U.S. patent number 3,854,866 [Application Number 05/298,167] was granted by the patent office on 1974-12-17 for recurable crosslinked cellulose fabrics from methylol reagents and polycarboxylic acids and method of making.
This patent grant is currently assigned to The United States of America as represented by the Secretary of. Invention is credited to William E. Franklin, Stanley P. Rowland.
United States Patent |
3,854,866 |
Franklin , et al. |
December 17, 1974 |
RECURABLE CROSSLINKED CELLULOSE FABRICS FROM METHYLOL REAGENTS AND
POLYCARBOXYLIC ACIDS AND METHOD OF MAKING
Abstract
Cellulosic fabrics are treated with formulations containing
methylol crosslinking reagents and polycarboxylic acids having
three or more acidic groups per molecule. The treated fabrics are
cured in a flat configuration and washed. The fabric is
subsequently heated in a folded configuration whereby the folded or
creased configuration is permanently imparted to the fabric. A
metal salt activating catalyst included in the formulation of the
textile treating solution decreases the time required to form
sharp, permanent creases in the cured fabrics.
Inventors: |
Franklin; William E. (New
Orleans, LA), Rowland; Stanley P. (New Orleans, LA) |
Assignee: |
The United States of America as
represented by the Secretary of (Washington, DC)
|
Family
ID: |
26939189 |
Appl.
No.: |
05/298,167 |
Filed: |
October 16, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
|
|
248200 |
Apr 27, 1972 |
3776692 |
|
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|
Current U.S.
Class: |
8/182; 8/185;
8/183; 8/186 |
Current CPC
Class: |
D06M
15/423 (20130101) |
Current International
Class: |
D06M
15/423 (20060101); D06M 15/37 (20060101); D06m
001/00 () |
Field of
Search: |
;8/116R,181,185,195,183,186,182 |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Lechert, Jr.; Stephen J.
Attorney, Agent or Firm: Hoffman; R.
Parent Case Text
A non-exclusive, irrevocable, royalty-free license in the invention
herein described, throughout all the world for all purposes of the
United States Government, with the power to grant sublicenses for
such purposes, is hereby granted to the Government of the United
States of America. This is a continuation-in-part of Ser. No.
248,200, filed Apr. 27, 1972, now U.S. Pat. No. 3,776,692.
Claims
We claim
1. An improvement in the process of impregnating a cellulosic
textile with a solution of a methylolated cellulose crosslinking
reagent and a polycarboxylic acid having at least three carboxylic
acid groups, curing the textile and thermally reforming the cured
textile, the improvement comprising including from about 0.25 to
1.0 weight percent of a latent acid catalyst in said solution.
2. A process for thermally reforming a resilient, smmoth-drying
crosslinked cellulosic textile subsequent to the crosslinking
treatment, which process consists of the following steps:
a. impregnating the cellulosic textile with a methylolated
crosslinking reagent augmented with from 1-6 weight percent of a
polycarboxylic acid having at least three carboxylic acid groups
and from 0.25 to 1.0 weight percnt of a latent acid catalyst;
b. curing the impregnated cellulosic textile at a temperature not
exceeding 160.degree.C. to produce a resilient, smooth-drying
crosslinked cellulosic textile, and
c. at any time subsequent to the cure, thermally reforming, with
constraint, the said crosslinked cellulosic textile at a
temperature of about 160.degree.C. for a time interval of at least
15 seconds.
3. The initially crosslinked and subsequently thermally reformed
cellulosic textile produced according to the process of claim 2.
Description
This invention relates to chemical treatment of cellulosic
textiles. Specifically, this invention relates to imparting durable
configurations to cellulosic textile products. More specifically,
this invention relates to the chemical treatment of cellulosic
textiles with mixtures containing a methylol crosslinking reagent
and a polycarboxylic acid to produce a product consisting of a
crosslinked cellulose derivative having acidic, catalytic groups
covalently bonded to the cellulose. More specifically yet, this
invention relates to the production of cellulosic textiles having
the properties of wrinkle resistance and smooth drying, but which
can be given a heat treatment subsequent to the cure in order to
impart a new durable crease or other configuration to the textile
product. By the process of the instant invention, cellulosic
textiles, garments, and other products may be treated to give them
the properties generally known as durable press, except that the
textiles, garments, or other products may be given a heat treatment
at any time subsequent to the cure, thereby imparting durable
creases, pleats, or other desired configurations to the textile
products. This invention constitutes a process which is useful in
the preparation of improved cellulosic fabrics or improved blended
fabrics.
The main object of this invention is to provide treated textiles or
textile products which have smooth drying and wrinkle-resistant
properties, but which can be given a heat treatment at any time
subsequent to the curing step of the finishing operation in order
to impart new, permanent creases, pleats, or other desired
configurations to the fabric.
Another object of this invention is to provide textile treating
compositions, formulations, and methods which can be used in
conventional textile treating processes to produce
wrinkle-resistant cellulosic textile products which can be
permanently creased or pleated at any time subsequent to a
conventional precure or postcure step by a further heat
treatment.
