 4 eg 2 to 4, and in which, when y is greaterthan 2, the values of x _ 5 _ ~723~
within the molecule may be the same or different; and preferably this polyaminoarnide constituent, especially in component (A), is used with an aminoamide compound, an aminoimidazoline compound or an aminoamide compound containing an imidazoline group, having an amine~hydrogen equivalent weight of from 90 to 500 ~ased on a polyalkylene amine of the general formula (II).
The polyaminoamide may also be used, especially in com-ponent (A), with an amine of the general formula (II) and an amine of the general formula (III) 10H2 -(CIIR)x NH2 . (III) in which R represents an alkyl radical containing 1 to ~ carbon atoms or especially a hydrogen atom, and x is an integer of Erom

2 to 6, especially 2.
The amine or mixture of amines used in preparing the polyaminoamide may also contain a Mannich base sui-table for hardening epoxy resins and containing at least two reactive amine-hydrogen atoms. More, usually, however, the use of a Mallnich base is as additional hardener for the epoxy resin especially for component (A).
~ As the acid constituent from which the polyaminoamide used in components (A) and (B) is obtained there may be used a mixture of acids which contains, in addition to the aliphatic dicarboxylic acid containing 6 to 13 carbon atoms, (i) an aromatic, araliphatic of hydroaromatic (unsatura-ted or saturated cycloaliphatic) ~- 6 -1~L723~

dicarboxylie acid, optionally substitu-ted by an alkyl radieal, or a mixture of any two or more of sueh acids, in a quantity of from 0.95 to 0.05, espeeially from 0.8 to 0.2, equivalents ealeulated on the total carboxyl group eontent, (ii) an aliphatie, hydroaromatie (unsaturated or saturated cycloaliphatie) or aromatie Mono-earboxylie acid or mono-funetionally acting aeid or anhydride, or (iii) a dimeric fatty aeid, an addition produc-t of acrylie acid with an unsaturated fatty acid or a heptadecane diear-boxylie aeid, or any two or more of such aeids as defined under(i), (iî) and (iii).
Advantageously the synthetie resin mix-tures of the invention also contain an epoxy-resin hardener in component (A), and optionally pigments.
In a modification of the synthetic resin mixtures of the invention the component (A) may eontain, instead of an adduet of the polyaminoamide and epoxy-resin, the separate substanees, that is, one or more of the polyaminoamides as specified.above and the epoxy-resin not pre-additively combined.
As the aliphatie dicarboxylie acids from which the solid polyaminoamides used in components (~) and (B) are prepared, there may be mentioned the following examples: adipic acid, pimelie aeid, suberie acid, ~ _ 7 _ azelaic acid, sebacic acid, decamethylene dicarboxylic acid and brassylic acid.
For the aliphatic, araliphatic and aromatic dicar-boxylic acids from which the solid po]yaminoamides are optionally prepared, there may be mentioned the following examples: tereph-thalic acid, isophthalic acid, tetrame-thyl-~erephthalic acid, cyclohexane-1,4-dicarboxylic acid, xylylene diacetic acid, phenylene diacetic acid, fluorene dicarboxylic acid, the addition products of acrylic acid with higher monomeric unsaturated fatty acids containing 16 ~o 22 carbon atoms, and the dicarboxylic acids obtained by the carboxylation of unsaturated higller monomeric fatty acids containing 16 to 22 carbon atoms.
There may be used difunctionally active polycarboxylic acids such, for example, as cyclopentane tetracarboxylic acid dianhydride, bicyclo-2,2,2-oct-7-ene tetracarboxylic acid dianhy-dride, bicyclo-2,2,2-oct-7-ene tricarboxylic acid, trimellitic acid anhydride and pyromellitic acid dianhydride.
As dicarboxylic acids there are preferred isophthalic acid and terephthalic acid, and optionally present alkyl substitu-ents may have 1 to 4, and preferably 1 or 2, carbon atoms.
A hydroaromatic dicarboxylic acid may be, forexample, cyclohexane-, cyclohexene- or cyclohexadiene-dicarboxylic acid.
For the adjustment or regulation of the necessary or desired degrees of polymerisation and also of the melt ~ ~ 8 -7239~

~iscosities o~ the condensation pxoducts there may be concomitant-ly used the anhydrides of the dicarboxylic acids, especially the dicarboxylic acids mentioned above, which under the given reaction conditions form with the amines predominantly imides, and also monocarboxylic acids. The eventual amount oE monoEunctional or monofunctionally acting compounds may be 0.01 to 0.5 equivalents calculated on the total acid equivalents, and especially 0.1 to 0.5.
As typical representatives of these compounds there may be mentioned: Aromatic series: Phthalic acid, phthalic anhydride, dimethyl-phthalic acid, dimethyl-phthalic anhydride, benzoic acid and naphthalene carboxylic acid.
The hydroaromatlc series: Tetrahydrophthalic anhydride, dimethyl-tetrahydrophthalic anhydride, endomethylene-tetrahydro-phthalic anhydride and hexahydrophthalic anhydride.
Aliphatic series: straight chained or branched, optional-ly unsaturated acids containing 2 to 22 carbon atoms such as acetic acid, propionic acid, butyric acid, stearic acid, palmi-tic acid, oleic acid and tall oil fatty acid.
There are preferably used tetrahydrophthalic acid, hexahydrophthalic acid, acetic acid and ortho-phthalic acid.

_ g _ ~7;~3~

Under the given reaction conditions compounds having a predominantly difunctional action such, for example, as aromatic tetracarboxylic acid dianhydrides, may also be used in small quantities. The quantities used are regulated by small amide-forming parts of the particular dianhydride, as they have a cross-linking action owing to their tri- or tetra-functionality and thus give a strong increase in viscosity, which may lead to gell-ing. The quantities used must therefore be so chosen in each case that these disadvantageous effects are reduced to a toler-able extent.
The dicarboxylic acids may also be usedin the form oftheir amide-forming derivatives, such, for example, as esters.

Among the dimeric fatty acids optionally also used there are to be understood polymerised acids, which are obtain-able by known methods from unsaturated natural or synthetic monobasic aliphatic fatty acids containing 16 to 22 carbon atoms, and preferably 18 carbon atoms, (see German Offenlegungsschrift 1,443,938 published June 18, 1963to ScheringAG and 1,443,968, published October 3, 1964 to Schering AG, German Patent Specifi-cation 2,118,702 published April 17, 1971 -to Schering AG and German Auslegeschrift 1,280,852 published August 24, 1960 to Unilever Emery N.V.).
Typical dimerised fatty acids obtainable in commerce have approximately the following composition:
monomeric acids 5 - 15 % by weight dimeric acids 60 - 80 % by weight - 10 - ' 723~L

trtmeric and higher-functional acids 10 - 35 % by weigh-t.
However, there may also be used dimeric fatty acids which have been hydrogenated by known methods and/or of which -the dimeric portion has been enriched by suitable methods of dis-tillation to more than 80~ by weight.
As an example of an addition product of acrylic acid and an unsaturated fatty acid there may be mentioned an ordinary commercial adduct of acrylic acid and a conjugated C18-monocar-boxylic acid. Products of this kind may also be hydrogenated.
The heptadecane dicarboxylic acid op-tionally also used can be ob-tained in accordance with German Pa-tent Specification 1,006,849.
These acids optionally also used may be used in quan-tities of 0.05 to 0.8 equivalents calculated on the -total equi-valents.
Within these limits these values must be varied in conformity with the particular acid components and also the na-ture and quantity of the other components in order to obtain the products used in the synthe-tic resin mixtures of the invention.
To an expert in this field such variations are self-evident and -their tendency and effect are comprehensible.
As diamines of the general formula (I) for preparing the polyaminoamides of components (A) and (B) there may be mentioned as preferred examples 3-aminomethyl

3( - 11 -: ~ .

