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Патент USA US2412125

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2,412,125
Patented Dec. 3, 1946
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UNITED STATES PATENT‘OFFICE
2,412,125
ARTICLE AND TREATMENT OF CASEIN '
FIBERS
John E. Conrad. Baia-Cynwyd, Pa., assignor to
Collins 8; Altman Corporation, Philadelphia,
Pa., a corporation of Delaware
No Drawing. Application October 18, 1,941,
~ Serial No. 415,631
11 Claims. (Cl. 8-21)
1
This invention relates to a process‘of preparing
synthetic ?bers derived from casein or from other
protein substances for dyeing in certain dyebaths
so that these synthetic fibers may be blended or
otherwise used together with wool and/or mohair
?bers in the manufacture of textile fabrics which
are to be dyed in the piece to a substantially
uniform shade without oblectionably noticeable
striations appearing. My improvements are of
‘particular utility in the union dyeing of fabrics,
both pile and ?at, containing cotton or other
cellulose ?bers as well as‘ wool and/or mohair.
By my improvements a novel ?ber and fabric are
produced.
2
When untreated synthetic casein fibers are in
cluded in the pile yarn blend together with wool
and/or mohair, and the fabric union dyed in a ‘
pad dyeing operation, the synthetic casein ?bers ‘
will ordinarily dye much darker or deeper than
the wool and mohair ?bers. As indicated here
inbefore, if such a fabric be union kettle dyed,
the difference will not be as great due to the
often repeated immerslons. but there will never
the less be a substantial contrast in shade.
A difference in color or shade will also occur ‘
ii’ untreated synthetic casein ?bers be blended
with wool and/or mohair ?bers in fabrics. such
as worsted ?at fabrics. having no cotton and
'
fabrics dye by pad dyeing methods with acid
Throughout this speci?cation the term “casein 15 the
dyestuiis in a substantially neutral bath.
?bers" will for brevity be used, but the term will
According to my improvements I may produce
be understood to include other synthetic protein
9. treated casein fiber which will dye to a shade
?bers such as those derived from the soy bean
approximating that of wool or mohair when the
20 two types of ?bers are dyed together in a sub
casein.
stantially neutral aqueous union bath contain
Synthetic casein ?bers are of protein material
ing neutral dyeing acid dyestuffs and substan
and accordingly have affinity for many of the
tive dyestutfs using either short time immersion
same dyes as have wool and mohair, but the ini
methods. as in pad dyeing. or long time repeated
tial a?lnity oi’ the synthetic casein ?bers for dye
stuffs is much stronger than that of the wool 25 treated
immersion
casein
methods.
?ber willasalso
in dye
kettle
similarly
dyeing.
to wool
My
or from zein (corn), as well as those derived from
and mchair ?bers. Consequently. if untreated
casein ?bers be blended with wool and/or mohair
or mohair when the two types are dyed together
by either pad or kettle methods in a substantially
?bers in yarns which are then dyed by short time
neutral aqueous bath containing only neutral
immersion methods, as in pad dyeing, the casein
dyeing acid dyestu?'s or when the two types are
?bers will dye so much darker than the wool and 30 pad dyed together with vat dyestu?s. My treated
mohair as to constitute a difference in color.
casein ?ber does not. however. dye like wool or
Where the time of immersion is long, as in kettle
mohair when the two are dyed together by either
dyeing, the stronger initial a?inity of the syn
pad or kettle methods in acid dye baths.
thetic casein ?bers will be partially overtaken but
The treatment given the casein ?ber to accom'
there will nevertheless be a substantial differ
ence in shade between the synthetic casein and
the natural wool and/or mohair ?bers.
In the manufacture in quantity of textile pile
pllsh the foregoing e?ects does not weaken the
or without other fibers, including casein ?bers,
in the pile. it is very desirable for reasons of
whereby a water insoluble metallic tannate is
incorporated with the casein ?ber. The tannate
?ber nor does it make the fiber sti? or hard or
harsh or gummy.
