CA2065640A1

CA2065640A1 - Polyamide resins and their use in relief printing

Info

Publication number: CA2065640A1
Application number: CA 2065640
Authority: CA
Inventors: Manfred Drawert; Horst Krase
Original assignee: Individual
Current assignee: Lanxess Organometallics GmbH
Priority date: 1991-04-10
Filing date: 1992-04-09
Publication date: 1992-10-11
Also published as: EP0508054A2; DE4111670A1; EP0508054A3; JPH05125184A

Abstract

ABSTRACT

Polyamide Resins and Their Use in Relief Printing The invention relates to polyamides based on mixtures of acids, amines and amino acids and to their use in making non-yellowing relief prints in particular

Description

206~640 PATENT

POLYAMID~ R~8IN~ AND TH~IR U8B ~N RELIEF PRINTING
The invention relates to polyamides based on mixtures of acids, amines and amino acids and to their use particularly in the production of non-yellowing relief printing which, moreover, shows good adhesion to various substrates.
The decoration of organic and inorganic substrates has long been known.
The original technique of applying relieflike imprints to paper or cardboard for book covers, promotional articles, postcards, calling cards, wrappers, etc., consists of producing the raised or depressed impression with engraved plates or with printing type on printing presses with or without ink transfer. The printing is done in one or several colors in one or more operations and then raised in relief.
In recent years, a modification of this process has steadily been gaininq ground. Here the substrates are still provided with an impression, but embossing is dispensed with.
The relief is produced by coating the impression with a thermoplastic resin.
In actual practice, the substrate is printed by the offset process with inks commonly used for this purpose. This is immediately followed by sprinkling a finely pulverized thermoplastic resin onto the still wet and tacky surface of the impression. The excess is drawn off by suction from the areas which have not been printed and therefore are not tacky.

20656~

During the heat treatment which follows, the resin is heated to temperatures above its melting point.
The thermoplastic resins used must meet a number of requirements. The most important of t:hese are that the resin should have no color of its own, or then as little as , possible, and that it should be capable of being ground to a fine powder which does not block even under conditions of use and thus remains free-flowing.
While the polyamide resins based on dimerized fatty acids and ethylenediamine which have been used up to now for this purpose do meet several of these requirements, they do not fully satisfy others, such as color index, resistance to discoloration, and adhesion to metal and glass in particular.
Moreover, hydrogenated fatty acids with iodine numbers above 10 are needed to produce them, and during condensation even minor amounts of atmospheric oxygen will result in an appreciable degradation of the color index.
The present invention seeks to overcome these drawbacks of the prior art and to provide resins which, in contrast to the resins used up to now which produce a smooth, glossy surface, impart to relief prints an effective, matte surface with a grainy structure which at the same time is scratch-resistant.
These resins should also provide good adhesion to various substrates, and particularly to paper, cardboard, metal and glass, good flexibility, compatibility with the background ink, and nontacky surfaces.

2~640 From German published patent application OS 35 10 415, polyamides are known whi.ch are based on a hydrogenated dimerized fatty acid, optionally a co-dicarboxylic acid, a specially matched combination of straight-chain and branched short-chain monocarboxylic acids, and an amine mixture of ethylenediamine and hexamethylene-dia~ine. While these products represent an improvement so far as ~urface properties, color index and discoloration resistance are concerned, their preparation still requires that the dimerized fatty acids be hydrogenated to the point where the iodine number is not higher than 25. Relief prints made with these resins show a smooth, glossy surface.
The present invention has as its object polyamides which can be prepared by condensation of (A1) at least one aliphatic dicarboxylic acid of the general formula HOOC-(CH2)n-COOH, where n = 4-11; and (A2) at least one of the acids of the general formula HOOC-R-COOH, where the radical R may be {~ -C~2 ~c~z~ ~ -C~:2 ~ C~2 and where the ratio of (Al) to (A2) ranges from 1:0.1 to 1:2 mols; and 20~56~0 (A3) a saturated monocarboxylic acid in an amount of up to 0.1 mol, based on the amount of the carboxylic acid of (Al); and (B) at least one diaminP from the group ~onsisting of 1,6-diaminohexane, 1,5-diamino 2-methylpentane, 2,4,4- or 4,4,2-trime~hyl-1,6-diaminohexane, 1,9-diaminononane and 1,12-diaminododecane, where the ratio of the components (Al) plus (A2) to (B) is essentially (based on amino and acid groups) equivalent; and (C) at least one amino acid of the general formula H2N- ( CH2 ) n-COOH, where n = 5-11, or its lactams, from 0.5 to 1.5 mols of amino acid or lactam being used per mol of carboxyl groups of the acids named under (A), by procedures known per se, at temperatures ranging from 200 to ~80 C, optionally employing commonly used amidation catalysts, and at a vacuum of less than 100 millibars applied at the end of the reaction.
A further object of the invention is characterized in that 1.0 mol of sebacic acid is used as component (Al), and from 0.3 to 0.8 mol of isophthalic acid as component (A2), dimerized fatty acid being optionally substituted for up to le~s than 0.05 mol of the isophthalic acid, and that from 1.3 to 1.8 mols of 1,6-diaminohexane is used as component (B), and from 2.6 to 3.6 mols of caprolactam as component (C).