3L~17Z3~

3,5,5-trimethyl=cyclohexylamine (isophorone diamine) and l-methyl-

4-(1-amino-1-methyl-ethyl)~cyclohexylamine (menthane diamine).
~he diamines or the invention may be used in admixture with one another or wlth other amines.
The amines optionally also used may be used in quanti-ties of 0.01 to 0.3, and especially 0.1 to 0.25, equivalents calculated on the total amount of amine. Within these limits-these values must be varied depending on the par-ticular acid components and also on the nature and ~uantity of the remaining components, in order to obtain -the products used in accordance with the invention. To an expert in thls field such variations are self-evident and their tendency and effect are comprehensible.
As examples of amines of the general formula (II) which are optionally used there may be mentioned diethylene triamine, triethylene tetramine, tetraethylene pentamine, dihexamethylene triamine and the hydrogenated cyane-thylation products of poly-valent amines such, for example, as N-aminopropyl-ethylene dia-mine and N,N'-bis-~aminopropyl)ethylene diamine.
These amines are ordinary commercial epoxy-resin har-deners and can likewise be used as hardeners in accordancewith the invention.
The carboxylic acids and the amines are condensed ~ - 12 -~ ~L7Z3~

in quantities such that the resulting polyaminoamides have amine numbers of from 30 to 200, especially from 50 to 150. Examples of their preparation are given in Table I.
As aminoamides, aminoimidazolines and aminoamides con-taining imidazoline groups there may be used the compounds known to be suitable as hardening agents for epoxy-compounds, for example, the epoxy-compounds described in German Patent Specifi-cations 972,757 issued September 17, 1977 to General Mills, Inc., and 1,074,856 issued April 13, 1961 to General Mills, Inc.,German Auslegeschriften 1,041,246 published February 14, 1956 to Riech-hold Chemie AG, 1,098,544 published March 5, 1959 to General Mills, Inc., 1,106,495 published June 25, 1959 to General Mills,Inc., ~, 95,8~9-~n~t-~,2~ 8, British Patent Specifications 803,517 published January 1, 1957 to Beck, Koller & Comp.,Ltd., 810,348 published August 29, 1957 to General Mills,Inc.,873,224 published April 13, 1959 to Bataafse Petroleum Maatschappij N.V., 865,656 published March 6, 1959 to General Mills,Inc., and 956,709 publish-ed July 19, 1960 to Schering AG, Belgian Patent Specification 593,299 issued January 23, 1961 to Schering AG, ~rench Patent Specification 1,264,244 issued October 13, 1961 to Schering AG, and also United States Patent Specifications 2,705,223issued March 29 1955 to General Mills,Inc., 2,712,001 issued June ~8, 1955 to Devoe & Reynolds Comp.,Inc., 2,881,194 issued April 7, 1959 to General Mills,Inc., 2,966r478 issued December 27, 1960 to General Mills,Inc., 3,002,941 issued October 3, 1961 to General Mills, Inc.,~ 3,062,773 issued November 6, 1962 to General Mills,Inc.
3~L~r~6~
There have been found advantageous aminoamides, amino-imidazolines and aminoamides containing imidazoline groups, which are prepared by the reaction of (1) a monocarboxylic acid such, for example, as a straight-chained or branched alkyl carboxylic acid ~i72;3 gL

containing 2 to 22 carbon atoms, and especially 2 to 4 and 1~ to 22, and preferably 18 carbon atoms, such, for example, as acetic acid, pro-pionic acid, butyric acid, caproic acid, capry-lic acid, capric acid, lauric acid, myristic acid and also especially the natural fatty acids such, for example, as stearic, oleic, linoleic, linolenic and tall oil fatty acid, or (2) a so-called dimeric fatty acid obtainable in accordance with known methods by the poly-merisation of unsaturated natural and synthetic monobasic aliphatic fatty acid containing 16 to 22 carbon atoms, perferably 18 carbon atoms (see, for example, German Offenlegungschrift 1,443,938 issued June 18, 1963 to Schering AG, German Offenlegungscrift 1,443,968 issued October 3, 1964 to Schering AG, German Patent Specifica-tion 2,118,702 issued April 17, 1971 to Schering AG, and German Auslegeschrift 1,280,852 published August 24, 1960 to Unilever Emery N.V.).
- Typical polymerised fatty acids obtainable in : commerce have approximately the following composi-tion: ~.
monomeric acids 5 - 15 ~ by weight dimeric acids 60 - 80 % by weight ;.
trimeric and higher-functional acids 10 - 35 % by weight However, there may also be used fatty acids of which the trimeric and higher functional content or of which the dimeric portion has been enriched by suitable distillation processes, or fatty acids which have been hydrogenated by known methods, or 2~

(3) a carboxylic acid obtained from an unsaturated higher fatty acid containing 16 to 22, and expe-cially 18, carbon atoms or an ester thereof by copolymerisation with aromatic vinyl compounds (for example, British Paten-t Specification 803,517 published January 1, 1957 to Beck, Koller & Comp., Ltd.), or (4) acids, prepared by the additive combination of phenol or substitution products thereof wlth un-saturated monocarboxylic acids such, for example, as hydroxyphenylstearic acid (for example, German Offenlegungsschrift 1,5~3,75~lpublished March 11,1966 to Minnesota Mining and Manufacturing Co.), or 2,2-bis-(hydroxyphenyl)-valeric acid, or addition pro-ducts of phenol with polycarboxylic acid such, for example, as dimeric fatty acids (for example, United States Paten-t Specification 3,468,920),issued September 23,1969to ~rcher-Daniels-Midland Company.
wlth polyaminesof aratio ofamino groups:carboxyl groups greater than 1.
Generally, acids of the groups mentioned above are used singly for condensation with the polyamines, but mixures thereof may also be used. Polyaminoamides and polyaminoimidazolines of the monomeric or polymeric fatty acids mentioned above under (1) and (2) have acquired special importance in the art, and they are therefore preferred for use in accordance with the invention.

~ - 15 -~723~

As amine components used for the preparation of the pol~aminoamides there may be mentioned polyamines such, for exam-ple, as (i) polyalkylenepolyamines of the yeneral formula (II) such, for example, as polyethylene polyamines such, for example, as diethylene triamine, triethylene tetramine, tetraethylene pentamine or polypropyl-ene polyamine, and also polyamines obtainedby the cyanethylation of polyamines, especially ethylene diamine, and subsequent hydro~enation (prospectus of the .irm BASF AG 1976), or (II) optionally substituted alkylene polyamines o-f the general formula (III) such, for example, as ethyl-ene diamine, propylene diamine, butylene diamine, hexylene diamine, but more especially ethylene diamine, or mixtures of two or more of the aminoamides, aminoimidiazolines and animoamides containins imidazoline groups, and amines of the general formulae (II) or (III) are used. In accordance with the invention there are preferably used the polyamines mentioned under (i) above. ~.
Preferred aminoamides or aminoamides containing imida-zoline gxoups for the i~vention have amine-hydrogen equivalent weights of about 90 to about 500.

