CH653042A5 - POLYAMINO AMID RESINS, POLYAMINO AMIDOIMMIDAZOLINICHE, THEIR EPOXY ADDUCTS AND KETIMMINE DERIVATIVES, AND RELATED SOLUTIONS FOR USE AS PLASTISOLS ADHESION PROMOTERS. - Google Patents

Description

The present invention has matured from the theoretical consideration that in reality the adhesive properties of the resins are dependent on their content of amino groups and amino bridges, as such or transformed into imidazolinic rings, as in the case of polyaminoamidoimidazolinic resins, and that therefore the activity such as adhesion promoters of such resins is specifically a function of their content of amino groups, amino bridges and imidazolin rings. Having considered this, the present invention therefore proposes to prepare polyaminoamide, or polyaminoimido-imino-linic resins, characterized by a high number of amino groups and amide bridges, as such or in the form of imidazolinic bridges, which are dispersible in the plastisols, thus giving high adhesion properties even if present in low concentration. With this idea of solution the problem of having to use known resins of the type defined above would be solved, resins which in general should be used in large quantities to give a satisfactory adhesion value, but which, as said, in such high quantities they irreparably alter certain basic properties of plastisols.

For this purpose, the present invention proposes polyamide resins mainly suitable for use as adhesion promoters of plastisols, according to claim 1.

Said resins according to the invention are therefore characterized in that they are condensation derivatives of dicarboxylic acids; if the latter are in a mixture with polymerized fatty acids according to the a) above defined, such dicarboxylic acids

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they are present in a mixture in an amount equal to at least 50% of equivalents of said fatty acids.

The aforesaid dicarboxylic acids can be: saturated or unsaturated linear or branched chain alified of not more than 12 carbon atoms, such as for example oxalic, malonic, succinic, glutaric, adipic, pimelic, suberic, azelaic, sebacic, trimethyladipic , maleic, fumaric; or saturated or unsaturated cycloaliphatic dicarboxylic acids, such as hexahydrophthalic acid, tetrahydrophthalic acid; or aromatic dicarboxylic acids, such as for example phthalic, isophthalic, terephthalic acid.

The invention also relates to epoxy adducts, obtained by treatment with epoxy resins such as the diglycidyl ether of the p.p'isopropylidendiphenol, of said polyamide and polyamide amidoimidazolinic resins; The object of the invention are also the corresponding ketimines, obtained by treating said resins with ketones, such as methyl ethyl ketone.

Resins, and their ketimine adducts or derivatives, according to the invention can be used as adhesion promoters for plastisols both as such and in solution. Both the concentration of the solution and the type of solvent can be varied according to the viscosity of the resin and its solubility.

The solvents suitable for the purpose can be selected from a wide range of organic compounds such as hydrocarbons, their chlorine and non-derivatives, alcohols, polyols, esters, ketones, amines and amides; a preferred solvent is benzyl alcohol.

In order to better describe the resins according to the invention, some examples of preparation are given below, numbered from 6 to 12, which should in no way be considered as limiting.

Said examples are preceded by examples, numbered from 1 to 5, concerning the preparation of resins according to the prior art; the latter are reported for the purpose of comparison with the resins according to the invention, as will be described below.

Example 1

Polyamide resin from polymerized fatty acids

285 parts by weight (1 equivalent) of polymerized fatty acids (obtained from unsaturated fatty acids with 18 carbon atoms, having the following composition: 1% monomers, 77% dimers, 22% tri-mers) are heated under stirring with 131, 4 parts by weight (1.8 equivalents) of triethylene tetramine, until reaching the temperature of 220 ° C and maintained at this temperature until the elimination of 18 parts by weight of water, after which heating is interrupted. The resin thus obtained is dissolved in 170 parts by weight of benzyl alcohol to lower its viscosity and make it easily and homogeneously dispersible in the plastisol.

Example 2

Polyamide resin epoxy adduct from polymerized fatty acids

To 100 parts by weight of the solution obtained as described in Example 1, 3.5 parts by weight of diglycidyl ether of the isopropylidendiphenol and 1.5 parts by weight of benzyl alcohol are added. Then the mass is kept for at least an hour at a temperature of about 100 ° C.

Example 3

Polyamide resin ketimine from polymerized fatty acids

A polyamide resin is prepared with the same raw materials, quantities and conditions indicated in example 1. Before proceeding to the benzyl alcohol solution, 288 parts by weight (4 moles) of methyl ethyl ketone and 74 parts by weight of cyclohexane (entrainer) are added. of water). The mass is brought to the boil by recycling the distillate in order to separate the water as it forms. The operation is continued until the cessation of water formation and then the excess of methyl ethyl ketone and cyclohexane are distilled. The product is then dissolved in 187 parts by weight of benzyl alcohol.

