U.S. patent number 3,616,176 [Application Number 04/681,231] was granted by the patent office on 1971-10-26 for polyamide decal.
This patent grant is currently assigned to General Mills, Inc.. Invention is credited to George A. Jachimowicz.
United States Patent |
3,616,176 |
Jachimowicz |
October 26, 1971 |
POLYAMIDE DECAL
Abstract
There is disclosed a dry thermal transfer decal consisting of a
single polyamide film having decoration thereon which film serves
as a carrier for the decoration, a protective coating for the
decoration and the adhesive layer. The polyamide is the thermal
amidification product of essentially equivalent amounts of a
polymeric fat acid having a dimeric fat acid content greater than
80 percent by weight and of a diprimary diamine.
Inventors: |
Jachimowicz; George A.
(Kankakee, IL) |
Assignee: |
General Mills, Inc.
(N/A)
|
Family
ID: |
24734366 |
Appl.
No.: |
04/681,231 |
Filed: |
November 7, 1967 |
Current U.S.
Class: |
428/200; 428/914;
156/240; 428/479.3; 428/211.1 |
Current CPC
Class: |
B44C
1/1712 (20130101); Y10T 428/24843 (20150115); Y10T
428/24934 (20150115); Y10T 428/31779 (20150401); Y10S
428/914 (20130101) |
Current International
Class: |
B44C
1/17 (20060101); B44c 001/16 (); C09j 007/00 () |
Field of
Search: |
;117/3.4,36.1
;161/167,165 ;156/230,231,240 ;260/404.5,407,18N,37N |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Burnett; Robert F.
Assistant Examiner: Roche; R. J.
Claims
The embodiments of the invention in which an exclusive property or
privilege is claimed are defined as follows:
1. In a dry thermal transfer decal consisting of a transfer
structure having decoration thereon the improvement wherein said
transfer structure consists of a single layer having a film
thickness of about 0.1 to 3.0 mils of a thermoplastic polymeric fat
acid polyamide having a softening point of from 70.degree. C. to
180.degree. C., said polyamide serving simultaneously as (a) a
carrier for said decoration (b) a protective coating for said
decoration and (c) the adhesive layer, said polyamide being the
thermal amidification product at temperatures between 100.degree.
C. and 300.degree. C. in which essentially equivalent amounts of
carboxyl and amine are employed, or a polymeric fat acid having a
dimeric fat acid content of greater than 80.degree. by weight and a
diprimary diamine of the formula H.sub.2 N--R--NH.sub.2 where R is
an aliphatic, cycloaliphatic or aromatic hydrocarbon radical having
from two to 40 carbon atoms.
2. A decal as defined in claim 1 wherein said polyamide layer
comprises a continuous film of said polyamide.
3. A decal as defined in claim 2 wherein said polyamide layer
comprises a fibrous material impregnated with said polyamide.
4. A decal as defined in claim 1 wherein said polyamide is the
thermal amidification product of polymerized tall oil fatty acids
and a mixture of ethylene diamine and diamino propane.
5. A decal as defined in claim 1 wherein said polyamide is the
thermal amidification product of a mixture of polymerized tall oil
fatty acids and sebacic acid and a mixture of ethylene diamine and
1,3-di(4-piperidyl)propane.
6. A decal as defined in claim 1 wherein said polyamide is the
thermal amidification product of polymerized tall oil fatty acids
and a mixture of ethylene diamine and a dimeric fat acid
diamine.
7. A decal as defined in claim 1 and further comprising a release
sheet on said transfer structure.
Description
This invention relates to decals employing polymeric fat acid
polyamides as a transfer structure. The polymeric fat acids having
a dimeric fat acid content of at least 80 percent by weight. These
polyamides possess a combination of properties which permit
utilization in virtually all types of hot transfer equipment and
application to a large variety of substrates. Thus the decal of the
present invention has general overall application in the decorative
barriers, decorative or printing field whereas other types of
decals have only limited application.
FIG. 1 shows an enlarged diagrammatic view of a preferred complete
decal structure of the present invention.
FIG. 2 illustrates diagrammatically a simplified version of
effecting transfer by utilization of thermal energy to a
substrate.