20~56~
Still another object of the present invention is a process for the preparation of polyamides by polycondensation of (Al) at least one aliphatic dicarboxylic acid of the general formula HOOC-(CH2)n-COOH, where n = 4-11, and optionally (A2) at least one of the acids of the general formula HOOC-R-COOH, where the radical R may be {~ - C El ~ F 8---DFS- representing the residue of the dimerized fatty acid, and where the ratio of (A1) to (A2) ranges from 1:0.05 to 1:2.0 mols and preferably is 1:0.5 mol; and (A3) a saturated monocarboxylic acid in an amount of up to 0.1 mol, based on the amount of the carboxylic acid of (A1);
and (B) at lea t one of the diamines selected from the group consisting of 1,6-diaminohexanP, 1,5-diamino-2-methylpentane, 2,4,4- or 4,4,2-trimethyl- 1,6-diaminohexane, l,9-diaminononane and 1,12-diaminododecane, where the ratio of the components (Al) plus (A2) to (B) is essentially (based on amino and acid groups) equivalent; and 20~6~

(C~ at least one amino acid of the general formula H2N--( CH2 ) n--COOH, where n = 5-11, or it~ lactams, from 0.5 to 1.5 mols of amino acid or lactam being used per mol of carboxyl groups of the acids named under (A~, by procedures known per se, at temperatures ranging from 200 to 280 C, optionally employing commonly used amidation catalysts, and at a vacuum of less than 100 millibars applied at the end of the reaction.
A further object of the invention is the use of the polyamide re~ins of the invention in the production of relief prints.
Suitable dicarboxylic acids according to (A1~ are ~traight-chain dicarboxylic acids having from 6 to 13 carbon atoms, such as adipic acid, suberic acid, azelaic acid, brassylic acid, and preferably sebacic acid and decamethylene-dicarboxylic acid. If desired, shorter-chain dicarboxylic acids such as adipic acid or pimelic acid may also be used.
Suitable dicarboxylic acids according to (A2) are 1,4- or lr3-cyclohexanedicarboxylic acid, 1,4- or 1,3-cyclo-hexanediacetic acid, terephthalic acid, 1,4- or 1,3-phenyl-diacetic acid, and particularly isophthalic acid.
By dimerized fatty acids are meant commercial polymerized fatty acids which have iodine numbers ranging from 20~6~