Another object of this invention is to provide a process whereby
sharp, permanent creases may be formed rapidly in wrinkle-resistant
cellulosic textiles using conventional equipment and pressing
times.
BACKGROUND AND PRIOR ART
It is well known to those versed in the art of textile treatment
that wrinkle-resistant and smooth-drying properties are imparted to
cellulosic or cellulosic blended fabrics by chemical treatments
which establish crosslinks between the molecules of the cellulosic
fibers. The crosslinks bind the fibers, and therefore the fabric,
in the configuration present at the time the crosslinks are
established. The covalent nature of the crosslinks makes it
impossible to change the configuration of the treated fabric
without a chemical reaction which involves breaking crosslinks and
reforming them in new positions to bind the fibers, and therefore
the fabric in the new configuration. Conventional delayed cure
processes are useful for imparting creases or other desired
configurations to textile products, but do not solve the problem of
unalterability of finished cellulosic textile products.
In examining the prior art for solutions to this problem of
unalterability of crosslinked cellulosic textile products, we find
several approaches to solutions of this problem. One approach is
through the use of thermally reversible crosslinks, that is,
crosslinks which break and reform in new positions when heated.
Examples of such crosslinks are those containing partial chemical
structure such as Diels-Alder adducts, aryl biscarbamates, and
partial esters of polycarboxylic acids. Fabrics with crosslinks
such as these can be given heat treatments to impart new, durable
configurations, but long periods of heat at high temperatures are
required to impart sharp, durable creases in these fabrics, and the
fabrics do not have the high wrinkle resistance and smooth drying
properties required of durable-press fabrics.
Another approach to alterable, crosslinked cellulosic fabrics is
through internally catalyzed fabrics, that is, fabrics containing
catalytic groups covalently bonded to the cellulose of the fibers,
along with conventional crosslinks. An example of such a fabric is
one prepared by first reacting a cotton fabric with reagents which
bond quaternary ammonium hydroxide groups to the cellulose, then
reacting the resulting fabric with divinyl sulfone to introduce
crosslinks into the cellulose. Such a fabric has high resilience
and can be given new, durable configurations by heat treatments,
but the manufacture of such a fabric requires a number of steps and
unusual reagents, and therefore is not widely accepted by textile
manufacturers on the basis of its high cost.
On further examination of the prior art, one finds that
polycarboxylic acids are used as crosslinking reagents in processes
for producing wrinkle-resistant cotton textiles. In these
processes, polycarboxylic acids are used as a sole crosslinking
agent and produce a modified textile fabric having partial ester
crosslinks, that is, part of the carboxyl groups of the reagents
are in the form of ester groups bonding the reagent and the
cellulose molecules, and the remainder of the carboxyl groups are
in the form of free acidic groups bonded to the cellulose
matrix.
In searching the prior art it is also found that numerous
carboxylic acids are used as catalysts for crosslinking reactions
of methylol reagents with cellulose. These carboxylic acids are
used, either alone or in conjunction with other inorganic
catalysts, in small, catalytic amounts to promote crosslinking
reactions of the methylol reagents, but it is not the practice or
intent to carry out the crosslinking reactions in such a manner
that large amounts of the carboxylic acids become permanently
attached to the cellulose.
It is also found in the prior art that crosslinked cellulosic
fabrics may be given new, durable configurations when a catalyst is
applied to the cured fabric and the fabric is given a heat
treatment. In these processes of the prior art, the ability to
accept a new, permanent configuration is dependent on the added
catalyst, which is not bonded to the fabric but may be washed out
of the fabric with water. The reagents employed in this type of
recuring process are usually strong catalysts, and consequently
have deleterious effects on the strength of the fabric and the
durable press properties of the treated areas of the fabric.
THE NEW INVENTION
We have now discovered that cellulosic textile products may be
impregnated with aqueous solutions of conventional methylol
crosslinking reagent and a polycarboxylic acid containing three or
more carboxyl groups per molecule, dried, and cured, and that the
resulting textile product which has high wrinkle resistance and
smooth drying properties and which may or may not be washed to
remove excess reagents and which may be given a heat treatment to
impart new, permanent creases, pleats, or other desired
configurations to the textile product. The essence of this
discovery may be stated as follows: Recurable durable-press fabrics
may be produced by reacting cellulosic textile products with
combinations of methylol reagents and polycarboxylic acids. In this
statement the terms recurability and durable press may be defined
as follows: Durable press (as applied to cellulosic fabrics) may be
defined as having the properties of high wrinkle resistance, good
smooth-drying appearance, and excellent retention of creases
imparted to the fabric during the cure. Durable press properties
are generally imparted to cellulosic fabrics by reactions which
form crosslinks in the cellulose. Recurability may be defined as
the property of crosslinked cellulosic fabrics being able to accept
new, durable configurations when subjected to a heat treatment, by
virtue of a chemical reaction which breaks the crosslinks and
reforms them in new positions.
