Note: Descriptions are shown in the official language in which they were submitted.
21~8~8 1
HOECHST AKTIENGESELLSCHAFT HOE 94/F 288 Dr.HU/do
Description
Production of aminated regenerated cellulose
Viscose fibers have essentially the same dyeing charac-
teristics as cotton fibers. At present, the dyeing of
natural or regenerated cellulosic fibers requires alkali-
donating agents and also electrolytes in order that
satisfactory fixation results may be obtained with
reactive dyes. It is precisely these necessary additions,
however, which are unacceptable for ecologically improved
dyeing processes. The future will therefore increasingly
belong to regenerated fibers, ba~ed on cellulose, which
have been converted beforehand without additional process
steps into modifications which have a high affinity for
dyes, i.e. which are dyeable without salt and alkali.
Fibers thus modified resemble animal fibers, such as wool
or silk, in their chemical behavior and can be dyed with
anionic dyes under neutral conditions without further
salt or alkali additions.
Modifications of viscose have already been described in
the literature. US-A-3 793 419, for instance, describes
a process for producing viscose fibers having modified
dyeing characteristics. However, the process is extremely
complicated and uneconomical. In addition, polyamine-
amides are used which significantly alter the nativecharacter of the fiber. This iB evident, for example,
from the use of disperse dyes in the later dyeing.
US-A-3 305 377 too iB concerned with "aminalized fibers".
The additions are aminoethyl- and diethylaminoethyl-
celluloses in high concentration, and the dyeing is doneexclusively with acid dyes.
It is an object of the present invention to provide
modified viscose fibers in order that textiles composed
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of such fibers may be dyed with anionic dyes with low
amounts of salt and alkali and a material with a soft
hand may be obtained.
It has been found that the use of proteins as addition to
the viscose dope or to the cellulose prior to the
alkalizing makes it possible to produce a viscose fiber
which surprisingly has significantly more affinity for
anionic dyes and differs greatly from conventional
viscose fibers in the other properties desired, for
example by a soft hand.
The present invention accordingly provides a process for
producing aminated regenerated cellulose fibers, which
comprises preparing a solution of cellulose and a protein
having a molecular weight of greater than 50,000 or a
natural product compriæing such a protein and spinning
fibers from this solution.
In a preferred embodiment, a) cellulose and a protein
having a molecular weight of greater than 50,000 or a
natural product comprising such a protein are mixed and
the mixture is alkalized and the resulting alkalized
mixture iæ reacted with carbon disulfide or b) a protein
having a molecular weight of greater than 50,000 or a
natural product comprising such a protein is dissolved in
sodium hydroxide solution and added to a fiber grade
viscose, and the viscose dope obtained from a) or b) is
forwarded into an acid spinbath and spun into fibers.
The reaction with carbon disulfide advantageously takes
place at temperatures from 15 to 30C. Subsequent spin-
ning into an acid spinbath affords the aminated cellulose
fibers of the invention.
It is also possible to produce the fibers of the
invention by other customary processes, familiar to the
person skilled in the art, for producing cellulosic
fibers from solution, for example the cupro process, the
215~81
Lyocell process or the process involving low-substituted
cellulose ethers. These processes involve dissolving the
cellulose and the protein in a suitable organic solvent,
for example N-methylmorpholine N-oxide/ water, reacting
them with each other and spinning fibers directly from
the solution.
Sp;nn;ng into an acid spinbath affords fibers which can
be dyed according to the invention using low-electrolyte
or completely electrolyte-free and low-alkali or alkali-
free dyeing liquors (including print pastes and inkjetfluids). For the purposes of the present invention, low-
electrolyte dyeing liquors are those having an electro-
lyte content below 15 g/l and low-alkali dyeing liquors
are those having a pH of not more than 8.5.
