U.S. patent number 3,644,080 [Application Number 04/857,843] was granted by the patent office on 1972-02-22 for method of printing synthetic linear polyester sheet materials.
This patent grant is currently assigned to Collins & Aikman Corporation. Invention is credited to Frederick E. Barwick, III, James B. Hobgood, Robert W. McCullough, Vernon C. Smith.
United States Patent |
3,644,080 |
McCullough , et al. |
February 22, 1972 |
**Please see images for:
( Certificate of Correction ) ** |
METHOD OF PRINTING SYNTHETIC LINEAR POLYESTER SHEET MATERIALS
Abstract
A method is provided for printing synthetic linear polyester
sheet materials such as films and fabrics, in which the area of
material which is to be printed is initially treated with a
halogenated aromatic hydrocarbon at an elevated temperature. The
halogenated aromatic hydrocarbon is then removed and a composition
containing a dyestuff is applied to the treated area to provided
desired indicia on the polyester material. The method of this
invention is particularly useful in providing printed polyester
films and printed heavy weight fabrics such as carpeting.
Inventors: |
McCullough; Robert W.
(Riverside, CT), Smith; Vernon C. (Huntersville, NC),
Barwick, III; Frederick E. (Charlotte, NC), Hobgood; James
B. (Roxboro, NC) |
Assignee: |
Collins & Aikman
Corporation (New York, NY)
|
Family
ID: |
25326841 |
Appl.
No.: |
04/857,843 |
Filed: |
September 15, 1969 |
Current U.S.
Class: |
8/492; 8/475;
8/615; 8/929; 8/512; 8/616 |
Current CPC
Class: |
B41M
1/305 (20130101); D06P 5/001 (20130101); D06P
1/65156 (20130101); Y10S 8/929 (20130101) |
Current International
Class: |
B41M
1/30 (20060101); B41M 1/26 (20060101); D06P
1/64 (20060101); D06P 1/651 (20060101); D06P
5/00 (20060101); D06p 003/00 () |
Field of
Search: |
;8/4,62,175,174,94 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Levy; Donald
Assistant Examiner: Bettis; B.
Claims
We claim:
1. The method for printing an indicia on a synthetic linear
polyester sheet material comprising contacting a predetermined
section of less than the total area of said material at an elevated
temperature above 120.degree. C. and below the shrink or
decomposition temperature of said material with a member selected
from the group consisting of a (a) substantially anhydrous
halogenated aromatic hydrocarbon of the formula
wherein R.sub.1 and R.sub.2 are the same or different and each
stands for a member selected from the group consisting of hydrogen,
alkyl having one to four carbon atoms and alkenyl having two to
four carbon atoms and R.sub.1 and R.sub.2 when attached to each
other and to vicinal carbon atoms stands for a five to six membered
ring, R.sub.3 is an alkylene having one to four carbon atoms or
phenylene X is a halogen selected from the group consisting of
fluorine, chlorine, bromine and iodine, n is a whole number from
one to three, m is a whole number from one to two and (b) mixtures
of said halogenated aromatic hydrocarbons; removing said member
from said polyester, to provide an area having improved dyeability,
and thereafter forming said indicia by applying a composition
containing a tinctorially effective amount of a dispersed dyestuff
for polyester sheet material to at least a portion of said
area.
2. The method according to claim 1 wherein said polyester sheet
material is contacted with said halogenated aromatic hydrocarbon in
the liquid phase at a temperature from about 120.degree. C.
-200.degree. C. for 10.sup..sup.-4 to 20 seconds.
3. The method according to claim 2 where said halogenated aromatic
hydrocarbon is a compound of the formula
wherein X' is chlorine or bromine and n' is two or three.
4. The method according to claim 2 where said halogenated aromatic
hydrocarbon is printed onto said polyester sheet material and
thereafter said material is heated to 120.degree.-200.degree.
C.
5. The process according to claim 1 where said polyester is
contacted with said aromatic hydrocarbon in the vapor phase at a
temperature below the shrink or decomposition temperature of said
polyester sheet material.
6. The process according to claim 5 wherein said polyester sheet
material is treated with an aromatic hydrocarbon of the formula
wherein X" is chlorine or bromine and n" is 1 or 2.