In other words. the treated
?ber retains substantially its initial strength.
fabrics having a. cotton backing or base por
?exibility.
elasticity and feel.
tion and wool. or mohair, or blends thereof. with 40
My method comprises a two bath treatment
speed and economy oi.’ production to dye the fabric
in the piece in a union dye bath in a continuous
is preferably light colored so as to affect as lit
tle as possible the color or shade to which the
A union 45 fiber is dyed. This is important in connection
dye bath which I contemplate is an aqueous bath
with producing shades currently used for most
containing (a) neutral dyeing acid dyestuffs for
operation using pad dyeing methods.
the wool. casein and mohair ?bers, and (bi sub
stantlve dyestuffs intended primarily for the cot
ton fibers. The wool. casein and mohair fibers
also have affinity for the‘substantive dyestuffs
so that the shade or color to which they dye is
the combined effect of both components of the
union dye bath. Application Serial No. 655,592
.Jh-ls-l
Fnv.‘ ,.
is a. uJvlbiGn
c.I Lk
....2 press...
ems.
automobile upholstery pile fabrics.
According to a preferred embodiment of‘ my
improvements, the casein ?bers are first sublect
ed to an aqueous solution of tennis acid. The ex
cess solution may then be removed and the ?bers
next immersed in an aqueous solution, preferably
of stannous chloride, whereby tin tannaie is in
corporated with the ?bers. The ?bers may then
$319,126
be rinsed and dried.
The second bath may if
desired be an aqueous solution of any water solu
ble aluminum salt such as aluminum sulphate or
aluminum acetate, whereby aluminum tannate
will be incorporated with the ?bers. Or the sec
ond bath may be an aqueous solution of tartar
emetic, whereby antimony tannate will be incor
porated with the ?bers. A small amount of
acetic acid may preferably be used in each bath,
i
4
mately 120° F., cdhtaining stannous
in
an amount approximating three‘ percent. of the
weight of the stock. A temperature substantially
higher than 120° F. would damage the available
casein ?bers, and a substantially lower tempera
ture would give markedly inferior-"resist e?'ects
for the contemplated dyebaths. Acetic‘acid in
an amount approximating one percent. ‘of the
weight of the stock may be contained in the sec
the presence of acetic acid being more important 10 ond bath. As'a result of the reaction between ,
in the second bath than in the ?rst. The time
the tannic acid and the stannous chloride, tin
of immersion, the temperature of the baths and
tannate is incorporated with the ?bers.
the concentration of the solutions will be more
The metallic salt of the second bath may. if
fully described hereinafter.
desired, be aluminum sulphate or aluminum ace
It is an object of this invention to prepare syn 16 tate. in which case aluminum tannate is in0or_
thetic ?bers derived from casein or other protein
porated with the ?bers. Or the second bath may
substances for dyeing so that the said synthetic
be an aqueous solution of tartar emetic, in which
?bers may be blended or otherwise used together
case antimony tannate is incorporated with the
with wool and/or mohair and cotton ?bers and
?bers. Tin tannate, aluminum tannate and an
dyed in arunion bath without objectionably no 20 timony tannate' are all light in color-and accord
ticeable striations appearing.
ing’ly will not substantially darken the natural
More speci?cally. it is an object of this inven
color of the casein ?ber so as to interfere with or
tion to prepare arti?cial ?bers derived from ca
limit the color or shade which it is desired to ap.
sein for dyeing in a union bath containing neutral
ply in the subsequent dyeing operation.
'
dyeing acid dyestuffs and substantive dyestuds, 25
In each bath the volume otaqueous solvent
or for dyeing with neutral acid dyestu?s, or with
should be su?lcient to work the ?ber stock there
vat dyestuffs using short time immersion methods
in. The weight of the aqueous solution‘ may
as in pad dyeing.
conveniently be aboutr?i'teen times the weight of
Another object is to produce a synthetic casein
the ‘?ber stock.
?ber having a water insoluble metallic tannate 80
Attention is directed to the (act ‘that in the
incorporated therewith. which when subjected to
preferred treatment described‘ above the tem
neutral dyeing acid dyestuffs, or to substantive
perature of the tannlc acid bath is approximate—
dyestu?s; or to both as in union dyeing, or .to vat
ly 160° F. This temperature is Just above the
dyestu?'s in a short time immersion operation will
point where the casein ?bers swell markedly and
dye to a shade approximating the shade of wool 35 at this temperature the ?bers will absorb the
?bers subjected to the same dye bath for the
tannic acid solution more readily than at sub
same length 0! time under the same conditions.
stantially lower temperatures. Temperatures
Another object is to provide a method of in
- below 160° F‘. may be employed if desired, but the
corporating a water insoluble tannate with the
time oi‘ immersion should be increased accord
casein ?ber.
40
Another obiect is to produce a unlormly dyed '
Higher temperatures than 160' I". may also be
inely.
textile fabric including casein, cotton and other
cellulose ?bers, and wool ?bers; said casein ?bers
having a water insoluble metallic tannate incor
Dorated therewith.