The proteins and protein-containing natural products used
for the process of the invention occur in nature for
example as keratins, collagen-containing natural products
and albumins. Examples of preferred keratins are body
hairs, hooves, horns, claws and nails of m G als, bird
feathers, spinning threads of insects, tortoiseshell and
fish scales. Examples of preferred collagen-containing
natural products are hide, leather, cartilage, connective
tissue, tendons, sinews of mammals, in particular
gelatin, glutin and boneglue. Suitable albumin is in
particular egg albumin or else eggs as such.
The protein-containing natural products used for the
process of the invention may also include other,
concomitant component~, in which case it is also possible
to use for example meat, meat meal, fish, fish meal or
processing products thereof.
The proteins are denatured in the course of the dissolv-
ing step. In addition to the animal proteins mentioned,
however, it is also possible to use synthetic proteins
having a molecular weight of greater than 50,000.
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The textile modified fiber material which i8 used in the
dyeing process of the invention can be present in all
stages of processing, for instance as yarn, staple,
slubbing and piece goods (fabrics).
The amination of the regenerated cellulose according to
the invention probably does not involve a chemical
reaction between the cellulose and the alkalized or
dissolved protein; instead the two components adhere to
each other in the fiber 80 strongly as a consequence of
Van-der-Waals interactions that the protein cannot be
washed out.
The aminated textile fiber materials are dyed according
to the invention analogously to known processes for
dyeing and printing fiber materials with water-soluble
textile dyes and through the use of the temperature
ranges and customary dyestuff quantities known for this
purpose, except that the dyebaths, padding liquors, print
pastes or inkjet formulations require no quantitative
addition of alkaline compounds, as customary for fixing
fiber-reactive dyes, nor customary additions of electro-
lyte salts. The dyeing of the modified viscose according
to the invention takes place between pH 4 and pH 8.5,
depending on the nature of the dye. If commercial textile
dyes are used, salt contents of 0.01 to 0.5% by weight,
based on the dyeing liquor, are normally present. Without
the amination of the cellulose fibers according to the
invention, however, this salt content would be too low
for a successful dyeing process by a factor of 50 to
1000 .
The alkalized or dissolved protein is advantageously
incorporated into the viscose spinning dope without
emulsifiers. The protein is added in an amount of 1 to
20% by weight, preferably 1 to 12% by weight, based on
the cellulose content of the sp; nn; ng dope, prior to the
precipitation and forming.
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The forming of the viscose i8 carried out by conventional
methods, for example by means of spinnerets openings, a
subsequent coagulation bath and optionally further
aftertreatment baths.
The fibers obtained by the methods described can be
processed into woven and knitted fabrics and then dyed by
a very wide range of processes, such as exhaust, padding
and modern printing processes, which also include inkjet
processes, without the use of salt or alkali.
The present invention also provides a process for dyeing
and printing cellulosic textiles with anionic dyes, which
comprises performing the dyeing with a dye solution which
is free of additional electrolyte salts, at a pH between
4 and 6 in the case of direct and acid dyes and at a pH
between 6 and 8.5 in the case of reactive dyes, while
uæing a regenerated cellulose fiber material aminated
according to the invention.
Suitable dyeing processes include for example various
exhaust processes, such as dyeing on the jigger or on the
reel beck or dyeing from long or short liquor, dyeing in
jet dyeing machines, dyeing by cold pad-batch processes
or by a pad-superheated steam fixation process. Suitable
printing processes include conventional printing tech-
niques, including inkjet printing and transfer printing.
The dyes which are used for dyeing the modified cellulose
are generally anionic in nature. In addition to the
so-called acid or direct dyes, it is the fiber-reactive
textile dyes which are capable of reacting with hydroxyl
groups, for example of cellulose, or amino and thiol
groups, for example of wool and silk, of synthetic
polymers, such as polyamides, or else the celluloses
aminated according to the present invention, to form a
covalent bond, which are particularly suitable. Suitable
fiber-reactive components on the textile dyes include in
particular sulfatoethylsulfonyl, vinylsulfonyl,
2 1 ~
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chlorotriazinyl and fluorotriazinyl and also combinations
thereof.