7. The process according to claim 1 wherein a portion of said
polyester is initially treated with a resist agent which is
insoluable in said halogenated aromatic hydrocarbon and thereafter
the untreated portions are contacted with said halogenated aromatic
hydrocarbon.
8. The process according to claim 1 wherein aid polyester sheet
material is a film 0.5 to 20 mil thick.
9. The process according to claim 1 wherein said polyester sheet
material is comprised of polyester fibers.
10. The polyester sheet material treated in accordance with the
method of claim 1.
Description
BACKGROUND OF THE INVENTION
1. Field of the Invention
This invention is concerned with a method for printing synthetic
linear polyester sheet materials.
2. Description of the Prior Art
Synthetic linear polyesters, for example, polyethylene
terephthalate, have excellent physical properties which make them
useful in many different types of applications. The polyesters
exhibit a high tensile strength, are water resistance, and have a
high modulus of elasticity, and other desirable properties. The
polyesters are produced in various forms such as films and fibers.
The films are used in applications wherein high strength is
required, such as packaging and the like. The polyester fibers are
used to make fabrics of various types from relatively light weight
materials, such as dress goods, to very heavy weight fabrics, such
as carpeting.
One of the major problems encountered with the polyester films and
fibers is their relatively poor dyeability. Polyesters have little
natural affinity for dyestuffs. In order to dye polyester fabrics
and films in solid shades the dyestuffs are usually applied along
with a relatively large amount of a carrier compound. However, even
using a carrier long dyeing times are required in order to exhaust
the dyebath. With medium to heavy shades, it is not uncommon to
require 60 minutes or more to exhaust the dyestuff from the
bath.
Heretofore, it has been virtually impossible to obtain satisfactory
prints on polyester fabrics and films. Because of the long dyeing
cycles which are required it is not feasible to use the carrier
dyeing method in printing. This is especially true in films since
the cost competition in the packaging art made it economically
impractical to use long and expensive dyeing techniques.
It has been suggested to print resin-bonded pigments on the films
and fabrics. This is not a satisfactory solution. Printing with
resin bonded pigments is expensive and the results are best at only
marginal. Polyesters do not form strong bonds with the resins and
accordingly the prints are relatively easy to remove. The poor
adhesion of the prints presented special problems in the packaging
art since if the printed indicia was removed, or even damaged, it
distracted from the overall appearance of the final package.
In the textile art the inability to obtain satisfactory prints with
polyesters has to some extent limited to the use of polyesters in
certain areas. This is particularly true in the carpeting field.
Polyester fibers have excellent properties for use in carpeting.
However, the polyesters have heretofore been restricted to uses in
carpeting wherein the yarn could be dyed prior to tufting or
weaving or dyed a solid shade in the piece goods. A large and
growing portion of the carpet market is in the printed carpeting
field. Since the polyesters have heretofore not been printable the
polyesters have been excluded from this market.
It is an object of this invention to provide a method for printing
synthetic linear polyester sheet materials.
It is a further object of this invention to provide a method which
is simple, inexpensive and in which the printing has improved
fastness to the polyester sheet material.
Other objects and advantages of this invention will become further
apparent from a further reading of the specification and subjoined
claims.
SUMMARY OF THE INVENTION
The objects of this invention have been achieved by contacting the
polyester sheet material to be printed in predetermined sections
with a halogenated aromatic hydrocarbon at an elevated temperature;
removing the aromatic halogenated hydrocarbon to provide areas
having improved dyeability and thereafter forming a desired indicia
on the polyester material by applying a composition containing a
dyestuff to at least a portion of the treated area.
BRIEF DESCRIPTION OF THE DRAWINGS
FIG. 1 is a schematic illustration of one method which may be
employed to improve the dyeability of polyester sheet
materials.
FIG. 2 is a schematic illustration of apparatus for printing of
polyester sheet materials.
FIG. 3 is a schematic illustration of an alternate embodiment of
apparatus for printing polyester sheet materials.
FIG. 4 is a top plane view of the polyester sheet materials taken
as indicated by the lines and arrows 4--4 of FIG. 2.
FIG. 5 is a top plane view of the polyester sheet materials taken
as indicated by the lines and arrows 5--5 of FIG. 3.
