U.S. patent number 3,862,224 [Application Number 05/298,481] was granted by the patent office on 1975-01-21 for production of textile finishes.
Invention is credited to Heinz Bille, Harro Petersen, Guenter Reuss.
United States Patent |
3,862,224 |
Petersen , et al. |
January 21, 1975 |
**Please see images for:
( Certificate of Correction ) ** |
PRODUCTION OF TEXTILE FINISHES
Abstract
A process for the production of textile finishes based on
ethylene glycol, formaldehyde, glyoxal and urea, particularly for
finishing union cloth containing cellulose.
Inventors: |
Petersen; Harro (6710
Frankenthal, DT), Bille; Heinz (6713 Limburgerhof,
DT), Reuss; Guenter (6700 Ludwigshafen,
DT) |
Family
ID: |
25761927 |
Appl.
No.: |
05/298,481 |
Filed: |
October 18, 1972 |
Current U.S.
Class: |
564/60; 524/598;
8/185; 528/245 |
Current CPC
Class: |
D06M
15/423 (20130101) |
Current International
Class: |
D06M
15/423 (20060101); D06M 15/37 (20060101); C07c
127/00 () |
Field of
Search: |
;260/555R,68,7R,7A,553CD |
References Cited
[Referenced By]
U.S. Patent Documents
Primary Examiner: Helfin; Bernard
Assistant Examiner: Glynn; Michael W.
Attorney, Agent or Firm: Johnston, Keil, Thompson &
Shurtleff
Claims
We claim:
1. A process for the production of a textile finishing agent
wherein ethylene glycol and formaldehyde are reacted for a period
of from 1 to 4 hours in a molar ratio of from 1:1.5 to 1:2.5 at a
temperature of from 80.degree. to 100.degree. C in the melt or an
aqueous solution in the presence of an acid having a dissociation
constant K or K.sub.1 of at least 10.sup.-.sup.4 and sufficient to
bring about a pH range in the reaction medium of from 0.4 to 1.5,
and the resulting mixture is reacted at a temperature of from
30.degree. to 50.degree. C for a period of from 3 to 5 hours with
an equal molar amount of from 0.3 to 0.4 mole, based on 1 mole of
ethylene glycol, of each of glyoxal and urea at a pH of from 6 to 7
which is brought about by the addition of alkali or sodium
carbonate so that from 5 to 15 percent of free formaldehyde is
contained in the solution after the reaction.
2. A process as claimed in claim 1 in which ethylene glycol and
formaldehyde are used in a molar ratio of from 1:2.0 to 1:2.5.
3. A process as claimed in claim 1 in which the acid is a mineral
acid.
4. A process as claimed in claim 1 wherein the reaction in the
second stage takes place at a pH of from 6.2 to 6.8.
Description
The invention relates to a process for the production of textile
finishing agents for fabrics consisting of or containing
cellulose.
In the finishing of union cloth based on cellulose and particularly
on mixtures of cotton and synthetic fibers, exceptionally high
standards are required. The cloth, after finishing, should exhibit
not only a high degree of wet and dry crease resistance but also a
pleasant soft handle. The finish also has to be fast to chlorine
and in the case of a colored cloth the coloration must not be
affected by the finishing agent.
It is known that impairment of color fastness can be avoided by
using N-dimethylol compounds of 4,5-dihydroxyethylenurea and also
some carbamates. Dimethylol-4,5-dihydroxyethylenurea finishes do
not however impart fastness to chlorine, whereas
dimethylolcarbamates may provide adequate fastness to chlorine in
some circumstances, although they usually result in more than
average damage to the cellulose fiber.
It is known from German Laid-open Specification No. 1,469,382 that
cellulosic textiles can be treated with an aqueous solution of an
acetal from formaldehyde and glycol, a catalyst mixture and an
additive acting as a buffer, for example melamine-formaldehyde,
dimethylolethylenurea or dimethyloldihydroxyethylenurea. This
method has the disadvantage that the said additives are injurious
to the achievement of a finish which is fast to chlorine.
