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_- Batented Aug. 9, 1938
2,125,901 _
- UNITED STATES PATENT, omoo - ‘
2,125,901
“
'
.
ri'ms'nmd 'rnx'rmn - MATERIALS
John Gwynant Evans and Charles Edward Sal
keld, Blackley, Manchester, England, 'assignors
to Imperial Chemical Industries Limited, a cor
poration of Great Britain
No Drawing. Application January 14, mi, se
rial No. 120,636. In Great Britain January 15,
1936
15 Claims.
- This invention relates to a novel process for
?nishing textile materials, including in this term
fabrics, ?lms and threads of natural or arti?cial
'cellulosic material, as well as paper. More par
5 ticularly this invention deals with a process of
?xing starch upon fabrics, yarns, woven or plaited
straw (as on hat material) or papers hereinafter
referred to as the materials, some of which are
(01. 91-70) ‘
Also in the general formula Y stands for the
anion or a salt forming acid, for instance chloride,
bromide, methyl-sulfate, acid-oxalate, etc., and
X stands for a non-carbonic ‘link selected from
,
the group‘ consisting of oxygen,‘ sulfur, imino 5
(NH), and substituted imino (N-alkyl, N-aralkyl,
N-aryl, N-acyl, N-carbo-alkoxy, etc);
I
R in the general formula stands‘ for any or
ganic radical which is free from water-solu
normally subjected to starching and some of
10 which are not, whereby to render said starching _ bilizing groups, and may be either aliphatic or l0
I
effect “permanent", that is, resistant to washing
aromatic, straight-chain or branched-chain, sat
or other aqueous'treatment processes.
As is well known, starches, e. g. wheat starch,
urated or ‘unsaturated, alkyl or acyl. Also it may
be divalent whereby the formula takes on a Si
tapioca starch, corn starch, potato starch, or rice
lii starch are wideiy'used, as ?nishing agents for tex
tiles. For certain purposes it is desirable for the
?nish so obtained to be resistant to removal from
the ?bre in washing or other operations involving
treatment with water.
20
It is accordingly an object of our invention to
provide a novel process for rendering starched
fabric resistant to washing. It is a further object
of ‘the invention to provide a process whereby
starch may be used as a ?nishing agent in paper
25 making and in the manufacture of straw hats and
the like. Other and further objects of this in
vention will appear as the description proceeds.
We have found ‘that when the materials re—
ferred to are treated with a quaternary organic
3" compound of the general formula:
Rr-X-CHg-N (tert.) -—Y
as more fully de?ned below, either before or after
or simultaneously with a starching operation, the
35 resulting starch ?nish- acquires a “permanent”
character in the sense that it is not removed by
washing. This effect is of tremendous practical
signi?cance in relation to textile fabrics because
it saves the labor, materials and cost of repeated
40 starching each time an article of apparel, for
instance, is laundered. By the operation of our
invention the starch becomes "?xed", so to speak,
upon the fabric.
In the above formula “N (tert.) " stands for the
amese-twin aspect. As typical illustrationsof B.
when X stands for oxygen or sulphur may be
mentioned methyl, butyl, octyl, undecyl, dodecyl, ‘
cetyl, octadecyl, and octadecenyl,—these are satu
rated and unsaturated aliphatic hydrocarbon
radicals; the radicals of the sperm oil alcohols
also come into consideration, a mixture being 20
used. When‘ X stands for NH or N-alkyl, B may
stand for stearamido, oleylamido or acetamido.
Other permissible variations of R. will become ap-
parent from the further examples given below.
The method of applying these "?xing agents” 25
to the material being treated may take the form '
of ‘at least three di?erent procedures, as follows:
For example, the starch ‘solution or paste, is
applied ‘and the material is thentreated in the
wet or dry state in a bath containing one of the 30
above mentioned quaternary salts, being then
optionally dried at ordinary or higher tempe'ra- -
tures and being ?nally heated for a short time
at still more elevated temperatures, e. g. above
100° C.
35
‘
Alternatively, the quaternary salt is initially
applied to the material and the starch solution or
paste is then applied, the material being then
dried at ordinary or somewhat higher temperature.
and heated as before described for a short period
at a still more elevated temperature, e. g. above
100° C., or being dried at this temperature di
rectly after application of the starch solution or
paste.