FIG. 6 is a top plane view of the polyester sheet materials taken
as indicated by the lines and arrows 6--6 of FIGS. 2 and 3.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
The synthetic linear polyesters which are preferably treated in
accordance with the present invention are the condensation
polymerization products of dicarboxylic acids and polyhydric
alcohols. The repeating structural units of the polymer chain
include at least one divalent carbocylic ring containing at least
six carbon atoms which is present as an integral part of the
polymer chain and have a minimum of four carbon atoms between the
points of attachment of the ring in the polymer chain. The
preferred synthetic linear polyesters are of the polyethylene
terephthalate type. Other types of polyesters are likewise
employable such as those obtained by polymerizing a dicarboxylic
acid such as terephthalic acid, bromoterephthalic acid, 4,
4'-benzophenonedi-carboxylic acid and so forth with glycols such as
those of the formula HO--(CH.sub.2).sub.n --OH wherein, n is a
whole number from two to 10, diethylene glycol, neopentylene glycol
and the like. The commercially available polyester materials of the
above described type are commercially known by the trade names
Dacron, Kodel II and Kodel 241, Mylar and Encron.
When referring to synthetic linear polyester sheet materials in
this specification, it is intended to include both polyesters which
are formed into continuous films and also fabrics which are made
from polyester fibers. The polyester films which are treated in
accordance with the present invention are preferably formed in
thicknesses from 0.5 mils to about 20 mils in thickness. The
textile fabrics which are printed in accordance with the present
invention may be of various structures and weights. The fabrics may
be woven, knitted or of a nonwoven construction. The fabrics may
also be a composite type fabric. Of this type of fabric particular
attention is directed to the tufted fabrics which can have, for
example, a cotton or jute backing and a polyester yarn face. The
weight of the goods treated can be from a fraction of an ounce per
square yard, such as dress goods or tricot fabrics to relatively
heavy weight goods such as tufted carpeting.
The textile fabrics treated in accordance with this invention are
preferably comprised of 100 percent polyester fibers but it is also
possible to treat blends such as cotton-polyester blends in
accordance with the present invention.
The halogenated aromatic hydrocarbons which are employed in the
present invention may be monocyclic or bicyclic hydrocarbons with
the monocyclic hydrocarbons being preferred. The halogenated
aromatic hydrocarbons are represented by the formula
wherein R.sub.1 and R.sub.2 are the same or different and represent
hydrogen, an alkyl having one to four carbon atoms such as methyl,
ethyl, n-propyl, isopropyl, and n-butyl or an alkenyl having two to
four carbon atoms such as vinyl, 1-propenyl and 2-butenyl. When
R.sub.1 and R.sub.2 are attached to vicinal carbon atoms they may
be attached to each other to form a five to six membered aliphatic
or aromatic ring when taken together with the vicinal carbon atoms
of the aromatic ring of the compound of formula I, with the
naphthalene ring system being the preferred ring systems when
R.sub.1 and R.sub.2 are joined together. R.sub.3 is a lower
alkylene having one to four carbon atoms such as methylene,
ethylene, propylene and butylene, stands for a halogen such as
fluorine, chlorine, bromine or iodine, n is a whole number from one
to three and when n is two or more X can stand for the same or
different halogens.
The polyester sheet material may be treated with the halogenated
aromatic hydrocarbon in either the liquid phase or the vapor phase
as will be explained in greater detail below.
The halogenated aromatic hydrocarbon employed in the liquid phase
method of the present invention should have a melting point below
120.degree. C. and be a liquid at the desired treating temperature.
The ideal compound for employment in the liquid phase method should
melt at a temperature below 130.degree. C. and have a boiling point
above 160.degree. C. and more preferably above 200.degree. C. The
halogenated aromatic hydrocarbon should be substantially anhydrous.
However, it can contain minor amounts of water and will tend to
pick up small amounts of water from the polyester being treated.
Since the treatment is conducted at elevated temperatures, the
water is volatilized and removed from the treating bath.
The preferred halogenated aromatic hydrocarbons for employment in
liquid phase method are represented by the formula
wherein X' is chlorine or bromine and n' is two and more preferably
three.