Example 4

Polyamide amido imidazolinic resin from polymerized fatty acids

285 parts by weight (1 equivalent) of polymerized fatty acids (as described in Example 1) are heated, under stirring, with 131.4 parts by weight (1.8 equivalent), of triethylene tetramine, until reaching the temperature of 260 ° C, this temperature is maintained until 27 parts by weight of water are eliminated after which heating is interrupted. The resin thus obtained is dissolved in 165 parts by weight of benzyl alcohol.

Example 5

Polyamide amido imidazolinic epoxy adduct

The solution obtained according to what is described in Example 4 is treated in the same way as described in Example 2.

Example 6

Polyamide resin from polymerized fatty acids and aliphatic dicarboxylic acid

85.5 parts by weight (0.3 equivalents) of polymerized fatty acids (as described in Example 1) and 51.1 parts by weight (0.7 equivalent) of adipic acid with 131.4 parts by weight (1, 8 equivalents) of triethylene tetramine are treated in the manner described in Example 1. The resin thus obtained is dissolved in 107 parts by weight of benzyl alcohol.

Example 7

Polyamide resin epoxy adduct from polymerized fatty acids and aliphatic dicarboxylic acid

The solution is obtained as described in Example 6 and treated in the same way as described in Example 2.

Example 8

Polyamide resin ketimine from polymerized fatty acids and aliphatic dicarboxylic acid

A polyamide resin is prepared with the same raw materials, quantities and conditions indicated in Example 6. Before proceeding with the solution in benzyl alcohol, it undergoes the ketimization treatment as described in Example 3 after which it is dissolved in 123 parts by weight. of benzyl alcohol.

Example 9

Polyamine amido imidazolinic resin from polymerized fatty acids and aliphatic dicarboxylic acid

The same quantities of substances indicated in example 6 are treated according to the process described in example 4. The resin thus obtained is dissolved in 99 parts by weight of benzyl alcohol.

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Example 10

Polyamide amido imidazolinic epoxy adduct from polymerized fatty acids and aliphatic dicarboxylic acid

The solution obtained according to what is described in Example 9 is treated in the same way as described in Example 2.

Example 11

Polyamide resin from polymerized fatty acids and aromatic dicarboxylic acid

85.5 parts by weight (0.3 equivalents) of polymerized fatty acids (as described in Example 1) and 58.1 parts by weight (0.7 equivalent) of isophthalic acid with 131.4 parts by weight (1, 8 equivalents) of triethylene tetramine are treated in the manner described in Example 1. The resin thus obtained is dissolved in 110 parts by weight of benzyl alcohol.

Example 12

Polyamide resin epoxy adduct from polymerized fatty acids and aromatic dicarboxylic acid

The solution obtained according to what is described in Example 9 is treated in the same way as described in Example 2.

All the products of the examples are constituted by solutions of resins or adducts of 70% in benzyl alcohol which acts as a solvent and dispersing agent.

Comparison tests were conducted to evaluate the extent of adhesion promotion on the plastisols of the resins (adhesion promoters) prepared according to the examples previously described.

These tests were performed on a plastisol of the following percentage composition:

Polyvinyl chloride 33 .-

Dioctylphthalate 34 .-

Titanium dioxide 8 .-

Kaolin 10.-

Colloidal silica 0.5

Diglycidyl ether of 1-4 butanediol 0.4

Adhesion promoter 1 .-

The tests were carried out by subjecting to the tensile shear test two steel plates of 100 x 25 mm, roughened with emery cloth, glued with a layer of plastisol under examination with a thickness of 2 mm, for a surface of 250 mm2 and 5 fired at 140 ° C for 30 minutes.

The results obtained with the products prepared in Examples 1 to 12 are reported in the following table:

Table I.

Adhesion promoter Tensile shear strength

(average 5 tests)

Kg / cm2

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Example No. 1 - 3.6

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3 7.5

4 4.6

5 4.8

6 17.5

7 18.1

8 28.2

9 18.9

25 10 19'5

11 17.3

12 17.9

30 As evidenced by these results, the products according to the invention (adhesion promoters of Examples 6 to 12) give the plastisol in question a significantly increased tensile shear strength compared to that obtainable with the products according to the prior art, and equal dosage in the 35 composition of the plastisol.

