Патент USA US2525902

Patented Oct. 17, 1950 .
2,525,898
‘UNITED STATES‘ PATENT OFFICE
1,3 -DIPHENYLIMIDAZOLIDINE AND CERTAIN
DERIVATIVES THEREOF USED AS ‘ACID
FADING INHIBITORS
‘
Harry‘Wilhelm Grimmel, Riegelsville, and Alfred
Guenther, Easton‘, Pa., assignors to General
Aniline & Film Corporation, New York, N. Y., a
corporation of Delaware
No Drawing. Application October 9, 1947,
Serial No. 778,749
,
12 Claims. (01. 8—--61)
1
‘This invention relates to improvements in the
dyeing of textile materials containing organic.
derivatives of ‘cellulose (i. e., cellulose esters and
ethers, such as cellulose acetate, ethyl cellulose,
Water or in dry-cleaning solvents so that they are
largely removed when textile materials treated
therewith are subjected to customary cleansing
> treatments.
and thelike) , whereby the coloratlons thereon are
‘In addition, from the standpoint of economy
and convenience,‘ it is highly. desirable that the
acid fading inhibitors be applicable to the goods
to be dyed together'with the dyestuff, so that a
rendered‘ fast to acid fading (also known ‘as
“atmospheric” or “gas” fading).
‘Many-1 of ‘the water-insoluble dyestuffs yielding
desirable shades onlorganic derivatives of cellu
separate pie-treatment or after-treatment can
lose in textile materials, and having satisfactory 1O beavpided. For this purpose,the.compounds em
fastness to light, washing and other agencies,
ployed ‘must have suitable ‘solubility properties,‘
have been found to be sensitive tofading upon
e. g., they should be insoluble but ‘dispersible in
prolonged exposure to acid fumes, particularly
water, ,‘and ‘should possess a natural af?nity for
the ‘combustion products of coal, gas and other
organic derivatives of cellulose.
fuels, which are present in minor concentration 15 Moreover, since the dyeing is often carried out
in the atmosphere, particularly in urban ‘com
atelevated temperatures, it is necessary that the
munities. In some cases, the brightness of the
compounds employed have a ,su?iciently high
dyeing‘is dulled,‘while in others a markedchange
melting point to avoid fusion in the dye bath.
in the shade of the coloration occurs. ‘This is
When such fusion occurs, the ‘molten compound
‘ , especially true of colorations produced with san 20 forms an oil ‘which generally separates from the
, Uthraquinone dyes, particularly those yielding
dispersion and ‘dissolves a substantial ,portionlof
‘valuable blue colorations'on organic ‘derivatives
the dispersedwater-insoluble dyestuff. The re
nae-sunse When textile materials dyed with
‘thesecompounds:are‘eaposed to acidnfumes, the
coloigation' changes to one of a reddish or brown.
ish cast; ,and on continuedexposuremay change,
toqa pink coloration. {This effect limits toa con
siderable extent the usefulness of such dyestuffs,
sultingliquidoil-dye mixtureis generally depos
ited ,on the ugoods‘tobe dyed, forming unsightly
25 spots or streaks.
While many of ‘the disclosures
‘in-the prior art of ‘ acid fading. inhibitors indicate
that they can be applied t‘oltextile materials at
any time during the processing thereof, includ
ing. simultaneous application with the dyestu?,
many ‘.of thesuggestedcompounds are liquid at
‘ which are (otherwise ‘highly satisfactory. ,‘ ‘Sensi
tivity to acid fumes is not restricted to anthrae'
quinone dyes, but is likewise noticeable in the case
ordinary‘ temperatures or are solids of such low
melting point thatthey are substantiallyluseless‘ ‘
of dyestuffs belonging to other‘classes.‘
_I‘-,-I_N,umerous proposals have been made'to over-1
forgxapplication from a..dye‘bath under ‘the usual
‘come .aoiclfading, ordinarily involving the ‘fapplie
‘ conditionslofcommercial dyeing.‘
cation to , the textile‘ material of compounds or,
35
‘compositions intended to ‘prevent such, fading ‘of
the- coloration. , Such compounds or compositions
derivatives, speci?cally 1,3-diphenylimidazolidine
‘and j‘certainderivatives thereof, are highly effec
tive. acid ,fadi'ngdnhibitors when applied in minor.
amounts to textile materials" containing organic
are ,referred to herein as acid fadinginhibitors.