Suitable reactive dyes for dyeing or printing cellulose
fibers modified according to the present invention
include all water-soluble, preferably anionic, dyes which
preferably have one or more sulfo and/or carboxyl groups
and which contain fiber-reactive groups. They can belong
to the class of the azoic dyes, the class of the direct
dyes, the class of the vat dyes, and the class of the
acid dyes, be copper complex, cobalt complex and chromium
complex azo dyes, copper and nickel phthalocyanine dyes,
anthraquinone, copper formazan, azomethine, nitroaryl,
dioxazine, triphendioxazine, phenazine and stilbene dyes.
These dyes have been extensively described in the
literature, for example in EP-A-0 513 656, and are
perfectly familiar to the person ~killed in the art.
Suitable acid or direct dyes for dyeing or printing
cellulose fibers modified according to the invention are
for example C.I. Acid Black 27 (C.I. No. 26 310), C.I.
Acid Black 35 (C.I. No. 26 320), C.I. Acid Blue 113 (C.I.
No. 26 360), C.I. Direct Orange 49 (C.I. No. 29 050),
C.I. Direct Orange 69 (C.I. No. 29 055), C.I. Direct
Yellow 34 (C.I. No. 29 060), C.I. Direct Red 79 (C.I. No.
29 065), C.I. Direct Yellow 67 (C.I. No. 29 080), C.I.
Direct Brown 126 (C.I. No. 29085), C.I. Direct Red 84
(C.I. No. 35 760), C.I. Direct Red 80 (C.I. No. 35 780),
C.I. Direct Red 194 (C.I. No. 35 785), C.I. Direct Red 81
(C.I. No. 28 160), C.I. Direct Red 32 (C.I. No. 35 790),
C.I. Direct Blue 162 (C.I. No. 35 770), C.I. Direct Blue
159 (C.I. No. 35 775), C.I. Direct Black 162:1 and C.I.
Direct Violet 9 (C.I. No. 27 885).
Unless otherwise stated, parts and percentages in the
examples which follow are by weight.
2158~8~
Example 1
A plant-customary fiber grade viscose having a cellulose
content of 8.9%, an alkali content of 5% and a viscosity
of 38 falling-ball seconds at 30C i8 admixed with an
alkaline solution of sheep wool as follows:
6 parts of wool are dissolved in a solution which con-
tains 10 parts of sodium hydroxide and 90 parts of water.
Of this solution, 59 parts are mixed with 1000 parts of
a plant-customary fiber grade viscose which contains 89
parts of cellulose. After devolatilization the spinning
dope is spun by plant-customary viscose spinning
processes into a bath which contains sulfuric acid,
sodium sulfate and zinc sulfate to form fibers, which are
stretched in acid baths, cut, washed, spinfinished and
dried.
10 parts of these dry viscose fibers are then admixed in
a dyeing apparatus with 100 parts of water. The
temperature is raised to 60C and a total of 0.1 part of
a 50% strength electrolyte(pre~ominAntly sodium)-contain-
ing dye powder of the formula, known from DE-A-l 943 904,
0 ~ N~Z
N~03S SO~N~
is metered in over a period of 30 min. Following a
further liquor circulation period of 5 min the remaining,
colorless liquor is dropped and the material is conven-
tionally washed and dried. The result obtained is a
strong and deep red dyeing having very good use fastness
properties.
2158~
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Example 2
10 parts of the viscose fibers modified and described in
Example 1 are transferred into a dyeing apparatus and
treated in a liquor ratio of 10:1 with an aqueous liquor
which, based on the weight of the dry fibers, contains in
solution 0.1 part of a reactive dye of the formula, known
from DE-A-24 12 964
o t~H2
SO~N
H~ ~~OSO~Na.
o
The fiber mixture is dyed at 60C for 30 minutes. The
dyeing thus produced is further treated by rinsing and
soaping in a conventional manner. The result obtained is
a deep blue dyeing having the usual very good use fast-
ness properties.