~ - 16 -, ~7Z3~

As ~annich bases there are to be understood reaction products of phenols, formaldehyde and secondary amines. As phenols there-may be used monophenols such, for example, as phenol, ortho-, meta- and para-cresol, the isomeric xylenols, parpa-tertiary-butyl-phenol, para-nonylphenol, ~naphthol, ~-naphthol and also di- and poly-phenols such, for example, as resorcinol, hydroquinone, 4,4'~dioxydiphenyl, 4,4~-dioxydiphenyl ether, 4,4'-dioxydiphenol sulphone, 4,4l-dioxydiphenyl-methane, bisphenol A, and also the condensation products of phenol and formàldehyde designa-ted as novolacs.
As secondary amines there may be used dimethylamine, diethylamine, dipropylamine, dibutylamine, piperidine, pyrroli-dine, morpholine and methyl-piperazine.
A comprehensive enumeration of -the phenols and amines capable of being used is given in M. Tramontini, Syntheses, 1973, pase 703. For the preparation of the Mannich bases this li-tera-ture reference may also be referred to.
The molar quantities of formaldehyde and amine per mol of phenol depend on the number of groups capable of substitution.
In phenol there are 3, in bisphenol A 4 and in para-tertiary butyl-phenol 2.
The preferred Mannich bases are reaction products of phenol or bis-phenol A, formaldehyde and dimethylamine containing 1 to 4 tertiary amino groups.

~ - 17 -~723~

When novolacs are used as phenol components there are obtained Mannich bases having up to 10 or more secondary amino groups.
In the reaction of Mannich bases with aminoamides all the tertiary amine groups of -the Mannich base can be exchanged.
The amine exchange reaction takes place when the Man-nich base and the aminoamide, optionally with the use of inert solvents, are heated while stirring at temperatures above 100C, preferably of 130 to 180C. The secondary amine liberated in the course of 0.5 to 3 hours is distilled into a cool receiver.
After gas-chromatographic analysis the amine dis-tilled oEf is so pure that it can be used again without further treatment for the preparation of the starting Mannich base.
Epoxy resins suitable for making the adducts used in the synthetic resin mixtures of the invention are glycidyl ethers containing more than one epoxy-group per molecule, which are de-rived from polyhydric phenols, especially bisphenols, and also novolacs and of which the epoxide values are between 0.100 and 0.600, but especailly between 0.200 and 0.550.
Depending on the amine number and epoxid~ value it is preferable to operate with the following mixing ratios:

~ - 18 -7%3l~

polyaminoamide hardene~ Epoxy-resin - Amine number Epoxide value 50-85 85-115 115~150 0.200-0.225 0.390-0.440 0.520-0.550 100 g - - 85-144 g 43-72 g 34-57 g - lOOg 144-195 g 72-98 g 57-77 g - - 100 g 195-254 g 98-127g 77-lOlg . .

In practice these mixiny ratios may be exceeded or not reached. However, they are to be so chosen tha-t printed Eilms produced therewith have good chemical and thermal resistances.
In general, the indivldual components and also the Einal products should -Eulfil the following requirements:
The aminoamide must be soluble in solvents free from aromatic substances; the aminoamide must be compatible with -the epoxide compounds used; -the adduct of component (A) must be com-patible with the adduct of component (B); and the mixture of the adducts must be clear both in the form of a physically dry film and ofa hardened-out film.
-~ If the hardenable synthetic resin systems of the invention are used as binding agents for printing colours, the individual components are best used in the form of their adducts as in this case the film dries physically very rapidly and also the harden- ::
ing-out takes place 1~7Z~4 rapidly. This is an essential factor for modorn printing pro-cesses working at high printing speeds.
If only one of -the components is used as an adduc-t or adduc-ting is wholly dispensed with, whlch is quite possible with the use of aromatic acid anhydrides, films are obtained having -the same physical and chemical final properties. As, however, more time isrcquired for obtaining a physically dry or hardened-ou-t Eilm this method of use is generally preferred for coa-tings and for printing processes having low speeds of operation.
For the synthetic resins used in accordance with the invention the solvents are chosen also by taking into considera-tion the printing process -to be used.
Thus, for printing processes having high printing speeds (rotary printing) rapidly evaporating solvents are used such, for example, as mixtures o~ lower aliphatic alcohols con-taining 2 to 4 carbon atoms, esters such, for example, as e-thyl, propyl, isopropyl, butyl and isobu-tyl acetate, ketones such, for example, as acetone, methyl ethyl ketone, methyl isobutyl ketone, methyl n-butyl ketone and petroleum ether mixtures boiling within the range of 60 to 160C., but especially mixtures of ethanol/
ethyl acetate.
For printing processes having low printing speeds such, for example, as screen printing processes or also for surface coatings, there may also be used solvents having rela-tively long evaporation times such, for - ~0 -Z3~

; example, as the glycol ethers and glycol acetates usllal in this field, optionally in admixture with other solvents suitable for the particular pri`nting process.
Inoryanic and organic substra-tes can be printed or coated by the process of the invention. There come in-to consi-deration the foils usual ~n the printing industry composed, for example, of polyamides, polyesters or polyesteramides, heat-sen-sitive foils, for example, of polyethylene and polypropylene, co-extrusion foils from polye-thylene and polypropylene, cellulose glass foils untrea-ted or coated with polymers or lac:quered with nitrocellulose, paper, cardboards and optionally polyvinyl chlor-ide or copolymers thereof, and also metal foils such, for example, as aluminium foils. Combinations of these materials are optionally also possible. The coatings may be applied to the materials us-ual in the building industry such, for example, as concrete, metal, wood and synthetic materials.
- Preparation of the adducts 1. Hardener adducts.
, (a) The polyaminoamide hardener -to be used is dissolved in a solvent or solvent mixture preferably at 50% strength and well mixed with a part of the quantity of epoxy-resin necessary for complete hardening, also dissolved in a solvent or solvent mix-ture preferably at 50% strength. After a period of about 2 days at room ~ - 21 -23~

