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Патент USA US2122100

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Patented June 28, 11938
strap stares
> 2.12am
Rudolf Kern, Qschatz, Germany, assignor to ‘the
- ?rm Chemische Fabrih lit. Baumheier Korn
manditgesellschaft Oschata-Zschollau
No Drawing. Application December 13, 1933, Se
rial No. 702,259. In Germany December .15,
2 Claims.
This invention relates to a process for simul
taneously coloring and water-proo?ng textile
materials in one bath.
It has been found that
the application of the dispersed water-proo?ng
- substances can be effected simultaneously‘ with
the coloring matter. The surprising discovery
has been made that coloring matter or dyestufi‘
and dispersed water-repelling particles do not
impair each other’s action in any operative
M phase, and that therefore, in spite of the pres
ence of an emulsion, the coloring or dyeing takes
~ place uniformly and. not, as might be expected,
irregularly, whereas for example uncleaned or
unscoured cotton ?bre containing a small quane
15 ‘city of wax, and readily repelling water, ‘colors
. very irregularly, and in addition it is known that
the parts of ?bres coated with paraiiin are not
colored at all.
The surprising technical effect is that in spite
‘go of this a uniform coloring takes place. The
process represents a very economical simpli?
cation of textile ?nishing since the operative‘
time is considerably shortened, one operation be
ing avoided._ Thus the cost in manufacture is
25 reduced considerably. After the dyeing it is not
necessary to dry, before impregnating and then
to dry again. The water-proo?ng emulsions are
, simply added to the coloring bath and the dye
ing is e?ected in the usual way. The resulting
3o wares are uniformly dyed and rep'el water to
remarkable extent. The impregnation produced
(oi. 91-68)
sions of these'emulsions, which relate to the pro
duction; ‘they are subdivided into
(0.) those homogenizedunde'r pressure.
lb) those emulsi?ed in .‘ ‘stirring machines,
emulsifying machines or colloid mills.
14 parts of oil soap are stirred up with 15 parts
of swollen bone glue and then diluted with wa
ter. This solution is stirred into 500 parts of
a solution of formate of alumina having a spe
ci?c gravity of 1.095. Thereupon 1-2% of hexa- 10
line, butanol, acetic ester, acetone and the like
are added. This emulsion is homogenized by ,
forcing through ducts by means of suitable ma
chines at a pressure of 60 atmospheres pressure.
‘(2) Emulsions according to (1 ) both as regards 15
composition and production, but characterized
by the addition of water-proo?ng substances
Water-proo?ng substances like paraf?ns,
waxes, resins, fats, fatty oils or mineral oils may 2@
be ,used. Here also a distinction is to be drawn
between emulsions which are
(a) homogenized under pressure and
(1)) stated briefly, “emulsi?ed”.
By saponifying a mixture of 3.10 kg. of fatty HO 5
acid with 4 kg. of mineral oil and 7.4 kg. of
para?ln an emulsion is produced to which are
added 1.29 kg. of high class glue dissolved in
water. This substance is mixed with‘ anialu
minium formate solution which. has been pre
pared by dlssolving 1.55 kg. of 50% hydroxide
of alumina in 1.75 kg. of 90% formic acid. The
in this way will stand rinsing even in the case
of moist articles, so that the auxiliary chemi
whole is then homogenized at 100 atmospheres~
' cals can be removed and in this manner subse-~
of a' white paste are then obtained after cooling,
a 2.5% solution of which is sufficient for impreg
nation purposes.
ga quent damage to the fibre is avoided.
_ g
All emulsions used for
water-proo?ng pur~
poses may be employed, consisting of aqueous
emulsions of water-proofing substances like
para?in, aluminium soaps, and so forth, or mixas tures of such substances.
The following special emulsions also belong to
emulsions of this type:
(1) Aqueous emulsions of soaps of 'polyvalent
. 45
The chief polyvalent metals are zinc, lead,
magnesium, aluminium and copper. The acids
which form soaps with these metals are fatty
5o acids of the oleic and stearic acid type, or natu=
rally occurring acid mixtures, such as, for ex
ample, acids of tallow, of palm oil, or of cocoa»
nut oil, or acids of the resin acid type such as
Distinction is made ostween ' further subdivi;
pressure. At the concentration employed 50 kg.
(3) Emulsions
which contain water-soluble salts of poly
talent metals, chie?y‘wcter-soluble aluminium 40
salts, with a positive disperse phase
All the above mentioned three groups of emul
sions are acidic, and their disperse'phase is posi
They all stabilize by means of
colloids which swell in- waterfmost advanta- 5%
.ge‘ously however by means'of glue and gelatin.
Allthree groups of the said emulsions may contain wetting agents.