' _ Q'Eor commercial use, an acid fading inhibitor
shduld 'bel-‘coljorless, ‘adaptedrlto ‘withstand ‘pro
40
longed exposure to light and/or combustion. gases
without discoloration, fast, to. dry-cleaning and
are‘ colorless,‘ substantially insoluble in-‘water, and
that it causesno skin irritations when materials
45
‘ anuinber .of these‘requirements, in, most cases
which irjemainlsolid at“ temperatures of the ‘aque
ous dye-baths inlwhichthey are ‘employed.
,The acid fading inhibitors of this invention are
1,3-diphenylimidazolidine which may contain
they aredefective insome ‘of ,said requirements,
non-solubilizing' nuclear substituent groups or
wherebystheir usefulness isconsiderably impaired.
In‘ particular, most . of the compounds f suggested
‘derivatives of cellulose colored with ‘organic dye-.
stuffs‘." l‘ForWthe purposes? of ‘this invention, we
employ compounds of the aforesaid ‘class which
. wetewesmsg, odorlesaand nonetoxi‘c in the sense»
treated therewith are worn.‘ whilemost of the
acid fading inhibitorsheretofore proposed satisfy
-
' rWehave discovered. that. certain imidazolidine ‘
50
radicals such as‘halogen, alkyl, nitro, cyano and
simila'r‘lgroups in the ‘phenyl residues, ‘and/or
aliphatic, l‘aromaticfor heterocyclic ‘radicals in,
heretofore arefsub‘j'ect .to discoloration oil-lex
posureto acid fumes and/or to light, ‘so that they
cannot be used on goods dyed in light colors or
the 2-position of the imida‘zolidine ring, the latter
having, white ,designs or backgrounds thereon,
radicals being unsubstituted or containing such
nonpsolubilizing substituents as are suitable for
Many, of the. proposed materials are toolsoluble
.
9,525,898
3
a
X
Y
CH2—CH2
4
ing, but is most conveniently and economically
inclusion in the phenyl radicals, e. g., halogen,
alkyl, nitro and cyano groups.
Thus, the acid fading inhibitors of this inven
tion are represented by the general formula
carried out simultaneously with the dyeing‘
Thus, the inhibitors of this invention can be dis-'
persed in the aqueous bath by any of the meth
ods commonly used for similar,‘ dispersion of
X
water-insoluble dyestuffs adapted for dyeing ore
- ganic derivatives of cellulose.
\ OH/
For instance, they
may be dissolved together with the dyestuff in
a water-miscible solvent, and brought into dis
Y
It
wherein X and Y are nuclear substituents selected
from the group consisting of hydrogen and non
solubilizing groups and radicals (e. g., alkyl,
halogen, nitro, and cyano groups), and R is
10 persion by addition of a concentrated aqueous
solution of a dispersing agent having soap-like
properties and/or protective
colloid
action,
whereupon the resulting mixture can be diluted
with sufficient water to yield a dye bath of the
selected from the group consisting of hydrogen, 15 desired concentration.
alkyl, aryl, and heterocyclic radicals which are
The amount of acid fading inhibitor of our in
free of solubilizing substituents.
vention which can be employed may be varied
The aforesaid compounds can be prepared by
within rather wide limits. Thus, we have found
reacting an aldehyde of the formula R.CHO
them to be fully effective in amounts correspond
with an NN’-diphenyl-ethylenediamine of the
20 ing to about 1% by weight of the quantity of or
formula
ganic derivative of cellulose subjected to treat- .
ment therewith, and can be applied from a dye
bath or treatment bath containing said com
Y
Y
pounds in concentrations from 0.01 to 0.1%, such
amounts being, for example, of the order of lto 5
times the amount of dyestuif employed. These,
proportions have been found adequate and high1y satisfactory to provide the desired fastncss
KC
wherein X and Y are nuclear substituents select
ed from the group consisting of hydrogen and
non~solubilizing groups and radicals (e. g., alkyl,
properties in the dyed material.
- '
halogen, nitro, and cyano groups), and R is se
lected from the group consisting of hydrogen, 30' The temperature of the dye-bath may be
chosen to suit the dyestuff and the textile mate-.
alkyl, aryl, and heterocyclic radicals which are
rial to be dyed. Thus, the dyeing may be carried
free of solubilizing substituents. For example, as
out at‘any desired temperature up to about 80,
disclosed by Moos in Berichte Der Deutchen
90° C. without injuring the dispersion and with
Chemischen Gesellschaft, vol. 20, page 732, 1,2,3
out production of spots or streaks from fusion of
triphenylimidazolidine can be prepared by heat
the acid fading inhibitor.
ing benzaldehyde with NN’—diphenyl-ethylenedi
The following examples wherein parts and’
amine to boiling temperatures. The resulting
percentages are by weight illustrate the manner
imidazole derivative can be puri?ed by recrystal
in which a number of acid fading inhibitors of
lization from alcohol, petroleum ether, benzene or
our invention can be used.