about 100 to 130 and whose dimeric fatty-acid content has been increased by commonly used processes to about 85-100 percent.
The iodine nu~ber is determined by methods commonly ~ployed in practice and is expressed in grams of iodine per 100 grams of substance.
The polymerized fatty acids can be prepared by the usual processes (see U. S. patent~ 2,482,761 and 3,256,304, for example) from unsaturated natural and synthetic monobasic aliphatic acids having from 12 to 22, and preferably 18, carbon atoms.
Typical commercial polymeric fatty acids have approximately the following composition prior to distillation:
~onomeric acids 5 to 15 wt. %
Dimeric acids 60 to 80 wt. %
Tri- and higher-polymeric acids 10 to 35 wt. %
After distillation, the dimeric acid fraction should be nearly free of monocarboxylic acids, and the proportion of trimerized and higher-polymerized fatty acids should be 1 -~eight percent or less.
Both the distilled and the undistilled fatty acids can be hydrogenated by known processes to lower the iodine number, preferably to the range from 10 to 40. In accordance with the invention, hydrogenated dimerized fatty acids with iodine numbers between 10 and 15 and a dimeric fatty acid content of not less than 90 weight percent are preferred.
The composition of the fatty acids is determined by the usual gas-liquid chromatography (GLC) techniques, with the 2~6~640 specification of the dimer content including, in addition to the dimerized fatty acids, the minor amounts of completely or partially decarboxylated dimerization ]products which are necessarily formed in the dimerization process.
The ratio of the carboxylic acids (A1) to (A2) should range from 1:0.1 to 1:2 mols, and preferably from 1:0.3 to 1:0.8 mol and will depend on the particular components (A1) and (A2)~ and in some measure on the amount and nature of component (c), that is, the amino acid or lactam. For the preparation of particularly lightfast polyamides, it is preferred, in accordance with the invention, that no dimeriz~d fatty acid, or then not more than 0.05 mol, be used.
For regulation of the molecular weight, mono-carboxylic acids having up to 18 carbon atoms may be used, the higher saturated and straight-chain acids having from 16 to 20 carbon atoms, such as palmitic acid and stearic acid in particular, being preferred in accordance with the invention.
These acids are preferably used in-amounts of from 0.05 to 0.1 mol, based on the carboxylic acids of (Al).
The molecular weight may also be regulated with excess acid or amine. However, since free carboxyl groups or amino groups are then present in the molecule, this approach is le6s preferred in accordance with the invention.
In addition to the preferred 1,6-diaminohexane, 2-methyl-1,5-diaminopentane and a mixture of isomerC of 2,4,4-or 4,4,2-trimethyl-1,6-diaminohexane, 1,9-diaminononane and 1,12-diaminododecane may also be used as amino components.

2~656~0 The ratio of tha acid component (A) to the amino components (B) i6 approximately equivalent. The polyamides preferably have amine and acid values not higher than 10, and the ~um of the acid and amine values should not exceed 10, either.
The amino acids of (C) which in accordance with the invention may also be used have the general formula H2N- ( CH2 ) n-COOH
where n = 5-11, or their lactams, preferably with n = 5.
From 0.5 to 1.5 mols, and preferably 1.0 mol, of amino acid or lactam should be used per mol of carboxyl groups of the dicarboxylic acids named under (A).
If necessary, minor amounts of commonly used monocarboxylic acids, and preferably of stearic acid, may be used for regulation of the molecular weight or of the ViSCOSity.
The polyamide resins used in accordance with the invention can be ground into a powder that will remain free-flowing even under conditions of use, possibly with the concurrent use of antiblocking agents such as stearates, Aerosil0, etc. The particle size of the powder may be varied as required and will range from 40 to 500, and preferably from 80 to 200, microns.
Ths melting point of the resins is adapted to the actual requirements. It is sufficiently lsw to prevent impairment of the substrate or of the background ink by the 2~64~
melting temperatures, yet high enough for no blocking to occur even at application temperatures.
The preferred melting range, as measured by the ring ~nd ball method, is from about 90 to 150 C, and preferably from 100 to 140 C.
The resins have a narrow melting range, which makes it possible rapidly to achieve freedom from tackiness and blocking during the cooling stage which follows the melting stage. This is an important factor in attaining short cycle times.
The melt viscosities, measured uniformly at 220 C
with a rotary cone-plate viscometer as directed by its manufacturer, Haake, range from about 10 to 200 Pa s, and more particularly from 15 to 80 Pa-s, and preferably from 20 to 50 Pa-s.
The polyamide resins of the invention, which are compatible with the background inks commonly used in this field, permit a combination of additional and novel properties and effects to be achieved in relief printing.
In contrast to the resins commonly used up to now, which provide a smooth, glossy, delicate surface, the resins of the invention impart to relief prints an effective, matte surface with a grainy texture or a fine-grained leather texture which has extraordinary scratch resistance.
In addition to good adhesion to the usual substrates, such as cardboard, paper, fabrics made of natural 2~65~40 and/or sy~thetic fibers, cloth and tapestries, the resins of the invention have excellent adhesion to metal and glass.
The grainy texture further impart~ sure-grip prop~rties to containers so imprinted, such as bottles and ~ar~ for cosmetics.
Because of the negligible intrinsic color and high transparency of the polyamide resins of the invention, shifts in hue of the 6ubjacent color print do not occur, and these resins are substantially non-yellowing both during application and on exposure to ultraviolet radiation.