It is known from Swiss Pat. No. 399,407 that a mixture of acetal
resins, for example reaction products of formaldehyde with
monohydric or polyhydric aliphatic alcohols, dimethylolalkylenurea
and methylolaminotriazine compounds can be used as a finishing
agent. Such mixtures have however a marked negative effect on the
shade and fastness of dyed textiles.
It is an object of the invention to provide a textile finishing
agent not having the said disadvantages.
Another object of the invention is to provide a finishing agent for
textiles consisting of or containing cellulose which combines high
resistance to hydrolysis and good fastness to chlorine with a
pleasant handle and does not cause any shade change in colored
goods.
Other objects of the invention will be evident from the following
detailed description.
We have found a process for the production of a textile finishing
agent in which ethylene glycol and formaldehyde are reacted in a
molar ratio of from 1:1.5 to 1:2.5 in the presence of an acid and
then the mixture is reacted with the same molar amount of 0.3 to
0.4 mole of each of glyoxal and urea based on 1 mole of ethylene
glycol at a pH of from 6 to 7 so that after the reaction from 5 to
15 percent of free formaldehyde is contained in the solution.
Textile finishing agents prepared by the said process may be used
in an outstanding way for finishing cellulose cloth or union cloth
containing cellulose in order to obtain a good, soft and smooth
hand, good fastness to chlorine of the finish and a high degree of
wet and dry crease resistance without affecting the shade and color
fastness. The new agents have also proved to be suitable on union
cloth containing other native cellulose fibers or regenerated
cellulose fibers instead of cotton.
The surprising superiority over prior art finishing agents is not
completely understood because the chemical processes taking place
during the preparation of the solution are not quite clear. It is
therefore advisable that the process conditions specified such as
molar ratios, pH, and sequence of addition should be adhered to as
closely as possible.
Ethylene glycol and formaldehyde are reacted in a molar ratio of
from 1:1.5 to 1:2.5, preferably from 1:2.0 to 1:2.5, in the
presence of an acid, conveniently within a period of from 1 hour to
4 hours at a temperature of from about 80.degree. to 100.degree.
C.
The acid used is a medium strength or strong acid, i.e. one having
a dissociation constant K or K.sub.1 of at least 10.sup.-.sup.4. It
is preferred to use a mineral acid, particularly sulfuric acid or
aqueous hydrochloric acid; p-toluenesulfonic acid, for example, may
however also be used. The amount of acid is advantageously choosen
so that a pH of from 0.4 to 1.5 is maintained during the reaction
of glycol with formaldehyde.
The reaction mixture is then adjusted to a pH of from 6 to 7 with
alkali, preferably with aqueous caustic soda solution or an aqueous
sodium carbonate solution. The preferred pH range is from 6.2 to
6.8.
Glyoxal and urea are then added to the mixture in the same molar
amounts of 0.3 to 0.4 based on the ethylene glycol. The mixture is
thereafter conveniently kept for about three to five hours with or
without stirring at about 30.degree. to 50.degree. C.
If desired the solution may then be adjusted to the optimum end pH
for the textile finishing which is from 6.5 to 6.8. It is essential
that under the said conditions from 5 to 15 percent of free
formaldehyde is present.
The ethylene glycol used is advantageously employed in the form of
a high percentage product having a water content of not more than
10 percent. Glyoxal and formaldehyde may be used in the form of
their commercially available aqueous solutions or in the form of
their polymerized products. Urea may be used in solid form or also
as an aqueous solution.
The solution obtained may be used as a finishing agent by all
methods used for the application of N-methylol compounds to textile
materials; these are methods in which the material to be finished
is impregnated with a solution or dispersion of the finishing agent
and an acid or potentially acid catalyst and reacted with the
finishing agent with the formation of acetal bonds between the
cellulose molecules of the textile material and the finishing
agent; this reaction may be carried out either in the wet condition
of the textile material or a partial or complete drying of the
textile material may be carried out between the impregnation and
the chemical reaction.