In the process of this invention, the polycarboxylic acid serves
two essential functions: (a) by virtue of its acidic nature, the
polycarboxylic acid serves as the catalyst for the crosslinking
reaction of the methylol reagent with the cellulose of the fibers,
and (b) the polycarboxylic acid reacts with the cellulose to form
partial ester groups which have free carboxylic acid groups which
are able to catalyze the breaking and reformation of the crosslinks
from the methylol reagent. The structure of the modified cellulose
may be depicted as follows: ##SPC1##
where the structure represents two cellulose chains joined by a
crosslink containing methylol groups and the non-methylol portion
of the reagent, represented as X. Attached to one of the cellulose
chains, by an ester group, is a polycarboxylic acid, shown as
having a free carboxylic acid group, and the remainder of the
molecule represented by R which may have more ester or carboxylic
acid groups.
In addition, we have discovered that activating catalysts can be
added to the textile treating formulations containing methylol
reagents and polycarboxylic acids. These activating catalysts,
which may be conventional metal salt catalysts normally used for
crosslinking reactions of methylol reagents with fibrous cellulose,
have the function of accelerating the recurring reaction and thus
reducing the time required to form sharp, durable creases in the
cured fabrics of this invention. This acceleration of the recuring
action therefore makes it possible to use fully cured durable press
fabrics in garment manufacturing operations in which the sewed
garments are pressed by conventional methods to form sharp creases
and flat seams and do not require a postcure step to make these
configurations permanent.
Since the combination of polycarboxylic acid and an activating
catalyst is a very active catalyst system, it is of course
necessary to adjust the conditions to the curing step to obtain a
full cure (generally defined as a good durable press appearance
rating and a conditioned wrinkle recovery angle of 280.degree.
(W+F) or greater) without causing excessive degradation of the
cellulose and consequent loss of strength in the fabric. Since the
activating catalyst does not become covalently bonded to the fabric
during the cure step, it is not completely retained in the fabric
if the fabric is washed after curing, but the polycarboxylic acid
does become bonded to the cellulose during the cure and the washed
fabric retains the same degree of recurability as the fabrics of
this invention not containing the activating catalysts.
The novelty of this additional discovery is based on the fact that
cellulosic fabrics treated with a combination of a methylol
crosslinking reagent with a polycarboxylic acid and an activating
catalyst are able to accept sharp, durable creases at any time
after they are cured if they are pressed under mild conditions of
time and temperature. This is in contrast to durable press fabrics
cured with conventional catalysts, which are relatively more
resistant to recuring, even if the original catalyst is allowed to
remain in the cured fabric, than the fabrics of this invention
containing the activating catalysts. It is possible that the higher
degree of recurability of these fabrics is a result of the presence
of relatively large amounts of carboxylic acids which would be
efficient "catalysts" for the breaking of the chemical bonds of the
crosslinks as well as for the formation of new crosslinking bonds.
This catalysis of the recuring reactions may be a result of the
formation of methylol carboxylate groups as intermediates in the
recuring reactions. These methylol carboxylate groups would be free
to move in the cellulose matrix to positions appropriate for the
new configuration being formed in the recuring process. Both the
formation of the intermediate groups and the reattachment of the
methylol groups to the cellulose hydroxyl groups would be catalyzed
by the activating catalysts. Cured fabrics containing conventional
catalysts or even the newer mixed acid catalysts would not have
sufficient amounts of carboxyl groups to catalyze recuring
reactions by this mechanism.
In the practice of the invention, substantially any cellulosic
textile material may be used, but our preferred materials are
textile materials made either entirely of cotton fibers or of
cotton fibers blended with other natural or synthetic fibers. The
cellulosic textile material is impregnated with an aqueous solution
containing from 8 to 40% of a methylol crosslinking reagent and
from 3 to 12% of a polycarboxylic acid. The solution may also
contain other useful textile finishing agents, such as wetting
agents or polymeric softeners. The preferred concentrations of the
methylol reagents in the treating solutions are from 8 to 12%,
depending on the weave of the fabric, and the preferred
concentration of the polycarboxylic acid is from 25 to 50% of that
of the methylol reagent.
The methylol crosslinking reagent may be any of the conventional
crosslinking reagents used for finishing cellulosic fabrics. The
preferred reagent is dimethyloldihydroxyethyleneurea, but other
reagents which also may be used include methylated methylol
melamines, methylated ureaformaldehyde reagents, methylolated
carbamates, formaldehyde, methylol urons, dimethylolpropyleneurea,
methylol triazones, and dimethylolethyleneurea.
The polycarboxylic acid may be an acidic organic compound having
three or more carboxylic acid groups per molecule and which is
soluble in water to the extent required in a treating solution. The
preferred polycarboxylic acids are cyclopentanetetracarboxylic acid
and tetrahydrofurantetracarboxylic acid. Other carboxylic acids
which may be used include mellitic acid, nitrilotriacetic acid,
(ethylenedinitrilo)tetraacetic acid, pyromellitic acid,
tris(carboxyethyl)isocyanurate, naphthalenetetracarboxylic acid,
and benzophenonetetracarboxylic acid.