‘
Another object is to incorporate tin tannate,
'
.
.
employed, but temperatures lubstantially in ex
cess oi 180° F. should not be used. as thestrength'
oi the casein ?l'irs will be impaired. I have
45 obtained satisfactory resist eflects using as a
?rst bath a one-half of one percent. aqueous
or aluminum tannate, or antimony tannate, with
solution of tannicacid at a_.temperature of. 180,’
the casein ?ber, whereby the ?ber will have an
F., the time of ‘llnmerslom‘bein-g- two‘ minutes;
a?inity approximating that or wool ?bers for
indicated, this is a-maxlmum temperature and
neutral dyeing acid dyestuffs. or substantive dye 50 aAstwo
minute immersion-period is minimum, as
stu?‘s, or both as in union dyeing.
.
shorter periods o-i' immersion do not give sum
Another object is to treat casein ?bers so that
ciently strong resist e?ects.
.
they may be blended together with wool and/or
The time of immersion in the second bath
mohair ?bers in the pile of pile fabrics having a
as indicated above, be ?ve minutes or 3
cotton backing, and dyed together therewith in a 55 should,
more and the amount 01' stannous chloride in
union bath using short time immersion methods
solution should neither greatly exceed nor be
as in continuous pad dyeing, all of the blended
greatly less than three percent. of the weight
?bers in the pile being dyed to nearly the same
of
the ?bers being treated, as in either case the
shade.
shade of the dye would be adversely ailected,
These and other objects of invention will be 60 and if more is used the ?bers may be weakened.
manifest from a consideration of the speci?cation
My improvements are particularly applicable for
and ot the claims.
'~
pad type union dyeing where the time of immer—
According to a preferred embodiment of my
invention, the synthetic casein ?bers are im
mersed in one quarter of one percent. aqueous
solution of tannic acid at'l??i' F‘. It is deslrab‘e
but not essential that the solution contain a small
quantity of acetic acid. After about ?ve or more
minutes of being worked in the solution as by
gentle agitation, the stock may be rinsed or
nipped or the solution may be merely permitted
to drain oil’.
The casein ?ber stock is then immersed for
five or more minutes in the second bath, which
is preferably an aqueous solution, at approxl—
sion is very short. that is, a matter of seconds.
This type of dyeing is widely used in the produc
tion of pile fabrics, as is set forth in United
States Patent to Drobile et al. No, 2,071,922. A‘
satisfactory dyebath immersion time in process
lllg according to the prior patent is ten seconds.
I have found that after a ten second immersion
my treated casein ?bers will approximate the
shade of wool and/or mohair blended therewith.
It is to be understood that wool and mohair do
not dye identically, but that they dye sufliciently
close in shade to permit blending without ob
jectionably noticeable striations in the ?nished
5
2,412,125
6__.
piece. My treated casein ?bers may be brought
within a shade range which permits blending with
with wool ?bers. and- ‘pad dyeing the blerided
?bers to approximately the same shade with a
wool or mohair to give a like uniiorm appearance
substantially neutral dyebath’ containing neutral
to the cloth utter a ten second immersion as set
dyeing acid colors.‘
forth. This result is accomplished by the treat
ment illustrated by this preferred embodiment.
A typical treatment -01' a commercial quantity
of casein‘?bers according to my method is as fol
120° F.
500 lbs, of synthetic casein ?bers is placed in a 10
suitable container or kettle. The aqueous solu
tion of tannic acid at about 135° F. is drawn from
a reservoir, placed in the kettle and then brought
to a temperature of 160° F. and held there for ap
proximately ten minutes, during which the ?ber 15
stock may be gently agitated. The tannic acid
solution is then drained out and pumped back
water or solution may be removed. The ?bers are
now ready for the second bath. Water and half
of the required acetic acid is poured into the
kettle, then the solution of stanncus chloride and
the remainder of the acetic acid is added and the
entire solution brought to 120'’ I". and held there.
The ?bers are kept in this solution for approxi
mately five minutes, after which the kettle is
- drained. the ?bers rinsed and then dried.
In
this condition the ?bers are ready for blending
.
6. A process of making blended fabrics con
taining casein ?bers and natural animal ?bers
of approximately the same shade, which includes
treating the casein ?bers so as to form a metallic
tannate on the ?bers, blending the treated casein
?bers with natural animal ?bers and then pad
dyeing the blended fabric to an approximately
uniform shade with a substantially neutral dye
bath containing neutral dyeing acid ‘colors.