temperature or correspondinyly shorter periods at raised tempera-tures (for example, at 40C for 16 hours) the pre-reaction is con-cluded and the adduct is ready for use.
(b) Tlle polyaminoamide harclener to be used is dissolved together with a part of the quantity of epoxy-resin required for complete hardening in a solvent mixture, preferably at 50% streng-th, at room temperature while stirring. After a period of about 2 days at room temperature or a correspondingly shorter time at higher temperatures (for example at ~0C for 16 hours) the pre-reac-tion is concluded and the adduct is ready fox use.
2. ~ox~-resin adduc-ts.
(a) The epoxy-resin to be used is dissolved in a solvent or mix-ture of solvents, preferably at 50% strength, and is well-mixed wi-th a part of the quan-tity of polyaminoamide hardener required for complete hardening, also dissolved in a solvent or solvent mix-ture preferably at 50% strength. After a period of about 2 days at room temperature or correspondingly shorter times at higher temperatures (for example, about 15 hours at 40C) the pre-reac-tion is concluded and the adduct is ready for use.
(b) The epoxy-resin to be used is dissolved together with a part of the quantity of polyaminoamide hardener required for complete hardening in a solvent or solvent mixture, preferably at 50%
s-trength, at room temperature while stirring. After a period of about 2 days or ~ - 22 -~7~3~
, correspondingly shorter times at higher temperatures (for example, about lS hours at 40C) the pre reaction is concluded and the adduct is ready for use.
(c) The epoxy-resin used is dissolved in a solvent or solvent mixture preferably at 50% strength and is well-mixed with a part of the quantity o~ hardener adduct according to l(A) and/or a(b) necessary for complete hardening. After a period of about 2 days at room temperature or correspondingly shorter -times at higher temperature or correspondingly shorter times at higher tempcratures (for example, at 40C for about 16 hours) the reactlon is concluded and the adduct is ready for use.
The degree of pre-addition in the case of individual adducts lies between 24 par-ts by weight of . 24 parts by weight of polyaminoamide epoxy resin or l part by weight of l par-t by weight of epoxy-resin po]yaminoamide and 15 parts by weight o~ 15 parts by weight of polyaminoamide epoxy resin or 10 parts by weight of lO parts by weight of epoxy-resin polyaminoamide, however especially between 22/3 and 17~8.
This range of pre-addition of the adduct solutions should if possible not be overstepped as otherwise gelling ~ _ 23 -3~

is liable to oCcuX within a short time.
The polyaminoamide and epoxy resin components mentioned in Tables II and III given below need not be identical in both adducts, bu-t may be varied as desired.
For the preparation of synthetic resin mixtures ready for use the individual adduct solutions may then be mixed as follows:
(A) Hardener adduct according to l(a~ + Epoxy-resin adduct ac-cording to 2(a).
(B) ITardener adduct according to l(a) -~ Epoxy-resin adduc-t ac-cording to 2(b).
(C) llardener adduct according to l(a) t- Epoxy-resin adduct ac-cording to 2(c) (D) Hardener adduct according to ~(b) + Epoxy-resin adduct ac-cording to 2(a).
(E) Hardener adduct according to l(b) + Epoxy-resin adduct ac-cording to 2(b).
(F) Hardener adduct according to l(b) + Epoxy-resin adduct ac-cording to 2(c).
: 20 For reasons of chemical engineering the procedure accor-ding to (C) in preparing the synthetic resin mix-tures is preferred in practice.
The following Examples illustrate the invention:
Example 1 44 gms of the polyaminoamide hardener according to No. 1 in Table I are dissolved in a mixture of 22 gms ~ - 24 -72~

of ethanol and 22 gms of e-thyl acetate while stirring and slightly warming. To this solution are added 12 gms of a solution of 50%
strength of a solid bisphenol-A-epoxy-resin a-ving an epoxide value of 0.210 in ethanol/ethyl acetate (1:1) and the whole is well mixed. After s-tanding for about 15 hours at 40C. the pre-reaction terminates and the hardener,adduct is ready for use.
Example 2 40 gms of a solid bisphenol-A-epoxy-resin having an epoxide value of 0.210 are dissolved in a mix-ture of 20 yms of ethanol and 20 gms of e-thyl aceta-te while stirring and sLightly warming. To this solution are added 20 gms of the hardener adduct solution according to Example l and the whole is well mixed.
After a period of about 2 days at room temperature the pre-reaction terminates and the epoxy-resin adduct is ready for use.
Preparation of the printing colours After being finished the hardener adduct solutions and-the epoxy-resin adduct solutions, and optionally both of them, can be pigmented with the dispersing apparatus customary in the printing colour industry. For this purpose there may be used organic or inorganic pigments and also soluble dyestuffs. After mixing the hardener adducts and epoxy-resin adducts in the correct proportions ~L7~

(see Table IV) the finished printing colours are diluted to the correct printing viscosity in accordance with the require-ments of the particular printing process. One choice for the use of the printing colours so prepared would be printing on to poly-ethylene from roll to roll with a commercially usual printing machine. The prints would be physically dry immediately after evaporation of the solvent, so that no sticking or impression of the colour on the rear side of the rolled-up foil would be observed. After a period of 7 days at room temperature the prints would undergo a complete test usual in the printing colour industryO The values for the properties of mechanical, chemical and thermal resistance are given in Table V.
Description of the test methods used.
1. Adhesiveness.

The test for the adhesiveness of printed films is carried out on a print carrier with strips of Tesafilm (Registered Trade Mark, a commercial adhesive tape consisting of a polyester supporting film coated with a self-adherent synthetic resin formula based on chlorinated rubber, terpene resin and colophony derivatives). Each of 10 strips are stuck on and torn off - rapidly or slowly.
2. Scratch resistance.
The printed films are scratched with the finger nail more or less strongly.
3. Chemical resistance.
After storage for 24 hours in the particular ~ ~7'~3~

-chemicals the mechanical properties such as the adhesion, scratch and scouring resistances of the printed films are tested and cor-respondingly eval~ated immediately after they have been removed from the test medium and also af-ter a recovery period of 10 minutes in the air.
4. Block point.

.
Under a load of 60 gms/cm2 the printed films folded against one ano-ther are stored at temperatures 10C higher than the ambient temperature. The evaluation criterion is the tem-perature at which the films after being separated by unfolding first e~hibi-t slight damage.
Evaluation of the test methods 1 - 3 1. Very good (film free from objection).
2. Good (isolated, point-like injuries).
3. Sa-tisfactory (visible injuries).
4. Adequate (film injuries of large surface).

5. Unsatisfactory (film destroyed).
Evaluation of test method 4 Statement of the critical temperature.
As the determined values show, there were ob-tained by the use of the synthetic resin mixtures of the invention as binding agents for printing colours better chemical resistance and above all distinctly higher heat resistance (block points) than with the usual one-component printing colours a-t -the present time (for example, based on polyamide resins and/or nitrocellulose).
It has also been found that the chemical resistance can be still further improved by replacing proportionate quan-tities of the polyaminoamide hardeners of the invention by ordinary commercial epoxy-resin hardeners (on an amine basis) that harden at room temperature, (see Table X).
The ratio of the described polyaminoamide hardener to the ordinary commercial epoxy-resin hardeners hereinbefore de-~ 27 _ z3/~

scribed shoula be between 10 : 1 to 0.5 ; 1, but preferably be-tween 6 : 1 to 2 : 1.
As the ord~nary commercial hardeners are prac-tically exclusively liquid products larger quan-tities are not suitable in printing colours for rapidly operating rotary printing machines, as otherwise, owing to the resulting surface adhesiveness, the printing speed would have to be decreased to a degree that could not be tolerated for economic reasons.
On the o-ther hand, in the case of slowly operating prin-ting processes such, for example, as screen printing, and with the usual surface coatings, -the mixing proportions can be broadened in accordance with the given re~uirements.
Among the groups of typical ordinary commercial epoxy-resin hardeners the products mentioned in Table VIIa have been tested.
Not all the polyamide hardeners specified in accordance with the invention can be combined in the commercially usual epoxy-resin hardeners. Thus, it has been found that the epoxy-resin hardeners of the types 1 to 4 in Table VIIa are compatible, that is to say, give clear, non-turbid solutions, only with those polyaminoamide hardeners that have been condensed with the com-mercially usual dimersed -fatty acid; On the other hand, hardeners of the types 5 to 11 in Table VIIa can be combined with all the polyaminoamide hardeners described without difficulty (see Table VI).
The reparation of hardener adducts (Table VII).
(c) the polyaminoamide hardener to be used is dissolved together withthe commercially usualhardenerin asolvent orsolven-tmixture preferablyat 50% strentgh and mixed well with a part of the quantity of epoxy-resin (also preferably dissolved in a solvent or solvent mixture preferably at 50% strength) neces-sary fQr complete hardening. After a period of about 2 days 23~

