U.S. patent number 3,811,131 [Application Number 05/238,983] was granted by the patent office on 1974-05-21 for durable press process for treating cellulosic material with methylolamides and acetic acid or formic acid vapors.
This patent grant is currently assigned to Cotton, Incorporated. Invention is credited to Jose P. Gamarra, Ronald Swidler, Katherine W. Wilson.
United States Patent |
3,811,131 |
Gamarra , et al. |
May 21, 1974 |
DURABLE PRESS PROCESS FOR TREATING CELLULOSIC MATERIAL WITH
METHYLOLAMIDES AND ACETIC ACID OR FORMIC ACID VAPORS
Abstract
The dimensional stability, wrinkle resistance, smooth drying
characteristics and total shape retentivity of cellulosic materials
such as cotton fabrics are improved by treatment with acetic acid
or formic acid vapors after impregnation of the materials with an
aqueous solution of a water-soluble crease-proofing agent
containing reactive N-methylol groups such as trimethylolmelamine
or DHDMEU, whereby the cellulosic fibers become crosslinked.
Inventors: |
Gamarra; Jose P. (San Jose,
CA), Swidler; Ronald (Palo Alto, CA), Wilson; Katherine
W. (Newport Beach, CA) |
Assignee: |
Cotton, Incorporated (New York,
NY)
|
Family
ID: |
26932159 |
Appl.
No.: |
05/238,983 |
Filed: |
March 28, 1972 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
Issue Date |
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762119 |
Sep 24, 1968 |
3653805 |
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Current U.S.
Class: |
8/183; 2/243.1;
8/DIG.9; 8/DIG.21; 8/149.3; 8/185; 8/187; 8/DIG.4; 8/DIG.10;
8/115.6; 8/115.7; 8/149.1; 8/182; 8/186; 38/144; 34/517; 8/129 |
Current CPC
Class: |
D06M
15/423 (20130101); D06M 13/127 (20130101); Y10S
8/09 (20130101); Y10S 8/10 (20130101); Y10S
8/21 (20130101); Y10S 8/04 (20130101) |
Current International
Class: |
D06M
15/423 (20060101); D06M 15/37 (20060101); D06m
001/16 (); D06m 015/56 (); D06m 015/58 () |
Field of
Search: |
;8/116.3,149.1,149.3,186,185,183,182,187 ;38/144 ;2/243 |
References Cited
[Referenced By]
U.S. Patent Documents
Foreign Patent Documents
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437,642 |
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Nov 1935 |
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GB |
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1,359,102 |
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Mar 1964 |
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FR |
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Other References
Prett, Melliand Textiberichte, 46(1) 73-74 (1965). .
Gagliardi et al., Textile Research Journal, 36, 168-177 (1966).
.
Mehta et al., Journal of the Textile Institute, 58, 279-292 (1967).
.
Campbell et al., Textile Chemist and Colorist, Vol. 1, No. 4, Feb.
12, 1969, pp. 33-36. .
Gagliardi, from Proceedings of the Conference on the Conference on
the Vapor Phase Finishing of Cotton, held at New Orleans, La. on
Feb. 24, 1967 published March 1968, p. 35..
|
Primary Examiner: Lesmes; George F.
Assistant Examiner: Cannon; J.
Attorney, Agent or Firm: Smolka; Peter H.
Parent Case Text
CROSS-REFERENCE
This application is a continuation-in-part of Ser. No. 762,119,
which was filed Sept. 24, 1968 and is now U.S. Pat. No. 3,653,805.
Claims
What is claimed:
1. A process for improving the dimensional stability, wrinkle
resistance, smooth drying characteristics and total shape
retentivity of a cellulose fiber-containing fabric which process
consists essentially of:
a. applying to the fabric an aqueous solution of a water-soluble
crease-proofing agent containing reactive N-methylol groups;
b. heating the impregnated fabric containing the said
crease-proofing agent in a non-reactive vapor atmosphere containing
a catalyst selected from the group consisting of formic acid and
acetic acid vapor as essentially the only reactive component to a
temperature between above 80.degree.C. and up to about
160.degree.C. for a time of between about 1 to about 20 minutes to
crosslink the cellulose fibers to a first level of crosslinking;
and
c. heating the said crosslinked fabric in an inert atmosphere in
the absence of additional catalyst to a temperature of above about
100.degree.C. to further cure the said crosslinked fabric to a
second level of cross-linking having increased Wrinkle Recovery
Angles and Wash-Wear Ratings while dissipating residual
reagents.
2. A process according to claim 1 wherein said aqueous solution
contains from about 1 to about 40 percent of the said
crease-proofing agent.
3. A process for improving the dimensional stability, crease
resistance, smooth drying characteristics and total shape
retentivity of cotton-containing fabrics which comprises in
sequence the steps of:
a. applying to the fabric an aqueous solution consisting
essentially of about 5 to about 15 percent by weight of a
water-soluble, crease-proofing agent containing reactive N-methylol
groups;
b. conditioning or drying the fabric to give the cotton a moisture
content of between about 2 to about 100 percent based on dry weight
of the fabric;
c. exposing the conditioned fabric to a non-reactive vapor phase
consisting essentially of a catalytically effective amount of
formic acid or acetic acid as essentially the only reactive
component in a reaction zone maintained at a temperature between
about 100.degree.C. and about 140.degree.C. for a time of between
about 1 and 20 minutes to crosslink the cotton fibers to a first
level of crosslinking;
d. at the end of said crosslinking step (c) heating said fabric in
an inert gaseous atmosphere in the absence of additional catalyst
at a temperature of from about 100.degree.C. to about
180.degree.C., to further cure the fabric to a second, higher level
of crosslinking while dissipating residual reagents thereby
directly producing a dry, crosslinked, essentially neutral
fabric.
4. A process according to claim 3 wherein said non-reactive vapor
phase consists essentially of formic acid.
5. A process according to claim 3 wherein said non-reactive vapor
phase consists essentially of acetic acid.