TESTING OF POLYAMIDE RESINS
Procedure A
The inventive polyamide resins of Examples 1 to 22 were coarsely crushed, chilled with dry ice and/or liquid nitrogen, and ground cold in an impact disk mill (made by Alpine). From the powder so obtained, a size fraction of from 40 to 500 microns wa~ then screened out by means of a set of screens. A black-pigmented high-viscosity offset ink was then applied by means of a simple manually operated letterpress to the coated (smooth) side of a white light-weight cardboard, and, after 10 to 20 seconds' airing, the screened powder was sprinkled onto it. Because of the tacky character of the ink, an amount of powder sufficient for the formation of a textured surface adhered while the surplus material could readily be removed. The cardboard so prepared was then heated in a special powder-melting apparatus (a Konvexograph, made by Grafra) with infrared lamps from above, at a distance of 20 to 206~4~
30 cm. After a retention time of about 5 to 10 seconds, highly scratch-resistant, grainy surface textures were obtained. Since the polyamide resins have virtually no intrinsic coloration and no tendency 1:o yellow, no graying of the black color of the printing ink could be observed.

.
procedure B
A variation of the application of a background ink consists in first printing a polyamide resin varnish capable of being reactivated, in the form of the desired designs, by gravure printing onto continuous sheets, such as a web of aluminum foil. Unlike the offset ink referred to above, this ~pecially formulated varnish is tackfree immediately after printing, and the aluminum foil wound into rolls after the printing operation can therefore be readily unwound. The foil or foil sections ~o unwound are heated ~hortly before the powder is ~prinkled onto them. As a result, the imprinted varnish becomes tacky and because of its special formulation remains tacky for from 3 to 10 seconds after cooling, with the powder sprinkled onto it adhering to the varnish in the desired amount. The further melting process takes place as described above.
The advantage of these so-called reactivatable inks is that they permit sheet material in the form of rolls with a background color to be produced and kept in stocX, which cannot be done with the previously mentioned tacky offset ink.
The texture of the surfaces in relief is independent of the above procedures.

2~6~40 Procedure C
Polyamide powder of a particle size of 300-400 ~icrons was applied at the rate of 20 g/m2 to strips 5 cm wide o~ a polyester/wool (55%/45%) fabric.
The fabric strips so treated were adhesive-bonded at temperatures about 20-30 C above the softening point of the polyamide ~dhesive to a second, untreated fabric strip. The bonding time wa~ about 15-20 seconds, and the bonding pressure, 400 g/cm2.
The adhesive-bonded fabric strips were completely immersed in a perchloroethylene bath, and after 30 minutes their peel strength was determined wet in conformity with DIN
53310.

pREPARATION OF POLYAMIDE RESINS
Example 1 In a 2-liter three-neck flask equipped with stirrer, thermometer and downward condenser, 202.0 g (1.0 mol) of sebacic acid (A1), 83.0 g (0.5 mol) of isophthalic acid (A2), 20.0 g (0.07 mol~ of stearic acid (A3), 339.0 g (3.0 mols) of caprolactam (C), 182.3 g (1.57 mols) of hexamethylenediamine (B), and 0.21 g of 85% phosphoric acid (0.25 wt. %, based on total weight of ingredients) as a catalyst, were mixed under nitrogen. In addition, 100.0 g of desalted water was added for better homogenization and heated over 2 hours to 240 C.
This temperature was maintained for 2 hours, a vacuum of 5 millibars being applied during the last 2 hours. This was followed by flushing with nitrogen, and the polyamide was then 2~6~40 discharged. The polyamide obtained had a ring-and-ball ~oftening point (DIN 52011) of 129 C~ a viscosi$y of 26.0 Pa-~ at 220 C (determined by means of the PK 401 W rotational viscometer a6 dir~cted by its manufact:urer, Haake of Rarlsruhe/Berlin), an acid value of 3.9, and an amine value of 0.7 The examples given in Table 1 which follows were prepared in the ~ame manner.

~P~NATORY NO~ TO TABLE 1 Ami~e ~alue = mg KOH/g of substance.
A~d ~alue = mg XOH/g of substance.
R~B = Softening point, as determined by the ring-and-ball method (DIN S2011).
~¢. = Viscosity, determined at 220 C directly from the melt by means of the PK 401 W cone-plate vi~cometer as directed by its manufacturer, Haake of Karlsruhe/Berlin.
Pripol0 = Trademark of Unichema International.
ripol~0 1009 = Hydrogenated polymerized fatty acid containing:
0.1% monomeric fatty acid 99.0% dimeric fatty acid 1.0% trimeric fatty acid Pripol0 1013 Polymerized fatty acids containing:
0.1% monomeric fatty acid 95.0% dimeric fatty acid 5.0% trimeric fatty acid 2~5640 ~- ~o o .~ ~ ~ o o~
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Claims

