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2,094,171

Patented Oct. 5, 1937.

UNITED STATES PATENT "OFFICE


_

2,094,711

COMPOSITION or MATTER
William Hale Charch', Buffalo, and Albert Hersh
berger, Kenmore, N. Y., assignors, by mesne as

signments, to E. I. du Pont de Nemours & Com- I


pany, Wilmington, Del., a corporation of Del
aware

'

No Drawing. Application February 24, 1934


Serial No. 712,793

(Cl. 134-79)
(4) Wax, cellulose derivativaresin or blend
This invention relates to moistureproof ma
terials and more particularly to a. composition ing agent, andsolvent.
As the- wax, a para?in wax having a melting
which will deposit a glass-clear, ?exible and
point between 50 C. and 60 C., and preferably
1 Claim.

moistureproof coating.

Prior to this invention, in order to produce

over 60 C., is preferred. Other waxes, such as

glass-clear andmoistureproof regenerated cellu beeswax, candelilla wax, bayberry, spermaceti


lose sheeting, the base regenerated cellulose and Montan wax may also be used. In some in
sheeting was coated with compositions containing
a minor portion' of a wax or waxy substance.

When a lacquer containing nitrocellulose wasl


. employed for the moistureproo?ng, the wax was

present in an amount less than 10% of the total


solids. According to the prior art, if the wax
in nitrocellulose lacquers were p' ssent in amounts
greater than 10% of the total solids, the coating
would have an undesirable wax blush or haze

which impaired the glass-clear transparency of


the coated ?lm.

'

Contrary to, the teachings of the prior art, we


20 have found that we can prepare glass-clear, trans

stances two or more waxes may be used in the

combination. For instance, when candelilla wax

is used conjointly with para?in wax, there results 10


a surface which is less susceptible to ?nger marks.
In other words, candelilla wax serves to impart a

hardness to the ultimate coating. Spermaceti


wax acts as a blending agent for paraf?nywith
pyroxylin. Certain synthetic waxes or wax-like 15
materials or esters obtained. chemically from
higher valcohols and acids, such as montanic acid
ester of lauryl alcohol, may be used.

As the cellulose derivative, a pyroxylin having


a high viscosity, such as 200 to 400 seconds and

20 .

- speci?cally of the order of 300 seconds, is pre- '

parent, moistureproof coatings from nitrocellu

lose lacquers, the solids of which contain wax in

ferred. -However, a pyroxylin of di?erent vis


cosity, such' as from one-half second up to one

excess of the cellulose nitrate and/or 50% or ' thousand seconds or more, may be used. It is ad
more of wax.

It is, therefore, an object of this invention to


provide a nitrocellulose lacquer, the solids of
which contain wax in excess of the cellulose

nitrate and/or 50% or more of wax, which will

deposit glass-clear, moistureproof, ?exible ?lms


30 or coatings upon the evaporation of'the solvent

at a temperature at least equal to the melting

\ point of the wax in the composition.

Another object of this invention is to provide

a moistureproof material, preferably glass-clear

vantageousto use a soluble pyroxylin of moder

ately high viscosity to give the coating composi


tion suf?cient body for satisfactory coating. 'In
so far as the nitrogen content of the nitrocellulose

is concerned it may be that which is ordinarily


used in lacquer grade nitrocelluloses. Though I
pyroxylin of the type above mentioned is pre
ferred, it is also possible to use other cellulose
derivatives such as higher cellulose esters, cellu- .

lose ethers or. mixed esters.

'In those compositions including a plasticizer, it


is possible to use 2~methyl-hexa-hydro-benzyl
comprising a transparent base thinly coated with phthalate or most of the common pyroxylin plas
a lacquer composition, the solids of which contain
ticizers, such as dibutyl phthalate, tricresyl phos
wax in_ excess of cellulose nitrate and/or 50% phate, etc. Certain plasticizers may function both
or more of wax.
.
'
,
as plasticizer and blending agent for the wax and 40
Other objects will appear from the following the
40
cellulose derivative. Dixylylethane isillus
and suitable'for use as a wrapping tissue, and

_ description and appended claim.

As is apparent from the foregoing objects, the


instant invention in one of its speci?c phases
relates 'to a composition, hereafter 'more fully
explained, the solids of which contain wax and
cellulose nitrate, the wax being in excess of the

quantity of the nitrocellulose present and/ or 50%


or more of said solidsand which will deposit a

moistureproof, glass-clear coating or film upon

the evaporation of the solvent at an-velevated


temperature.

In general, the compositions to which the in


stant invention relate may be classified into .four
classes, the constituents of which consist of the
following:

, .

.,.-. (l), Wax, cellulose derivative and solvent; .

(2)Wax, cellulose derivative, plastlcizer and


solvent;

(3,),QWa'X, cellulose derivative, plasticizer, resin


Y
60 or bike, 'ding agent, and solvent;

trative of such a material which so functions

when the cellulose derivative is ethyl cellulose.