6. A process for improving the dimensional stability, wrinkle
resistance, smooth drying characteristics and total shape
retentivity of cotton-containing fabrics which consists of the
sequential steps of:
a. impregnating the fabric with an aqueous solution containing
about 5 to 15 percent trimethylolmelamine or
dihydroxydimethylolethyleneurea to give a wet pick-up between about
65 and 85 percent based on dry cotton weight;
b. drying and conditioning the impregnated fabric to a moisture
content of between about 3 to about 65 percent;
c. exposing the fabric to a non-reactive gaseous atmosphere
consisting of from about 20 to 50 volume percent of a catalytic
material taken from the group consisting of formic acid and acetic
acid, balance inert gaseous material, at a temperature between
110.degree. and 125.degree.C. for a time of about 2 to about 15
minutes, thereby effecting a first level of crosslinking;
d. removing said fabric from said atmosphere; and
e. postheating the said fabric at a temperature of from about
140.degree.C. to about 160.degree.C. to further cure the fabric to
a second level of crosslinking while dissipating residual
reagents.
7. A process according to claim 6 wherein the fabric is introduced
into the process as a flat fabric, and prior to step (c) is formed
into a garment.
8. A process according to claim 6 which process is continuous and
in which the fabric being treated is flat fabric.
9. A process according to claim 6 which process is continuous and
in which the fabric being treated is a garment.
Description
BACKGROUND OF THE INVENTION
In recent years various methods have been devised for treating
cellulosic fiber-containing products, such as cloth made of cotton
or cotton blends, in order to impart durable crease resistance and
smooth drying characteristics thereto. For example, cellulosic
materials have been crosslinked with formaldehyde, giving durable
crosslinks having good resistance to repeated laundering and also
to various acids and alkalis, and chlorine bleaches. These
formaldehyde treated cellulosic materials have certain advantageous
features. For example, they are resistant to discoloration and
yellowing.
However, while formaldehyde has made a significant contribution to
the cotton finishing art, the results have been far from perfect.
For instance, in some cases the formaldehyde crosslinking treatment
has tended to lack reproducibility, since control of the
formaldehyde crosslinking reaction heretofore has been difficult.
When high curing temperatures were used with an acid or potential
acid catalyst, overreaction and degradation of the cotton often
happened which considerably impaired its strength. On the other
hand, when attempts were made to achieve reproducibility at
temperatures of 50.degree.C. or less, much longer reaction or
finishing times were usually required, rendering the process
economically relatively unattractive. See for example, British
Patent 980,980. In other cases, formaldehyde crosslinking has not
been able to meet commercial standards with respect to dry wrinkle
recovery. For these and similar reasons, efforts have been
continuing to develop new and better cellulosic and cotton
finishing processes.
The use of an atmosphere containing hydrochloric acid to catalyze
crosslinking between a crease-proofing agent and a cellulosic
fabric material in which the agent is impregnated has been
suggested in the prior art. Control of such a reaction is difficult
but important since the strong mineral acid catalyst may degrade
the fabric itself. Hydrochloric acid-catalyzed fabric materials
also have been found to have low tensile strength properties,
particularly if the crosslinked fabric is post-heated.
SUMMARY OF THE INVENTION
Accordingly, a primary object of the present invention is to
provide a practical process for treating cellulosic materials with
a suitable crease-proofing agent which process substantially
prevents or alleviates the problems mentioned above.
A more specific object has been to develop a process for
crosslinking cotton with the aid of a water-soluble crease-proofing
agent containing reactive N-methylol groups, using an acid catalyst
used in the vapor phase, so as to keep fiber injury to a
minimum.
Another more specific object is to provide a process for
crease-proofing cotton or other cellulosic materials using a
water-soluble crease-proofing agent containing reactive N-methylol
groups which permits the cure of the treated material to be safely
delayed for long or indefinite periods until after completion of
desired articles therefrom including, for instance, the cutting,
sewing and pressing of garments.
Another specific object is to provide a crease-proofing process for
use with cellulosic materials which produces good wrinkle recovery
and smooth drying characteristics, keeps loss of tensile strength
and abrasion resistance to a minimum, gives good laundering life
and chlorine resistance, employs simple reactants and, if desired,
can produce a pre-treated fabric which is relatively insensitive to
surrounding conditions and has virtually infinite shelf life prior
to final cure.
It is further an object of this invention to provide a process for
treating cellulosic materials with an acidic catalyst in the vapor
phase without the degrading characteristics of strong mineral acids
such as hydrochloric acid.
These and other objects, as well as the scope, nature, and
utilization of the invention will become more clearly apparent from
the following more detailed description. Unless otherwise
indicated, all proportions and percentages of materials or
compounds are expressed on a weight basis throughout this
specification and appended claims.
In accordance with the present invention, a process is provided for
improving the dimensional stability, wrinkle resistance, smooth
drying characteristics and total shape retentivity of a cellulosic
fiber-containing fabric which comprises: (a) applying to the fabric
an aqueous solution of a water-soluble crease-proofing agent
containing reactive N-methylol groups; and (b) heating the
impregnated fabric containing the water-soluble crease-proofing
agent containing reactive N-methylol groups in a non-reactive vapor
atmosphere containing a catalyst selected from the group consisting
of formic acid and acetic acid to a temperature between above
80.degree.C. up to about 160.degree.C. for a time of between about
10 seconds and 2 hours until the cellulose fibers become
effectively crosslinked.
The process requires relatively short reaction times and gives high
wrinkle recoveries while at the same time producing satisfactory
tensile and tear strengths.
The process of the present invention has substantial advantages of
use as compared with typical prior art processes such as
hydrochloric acid vapor-catalyzed durable press systems. For
example, the process of the present invention prevents excessive
degradation of cellulosic fibers and does not require
neutralization of the fabric after treatment. Also, there is no
need for an afterwash of the fiber. Reproducibility of the reaction
is substantially improved and special controls and equipment for
handling the highly toxic and corrosive hydrochloric acid is not
necessary.
DESCRIPTION OF PREFERRED EMBODIMENTS
In the embodiment disclosed and claimed herein, the cotton or
cellulose-containing fabric is impregnated with an aqueous solution
containing about 1 to about 40 percent, preferably from about 2 to
about 20 percent, most preferably from about 5 to 15 percent, of a
water-soluble crease-proofing agent containing reactive N-methylol
groups to give a wet pick-up of between about 50 and about 100
percent, preferably from about 60 to about 90 percent, most
preferably from about 65 to 85 percent, based on dry fabric
weight.
