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Патент USA US2132491

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2,132,491
iatented Oct- 11,
1' 715955
UN )L oatoy
OFFICE
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2,132,491
MANUFACTURE OF ARTIFICIAL SILK
2 r>
Harry Donald Mudford, Blackley, Manchester,
England, assignor to Imperial Chemical Industries Limited, a corporation of Great Britain
_
11 W»
No Drawing. Application November 23, 1935, Se
rial No. 51,272. In Great Britain December 28,
1933
18 Claims.
A?‘ This invention relates to arti?cial cellulosic
bodies, and particularly to arti?cial ?bers and
threads. The invention also relates to improve
ments in dyeing. The invention also relates to
new compositions of matter useful in the manu
facture of arti?cial oellulosic bodies. The inven
tion also relates to cellulosic ?bers and threads
and to methods of making them light-fast when
delustered and dyed with direct dyes. The inven
10 tion will be described for purposes of illustration
in its application to the manufacture of regen
erated cellulose ?ber, but it is to be understood
that this particular description does not limit
the invention which is applicable to all situations
15 in which an arti?cial cellulosic body is delustered
with a titanium delustrant and dyed with a direct
dye.
In the earlier days of its manufacture rayon
was lustrous, but more recently a delustered
20 material has found the greater favor. Of the
delustrants so far discovered, the best is titanium
dioxide. The delustered material including tita
nium dioxide has a ?ne appearance and good
properties but it fails in this respect that regen
25 erated cellulose so delustered, when dyed with a
direct dye, is far more fugitive to light, particu
larly in the Wet state, than the undelustered
material, and cellulose esters and ethers when
30
dyed with a direct dye and when so delustered
are far more fugitive to light, particularly in
the dry state, than the undelustered material.
This condition has heretofore forced the aban
donment of a large number of most satisfactory
dyes and the substitution of more expensive
35
colprs,
Q; It is an object of this invention to manufac
tur'e delustered rayon which is light-fast when
dyed with direct cottondyes. Another object of
the invention is to prepare light-fast delustered
rayon dyed with direct cotton dyes by economi
40 cally and technically satisfactory processes. An
.other object of the invention is to prepare delus
tered rayon which will be light-fast when dyed
with direct dyes. Another object of the inven
tion is to prepare a composition of matter useful
45 in the manufacture of delustered rayon. Other
objects of the invention will be in part apparent
to persons skilled in the art and in part herein
after set forth.
(D1) The objects of the invention are accom
50 plished, generally speaking, by treating the tita
nium delustrant with a compound of chromium
(Cl. 8-5)
tering agents and the time of application may be
chosen practically at will, but in all such varia
tio the above principle should be incorporated.
In one process of using my invention tita
nium dioxide which is to be used for the delus
tering of rayon is treated previously to its incor
poration in a spinning mass with a water-soluble
chromium compound (for instance a water-solu
ble chromium salt). The delustrant so prepared
is then incorporated with the cellulose solution 10
before spinning and the cellulosic solution is
spun in the usual way. The resulting delustered
arti?cial silk, when dyed with direct coloring
matters, does not tend to fade rapidly when ex
posed to daylight.
15
{lf'glnstead of treating the titanium dioxide
previous to incorporation in the spinning mass
with a compound of chromium, there may be
added to the spinning mass a mixture of tita
nium dioxide and a water-soluble chromium com 20
pound.
lg_.,;In a preferred form of the invention the
use of a water-soluble chromium compound will
probably be preferred, but water-insoluble chro
mium compounds can also be used. For instance, 25
there can be incorporated with titanium dioxide
freshly precipitated chromium hydroxide, or ti
tanium dioxide can be mixed with a soluble chro
mium salt in the presence of a reagent that will
precipitate chromium hydroxide on the titanium 30
dioxide. Such mixtures may be incorporated
with delustering solutions and used for deluster
ing in the moist condition, or they may be dried,
in which case more or less chromium oxide will
be formed from the chromium hydroxide. Again, 35
one may mix together ?nely divided chromium
sesquioxide and titanium dioxide and use it for
delustering.