- A further method of carrying the invention 45
45 nitrogen atom of a tertiary base capable of form
ing a salt or quaternary compound. The tertiary into practical effect is to mix-the quaternary salt
and the starch in any convenient manner, to
base may be heterocyclic such as pyridine, pico
apply the mixture to the material, and to heat
line, quinoline, or it may be aliphatic, for in
with or without intermediate drying, as before
stance trimethylamine, triethylamine or trieth
50
50 anal-amine. Tertiary aromatic bases, for in-v
It will be noted that each‘ of the above proce
' stance, dimethylaniline are preferably not in
dures involves as a ?nal step the heating of the‘
cluded as their use in the manufacture of com
treated and starched material at a temperature
pounds of the formula given is attended with dif
. ?culty, because there is a, liability that nuclear ‘of about 1000 c. This step will hereinafter be
referred to as the “baking" step, and has as‘ its 85
56- substitution takes place.
._
described.
_
-
'
62
2,125,001
object to decompose the quaternary compound
liberating the tertiary base, which evaporates
Without limiting our invention to any partic
ular procedure, the following examples ar given
oil’, and leaving behind the remainder of the
molecule in some form which apparently enters
into some sort of physical or chemical combina
tion with the fabric or with the starch. The
Parts mentioned are by weight.
baking temperature therefore may vary between
the lowest value which will bring about decom
position with liberation of the free base and the
10 highest temperature tolerable by the starch or
the fabric. A practical thumb-rule is to bake
at a temperature between 90 and 140° C.
For best results it is preferable to dry the
material after impregnation with starch and fix
15
ing agent but before the baking step. However,
this step is not a limitation upon this invention,
since good results are in many cases obtained by
omitting it. In other words, in these cases the
drying step is merged into the baking step. The
20 temperature of the drying step is in the average
to illustrate our preferred mode of operation.
Example 1
Cotton sheeting is treated at 100° C. with a
starch paste containing 10 parts by weight of
corn starch in 90 parts by weight of water. The
material is squeezed and is then dried. This dry 10
starched material is padded at room tempera
ture in a solution containing 1 part by weight
of methyloxymethyi pyridinium chloride in 99
parts by weight of water. It is then squeezed,
dried below 40° C. and baked for 30 minutes at 15
a temperature of 105° C.
The treated material now possesses a smooth
stiif ?nish which is resistant to removal by laun
dering treatments.
case not higher than about 40-50° C. But in
some cases, temperatures as high as 90° C. may
be employed. In general, the object of the dry
ing step is to avoid hydrolysis of the ?xing agent
25 as the temperature of baking is approached.
Consequently, a choice of conditions for drying
will in the cases of each compound be guided by
its stability in the presence of moisture at ele
vated temperatures.
The ?nish produced on fabrics processed in
30
the above manner is highly resistant to the ac
tion of aqueous liquors, hot or cold. At the same
time, when quaternary salts containing an alkyl
chain of 10 or more carbon atoms are used, the
35 fabric becomes particularly smooth and pleasant
to handle. It also'becomes water repellent.
To prevent possible injury to the material dur
ing the baking step due to any acid which might
be liberated, the entire process may if desired
40 be carried out in the presence of acid binding
agents, or in the presence of salts of mild acids
which are capable of acting as bu?ers. vAs il
lustrations of such compounds maybementioned:
,borax, magnesium hydroxide, pyridine, aniline,
and other weakly basic substances; sodium ace
M45 .-tate.
and other
buffers. Acetic acid, phthalic
_
Example 2
Cotton sheeting is impregnated at 100° C. with
a starch paste containing 10 parts by weight of
potato starch and 1 part by weight of cetoxy
methyl pyridinium chloride in 89 parts of water. 25
The material is then squeezed and dried for 10
minutes at a temperature of 120° C.
It now possesses a smooth stl? ?nish which is
resistant to laundering treatments.
Example 3
desired.
50
may be added to the treatment ?uids referred to
.above, for the purpose of facilitating the appli
cation of either the starch or the ?xing agent,
or for the purpose of effecting their own speci?c
functions on the ?bre. For instance, there may
be added suitable wetting or dispersing agents.
55 or, as illustrations of additional functional agents
there may be mentioned water-insoluble pig
ments (such as are used as dulling agents for
30
Cotton sheeting is padded at room temperature
in a‘solution containing 2 parts of octadecoxy
methyl pyridinium chloride in 98 parts of water.