at room temperature or correspondingly shorter residence time at higher temperatures (for example, at 40C for 16 hours) the pre-reaction is practically concluded and the adduct is ready for use.
; (d) The polyaminoamide hardener to be used ls dissolved while stirring at room temperature together with the commercially usual hardener and a part of the quantity of epoxy-resin necessary for complete hardening in a solvent or solvent mixture preferably at 50~ streng-th. After a pexiod of about 2 days at room temperature or correspondingly ]ower residence times at higher temperatures (for example, a-t 40C for 16 hours) the pre-reaction is practically concluded and the ad-duct is ready for use.
P e_aration of the epoxy-resin adducts (Table VIII).
The preparation of epoxy-adducts stable to storage can be carried out only with the use of the polyaminoamide hardeners mentioned under "Preparation of the epoxy-resin adducts a + _ , because with the use of proportionate quantities of the usual commercial hardeners premature gelling of the ~poxy-resin adducts would occur. It is-for this reason that the preparation of epoxy-resin adducts in accordance with the described "Process c" is not suitable.
The degree of pre-addition in the case of the individual adducts is likewise between 24 parts by weight of 24 parts by weight of polyaminoamide epoxy-resin ` ` - or 1 part by weight of 1 part by weight of epoxy-resin polyaminoamide and 30 15 parts by weight of 15 parts by weight of polyaminoamide epoxy-resin or ;10 parts by weight of 10 parts by weight of ~ - 29 ~

9 ~7Z~q~

epoxy-resin polyaminoamide but especially between 22/3 and 17/8.
This range of pre-addition of the adduct solutions should not be overstepped, as othe~wise gelling phenomena will occur wi-thin a short -time.
~he polyaminoamide and epoxy-resin components mentioned in Tables VII and VIII need not be identical in both adducts but may be varied as desired.
Fox the preparatlon of synthe-tic resin mixtures ready for use the individual adduct solutions may then be mixed as follo~s:
A Hardener adduct according -t~ l(c) + Epoxy-resin adduct ac-cording to 2(a).
B Hardener adduct according to l(c) ~ Epoxy-resin adduct ac-cording to 2(b).
C Hardener adduct according to l(d) + Epoxy-resin adduc-t ac-cording to 2(a).
D Hardener adduct according to l(d) ~ Epoxy-resin adduct ac-cording to 2(b).
For chemical engineering reasons in preparing the syn-thetic resin mixtures it is preferred in practice to work in ac-cordance with A.
In special cases it is also possible to prepare mixtures ready for use by combining the epoxy-resin adduct with a non-adducted hardener mixture. In these cases, however, it is ne-cessary to reckon to some extent with considerably lower printing speeds. However, for normal surface coatings the retarded surface adhesiveness is not of decisive importance, so that in this case it is quite feasible to use such mixtures. This applies also to printing processes that operate slowly such, for example, as screen printing.

~ - 30 -~7;~

Example 3 33 gms of polyaminoamide hardener No. 35 (Table I) and 11 gms o~ usual commercial epoxy-resin hardener N0. 6 (Table VII a) are toyether dissolved in a mixture of 22 gms of ethanol and 22 gms of ethyl acctate while stirring and sligllt warming. To this solution 12 gms of a solution of S0~ strength of a solid bls-phenol A-epoxy-resin having an epoxide value of 0.210 in ethanol/
ethyl acetate (l : 1) are added and well mixed. After a period of about 15 hours at 40C the pre-reaction is practically conclu-ded and -the hardener adduct is ready for use.
Example 4 42 gms of a solid bisphenol A-epoxy-resin having an epoxide value of 0.210 are dissolved in a mixture of 21 gms of ethanol and 21 gms of ethyl acetate while stirring and slight warming. To this solution 16 gms of a solution of 50% strength of polyaminoamide hardener No. 35 (Table I) in ethanol/ethyl acetate (l : 1) are added and well mixed. After a period of about 3 days at room temperature the pre-reaction is prac-tically concluded and the epoxy-resin adduct is ready for use.
- The following combinations mentioned in Table IX were prepared in a manner corresponding t~ the foregoing Examples 3 and 4.
The abbreviations used in the following Examples in Table I have the following meanings:
IPD = Isophorone diamine.
AN = Amine number.
Melting point = Melt microscope.
Acids T~PA = Tetrahydrophthalic anhydride.
HHPA = Hexahydrophthalic anhydride.
PA = Phthalic anhydride.

DMT = Dimethyl terephthalate.
IPA = Isophthalic acid.

~ 31 7;239L

CPTD = Cyclopentane te-tracarboxylic acid dianhydride.
DTI]PA = Dimethyl te-trahydrophthalic anhydride.
BTDA = Bicyclo-2,2,2-oct-7-ene tetracar-boxylic acid dianhydride.
ETHPA = Endomethylene tetrahydrophthalic anhydride.
DFA = Dlmeric fatty acid.
10DCMB = 2,6-Dimethyl-4-carboxymethyl-benzene.
Diacid 1550 = Addition product o~ acrylic acid with unsaturated C18-monocarboxylic 6 ' acid.
Amines DTA = Diethylene triamine.
DPTA = Dipropylene -triamine.
DHTA = Dihexamethylene triamine.
N4-Amine = N,N'~ -Aminopropyl-1,2-diamino-ethane.

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Table II llardener adducts (see Example 1) _ . __ Example Polyaminoamide Epoxy resin Appearanc~
hardener o~ -the parts* type No.parts* type of epoxide adduct by wt. (Table I) by wt. resin value solutions ` _ _ 1 22 1 3 nol A 0.210 clear 2 20 1 5 ,- 0.21.0clear 3 17 1 8 ll 0.210 clear 4 20 1 5 ll 0.150 clear 22 2 3 l 0.210 .clear

6 22 3 3 , 0.210 clear

7 20 5 5 - 0.150 clear

8 22 4 3 - 0.210 clear

9 22 5 3 ll 0.210 clear ll 0.210 clear 11 22 6 3 ll 0.210 clear 12 22 7 3 ll 0.210 clear 13 22 8 3 .l 0.210 clear 14 22 9 3 ll 0.210 clear 22 10 3 ll 0.210 clear . .
16 20 10 5 ll 0.210 clear 17 22 11 3 ll 0.210 clear 18 22 11 3 ll 0.210 clear 19 22 12 3 ll 0.210 c1ear 22 13 3 ll 0.210 clear 21 22 14 3 ll 0.210 clear 22 22 15 3 ll 0.210 clear 23 22 1 3novolac 0.510 clear 24 22 1 3bisphe- 0.210 clear nol A
4 5 ll 0.210 clear ::
26 22 16 3 ll 0.210~clear 27 22 17 3 n 0.210 clear 28 22 18 3 ll 0.210 clear 29 20 19 5 ll 0.210 clear 22 19 3 ll 0.210 clear 31 22 20 3 ll l .210 clear :
32 22 21 3 ll l .210 clear 33 22 22 3 u 0.150 clear :
34 22 23 3.~1 1 .210 clear 22 23 3 ,- I .210 clear 36 22 24 3 ., I .210 clear 37 22 25 3 n l .210 clear 38 20 25 5 ll .210 clear ~7Z3~