{H} In the manner of treatment set forth above,
and of which Examples I, II, III, and IV herein 40
after are specimen, the delustered arti?cial silk
itself is not treated with a chromium compound,
which is in itself an advantage.
Example I
Titanium dioxide which is to be used for in 45
corporation in arti?cial silk as a delustering
agent is treated for one hour at 85-95° C. in a
1% solution of potassium or sodium bichromate.
'I'hereupon it is thoroughly washed, collected and
or of one of the metals in the chromium group.
Example II
The treatment of the titanium dioxide is ef
The process has considerable variation which
fected by means of a solution of 3 parts of potas
adapts it to varieties of materials and of delus
55
50
dried.
sium bichromate and 1 part formic acid (80%)
"1"
I
2
2,182,491
in 1,000 parts of water, the procedure being
otherwise the same as that of Example I.
In
place of the potassium bichromate and formic
acid there may be used 2 parts of chromic acid.
Example III
of titanium dioxide in the mass, is treated for
half an hour at 85° C. in an 0.3% aqueous sodium
The liquor contains 10 parts of chromium chlo
added, if desired, 0.2% formic acid, and is dyed
with Chlorazol Orange PO. Exposure to light
ride or chromium ?uoride per litre but otherwise
the procedure is as Example I.
10
Example IV
bichromate solution, to which there may be
before drying failed to produce determinable
fading.
Example VI
_ Finely divided titanium dioxide treated as in
Arti?cial silk delustered by the incorporation
any of the above examples is incorporated with
of titanium dioxide in the mass was treated for
half an hour at 85° C. in a 0.5% aqueous chro
a viscose spinning mass and a ?nished thread
15 produced in the known manner. It is then dyed
with one per cent of Chlorazol Fast Black BK.
The dyeing in the wet condition will be found
faster to light than one produced on viscose arti
?cial silk thread which is delustered with un
20 tre ted titanium dioxide.
I.‘ In another method of using the invention,
th rayon is spun in the usual way and is treated
with a chromium-containing compound, for in
stance a hot aqueous solution of a water-soluble
chromium salt, and with or without rinsing
and/or drying, and dyed with direct colors in
the usual way. In the practice of this form of
the invention, regenerated cellulose is made ac
cording to any of the known methods, for in
30 stance by ejecting viscose or cuprammonium
cellulose solutions containing delustrant into the
Example VII
Regenerated celulose arti?cial silk delustered 20
by treatment with titanium dioxide and treated
according to Examples V and VI is rinsed and
dyed with 2% of the substantive dyestuff Chlora
zol Fast Helio BK (C. I. No. 390) with the addi
tion of 10% of Glauber’s salt for three-quarters 25
of an hour at 80° C. The dyeing thus obtained
is of good fastness to light when in the wet condi
tion whereas when not treated according to the
present process the shade of the moist material
30
is of’ poor fastness to light.
" The processes of the invention are equally
applicable to the manufacture of regenerated
the threadin the usual way.
cellulose by any method and to the manufacture
of esters and ethers of cellulose which have been
In the process, how
result in about half an hour.
The time will vary
with the temperature and concentration of the
bath. It is not essential to heat the bath, but
improved results are secured thereby. The con
50 centration of the chromium salt is also to a con-,
siderable extent a matter of choice. Extremely
low concentrations, in the neighborhood of 0.3
to 0.5% normally give excellent results and, con
sequently, for reasons of economy, stronger con
55 ce trations are unnecessary.
J Following the treatment of the regener
ated cellulose with the solution of the chromium
salt, the regenerated cellulose may be rinsed and
dried and dyed. The rinsing and drying may be
If the regenerated cellulose
article is- dried before dyeing, the chromium
60 omitted if desired.
treatment may follow the drying, but it is con
sidered advantageous to carry out the treatment
wiI the chromium salt solution before drying.