Essentially the decal comprises a release sheet 10, a polymeric
fact acid polyamide layer 11 to which is applied a decorative layer
12, layers 11 and 12 forming the transfer structure. The decal is a
dry transfer one which means that no soaking of the decal in a
liquid such as water is necessary to transfer the decorative
material to the substrate to which it is to be applied. Because of
the nature of the polyamide employed, the decal is a hot transfer
label by which is meant that thermal energy is required to effect
transfer of the decorative material.
In FIG. 2, there is shown diagrammatically a simple version of
application of the decal to the substrate. In this version a
thermal energy source 13 shown as a heated roller, is employed to
transfer the decal comprising 10, 11 and 12 to the substrate 14. In
this version, the decal is brought into contract with the substrate
14 and the heated roller applied to the decal for a time sufficient
to heat seal the decal to the substrate. The time period is not
critical and in most instances is measured in few seconds. It is
important, however, that the heat be applied so that the polyamide
layer is heated near or above its softening point so that the layer
may be heat sealed or fused to the substrate. Upon withdrawal of
the heat source, the polyamide layer quickly cools to a temperature
below its softening point and the release sheet is removed, the
polyamide layer with the decorative layer being bonded, fused or
sealed to the substrate. In some use applications, the release
sheet may be dispensed with, such as applications in which the
thermal energy or heat source will not come into direct contact
with the decal. In instances where direct contact of the heat
source or where application of pressure is necessary, a release
sheet may be necessary.
In this invention, the polyamide layer acts as the decorative or
printing material acceptor or carrier, the adhesive layer and a
coating layer which protects the decorative layer. In decals of the
past, it was common to use a separate layer upon which the
decorative material was applied, and/or a separate adhesive layer
and/or a separate protective coating layer. In this invention, the
polyamide layer serves all three functions. Further, while the
decals are decorative to the eye, they may also perform
functionally as a barrier for gas permeability, such as for
nitrogen gas. Where this barrier function is important or
desirable, the decal is applied over the whole or major part of the
container wall or substrate, as an overlay. Thus both a decorative
and functional film is applied.
The decals find particular utility in the container field, of
interest to the producer, decorator and packer of conventional
containers such as blow-molded containers or prefabricated
containers such as boxes, bottles or tubes. The decal will also
find use as a label to provide a clear printed or other decorative
layer to any items, including, but not limited to, identification
catalog indicia on books in libraries or decorative protective
covers for books, and on virtually any item desired since the
polyamide layer will bond to metal, wood, leather, paper, plastics
such as vinyl, polyethylene, polypropylene. The particular
polyamide layer employed, of course, will be selected for the
optimum adhesion properties to the desired item.
The invention will therefore be useful in any industry where
decorative or printed material is found on the items such as gift
papers, sporting goods, appliances, automotive, shoe and luggage,
furniture, publishing and stationery, apparel and haberdashery.
The decal provides a total container or labeling service technology
in a market where customers require surfaces exposed to wear and
abuse, a multiplicity of colors and shapes, adhesion to substrates
hard to decorate, daily short production runs, flexibility in high
speed applications and favorable economics for decorating
disposable items.
As indicated, the polyamide layer is the acceptor or carrier for
the decorative material whether the decorative material be a
continuous uninterrupted surface or a discontinuous surface such as
in printing. The polyamide layer itself may be clear, virtually
water white or may be dyed or colored to provide a colored but
clear and transparent layer or it may be an opacified layer. A wide
variety of printing methods may be employed as the polyamide layer
is receptive to a wide range of inks of varying properties.
Accordingly, there may be employed offset methods, lithographic,
rotogravure or flexographic printing techniques.
As indicated the decal may be transferred to the finished object or
package or during fabrication of the item such as blow-molded
containers where there is fusion with the substrate. Hot-stamping
presses, a relatively high-pressure method, may be employed for
application of the decal. Also low-pressure methods such as hot
roller or hot air contacts may be employed. The hot-roller method
is exemplified in the drawing. Any conventional method or
equipment, by which thermal energy may be applied to the decal, may
be employed.