Table II (continued) Example ~olyaminoamide Epoxy~resin Appearance hardener . of the parts* type No. parts* type of epoxide adduct ~ _ by wt. (Table I) by wt. resln value . solutions . 39 22 26 3 bisphe- 0.210 clear nol A
22 27 3 , 0.210 clear 41 22 28 - 3 ll 0.210 clear 42 22 29 3 ll 0.210 clear 43 22 30 3 " 0.150 clear 44 22 31 3 ll 0.210 clear 22 32 3 ll 0.210 clear 46 22 33 3 ll 0.210 clear 47 22 34 3 ll 0.210 clear 48 22 35 3 ,- 0.210 clear 49 20 36 5 ll 0.210 clear 22 36 3 ll 0.210 clear 51 22 36 3 ll 0.150 clear 52 22 37 3 ll 0.210 clear 53 22 38 3 ll 0.210 clear 54 22 39 3 ll 0.210 clear 22 40 3 .l 0.210 clear 56 22 41 3 'l q.210 clear 57 22 42 3 ll 0.210 clear 58 22 43 3 ll 0.210 clear 59 22 44 3 ll 0.210 clear 22 45 3 ll 0.210 clear ~:
61 23.4 41 . 1.6 ll 0.420 clear 62 23.7 41 1.3 ll 0.530 clear Example for com_ar son 63 22 ~ 46 3 .- 0.210 le, stron~-. ly turbid * ~11 auantity data refer to solutions containing 50~ resin in (a) Examples 1-22, 26-60 = ethanol/ethyl acetate=
(h) Examples 23 = ethanol/ethyl acetate/methyl .
ethyl ketone = 1 ~
(c) Examples 24-25 = ethyl glycol/ethyl glycol acetate = 1 : 1 .

)~
. .

72~

Table_III o~y-resin adducts (as described in Example 2) Exampl ~ Epoxy-resin __ _ _ Hardener adduet Appearance par-ts* type of epoxide parts* adduet No. adduet _ _ _ by wt. resin value by wt. (see Table solutions 1 20 nbolPAe~ 0.210 5 1 elear 2 20 - 0.210 5 2 clear 3 24 - 0.210 1 3 elear 4 20 ,- 0.150 5 4 clear ll 0.210 5 5 elear 6 20 ll 0.210 5 6 clear 7 20 ll 0.150 5 7 elear 8 20 ll 0.210 5 8 elear 9 20 .l 0.210 5 9 elear ll 0.210 5 10 elear 11 ,20 ll 0.210 5 11 elear 12; 20 ll 0.210 5 12 elear 13 20 ll 0.210 5 13 elear 14 20 ll 0.210 5 14 elear ll 0.210 5 15 elear 16 20 ll 0.210 5 16 elear 17 20 ll 0.210 5 17 elear .
18 20 ll 0.150 5 18 elear 19 20 ll 0.210 5 19 elear ll 0.210 5 20 elear -:
21 20 ll 0.210 5 21 elear 22 20 ll 0.210 5 22 elear 23 20 novolae 0.510 5 23 clear :
24 20 nbolPAe~ 0.210 5 24 elear ~. 0.210 5 25 elear : 26 20 ll 0.210 5 26 elear 27 20 ll 0.210 5 27 elear 28 20 ll 0.210 5 28 elear 29 20 ll 0.210 5 29 elear `
ll 0.210 5 30 clear : 31 20 ll 0.210 . 5 31 clear 32 20 .l 0.210 5 32 clear : 33 20 ll 0.150 5 33 clear 34 20 ll 0.210 5 34 clear ll 0.210 5 35 clear 36 20 ll 0.210 5 36 clear 37 20 ll 0.210 5 37 clear Z39~

Table III (continued) . Exampl~ Epoxy-resin _ Hardener adduct Appearance ~arts* type of epoxide parts* adduct No. of the by wt. resin value by wt (see Table solutions . _ __ _ _ 38 20 bnOlspAe- 0.210 5 38 clear 39 20 ll 0.210 5 39 clear - 0.210 5 40 clear ~ :' 41 20 - 0.210 5 41 clear 42 20 - 0.210 5 42 clear 43 20 n 0.150 5 43 clear ::
44 20 - 0.210 5 44 clear .. 0.210 5 45 clear 46 20 ll 0.210 5 46 clear 47 20 ,. 0.210 5 47 clear 48, 20 n 0.210 5 clear 49 20 ll 0.210 5 49 clear , 0.210 5 50 elear 51 20 ll 0.150 5 51 elear 52 20 .l 0.210 5 52 clear ~:
53 20 0.210 ~ 5 53 elear 54 20 ll 0.210 5 54 elear ll 0.210 5 55 elear 56 20 ll 0.210 5 56 elear 57 20 ll 0.210 5 57 elear 58 20 ll 0.210 5 58 elear 59 20 ll 0.210 5 59 elear :~-ll 0.210 5 60 elear 61 19 ll 0.420 6 61 elear 62 17 ll 0.530 8 62 elear Exampl~ for co mparison 63 20 bisphe- 0.210 strongly turbid, not produc- ..
nol A not usable. ible as .
hardener adduct not .
usable. ~:
_ ~

*All quantity data refer to solutions containing 50% resin in (a) Examples 1-22, 26-62 = ethanol/ethyl acetate = 1 : 1 (b) Examples 23 = ethanol/ethyl acetate/methyl ethyl ke-tone = 1 : 1 : 1 (c) Examples 24 = 25 = ethyl glycol/ethyl ~lycol acetate =
1: 1 _ 41 -3~

Table IV Mixing ratios of the adducts "
_ ~xample l~ardener Epoxy- Mixing Appearance o~ the adduct No. resin ratio mixed unpigment-(Tab. II) adduct No. adducts ed printed (Tab. III) films _ ~_ _ _ .
1 1 1 1:1.75 clear clear 2 2 2 1:1.5 ., "
3 3 3 1:0.77 " "
4 4 4 1 22 7~ ll ll 6 6 6 1:1.3 " "
7 7 7 l:Z.l " "
8 8 8 1:1.75 " "
9 9 9 1:1.75 " "
1:1.5 " "
11 11 11 1:1.75 ., ..
12 12 12 1:1.75 13 13 13 1:1.75 ll ., 14 14 14 1:1.75 ll "
1:1.75 16 16 16 1:1.5 ll -17 17 17 1:1.75 18 18 18 1:2.4 ..
19 19 19 1:1.75 1:1.75 ll ll 21 21 21 1:1.3 ll "
22 22 22 1:1,3 73 23 23 1:0.76 ll ,.
24 24 24 1:1.75 .. " -~
1:1.5 26 26 26 1:1.3 ,-27 27 27 1:1.75 28 28 28 1:1.3 29 29 29 1:1.5 1:1.7 31 31 31 1:1.3 . ll 32 32 32 1:1.3 ., "
33 33 33 1:2.4 , 34 34 34 1:1.3 "
1:1O3 36 36 36 1-1.3ll ll 37 37 37 1:1.75 ll ,-38 38 38 1:1.5 ~723~