After the cellulosic textile is impregnated, it may be dried
immediately or it may be stored in the wet state or subjected to a
fixation process before it is dried. The methylol reagent may also
be fixed to the cotton fabric, the fabric washed, and the
polycarboxylic acid applied in a second impregnation step. The
impregnated and dried textile may be cured immediately or it may be
stored or manufactured into garments or other useful articles
before it is cured. The curing step consists of a high temperature
treatment carried out in an oven or apparatus such as a hot-head
press. The curing step may be carried out at any temperature
between 130.degree.C and 205.degree.C, and for times varying
between 15 seconds and 12 minutes. The preferred curing conditions
are eight minutes at 160.degree.C, in either a forced draft oven or
a tenter frame. The cured textile may be washed with water
containing a nonionic detergent to remove unreacted reagents, but
this washing is not essential. The cured textile, prepared
according to the preferred conditions, has a conditioned wrinkle
recovery angle of 270.degree. to 295.degree. (W+F) if no softener
is used in the treating solution, and 290.degree. to 310.degree.
(W+F) if a softener is used. Textile fabrics prepared according to
the preferred conditions of this invention have strength retentions
comparable to conventional durable press fabrics.
The cured fabric of this invention is subjected to a heat treatment
during which it is constrained in the new desired configuration.
The textile may be constrained by folding it in the desired
configuration and applying pressure from a hand iron or other
heated object. This may also be accomplished with a stem or
electrically heated hot-head press. Pressure may be applied in
order to produce sharp creases. The textile may be wet or dry when
it is constrained and heated, but of course it becomes dried during
the heating. The temperatures of the heat treatment may vary
between 130.degree.C and 205.degree.C, and the time of the heat
treatment may vary from 15 seconds to 8 minutes. In the preferred
process, the textile is wet, folded at the position of the desired
new crease, placed on a preheated surface, and covered with a
heated hand iron. The temperature in the textile is maintained at
160.degree.C and the textile is held at this temperature for four
to five minutes.
If the cured textile has been washed with an alkaline detergent, it
may lose its ability to accept durable creases or other
configurations when subjected to a heat treatment. In this case,
the recurability of the fabric may be restored by soaking it for a
short time in a very dilute solution of an acid, for example a
solution of 5% or less of acetic acid in water. After this acid
treatment, the fabric may be creased by the usual heat treatment as
described above.
Fabrics prepared and given heat treatments according to the process
of this invention permanently retain the creases or other
configurations imparted by the heat treatments. Thus, textiles
prepared by the preferred process and given creases according to
the preferred heat treatments retain creases rated at 4.0 or better
according to the AATCC crease appearance test after five machine
wash and tumble dry cycles.
In addition, if an activating catalyst is to be used in the fabric
treatment, substantially any catalyst normally used for the curing
of crosslinking reactions of methylol reagents with cellulosic
fibers may be added to the treatment solution also containing the
polycarboxylic acid and the methylol reagent. Our preferred
activating catalysts are magnesium chloride hexahydrate and zinc
nitrate hexahydrate, but any metal salt which behaves as a latent
acid when heated to curing temperatures may be used in the practice
of this invention. Other examples of such activating catalysts
include zinc chloride, aluminum chloride, aluminum chlorohydroxide,
ammonium chloride, calcium chloride, and magnesium dihyrogen
phosphate.
The amount of activating catalyst to be included in the formulation
of the fabric treating solution is chosen to give the optimum
response to both the curing step and the recuring step. Generally
0.25 to 1.0% of the activating catalyst is used in the treating
solution, depending on the nature and construction of the fabric,
the other reagents used, the time and temperature of the cure, and
the degree of cure and recurability desired in the finished fabric.
Larger amounts of activating catalysts generally cause severe
strength loss and smaller amounts of activating catalysts require
more strenous curing conditions and result in lower recurability of
the finished fabric. It is generally preferable to use smaller
amounts of the polycarboxylic acid in the treating solution if an
activating catalyst is also used.
Since the combination of the polycarboxylic acid and the activating
catalyst constitutes a very active catalyst system, it is possible
and preferred to use milder conditions of time and temperature in
the curing operation. Thus, there activated fabrics may be cured
with lower input of thermal energy and/or with shorter dwell time
of fabric in the tenter frame. The optimum curing conditions for
each combination of fabric, methylol crosslinking agent,
polycarboxylic acid, and activating catalyst must be determined by
experiments appropriate to the equipment to be used and the
properties desired of the finished fabrics. In general, the
addition of 0.5% of an activating catalyst to the treating solution
allows a decrease of about 30.degree.C in the curing temperature
and a decrease of about half of the curing time to obtain wrinkle
recovery and strength retention properties similar to those in
corresponding treatments without activating catalysts. The dried
fabrics containing the methylol reagent, the polycarboxylic acid,
and the activating catalyst may also be cured by storing them at
ambient conditions (20.degree.-30.degree.C) for 30-90 days.