The material is squeezed and dried at a tem 35
perature "of 30°-40° C. It is now treated at
60° C.'with a starch paste containing 10 parts of
potato starch in 90 parts of water. The mate
rial is squeezed, dried at a temperature of 40°
50° C. and is then heated in an oven for 10
minutes at a temperature of 105° C.
The material now possesses a pleasing smooth
stiif ?nish which is resistant to laundering treat
ments. The material is also water repellent.
45
Example 4
acid, or other mild acid may also be present if
, _If;desired, other ?nishing agents or adjuvants
20
Cotton sheeting is treated at 80° C. in a starch
paste containing 10 parts of potato starch in 90
parts of water. . The material is squeezed and, 50
dried. The dry, stiffened material is padded at
room temperature in a solution containing 1 part
of octadecoxymethylpyridinium chloride and 1
part of pyridine in 98 parts of water. The ma
terial is squeezed, dried below 40° C. and baked 56
for 1 hour at 90° C.
.
The material now possesses a pleasing. smooth
arti?cial silks), for instance, china clay, barytes, stiff ?nish which is resistant to laundering treat
titanium dioxide; ?nishing agents, for instance,‘ ments.
The pyridine in the above example may be re
magnesium sulphate; softening agents, for in
stance, Turkey red oil, tallow, soaps, sulphuric placed by other basic substances such as borax,
esters of long chain alcohols, or waxes, for in
stance, paraf?n wax, carnauba wax, Japan wax,
or by acidic substances such as acetic acid.
' Example 5
also adhesives, for- instance, dextrine, gums,
glues, Iceland moss.
The concentration of ?xing agent in the treat
ment bath will vary depending on the relative
proportion of starch which it is desired to a?ix
to the ?bre.
As a general rule it may be said
70 that the quantity of agents to be used will be
about one part to every 10 parts of starch to be
?xed. For adequate ?xation of starch ?llings
on textiles it may sometimes be necessary to use
proportionately more ?xing agent. However for
particular ?nishes it is possible to use less.
Cotton sheeting is treated at 100° C. in a starch 65
paste containing 10 parts of potato starch in 90
parts of water. The material is squeezed and
dried at 100° C. It is now treated, in a continu
ous padding operation with a hot solution con
taining 1 part of octadecoxymethyl pyridinium 70
chloride in 99 parts of water. The material is
squeezed, dried and then heated for 30 minutes
at a temperature of 105° C.
It now possesses a stiff ?nish whichis resistant
to laundering.
3.
0,125,601 ,jiif..,_,
I hampers ' ,
,
product obtained by reacting stearamide, _ pyriQ
starchpastelcontaining 10 parts by weight dine and paraiormaldehyde with gaseous sulphur,
dioxide as described in Recipe F below.‘ The lab
of ‘potato- starch in90- parts by weight 01' water is ri'c
is squeezed and dried at a temperature at;
applied toeotton sheeting at 100°C. The mate
40°
C.
It is then heated for 30 minutes at a tem-,
rialiis-squeezedanmdricd at, 100° C. It is then
treated’ at 45°C. in azc'ontinuous padding opera perature of 105° C. The resulting fabric hasa
tion, with a solution containing 2 parts by weight sti? ?nish which is not readily removed or-dam- '
aged by washing. 5
>
of. cetoxymethyl'pyridinium acid oxalate (pre
'
Example 12 pared as described below in Recipe C) in 198 parts
10
10" by weight oi.- water. They material is squeezed,
' ' Cotton fabric is impregnated with an aqueous
driedat 60° C. and-heatedi’or 3 minutes at 140° C. .
"The. material - now-possessesa pleasing smooth
s'tim-?nish. whichisiresistantx to- laundering.
"A, linen ydamaskjtable cloth is treated at 50° C.
with-a starch. paste containing 10 parts of potato
starch, 6 parts of a .1$% aqueous emulsion of par
amn wax and 1 part of octadecoxymethyl pyri
diniumpliloride in. .183. parts of water. The mate
rial. is squeezed, dried at 60° (hand baked for 15'
minutes at 105° C.
..
‘
'
I
v
_
Thematerial ,now possesses a pleasing smooth,
sti?? ?nish, and is also water repellent. The stiii
25 ?nish and water repelling are resistant. to laun
dering treatments.