Briefly, the decal is formed by applying to the release sheet the
polyamide layer upon which the decorative material may be then
applied. The polyamide layer is preferably applied from a solution
to the release sheets. Upon evaporation of the solvent, a
continuous film is left on the release sheet. The polyamide may
also be applied to the release sheet by extrusion of a continuous
film thereon. Colors, dyes or opacifying agents may be included in
the polyamide. Alternatively, the polyamide layer may comprise a
fibrous material which has been impregnated with the polyamide,
which impregnated fibrous material may then be applied to the
release sheet either in its wet state directly after impregnation
from a solution or by heat activation thereof prior to application
to the release sheet. In these cases, the polyamide layer is a
fibrous reinforced film. The fibrous material may be paper, glass
fibers or textile materials, both natural or synthetic.
The release sheet or layer must be of such character that any bond
formed between it and the polyamide layer to be transferred is
sufficient to maintain the materials in place prior to the
transferring operation and yet such bond must be sufficiently weak
so as to clearly release from the polyamide layer during a
transferring operation. Further, the surface of the release sheet
preferably presents a smooth and shiny surface. Thus the release
sheet or layer should show as little adhesion and cohesion as
possible with the polyamide layer.
The exact specific material employed as the release sheet or layer
will depend to some extent on the nature of the specific polyamide
layer. For example, if the specific polyamide is one which bonds
well to vinyl, polyethylene or polypropylene, such materials could
not be employed as release sheets. With specific polyamides which
exhibit poor adhesion to such materials, these materials could be
employed as the release material or sheet. Generally, a paper
coated or treated with a material that will provide little adhesion
or cohesion to the polyamide layer is preferred. Illustrative
thereof is a wax-laminated or adhesive-laminated paper where the
heat-sealable material will melt at lower temperatures than the
polyamide layer and, While molten, will exhibit substantially
complete lack of adhesion, cohesion or compatibility with the
polyamide transfer layer. A conventional type release coating such
as a silicone coating, silicone polymer of silene, may be employed
provided it does not exhibit affinity for or migrate to the
polyamide side when the polyamide layer is applied from solution
or, later on, when it is heat activated during the transfer
operation. Thermoplastic or thermosetting coating may be employed
from which the polyamide layer will release at temperatures below
the sealing point of the coating material. Teflon
(tetrafluoroethylene) coatings may be employed. The preferred form
of release sheet is paper coated with a silicone.
As indicated above, the decal comprises a polymeric fat acid
polyamide layer of polymeric fat acid having a dimeric fat acid
content greater than 80 percent by weight to which is applied a
decorative layer, Preferably the decal also has a release sheet or
layer.
The polyamide resins accordingly employed in the present invention
are the thermal condensation or amidification products of a
polymeric fat acid having a dimeric fat acid content greater than
80 percent by weight and preferably greater than 90 percent by
weight and an aliphatic, cycloaliphatic or aromatic diprimary
diamine. The polyamides are prepared by conventional amidification
procedures, which usually include heating at temperatures between
100.degree. and 300.degree. C., preferably 200.degree. to
275.degree. C., for a time sufficient to complete reaction usually
about 2 to 8 hours and most usually about 4 to 6 hours. The
reaction is generally conducted while removing the by-product water
of reaction.
Polymeric fat acids are well known and commercially available. One
method of preparation of polymeric fat acids can be seen in U.S.
Pat. No. 3,157,681. The preparation of very light-colored polymeric
fat acids and polyamides thereof which are preferred for use in the
present invention can also be seen from U.S. Pat. No.
3,256,304.
Typical compositions of commercially available polymeric fat acids,
based on unsaturated C.sub.18 fat acids (tall oil fatty acids)
are
C.sub.18 monobasic or monomeric fat acids (monomer) 5-15% by weight
C.sub.36 dibasic or dimeric fat acids ("dimer") 60-80% by weight
C.sub.54 (and higher) polybasic or trimeric fat acids ("trimer")
10-35% by weight
While the foregoing commercially available product is prepared by
polymerization of unsaturated fatty acids in tall oil fatty acids,
similar polymeric fat acids may be prepared from other monobasic or
monocarboxylic aliphatic acids, naturally occurring or synthetic,
having hydrocarbon chains or eight to 24 carbon atoms which will be
referred to herein as a fat acid or monomeric fat acid.