1; Examples V, VI, and VII of this speci?ca
tion are exemplary of the method of treating the
delustered material after its formation. In the
process it is preferable to use a water-soluble salt
of chromium, but advantages of the invention
70 may be obtained by treating the delustered ma
terial with a suspension of an insoluble chromium
compound. The treatment with a water-soluble
or with a water-insoluble compound is preferably
given before dyeing, but advantages of the inven
76 tion may be secured by treatment after dyeing.
10
mium chloride solution, and was dyed with 15
Chlorazol Fast Black BK. No fading occurred on
exposure to light either before or after drying.
customary regenerating bath and by processing
ever, preferably after the viscose solution has
35 been set, the rayon is immersed in an aqueous
solution of a chromium salt for a length of time
suf?cient to make effective the action of the chro
mium salt. The length of time will be selected
by the chemist to secure the optimum results at
40 the temperature at which the treatment is car
ried out. The aqueous bath containing the chro
mium salt is preferably heated in order to lessen
the time required for the treatment. At a tem
perature of 85° C. a 0.3% aqueous solution of
45 sodium bichromate will produce a satisfactory
65
Example V
Arti?cial silk, delustered by the incorporation
delustered by incorporation into the spinning 35
mass of titanium dioxide. The esters and ethers
are not abnormally sensitive to light when wet,
but there is a general decline in the fastness to
light‘in dyeings on the dry ?ber thus delustered.
:?I/lBy treating the titanium dioxide used for 40
dekifstering purposes, either before or after in
corporation in the spinning mass, and either
before or after the formation of the end product
with a soluble chromium compound such as chro
mium chloride, or chromium ?uoride, or chro
45
mium trioxide, this increase in fugitiveness to
light of dyeings on cellulose esters and ethers may
be entirely prevented or appreciably diminished.
)éTitanium dioxide which has been incorpo
rated with the ?ber may be treated with chro 50
mium compounds either before or after dyeing,
provided, however, that care is taken that any
after-treatment does not undesirably affect the
dyestu? on the ?ber. Titanium dioxide which is
to be treated prior to incorporation in a spinning 55
mass, may also be treated with insoluble chro
mium compounds. For instance, titanium di
oxide paste may be thoroughly mixed with freshly
precipitatedchromium hydroxide, or chromium
hydroxide may be precipitated in situ by stirring 60
the titanium dioxide paste with a solution of a
chromium sesquioxide salt in ‘the presence of am
mgriia or an alkali carbonate.
‘IQ; Dyeings produced in the usual manner on
acetate arti?cial silk delustered by titanium di 65
oxide which has been treated with chromium are
of improved fastness to light as compared with
dyeings produced on similar material containing
untreated delustrant.
{13; Examples VIII, IX, and X of this speci?ca 70
tion illustrate the applicability of the invention
to dyeings on cellulose esters and ethers. Cel
lulose acetate was chosen in each instance be
cause it is the most widely used of those com
pounds, but the processes are equally applicable
3
t‘o'the other esters and
Exemplary
lose, benzyl
»
> Example VIII’
Cellulose, acetate arti?cial silk delustered by
incorporation of titanium dioxide in the mass be-‘ ' Titanium dioxideis treated with sodium molyb
the conditions described in Exam
tom spinning, is treated, before dyeing, in a date
_
Y ,
’. '
liquor containing 3 parts sodium bichromate-and ple XIV.
10 1 part formic acid (80%) for 1000parts water a
v
_
Example xvi
for one-halt hour at 85° C. The material is then
Titanium dioxide is ‘treated for one-half hour
“wellrinsed-anddyedin
C.inaliquorcontaining5partsuranium‘
the usual way. ‘
'
,
at 85°
- In place of sodium bichromate as above‘there "nitrate per 1000 parts water after which it is
maybe employed5 parts of chromium chloride weli-washul with water, ?ltered and dried.
.
15
or i‘iuoiride._
.
Example IX
“I
Acetate-arti?cial silk is delustered by incor
g
i
Example XVIL:
v.
v
>
15,
.