The new finishing agents are used in known manner, preferably in
the form of aqueous impregnating liquors. The concentration of
finishing agent depends in the usual way on the effect aimed at. It
is generally from 50 to 200 g/liter. The material to be treated is
impregnated with the impregnating liquor in the usual way,
preferably by padding. The impregnated material is freed from
excess impregnating liquor by a known method, for example by
squeezing. The impregnated fibrous material may be dried and then
heated in the presence of an acid or potentially acid catalyst to a
temperature of up to 210.degree. C, preferably at from 130.degree.
to 180.degree. C. The reaction is generally over under these
conditions within one minute to six minutes. The fibrous material,
during drying or thereafter, may be mechanically shaped, for
example by compression, crimping, ironing, calendering, embossing
or pleating. After the reaction the fibrous material has a high dry
crease recovery angle; moreover the shape imparted to the fibrous
material is fixed therein in a washproof manner.
The treated material may be washed, rinsed and dried by
conventional methods.
Furthermore the very advantageous possibility is available of
leaving the impregnated and squeezed material wet or drying it to a
moisture level of from 10 to 35 percent based on the weight of the
amorphous regions contained in the cellulose, i.e. in the case of
native cellulose, for example cotton, to a moisture level of from 3
to 10.5 percent, in the case of regenerated cellulose to a moisture
level of from 6 to 21 percent, in each case based on the whole of
the cellulose component and then storing it at room or elevated
temperature, preferably at a temperature of not more than
50.degree. C without appreciable loss of water in the presence of
an acid and/or potentially acid catalyst. Instead of drying the wet
material to the said moisture content, it may also first be dried
completely and then moistened again to the said content. In a
method which has proved to be very suitable the controlled
moistening is carried out by impregnating the dry textile material
with an inert non-aqueous liquid which contains the small amount of
water necessary and also the catalyst or catalysts. The reaction
with the cellulose under these conditions generally requires from 5
to 20 hours or even less at temperatures above 50.degree. C. This
embodiment of the process makes it possible to finish fibrous
material consisting of or containing cellulose in a simple and
reliable way in a single operation so that it has a high to very
high wet crease recovery angle to 140.degree. or more and an
average dry crease recovery angle of 110.degree. or more. It is
possible by varying the process conditions to adapt the level and
difference between wet and dry crease recovery angles to the
particular requirements.
Acid and potentially acid catalysts are generally known and
conventional for the purpose of creaseproof finishing. Examples are
inorganic and organic acids such as sulfuric acid, hydrochloric
acid, phosphoric acid, boric acid, formic acid, acetic acid, oxalic
acid, tartaric acid, maleic acid, and salts which have an acid
reaction or which form acids by the action of heat and/or by
hydrolysis, for example ammonium salts and amine salts of strong
acids, magnesium chloride, zinc chloride and zinc nitrate. Mixtures
of two or more catalysts may also be used. It is preferable to use
magnesium chloride, zinc nitrate and zinc chloride for the process
of deferred curing. The reaction of the finishing agents to be used
according to the invention is carried out in the presence of these
catalysts as already stated above. This may be effected by applying
the catalysts, preferably in the form of aqueous solutions, to the
material to be finished before or after impregnation of the same.
It is preferred however to add the catalysts direct to the
impregnating liquor containing the finishing agent. The
concentration of the catalysts is chosen within the conventional
range for the particular finishing method used. Catalyst
concentrations of from 1 to 40 g/liter have generally proved to be
suitable for finishing at high temperature and deferred cure and,
based on the weight of finishing agent, amounts of catalyst of from
4 to 60 percent, preferably from 20 to 40 percent, whereas for
finishing in a swollen condition of the fiber, i.e. in the presence
of a considerable amount of water, and at lower reaction
temperature it may be necessary, as already known, to use strongly
acid catalysts in a concentration of up to 20N.
Conventional water-repellent, softening, leveling, wetting and
finishing agents such as particularly polymer solutions or
dispersions may be used together with the new finishing agents.