When the composition is of the type which
includes them, any resin or blending agent com 45
patible with the cellulose derivativeand the wax
may be used. Those resins which act as blend
ing agents for the wax and the cellulose deriva
tive and which impart a hard, non-greasy sur
face to the coating are especially desirable. As 50

several illustrative examples of the especially suit


ed resins may bementioned rosin and its esters,v

hydrogenated rosin, esters of hydrogenated rosin


and also synthetic resins, such as are sold under
the trade names Albertols and Amberols. .

The solvent employed in the composition is very

important, since it determines whether the coat


ing or ?lm will be clear or hazy. As the solvent,
a solvent for' pyroxylin, which is also at once an

active solvent for the wax, is preferred. Prefer

55

2,094,771

ably, the solvent is one which boils at 80 C. or


100 C. or higher. This solvent is further gen

hereafter in any suitable and convenient man

ner, such as dipping, spraying, etc. i' The excess


' erally characterized by being completely miscible ' composition is removed in any suitable manner,

in all proportions with the waxy constituent of


the solids at a temperature higher than the melt
ing point of the wax in the composition. In ad
dition, such solvent should possess the property
of dissolving considerable amounts of wax even

at temperatures appreciably lower than the melt


10 ing point of the wax, such as 10 C. or 20 C. lower,
or, in- certain cases, still lower.- Av convenient

criterion for classifying the pyroxylin solvent


"femployed is as follows:

'

A 2% solution of para?in wax melting at ap


15 proximately 60" C. to 62 C. is prepared in the

solvent at a temperature above the melting point

such as by means of scraper rods, doctor knives

or doctor rolls, and preferably, either heated doc


tor rods or heated doctor knives. The coated
sheets are then transferred to a drier, the tem

perature of which'is held at approximately


80 C.-120 C. After drying, the coated material
may be given a humidifylng treatment, whereby
the residual solvents are removed, and also a suit

10.

able amount of moisture is introduced into the


base sheet.

The compositions are to be ap', Led to the base

in a relatively thin coating. The total coating

thickness on both sides of the base ?lm may 15

of the wax. This solution is then allowed to cool ' range from approximately 0.00001 to 0.00010 of

gradually and the temperature at which the wax an inch, although, in certain special instances,
begins to crystallize is noted. If the tempera -it may be possible to use coatings of somewhat
20 ture at which the wax begins to crystallize lies greater thickness. When the solids oi the com
above 50 C. and solvent, in general will not be _ position consist of a mixture of wax and nitro 20
suitable for the herein described purpose. 0n cellulose, the coating thickness should generally
the other hand, if the temperature of crystalliza
be less than the coating thickness used when the
tion lies under 50 C. the solvent in general will composition also contains a blending agent and
be found to be suitable. By the same test it should generally approach the lower limits of
25
has also been found that the lower the tempera
the thickness range above set forth.
ture of crystallization of the wax from such a
The compositions herein described are particu
solution, the more e?ective will be the solvent for larly suitable for application to a transparent
the herein described purpose. For instance, cer
sheeting base, such'as regenerated cellulose,-gly
30 tain very effective solvents when submitted to the
col cellulose, casein, gelatin, cellulose acetate, etc. 30
above test retain the wax in solution at tempera
They may also be used onpapers, such as glass
tures as low as 40C. or even lower.
ine or other smooth, semi-transparent papers.
Several illustrative solvents which have given It is to be understood that the solvents of the

satisfactory results'are the higher boiling sol

applied composition will be selected so as not to

butyl butyrate, acetone oil, monobutyl ether of

deleteriously affect the base to which it is applied. 35

35 vents, such as amyl acetate or higher amtates,

ethylene glycol, methyl butyl ketone, beta ethoxy


ethyl acetate and cyclohexanone.
As above explained, the aforementioned sol
310 vents may be'used alone, that is, without the

addition of any other solvent material or diluent.

When the process is carried out as hereinbe

fore described, the product is moistureproof,


?exible, non-tacky, odorless and, when the base
is transparent, the ?nal product is also trans
parent.