30 parts of good gelatin are swollen in 550
parts of water, the glue is meltedby heating 543*
and, with the aid of stirring mechanism, a mix
ture of 110 parts of paramn (:iiow point 54°), 20 '\
parts of bleached Montan wax and 80 parts of
paramn oil are stirred in. Whilst further stir
ring in the hot, 80 parts of aluminium formate 55
, 2
dissolved in 400 parts of water are slowly added,
and' the mixture thereupon homogenized under
pressure and then cooled down.
The emulsions according to (1) and (2) form
the subject matter of U. S. Patent application
No. 555,148 ofApril 8, 1931, (Fabric impregnated
with dispersed substances, etc.).
and 40 parts of para?in oil are emulsi?ed therein.
This emulsion is treated with formate of alumina
of 7° Bé. I The diluted emulsion solution is poured
into a bath of the following composition:
Parts 5
Diamine black‘ BH, (Schultz Farbsto?’ta
bellen 7th edition, volume 1, No. 393) _____
(4) Emulsions having a negative dispersed part
consisting of soap,‘ glue, gelatin, starch, dex
Glauber’s salt
trin, aliphatic or aromatic sulphonic acids as
Calcined soda_, _________________________ __
emulsifying agent
The cotton fabric is introduced in this solution at
60° C. and, whilst thoroughly stirring, the whole
15 10
The disperse phase consists of the water
brought to boiling, maintained at the boiling
proo?ng substances already mentioned above.
point for 20 minutes after which the fabric‘ is
rinsed, squeezed out and dried. The waterproof 15
" water and to this solution are added 4 parts of
the sodium salt of amylnaphthalene sulphonic qualities are determined according to U. S. speci
acid. Into this emulsifying solution is stirred a ?cation Serial No. 684,074, of July 8, 1933, (Meth
"mixture of 22 parts of paraffin, 4 parts of cetyl od of and system for testing the imperviousness to
20 alcohol and 6 parts of olive oil. The whole is water of impregnated textiles).
The following constants are used in the present 20
worked up in a colloid mill to a ?ne emulsion.
The process may be carried out by adding the determination:
waterproofing substance as such to the dye bath, _Reduction in height in the examination of
for example in the case of substantive dyes or
25 acid .wool dyes.
The‘water-proo?ng substance,
however,-may also be added to the individual
treatment baths in the dyeing, for example to the
copper bath, to the after-chroming bath, to the
generating bath of naphtol dyes, to “the vat or to
30 the aluminous mordant. In the latter case those
emulsions are advantageously preferred which
already contain aluminium salts. Such emul
sions occur in commerce in gelatinous form and
consist of aqueous aluminium formate solution
35 as continuous phase, paramn or paraf?n-like sub
~ stance as the disperse phase, and glue as stabiliz
the cotton ________ ___ ______ __- ____ __cms".
Drop sequence________ __drops in 7 seconds_.
Drop weight ________ __l _____________ __mg__ 125
The following drop values are obtained:
Cotton dyed without water-proo?ng agent in
the dye bath __________________________ __
2 30
Material impregnated in the usual way with
the Waterproofing substance as previously
described diluted 1:100, i. e. as 10 g./litre,
impregnated 10 min. at 60° C __________ -_
Dyed and impregnated as described above
in Example 1
ing and gelatinizing agent. The following manu
facturing receipt will illustrate the composition of,
It follows from this that the water-proof qual
ity when waterproo?ng in the dye bath is con
higher than is produced by- impreg
30 parts of good quality gelatin are swollen in
550 parts of water; the glue is melted by. heating nating in the usual way.
In order to examine the fastness to rinsing and
and, by means of a stirring mechanism, a mix
ture of 110 parts of paraffin (?ow point 54°), 20 to prove that the impregnating substance adheresv
parts of ~bleached Montanlwax and 80 parts of very ?rmly, the piece impregnated in the dye
paraffin oil are stirred in. Whilst continuously Y bath is to be, boiled in pure water for 3 minutes
45 stirring in the hot, 80 parts of aluminium for
and then dried. The imperviousness to water
vmate dissolved in 400 parts of water are slowly still amounted to 10 drops after this treatment.
added after which homogenization is effected
Example 2.--Chroming dyestu?
under pressure and the whole then cooled down.
Cotton fabric is dyed in the following bath:
When using such emulsions in alkaline baths
50 the aluminium formate for the purpose ‘of avoid
' Water ____ __'_a ________________________ __ 1200
ing precipitation of aluminium hydroxide, is con
Dianil chrome brown R (Schultz Farbsto?
verted into an alkali-stable complex form by ad
tabellen 7th edition, volume 1, No. 682) ___
dition of tartrates or other polyoxy-compounds. Calcined soda _______ _; ________________ __
the emulsion.