'
Example 8'
I
Cotton sheeting is treated with a‘ hot starch‘
30 paste containing 5 parts of potato starch in 95
parts of water. The material is squeezed and
dried. The dry material is padded at 35° C. in a
paste of Iarina (potato starch)v containing per‘
100 parts 01 paste 5 parts 01 iarina and 0.2 part,
or the reaction product from cetyl alcohol, pyri
dine, ,paraiormaldehyde and gaseous sulphur di
oxide (see Example 10 above and Recipe E be
low). The impregnated fabric is then treated as
described in Example 1. The resulting iabric has
a still finish which is not readily removed or
damaged by washing.
Example 13
20
Both surfaces or cotton sheeting are treated’
with a hot starch paste containing 10 parts of
potato starch and 2 parts of ?nely powdered 5
Monolite Fast Red R (Colour-Index No. 69) in
88 parts of water. The material is squeezed and
dried. The coloured, stiilened material thus ob
tained is padded at room temperature in a solu
tion containing 1 part of octadecoxymethyl pyri
dinium chloride in 99 parts 01' water. It is
squeezed, dried below 40° C. and heated for 30
minutes at 105° C.
The material now possesses a coloured sti?
?nish which is resistant to laundering, the col 35
solution containing 1 part of stearamidomethyl
pyridinium chloride in 99 parts oi.‘ water. It is
35 squeezed, dried below 40° C. and heated for 5 ' oured pigment adhering to the cloth during wash
minutes at 120° C.
ing treatments.
The material now possesses a pleasing smooth _
' stifi' ?nish which is ‘also water repellent. ‘The
still ?nish is resistant to laundering.
Example 9
40
parts of potato starch and 2.5% parts of ?nely
‘ treated with a starch paste containing 5 parts of
wheat starch in 95 parts 01 water is squeezed,
45 dried and then padded at room temperature in a
solution containing 1. part of the bis(chloro-py
ridinium-methyl-ether) oi’ ethyleneglycol (pre
pared as described below, Recipe D) in 199 parts
of water. The material is squeezed, dried at a
temperature of 30°-40° C. and is then heated for
The full stiilf handle on the material is thus
rendered resistant to laundering.
in a current of warm air at. a temperature of 30°
40" C. and is then heated for 30 minutes at
105° C.
50
the action 01 water, the incorporated blue pig
ment showing no tendency to tall away from the
cloth during washing treatments.
Eaample 1a
A “butter muslin” material is ?lled with a
starch paste containing 10 parts of potato starch
and '20 parts of china clay in Il0 parts of water.
‘ The quantity of ?lling applied is from 100% to
60 150%, on the weight of- un?lled material.
powdered Prussian Blue in 90 parts of water. The
material is squeezed and dried. The stiff col
oured material thus obtained is now padded at
45° C. in a solution containing 1 part of cetoxy 45
methyipyridinium acid oxalate (see above) , in 99
parts of water. The material is squeezed,v dried
The still.’ ?nish on the material is resistant to .
I a period of 15 minutes at 105° C.
55
Example 14
Plain weave gray cotton cloth is treated on
both surfaces with a starch paste containing 10
A linen damask table cloth which has been
50
-
The
'
Example 15
Finely woven cotton material, so called cotton
limbric, is padded with a 10% aqueous potato
starch paste. .The' padded material is squeezed,
dried and then padded for ten minutes at 20° C. 00
in a 1.0% aqueous solution of a compound ob-_
filled material is dried and is padded at room
temperature in a solution containing 5 parts of ‘tained by reacting stearamide, paraformaldehyde
cetoxymethyl pyridinium pyridine sulphite or py
rosulphite (prepared as described below, Recipe
65 E) in 95' parts of water. The material is squeezed,
dried at a“ temperature of 30-40°‘ C. and is then
baked for 30 minutes at 105° C.
The ?lling in the material is now resistant to
and Pyridine hydrochloride in pyridine as de
scribed in Recipe A below. The material is then
squeezed, dried at 35°-40° C. and ?nally heated
at 120° C. for 30 minutes. The resulting fabric
has a stiff ?nish which is not spoiled by washing
with soap and water.
, '
laundering, the china clay particles adhering to
70 the material during washing treatments.
