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Патент USA US2408418

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2,408,417
Patented Oct. 1, 1.946
7
,
Y
AGENTS AND \"Marnonsr or
“mwimmme ale-ES “WSW-813111;?!“
' “William; To. Ellenbogen, York, Pa.
7v Claims. 1 (eras-194.72g‘;
,
1
_
-
nut'oii fatty .acid',1as well as derivatives of such
The present invention rel-ates‘to the tanning
0f hidésiand skins} and particularly lto'tarin'ing
amidinfesi in which ' one‘ or‘ more of, thehydrogen
compoundsiiora 'xtures of c-oinpouridscontain
straight" ‘for ib‘ra’niched f chain‘, aliphatic radical.
processes"
matron;
atoms ‘attached ‘to "nitrogen ‘is replaced ‘with ‘a
employ} a‘s‘iithe‘i tanning agent
1"
t-.
*‘
r
,7
=1
,-1='.:1;“-'.1:'.:
x
The amidines are‘u'sually"employed'in theiiform
,
"i‘Va ious- compounds or‘ substances containing
o'i‘one of 'their'additionlsaltstsuchjasithe chloride
nominate teen ‘usédg-foi‘tanning/purposes iii-‘the
past,"iblit- in‘a'practieany an aséstt'lie" leather ob
tained was not yeryir'esistan't‘ito tearing nor sta
ble on storing. ‘Thus iron tanneddeather-tended 10
sfou'nr‘ées or ‘ as
to aeyi:harag-fanafia‘generar pr'ovedito‘be --unsatis
rwhenv cam-pared
or sulfate, ‘but‘in‘scme'instances it is possibleto
use the amidine per se,-">:as1 when su?icient acid is
furnished to ,the tanning solution from other
result offthe treatment prelimir
The ionowingexampies wmilzurther illustrate ‘
'yev'getable-?or
invention and» how it may ‘be
carrieaootinl practicaput it islto be understood
It isaccordingly?a‘primary object- of this in-'
vention ‘to provide aliiiethodiofitanningi with iron 15 that théiinvéntion‘is 119§l1inf?tedto thedetailsldér
scjribed' therein, .exceptias de?ned ‘in the appended
cciripound’s'"whichl results inllleatHer 'of “good ten
tileE sitr'en'gthiland-increased resistance» to aging.
chrome-tanned leather‘. f 4
‘
-
~
the ‘nature > ‘of
~
Grams.’
“A‘furth'er' objectioflthe'invention ‘is to provide
improved '--‘iron=contaihirig tanning agents which
are'e‘a'pable 56f ipreeucmgi leathers haying-not‘i'only
the above’? desirableproperties but'l-increasedf full
nes's anaseefr resistance.-"
- ~
~
,
.
.
.,
:1
I:
V , Example ‘.I
the-usual
WEY‘QITOI‘QU)? tanning, as bydehairingg-bating,
degreasingsand“pickling;éwere: milled- in anl equal
mightier ,a- 5%:- r'salt' solution i-fon about! 1-5, ‘min,
>
'
.,
(one, hundred pounds oifsheepskins (pickled
venticd will appear ifforri- théfalldwi?g 'tfe'Scfi-p
*
,.
20 weight) wwhich-zhad *beemconditioneld"
*' Still furtherobjects-i and advantagesoi the in
t‘i'onand appended claims-1*
.
utesv- Altanmngisolution'consisting of 12:poumls
I
25 of ierrio-isultateg?;munds<.ot.1so,dium citratesa’nd
~ "The-invention- “a "be carried cutby treating
hides or skins with dilute ia‘duebuslsolutio?sf con‘
n'g'yai ferrici'salt; steamer a} short chain mono
1.5? pounds-tof- the-hydrogen :~ chloride ‘addition
salt of oleyl amidine dissolved in su?icient water
to‘v make ' 8-,.gaIlons,;\ was then added, :atter which
'ycai'bbxyl-ic acid hayingat ' leastf one 7 hy
the skins iweneritumbledl in the"resultingsolution
totem-1 of i a polycarboxylieiacidihaying 30 ion-salient oneand». alih'alfirhours, Eight/‘pounds
at‘fwrl‘east ‘ T '
of sodiumvibicarbonate were-then; added-‘ta the
amidine of a5 h‘i'giieii‘oblong-‘chain fatty? acid.
bath insmalkadditions zatiintervalsv over: azpe'riod '
Prior to 'b'jecti‘ng-the hides or'sk’ins tcii-thev ac
or _ he above
"
‘solutions {ofv therpurposéiof
of ‘one hour. =1 i'léhis‘ ?xed.» the-7 tan. " =The I leather I
in the, usual way. as tor example, by de‘nairing.
bati?g’a?d ‘pickling the-same; It is also cus
?ec'ted; .t'o theé‘susual'. steps-ifollowingiitanninggin
tanningithe‘isamef‘thei-hides ‘may be conditioned
tomary subsequently to ?x the tan with a dilute
solution of alkali bicarbonate or other equivalent
alkali, after which the leather is tumbled and 40
washed, and subjected to the usual treatment
‘following tanning, such as fat liquoring, dyeing,
wasthen :tumbled. foraanother half ' hour, after
which it was washed in water; 'rltzwasithemsub
eluding fat liquoring, dyeing, drying and ?nish
ing.
.