The mono-halogenated compounds wherein R.sub.1 and R.sub.2 are
hydrogen, that is, the mono-halo-benzenes, are generally not
employed in liquid phase method of this invention because of their
relatively low boiling points. However, the mono-halogenated
benzenes can be employed if the process is conducted at a
temperature below their boiling point or if the process is
conducted under pressure conditions. Even if the process is
conducted at normal pressures, compounds such as bromobenzene and
iodobenzene can be employed to some advantage.
The dihalogenated benzenes are quite useful in the liquid phase
method of the present invention and are one of the preferred class
of compounds. All of the isomers of the dihalogenated benzenes such
as the dichloro, the dibromo and the diiodo benzenes give excellent
results. The mixed dihalogenated compounds, such as, m- and
p-bromochlorobenzenes and the iodobromobenzene compounds, such as
the ortho and meta isomers are likewise useful.
The most important class of compounds for employment in the liquid
phase of the present invention are the trihalogenated benzenes. All
of the isomers of the trichloro benzenes, such as the 1, 2, 3
-trichloro, 1, 2, 4 -trichloro and the 1, 2, 5 -trichloro benzenes
are the most preferred compounds for employment in the present
invention. The other trihalogenated benzenes, such as the
trifluoro, the tribromo and the triiodo and the various mixed
halogen compounds are likewise useful and are in the preferred
class compounds.
Of the compounds wherein R.sub.1 and R.sub.2 represent alkyls
having one to four carbon atoms, by far the most important class of
compounds are the halogenated toluenes and halogenated xylenes
compounds. With even the monohalogenated compounds, such compound
as the chlorotoluenes and bromoxylenes, are quite suitable for use
in the liquid phase method.
Of the compounds wherein R.sub.1 and R.sub.2 are attached to each
other to form a five to six-membered ring, particular attention is
directed to the halogenated compounds of the naphthalene series
such as the monohalogenated naphthalene such as 1 -bromo-5 2
-bromo-, and 1 -chloro-naphthalenes and the dihalogenated
naphthalenes such as 1, 2 -dichloro, 1, 3 -dichloro and 1, 4
-dichloro naphthalenes.
Of the compounds were R.sub.3 is a lower alkylene and m is two
particular attention is directed to compounds such as .alpha.
chlorotoluene, .alpha.o-dichloro-toluene, .alpha. bromotoluene and
.alpha. bromo-o-xylene.
The same type of compounds that are employed in the liquid phase
method can likewise be employed in the vapor phase method. It is,
however, of considerable advantage to use compounds which have a
lower boiling point. In this regard it should be noted that the
compound of the general formula
wherein X" is a halogen such as fluorine, chlorine, bromine or
iodine and n" is a whole number from one and two are the preferred
compounds. Of this class of compounds the most important compounds
are the monohalogenated benzene such as chloro- and bromo-benzene
and the dihalogenated benzenes such as dichloro-dibromo and
chloro-bromo-benzene.
It has been found that when polyester sheet materials such as the
fabric and films of the type described above are initially treated
with the halogenated aromatic hydrocarbon at an elevated
temperature and then the halogenated aromatic hydrocarbon is
removed from the polyester material, that the treated area can
readily be printed using conventional printing method. The prints
that are obtained are characterized by being true dyeing, that is,
the dyestuff is penetrated into the structure of the fibers and
films.
The halogenated aromatic hydrocarbons can be applied to the
polyesters by immersing the polyester in a bath of the halogenated
aromatic hydrocarbon. The bath should be heated to a temperature of
between about 120.degree. C. and 200.degree. C. with temperatures
of 130.degree. to 160.degree. C. being most preferred. The
immersion time should be limited to 10.sup..sup.-4 to about 20
seconds. The exact temperatures and times which are optimum for
each type of fabric and film is dependent upon a number of factors.
The most important factors are the particular halogenated aromatic
hydrocarbon that is employed and the weight per square yard of the
polyester sheet materials that are being treated. The boiling point
of the particular halogenated aromatic hydrocarbon is the limiting
factor on the upper temperature which can be employed in the liquid
phase method. Heavy weight goods should be treated at higher
temperatures or for longer periods of time than that required for
the treatment of relatively thin polyester sheet materials in order
to obtain an equivalent treatment. The time of 10.sup..sup.-4
seconds is about the shortest time which can be employed and still
obtain satisfactory results. It should be noted that shorter
treatment times can be employed and that these will to some extent
improve the dyeability of the polyester fibers. Treatment times in
excess of 20 seconds do not have any particular advantage since the
excess time over 20 seconds does not cause any significant
improvement in the printability of the polyester films and
fabrics.