Titanium dioxide ( _..parts) is mixed with'so
porating in the mass- before spinning titanium
dium
dioxide which has been treated in a liquor con
the-whole employed as
taining 10 parts sodiumcbichrornate for 1000
parts water for one-halt hour at 85° C. followed by'
"
‘ thorough rinsing, ?ltration and drying
'
teor sodium molybdate (1 part) and
_
t.
_
-
sample xvm
20.
‘
_ ' 100 parts or titanium‘ dioxide are treatedwith
In place 'of sodium bichromate in the above
a solution 0151M perm chromium chloride at
example there may be used parts of chromium
85° C. and suineient dilute caustic soda solution
chloride or ?uoride and a similar eil'ect obtained.
(say 5%) gradually added under agitationito prel
25
cipitate the chromium as chromium hydroxide.
The resulting product is collectedrwashed, dried '
Ezamplex " 7'
Acetate arti?cial silk is delustered by incorpo
and groimd.
rating in the mass before spinning titanium
_
di-' .
oxide which has been mixed with_‘sodi1un bi-'
»
'
-
\
_
_
Example XIX
Y
_
99 parts of ?nely divided titanium dioxide are 30
ground with 1 part of finely divided chromium
’Q. The advantages of the .invention accrue sesquioxide until a homogeneous mixture. is ob
not only to the water-soluble or water-insoluble
compounds of chromium but can be obtained by ‘
Example XX
chromate in the proportion of 99 parts of the‘
former and 1 partlof the latter.
‘
the use of water-soluble cr_water-insoluble met- '
als in the. same periodic group as chromium,
' namely tungsten,‘ molybdenum. and_ uranium.
Arti?cial silk from regenerated cellulose or from
~35
Arti?cial silk delustred by means of titanium
dioxide is treated for half an hour at- 70° C. with
an 0.2% aqueous solution of chromium trioxide.
" 8. Examples of ‘direct colors have hereinabove
40
incorporated in any of the above described meth-v
- T. 'I‘heproceas of treatment which hashereods with a water-soluble or water-insoluble salt‘v inbefore
been described prevents the rapid wet
of any of these elements. ‘Such arti?cial silk in
iading which has heretofore been a feature _of
the wet or‘moist condition
deluster'ed rayon when dyed with direct cotton
‘ colors.
' has not been thus treated.
R. Examples in, m, xm, xw. xv, xvi,
1 and XVII illustrate the applicability of these com
pounds to the ‘process. '
7
Example Xi
_
Arti?cial silk containing titanium dioxide as
which it is
and dy
,
Example XII
7
‘
makes the dyeing oi rayon a perfectly straight
forward matter, which has not heretofore been
the case. My delusfered ‘rayon, when dyed with a'
.diiectdyaisequalin light i’astness to'similar
V
, delustrant is treated for
The process permits dyeing with the
dyestu?s ‘and processes commercially‘employed
for dyeing rayon with direct cotton colors and
undelustered material.
>
U. Great modi?cations and variations may be 55
_
manyofitsphasesasisconsistentwiththespace
:' which may be allotted to the disclosure of an in
Arti?cial silk‘ as above-is treated for one-half ' "vention in a patent application. Obviously where
so many variables enter not all can .be illustrated
hour at 85° 0., ‘in a liquor containing 3 parts so
r .
_
dium molybdate andi1 partformic acid per 1000' . by a speci?c example. >
V. 'llhis application is- a continuation-in-part
partswater. after which it is rinsed and dyed.
Example > XIII '
'of my prior‘application Serial No. 758,684, now
abandoned, ?led December 21, 19 .
W. As many} apparently widely di?erent
70
which it is
and dyed. '
reampiexiv
, ‘Titanium dioxide intendedfor use as deluatrant
75 is treated for one-half hour at 85° C. in a liquor
_
- <t'o the speci?c embodiments thereof‘ except, as
' de?ned in ‘the appended claims. a
70.