'
'- a ‘
other suitable solvents. 2-methyl-1,3-diphenyl
imidazolidine can be prepared in an analogous
Example I
manner by substituting acetaldehyde for benz
aldehyde in the aforesaid procedure, and Z-furyl
l to 2 parts of 2-methy1-1,3-diphenylimidazoliaY
1,3-ditolylimidazolidine can be similarly prepared
dine and 0.6 part of a blue cellulose acetate dye
from furfural and NN’-ditolyl-ethylenediamine.
consisting essentially of ,l-(2’-hydroXy-ethyl
The resulting compounds have been. found
amino) - 4 - (monoinethylamino) _- anthraquil
eminently satisfactory as acid fading inhibitors
none are dissolved in a small quantity of a sol,
for use in accordance with this invention;- They
vent composed of equal proportions of- alcohol
have been found to possess not only all of the de
and acetone (or another suitable water-miscible
sired properties required in general for acid 50 solvent), and 40-parts of a 5% aqueous solution
fading inhibitors but, in addition, can be ad
of N,N-oleyl-methyl—taurine sodium salt, or ‘of
vantageously applied to textile materials con-.v
another suitable saponaceous dispersing agent,
taining ‘organic derivatives of cellulose from a
are added to the aforesaid solution; The‘ result
dye-bath together with the dyestuff. Thus, they
ing mixture is diluted with 5000 parts of warm’
are colorless, are notv discoloredon .prolonged ’ water at a temperature of 45~55° C. One'hunf’
exposure to light or combustion gases, are in
dred parts of cellulose acetate silk in the form of
soluble in water, and fast to dry-'cleam'ngof the
yarn or fabric is immersed in the dye-bath, the
textile materials with the usual dry-cleaningv sol
temperature gradually raised 1 to 80-90° 0., and
vents, so that they withstand the. effects of usual
cleaning operations of materials in which they
the material worked in the dye-'bathat this tem.-_ - ’
UL
are incorporated without loss of their effective
ness. Moreover, they are odorless and non
irritating to the skin when incorporated in textile
materials. In addition, they can be readily dis
dried.
persed in water in the same manner as is usual
c
for dyestuffs employed for coloring organic cellu
lose derivatives, have no, tendency to liquefy in ,
the dye bath at the temperatures ordinarily em
ployed, and show a natural af?nity for organic
derivatives of cellulose.
'
‘
Application of the acid fading inhibitors of
perature for an hour. When‘ the dyeing opera-_
tion is complete, the cellulose acetate material is
removed from the dye-bath,‘ washed with ‘a dilute
aqueous soap solution, rinsed with water and
'
‘j
Blue coloration of the cellulose acetate silk,
dyed in the foregoing manner,shows excellent re;
sistance to acid fumes as demonstrated by a test
wherein the dyedmaterial was exposed for a pro
longed period to the combustion products of i1
70 luminating gas produced by1a Bunsen burner. ’
our invention to textile materials containing or
Similar results are obtained when other cel
lulose acetate dyes of the anthraquinone or azo»
ganic derivatives of cellulose may be carried out
series, especially dyestuffs yielding ‘blue comm:
by treatment of the goods with an aqueous dis
persion of the’inhibitor before or after the dye
tion, are substituted for the blue amino-anthra
75 quinone dyestuff of the foregoing example;
2,525,898
5
6
and/or :upori substituting, a corresponding amount
of another :watereinsoluble LB-diphenylirrlidazob;
hereinbefore set forth :canz'be zused inlike man-‘
ner with equally advantageous results.
idine of the general ‘formula hereinbefore set
.
If desired, the treatment of Example II can
forth, for the ‘Z-methyl-1,3-diphenylimidazolidine
be applied to undyed textile materials containing '
of the example.
organic derivatives of cellulose, before carrying
‘_
‘
‘
ErampZe‘II
out a ‘dyeing operation thereon in order to render
‘
the resulting coloration ‘fast to acid fumes.
- 1 to‘ 2 parts of .Z-furyle1,3-ditolylimidazolidine
The acid fading inhibitors of this invention can
be applied singly,.or combinations of two or more
‘ are dissolved, as in the preceding example, in a
mixture of equal parts of alcohol. and acetone, 10 inhibitors can be used.
‘
i
.