Example 3
A fiber grade viscose prepared a~ described in Example 1
is spun, after devolatilization, by a plant-customary
viscose sp; nn; ng process into a bath containing sulfuric
acid, sodium sulfate and zinc sulfate to form fibers,
which are stretched in acid baths, cut, washed,
~pinfinished and dried. Weaving gives a textile viscose
fabric which can be further processed directly in a pad-
dyeing process. For this the fabric ha~ applied to it at
25C an aqueous dye ~olution which, per 1000 parts by
volume, contains in solution 20 part~ of the dye of the
formula
- 9 -21S8~8~
N ~ 0 3 S ~ N~ ~ O C H 3
CH30 o OSO~N~
known from EP-A-0 158 233, Example 1, and 3 parts of a
commercial nonionic wetting agent, by means of a pad-
mangle to a liquor pickup of 80%, ba~ed on the weight of
the fabric. The fabric padded with the dye solution is
wound onto a batching roller, wrapped in plastic film,
left at from 40 to 50C for 4 hours and then rin~ed with
cold and hot water, which may contain a commercial
surfactant, and if necessary subseguently rinsed once
more with cold water and dried. The result obtained i8 a
strong level yellow dyeing which has good all round
fastness properties, especially good rub and light
fastness properties.
Example 4
A plant-customary fiber grade viscose having a cellulose
content of 9%, an alkali content of 5.5% and a viscosity
of 40 falling-ball seconds at 30C has an alkaline
solution of a commercial gelatin stirred into it as
follows:
6 parts of gelatin are dissolved in a solution which
contains 10 parts of sodium hydroxide and 90 parts of
water. Of this solution, 59 parts are mixed with 1000
parts of a plant-customary fiber grade viscose which
contains 89 parts of cellulose. Devolatilization, spin-
ning, stretching, cutting, washing and drying affords a
fiber which can be dyed by a conventional exhaust
process. For this 20 parts of the pretreated viscose
fiber are treated in a dyeing apparatus with 200 parts of
an aqueous liquor which, based on the weight of the dry
2158~8~
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fiber, contains 1.5% of the reactive dye of the formula
Na 03SO~ ~ OH
~`N' N~N H ~ c
known from EP-A-00 61 151, Example 4, in commercial form
and consistency. The fiber i8 dyed with this liquor at
60C for 30 min. The dyeing thus obtained is further
treated by rinsing and soaping in a conventional manner.
The result obtained is a vivid orange dyeing having the
customary good fastness properties of reactive dyes.
Example 5
A plant-customary fiber grade viscose having a cellulose
content of 8.8%, an alkali content of 5% and a viscosity
of 41 falling-ball seconds at 30C has an alkaline
solution of horsehair stirred into it. For this 8 parts
of horsehair are dissolved in a solution which contains
11 parts of sodium hydroxide and 100 parts of water. Of
this solution, 65 parts are mixed with 1000 parts of a
plant-customary fiber grade viscose which contains 89
parts of cellulose. Further processing by the process
steps customary for fiber grade viscoses affords a fiber
of modified viscose which can be reactively dyed in an
exhaust process without salt and at a pH of 8. For this,
30 parts of viscose fiber are wound onto a package and
the yarn is treated in a yarn-dyeing apparatus which
contains 450 parts (based on the weight of fiber) of a
liquor which contains 0.6 part, based on the initial
weight of the fiber, of an electrolyte(pre~s~;nAntly
sodium chloride)-containing dye of the general formula
- 2 1 ~
S03Na
~N~N~ N~N
N~03S~So NaHN~CoNH F
known from DE-A-28 40 380, Example 1. The pH is adjusted
to 8 with sodium bicarbonate. The temperature is raised
to 60C, and the liquor is pumped alternately from in to
out and from out to in. After 60 min at this temperature,
the liquor is dropped, and the dyeing obtained is rinsed
and washed according to the customary conditions. The
result obtained is a level yellow fiber having the
generally good fastness properties of reactive dyes.