The relative ratios of monomer, dimer and trimer in such
unfractionated polymeric fat acids are dependent on the nature of
the starting material and the conditions of polymerization. For the
purposes of this invention, the term monomeric fat acids refers to
the unpolymerized monomeric acids, the term dimeric fat acids
refers to the dimer of the fat acids and the term trimeric fat
acids refers to the residual higher polymeric forms consisting
primarily of trimer acids but containing some higher polymeric
forms. The term polymeric fat acids as used herein is intended to
be generic to polymerized acids obtained from fat acids and
consists of a mixture of monomeric, dimeric and trimeric fat
acids.
The saturated fat acids are generally polymerized by somewhat
different techniques than those described in U.S. Pat. No.
3,157,681, but because of the functional similarity of the
polymerization product, they are considered equivalent to those
prepared by the methods described as applicable to the
ethylenically and acetylenically unsaturated fat acids. While
saturated acids are difficult to polymerize, polymerization can be
obtained at elevated temperatures with a peroxidic catalyst such as
di-t-butyl peroxide. Because of the generally low yields of
polymeric products, these materials are not currently commercially
significant. Suitable saturated fat acids include branched and
straight chain acids such as caprylic acid, pelargonic acid, capric
acid, lauric acid, myristic acid, palmitic acid, isopalmitic,
stearic acid, arachidic acid, behenic acid, and lignoceric
acid.
The ethylenically and acetylenically unsaturated fat acids which
may be polymerized and their method of polymerization are described
in the above mentioned U.S. Pat. No. 3,157,681.
Reference has been made hereinabove to the monomeric, dimeric and
trimeric fat acids present in the polymeric fat acids. The amounts
of monomeric fat acids, often referred to as monomer, dimeric fat
acids, often referred to as dimer, and trimeric or higher polymeric
fat acids, often referred to as trimer, present in polymeric fat
acids may be determined analytically by conventional gas-liquid
chromatography of the corresponding methyl esters. Another method
of determination is a micromolecular distillation analytical
method. This method is that of R. F. Paschke et. al., J. Am. Oil
Chem. Soc., XXXI (No. 1), 5, (1954), wherein the distillation is
carried out under high vacuum (below 5 microns) and the monomeric
fraction is calculated from the weight of product distilling at
155.degree. C., the dimeric fraction calculated from that
distilling between 155.degree. C. and 250.degree. C., and the
trimeric (or higher) fraction is calculated based on the residue.
Unless otherwise indicated herein, the chromatography analytical
method was employed in the analysis of the polymeric fat acids
employed in this invention and all limitations on dimeric fat acid
content herein are based on this method. When the gas-liquid
chromatography technique is employed, a portion intermediate
between monomeric fat acids and dimeric fat acids is seen, and is
termed herein merely as intermediate, since the exact nature
thereof is not fully known. For this reason, the dimeric fat acid
value determined by this method is slightly lower than the value
determined by the micromolecular distillation method. Generally,
the monomeric fat acid content determined by the micromolecular
distillation method will be somewhat higher than that of the
chromatography method. Because of the difference of the two
methods, there will be some variation in the values of the contents
of various fat acid fractions. Unfortunately, there is no known
simple direct mathematical relationship correlating the value of
one technique with the other.
As earlier indicated, the preferred polyamides employed in the
present invention are those in which the polymeric fat acids
employed to prepare the polyamides used in this invention have a
dimeric fat acid content in excess of 80 percent by weight and
preferably in excess of 90 percent by weight since these resins
have higher molecular weights. Such polymeric fat acids are
obtained by fractionation by suitable means such as high vacuum
distillation or by solvent extraction techniques from polymeric fat
acids having lower dimeric fact acid contents, such as the common
commercially available products described earlier.
In order that the polymeric fat acid polyamides have the properties
desired for this invention, it is generally preferable that the
polymeric fat acids employed have a dimeric fat acid content
greater than about 80 percent by weight, more preferably above 90
percent by weight and most desirably in excess of 95 percent by
weight. This preference arises as a practical matter due to the
lack of necessity for trimer or monomer content control at the
higher dimer contents to provide polyamides having the desired
properties such as tensile strength and elongation. At dimeric fat
acid contents about 95 percent by weight, virtually no control of
trimer or monomer content is necessary. At the lowest dimeric fat
acid contents, i.e., about 80 percent, it is preferred that the
trimer to monomer ratio by weight be within the range of about 1:1
to 2:1. As the dimeric fat acid content increases, lesser control
is needed and the range of the trimer to monomer ratio widens to
the point where virtually no attention is required when the dimeric
fat acid content approaches values above 95 percent by weight. At a
dimeric fat acid content of about 85 percent by weight, it is
preferred that the trimer to monomer ratio be within the range of
about 0.6:1 to 4.0:1. At about 90 percent dimeric fat acid content,
this ratio preferably lies in the range of about 0.3:1 to 10:1. Of
course, under idealized conditions, such as 100 percent dimeric fat
acid content, there is no trimer or monomer and the ratio thereby
varies theoretically from 0 to infinity.