'
and ‘40. ‘parts of a “5% aqueous solution of ‘N,N-‘
We claim: _
,
oleyl-methyl-taurine sodium salt, or another suit
1.. The process for increasing the resistance to
able asaponaceous dispersing agent, are added.
acid fading of colorations of water-insoluble dye;
The resulting concentrated ‘dispersion of the 1,3
stuifs on organic derivatives ‘.of cellulose intextile
ditolylimidazolidine derivative is “diluted with
5000 partsof water at 45-55" C., and 100 “parts
of ‘cellulose acetate :silk, previously ‘dyed with
materials, which colorations are normally ‘ sub
ject to fading when exposed to acid fumes,‘whicl1
comprises incorporating in such material avcolor
less water insoluble 1,3-diphenylimidazolidine‘
1,4 “- .di ( monomethylamino) - . anthraquinone ‘I are
worked in'the “bath while gradually raising ‘the
having the general formula
‘l
.
@
temperature to .80° 1C.,‘:and thereaftergat the same‘ 20
X‘
i
CHz-CH:
X
temperature ifor a, period of ‘1% to lhour. The
cellulose acetate silk 'is then (removed, washed
with ‘dilute aqueous soap solution, rinsed with
Y
,
Y‘
e
\CH/
11%,
water and‘dried.‘ ‘Theblue coloration of the dyed
material thus obtained‘shows excellent.resist 25
ance to acid fading, similar to that obtained in
wherein X and Y are. nuclearsubstituents selected
the case of the‘dyed material of Example I,‘ as‘ ~ from the group consisting of hydrogen, ‘alkyl,
indicated by subjecting it to a similar test in
halo, nitro and cyano groups, and R isselected
‘ volving ‘prolonged exposure to the ‘fumes of a
from the group consisting of hydrogen, alkyl, aryl,
Bunsen burner burning illuminating gas‘.
30, and furyl radicals which are. free of solubilizing
Cellulosehacetategimaterials dyed with other
dyestu?s; particularly those. of the blue range,
‘2. Theprocess for increasing‘ the resistanceito.
substituents.
can be treated inthe same manner as in the. fore
'
“
"
'
‘
“
‘
‘
acid fading of colorations of water-insoluble dye,- ,
going example, and other 1,3-diphenylimidazol
stuifs on organic derivatives of cellulose in textile
materials, which colorations are ‘normally ‘sub
idines (can be employed instead of the 2-furyl~
1,31ditolylimidazolidine of the ‘example, with sim
j set to fading whenexposed to acid fumes,‘ which‘
, comprises incorporating in such material .‘zl-gm'ethl
ilarly advantageous rsults.
yl-,1,3-diphenylimidazolidine.
Example III ‘
‘
3. The “process-for increasing the resistance to -
‘.1. we ‘parts. of 1,2,3etriphenylimidazolidine,
acid fading of colorationsof water-insoluble, dye-f
stuffs on organic derivatives of cellulose in textile
materials, which colorations are ‘normally sub
‘ ‘and 0.6 part of 1,4-di-(2’-hydroxyethylamino)
anthraquinone (a blue cellulose acetate‘ dyestuff)
ject to ‘fading when exposed to acid fumes, which
comprises incorporating in such material Z-Ifuryl
are dissolved in a small quantity of a solvent com
posed of equal proportions of alcohol and acetone,
and 40 parts of a 5% {aqueous solution of N,N
oleyl-methyl taurine sodium salt, or of another
suitable saponaceous dispersing agent, are added
‘
4;
l,3-ditolylimidazolidine.
‘
4. The process for increasing the resistance to
acid fading of colorations of water-insoluble dye
to the aforesaid solution.‘ The resulting mixture
stu?son organic derivatives of cellulose in textile
is diluted with 5000 parts of warm‘water at a
temperature of 110-130” F. .100 parts of cellulose -
materials, which colorations are normally sub
ject to fading when exposed to acid fumes, which
comprises incorporating in such material 1,2,3
acetate silk fabric areimmersed in the dye-bath,
and the temperature is gradually raised to. 175
195° 'F., the cellulose acetate ,material being
triphenylimidaz'olidine.
,
5. Textile material comprising ‘dyed ?bers 'of
worked in the bath for one hour at the latter
an organic derivative of cellulose dyed with a
temperature. When the dyeing operation is
complete, the cellulose acetate material is re
moved from the dye-bath, washed with dilute
water-insoluble .dyestuff yielding colorations on
said ?bers normally subject to fading when ex
posed to acid fumes, having incorporated in said
?bers a colorless water-insoluble 1,3-diphenyl- .
aqueous soap solution, rinsed with water and
imidazolidine having the general formula
dried.
The blue coloration of the cellulose acetate ma 60
x
‘onhom ’
X
terial, dyed in the foregoing manner, shows ex
“ cellent resistance to acid fumes when tested in
the manner described in the preceding example.