As noted above the halogenated aromatic hydrocarbons can be applied
to the polyester sheet material in the vapor phase. The advantage
of this method is that the vapors tend to penetrate the polyester
fabrics and films at a faster rate than the liquid materials and
higher treatment temperatures can more readily be obtained. The
lower temperature limit for the vapor treatment is the boiling
point of the halogenated aromatic hydrocarbon employed. In the case
of one of the preferred compounds for employment in the present
invention, namely monochloro-benzene, the lower limit is
132.degree. C. The upper temperature limit in the vapor phase
method is that temperature wherein the vapors tend to heat the
polyester sheet material being treated above their shrink or
decomposition temperatures. The most preferred method of conducting
the vapor phase treatment is to control the relative temperature of
the halogenated aromatic hydrocarbon vapor and the polyester sheet
material to be treated in a ratio such that the vapors will tend to
condense in a thin film on the polyester material during treatment.
The time limit for treatment in the vapor phase is about the same
as that employed in the liquid method, that is, 10.sup..sup.-4 to
20 seconds. In general, however, shorter treatment times are more
preferred used with the vapor phase method than with the liquid
phase method.
After treating the polyester sheet material the halogenated
aromatic hydrocarbon is removed from the polyester. Various types
of extraction methods can be employed for this step. One of the
preferred methods is to pass the treated material through a series
of rinse baths of a solvent with which the halogenated aromatic
hydrocarbon is miscible until all or substantially all of the
treating agent is removed. The extraction solvent is then removed
by conventional means such as passing the extracted polyester sheet
material over a set of can dryers. Extraction solvents which have
proven to be most useful are the aliphatic halogenated hydrocarbons
such as methylene chloride, trichloroethylene, 1, 1, 1- trichloro
ethane, perchloroethylene and mixtures thereof.
The halogenated aromatic hydrocarbons treating media can also be
removed by passing the treated material into a vacuum chamber which
causes the treating media to volatilize.
In a commercial practice substantially all of the aromatic
halogenated hydrocarbons and the extraction solvents are recovered
and purified for reuse in the process which substantially reduces
the total cost of the process.
The treated areas of the polyester sheet material have
substantially improved dyeability. These areas can be printed with
compositions containing conventional dyestuffs used for the
polyester material, such as the dispersed dyestuffs including
dyestuffs in the azo, azomethine, nitroarene and anthraquinone
chemical classes. The dyeing can be conducted in a relatively short
time without the requirement of the use of a carrier or other
expedients to force the dyestuff onto the polyester fibers or
films. The treatment areas can readily be dyed using printing
methods, such as the pad steam and the like. The dyestuffs are
rapidly fixed onto the polyester fabrics and films. This is not
possible with the use of the untreated polyester fibers and films.
The resulting prints on the polyester sheet material are
characterized by having the dyes penetrated into the polyester
structure rather than being simply adhered to the surface of the
material as was common in the prior art methods. Particularly good
results are obtained on films in that the printed area can be
printed so as to remain transparent even though dyed. This type of
film is extremely useful in the packaging art since the desired
indicia can be printed onto the film without hiding the contents of
the package.
In order to further illustrate the methods of the present
invention, reference is made to the drawings. In FIG. 1 the
treatment of an entire sheet of a polyester material is
schematically shown. In the illustrated process a continuous strip
of material 10 which may be either a film or fabric is immersed in
a bath 12 of a halogenated aromatic hydrocarbon for the times and
at the temperatures noted above. The entire width of the strip 10
is treated with the halogenated aromatic hydrocarbon treating
agent. The treating agent is then extracted from the polyester
sheet material in a bath 14 of a solvent with which the treating
agent is miscible. As illustrated a single bath is shown. However,
in practice a series of extraction baths would be used. The
extraction solvent is then removed by passing the treated polyester
through a dryer 16. The entire area of the final product 18 has
improved dyeability. This material can now be printed in the
conventional manner with the desired indicia. This method of
treatment is particularly useful when large areas of the polyester
sheet material are to be printed or when several different colors
are to be applied to the treated material.