Table IV (continued -- :
Example Hardener Epoxy- ~ixing Appearance of the adduct No. resin ratio mixed unpigment-(Tab. II) adduct No. adducts ed printed (Tab. III) films.
_ _ 39 39 39 1:1.75 clear clear 1:1.3 41 41 41 1:1.75 42 42 42 1:1.75 43 43 43 1:2.4 44 44 44 ]:1.3 1:1.75 46 46 46 1:1.75 47 47 1:1.75 48 48 48 1:1.3 49 49 49 l:l.S
1:1.75 51 51 51 1:2.4 52 52 52 1:1.75 53 53 53 1:1.75 54 54 54 1:1.75 1:1.75 56 56 56 1:1.75 57 57 57 1:1.75 58 58 58 1:1.75 59 59 59 1:1.75 .. ll ., 1:1.75 61 61 61 1:1.3 ll 62 61 62 1:1.3 ll ll ~;
Example for comparison ,~
63 not not inapp- inappl- inappl usable, produc- licab- icable icable turbid ible , le The mixing ratios may be overstepped or fallen short of.
- However, the proportions must be so chosen that printed films having good mechanical, chemical and thermal resistances are obtained.

. .

~ - 43-Z3~;L

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Table VI
__ .
Example Polyaminoamide Commercially usual epoxy-resin hardener No. hardener No.
.(from Tab. I) 1 2 3 4 5 6 7 8 9 10 11 _ _ _ _ + + + + .~ + +
2 4 _ _ _ _ + + + + + + +
3 5 _ _ _ _ + + + + + ~ +
4 9 + + + + + + + + + + +
11 + + + + + + + + ~ +
6 18 _ _ _ _ + + + + + + +
7 24 _ _ _ _ + + + + + + +
8 25 _ _ _ _ + + + + + + +
9 27 _ _ _ _ + + + ~ + + +
1.0 28 _ _ _ _ + + + + + + +
11 29 _ _ _ _ + + ~ + + + +
12 32 _ ~ + + + + ~ +
13 35 _ _ _ _ + + + + ~ + +
14 37 _ _ _ _ + + + + + + +
39 _ _ _ _ + + + + + + +
16 40 + + + + + + + -~ + + +
17 41 + + + + + + + + + + +
18 42 + + + + + + + + + + +

Symbols : + = compatible - = not compatible 3~

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Table VIII
Epoxy-resin adducts (see Example (a)) _ _ _ ._ Example Epoxy-resin Parts Polyaminoamide Appearance resin epoxide by wt.* hardener of the type value type No. parts* adduct . . (Tab.I) by wt. solutions _ _ 1 bis- 0.210 21 9 4 clear 2 nphel- 0.210 21 11 4 ..
3 A 0.210 21 40 4 ll 4 ll 0.210 21 41 4 ll :
ll 3.210 21 4~ 4 6 ll 0.210 21 1 4 7 ll 0.210 21 4 4 8 ll 0.210 21 5 4 9 ll 0.210 21 18 4 ll 0.210 21 9 4 11 ll 0.210 21 25 4 ll 12 ll 0.210 21 27 4 ,.
13 ll 0.210 21 28 ~I "
14 ll 0.210 21 29 4 " : ;
lS . ll 0.210 21 32 4 ..
16 ll 0.210 21 35 4 " : :
17 - 0.210 21 27 4 ~-18 ll 0.210 21 39 4 19 ll -0.430 10.5 1 4 ,. 0.52Q 8.3 1 4 * All the quantity data refer to solutions containing 50% resin in :~
(a) 1 - 17 and 19 - 20 = ethanol/ethyl acetate = 1 : 1 `
(b) 18 = ethyl glycol/ethyl glycol acetate = 1 : 1 _ 49 -.

Table IX
Mixing ratios of the adducts ____ _ - . .
Example Hardener Epoxy- Mixing Appearance of -the adduct resin ratios mixed unpigmented No. adduct No. adducts printed (Tab.VII) (Tab.VIII) ~ilms ,~
1 1 1 1:1.87 clear clear :
2 2 2 1:1.76 3 3 3 1:2.12 ,.
4 4 4 1:2.13 1:2.12 ll ll 6 6 6 1:2.72 ll ll ~.
7 7 7 1:5.1 8 8 8 1:2.90 9 9 9 1:1.85 ll ll : .
1:3.22 11 11 11 1:2.69 12 12 12. 1:2.20 13 13 13 1:5.74 ll ll 14 14 14 1:3.03 ll . . - ~:
1.3.06 16- 16 16 1:2.89 ll ll 17 17 17 1:2.41 ll ll .
18 18 18 1:2.98 ll ll 19 19 19 1:1.16 ,- ..
1:1 ll ll ..

The mixing ratios may be overstepped or fallen short of. However, the mixing ratio must be so chosen that printed films having good mechanical, chemical and thermal resistances are obtained.

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Claims (30)

THE EMBODIMENTS OF THE INVENTION IN WHICH AN EXCLUSIVE
PROPERTY OR PRIVILEGE IS CLAIMED ARE DEFINED AS FOLLOWS:

1. A clear hardenable synthetic resin mixture, which comprises (A) a synthetic resin component containing free amino groups, composed of an adduct of an excess of a solid polyamino-amide and an epoxy resin or a mixture of said amide and epoxy resin, (B) a synthetic resin component containing an excess of epoxy groups, composed of an adduct of an excess of an epoxy resin and a solid polyaminoamide or a mixture of said amide and epoxy resin, and (C) one or more solvents free from aromatic compounds, the polyaminoamide used in components (A) and (B) having an amine number of 30 to 200, and being obtained from one or more aliphatic dicarboxylic acids containing 6 to 13 carbon atoms and from an excess of one or more diamines of the general formula (I) (I) in which R1 is H or CH3 and R2 is a -CH2-NH2 or -C(CH3)2-NH2 group.

2. A synthetic resin mixture as claimed in claim 1, wherein the polyaminoamide used in component (A) and/or the poly-aminoamide used in component (B) is or are obtained from an excess of a mixture of amines comprising, in addition to a diamine of the general formula (I), an amine of the general formula (II) (II) in which R is an alkyl radical containing 1 to 4 carbon atoms or a hydrogen atom, x is an integer of from 2 to 6 and y is an integer of from 1 to 4.

3. A synthetic resin mixture as claimed in claim 2, wherein the polyaminoamide used in component (A) and/or the polyaminoamide used in component (B) is or are used in admixture with an aminoamide compound, an aminoimidazoline compound or an aminoamide compound containing an imidazoline group, having an aminehydrogen equivalent weight of from 90 to 500 based on a poly-alkylene amine of the general formula (II).

4. A synthetic resin mixture as claimed in claim 2, wherein the polyaminoamide used in component (A) and/or the poly-aminoamide used in component (B) is or are used in admixture with an amine of the general formula (III) (III) in which R represents an alkyl radical containing 1 to 4 carbon atoms or a hydrogen atom, and x is an integer of from 2 to 6 and with an amine of the general formula (II) specified in claim 2.

5. A synthetic resin mixture as claimed in claim 1, wherein the polyaminoamide used in component (A) and/or component (B), is in admixture with a Mannich base suitable for hardening epoxy resins and containing at least two reactive amine hydrogen atoms.