Example 11
Cotton iabric is impregnated with a 5% aque
Cotton material as used in Example 15 which
has previously been padded in a 10% aqueous po
tato starch paste is queezed and then immersed
ous paste of iarina (potato starch) containing
75 per 1,000 parts of paste 2 parts 01' the reaction
tion or a compound obtained by reacting stearo
Example , 16
for ten minutes at 20° C. in a 1.0% aqueous solu
70
4
8,185,901
hydroxymethylamide with pyridine-sulphur tri
chloride is replaced by molecular equivalent
amounts of pyridine hydrobromide, pyridine ni
oxide in pyridine as described in Recipe 8 be
low. The cotton material is again squeezed, dried
below 40° C. and then heated for 30 minutes at
120° C. The resulting cotton material has a stilt
finish which is not spoiled by washing with soap
and water.
trate or pyridine-m-nitrobenzoate, similar prod
ucts which are readily soluble in water to give
clear, foaming solutions, are obtained.
Recipe B.--Preparation of the compound men
I
tioned in Example 16
In a manner similar to the above examples,
other compounds of the general formula above
10 may be applied for the purpose of this invention,
either before, or after, or simultaneously with
15
33 parts of sodium pyrosulphate and 50 parts
of pyridine are heated together at 90°-95° C. for 10
30 minutes. The resulting mixture of pyridine
the application of starch. The following is a list
of compounds actually tried by us in this inven
sulphur trioxide and pyridine is cooled to 45-50‘
C. and 31.3 parts ‘of stearo-hydroxymethylamide
tion and found satisfactory more or less:».
are added. The reaction mixture is stirred at
45°40° C. until (about 30 minutes) a test sample
dissolves readily in water to give a clear foaming 16
solution. The reaction mixture is then filtered.
The ?ltrate on cooling is a viscous liquid. The
excess of pyridine may be removed from the ?l
trate by distillation at 50-55“ C. under reduced 20
pressure. The new compound is thus obtained
as a white crystalline powder, almost insoluble
in acetone.
Alternatively, the new compound,
which is also sparingly soluble in ice-water, may
Ociadecyloxymethyl quinolinium chloride.
Octadecyloxymethyl
triethanolammonium
chloride.
Octyloxymethyl pyridinium chloride.
Sec. dodecyloxymethyl pyridinium chloride.
N-carbomethoxyundecylamino methyl pyri
dinium chloride.
N-carbomethoxybutylaminomethyl pyridinium
chloride.
'
Stearanilidomethyl pyridinium chloride.
Acetoundecylamido methyl pyridinium chlo
ride.
Oleamidomethyl pyridinium chloride.
Bis(methyl pyridinium chloride)ether of ethy
lene glycol.
Cetyloxymethyl pyridinium acid oxalate.
Octadecyloxymethyl pyridinium chloride.
Cetyloxy methyl pyridinium chloride.
“
.
Pyridinium derivative from chloromethyl eth
ers of sperm oil alcohols.
Dodecyloxymethyl pyridinium chloride.
Cetyloxymethyl trimethyl ammonium chloride.
N-methyl stearamido methyl pyridinium chlo
ride.
'40
'
N-carbomethoxyheptadecyl amino methyl pyri
dinium chloride.
Stearamido methyl pyridinium chloride or sul
fate.
-
Cetyloxy methyl pyridinium sul?te or pyro
sulphite as pyridine salt.
Stearamido methoxy methyl pyridinium sul?te
45
or pyrosulphite as pyridine salt.
p-Stearamido phenyl amino methyl pyridinium
sul?te or pyrosulphite as pyridine salt.
Stearamido methyl pyridinium chloride.
Butyloxy methyl pyridinium chloride.
Methyloxy methyl pyridinium chloride.
Some of the agents in the above table are
known compounds, and their preparation has
been described in the literature (see for instance,
55 Br. Pats. No. 390,553, and 394,196). Others are
novel compounds, and are prepared by methods
of\ which the following recipes, showing the
preparation of the compounds mentioned in Ex-_
amples 6, 9, i0, 14, 15, and 16 above are typical. 4
Recipe A.-Preparation of the compound men
tioned in Example 15
10 parts of stearamide, 2 parts of paraformal
dehyde, 10 parts of anhydrous pyridine hydro
chloride and 40 parts of pyridine are heated and
stirred under re?ux at 70°40’ C. until a test
sample otthe reaction mixture gives a clear solu
tion in water. The mixture is now cooled,
whereupon the product crystallizes out almost en
70 tirely and is ?ltered oil. The new compound,
which may be further puri?ed, if desired, by re
crystallization from acetone, is readily soluble
in water at'40°-50° C. to give clear, foaming solu
tions.