The polyamides are prepared by reacting the polymeric fat acids
with a diamine. The resins may also include other copolymerizing
acid and amine components and the copolymerizing acids or diamines
employed may be a single diamine or a mixture of two different
copolymerizing reactants. In addition, small amounts of monomeric,
monocarboxylic acids may be present. With regard to any of the acid
components, any of the equivalent amide-forming derivatives thereof
may be employed, such as the alkyl and aryl esters, preferably
alkyl esters having from one to eight carbon atoms, the anhydrides
or the chlorides.
The diamines employed may be aliphatic, cycloaliphatic or aromatic
diprimary diamines, which may be ideally represented by the
formula
H.sub.2 N--R--NH.sub.2
where R is an aliphatic, cycloaliphatic or aromatic hydrocarbon
radical preferably having from two to about 40 carbon atoms.
Representative of such diamines are ethylene diamine, 1,2-diamino
propane, 1,3-diamino propane, 1,3-diamino butane, tetramethylene
diamine, pentamethylene diamine, hexamethylene diamine,
decamethylene diamine, octadecamethylene diamine, metaxylylene
diamine, paraxylylene diamine, cyclohexylene diamine,
bis-(aminoethyl)-benzene, cyclohexane-bis-(methyl amine,)
diamino-dicyclohexyl methane, methylene dianiline, piperazine,
dimethylpiperazine, and dimeric fat diamine. The diamine may be
employed alone or mixtures of two or more may be employed. The most
preferred diamines are the alkylene diamines in which the alkylene
group has from two to six carbon atoms and mixtures thereof with
dimeric fat diamine (preferably having 36 carbon atoms).
The dimeric fat diamine, sometimes referred to as dimer diamine,
dimeric fat amine, or polymeric fat acid diamine are the diamines
prepared by amination of dimeric fat acids. Reference is made
thereto in U.S. Pat. No. 3,010,782. As indicated therein, these are
prepared by reacting polymeric fat acids with ammonia to produce
the corresponding nitriles and subsequently hydrogenating the
nitriles to the corresponding amines. Upon distillation, the
dimeric fat diamine is provided which has essentially the same
structure as a dimeric fat acid except that the carboxyl groups are
replaced by -CH.sub.2 NH.sub.2 groups. Further, this diamine is
also described in Research and Development Products Bulletin, CDS
2-63 by General Mills, Inc., June 1, 1963, as "Dimer Diamine"
illustrated by the formula H.sub.2 N--D--NH.sub.2 where D is a
36-carbon hydrocarbon radical of a dimeric fat acid.
The copolymerizing compounds commonly employed are aliphatic,
cycloaliphatic or aromatic dicarboxylic acids or esters which may
be defined ideally by the formulae:
R.sub.1 OOC--COOR.sub.1 and R.sub.1 OOC--R'--COOR.sub.1
where R' is an aliphatic, cycloaliphatic or aromatic hydrocarbon
radical preferably having from one to 20 carbon atoms and R.sub.1
is hydrogen or an alkyl group (preferably having from one to eight
carbon atoms.) Illustrative of such acids are oxalic, malonic,
adipic, sebacic, suberic, pimelic, azelaic, succinic, glutaric,
isophthalic, terephthalic, phthalic acids, naphthalene dicarboxylic
acids and 1,4- or 1,3-cyclohexane dicarboxylic acid.
Other copolymerizing reactants may be amino acids or the
corresponding lactams represented by the following formula
H.sub.2 N (CH.sub.2).sub.x COOH
where x is an integer from 2 to 15, the corresponding lactams being
represented by the formula
In general, the most common amino acids or corresponding lactams
are aminocaproic acid (or epsilon caprolactam), aminoundecanoic
acid and omega caprylactam where x is 5, 10, and 7
respectively.