The heat treatments used to form permanent creases or other
configurations in the cure fabrics containing the activating
catalysts are the same as those used for this purpose with the
fabrics of this invention without the activating catalysts, except
that shorter times and/or lower temperatures are required to give
equivalent creases. Thus, heat treatments of 15 sec. at 135 to
160.degree.C are sufficient to produce creases rated at 5 on the
AATCC scale (after 5 laundering cycles) in the fabrics containing
the activating catalysts.
SUMMARY
This invention can be summarized as a new process and cellulosic
ether derivatives produced by the new process. The cellulosic
derivatives being those resulting from reactions involving
polycarboxylic acids and di- or poly functional N-methylol
agents.
The process being one for imparting to cellulosic textiles high
resilience and smooth-drying qqualities and capability of qualities
to thermal formation and reformation at any time after the cure,
the process comprising these steps:
a. impregnating the cellulosic textile with an aqueous solution
containing:
1. a methylol crosslinking agent selected from the group consisting
of
formaldehyde
dimethylolpropyleneurea
bis(methoxymethyl)uron
tris(methoxymethyl)urea
dimethyloltriazone
dimethyloldihydroxyethyleneurea
highly methylated, fully-methylolated melamine
dimethylolethyleneurea
dimethylolmethylcarbamate, and
partially-methylated trimethylolmelamine; and
2. a polycarboxylic aicid having 3 or more carboxylic acid groups
to the molecule, said polycarboxylic acid selected from the group
consisting of:
mellitic acid
pyromellitic acid
nitriloltracetic acid
cyclopentanetetracarboxylic acid
(ethylenedinitrilo)tetracetic acid
tetrahydrofurantetracarboxylic acid
tris(carboxyethyl)isocyanurate
naphthalenetetracarboxylic acid, and
benzophenonetetracarboxylic acid;
b. curing the impregnated cellulosic textile for about from 2 to
12.5 minutes at temperatures about from 130.degree. to
205.degree.C,
c. optionally washing the cured cellulosic textile with a nonionic
detergent and drying the washed cellulosic textile, and
d. optionally subjecting the cellulosic textile to a heat treatment
while constrained with or without pressure for about from 0.25 to 8
minutes at a temperature of about from 130.degree. to 205.degree.C.
c
Note: There are instances where a drying step would be more
suitable prior to the curing step of the process.
This invention also includes a modification of the above process
comprising of these steps:
a. impregnating a cellulosic textile with an aqueous solution
containing:
1. a methylol crosslinking agent selected from the same group as
above,
2. a polycarboxylic acid selected from the same group as above,
and
3. an activating catalyst, which is a metal salt which behaves as a
latent acid at elevated temperatures, said activating catalyst
selected from the group consisting of
magnesium chloride
zinc nitrate
zinc chloride
aluminum chloride
aluminum chlorohydroxide
ammonium chloride
calcium chloride, and
magnesium dihydrogen phosphate;
b. curing the impregnated cellulosic textile as above or under
milder conditions of time and/or temperature; and at any time
subsequent to the cure,
c. subjecting the cured cellulosic textile or articles manufactured
therefrom to a heat treatment while constrained with or withour
pressure, said heat treatment being of short duration and/or at
mild temperatures to produce sharp, permanent creases or other
configurations in the textiles or textile products. s
Percentage composition values as employed hereinafter refer to
percent by weight.
The following list of examples is presented to illustrate this
invention and is not meant to limit its scope in any manner
whatever.
EXAMPLE 1
Cotton twill fabric (7.6 oz/yd.sup.2) was impregnated to 70% wet
pick-up with a solution containing 12% of
dimethyloldihydroxyethyleneurea (DMDHEU), 6% of
cyclopentanetetracarboxylic acid (CPTA), 2% of an emulsified
polyethylene softener, and 0.1% of a nonionic wetting agent. The
fiber was dried on a pin frame in a forced draft oven for 8 minutes
at 70.degree.C, then cured in the same equipment for 8 minutes at
160.degree.C. After washing in water with a nonionic detergent, the
fabric had an add-on of 9.1% and a conditioned wrinkle recovery
angle (WRA) (determined by the procedure of ASTM designation
B1295-67) of 306.degree. (W+F), a wet WRA of 276.degree. (W+F), a
Stroll flex abrasion resistance in the warp direction (determined
by the method of ASTM designation D1175-64 T) of 30% of that of the
unmodified, laundered fabric, and a tearing strength in the fill
direction (measured by the Elmendorf method, as described in ASTM
Designation D1424-63) of 50% of that of the unmodified control.
These physical properties are similar to those of cotton fabrics
treated by conventional durable press processes.
