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Патент USA US2135151

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‘2,135,151,
UNITED STATES ‘PATENT OFFICE
Patented Nov. 1, 1938 .~
‘
2,135,151
METHOD OF MULTIPLE-COATING OR
'
FINISHING
\._.,Milton 0. Schnr, Berlin, N. H., assignor to Brown
. Company, 'Berlin
Maine
N. IL, a corporation of
’
No Drawing. Application May 23, 1936,
>
Serial No. v81,486
9 Claims. (01. si-ts)
blotchiness of surface. Evidently the rubber sol
This invention relates to a method of coating
or ?nishing involving more particularly the use
of a rubber latex coating composition of the sort
that isto be applied to sheet material or the
like a number’ of times and that is designed to
'dry smoothly and with‘proper amalgamation or
merger of the separately applied thicknesses.
.‘ While not limited thereto, the method of the
present invention may be applied advantageously
vent not only softens and swells the dispersed
rubber particles of the composition so as to tran‘s- .
form them to a stickier or tackier state, but
softens an already deposited dried layer of com 5
position so as to result in an autogenous weld
between layers, each layer being in effect an in
crement that contributes to the masking of sur
face blemishes on'the base being coated and to
the building up of an adequately thick wear 10
10 in ?nishing the surface of arti?cial leather base
or sheet material of the kind comprising. a ?brous resistant structure whose integrality is perhaps
base,
for instance, a felted ?brous base,‘ itself im ' bestshown by "the fact that under scu?’ or abrae.
pregnated
with rubber'latex- or similar rubber or ’
sion tests there is no observable tendency for
rubber-like composition and dried. Indeed, the ~ peeling
or separation between layers such as
1,5 method hereof has been found to be of great
from the serviceability of a coated 16,
vutility in ?nishing arti?cial leathers intended for woulddetract
arti?cial
leather
for such ‘uses, e. g. shoe upper
Such- exacting service as shoe-upper stock and
require high wet and dry scuff resistance‘.
comprising a rubber-impregnated web of felted stoc_k,~as
I shall now describe typical coatingv composi- '
?bers fabricated from re?ned wood pulps on ma- _ tions answering the purposes of my invention and
20
how they were prepared. It might be remarked 20
that the compositions about to be. described were
ture and evenness of surface;
,
prepared with a view toward being used in coat
I have found that an aqueous ‘coating composi
ing arti?cial leather of the general character dis
tion comprising water-dispersed rubber, such as’ closed
in my already-mentioned patent applica
25 rubber latex solids,and preferably also water
tion- Serial No.‘ 575,164. According to that ap—
soluble glue or other water-soluble, ?lm-forming plication,
arti?cial leather is made by impregnat
ing a ?brous base with rglycerinated latex and
then drying the impregnated base. Thatv ap
30 b
plication dwells in particular upon the use of a
soft, highly absorbent base such as is fabricated
_
_
composition lends ‘to an
on machinery of the ‘paper-making type from ?ber 30
arti?cialleather a surface reminiscent in many furnishes containing largely re?ned but substan
respects of the skin or, enamel side
of vnatural ~ ' tially unhydrated cellulose pulp, e. g. wood pulp
leather, particularly when it contains glue and of an alpha cellulose content of at least about
35 its glue content undergoes an after-tanning treat
93%. It further stresses the value of the glycer
ment with formaldehyde or other
‘
'
v
ine in developing the desired pliancy or mellow 35
agent that develops maximum wet scu?-resisiw ness [in the arti?cial leather without detracting
ance therein and when‘ it contains‘ glycerine as a from its toughness and other leather-like qualif
?exibilizing agent that imparts a mellow or pliant‘ ties.
When the coating compositions of the pres;
40 feel thereto as well asincreases its ?ex endurance ent invention are applied to such arti?cial leather,
and prevents migration thereinto ofsuclr glycer- .
ine as may have been introduced along with latex
solids into ‘the body of the arti?cial leather in
-45
the manner and for the purpose disclosed in my
application Serial No. 575,164, ?led November 14,
1931. I have further found that for the multiple
50
it is desirable to'introd‘uce glycerine thereinto for
the reasons already indicated. Here is the for— v
mula of a typical coating composition in terms
of its non-aqueous ingredients other than the
rubber-swelling agent:
'
_. Percent by weight
coating method hereof it is most desirable to
emulsify into the aqueous coating composition in. Rubber latex solids___________ __ _________ .. 72
a substantially non~separating state su?lcient Glue___~_________________________________ __ 16
water-immiscible but volatile rubber solvent to Glycerine ____________ __>_i _______________ __ 10 50
swell the dispersed rubber particles appreciably ' Remainder black dye, anti-oxidant and a wet
ting-out agent.