;I claim:
1. The material which comprises a regenerated
cellulose. nbeited with a titanium oxide 75
2,132,491 l
‘ 12. In the process of manufacturing a cellulosic‘
body from a material of the class consisting oi
Ldelustrant, and sodium bichromate, ‘and dyed with
cellulose esters, cellulose ethers, and regenerated
cellulose, delustered with a tita ‘um delustrant,
a direct cotton dye.
comprises a regenerated
titanirm
cellulose ?ber impregnated with a and
dyed
delustrant, and a chromium compound,
2. The material which
the steps which involve treating the titanium
delustrant with one of /
3. The material which comprises a regenerated
cellulose ?ber impregnated with a titanium
delustrant, and a. water-soluble chromium com
pound, and dyed with a direct cotton dye.
10
4. The material which comprises a regenerated
cellulose ‘?ber impregnated with a titanium oxide
,
.
13. In the process of manufacturing a "cellulosic 10;
body from a material of the class consisting of
ingredients.
cellulose esters, cellulose ethers, and regenerated
cellulose, delustered with a titanium
the steps which involve treating the titanium
. delustrant, and a water-insoluble chromium com
delustrant with one of a. group of. materials con
pound, and dyed with a direct cotton dye.
5. The material which comprises a regenerated
15 cellulose ?ber impregnated with a titanium oxide
delustrant, and a compound of one of the metals
of .the chromium group, and dyed with a direct.
cotton dye.
'
.
-
/
15
sisting of the compounds of the metals of the,
chromium group before the formation of the cel
lulosic body.
14. In the process of manufacturing a. cellulosic
body from a material of the class consisting of' 20
cellulose esters, cellulose ethers, and regenerated
cellulose, delustered with a titanium delustrant,
I
. 6-. The material which comprises a regenerated
cellulose ?ber impregnated with a titanium oxide
delustrant, and a water-soluble compound . of
the steps which involve treating the titanium
one of the metals of the chromium group, and
sisting of the compounds of the metals of the 25
chromium group after the formation of the cel
dyed with a direct cotton dye.
25
roup of materials con
sisting of the compounds of the metals of the
chromium group before mixing it with the other
with a direct cotton dye.
delustrant with one of a group of materials con
'
7. The material which comprises a regenerated
impregnated with a titanium oxide
delustrant,_ and a water-insoluble compound of
lulosic body.
'
15. A_ composition ‘of matter comprising an
7
' cellulose ?ber
one of the metals of the chromium group. ‘ 8. The material which comprises anv arti?cial
aqueous caustic alkali solution of an alkali metal 30
salt of cellulose xanthic acid, a titanium delus
cellulosic body impregnated with a titanium
trant, and a chromium compound.
of the chromium group.
aqueous caustic alkali solution of an alkali. metal ’
9. The materiabwhich comprises an arti?cial
cellulosic ?ber impregnated with a titanium oxide
35
-
_
16. A composition of matter comprising an
30 delustrant, and a compoundcf one of the metals
salt of cellulose xanthic acid, a
titanium delus
trant, and sodium bichromate.
.
.35.
1'7. _A composition of matter comprising a cel
>
10. The material which comprises an arti?cial lulosic solution, a titanium adelustrant, and a
cellulosic ?ber impregnated with. a titanium‘ compound of a metal ofv the chromium group.
18. In the manufacture of‘ delustéred arti?cial
delustrant,v and a chromium compound.
d'elustrant 40
11. In the process of manufacturing a cellulosic cellulosic bodies containing a__titanium
the step which com- 7
delustrant,. and sodium bichromate.
_
body from a material of the
class consisting‘of
‘and dyed with a direct
'
dye,
I
' prises treating the d'elustrant with a dye- ?xative
cellulose, delustered with a titanium 'delustrant, comprising a compound of a metal of the chro
40 cellulose esters, cellulose ethers, and regenerated
the steps which involve treating the titanium
mium group.
chromium group.
'
.
'
HARRY DONALD MUDFORD.
delustrant with one of a group of materials. con
sisting of the compounds of the metals of the
'
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