A portion of the fabric was analyzed for nitrogen by the Kjeldahl
method and for formaldehyde by the chromotropic acid method. The
fabric was found to contain 1.29% N and 1.43% formaldehyde. Another
portion of the fabric was analyzed for saponification equivalent by
a modified Eberstadt method (as described by Tanghe, et al. in
"Methods of Carbohydrate Chemistry," Vol. III, R. L. Whistler, Ed.,
1963, pp. 201-203) and free carboxyl groups by a titration (as
described by Reinhardt, Fenner, and Reid in Textile Research
Journal, Vol. 27, p. 873 (1957). The fabric was found to contain
0.54 meq/g of saponifiable groups (ester and carboxyl) and 0.33
meq/g of free carboxylic acid groups. These analyses indicate that
the textile contained crosslinks from the methylol reagent
dimethyloldihydroxyethyleneurea (DMDHEU), chemically known as
1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone) and ester
and free carboxylic acid groups from the polycarboxylic acid
cyclopentanetetracarboxylic acid. The textile therefore consisted
of the cellulosic derivative, the
1,3-dimethylene-4,5-dihydroxy-2-imidazolidinone ether of cellulose
cyclopentanetetracarboxylate.
EXAMPLE 2
A portion of the textile prepared according to Example 1 was soaked
in distilled water, folded so that the warp yarns were bent, and
placed on a preheated cloth surface. A thermocouple was placed
between the sides of the fabric sample and the assembly was covered
with a heated hand iron. The temperature of the iron was controlled
by an apparatus attached to the thermocouple. The fabric sample was
heated at 160.degree.C for 5 minutes. After the creasing treatment,
the fabric sample was rinsed in hot, running water, then stapled to
a towel and subjected to five machine washing and tumble drying
cycles. After the last drying cycle, the crease remaining in the
fabric sample was evaluated by the AATCC method (AATCC Test Method
88 C-1969) modified as described by Hobart in Textile Research
Journal, Vol. 37, p. 380 (1967). The crease retained in this fabric
after the laundering cycles was rated at 4.3 on the AATCC scale
(running from 0 -- no crease-- to 5-- excellent). This example
indicates that good, very durable creases are imparted to fabrics
prepared according to Example 1 and treated according to this
Example by a heat treatment. The most reasonable explanation for
the formation of durable creases in the heat treatment is that a
recure (as defined above) occurred during the heat treatment and
was catalyzed by the free acid groups in the fabric.
EXAMPLE 3
Cotton twill fabric was treated according to the process of Example
1 except that it was dried at 70.degree.C for 4 minutes in a tenter
frame and cured at 160.degree.C for 4 minutes in the tenter frame.
This fabric had a conditioned WRA of 292.degree. (W+F). Other
physical and chemical tests gave results similar to those in
Example 1. This fabric was given a heat treatment according to the
process of Example 2. After the five laundering cycles the fabric
retained a crease with an AATCC crease rating of 5.0.
EXAMPLE 4
Cotton twill fabrics were treated according to the process of
Example 1 except that the curing times were varied from 30 seconds
to 6 minutes. The fabric samples were given heat treatments
according to the process of Example 2. The conditioned WRA and the
AATCC crease ratings after five launderings are reported in Table
1.
Table I ______________________________________ Cure Time Cond , WRA
AATCC Crease (min.) (.degree.,W+F) Rating
______________________________________ 0.5 260 4.6 1.0 273 5.0 2.0
280 4.9 3.0 279 5.0 4.0 286 4.9 5.0 278 4.6 6.0 287 4.5
______________________________________
EXAMPLE 5
Cotton twill fabric was heated according to Example 1 except that
different concentrations fo various polycarboxylic acids were used
in the treating solutions. These fabrics were creased according to
the procedure of Example 2. The conditioned WRA and AATCC crease
ratings after five launderings are given along with the name and
concentration of the polycarboxylic acids in Table II.
Table II ______________________________________ Concen-
Polycarboxylic tration Cond.WRA AATCC Crease Acid (%)
(.degree.,W+F) Rating ______________________________________
Tetrahydrofurantetra- carboxylic Acid 3 302 4.1
Tetrahydrofurantetra- carboxylic Acid 6 309 4.0
Tetrahydrofurantetra- carboxylic Acid 12 300 4.0 Nitrilotriacetic
Acid 3 286 0.8 (Ethylenedinitrilo)tetra- acetic Acid 3 280 1.0
______________________________________
EXAMPLE 6
Cotton printcloth (3.2 oz/yd.sup.2) was impregnated with a solution
containing 8% of DMDHEU, 6.3% of a polycarboxylic acid, and a trace
of a nonionic wetting agent. The impregnated fabric samples were
dried and cured according to the procedure of Example 1. The cured
fabrics were creased according to the procedure of Example 2. The
concentration of DMDHEU, the polycarboxylic acid and its
concentration are given along with the conditioned WRA and the
AATCC rating of the crease remaining after the five laundering
cycles are given in Table III.