This shows that the resins of the invention, as well as their epoxy and ketimine derivatives, are able to significantly increase the adhesion of plastisols to metal surfaces even in low concentrations, to which there is no danger of 40 negatively affecting the remaining properties of plastisols, such as applicability and cohesion of the final coating.

Claims (11)

653 042 1. Polyamide resins consisting of units derived from: a) polycarboxylic acids, from 0 to 0.5 equivalents, in turn derived from unsaturated fatty acids consisting of: 0-2% by weight monomers, 58-98% by weight dimers, 2-40% by weight trimers, and b) from 0.5 to 1 equivalents of dicarboxylic acids, c) with from 1 to 2 equivalents of aliphatic polyamines of general formula: H2N- (CH2) x- (NH (CH2) y) n-NH2 where x, y and n are integers equal to or different from each other, greater than 2, either from their epoxy adduct, or from a corresponding ketimine. 2. Resins according to claim 1, characterized in that they are polyamine amidoimidazolinic resins. 2 3. Resins according to claim 1, characterized in that said dicarboxylic acids are aliphatic, saturated or unsaturated, with a straight or branched chain not exceeding 12 carbon atoms. 4. Resins according to claim 1, characterized in that said dicarboxylic acids are cycloaliphatic, saturated or unsaturated. 5. Resins according to claim 1, characterized in that said dicarboxylic acids are aromatic. 6. Resins according to claim 3, characterized in that said aliphatic dicarboxylic acids are selected in the following group: adipic, oxalic, malonic, succinic, glutaric, polic, suberic, azelaic, sebacic, trimethyladipic, maleic, fu-maric. 7. Resins according to claim 4, characterized in that said cycloaliphatic dicarboxylic acids are selected in the following group: hexahydrophthalic, tetrahydrophthalic. 8. Resins according to claim 5, characterized in that said aromatic dicarboxylic acids are selected in the following group: phthalic, isophthalic, terephthalic. 9. Resins according to claim 1, characterized in that said epoxy resin is the diglycidyl ether of p.p'.iso-propylidendiphenol. 10. Resins according to claim 1, characterized in that said ketone is methyl ethyl ketone. 11. Use of resins according to claim 1 as adhesion promoters of plastisols. It is known that plastisols essentially consist of a liquid dispersion of a polymer powder in a plasticizer in which the polymer must not be appreciably soluble at room temperature. When the plastisols are subjected to the action of heat, a dissolution of the polymer in the plasticizer takes place, with the formation of a more or less elastic homogeneous mass. The plastisols are mostly used as insulating and soundproofing coatings, for example in the automotive industry, by application on different types of metal surfaces, to which however they have very little adhesion. It has long been known from common experimentation that this adhesion is increased if polyamide resins which are homogeneously dispersed in them are added to the plastisol. According to the prior art, suitable for the purpose, the polyaminoamide and polyamidoimidazolinium resins prepared by condensation of aliphatic polyamines with polycarboxylic acids obtained by the polymerization of unsaturated fatty acids, the adducts with epoxy resins obtained from them and the ketimines obtainable of the same resins are obtained. ketone treatment. The aliphatic polyamines mentioned above are those having the general formula H2N- (CH2) x- (NH (CH2) y) nNH2 where x, y and n are integers, equal or different than 2. Said polycarboxylic acids, obtained by the polymerization of unsaturated fatty acids, are made up of mixtures of polymers of unsaturated fatty acids with 18 carbon atoms, with a composition comprised between the following limits: 0-2% monomers, 58-98% dimers, 2- 40% trimers. The epoxy adducts derived from the aforementioned resins are those which are obtained by reacting the same with the products containing terminal epoxy groups such as the polyglycol-diethers of polyhydroxylated phenols. Ketamines are those obtained by treating the above resins with ketones, so as to give rise to the transformation of the primary amino groups into ketymine groups with the elimination of water according to the following reaction: R R I I -NH2 + CO ► -N = C + HzO I I R '. R ' However, it has been found experimentally that with known polyaminoamide and polyaminoimidazolinic resins of the type defined above, and with the adducts and ketimines obtained from them, limited results are obtained because, while the adhesion strength of plastisol increases with increasing quantity of added resin, this quantity cannot practically exceed a certain level beyond which certain properties of the plastisol, such as the applicability and cohesion of the final coating, would be altered; in addition, it should be considered that the use of such resins in high quantities is not cheap. The properties of increasing the adhesion of the plastisols of the polyaminoamide and polyaminoimido-amino acids resins, and their adducts with epoxy resins, has been discovered empirically by experimenting with various products.