If, in the above example, the pyridine hydro
be isolated from the reaction mixture or the
viscous ?ltrate by diluting with ice-water. The 25
suspension so obtained is ?ltered whilst ice-cold
and the‘product washed with ice-water. The‘new
compound is thus obtained as a white powder
which is soluble in warm water to give clear, 30
foaming solutions.
The stearohydroxymethylamide used as start
ing material is a new compound. It is prepared
as follows:
28.3 parts of stearamide, 3 parts of paraformal
dehyde, 7 parts of pulverized anhydrous potas
sium carbonate and 50 parts of benzene are
stirred together at 50° C. In a short time reac
tion takes place; the temperature rises sharply
to about 60° C. and the reaction mixture be
comes a stiif, white paste. The pasty mass is 40
allowed to cool and is then ?ltered, pressed, dried,
washed free from potassium carbonate with warm
water and again dried. The new compound is
a light coloured powder. It is very sparingly
soluble in acetone or benzene, but soluble in
methyl alcohol from which it may be crystallized
as white needles, M. P.-115° C.
Recipe C'.--Preparation of the cetomumethyl
pyridinium acid oxalate mentioned in Example:
6 and 12 i
25 parts of cetyl alcohol, 8 parts of para
formaldehyde and 64 parts of pyridine are mixed
together and heated to 80° C. Sulphur dioxide
is passed into the mixture, the temperature be
ing maintained at 80-90° C. The introduction
of sulphur dioxide is continued until the mixture
becomes completely soluble in cold water as
shown by a test. 9.3 parts oi’ anhydrous oxalic
acid are then added and the mass stirred at
85-90° C. until the oxalic acid has dissolved.
The solution is allowed to stand until no more
crystals separate. The crystalline material is ?l
tered off and washed with pyridine. The colour
less crystalline oxalate so obtained is dried.
Recipe D.—Preparation of the bis(chlm-o-py
ridiniummethul) -ether of ethylene-glycol, men
tioned in Example 9
124 parts of ethylene glycol and 120 parts of 70
paraformaldehyde are mixed, kept cool, and
stirred whilst hydrogen chloride is passed in.
When the 120 parts of. paraformaldehyde has dis
solved a further 60 parts is added. Hydrogen
chloride is introduced until no more is absorbed. 1i
5.
9,125,901
‘7 To the liquid obtained 200 parts of carbon tetra-. organic radical free‘ from water-solubilizing
chloride are added and an aqueous layer which groups. and heating the material at a tempera
separates is decanted away. The carbon tetra
ture su?lcient to decompose said quaternary
'_ chloride solution is dried over anhydrous mag» ‘compound.
nesium sulphate, ?ltered and the carbon tetra-~
3. The process of producing I a vpermanent
‘ chloride is distilled oil. The oil is distilled (B. starch ?nish upon cellulosic textile material};
P. 93-98° C./l2 m. m. pressure).
, I
which comprises impregnating said material in
This compound is the bis(chlormethyl) ether of optional order, with an aqueous starch prepara
‘ethylene glycol.
tion and a solution of a quaternary ammonium
10 _To 50 parts‘cf pyridine in 300 parts of dry compound of the‘ general formula
'
benzene are slowly added with stirring 50 parts
of the above ether. A crystalline solid separates,
Whi?l is'quiekly ?ltered oil? and dried, as the wherein N(tert.) represents the molecule of a‘
compound is‘ hygroscopic. The new compound tertiary organic base, Y represents the anion .of
is conveniently kept in aqueous solution.
a salt-forming acid, X stands for a non-carbonic 15
Recipe E.—Preparatiml. of the pyridine-catam
methyl 'pyridinium sul?te,
I
20
Earample 10
in
'
Recipe F
30. parts byweight of stearamide, 120 parts by
weight of pyridine and 12 parts by weight of
paraformaldehyde are stirred together at 90—95°
:30 ‘C.
and gaseous sulphur dioxide is bubbled ‘into
the solution until a test sample of the reaction
mixture dissolves to a, clear solution in water.