An alternate method is shown in FIG. 2 which is especially useful
for manufacturing printed films. The polyester sheet material 20 is
padded with a thickened halogenated aromatic hydrocarbon
composition 22. To prepare the thickened composition materials such
as soaps, silica thickeners and special carboxymethyl cellulose
derivatives can be used as the thickeners. The thickened
compositions 22 are printed onto the polyester sheet material with
an engraved roll 24 having the desired indicia. The printed sheet
22 is then advantageously fed under a heated roll 28 and/or under a
series of heat lamps 30 which supply sufficient heat to the printed
sheet 26 to cause the halogenated aromatic hydrocarbon printed onto
the sheet to penetrate through the sheet. If the residual
thickening agents are removed at this point the printed sheet 24
would appear to be unchanged. However, it would have visibly
indistinguishable areas 32 which have improved dyeability wherein
the halogenated aromatic hydrocarbon was printed onto the material
24.
The halogenated aromatic hydrocarbon is removed in a vacuum chamber
34. It could, of course, also be removed in a series of extraction
baths as is shown in the method illustrated in FIG. 1.
The treated material 36 is fed into a continuous dyeing apparatus
38 and dyed with a formulation which contains the dyestuffs and
other usual additives but does not contain any carrier. Since the
polyester which is untreated has little natural affinity for the
dyestuff in the untreated form, the untreated area 40 does not dye,
but the treated area 32 readily accepts the dyestuff. The dyed
material is then removed and passed through a dryer 42. The final
product has treated areas 32 which are dyed the desired shade and
untreated areas 40 which are undyed.
An alternate method of obtaining sharp prints on polyester sheet
materials is shown in FIG. 3. A polyester sheet material 46 is
printed with a printing apparatus 48 with a resist agent 50 which
is insoluble in the halogenated aromatic hydrocarbon under the
treating conditions which will be employed. One of the most
inexpensive but highly effective materials for the purpose is
starch. The resist agent is dried in an oven 52. The polyester
sheet material at this point has a resist coated area 56 and an
exposed untreated area 58. This material is then advanced through a
vapor chamber 56 and treated with a vapor of the halogenated
aromatic hydrocarbon. The halogenated aromatic hydrocarbon is then
removed from the treated material in the vapor chamber 58. The
exposed area 58 of the treated material are now readily dyeable.
The polyester material is dyed in a dyebath which contains the
dyestuff but no carrier. The resist is removed leaving undyed areas
44 and dyed areas 32.
The method described above were illustrated in a continuous manner.
However, it should be appreciated that the process can be conducted
in a noncontinuous manner. In addition, the equipment can be
varied, such as the extraction means and still be within the scope
of the present invention. Furthermore, the dyestuff can be printed
onto treated material in the method illustrated in FIG. 2 and 3
rather than being applied from an aquous dyebath.
In order to further illustrate this invention, reference is made to
the following examples. These examples are given here for the
purposes of illustrating the present invention and are not intended
to limit the scope of the subjoined claims. All percentages are
percents by weight, not percents by volume unless otherwise
noted.
EXAMPLE 1
A 4 ounce 80 square fabric made of spun polyethylene terephthalate
fiber, commercially known as Dacron, was immersed in 1, 2, 4-
trichlorobenzene which had been heated to 120.degree. C. for 10
seconds. The 1, 2, 4- trichlorobenzene was removed in a series of
three extractions with 1, 1, 1- trichloroethane and the fabric was
dried at 90.degree. C. for 30 seconds to remove the residual 1, 1,
1- trichloroethane. After drying, the fabric was then
screen-printed with the design "CA" with a printing paste of the
following composition:
1.5 g./l. wetting agent (Barasol BRM)
1.5 g./l. ammonium sulfate
1.5 g./l. locust bean extract (Polygum 260)
4 g./l. thiodiglycol
1.5 g./l. CI Disperse Blue 27
After applying the printing paste, the fabric was steamed at
100.degree. C. for 6 minutes. The fabric was scoured in water at
30.degree. C. Complete fixation of the dyestuff on the fabric was
obtained.