7. An undyed synthetic ?ber derived from 1
casein and having a water insoluble/metallic tan
nate incorporated therewith in an amount which
will provide a partial resist for neutral dyeing
acid colors to an extent that it will cause said
?ber when immersed for a period of ten seconds
25 in a substantially neutral aqueous medium con
so
. taining neutral dyeing acid colors and then
nipped as in pad dyeing to dye to approximately
the shade of wool ?bers immersed in the same
dye bath for the same period of time under the
with wool or other ?bers or for use alone in the 80 same practical dyeing conditions.
formation of yarns.
.
perature of the tin salt solution approximates
lows:
into the reservoir. A light rinse may then be
given the casein ?bers, after which any excess
,
5. A process as set forth in claim 4 further
characterized in that the temperature of the tan- .
nic acid solution is less than 180° F. and the tem- %
'
8. In a process of 'preparing synthetic‘?bers
As indicated hereinbei'ore, casein ?bers treated
derived from casein so that they will be partially ,
according to my methods will dye approximately
resisted and, will dye approximately like wool in
like wool when the two types 0! ?bers are dyed
a substantially neutral aqueous medium contain
together, by either pad or kettle methods, in a
ing
neutral dyeing acid colors in ill-second im
substantially neutral aqueous medium containing
mersion pad dyeing operations, the steps which
neutral dyeing acid dyestu?s or substantive dye
consist in treating the ?ber with each of two
stuffs, or both as in union dyeing, or pad dyed
separate aqueous solutions, one solution contain
with vat dyestu?’s. .Casein ?bers treated accord
ing tannic acid and the other being an aqueous
ing to my method will not, however, dye like wool (0 solution of stannous chloride, said stannous chlo
where the two are immersed together in an acid
ride being present in an amount approximating
bath containing acid dyeing acid dyestuffs,
3% by weight of the ?bers being treated and the
Having descrlbedmy invention, I claim:
temperature of said stannous chloride solution
1. A process of making blended fabrics con
being approximately 120° F. during processing.
taining casein ?bers and natural animal ?bers 45 9. An undyed textile fabric including cotton,
of approximately the same shade which includes
wool, and casein?bers, said casein ?bers con-L,
treating the casein ?bers so as to form a tin
taming a metallic tannate in an amount that
tannate on the ?bers, blending the treated casein
the casein ?bers are partially resisted to neu
?bers with natural animal ?bers'and then pad
tral dyeing acid colors in a manner which
dyeing the blended fabric to an approximately 50 causes
them to dye to approximately the same
uniform shade with a substantially neutral dye
shade
as
the natural wool ?bers when the fabric
bath containing neutral dyeing acid colors.
is immersed for ten seconds in a substantially
2. A process as set forth‘in claim 1 further
neutral dye bath containing neutral dyeing acid
characterized in that the tin tannate is formed
dyestuffs and substantive dyestuffs and then
by treating the casein fibers with each of two 55 nipped as in pad dyeing.
separate solutions, one of which contains tannic
10. An undyed textile fabric including wool and
acid and the other of which contains a tin salt.
casein ?bers, said casein ?bers containing a light
3. A process of treating‘ textiles which includes
colored metallic tannate in such percentage that
the steps of treating synthetic ?bers derived from
the casein ?bers are partially resisted to neutral
casein with each of two separate aqueous solu 60 dyeing acid colors in a manner which will cause
tions, one of which contains tannic acid and the
the fabric, when immersed for ten seconds in a
other of which contains a tin salt, then drying
substantially neutral dye bath containing neu
the treated ?bers, blending the treated synthetic
tral dyeing acid dyestu?‘s and then nipped as in
?bers with wool and dyeing the blended fibers
pad dyeing, to dye to an approximately uniform
to approximately the same shade with a sub
shade.
stantially neutral dyebath containing neutral
11. A synthetic ?ber derived from casein, said
dyeing acid colors.
?ber having a water insoluble metallic tannate
4. A process oi’ treating~ textiles which includes
incorporated therein in such an amount that the
the steps of treating synthetic ?bers derived from
?ber will be partially resisted for neutral dyeing
70
casein with each of two separate aqueous solu
acid colors but will dye to a uniform shade in a
tions, one of which contains tannic acid and the
substantially neutral aqueous dyebath containing
other 01’ which contains a tin salt, then drying
neutral dyeing acid colors.
the ?bers, blending the treated synthetic ?bers
JOHN’ E. CONRAD.
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