i
but short of inducing their coagulation. Through
such use of a rubber solvent in the composition,
The composition contains additionally 75% by
55 it is possible to gain such important bene?ts as . weight of toluol, based'onall of its non-aqueous
perfect ‘amalgamation orwelding or successive ingredients exclusive of the toluol. ' 'The total
55
coats even though each coat is substantially com~ water content of the ?nished composition may be
adjusted
so
that
it
contains
about
15%
by weight j
pletely dried before the next one is applied so as
- to avoid otherwise existing "running" tendencies
60 in the composition and atteudant'streakiness or
of all non-aqueous ingredients exclusive of the
toluol: In addition to the'advantages already
mentioned, it has been found that the composi
2
2,135,151
.
tion deposits smoothly on the arti?cial leather
‘possessing sufficient volatility to ‘be volatilized
with su?icient rapidity in a current of warm air..
In this connection, it might be noted that when
solve such greasy or other surface-‘resistant im- ' arti?cial leather is repeatedly coated with the
purities as would otherwise cause localized shed
composition of the present invention, it is re.
ding and thinning out of the aqueous composition. peatedly run through a closed chamber in which
The toluol also has a preservative effect on the currents of warm air are brought to play on each‘
composition, permitting the composition to be coating to dry it quickly so that a succeeding
kept longer without putrefaction than is other
coating may be applied thereover. Toluol not
wise the case.
only gives satisfactory results in the foregoing
In preparing the foregoing composition, it is coating practice, but is reasonably cheap, not too
10
preferable ?rst to deammoniate the usual am
hazardous from either a ?re or health standpoint,
' mania-preserved rubber latex of commerce used
and lends itself to‘easy emulsi?cation as herein
as a principal raw material. Otherwise the ad
before described. It is possible to reduce or in
dition of rubber solvent to the rubber latex may crease the amount of toluol in the compositions
cause'undue
thickening
and
subsequent
coagu
15
hereinbefore described but without any particular
lation to take place. Deammoniation of the latex bene?t. In any event, sufficient rubber solvent is
may be effected by aerating it until substantially used to swell the dispersed rubber particles ap
all of its ammonia content has been expelled. preciably but far short of inducing their coagula
Substantially complete deammoniation of the ~ tion. While the ratio between the rubber latex
20 latex may also be had with little danger of local
solids and water-soluble glue in the composition .
coagulation by the addition thereto of such mild is also subject to considerable variation, a com
acids as citric, oleic, lactic, oxalic, etc. However, positionv intended for coating arti?cial leather
deammoniation of the latex by aeration is prefer
preferably contains distinctly less glue than rub
able in that such practice avoids an infusion into ber latex solids and, correspondingly, contains
25 the latex of bodies that may be undesirable there» much less glycerine than rubber solvent.
in even in such small amount as attends substan
'Despite the fact that the coating compositions
base, probably because the toluol tends to dis
tial neutralization of the ammonia content of
used in the method hereof contain the very in
The glycerine, dye,- and anti-oxidant may be
gredients, namely,v rubber and rubber solvent that
go‘ to make the viscous and extremely sticky
ordinary ammonia-preservedlatex of commerce.’
30 mixed directly into the latex.‘ To this latex mix-' ‘ . mixtures or so-called rubber cements of the prior
ture is then added an aqueous solution of the glue’ art, they are very fluent and in no way resemble
containing stably emulsi?edtherein thetoluol,
a suitable wetting-out agent, such as “Nekal BX”,
a sodium salt of a naphthalene sulphonic acid
35 with side chains, preferably being present in
in outward appearance such rubber cements. It
might be observed that although the, glue in
gredient is primarily valued because of the quali
ties that it imparts to the dried coatings yielded
> slight amount to enhance the stability ofthe
by the coating composition of the present inven
emulsion. The desired emulsion of toluol in the tion, yet it serves additionally as a remarkably ef
aqueous glue solution may readily be prepared ?ci_ent emulsifying agent for the rubber solvent
by dissolving the glue and wetting-out agent in so that there is no tendency whatever for the _
40 water, raising it to a temperature of, say, about rubber solvent to separate out from the composi
100° F., and gradually adding the toluolto the tions. ' In using the term “glue" herein and in
solution with stirring. The emulsion is gradually the appended claims, it should be understood
added with gentle stirring to the latex mixture. that I mean to include albuminous substances,
The viscosity of the ?nal mixture slowly rises dur
such as blood albumen, ‘constituting equivalents
45 ing the ?rst hour or two as therubber particles
therein absorb and are swollen by the toluol and
of glue.‘
_
a.