Y
.
Y
‘\CH/ '
Colorations on textile materialscontaining or
i ,
made up of organic derivatives of cellulose other 65
than cellulose acetate, e. g. other cellulose esters,
wherein X and Y are nuclear substituents selected
or ethers such as ethyl cellulose, can be rendered
from the group consisting of hydrogen, alkyl,
fast to acid fading in the same manner in the ‘ halo, nitro and cyano groups, and R is' selected
foregoing examples. Similarly, colorations pro
from the group consisting of hydrogen, alkyl,
duced with other dyestuffs than those of the 70 iaryl, and ‘furyl radicals which are free of solubil
type employed in the examples are improved to
iz‘ing substituents.
,
a similar degree.
‘
6.- Textile material comprising dyed ?bers of
Furthermore, instead of thespeci?c acid fading
an organic derivative of cellulose dyed with a
‘ inhibitors employed in the examples, other ‘com-
‘ pounds corresponding to the general formula
‘water-insoluble dyestu? yielding colorations on
75 said ?bers normally subject to fading when ex- ,
2,525,898
7
8
.posed to acid fumes, having incorporated in said‘
‘?bers Z-methyl-1,3-diphenyimidazolidine.
ing a water-insoluble dyestuff for said organic
derivative of cellulose, yielding colorations there
on which are normally subject to fading when
exposed to acid fumes, and working said material
in the resulting bath until dyeing is complete.
11. In a process for dyeing textile material con
taining an organic derivative of cellulose, the im
provement which comprises dispersing Z-furyl
l,3-dito1ylimidazolidine in a dye-bath containing:
7. Textile material comprising dyed ?bers of
an organic derivative of cellulose dyed With a
‘water-insoluble dyestuif yielding colorations on
‘said ?bers normally subject to fading when ex
posed to acid fumes, having incorporated in said
‘fibers Z-furyl-1,3-ditolylimidazolidine.
8. Textile material comprising dyed ?bers of
an organic derivative of “cellulose dyed with a
a water-insoluble dyestulf for said organic de
water-insoluble dyestuff yielding colorations on
said ?bers normally subject to fading when ex
posed to acid fumes, having incorporated in said
?bers 1,2,3-triphenyimidazolidine.
rivative of cellulose, yielding colorations thereon.
which are normally subject to fading when ex-.
posed to acid fumes, and working said material
in the resulting bath until dyeing is complete.
12. In a process for dyeing textile material con‘,
9. In a process for dyeing textile material con 15
vtaining an organic derivative of cellulose, the.
taining an organic derivative of cellulose, the im
improvement which comprises dispersing 1,2,3
provement which comprises dispersing a colorless
ltriphenylimidazolidine in a dye-bath containing,
water-insoluble 1,3-diphenylimidazolidine having
a water-insoluble dyestuff for said‘ organicdee
the general formula
20 rivative of cellulose, yielding colorations thereon
which are normally subject to fading when.;ex.-5
posed to acid fumes, andiworkingsaid material
in the resulting bath until dyeing is complete;
Y
HARRY WILHELM GRIMMEL.
25
ALFRED GUENTHERQ .
wherein X and Y are nuclear substituents selected
REFERENCES CITED
from the group consisting of hydrogen, alkyl,
halo, nitro and cyano groups, and R is selected
The following references .are of record in the
from the group ‘consisting of hydrogen, alkyl,
?le of "this patent:
' '
30
aryl, and furyl radicals which are free of solubil
_ UNITED STATES PATENTS
.
izing substituents, in a dye-bath containing a
Number
Name '
‘
Date
water-insoluble dyestuff for said organic deriva
2 1,930,232
Ellis' __________ __,-__ Oct. 10,1933
tive of cellulose, yielding colorations thereon
which are normally subject to fading when ex-'
\, 2,083,122
posed to acid fumes, and working said material
in the resulting bath until dyeing is-complete.
2,148,655
Seymour ____ __-_'__-_ Feb/28,1939
2,176,506
McNally _____ __‘___.: Oct. 17, 1939,
O1pin‘_____________ __ June 8, 1937
10. In a process for dyeing textile material con
2,255,690
Tinker _____ _‘___'____ Sept. 9,1941
taining an organic derivative of cellulose, the im
' provement which comprises dispersing 2-methyl
2,298,401
McNally _________ __ Oct. 13, 1942
1,3-diphenylimidazolidine in a dye-bath \contain- ‘
2,340,375
2,416,380
,
Giles _;___; _______ __ Feb. 1, 1944
'Collie ____‘~ ________ __ Feb. 25, 1947
'