Table III ______________________________________ Polycarboxylic
Acid Cond. WRA AATCC Crease (.degree.,w+F) Rating
______________________________________ Mellitic Acid 283 2.8
Tris(carboxyethyl)isocyanurate 258 2.8 Benzophenonetetracarboxylic
Acid 286 4.2 ______________________________________
EXAMPLE 7
Samples of cotton printcloth were impregnated with solutions
containing 8% of a methylol crosslinking reagent, 4% of CPTA, 2% of
polyethylene softener, and a trace of a nonionic wetting agent. The
fabric samples were dried and cured according to the process of
Example 1 and creased according to the process of Example 2. The
methylol crosslinking reagents, conditioned WRA and AATCC crease
ratings after five laundering cycles are given in Table IV.
Table IV ______________________________________ Methylol Reagent
Cond. WRA AATCC Crease (.degree.,W+F) Rating
______________________________________ Formaldehyde 309 1.0
Dimethylolpropyleneurea 258 2.3 Bis(methoxymethyl)uron 298 3.5
Tris(methoxymethyl)urea 311 4.0 Dimethyloltriazone 296 3.8
Dimethyloldihydroxyethyleneurea 318 4.0 Highly methylated, fully
methylolated melamine 298 3.0 Dimethylolethyleneurea: 230 2.0
Dimethylolmethylcarbamate 261 0.6 Partially methylated trimethylol-
melamine 240 2.1 ______________________________________
EXAMPLE 8
Cotton twill fabric was impregnated with a solution containing 20%
of DMDHEU, 20% of a highly methylated fully methololated melamine,
and sufficient hydrochloric acid to lower the pH of the solution to
2.0. The fabric was stored in the wet state for 24 hours, then
washed to remove the excess reagents. The fabeic was then
impregnated with a solution containing 15% of mellitic acid, dried
for 8 minutes at 80.degree.C, and cured for 12.5 minutes at
160.degree.C. The cured fabric had a conditioned WRA of 265.degree.
(W+F). This fabric was creased according to the process of Example
2. After five laundering cycles it had an AATCC crease rating of
3.3.
EXAMPLE 9
Cotton twill fabric was impregnated and dried according to the
process of Example 3. Portions of this fabric were cured by heating
the in an electrically heat hot-head press for 2 minutes at various
temperatures between 130.degree. and 205.degree.C. These fabric
samples all had very good smooth drying appearances and retained
creases which were present during the heating process to repeated
washing and drying cycles. This demonstrates that at least a fair
cure was obtained in all of the samples by heating them in a
hot-heat press.
EXAMPLE 10
Portions of the fabric prepared and cured in Example 3 were creased
according to the process of Example 2, except that a series of
different times and temperature were used for the heat treatments.
The times and temperatures of the heat treatments are given along
with crease ratings of the fabrics after five washing and drying
cycles in Table V.
Table V ______________________________________ Temperature
(.degree.C) Time (min.) AATCC Crease Rating
______________________________________ 130 0.25 1.2 145 0.25 1.3
160 0.25 2.0 180 0.25 2.7 205 2.0 5.0 160 1.0 3.3 160 5.0 4.0 160
8.0 5.0 ______________________________________
EXAMPLE 11
A portion of the cotton twill fabric treated according to the
process of Example 3 was creased according to the process of
Example 2. After five laundering cycles it had an AATCC crease
rating of 4.0. Another portion of the fabric prepared according to
Example 3 was given one washing cycle with an alkaline detergent,
followed by tumble drying. This washed fabric was creased according
to of process osf Example 2. After five machine wash and dry cycles
this fabric retained a crease with an AATCC crease rating of 1.7. A
portion of the fabric washed with the alkaline detergent was soaked
in a water solution containing 5% acetic acid for 30 minutes, then
rinsed with distilled water. The acidified fabric was creased
according to the process of Example 2. After five washing and
drying cycles this fabric retained a crease with an AATCC crease
rating of 3.7.
EXAMPLE 12
Cotton twill fabric was treated according to the process of Example
1 except that 6% of tetrahydrofurantetracarboxylic acid was used in
place of the cyclopentanetetracarboxylic acid. This fabric had a
conditioned WRA of 309.degree. (W+F). A portion of the fabric was
subjected to a heat treatment according to the process of Example
2. After five washing and drying cycles, this portion of the fabric
retained a crease rated at 4.0 on the AATCC scale. Portions of the
fabric were analyzed for nitrogen, formaldehyde, saponification
equivalent, and free carboxyl groups by the methods given in
Example 1. The fabric was found to contain 1.14% nitrogen, 1.22%
formaldehyde, 0.33 meq/g of saponifiable groups, and 0.21 meq/g of
free carboxyl groups. These analyses indicated that the textile
contained crosslinks from the methylol reagent
dimethyloldihydroxyethyleneurea (DMDHEU, chemically known as
1,3-bis(hydroxymethyl)-4,5-dihydroxy-2-imidazolidinone) and ester
and free carboxylic acid groups from the polycarboxylic acid
tetrahydrofurantetracarboxylic acid. The textile therefore
consisted of the cellulosic derivative, the
1,3-dimethylene-4,5-dihydroxy-2-imidazolidinone ether of cellulose
tetrahydrofurantetracarboxylate.