‘To the above emulsion. for example 3 kg. of
Glauber’s salt ______________________ _-___
‘15 55
sodium tartrate are added and the emulsion then Tartaric acid __________________ ___ ______ ___
neutralized or rendered alkaline with caustic
soda. The statements made in respect of the The imperviousness to water amounts under the
above emulsions illustrate the composition only same conditions as in Example 1 to 3 drops,
after-chromed at 60° C. for half an hour,~—Drop
61% of one group of emulsions. which can contain the value: 2 drops. _
various substances compounded together in vary- .
ing amounts. The use as well of the oils which
are usual in dyeing operations, which consist of in which 10 parts of ‘the same gelatinous emulsion .
as in Example 1 were added to 1000, parts of
sulphonated fatty acids or aromatic substances, bath, after‘ which dyeing was effected at 60° C.
for half an hour, and "the material rinsed,
poses, does not impair the action of the impregna
squeezed out and ironed-Drop value: 19 drops.
Example 1.—Substantive dyeing
After-chroming was then carried out in the fol
lowing bath:
“Makko” fabric is treated with the following
bath: Ten grams of a-gelatinized emulsion are
dispersed in 500 grams of a 1% tartaric acid solu
tion. The emulsion used has the following com
Potassium dichromate_'_ ______________ __
Glacial acetic acid ___________________ __
80 parts of gelatin are dissolved in 1000 parts of '_An emulsion as in Example 1 _______._'__-_
75 water and a. mixture of 40 parts of cake paramn
Drop value: 25 drops.
Water _______ __'_~___\ _______________ ___..- 1150
Copper sulphate- ___' _______ __,_________ __
2. 5
r i
minium formate solution which has been pre
~ A piece of fabric treated in this way is boiled
for 10 minutes. The imperviousness to water
pared by dissolving 1.55 leg. of 50% hydroxide of
alumina in 1.75 kg. of 90% formic acld. Homo- ,
still amounted to" Mumps after this treatment ,genlzation
is then carried out at a pressure of
100 atmospheres. With the concentration em
ployed 50 kg. of a white paste are obtained after
Generation of the dye is carried'out for 30
- delay ?xed during half an hour at 50° C. with a minutes at 31° 0.; the material is then twice
solution of‘ aluminium salt-containing emulsion rinsed, dried and ironed.
of 15 g. per litre. This emulsion has the follow- ‘
Drop value: 26 drops.
Example 3.--;Basic dyestu?s
, Artificial silk is preliminarily mordanted with
a 2% tannin solution, and after a considerable
ing composition: _
Example _6.-Indigo vat
30 parts of good quality gelatin are swollen
in 550 parts of water and the glue is caused to
White raw wool fabric is boiled out and intro
duced into a ‘oath of the. following composition: 15
melt by application of heat; by means of a stir
ring mechanism a mixture of 110 parts of paraf?n
(flow point 5t°), 20 parts of bleached Montan
Water; _____________________ -l ________ __ 4500
Sodium hyposulphite ____ __-_ __________ __
wax and 80 parts of para?in oil are stirred in.
Whilst further stirringin the hot‘la solution of Indigo (Schultz, Farbstofftabellen, 7th
80 parts of aluminium‘ formate dissolved in 400
edition, volume 1, No. 1301) ________ __
parts of water arevslowly added, and thereupon
emulsion made as in Ex
the whole is homogenized under pressure and
ample 5 _______________ __~ _________ __
then cooled down.
The ‘material is then rinsed in ‘the cold and
acid _______________________ __
The impregnating substance, together with the 25
quarters of an hour at 60°? C. in a bath of 1000 tartaric acid, isv neutralized by means of am
' parts of water, 2 parts vof rhodamine B (Schultz, ‘ monia. ‘The fabric is dyed in the usual way and
Farbstoiftabellen, volume 1, 7th edition, No. 864) after hanging awhile is dried. The value for
and 5 parts of glacial acetic acid, after which it the imperviousness to water for a falling height
is rinsed. hot and cold. in the usual manner, of 20 cms. amounted to 12 drops. Operations 30
squeezed out and after drying dyed ,for three
squeezed out, dried and ironed. The water re
polling e?ect is very marked.
Example 4
are carried out in a similar manner with hydro'ne
, blue B (Schultz, Farbsto?tabellen, 7th edition,
‘volume 1, No. i113);
Example 7
Arti?cial sills is mord‘anted as in the above ex
ample, ?xed, and then simultaneously dyed and
‘impregnated with ‘methylene. blue (Schultz,v
Farbsto?tabellen, 7th edition, volume 1, No.