The present invention is useful for treating various natural or
artificial cellulosic fibers alone or as mixtures with each other
in various proportions or as mixtures with other fibers. Such
natural cellulosic fibers include cotton, linen and hemp, and
regenerated or artificial cellulosic fibers useful herein include,
for example, viscose rayon and cuprammonium rayon. Other fibers
which may be used in blends with one or more of the above-mentioned
cellulosic fibers are, for example, cellulose acetate, polyamides,
polyesters, polyacrylonitrite, polyolefins, polyvinyl chloride,
polyvinylidine chloride and polyvinyl alcohol fibers. Such blends
preferably include at least about 20 percent by weight and most
preferably at least about 40 percent by weight, of cotton or other
cellulosic fibers.
The fabric may be knit, woven or non-woven, or be any otherwise
constructed fabric. The fabric may be flat, creased, pleated,
hemmed or sewn or otherwise formed to produce an article such as a
garment of any desired shape prior to contact with the acetic acid
or formic acid catalyst-containing atmosphere. After processing,
the formed crosslinked fabric will maintain substantially the
original configuration for the life of the article, that is, a
wash-wear or durable press fabric will be produced.
The crease-proofing agents useful herein include particularly the
easily hardenable precondensates which are substantially water
soluble and are obtained by condensation of formaldehyde with a
compound such as a lower alkyl substituted melamine, a urea, or a
phenol such as resorcinol. As is well known in the resin treating
art, these precondensates are capable of being applied to the
cellulosic material from an aqueous solution. Triazines obtained by
condensing a lower alkyl substituted melamine and formaldehyde are
examples of such precondensates. Good results are obtained, for
instance, using precondensates obtained by condensing 1 mole of
melamine or an alkyl substituted melamine with 2 to 6 moles of
formaldehyde, i.e., using di-, tri- or hexamethylol melamine.
Commercially available products of this kind include Aerotex 23, a
triazine-formaldehyde precondensate; Aerotex M--3, a
melamine-formaldehyde condensate; Aerotex P-225,
hexakis-(methoxymethyl) melamine; and Aerotex 19, which is a less
completely fractionated modification of Aerotex P-225. These
products are supplied in the form of aqueous solutions by American
Cyanamid Company.
Other suitable crease-proofing agents include products such as
dihydroxydimethylolethyleneurea, DHDMEU, available as Permafresh
183 or in a somewhat modified, less reactive form as Permafresh
113B from Sun Chemical Company, as well as modified propylene urea
compounds such as Fixapret PCL, available from Badische Anilin und
Soda-Fabrik. Compounds having at least 11/2 moles of formaldehyde
combined as methylol formaldehyde with a cyclic urea or cyclic
propylene urea are suitable and the dimethylol derivatives are
preferred. However, it is similarly feasible to use other known
crease-proofing agents such as N-methylol carbamates and methylol
urea compounds.
Pretreatment of the cloth, prior to the vapor phase catalytic
treatment, with polymeric resinous additives that form soft films,
such as conventional dispersions or latexes, can result in an
unusually great incremental improvement in wrinkle recovery of the
treated fabric. Polymer additives can also improve the flex
abrasion resistance and tear strength, or alter the ratio of dry
wrinkle recovery to wet wrinkle recovery, or in some instances
shorten the reaction time needed to produce an acceptable durable
press fabric. Polymeric additives suitable for such purposes are,
in most cases, available commercially in concentrated aqueous latex
form, and it is desirable to dilute these to a concentration of 1
to 10 percent polymer before padding onto the fabric. Suitable
polymeric additives include solid resinous or rubbery
acrylonitrile-butadiene copolymers and mixtures containing the same
with various vinyl resins; polyethylene; deacetylated copolymers of
ethylene and vinyl acetate; polyurethanes and various polymers of
alkyl acrylates, other polyesters and polyamides.
The impregnated fabric may be dried or conditioned to a moisture
content of from about 2 up to about 100, preferably from about 3 to
about 65 percent by weight of the dry cellulosic fabric material.
The impregnated fabric may thus be catalyzed in a condition ranging
from about essentially dry to about essentially wet condition.
The fabric is then passed into a non-reactive, catalyzing
atmosphere containing a catalytically effective amount of formic
acid or acetic acid which may be obtained from any convenient
source. In addition to the catalyst, the treating atmosphere may
contain inert gases such as air, nitrogen, carbon dioxide, helium,
steam and the like. The treating atmosphere is "non-reactive" in
that it contains the gaseous catalyst and an inert gas. Gaseous
materials or monomers that could react, condense or polymerize with
the fabric or methylolamide crease-proofing agent should not be
present in the treating atmosphere.
The non-reactive atmosphere can contain up to about 100, often from
about 5 to 90 volume percent acetic acid or formic acid, balance,
(if any) inert gas.
Contact of the conditioned fabric with the non-reactive atmosphere
is performed at a temperature of from about 80.degree. and
160.degree.C., preferably from about 100.degree.C. to about
140.degree.C. most preferably from about 110.degree.C. to about
125.degree.C., for a time of between about 10 seconds and 2 hours,
preferably from about 1 to about 20 minutes, most preferably from
about 2 to about 15 minutes.
Any suitable means to contact the fabric with the gaseous acetic
acid or formic acid catalyst may be employed. For example, a batch
system utilizing a closed vessel or tube containing the gaseous
catalyst may be used into which the conditioned, crease-proofing
agent-containing fabric may be placed and there exposed to the
treating atmosphere for the appropriate time. In the alternative, a
dynamic or continuous system can be used such as one wherein a gas
stream containing acetic acid or formic acid catalyst, is passed
through a closed elongated chamber through which the impregnated
fabric or articles are also passed at an appropriate rate, either
concurrently or countercurrently relative to the gas. It is also
possible to use combinations of the above, that is, such as by
passing a stream of the catalyst-containing atmosphere over a
stationary fabric.