Example II
One hundred pounds of cow hide (lime split
weight), which had been dehaired, limed and
bated in the usual manner, were pickled for two
drying and ?nishing. It is to be understood,
hours in a solution consisting of 6 gallons of wa
however, that the invention is not to be limited
to these customary procedures as applied either 45 ter, 2 pounds of 66° Bé. sulfuric acid and 9
pounds of common salt. A tanning solution con
_
sisting of 8 pounds of ferric sulfate, 4 pounds of
In carrying out the tanning step as herein
sodium tartrate, 1 pound of the’ hydrogen chlo
before described any suitable ferric salt mayv be
ride addition salt of oleyl amidine and 1 pound
used, such as ferric sulfate, ferric chlorideand
ferric ?uoride, or *mixtures'thereof. The mono 50 of caustic. soda dissolved in su?icient water to
make 5 gallons, was then added. The hides were
or polycarboxylic acids, which may be used in
tumbled in the resulting solution for about v2
the form of their alkali salts include tartaric, cit
hours. Six pounds of sodium bicarbonate were
ric, glycolic, malic, phthalic and maleic acids.
then added to the bath in small additions at in-.
As suitable amidines there may be used oleyl
amidine, stearyl amidine, the amidine of palm 55 tervals over a period of one hour, which ?xed
before or after the tanning.
,
2408,41’?
3
4
the tan. The resulting leather was then fat liq
herein may be prepared either by separately
adding and dissolving the various ingredients
uored, dried and ?nished in the usual manner.
Example III
constituting the active tanning agent, or by pre
viously mixing these ingredients and then dis
solving the mixture.
One hundred pounds of calf skin (pickled
Weight), which has been dehaired, limed, bated
and pickled in'the usual-manner, were tanned by
It is believed that the various constituents of
thetanning solutions described herein interact,
tumbling them for two hours in a tanning solu
tion consisting of 8 pounds of ferric sulfate, 4
pounds of sodium glycolate and 1 pound of the .10
hydrogen chloride addition salt of stearyl ami-,
dine dissolved in su?icient water, to make 5 gale
lens. The resulting leather was then further
treated and ?nished as described in Example I.
Example IV
One hundred pounds of steer bellies (pickledv
weight) which had been treated in the usualv
manner to prepare them for tanning, were
when dissolved, to form‘organicliron'lcomplexes
which raise the precipitation point of the iron,
thereby allowing proper penetration of the tan
ning agent into the hide. Regardless, however,
of the way the materials interact in solution, they
produce the above described desirable e?ects on
the leathers tanned therewith.
Where mention is made herein and in the ap
pended claims of oleyl amidine and stearyl ami
' dine, it is to be understood that this has refer
ence to the amidines of oleic and stearic acids
respectively.
‘
tanned by tumbling them for two hours in a tan '20
What I claim is:
ning liquor prepared by dissolving 12 pounds of
l. A tanning agent comprising an. iron salt, a
ferric sulfate, 6 pounds of phthalic anhydride,
substance selected from the group consisting of
3.5 pounds of caustic soda, and 1.5 pounds of the
the salts ofhydroxy mono and polycarboxylic
hydrogen chloride addition salt of stearyl ami
acids and polycarboxylic acids having at least
dine in sufficient water to makeB gallons. The 25 one double linkage, and a substance selected
resulting leather was then further treated and
from the group consisting of the salts of ami
?nished as described in Example II.
dines of higher fatty ‘acids and derivatives of
Example V , '
such amidines in which at least one of the hydro
gen atoms attached to nitrogen is replaced by an
.' .Four hundred pounds of cow hide \(limed
weight), which had been dehaired, limed and
hated ‘in the usual manner, were pickled‘ in a
solution consisting of 35 ‘gallons of water, 4
pounds of 66° Be‘. sulfuric acid and 32 pounds of
common salt for about twenty minutes. The
pickled‘hides were then tanned by tumbling them
for two hours in a tanning solution prepared by
dissolving 32 pounds of ferric sulfate, 10 pounds
aliphatic radical.
;
.
2. Avltanning agent comprising ferric sulfate,
sodium tartrate and a salt of oleyl amidine.
3. A tanning agent comprising ferric sulfate,
I sodium citrate and a salt of oleyl amidine.
4. A tanning agent comprising ferric sulfate,
sodium tartrate and a salt of stearyl amidine.
5. The process of tanning hides or skins which
comprises treating them with an aqueous solu
of cream of tartar, 6 pounds of caustic soda and
tion containing an iron salt, a substance selected
‘3.'pounds of the hydrogen chloride addition salt
from the group consisting of the salts of hydroxy
14G
‘of oleyl amidine'in sufficient. waterv to make 25
mono and polycarboxylic acids and polycarbox
gallons. Twenty pounds of sodium bicarbonate
ylic acids having at least one double linkage, and
were then added to the bath'rin small additions at
a substance selected from the group consisting of
‘intervals over a period of one hour, which ?xed
the tan. The leather was then tumbled for an
other half hour, after which it was washed in
the salts of amidines of higher fatty acids and
derivatives of such amidines in which at least
one of the hydrogen atoms attached to nitrogen
isreplaced by an aliphatic radical.
usual manner.
'
6. ‘The process of tanning hides or skins which
“The leathers obtained in accordance with‘ the
comprises treating them with anaqueous solu
.above‘examples were found to'have a fine and 50 tion containinga ferric salt, an alkali tartrate
smooth grain, and a full round‘ feel. Moreover,
and a salt of an amidine of a higher fatty acid.
they possess exceptionally high tensile strength
, 7. The process of tanning hides or skins which
and resistance to scuffing, and have very good
comprises treating them with an aqueous solu
aging characteristics substantiallyequal to, or
tion containing a ferric salt, an alkali citrate and
‘even better‘ in someinstances than those of 55 a, salt of an amidine of a higher fatty acid.
chrome-tanned leather.
water, fat liquored, dried and ?nished in the
The tanning. solutions employed as described
WILLIAM C. ELLENBOGEN.
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