1038).‘The bath has the following composition:
Skelned wool is dyed in the known manner by .
means of eriochrome red (Schultz,'Farbsto?tabel
‘ len, 7th edition, volume 1, No. 745) and there
upon afterchromed with potassium chromate in
A solution of one gram of methylene blue R,
acid emulsion, which is made as follows:- f
so 500 grams of water-(50° C.) and 5 g. of glacial
‘ acetic acid are ?ltered into an emulsion of 10 g.
oi a substance according to Example 5 and 500
~ .14 parts'of sodium oleate are stirred up with
at ordinary temperature) and thereupon rinsed
and dried. The water-repelling action of the
material treated in this way is very good.
by forcing through ducts. The foregoing-emul
sion is diluted fourfold and represents the above
15 parts oflswollen bone glue and the whole di»
luted with water. This solution is then stirred
g. of water (50‘ 0.). The material is then intro» , into 500 parts of a solution of for-mate of alumina;
ducedat 50° 0. and dyed for one hour at 60° C. having a speci?c gravity of 1.095.
. This emulsion is homogenized at 60 atmos
_ It is then ?xed in a 0.1% solution of tartar emetic
' (the treatment being effected for half an hour pheres pressure with the aid of suitable machines
emulsion in the condition for use, in which after 60
chroming is carried out. The skeined wool is
l'l‘arample 5.--Ncphtol dyeing
satisfactorily water-repelling and can be worked
Cotton'is bottomed or 30 minutes in a seat . 'up into water-proof? articles of apparel.
_ When working in a suitable manner the uni
solutionaof sodium naphtholate AS SW (beta
hydroxynaphthoic acid; beta—naphthallde) and
then rinsed and squeezed out. The fabric treated
in this way is thenlntroduced into a bath oi the
following composition
. 1
>____'_ root
Parts ,
co ‘Water-proo?ng emulsion made as described below
dust red m base (d-chlor-o-toluidine
rdchults, Fnrbsto?tabehen, 7th edition,
volume 1, No. 82) dissolved-in glacial ace;
After thorough stirring potassium nitrite
‘dissolved in distilled water'is added"IOWSI-r
ample not irrthe presence of dyestuffs which
actas tanning agents in acid solution. "Wall<:” 60
yellow (Schultz, Farbsto?tabellen, 7th edition,
‘volume 1, No. 230) has been found to be such
a dyestu?. This dyestu? acts in acid solution as
a tanning agent, precipitates the glue and breaks
down the emulsion. In this/case emulsions are 65
used which are stabilized for example by means
after-chroming bath which may be usedkas in I‘
of starch, dextrln, or mucilage. lIowever, in any _
The emulsion referred to above is made as lol
iorrnity oi the dyeing is in all cases perfectly 55
satisfactory. Since most impregnating agents
are stabilized with glue or gelatin such products
cannot be used for all dyeing processes,‘ for ex
the 'aitenchroming bath of Example ‘7, glue
containing emulsion may be used.‘ Outstanding 70
waterproo?ng e?ects are. already produced when
By saponi?cation oi a mixture of tiling; of fractions of a ‘gram of impregnating agent per
fatty acid with 4 kg. oi‘ mineral oil and "hi lag. litre are used. The in'ipregnationdescribed can
of paramn an emulsion is obtained to which‘ is be used in the known manner in all dyeing ap
added 1.29 lrg. of high class glue dissolved in pliances or apparatus.
water. This substance is mined with an alu
Eaample 8.—Inda.nthrene "cat
A cotton fabric is treated at 60° C. in a hypo-_
sulphite vat of the following composition:
15 g. of‘ a substance
500 g. of water
warm and twice cold“ Five cos. of an alumina so
2 g. of dyestu? (invdanthrenegolden orange G
double paste: Schultz, Farbstoiftabellen,
7th edition, volume 1, No.- 1245)
3 g. of hyposulphite (Na2SaO4)
10 g. of common salt
5 g. of an emulsion of the following compo
The fabric is dyed for one hour at about 60° C'.,
rinsed, soaped in a 0.5% soap solution contain
ing 1% of the above emulsion, and rinsed once
1.5 kg. of 50% aluminium hydroxide.
2.1 kg. of’ formic acid
375 kg. of water
2 kg. of tartaric acid
. of concentrated ammonia
99 kg. of paramn
30 kg. of an oil fatty acid
10 kg. of potash lye (45° Bé.)
20 kg. ofalue
lution of‘ 7° Bé. are added per litre of the last
rinsing bath. For a falling height of 30 cm. the
waterproof value amounts to 21 drops.
What I claim is:
1. A method of simultaneously and uniformly
dyeing and waterproo?ng textile materials, com~ 10
prising treating said materials in usual alkaline
dyestu? bath containing. also a stable emulsion
of substantially. colorless water-repellent sub
stances and aluminium formate and a. substance
selected from a group consisting of tartaric acid 15
and tartrates, added for the purpose of convert
ing the aluminium salt into a complex compound;
2. The method of claim 1, as modi?ed in that
the “tartrate” recited therein is tartaric acid.
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