The crosslinked fabric is thereafter desirably heated to a
temperature above about 100.degree.C., e.g., in the range of from
about 100.degree. to 180.degree.C., preferably from about
140.degree.C. to about 160.degree.C., to volatilize and remove
water vapor, residual catalyst and any unbound, volatile,
crease-proofing agent. In addition, this heating step further cures
the crosslinked fabric thus improving its durability to laundering
as well as improving the duration press characteristics of the
treated fabric. This heating and curing step may also allow a
reduction in the time of exposure to the gaseous
catalyst-containing atmosphere without sacrificing durable press
performance.
Heating the crosslinked fabric may advantageously be performed in
any suitable fabric heating chamber.
The temperature of the post-heating step can be reduced or the
post-heating step entirely eliminated without impairing wash-wear
performance by using crease-proofing agents more reactive than
dihydroxydimethylolethyleneurea. These fabrics containing the more
reactive crease-proofing agents may be neutralized with a slightly
alkaline solution (such as a 1 percent solution of sodium
carbonate) and washed to remove all traces of catalyst or unbound
crease-proofing agent.
The invention is additionally illustrated in connection with the
following examples which are to be considered as illustrative of
the present invention. It should be understood, however, that the
invention is not limited to the specific details of the
Examples.
EXAMPLES
The reactor used in this work was a cylindrical vessel having a
capacity of about 71 liters, constructed of 1/8-inch aluminum (42
cm. inside diameter and 57 cm. high). The walls of this reactor are
heated with band heaters equipped with a three-way switch which
permits operation at 600, 1,200 or 2,400 watts. The reactor wall
temperature is controlled by an adjustable bimetallic thermostat,
and the reactor is surrounded by an insulating blanket. The gas
content of the reactor is recirculated through an external recycle
line by an aluminum pressure blower equipped with a heat slinger
and high-temperature, lubricated sealed bearings. An adjustable
damper in the recycle line permits some control of the pressure
within the reactor, but during normal operation nearly atmospheric
reactor pressure is preferred.
This reactor was fitted with aluminum tubing through which a
solution containing 85 percent by weight of formic acid is poured
to fall onto an evaporating dish in the bottom of the reactor.
Substantially all of the vapors in the reactor are in each of the
following Examples formic acid vapors evaporated from the
evaporating dish. Some water vapor is also present. The acetic acid
and hydrochloric acid atmospheres in the Examples are provided in
the same manner.
EXAMPLE I
Cotton twill fabric samples and trouser cuffs were padded to 70
percent wet pickup with aqueous solutions containing the amounts of
crease-proofing agent and polymeric additive shown in Table I.
Crease-proofing agents included trimethylolmelamine (Resloom HP,
Monsanto Chemical Co.), methylated methylolmelamine (Resloom M-75,
Monsanto Chemical Co.), a mixed amide product including a
methylolmelamine (Aerotex 23, American Cyanamid Co.) and dimethylol
dihydroxyethylene urea (Permafresh 183, Sun Chemical Co.).
Polymeric additives included polyethylene (Mykon SF), and an
acrylic resin (Rhoplex K-87). After impregnation, fabric samples
were dried to moisture content of about 7-10 percent, exposed to
formic acid vapor in the reaction chamber described above at about
115.degree.C. for various reaction times, washed, dried, and
tested.
The tabulated data show that high levels of wrinkle recovery were
achieved in all cases. Generally, shorter reaction times were
necessary and higher tensile strength retentions recorded, when the
melamine derivatives were used, which are more polymerizable than
the dihydroxyethylene urea derivative.
TABLE I-A
__________________________________________________________________________
Stoll HCO.sub.2 H Wrinkle Recovery Angle Tearing Flex Exposure
Total (degrees) Strength Abrasion, Run Pad Bath Composition Time
Add-On Warp Fill (grams) Warp No. Methylol Softener (min) (%) Dry
Wet Dry Wet Warp Fill (cycles) Compound
__________________________________________________________________________
15% 1 Resloom M-75 2% Mykon SF 5 2.4% 146 139 117 110 2420 1580 550
2 4 2.7 154 142 120 111 2090 1660 445 3 3 2.8 146 139 126 119 2620
1670 670 4 2 3.0 131 124 124 111 2820 1880 660 10% 5 Aerotex 23 3%
Rhoplex K-87 4 7.6 149 148 128 136 1740 1020 580 6 3 7.9 148 147
126 132 1810 1100 560 7 2 8.7 148 150 132 136 1740 1080 460 8 11/2
8.6 142 142 122 125 2120 1180 520 9% 9 Permafresh 183 2% Mykon SF 5
-- 146 136 118 129 2860 1660 1550 10 10 -- 144 140 114 122 2620
1780 1180 11 121/2 -- 144 140 119 132 2600 1570 730 12 15 -- 148
139 126 128 2440 1620 680 13 n.a. n.a. n.a. n.a. 90 88 84 82 4240
2780 620
__________________________________________________________________________
n.a. = not applicable. a. methylated methylolmelamine b. a misture
of dimethylolurea and trimethylolmelamine c.