6. A synthetic resin mixture as claimed in claim 1, 2 or 3, wherein the polyaminoamide used in component (A) and/or the polyaminoamide used in component (B) is or are obtained from a mixture of carboxylic acids comprising, in addition to an ali-phatic dicarboxylic acid containing 6 to 13 carbon atoms, (i) an aromatic, araliphatic or cycloaliphatic dicarboxylic acid, optionally substituted by an alkyl radical, or a mixture of any two or more of such acids, in a quantity of from 0.95 to 0.05 equivalents calculated on the total carboxyl group content, (ii) an aliphatic, cycloaliphatic or aromatic mono-carboxylic acid or a mono-functionally acting acid or anhydride, and (iii) a dimeric fatty acid or a heptadecane dicarboxylic acid, or a mixture of any two or more of such acids as defined under (i), (ii) and (iii).

7. A synthetic resin mixture as claimed in claim 1, 2 or 3 wherein the aliphatic dicarboxylic acid is adipic acid, pi-melic acid, suberic acid, azelaic acid, sebacic acid, decamethyl-ene dicarboxylic acid or brassylic acid.

8. A synthetic resin mixture as claimed in claim 1, 2 or 3 wherein the diamine of the general formula (I) is 3-aminomethyl-3,5,5-trimethyl-cyclohexylamine (isophorone diamine), or 1-methyl-4-(1-amino-1-methyl-ethyl)-cyclohexylamine (mentane diamine).

9. A synthetic resin mixture as claimed in claim 1, 2 or 3 wherein component (A) also contains an epoxy-resin hardener.

10. A synthetic resin mixture as claimed in claim 1, 2 or 3 wherein the polyaminoamide used in components (A) and (B) has an amine number of from 50 to 150.

11. A synthetic resin mixture as claimed in claim 2 or wherein an amine of the general formula (II) and/or an amine of the general formula (III) is used in a quantity of from 0.01 to 0.3 equivalents calculated on the total amount of amine.

12. A synthetic resin mixture as claimed in claim 3 wherein the aminoamide compound, aminoimidazoline compound or the aminoamide compound containing an imidazoline group is obtained be reaction of (i) a monocarboxylic acid, or (ii) a dimeric fatty acid, or (iii) a carboxylic acid obtained from an unsaturated high fatty acid containing 16 to 22 carbon atoms or an ester thereof by copolymerization with an aromatic vinyl compound, or (iv) an acid prepared by the additive combination of phenol or a substitution product thereof with an unsaturated monocarboxylic acid, or an addition product of phenol with a polycarboxylic acid, or a mixture of any two or more of the acids (i) to (iv) with a polyamine in a ratio of amino groups: carboxyl groups greater than 1.

13. A synthetic resin mixture as claimed in claim 5 wherein the Mannich base is suitable for hardening epoxy resins and containing at least two reactive amino hydrogen atoms and is a reaction product of phenol or bis-phenol A, formaldehyde and dimethylamine containing 1 to 4 tertiary amino groups.

14. A synthetic resin mixture as claimed in claim 1, 2 or 3 wherein the epoxy-resin used in component (A) and/or compon-ent (B) is a glycidyl ether containing more than one epoxy group per molecule, which is derived from a polyhydric phenol or novo-lac and of which the epoxide value is between 0.100 and 0.600.

15. A synthetic resin mixture as claimed in claim 1, 2 or 3 including an adduct of the polyaminoamide and epoxy-resin in component (A) and/or component (B).

16 . A synthetic resin mixture as claimed in claim 1, 2 or 3 including a mixture of the polyaminoamide and epoxy resin in component (A) and/or (B).

17. A mixture as claimed in claim 1, 2 or 3 which contains a pigment.

18. A printed film or other substrate containing a clear surface coating, which has been obtained from a composition as claimed in claim 1, 2 or 3.

19. In intaglio printing, flexo-printing or screen printing the improvement in which a surface coating or a printing colour is prepared for a clear hardenable synthetic resin mixture as a binding agent, said mixture comprising: (A) a solid synthetic resin component containing free amino groups which is an adduct or a mixture of an epoxy resin and an excess of a polyamino-amide, having an amine number of 30 to 200 prepared from aliphatic dicarboxylic acids containing 6 to 13 carbon atoms or mixtures thereof and an excess of one or more diamines of the general formula (I) (I) in which R1 = H or CH3 and R2 = -CH2-NH2 or -C(CH3)2-NH2, aminoamide compounds and/or aminoimidazoline compounds and/or aminoamide compounds containing imidazoline groups, having amine-hydrogen equivalent weights of 90 to 500 based on poly-alkylene-polyamines of the general formula (II) (II) in which R may be an alkyl radical containing 1 to 4 carbon atoms or H, and x has the values 2 to 6 and y has the values 2 to 4, (a) amines of the general formula (II) or (b) amines of the general formula (III) H2N - (CHR)X -NH2 (III) in which R may be an alkyl radical containing 1 to 4 carbon atoms or especially H and x may have the values 2 to 6, Mannich bases suitable for hardening epoxy-resins and containing at least two reactive amine-hydrogen atoms and (B) a synthetic resin component containing free epoxy-groups, composed of an adduct of the solid polyaminoamides as in A and an excess of an epoxy-resin and containing (C) solvents free from aromatic substances.

20. A method as claimed in claim 19 in which the polyaminoamide of the solid synthetic resin component (A) is prepared additionally from aromatic and/or araliphatic and/or hydroaromatic dicarboxylic acids, which may be substituted by alkyl, and mixtures thereof in quantities of 0.95 to 0.05 equivalents, calculated on the total of carboxyl groups.

21. A method as claimed in claim 19 in which the polyaminoamide of the solid synthetic resin component (A) is prepared additionally from aliphatic, hydroaromatic and aromatic monocarboxylic acids or monofunctionally acting acids or ahydrides.

22. A method as claimed in claim 19 in which the polyaminoamide of the solid synthetic resin component (A) is prepared additionally from dimeric fatty acids and/or addition products of acrylic acid with unsaturated fatty acids and/or heptadecane dicarboxylic acids.

23. A method as claimed in claim 19 in which the polyaminoamide of the solid synthetic resin component (A) is prepared additionally from amines of the general formula (II) (II) in which R may be an alkyl radical containing 1 to 4 carbon atoms or H, and x has the values 2 to 6 and y has the values 2 to 4.

24. A method as claimed in claim 19 in which the resin component (A) includes aminoamide compounds and/or amino-imidazoline compounds and/or aminoamide compounds containing imi-dazoline groups, having amine-hydrogen equivalent weights of 90 to 500 based on polyalkyene-polyamines of the general formula (II).

25. A method as claimed in claim 19 in which the resin component (A) includes (a) amines of the general formula (II) or (b) amines of the general formula (III) H2N - (CHR)X-NH2 (III) in which R may be an alkyl radical containing 1 to 4 carbon atoms or especially H and x may have the values 2 to 6.

26. A method as claimed in claim 19 in which the resin component (A) includes Mannich bases suitable for hardening epoxy-resins and containing at least two reactive amine-hydrogen atoms.

27. A method as claimed in claim 19 in which the polyaminoamide in the adduct (A) is prepared only from the acids and diamines of formula (I).

28. A process as claimed in claim 19, 24 or 25 in which the resin component (A) is an admixture.

29. A process as claimed in claim 26 in which the resin component (A) is an admixture.

30. A method as claimed in claim 19 in which the mixture contains a pigment.