' Ihave hereinbefore indicated that the glue con
then remains substantially constant.
tent of the coating composition is preferably in
Another typical coating composition useful in ’ solubilized or tanned in order tovacquire maxi
the method hereof has substantially the following
formula in terms of its non-aqueous ingredients
~ other than the rubber-swelling agent:
Per cent by weight
_ vRubber latex solids ____________________ .__ 66.2
Glue ____- ______ -__..__'.. ____________ __-_____ 14.5
55
Glycerine
Pigment_____
60
___ ‘
_
9.2
-__
9.27 .
Wetting-out agent _____________ ___ ____ __'___
0.5
Anti-oxidant _________________ _'_ ________ __
0.33
This composition also contains additionally ‘75%
by weight of toluol, based _ on all of its non
aqueous ingredients exclusive of the toluol; and
the concentration of all the ‘non-aqueous in
gredients other than the toluol in the ?nished
65
‘ composition is 15% by weight of the ?nished com
position. The composition may be prepared ad
mum wet scuff-resistance. To this end, afterthe ,.
successive coats of composition have'been dried
or set on the arti?cial leather base, the coated
base may be‘exposed to formaldehyde fumes or‘
vapors at elevated temperature, under which con
ditionsthe glue content of the successive coats
' is tanned or insolubilized.
If ‘desired, such ?lm-forming substances as
viscose, waterglass, water-soluble starches, etc.,
which are compatiblewith rubber latex, may be
used in lieu of, or together with, the water-in
soluble glue so as to develop the desired hardness
and smoothness in the layer or. coating deposited
from the compositions employed in the method ,
hereof. So, too, the method hereof might be em
ployed with the coating compositions hereof con
taining, in lieu of glycerine,'such equivalents'of
glycerine as ethylene glycol and other homo- .
blogues, glucose, etc., which function to plasticize
vantageously in the same way as the ?rst-named ‘ the protein and resin content of the rubber latex
and/or to soften the ?ber of the base to which
The formulae of the foregoing compositions are such compositions are applied and more especially
subject to considerable variation. Thus, the vola ‘ a rubber-impregnated,‘ ?brous base itself contain
tile rubbersolvent employed may be xylol, gaso
ing glycerine or other ?ber-softening agents that
line, benzol, or their equivalents. However, toluol impart thereto a'mellow or pliant feel and in
has worked out well in routine production because creased ?ex endurance, as hereinbefore described. 75
composition.
_
,
'
'
.
75 it is not too volatile at room temperature while
, ‘
~
‘
3
2,185,151
So far as concerns subject matter, this applica
tion'is a continuation-in-part of my application
Serial No. 759,801, filed December _29, 1934, now
Patent
‘No. 2,060,l29,~date_d Nov. 10, 1936.
5%.
I claim:
I
l. A method of smoothly coating a base which
comprises applying thereto as successive smooth
coats a very ?uent aqueous composition containing
ing water-dispersed rubber, water-soluble glue,
and su?icient water-immiscible but volatile rub- "
ber solvent to swell the dispersed rubber particles
appreciably but short of inducing their coagula
tion; and drying the coats and insolubilizing their
glue content; said rubber solvent not only swelling
the dispersed rubber particles and transforming
them to a stickier state but softening an already
water-dispersed rubberfand su?lcient water-im
applied and dried coat so as to ensure a 'non
10 miscible but volatile rubber solvent to swell the
dispersed rubber particles appreciably but-short of
inducing their coagulation; and developing a
smooth multiple coating substantially devoid of
streakiness and blotchiness by drying each coat
15 before a successive coatv is applied; said rubber
solvent not only swelling the dispersed rubber
peeling, autogenous weld or fusion between coats. 10
6. A method of smoothly coating a‘ rubber-im
pregnated ?brous base, which comprises applying
thereto as successive smooth coats a very ?uent
aqueous composition. comprising water-dispersed
rubber, water-soluble glue, a plasticizing agent ~15
for sa’d glue, and su?icient water-immiscible but
particles and transforming them to a stickier state
but softening an already applied and dried coat
volatile rubber so vent to swell the dispersed rub
ber particles ap reciably but short of inducing
20 fusion between coats.