dihydroxydimethylolethyleneurea
Tensile Properties Warp Fill Wash-Wear Work to Extension Tensile
Work to Extension Tensile Rating Rupture at Break Strength Rupture
at Break Strength Tumble Line Run No. (in.-lb) (%) (lb) (in.-lb)
(%) (lb) Dried Dried
__________________________________________________________________________
1 20.0 12.9 141 5.9 15.4 52 31/2 3 2 17.0 12.3 126 5.8 14.8 50 4 3
3 20.0 13.0 137 6.3 16.6 51 4 3 4 21.1 13.4 144 6.2 15.8 51 31/2 3
5 14.4 11.0 125 4.7 13.8 45 31/2 3 6 14.9 11.2 127 5.7 15.2 50 4 3
7 15.8 11.4 130 5.8 15.0 50 4 3 8 17.8 12.4 136 6.6 16.2 51 31/2 3
9 13.7 12.4 114 5.1 16.7 44 31/2 3 10 13.9 12.7 114 4.6 15.8 42 4 3
11 13.0 12.4 110 4.5 16.8 41 4 31/2 12 13.1 12.3 110 4.8 16.0 44 4
4 13 28.3 12.6 174 11.2 19.9 70 -- --
__________________________________________________________________________
TABLE I-B
__________________________________________________________________________
Stoll Wrinkle Recovery Tearing Flex Exposure Total Angle (degrees)
Strength Abrasion, Run Pad Bath Composition Time.sup.a Add-On Warp
Fill (grams) Warp No Methylol Compound Softener (min) (%) Dry Wet
Dry Wet Warp Fill (cycles)
__________________________________________________________________________
1 15%.sup.b TMM 3%.sup.b Rhoplex K-87 1 6.3 124 114 112 102 2380
2480 1300 2 2 8.5 152 136 135 118 1850 1670 560 3 4 8.8 158 140 136
126 1710 1440 410 4 5 8.8 158 146 140 130 1620 1390 450 5 9%.sup.b
Permafresh 183 5 7.9 134 140 104 123 1990 1870 700 6 71/2 8.6 151
142 134 139 1530 1450 850 7 10 8.3 152 145 124 131 1570 1680 840 8
n.a. n.a. n.a. n.a. 93 89 85 84 3100 2940 670 (Untreated control)
__________________________________________________________________________
n.a. = not applicable a. Time exposed to formic acid at
120.degree.C. b. Percentage solids c. Trimethylolmelamine d.
Dihydroxydimethylolethylene urea
Damage by Tensile Properties Retained Run No. Warp Fill Chlorine
Work to Extension Tensile Work to Extension Tensile (% loss in
Rupture at Break Strength Rupture at Break Strength tensile
(in.-lb) (%) (lb) (in.-lb) (%) (lb) strength)
__________________________________________________________________________
1 26.9 18.8 133 17.5 20.0 90 -- 2 19.0 15.2 126 8.7 15.2 65 -- 3
16.1 13.8 114 8.4 15.5 59 -- 4 15.4 14.9 107 6.9 14.8 55 -- 5 19.9
14.6 124 9.0 14.9 64 70 6 14.1 12.4 105 7.6 16.7 56 17 7 14.5 12.6
108 9.2 18.6 60 31 8 29.5 13.7 156 16.1 19.9 86 n.a.
__________________________________________________________________________
TABLE I-C
__________________________________________________________________________
Stoll Wrinkle Recovery Tearing Flex Exposure Angle (degrees)
Strength Abrasion, Pad Bath Time.sup.a Warp Fill (grams) Warp Run
No. Composition (min) Dry Wet Dry Wet Warp Fill (cycles)
__________________________________________________________________________
1 15% TMM 2 138 134 113 110 2360 2280 1420 2 3 149 138 136 120 2320
1970 2010 3 4 150 145 136 127 1970 1600 740 4 5 152 144 140 124
2080 1660 870 5 2 133 116 94 116 2280 2160 840 6 3 140 120 110 110
2140 2220 1120 7 4 148 130 122 115 1920 1600 1280 8 5 141 130 120
124 2100 1920 680 9 n.a. n.a. 93 89 85 84 3100 2940 670 (Untreated
control)
__________________________________________________________________________
n.a. = Not applicable a. Time exposed to formic acid at
110.degree.C. b. Trimethylolmelamine Tensile Properties Wash-Wear
Warp Fill Ratings Number of Work to Extension Tensile Work to
Extension Tensile Tumble Dried Line Dried Wash-Dry Run Rupture at
Break Strength Rupture at Break Strength Wash- Crease Wash- Crease
Cycles No. (in.-lb) (%) (lb) (in.-lb) (%) (lb) Wear Retention Wear
Retention to
__________________________________________________________________________
Holes Properties After 1 Washing 1 21.4 14.8 148 13.2 19.0 88 31/2
41/2 31/2 4 -- 2 21.0 14.0 151 10.9 17.1 82 4 5 4 4 -- 3 16.2 12.4
135 7.7 16.2 66 4 5 31/2 4 -- 4 16.5 12.2 136 8.9 16.8 72 4 5 4 4
-- Properties After 20 Washings 5 23.7 16.6 141 12.5 18.0 82 31/2
31/2 3 3 >20 6 22.1 15.2 138 11.3 16.4 79 31/2 4 31/2 4 18,20 7
17.5 13.4 128 9.8 16.0 72 4 4 4 4 10,12 8 19.4 13.7 132 7.5 15.4 61
4 4 4 4 11,14 9 29.5 13.7 156 16.1 19.9 86 n.a. n.a. n.a. n.a. n.a.
__________________________________________________________________________
EXAMPLE II
Cotton twill fabric samples ("Twist twill", J. P. Stevens &
Co.) were padded with 70 percent wet pickup with an aqueous
solution containing 10 percent (solids) of various water-soluble
crease-proofing agents having reactive N-methylol groups and 2.5
percent (solids) of urethane Latex E-502, (Wyandotte Chemical Co.),
and, without prior drying, were exposed to formic acid vapor in the
reaction chamber described above for 2 minutes at 115.degree.C.,
and then heated in air for 5 minutes at 160.degree.C. Fabric
samples were then washed, dried and tested. Results are shown in
Table II.
The tabulated results show that a high degree of useful reaction
could be achieved with all crease-proofing agents used. Similarly,
good results are achieved using 10 percent (solids) solutions of
hexamethoxymethylmelamine, trimethylolmelamine and
trimethylolmelaminedimethylolurea.
TABLE II
__________________________________________________________________________
Wrinkle Recovery Angle Tearing Stoll Flex Tensile (degrees)
Strength Abrasion, Strength Dry Wet (grams) Warp (lb) Methylolamide
Warp Fill Warp Fill Warp Fill (cycles) Warp Fill
__________________________________________________________________________
Properties After 1 Washing Dimethylol- 154 134 162 139 (a) 1060 550
100 30 propyleneurea Dimethyloluron 161 134 158 144 (a) 890 190 98
27 Dimethylol- Carbamate 131 110 147 130 2390 1520 960 110 46
Trimethylol- Melamine 164 142 154 146 (a) 940 200 105 33 Properties
After 10 Washings Dimethylol- 158 130 154 140 2000 1190 480 98 36
propyleneurea Dimethyloluron 160 131 158 144 (a) 930 180 93 30
Dimethylol- carbamate 120 109 141 123 2590 1590 940 124 49
Trimethylol- melamine 155 138 158 133 (a) 970 230 104 30 Untreated
(unwashed) 78 71 74 78 3800 2060 640 175 66 Untreated (Washed) 70
68 69 72 2840 1630 670 161 74
__________________________________________________________________________
n.a. = not applicable (a) Fabric specimens tore across filling
yarns only.