Example 6
A plant-customary fiber grade viscose having a cellulose
content of 8.9%, an alkali content of 5% and a viscosity
of 38 falling-ball seconds at 30C has an alkaline
solution of ground horn chips stirred into it as follow~:
7 parts of ground horn chips are dissolved in a solution
which contains 11 parts of sodium hydroxide and 100 parts
of water. Of this solution, 55 parts are mixed with 1000
part~ of a plant-customary fiber grade viscose which
contains 90 parts of cellulose.
Devolatilization, sp; nn; ng, stretching, cutting, washing
and drying affords a fiber which can be dyed at pH 4.5 by
a customary exhaust process.
For this, 20 parts of the pretreated viscose fiber are
treated in a dyeing apparatus with 200 parts of an
aqueous liquor which, based on the weight of dry fiber,
contains 2% of the direct dye of the formula (C.I. Direct
Blue 108, C.I. 51320)
2 ~
- 12 -
Cl El
N ~ (S03Nc)3
Et Cl
The pH of the liquor is first adjusted to 4.5 with acetic
acid. The fiber is dyed with this liquor at 80C for 30
min. The dyeing thus obtained is further treated by
rinsing and soaping in a conventional manner. The result
is a deep blue dyeing having fastness properties which
are far superior to those of conventional direct dyeings.
ThiB i8 true in particular of the wash fastness
properties.
Example 7
A plant-customary fiber grade viscose having a cellulose
content of 9%, an alkali content of 6% and a viscosity of
42 falling-ball seconds at 30C has an alkaline solution
of pig leather stirred into it as follows:
6 parts of pig hide are dissolved in a solution which
contains 10 parts of sodium hydroxide and 90 parts of
water. Of this solution, 55 parts are mixed with 1000
parts of a plant-customary fiber grade viscose which
contains 90 parts of cellulose. The customary process of
fibermaking and weaving afford a textile viscose fabric
which can be further processed directly in a dyeing
process according to the padding principle. For this, an
aqueous dye solution which per 1000 parts by volume
contains 20 parts of the direct dye of the formula (C.I.
Direct Blue 199)
~S03NH4
CuPc
~(S02NH2)3
(CuPc = copper phthalocyanine)
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- 13 -
and 3 parts of a commercial nonionic wetting agent in
BolUtion i8 applied to the fabric at 25C by mean~ of a
pad-mangle at a liquor pickup of 80%, ba~ed on the weight
of the fabric. The dye solution was fir~t adjusted to
pH 5 with acetic acid. The fabric padded with the dye
solution i8 then steamed for 2 minutes. The dyeing thus
produced is further treated by rinsing and soaping in a
conventional manner. The result is a strong tur~uoise
dyeing having very good allround fastnesR properties.
Further examples:
The directions of Example 4, 5, 6 or 7 are followed and
the modified viscoRe fiber is dyed in accordance with the
directions of Example 6 using the below-listed dyes.
Similar result~ are obtained.
C.I. Acid Black 27
NoO~S~H . N ~N N ~NH2
SO~Na
C.I. Acid Blue 113
N~03S
~3N N ~N ~ N ~NH
~) ~ SO~Na
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- 14 -
C.I. Direct Orange 49
NoO~S OCH, N~CO SO~Na
N N ~ NH - CO - NN ~ N N
SO~No SO~No
C.I. Direct Red 79
HoO~5 OCH~ HICO ~ SO~No
N ~ NH - CO - NN ~ N N
~ CH~ CH HO ~
boO~S SO~No
C.I. Direct Red 84
~0~5 ~ . co . ~ 0,--
~0,~ ~0~
C.I. Direct Red 80
. O ~ . . O
C.I. Direct Red 194
~ 0, ~ s ~ , 0 "
215~8~ -
- 15 -
C.I. Direct Red 32
.. c, ~ .~ .....
C.I. Direct Red 81
NoO35 ~N ~ N ~ ~, NH - C0
C.I. Direct Violet 9
OCH~ HO
N~O~S ~N N ~11 ~l ~NH
S03No
R - N ~ N ~NH ~N ~ N - R
where R ~
OH H2N
NaO3S ~N N ~NH - CH2 - COOH