Other difunctional coreactants are the monoalkanol amines which may
ideally be represented by the formula
H.sub.2 N R" OH
where R" is a divalent aliphatic hydrocarbon radical, desirably
having from two to eight carbon atoms and preferably an alkylene
radical having from two to eight carbon atoms such as
monoethanolamine, propanolamine, butanolamine, 2-amino-3-hexanol,
2-amino-4-pentanol, 5-amino-4-octanol, 3-amino-3-methyl-2-butanol.
Where an alkanol amine is employed, a polyester-polyamide product
is provided.
Essentially molar equivalent amounts of carboxyl and amine groups
are employed in preparing the polyamide. Where an alkanol amine is
employed the carboxyl groups employed are essentially equivalent to
the amine plus hydroxyl groups. Where copolymerizing dicarboxylic
acids or amino acids are employed, it is preferred that the
carboxyl groups from the polymeric fat acid should account for at
least 50 equivalent percent of the total carboxyl groups present.
Also, where an alkanol amine or amino acid is employed, it is
preferable that the amine groups from the diprimary diamine or
diamines should account for at least 50 equivalent percent of the
total amine groups present.
The following examples will serve to more clearly illustrate the
invention. In these examples, the polymeric fat acid was derived
from tall oil fatty acids by polymerization of tall oil fatty acids
which are composed predominantly of a mixture of linoleic and oleic
acids.
EXAMPLE I
There was cast from a solution-roller coater a polyamide resin
directly onto a silicone treated bleached Kraft (40 lb./ream)
release paper. The solution was a 25 percent solids of polyamide in
a solvent system of isopropanol, toluene and water in a weight
ratio of 50:40:10 respectively. This was done at room temperature
(72.degree. F.) with a feed and metering rolls spread of 8 mils.
The resin coated release paper was then dried by blowing hot air
(under 200.degree. F.).
The polyamide resin was the thermal condensation product at a
temperature of 440.degree. F. for a period of 6 hours of a mixture
of 132 pounds (4.46 eq.) of ethylene diamine and 57 pounds (1.42
eq.) of 1,2-propylenediamine and 1,716 pounds (6.14 eq.) of a
polymeric fat acid having the following analysis:
* % M (monomer) 0.8 * % D (dimer) 96.3 * % T (trimer) 2.9 I. V.
(iodine value) A. V. (acid value) 195 S. V. (saponification value)
201 *Micromolecular distillation method--JAOCS XXXI (No. 1 ), 5 ,
1954.
The polyamide resin had the following properties:
Softening point 100.degree. C. Acid value 9.7 Amine value 1.2
Viscosity at 210.degree. C. 33.5 Color, 40% Solution 0.6-
After solvent evaporation a polyamide resin continuous dry film
(1mil thick) substantially water white in color was obtained. About
3 grams of dry resin produced 1,000 square cm..sup.2 of cast film.
Samples of the product showed easy release or the resin from the
release sheet.
Printing was applied to the resin layer by the offset method. The
printing was in reverse, that is from right to left. In this form,
the printing can be read when it is projected on a mirror. When
applied to the substrate the printing can be read in the
conventional manner.
The printed stock was then heat sealed to the base material or
substrate (in this case paper and treated high density
polyethylene.) The thermal energy source was an electric iron with
the heating element set at 375.degree. F. After applying heat to
the release sheet for 5-10 seconds with hand pressure the thermal
source was removed. After cooling (a few seconds,) the release
sheet was removed leaving the polyamide resin film fused to the
substrate and a sharp enhanced print was obtained. The polyamide
resin film acts as a decorative or print protecting surface as well
as the bonding agent to the substrate.
EXAMPLE II
In this example, decals were formed of a one-half mil film of the
same polyamide and on the same release sheet as in example I and
tested with various substrates. In this instance a dye was added to
the resin solution resulting in a whiter film than example I
without impairing transparency of the material. The dye was GAF
heliogen blue, B. C. toner 56-6 001 and was added in an amount of
0.1 percent based on the solids content of the resin solution. The
results on application to the various substrates can be seen from
the following table. ##SPC1##
EXAMPLE III
Decals were prepared with a 1-mil.-thick polyamide layer on the
same release sheet as in example I. The polyamide resin layer was
cast in the release sheet in the same manner as example I employing
a 20 percent solution of the polyamide in a solvent mixture of
isopropanol, toluol and water in a weight ratio of 40:32:8
respectively. In this instance, the polyamide was the thermal
condensation product at a temperature of 250.degree. C. for about 8
hours of 1.61 equivalents of polymerized tall oil fatty acids
having the following analysis:
% M 0.5 % I 5.4 % D 91.6 % T 2.5 A. V. 195.3 S. V. 197.6 I. V.