Most of the excess pyridine and paraformalde
hyde are removed from the reaction mixture by,
as
distillation below 50° C. under reduced pressure,
e. g. 15 mm. and: the residue, a viscous liquid con
stitutes the desired product, which may be fur
ther puri?ed,‘ if desired, by crystallization from
acetone.v
40
,
It will be understood that while in the above
examples we illustrated our invention ‘byrapply
ing it throughout to cotton fabric, our invention '
is not limited to fabric but may be applied to
, cellulosic material in any form, whether textile
fabric, yarn, thread, gauze, or even paper.
‘
link of the group consisting of oxygen, sulfur," -
imino and substituted imino, and R. stands for an
organic radical free from water-solubilizing
groups, drying said material at a temperature
insu?lcient to cause substantial decomposition. 20.
of said quaternary compound, and thén baking
30 parts of cetyl alcohol, 12, parts ‘of parafor
maldehyde and 120 parts of pyridine are heated
together at‘90-100° C. under a re?ux condenser. ‘said material in the absence of moisture at a
Gaseous sulphur dioxide is passed into the heated temperature favoring decomposition of said qua
mixture until a test sample from‘ the mixture ternary compound.
dissolves readily in water to give a clear solution.
.25
1
mentioned
.
We
claim:
‘
I 1. The process of improving the‘ fastness of
starch upon textile material, which comprises in-v
corporating into, the material in‘ addition to the
starch, a quaternary ammonium compound of
the general formula.
‘
-
‘ 55 wherein N‘(tert.) represents the molecule of a
4. The process of producing a permanent 25
starch ?nish upon cellulosic textile material,
which comprises impregnating said material in
‘optional time relation with an aqueous starch ‘ ‘
preparation and with an aqueous solution of a
quaternary organic compound of the general
wherein N(tert.) represents the molecule of a
tertiary organic base, -Y represents the anion
portion of a salt-forming acid, and R stands for
an aliphatic radical. free from water-solubilizing
groups,‘ drying said material at a temperature not
exceeding 40° C. and then‘ further heating said
material, in the absence of moisture, at a tem
perature between 90 and 140° C. whereby to
decompose said quaternary compound.
3.0
as
‘5.’The “process of producing a permanent
starch ?nish upon cellulosic textile materiaL'
which comprises impregnating said material in
optional time relation with an aqueous starchv
preparation and with an aqueous solution of a
45
quaternary organic compound of the general
formula
'
50
wherein N(tert.) represents the molecule of a
tertiary organic base, Y represents the anion
portion of a salt-forming acid, R stands for an
alkvl radical, while R1 stands for hydrogen or an
alkyl radical, drying said material at a tempera-y
ture not exceeding 90° C. and then heating said
link of the group consisting of oxygen, sulfur, material, in the absence of moisture, at a tem
- imino and substituted imino, and R stands for an " perature between, 90 and 140° 0., wherebyv to
organic radical free from water-solubilizulng decompose said quaternary compound and split
01! its tertiary base.
groups, and heating the material at a tempera
6. The process of fixing starch upon cellulosic
ture sufficient to decompose said quaternary
., compound.
fabric, whereby to render it resistant to washing.
‘
2. The process of improving the fastness of which comprises treating the starched fabric in
starch upon cellulosic material, which comprises an aqueous bath of a quaternary ammonium
65 impregnating said material in optional time re
65
compound of the general formula
tertiary organic base, Y represents the anion of
a salt-forming acid, X stands for a non-carbonic
lation to the starching operation, with an aque
ous solution of a quaternary ammonium com
pound of the general formula
wherein N(tert.) represents the molecule of a
tertiary organic base, Y represents the anion of
70
a salt-forming acid, X stands for a non-carbonic 70
wherein N(tert.) represents the molecule of a ter
tiary organic base, Y represents the anion of a
salt-forming acid, X stands for a non-carbonic
slink of the group consisting of axygen, sulfur,
, _7 5 imino and substituteddmino, and R stands for an
link of the group consistinglof oxygen, sulfur,
imino and substituted imino, and R stands for an
organic radical free from water-solubilizing
groups, drying said fabric under conditions avoid
ing undue decomposition of the quaternary com 76
9,195,901
pound, and then heating the dried, starched fab- - sents the anion of a salt forming acid, and‘heat
ric at a temperature favoring the decomposition ing the material at a temperature suiiicient to
of said quaternary compound in the abunce of
moisture
‘I. The process of producing a permanent starch
?nish upon cellulosic fabric which comprises im
pregnating said fabric with an aqueous solution
of a quaternary ammonium compound of the
decompose said quaternary compound.