Examples of water-repellents are the known paraffin wax emulsions
containing aluminum or zirconium and also preparations containing
silicones and perfluorinated aliphatic compounds. Examples of
softeners are oxyethylation products of high molecular weight fatty
acids, fatty alcohols or fatty acid amides, high molecular weight
polyglycol ethers and their esters, high molecular weight fatty
acids, fatty alcohol sulfonates, stearyl-N,N-ethylenurea and
stearylamidomethylpyridinium chloride. Examples of leveling agents
are water-soluble salts of acid esters of polybasic acids with
ethylene oxide or propylene oxide adducts of long chain
oxyalkylatable base materials. Examples of wetting agents are salts
of alkylnaphthalenesulfonic acids, alkali metal salts of sulfonated
dioctyl succinate and the adducts of alkylene oxides to fatty
alcohols, alkylphenols, fatty amines and the like. Examples of
finishing agents are cellulose ethers or esters and alginates, and
also solutions or dispersions of synthetic polymers and
polycondensates, for example of polyethylene, polyamides,
oxyethylated polyamides, polyvinyl ethers, polyvinyl alcohols,
polyacrylic acids or their esters and amides and also the
corresponding polymethacrylic compounds, polyvinyl propionate,
polyvinylpyrrolidone, copolymers, for example those of vinyl
chloride and acrylic esters, of butadiene and styrene or
acrylonitrile or of .alpha.-dichloroethylene,
.beta.-chloroalkylacrylic esters or vinyl-.beta.-ethyl ethers and
acrylamide, or the amides of crotonic acid or maleic acid or of
N-methylolmethacrylamide and other polymerizable compounds. These
additional auxiliaries are generally used in amounts of from 0.3 to
4 percent, preferably from 1 to 2.5 percent, based on the weight of
the dry textile material; in special cases these amounts may
however be exceeded.
The finishing agents of the invention give finishes on union cloth
and cellulose cloths which have a very high resistance to
hydrolysis and good fastness to chlorine. In particular a pleasant
handle is imparted to the cloth. It may be emphasized that the
agents are also suitable for colored materials because no
variations in shade occur during the finishing.
The following Examples illustrate the invention. The parts and
percentages specified are by weight. Parts by weight bear the same
relation to parts by volume as the kilogram to the liter.
EXAMPLE 1
A mixture of 620 parts of ethylene glycol and 1,672 parts of 40
percent formaldehyde solution has 14 parts of 50 percent sulfuric
acid added to it and the whole is heated to refluxing temperature
while stirring for 1 hour. After cooling to about 50.degree. C a pH
of 6.5 is set up with concentrated caustic soda solution. 5,200
parts of 40 percent glyoxal solution and 218 parts of urea are then
added. The whole is stirred for another 2 hours at 30.degree. to
35.degree. C and then a final pH of 6.5 to 6.8 is set up.
EXAMPLE 2
620 parts of ethylene glycol is heated under reflux with 678 parts
of paraformaldehyde and 9 parts of concentrated sulfuric acid for
ninety minutes while stirring. A pH of 6.5 is set up and then 535
parts of glyoxal and 222 parts of urea are added to the reaction
mixture and the whole is heated for another 2 hours at 35.degree. C
while stirring. After filtration 2,050 parts of finishing agent is
obtained.
EXAMPLE 3
The superiority of the finishing agent as regards resistance to
chlorine (measured as the tear resistance of the impregnated cloth)
is demonstrated.
A mixture of:
I. 150 parts of the product of the invention prepared as described
in Example 1 (50 percent aqueous solution) and
30 parts magnesium chloride hexahydrate; and for comparison
Ii. 150 parts dimethylolglyoxalmonoureine (50 percent aqueous
solution) prepared by reaction of urea, glyoxal and formaldehyde in
the ratio 1:1:2; and
22 parts magnesium chloride hexahydrate
is made up in each case to 1 liter of solution.
Pure cotton cloth is impregnated with this solution in each case.
The liquor pick-up is 70 percent. After the impregnated cloth has
been dried condensation is carried out for about 5 minutes at
155.degree. C.
The tear resistance (measured on a strip of 50 mm .times. 200 mm)
indicates the resistance of the finish in the case of one or more
chlorinations as follows:
(I) (II) ______________________________________ untreated cloth 35
kg 35 kg finished cloth 22 kg 24 kg one chlorination 23 kg 18 kg
three chlorinations 23.5 kg 7.5 kg five chlorinations 20.0 kg
destroyed ______________________________________
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