EXAMPLE III
Samples of the same twill fabric as used in Example II were
impregnated with an aqueous solution containing 9 percent (solids)
of Permafresh 113B (dimethylol dihydroxyethylene urea) and 2.5
percent (solids) urethane Latex E-502 to 50 percent wet pickup,
and, without prior drying, were exposed to formic acid or acetic
acid for different times, and then post-heated for different times
and at different temperatures as shown in Table III. The samples
were then washed, dried and tested. Results are shown in Table
III.
TABLE III
__________________________________________________________________________
Exposure Heating Time Wrinkle Recovery Angle Tearing Stoll Flex
Tensile Time and and (degrees) Strength Abrasion, Strength Gaseous
Temperature Temperature Dry Wet (grams) Warp (lb) Catalyst
(min/.degree.C) (min/.degree.C) Warp Fill Warp Fill Warp Fill
(cycles) Warp Fill
__________________________________________________________________________
HCOOH 3/115 5/160 158 136 152 142 1990 1160 690 105 35 do. 2/115
5/160 150 132 151 134 2050 1270 530 110 40 do. 1.5/115 5/160 154
129 148 134 2150 1250 560 109 34 do. 1/115 5/160 154 128 148 136
2140 1340 570 112 39 do. 2/115 5/150 148 128 136 124 1900 1130 400
118 42 do. 2/115 5/140 146 130 131 122 2030 1200 510 119 45 do.
2/115 5/130 130 120 123 118 2280 1440 700 126 51 CH.sub.3 COOH
3/115 5/160 131 122 140 130 2440 1430 720 129 44 do. 2/115 5/160
132 124 137 128 2190 1280 670 111 43 do. 1.5/115 5/160 138 122 138
128 2430 1450 660 121 46 do. 1/115 5/160 140 123 138 128 2410 1350
650 127 43 Untreated -- 78 71 74 78 3800 2060 640 175 66 (unwashed)
Untreated -- 70 68 69 72 2840 1630 670 161 74 (washed)
__________________________________________________________________________
These tabulated results show that a short exposure to acetic acid,
as well as to formic acid, is sufficient to allow a high level of
wrinkle recovery to be achieved after a subsequent heat treatment.
The balance of wrinkle recovery gained to strength and abrasion
resistance lost is about the same for each catalyst, and comparable
with a conventional pad/dry/cure system using the same
crease-proofing agent.
EXAMPLE IV
The twill samples of Example II are impregnated with an aqueous
solution containing 20 percent dimethylolurea (Permafresh 477) and
10 percent urethane Latex (E-502) and dried to various add-ons as
shown in Table IV-A. These impregnated twill samples were exposed
to formic or hydrochloric acid vapors at temperatures between
60.degree. and 120.degree.C. and either post-heated in air for 5
minutes at 150.degree.C. or neutralized and washed. Conditions and
results are shown in Table IV-A.
These results show the advantages of the present invention as
compared with hydrochloric acid systems.
TABLE IV-A
__________________________________________________________________________
Exposure Postheated Wrinkle Recovery Angle, Tensile Strength Wash-
Temp. at 150.degree.C Add-on W + F (degrees) (% retention) Wear
Catalyst (.degree.C) for 5 min (%) Dry Wet Warp Fill Ratings
__________________________________________________________________________
HCOOH 60 No.sup.(b) 2.6 146 208 82 97 2.7 do. 80 do. 3.4 150 210 79
98 3.0 do. 100 do. 5.1 223 257 65 77 3.0 do. 120 do. 5.7 286 270 61
69 4.2 do. 60 Yes 5.2 293 292 56 60 4.4 do. 80 do. 5.4 289 295 53
51 4.4 do. 100 do. 5.4 306 307 54 55 4.3 do. 120 do. 5.5 308 306 52
53 3.9 HCl 60 No.sup.(b) -- 258 254 51 62 3.0 do. 80 do. -- 282 284
37 63 3.0 do. 100 do. -- 286 290 34 32 3.6 do. 120 do. -- 305 304
27 16 4.0 do. 60 Yes -- a a a a a do. 80 do. -- a a a a a do. 100
do. -- a a a a a do. 120 do. -- a a a a a 100 100 -- Untreated --
-- -- 152 160 (186 lb) (74 lb) Control
__________________________________________________________________________
.sup.a Fabrics too weak to test. .sup.b Neutralized with a 1
percent sodium carbonate solution and washed
Prior to the post-heating step, fabrics treated with the
hydrochloric acid system showed good degrees of wrinkle recovery
angles, but rather low tensile strength retentions. The
post-heating step, however, proved to be highly detrimental to the
strength of these HCl-system fabrics. As in the case of the
Permafresh 113B-treated fabrics, the acid degradation was such that
it was imposible to measure any of their physical properties.
To show that post-heating at lower temperatures could yield fabrics
with acceptable degrees of strength retention for formic acid but
not hydrochloric acid systems, further runs were conducted in which
fabrics impregnated with dimethylolurea (Permafresh 477) and
urethane Latex-502 were exposed to formic or hydrochloric acid
vapors for 5 min. at 120.degree. or 60.degree.C., respectively, and
then post-heated at 100.degree.-140.degree.C. The resulting fabric
properties are listed in Table IV-B.
TABLE IV-B
__________________________________________________________________________
Exposure Postheating Wrinkle Recovery Angle Tensile Strength
Wash-Wear Time/Temp Time/Temp W + F (degrees) (% retention) Ratings
Catalyst (min/.degree.C) (min/.degree.C) Dry Wet Warp Fill
__________________________________________________________________________
HCOOH 5/120 5/100 296 284 66 61 4.2 do. do. 5/120 288 281 68 60 4.2
do. do. 5/130 302 297 66 65 4.2 do. do. 5/140 309 294 66 61 4.2 HCl
5/60 5/100 290 296 35 31 3.8 do. do. 5/120 275 304 17 4 3.7 do. do.