13. The process of improving the fastness of
starch upon cellulosic textile material which com
prises incorporating into said material, in addi
tion to starch, a quaternary ammonium com
pound of the general formula
general formula
10
10
'wherein N(tert.) represents the molecule of a
tertiary organic base, Y represents the anion of a
salt-forming acid, X stands for a non-carbonic
ll link of the group consisting of oxygen, sulfur,
imino and substituted imino, and R stands for
an organic radical free from water-solubilizing
groups, applying an aqueous starch preparation
to said fabric, drying said fabric at a tempera
ture insu?icient to decompose said quaternary
compound, and ?nally heating the dried i'abricat
a temperature favoring the decomposition of
said quaternary compound in the absence of
moisture.
wherein R stands for an aliphatic radical contain 15
ing a chain of at least 8 carbon atoms and being
free from water-solubilizing groups, X stands for
an inorganic link of the group consisting of oxy
gen, sulfur, imino and substituted imino, and Y 20
represents the anion of a salt forming acid, and
heating the material at a temperature su?lcient
to decompose said quaternary compound.
14. The process of producing a permanent
starch ?nish upon cellulosic material, which com
8. The process oi’ producing a permanent starch I prises impregnating said material in optional time 25
?nish upon cellulosic textile material, which com
prises impregnating said material with an aque
‘ ous preparation containing starch and a quater
nary ammonium compound of the general for
relation with an aqueous starch preparation and
with an aqueous solution of a quaternary organic
compound of the general formula
30
mula
R—X——CHs——N (tert.) —Y
wherein N(tert.) represents the molecule of a
tertiary organic base, Y represents the anion
of a salt-forming acid, x stands for a non-oar
bonic link of the group consisting of oxygen,
sulfur, imino and substituted imino, and R stands
, for an organic radical tree from water-solubiliz
ing groups, drying the material thus impregnated
at a temperature insu?icient to decompose the
bulk of said quaternary compounds and then
heating the dried material in the absence oi’
moisture at a temperature favoring the decom
position of said quaternarycompound.
9. Btarched textile material impregnated with
a decomposition product of‘a quaternary am
monium compound as de?ned in claim 1.
10. Cellulosic material containing a starch ?n
ish and a starch ?xing agent as de?ned in claim 4.
11. Cellulosic material containing a starch ?n
ish and a starch ?xing agent as de?ned in claim 5.
12. The process of improving the fastness of
starch upon cellulosic textile material which
35
wherein R stands for an aliphatic hydrocarbon
radical, while -Y represents the anion of a salt
forming acid, drying said material at a tempera
ture not exceeding 40° C. and then further heat
ing said material, in the absence of moisture, 40
at a temperature between 90 and 140° C. whereby
to decompose said quaternary compound.
15. The process of producing a permanent
starch ?nish upon cellulosic material, which com
prises impregnating said material in optional time 45
relation with an aqueous starch preparation and
with an aqueous solution of a quaternary organic '
compound of the general formula
R_oo'-Na,_cm
Y
\ /
50
/N
comprises incorporating into said material, in ad
dition to starch, a quaternary ammonium com
wherein R represents an aliphatic hydrocarbon 55
radical, R1 represents hydrogen or an aliphatic
hydrocarbon radical, while Y represents the anion
wherein it stands for an aliphatic radical con
of a salt forming acid, drying said material at
taining a chain of at least 8 carbon atoms and a temperature not exceeding 90° C. and then heat 60
being free from water-solubilizing groups, x ing said material, in the absence of moisture, at
stands for an inorganic link oi’ the group con-. a temperature between 90°. and 140° 0., whereby
sisting of oxygen, sulfur, imino and substituted . to decompose said quaternary compound and split
imino, Z stands for a tertiary nitrogenous base o?! its tertiary base.
of the group consisting of aliphatic, cycloaliphatic
.
JOHN GWYNANT EVANS.
and heterocyclic-nitrogenous bases, and Y repre
CHARLES EDWARD SALKELD.
pound of the general formula
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