EXAMPLE 2
A sample of fabric as described in Example 1 but which had not been
treated with 1, 2, 4- trichlorobenzene was printed with the
printing paste as previously described. After steaming at
100.degree. C. for 6 minutes and a scour in water at 30.degree. C.,
almost no fixation of the dyestuff occurred.
EXAMPLE 3
A 4 ounce 80 square fabric made of spun polyethylene terephthalate
fiber, commercially known as Dacron, was screen-printed with the
design "CA" with a printing paste of the following composition:
92 percent 1, 2, 4- trichlorobenzene
8 percent Thixin-R (A thixotropic agent for solvents)
The fabric was then heated at 120.degree. C. for 10 seconds. The 1,
2, 4- trichlorobenzene was removed in a series of three extractions
with 1, 1, 1- trichloro-ethane and the fabric was dried at
90.degree. C. for 30 seconds to remove the residual 1, 1, 1-
trichloroethane. The fabric was unchanged in physical appearance
after drying.
The printed fabric was dyed at 99.degree.-100.degree. C. for
one-quarter hour in 30:1 liquor ratio dyebath containing
1.0 percent OWF CI Disperse Red 60
0.5 percent OWF Sodium acetate
After dyeing the fabric was washed to remove any excess dyestuff.
The design "CA" which had previously been printed with 1, 2, 4-
trichlorobenzene on the fabric was a bright red shade. Areas
adjacent to the print were stained a pale pinkish shade.
EXAMPLE 4
A 4 ounce 80 square fabric made of spun polyethylene terephthalate
fiber, commercially known as Dacron was printed with an engraved
roller designed such that the design "CA" was not covered with the
following composition:
10 percent Corn starch
2 percent thickener (Polygum 260)
88 percent water
The fabric was dried at 100.degree. C. until it was essentially
free of water. After drying the fiber was allowed to pass into a
chamber which was saturated with vapors of 1, 2- dichlorobenzene at
180.degree. C. for a period of 10 seconds. The 1, 2-
dichlorobenzene was removed in a series of three extractions with
1, 1, 1- trichloroethane and the fabric was dried at 90.degree. C.
for 30 seconds to remove the residual 1, 1, 1- trichloroethane.
The treated fabric was dyed at 99.degree.-100.degree. C. for
one-quarter hour in 30:1 liquor ratio dyebath containing
1.0 percent OWF CI Disperse Red 65
0.5 percent OWF Sodium Acetate
After dyeing the fabric was washed to remove any excess dyestuff.
The design "CA" was a full shade of red whereas the areas adjacent
to it were stained a light shade of red.
EXAMPLE 5
Fabric samples of 4 ounce 80 square fabric made of spun
polyethylene terephthalate fiber, commercially known as Dacron,
were printed with 1, 2, 4- trichlorobenzene thickened with Thixin-R
as described in Example 3. The samples were heated at various
temperatures and for varying periods of time, rinsed with three
portions of 1, 1, 1- trichloroethane to remove the 1, 2, 4-
trichlorobenzene and dried at 90.degree. C. for 30 seconds to
remove the residual 1, 1, 1- trichloroethane. The samples were dyed
at 99.degree.-100.degree. C. for one-quarter hour in 30:1 liquor
ratio dyebath containing
1.0 percent OWF CI Disperse Blue 27
0.5 percent OWF Sodium Acetate
After dyeing the samples were washed to remove any excess dyestuff.
The shades of the dyeing were as follows:
Sample Temperature Time Depth of Shade
__________________________________________________________________________
1 120.degree. C. 10.sup..sup.-4 seconds Full blue shade 2
120.degree. C. 1 second As above 3 120.degree. C. 5 seconds As
above 4 120.degree. C. 10 seconds As above 5 120.degree. C. 20
seconds As above 6 140.degree. C. 1 second As above 7 160.degree.