5/130 297 309 10 6 4.0 do. do. 5/140 294 304 10 8 3.5 Untreated --
-- 152 160 100 100 -- Control (186 lb) (74 lb)
__________________________________________________________________________
EXAMPLE V
Cotton twill fabric (7.8 oz./sq. yd., J. P. Stevens twist twill
having 112/50 threads per inch) was treated with a 20 percent
solution of dihydroxydimethylolethyleneurea (Permafresh 113B, Sun
Chemicals Corporation) to 65 percent wet pickup. The solution also
contained 5 percent (solids) of an acrylic emulsion (Rhoplex K-14,
Rohm and Haas Co.). The impregnated fabric samples were dried,
exposed to a formic acid or hydrochloric acid atmosphere at varying
temperatures and times.
TABLE V-A
__________________________________________________________________________
HCOOH Warp Exposure Wrinkle Recovery Angle, Tearing Strength
Tensile Strength Stoll Wash- Add-on Time/Temp. W +F, (degrees) (%
retention) (% retention) Abrasion(% Wear (%) (min/.degree.C) Dry
Wet Warp Fill Warp Fill retention) Ratings
__________________________________________________________________________
Properties Prior to Post-heating 2.2 1/120 236(207).sup.a
218(201).sup.a 155 144 71 82 308 2.0 4.0 5/120 274(224) 264(254)
105 118 68 77 272 2.2 5.0 10/120 276(260) 285(270) 98 91 60 63 306
3.0 5.0 15/120 281(262) 280(272) 96 99 62 66 253 2.8 4.9 20/120
302(271) 284(282) 91 95 63 65 279 2.4 1.6 1/100 190(179) 214(198)
106 114 92 82 185 2.0 2.5 5/100 225(217) 260(255) 80 96 74 83 162
2.6 5.2 10/100 268(260) 286(278) 76 77 68 67 153 3.2 6.2 15/100
274(264) 295(288) 73 79 65 71 151 3.4 6.2 20/100 268(260) 280(278)
73 75 65 65 156 3.3 2.6 1/80 177(179) 202(194) 104 123 90 95 179
2.0 3.4 5/80 199(180) 204(202) 100 113 89 94 169 2.0 5.1 10.80
206(179) 249(219) 89 101 77 91 157 2.4 5.4 15/80 221(196) 243(246)
85 99 82 86 174 2.3 3.7 20/80 226(212) 250(252) 83 94 79 85 188 2.4
2.8 1/60 178(183) 187(184) 110 121 87 100 193 2.0 3.1 5/60 193(178)
200(186) 116 125 96 110 191 2.0 3.7 10/60 211(193) 201(200) 112 125
94 104 180 2.1 3.7 15/60 197(185) 194(200) 120 124 92 103 177 2.0
4.2 20/60 200(189) 207(192) 117 120 92 102 219 2.0 Properties After
Post-Heating 5.0 1/120 248(212) 250(231) 127 132 72 69 394 3.0 4.8
5/120 286(275) 272(272) 97 93 60 56 312 3.6 5.4 10/120 296(285)
296(282) 80 84 58 56 151 3.8 5.5 15/120 290(282) 279(285) 93 98 66
60 283 4.0 6.0 20/120 310(285) 285(292) 78 80 60 61 220 3.6 5.6
1/100 241(234) 270(267) 76 84 69 72 168 3.2 6.3 5/100 272(263)
267(274) 69 70 65 61 165 3.4 6.4 10/100 296(281) 301(288) 64 62 58
59 144 4.0 6.3 15/100 291(288) 289(287) 66 61 58 58 133 3.8 6.6
20/100 295(288) 296(291) 64 62 56 57 136 3.6 6.5 1/80 274(251)
289(274) 59 68 64 69 153 3.6 6.8 5/80 268(273) 276(272) 60 64 61 65
148 3.6 7.0 10/80 289(276) 289(276) 59 65 61 62 107 3.5 6.8 15/80
289(276) 286(278) 55 69 62 64 105 3.8 6.2 20/80 290(282) 286(280)
57 59 58 63 123 3.8 4.6 1/60 274(238) 246(242) 90 104 81 88 202 3.1
6.6 5/60 270(265) 270(242) 70 84 73 79 180 3.7 6.6 10/60 257(252)
262(255) 66 82 69 72 192 3.8 6.8 15/60 276(268) 277(261) 68 74 72
69 170 3.7 7.0 20/60 284(272) 277(279) 63 73 70 75 208 4.4 Control
-- -- 152 160 100 100 100 100 100 (3024 g) (1827 g) (186 lb) (74
lb) (602 cycles)
__________________________________________________________________________
a. WRAs determined after 10 launderings
TABLE V-B
__________________________________________________________________________
HCl Warp Exposure Wrinkle Recovery Angle, Tearing Strength Tensile
Strength Stoll Wash- Add-on Time/Temp. W + F, (degrees) (%
retention) (% retention) Abrasion Wear (%) (min/.degree.C) Dry Wet
Warp Fill Warp Fill (% retention) Ratings
__________________________________________________________________________
5.5 1/120 309(302).sup.b 308(305).sup.b 66 74 51 54 89 3.0 4.8
2/120 314(305) 304(303) 44 75 23 17 59 3.4 5.0 3/120 322(a) 320(a)
31 11 24 16 21 4.3 4.8 4/120 312(a) 297(a) a 31 a a a a a 5/120 a a
a a a a a a a 10/120 a a a a a a a a 6.4 1/100 275(267) 299(285) 77
93 51 53 128 3.5 6.2 2/100 310(284) 312(289) 26 31 45 34 15 3.6 5.9
3/100 310(293) 304(299) 17 18 47 14 12 3.8 -- 4/100 312(a) 314(a) 2
13 30 9 3 3.8 a 5/100 a a 2 a a a a a a 10/100 a a 2 a a a a a 5.8
1/80 280(266) 295(252) 68 89 52 63 175 3.5 6.1 2/80 286(288)
308(280) 67 82 51 60 158 3.6 5.9 3/80 307(291) 303(290) 32 27 33 37
52 3.8 4.7 4/80 293(290) 316(301) 26 28 27 34 22 3.7 5.2 5/80
304(294) 312(293) a 23 16 16 12 4.0 a 10/80 a a a a a a a a 4.8
1/60 286(260) 279(270) 87 94 67 72 166 3.6 5.5 2/60 299(262)
292(282) 53 78 59 55 98 4.3 6.1 3/60 303(291) 304(296) 46 38 40 49
68 4.0 5.9 4/60 302(296) 316(298) a 31 35 35 50 4.2 5.7 5/60
306(291) 307(301) a 21 26 29 16 3.6 a 10/60 a a a a a a a a Control
-- -- 152 160 100 100 100 100 100 -- (3024 g) (1827 g) (186 lb) (74
lb) (602 cycles)
__________________________________________________________________________
a. Too weak to test b. WRAs determined after 10 launderings
With respect to the formic acid system, it is evident from these
data that the degree of crosslinking of fabrics as measured by the
development of WRA's (wrinkle recovery angles) increased as the
length of exposure time or reaction temperature increased.