1. A polyamide prepared by condensation of (A1) at least one aliphatic dicarboxylic acid of the general formula HOOC-(CH2)n-COOH
where n = 4-11;
(A2) at least one of the acids of the general formula HOOC-R-COOH
where the radical R is , , or , and where the ratio of (A1) to (A2) ranges from 1:0.1 to 1:2 mols; and optionally (A3) a saturated monocarboxylic acid in an amount of up to 0.1 mol, based on the amount of the carboxylic acid of (A1); and (B) at least one diamine selected from the group consisting of 1,6-diaminohexane, 1,5-diamino-2-methylpentane,

2,4,4- or 4,4,2-trimethyl-1,6-diaminohexane, 1,9-diaminononane and 1,12-diaminododecane, where the ratio of the components (A1) plus (A2) to (B) is essentially equivalent based on amino and acid groups;
and (C) at least one amino acid of the general formula H2N-(CH2)n-COOH

where n = 5-11, or its lactams, from 0.5 to 1.5 mols of amino acid or lactam is used per mol of carboxyl groups of the acids named under (A), at temperatures ranging from 200 to 280° C, optionally employing commonly use damidation catalysts, and at a vacuum of less than 100 millibars applied at the end of the reaction.

2. The polyamide as defined in claim 1, wherein .epsilon.-aminocaproic acid, caprolactam, or both, are used as the amino acid (C).

3. The polyamide as defined in claim 1, wherein dimerized fatty acid is substituted for up to less than 0.05 mol of the co-dicarboxylic acid of (A2).

4. The polyamide as defined in claim 1, wherein 1.0 mol of sebacic acid is used as component (A1), from 0.3 to 0.8 mol of isophthalic acid is used as component (A2), dimerized fatty acid is optionally substituted for up to less than 0.05 mol of the isophthalic acid, from 1.3 to 1.6 mols of 1,6-diaminohexane is used as component (B), and from 2.6 to 3.6 mols of caprolactam is used as component (C).

5. A process for the preparation of a polyamide comprising polycondensation of (A1) at least one aliphatic dicarboxylic acid of the general formula HOOC-(CH2)n-COOH
where n = 4-11;

(A2) at least one of the acids of the general formula HOOC-R-COOH
where the radical R is , , , or -DFS- , where -DFS- represents the residue of dimerized fatty acids, and where the ratio of (A1) to (A2) ranges from 1:0.05 to 1:2.0 mols; and optionally (A3) a saturated monocarboxylic acid in an amount of up to 0.1 mol, based on the amount of the carboxylic acid of (A);
(B) at least one of the diamines selected from the group consisting of 1,6-diaminohexane, 1,5-diamino-2-methylpentane, 2,4,4- or 4,4,2-trimethyl-1,6-diaminohexane, 1,9-diaminononane and 1,12-diaminododecane, where the ratio of the components (A1) plus (A2) to (B) is essentially equivalent based on amino and acid groups;
and (C) at least one amino acid of the general formula H2N-(CH2)nCOOH
where n = 5-11, or its lactams, from 0.5 to 1.5 mols of amino acid or lactam is used per mol of carboxyl groups of the acids named under (A), at temperatures ranging from 200 to 280° C, optionally employing commonly used amidation catalysts, and at a vacuum of less than 100 millibars applied at the end of the reaction.

6. The process as defined in claim 5, wherein 1.0 mol of sebacic acid is used as component (A1), 0.5 mol of isophthalic acid is used as component (A2), dimerized fatty acid is optionally substituted for up to 0.05 mol, 1.5 mols of 1,6-diaminohexane is used as component (B), and 3 mols of caprolactam is used as component (C).

7. The process as defined in claim 5, wherein the components (A) to (C) and their ratios are chosen so that the polyamides have melting points between 90 and 150° C.

8. The process as defined in claim 5, wherein the components (A) to (C) and their ratios are chosen so that the viscosities, determined at 220°C, range from 10 to 150 Pa?s.

9. The process as defined in claim 5, wherein the ratio of (A1) to (A2) is 1:0.5 mol.

10. The process as defined in claim 6, wherein the components (A) to (C) and their ratios are chosen so that the viscosities, determined at 220°C, range from 10 to 150 Pa?s.

11. The process as defined in claim 7, wherein the components (A) to (C) and their ratios are chosen so that the viscosities, determined at 220°C, range from 10 to 150 Pa?s.