Note: Descriptions are shown in the official language in which they were submitted.
206~640
PATENT
517710-2530
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.
12
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
13
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
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