C. 10.sup..sup.-4 seconds As above 8 160.degree. C. 1 second As
above 9 160.degree. C. 5 seconds Full blue shade, Slight shrinkage
10 160.degree. C. 10 seconds As above 11 160.degree. C. 20 seconds
Full blue shade, Shrinkage
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EXAMPLE 6
Samples of 2 mil polyethylene terephthalate film, commercially
known as Mylar, were printed with 1, 2, 4- trichlorobenzene
thickened with Thixin-R as described in Example 3. The samples were
heated at various temperatures and for varying periods of time,
rinsed with several portions of 1, 1, 1- trichloroethane to remove
the 1, 2, 4- trichlorobenzene and dried at 90.degree. C. for 30
seconds to remove the residual 1, 1, 1- trichloroethane. The
samples were dyed at 99.degree.-100.degree. C. for one-quarter hour
in 30:1 liquor ratio dyebath containing
1.0 percent OWF Disperse Yellow 54
0.5 percent OWF Sodium Acetate
After dyeing the samples were washed to remove any excess dyestuff.
The shades of the dyeing were as follows:
Sample Temperature Time Depth of Shade
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1 120.degree. C. 10.sup..sup.-4 seconds Yellow 2 120.degree. C. 1
second Bright Yellow 3 120.degree. C. 5 seconds As above 4
120.degree. C. 20 seconds As above 5 160.degree. C. 10.sup..sup.-4
seconds As above 6 160.degree. C. 1 second As above 7 160.degree.
C. 20 seconds Full Yellow, Slight Shrinkage 8 180.degree. C. 20
seconds Full Yellow, Slight Shrinkage
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EXAMPLE 7
A tufted carpet sample made Encron brand polyethylene terephthalate
fiber was immersed in a bath of 1, 2, 4- trichlorobenzene heated to
120.degree. C. for a period of 12 seconds and then rinsed in three
separate portions of 1, 1, 1- trichloroethane. Subsequently, the
carpet was dried at 90.degree. C. for 30 seconds to remove the
residual rinse liquid. The carpet was then screen-printed with a
printing paste as described in Example 1. After applying the
printing paste, the carpet was steamed at 100.degree. C. for 6
minutes. Complete fixation of the dyestuff on the carpet was
obtained as evidenced by the clear rinse liquid obtained from a
water wash after steaming.
EXAMPLE 8
A tufted carpet sample as described in Example 7 which had not been
treated with 1, 2, 4- trichlorobenzene was screen-printed with the
printing paste as described in Example 1 and after subsequent
steaming showed almost no fixation of dyestuff.
EXAMPLE 7
The procedure described in Example 6 was repeated with the sample
being treated at 140.degree. C. with various other halogenated
aromatic hydrocarbons as noted below.
Sample Halogenated Aromatic Hydrocarbon Color
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1 1,3,5 -trichlorobenzene Deep level blue 2 1,2 -dichlorobenzene As
above 3 1,4 -dichlorobenzene As above 4 1-bromo-4-chlorobenzene As
above 5 4-chlorotoluene As above 6 .alpha.-chlorotoluene As above 7
.alpha.-4-dichlorotoluene As above 8 2-chloro-p-xylene As above 9
1-chloronaphthalene As above
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EXAMPLE 10
The procedure described in Example 1 was repeated with the sample
being treated at 130.degree. C. with 1,2,4 -trichlorobenzene and
subsequently rinsed with various other 1,2,4 -trichlorobenzene
miscible solvents as noted above.
Sample Miscible Hydrocarbon Color
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1 Freon TF (trichlorotrifluoroethane) Full Blue 2 Methylene
chloride As above 3 Acetone As above 4 Perchloroethylene As above 5
Ethanol As above 6 Toluene As above 7 Trichloroethylene As above 8
Ethylacetate As above 9 Methylethyl Ketone As above
__________________________________________________________________________
EXAMPLE 11
A 2.0 mil film made of polyethylene terephthalate, commercially
known as Mylar, was screen-printed as described in Example 4. The
film was dried at 100.degree. C. and subsequently passed into a
chamber which was saturated with vapors of chlorobenzene at
132.degree. C. for a period of 10 seconds. The treated film was
flash-dried by passing through an evacuated chamber maintained at
100.degree. C. in order to remove the chlorobenzene.
The treated film was dyed at 99.degree.-100.degree. C. for
one-quarter hour in 30:1 liquor ratio dyebath containing
1.0 percent OWF Disperse Blue 27
0.5 percent OWF Sodium Acetate
After dyeing the fabric was washed to remove any excess dyestuff.
The design "CA" was a full blue shade whereas the areas adjacent to
it were stained a light shade of blue.
* * * * *