EXAMPLE 13
Cotton twill fabric was treated according to the process of Example
1, except that the impregnating solution contained only 4% of
cyclopentanetetracarboxylic acid and in addition contained 0.5% of
magnesium chloride hexahydrate. The fabric sample was cured for 4
min, at 130.degree.C instead of for 8 min. at 160.degree.C. The
fabric sample was not washed after the cure and had a conditioned
wrinkle recovery angle of 298.degree. (W+F). A sample of this
fabric was subjected to a heat treatment according to the process
of Example 2, except that the folded fabric sample was heated for
15 sec. at 160.degree.C. The fabric sample retained a crease rated
at 5 on the AATCC scale after five laundering cycles.
EXAMPLE 14
Cotton twill fabric was treated according to the process of Example
13, except that 0.5% of zinc nitrate hexahydrate was used in place
of the magnesium chloride hexahydrate. This fabric had a
conditioned wrinkle recovery angle of 303.degree. (W+F) after the
cure and retained a crease rated at 3.1 on the AATCC scale after
the heat treatment and five laundering cycles.
EXAMPLE 15
Samples of cotton printcloth were impregnated with solutions
containing 8% of DMDHEU, 3% of cyclopentanetetracarboxylic acid,
0.5% of an activating catalyst, 2% of emulsified polyethylene
softener, and a trace of a nonionic wetting agent. The fabric
samples were then dried at 70.degree.C for 8 min. and cured at
130.degree.C for 4 min. Portions of each of the cured fabric
samples were subjected to heat treatments according to the process
of Exmaple 2, except that the fabric samples were heated for 15
sec. at 160.degree.C. The activating catalyst, the conditioned WRA
of the cured samples, and the AATCC crease ratings of the recured
fabrics after five laundering cycles are given in Table VI.
Table VI ______________________________________ Activating Catalyst
Cond. WRA AATCC Crease (.degree., W+F) Rating
______________________________________ Aluminum Chloride 315 3.0
Calcium Chloride 305 4.1 Magnesium Dihydrogen Phosphate 296 3.5
Ammonium Chloride 302 3.6 Zinc Chloride 291 3.8 Aluminum
Chlorohydroxide 312 4.3 ______________________________________
EXAMPLE 16
Cotton twill fabric was treated according to the process of Example
1, except that the impregnating solution contained 4%
cyclopentanetetracarboxylic acid and in addition contained 1% of
magnesium chloride hexahyrate. The fabric sample was not subjected
to a high temperature cure, but was stored at ambient temperature
for 60 days. After this time the fabric sample had a conditioned
wrinkle recovery angle of 280.degree. (W+F). A sample of this
fabric was subjected to a heat treatment according to the process
of Example 2, except that the folded fabric sample was heated for
15 sec. at 160.degree.C. This fabric sample retained a crease rated
at 4.2 on the AATCC scale after five laundering cycles.
EXAMPLE 17
Samples of cotton printcloth were treated according to the process
of Example 15, except that magnesium chloride hexahydrate was used
as the activating catalyst and the dried fabric samples were cured
at different temperatures and for different times. Portions of the
cured fabric samples were subjected to heat treatments according to
the process of Example 2, except that the fabric samples were
heated for 15 sec. at 160.degree.C. The times and temperatures of
the cures, the conditioned WRA of the cured fabric samples, and the
AATCC crease ratings of the recured fabrics after five laundering
cycles are given in Table VII.
Table VII ______________________________________ Cure Time Cure
Temperature Cond. WRA AATCC Crease (min) (.degree.C.) (.degree.,
W+F) Rating ______________________________________ 4 100 271 4.8 4
115 292 3.2 4 130 303 2.4 4 145 309 3.0 4 160 310 2.7 2 130 302 4.7
6 130 309 2.5 8 130 303 2.5
______________________________________
EXAMPLE 18
Samples of cotton printcloth were treated according to the process
of Example 15, except that various concentrains of
cyclopentanetetrcarboxylic acid and magnesium chloride hexahyrate
were used in the pad bath. The dried fabric samples were cured at
130.degree.C for 4 min. Portions of the cured fabrics were
subjected to heat treatments according to the process of Example 2,
except that the fabric samples were heated for 15 sec. at
160.degree.c. The concentrations of cyclopentanetetracarboxylic
acid (CPTA) and magnesium chloride hexahydrate in the pad bath, the
conditioned WRA of the cured fabric samples, and the AATCC crease
ratings of the recured fabrics after five laundering cycles are
given in Table VIII.
Table VIII ______________________________________ Concentration of
Concentration of Cond. WRA AATCC Crease CPTA (%) MgCl.sub.2
6H.sub.2 O (%) (.degree., W+F) Rating
______________________________________ 4 0.5 303 3.2 3 0.5 305 3.1
2 0.5 304 3.7 1 0.5 302 3.8 3 0.1 276 2.8 3 0.25 294 4.2 3 1.0 301
4.0 3 2.0 309 4.2 ______________________________________
* * * * *