..
their coagulation; and drying the coats and tan
2. A method of smoothly coating a base which tning their glue content; said rubber solvent not 20
comprises applying thereto as successive smooth’ * only swelling the dispersed rubberparticles and
transforming them to a stickier state'but soften-_
coats a very ?uent aqueous composition’ contain
ing water-dispersed-rubber and sufficient water ing an already applied and dried coat/so as to
ensure a non-‘peeling, autogenous weld or fusion
25 immiscible but volatile rubber solvent to swell the between
coats.
dispersed rubber particles appreciably but short
_7. A method of smoothly coating a glycerinated,~ 25
of inducing .their ‘coagulation; and developing a.
smooth multiple coating substantially devoid of rubber-impregnated ?ber base, which comprises
streakiness and blotchiness by drying each coat in applying thereto as‘ successive smooth coats "a
so as to ensure a non-peeling, autogenous weld or -
30 the presence of warm air before a successive coat
is applied; said rubber- solvent
the dispersed rubber particles
very ?uent aqueous composition containing water- '
dispersed rubber, glycerine, water-soluble glue,
and suilicient water-immiscible but volatile rub
them to a stickier state
applied and dried coat so as
so,
> ber solvent to swell the‘dispersed rubber par
_ ‘ ticles appreciably but short
of inducing their co.
35 peeling, autogenous weld or fusion between coats. . agulation; and drying the successive coats ‘and
3. A method of smoothly coating a base which
comprises applying thereto as
'
tanning their glue content; said rubber solvent
not only swelling the dispersed‘ rubberparticles
as
and transforming them to a stickier state but
softening an already applied and driedjcoat so as
coats a very ?uent aqueous composition contain
ing water-dispersed rubber, a water-soluble, ?lm
to ensure‘ a non-peeling, autogenous weld or
40 forming substance compatible with the water
dispersed rubber and capable of developing hard
fusion between coats.
ness and smoothness in said coats, and su?lcient
"
"
8. In- a method that involves applying a'very 40
\?uent aqueous composition containing water
dispersed rubber as a succession of smooth coat
45
‘but short of inducing their coagulation; and de
veloping a smooth multiple coating substantially
ings and drying the'composition between the suc
cessive coatings, the practice of preventing, the
peeling of the successive coatings which coni 45
prises‘ adding a water-immiscible but volatile rub
ber~swelling agent to such aqueous composition
containing the water-dispersed rubber in amount
to swell the dispersed rubber particles appreciably
but short of‘inducing their coagulation, said rube
togenous weld or fusion between coats.
55
.
ber-swelling agent not only swelling the dispersed
4. A method of smoothly. coating a base which rubber particles and transforming them to _ a
comprises applying thereto assuccessive smooth "_stickier state but softening a previously‘ applied
coating so as to ensure a _nonepeeling, autog
55
enous weld or fusiont betweenv coatings.
v
- 9. In a method that involves applying a very
?uent aqueous composition containing water
. dispersed rubber and water-soluble glue-as a suc
cession of smooth coatings and drying the com
position between the successive coatings, the prac
tice of preventing the peeling of the successive
coatings, which comprises including in said com
position in emulsi?ed form stabilized at least in
65
vpart by theglue'content of said composition a
water~immiscible - but volatile
rubber-swelling
agent in amount to swell the dispersed rubber
70
to ensure a non-peeling, autogenous weld or fusion
between coats.
-
particles appreciably but short of inducing their
coagulation, said rubber-swelling agent not only
swelling the dispersed rubber particles and trans
‘ forming them to a
-
70
stickier state but softening a -
5. A method of smoothly-‘coating a base, which’ previously applied coating so as to ensure a non
comprises applying thereto as‘ successive smooth peeling, autogenous weld or’ fusion between
coatings.
. coats a very ?uent aqueous'composition compris
MILTON O.
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