101.8
0.80 equivalents of sebacic acid, 1.25 equivalents of
ethylenediamine and 1.25 equivalents of 1,3-di(4-piperidyl)
propane.
The polyamide had the following properties:
Acid Value 0 .7 Amine Value 6 .4 Ball & Ring Softening Point
.degree.C. 138 Tensile Yield 392 Tensile Strength 728 % Elongation
820
The decals were applied to polystyrene, polyethylene and flexible
polyvinyl chloride substrates using a roll-stamping automatic
equipment with flat surface dies instead of letter dies under the
following conditions:
Thermostat temperature 375.degree.-400.degree. F. Die temperature
350.degree.-375.degree. F. Pressure 40 lbs. on 1 in. by 2 in.
surface Dwell time 2 seconds
In each instance a satisfactory hot transfer was achieved with
adhesion to the substrates.
EXAMPLE IV
In this example a fibrous impregnated film was employed as the
polyamide layer. The fibrous material was a sheet of 7.5-inch by
11-inch paper to which printing had been applied by offset
method.
This paper was submerged into a 30 percent solids solution of a
polyamide resin in a 50:50 mixture of toluol and isopropanol. After
the paper was completely wetted with the resin it was air dried for
about 2 hours at 95.degree. F. and 50 percent relative
humidity.
The polyamide employed was the thermal amidification product at
225.degree. C. for about 3 hours, 16,790 gm. of polymerized tall
oil fatty acids having the following analysis:
% M 0 .8 % I 5 .4 % D 88 .6 % T 5 .2 Acid Value 197 Saponification
Value 201 Color (Gardner) 5- % Unsaponifiables 0 .1
and a mixture of 1,379 gm. of ethylene diamine and the diamine of
polymerized tall oil fatty acids, said diamine having the following
analysis:
Total Amine Value 186 Secondary and Tertiary Amine 14 .7% Color
(Gardner) 5 + Iodine Value 94 .2 % Nonamine 3 .0%
The fiber reinforced printed polyamide film layer was then bonded
to a treated polyethylene film substrate by placing the polyamide
film over the substrate, placing a silicone release paper thereover
and applying a thermal source thereto (an electric iron at
280.degree. F.) for a few seconds. After cooling and removal of the
release sheet, the printed decal or label was adhesively bonded to
the polyethylene with the printing showing through the
substantially transparent fiber reinforced polyamide layer.
The polyamide layer is preferably a cast film. The resin is cast
onto the release sheet from a solution. When cast, solutions of
from 50 to 15 percent solids of resin are employed, preferably
about 25 percent. The solvents used will vary dependent on the
particular polyamide resin. The solvent should be inert or
nonreactive with the polyamide resin and where employed with the
release sheet. The solvent should be volatile so that the cast film
may be left in dry form ready for printing. The most advantageous
solvents employed are alcohols, preferably aliphatic hydrocarbon
alcohols having from two to six carbon atoms, such as ethanol,
isopropanol, butanol, aromatic hydrocarbons, such as xylene and
toluene; and mono- and dialkyl (two to six carbon atoms) ethers of
ethylene glycol such as various cellosolves. The preferred solvents
are isopropanol and toluene, particularly when employed in
admixture with small amounts of water added, the most preferred
being a mixture of 50 parts of isopropanol, 40 parts of toluene and
10 parts of water.
The polyamide film thickness may desirably vary from about 0.1 mil
to about 3.0 mil, preferably about 0.5 mil is the optimum film
thickness for most applications.
In the hot transfer of the decal or label to the substrate, heat
must be applied at or near the softening point of the polyamide
layer, which will vary dependent on the particular polyamide
employed. The preferred polyamides have softening points of about
70.degree. to 180.degree. C.
* * * * *