Conversely, the strength retention of these fabrics diminished
somewhat as the reaction temperature increased. However, strength
losses exhibited by the postheated fabrics were considerably
smaller than those shown by the control fabrics. Reaction time, on
the other hand, had a less pronounced effect on strength retention.
Fabrics exposed for 5 to 20 minutes exhibited similar degrees of
strength retentions.
Thus, these results indicate that the process of this invention can
be operated within a wide range of reaction times without
significantly adversely affecting the strength retention of the
treated fabrics. The use of temperatures above 80.degree.C.
(100.degree. or 120.degree.C.) is preferred in order to obtain high
levels of crosslinking when using Permafresh 113B. The use of other
crosslinking agents such as methylated methylolmelamine (Resloom
M-75, Monsanto), methylolmelamine (Resloom HP, Monsanto), and a
triazineformaldehyde condensate (Aerotex special resin 23, American
Cyanamid) reduce the reaction time considerably.
As shown in Table V-B, fabrics treated with the Permafresh
113B-hydrochloric acid system developed high levels of WRAs in very
short lengths of time. Fabrics treated for 1 or 2 minutes exhibited
significant strength losses comparable to those obtained with the
conventional pad-dry-cure process particularly at the lowest
reaction temperatures. Samples treated for 3 to 5 minutes were
extremely weak and those treated for longer than 5 minutes were too
weak to be tested.
Due to the extreme acid degradation exhibited by all hydrochloric
acid-catalyzed samples after the post-heating step, it was
impossible to measure any of their physical properties.
From the above observations, it can be concluded that some of the
basic differences between the hydrochloric and formic acid or
acetic acid catalyzed systems using fabrics impregnated with
methylolamides are: (1) the range of reaction times and
temperatures uder which both systems operate, (2) the method of
removing the volatile residues (i.e., by washing or heat soaking),
and (3) the possibility of treating garments rather than flat goods
due to the omission of the neutralizing and washing steps in the
formic acid- or acetic acid-catalyzed process.
Some of the disadvantages of the hydrochloric acid-catalyzed system
are: (1) excessive degradation of the cotton fibers, (2) the need
for neutralization of the fabric after treatment, (3) the need for
afterwash, (4) lack of reproducibility due to the narrow range of
reaction times and temperatures under which the process operates,
and (5) the need for special controls and equipment for handling
the highly corrosive and toxid hydrochloric acid.
EXAMPLE VI
The twill samples of Example V were treated with an aqueous
solution containing 20 percent dimethylolethyleneurea (Rhonite R-1,
Rohm and Haas Co.) and 10 percent Rhoplex K-14, dried and exposed
to gaseous formic acid for 5 minutes at 120.degree.C. Conditions
and results are shown in Table VI.
TABLE VI
__________________________________________________________________________
Warp Wash- Postheating Wrinkle Recovery Angles, Tearing Strength
Tensile Strength Stoll Wear Add-on Time & Temp W + F, (degrees)
(% retention) (% retention) Abrasion Ratings (%) (min/.degree.C)
Dry Wet Warp Fill Warp Fill (%retention)
__________________________________________________________________________
6.7 0 302 284 88 92 69 63 262 3.6 7.4 5/130 299 287 72 77 58 56 204
3.7 7.6 5/140 308 294 68 76 56 60 174 3.5 7.4 5/150 313 294 67 70
58 56 168 3.7 -- 152 160 100 100 100 100 100 -- (3024 g) (1827 g)
(186 lb) (74 lb) (602 cycles)
__________________________________________________________________________
These data show that the post-heating temperature can be reduced or
the post-heating step entirely eliminated without diminishing the
degree of wash-wear performance by using methylolamides that are
more reactive than dihydroxydimethylolethyleneurea. The results
shown in Table VI indicate that the WRAs and wash-wear ratings of
fabrics treated with dimethylolethyleneurea were not affected by
reducing the temperature of or omitting the post-heating step.
EXAMPLE VII
Cotton twill fabrics (7.8 oz/sq yd NCC standard twill) were padded
to 70 percent wet pickup with an aqueous solution containing 15
percent trimethylolmelamine (Resloom HP, Monsanto) and either 2.5
percent (solids) Urethane Latex E-502 (Wyandotte Chem. Corp.), 2.0
percent (solids) high density polyethylene or 3.2 percent (solids)
Rhoplex K-87, dried, and then exposed to acetic acid vapor at
115.degree.C. Conditions and results are shown in Table VII.
##SPC1##
It is evident from Table VII that acetic acid is capable of
producing samples with wrinkle recovery and tensile strengths
retention comparable to those obtained with formic acid vapor.
The principles, preferred embodiments and modes of operation of the
present invention have been described in the foregoing
specification. The invention which is intended to be protected
herein, however, is not to be construed as limited to the
particular forms disclosed, since these are to be regarded as
illustrative rather than restrictive. Variations and changes may be
made by those skilled in the art without departing from the spirit
of the invention.
* * * * *