40
For the purposes of this speci?cation and '

However, they may be used with other suitable .claim, we de?ne moistureproof materials as those
solvents 'of similar nature or they may be used which, in the form of continuous, unbroken
with hydrocarbon diluents, such as toluol, benzol,
45 etc., provided such diluents are not present in ' sheets or ?lms, permit the passage of not more
than 690 grams of water vapor per 100 square 45
such large quantities as would cause the precipi
meters per hour, over a period of 24 hours, at
tation of thenitrocellulose during the'evapora
approximately 39.5" C.i0.5 C., the relative hu
tion of the solvent. In general, the use in any midity of the atmosphere at one side of the ?lm
solvent mixture of appreciable quantities of sol
being maintained at least at 98% and the rela
vents which are not active para?in solvents. such tive humidity of the atmosphere at the other side
as alcohol, acetone, etc., is to be avoided. Small being maintained at such a value as to give a
quantities of these materials, however, may be humidity differential of at least 95%.
> .
present without deleterious e?ect. For example,
Moistureproo?ng-coating compositions are de
alcohol should not'bepr'esent in an amount of
55 more than 15%. Generally, if alcohol is used, it ?ned as those which, when laid down in the form
a thin, continuous? unbroken ?lm applied uni
should be present in an amount less than 10%, of
formly as a coating with a total coating thick
and preferably 1% or less. A preferred solvent ness not exceeding 0.0005" to both sides of a
-mixture consists of pyroxylin solvent of the type sheet of regenerated cellulose of thickness ap
described, with or without small quantities of
60 alcohol, and a hydrocarbon diluent, preferably an proximately 0'.0009", will produce a coated prod
uct which is moistureproof.
aromatic hydrocarbon diluent or chlorinated ali
For the purposes of experimental tests, espe
phatic hydrocarbon solvent, and the said diluent cially
for those materials adaptable as coating
being present in quantities insu?lcient to cause compositions,
moistureproof materials include
the precipitation of the nitrocellulose during those substances,
compounds or compositions
evaporation of the solvent.
In- all cases the ingredients of the solvent are
of such a nature as to. maintain all the solid
. ingredients in solution until substantially all the

70

solvents have been evaporated.


The solids content of the coating composition
may vary between 2% and 20% by weight. How
ever, 5% to 10% solids content gives very good
results.

"

The composition hereinbefore described is ap


75 plied to a'base of the type more fully explained

' which, when laid down in the form of a continu

ous, unbroken ?lm applied uniformly as a coat

ing, with a total coating thickness not exceeding


0.0005" to both sides of a sheet of regenerated

vcellulose of thickness approximately 0.0009", will


produce a coated sheet which will permit the pas 70
sage therethrough of not more than 690 grams of
water vapor per'100 square meters per hour over
a period of approximately 24 hours, at a tempera

ture of 39.5 0.10.5 C. (preferably 39.5 C.:0.25

6.), with a water vapor pressure di?eren

2,094,771
tial of 50455 mm. (preferably 534:0.7 mm.) of
mercury. For convenience, the number of grams
of water vapor passed under these conditions may
be referred to as the permeability value." An
uncoated sheet of regenerated cellulose having a
thickness of approximately 0.0009" will show a

permeability valuaof the order of 6900.

coating composition is the same as that described


under 1(a) .

The coating thickness is about

0.00001 0! an inch. The coated sheet is ?exible,

non-tacky, and glass-clear. The coating has the


same surface properties as Example 1(a). \_\J 5
h

'

Parts by weight

(c) Parafiln wax (M. P. 48,C.-50 C.) _____

8.0

From the foregoing, it is apparent that under

Pyroxylin (283 seconds) _'_, ________ __

2.0

the conditions set forth, a moistureproofed re


. generated cellulose sheet is capable of resisting

Amyl acetate ______ __'.._-_ ____ _'_ _____ __

123.5

Alcohol __________ _; ____ ____ ________ __

20.0

Toluol ____________________ __. ______ __

4775

the passage of moisture 'orwater vapor there


through at least ten times as eifectively as the

uncoated regenerated cellulose sheet.


In order to more clearly explain the nature of
the invention, the following speci?c examples are
set forth:

The process for application and the properties


of the sheet are the same as those described in
Example 1(a).

'

15

The method oi application and the properties

Parts by weight
(a) Paramn wax (M. P. so" C.-62 c.)__-___ 7.5
Pyroxylin (283 seconds) .. ___________ __

2.5

Ethyl

1.11

alcohol....___\________________ __

?n wax of Example I(e).

Example I'-Wax'-pyro:nylin composition

Acetic acid esters of high molecular _


weight synthetic alcohols (B. P.

'

v p (J!) White beeswaxis substitutedfor the paraf

of the ?nished sheet are approximately the same


as those described under Example1(a) .

2,0.

(g) Candelilla wax is substituted for the paraf


fin wax of Formula 1(e) .

This sheet is glossy, clear and non-smearing.

(h) Montan wax is substituted for the paraf

?n wax of Formula 1(a).


I The sheet is glossy, clear and non-smearing.

140 C.-180 C.) __________ .._' _____ __._189.0

25

A sheet of regenerated cellulose, or other trans


.
'
Parts by weight
parentumaterial, is dipped into this solution and - (i) Paramn wax (M. P. 60_ (3.432 C.) ____ 7.5
the excess coating composition removed by any .
Pyroxylin (283 seconds) ____ __' ______ .4 4 2.5
suitable means, such as by means of scraper rods,
doctor knives, or doctor rolls. The coated sheets
are transferred to a drier, the temperature of

Iloiuol ________ _-i __________________ __

which is held at approximately 100 C. to 120 C.


After the .sheet is thoroughly dry, which may re
quire anywhere from 30 secondslto 3 minutes, it
vi may either be removed or it may be subjected to
a humidifying step. The humidifying step re

Example II-Wax-pyro:cylin-resin
. Parts by weight 40
(a) Paramn; wax (M. P. 60 C.-62 C.)_...._ . 7.5

The'total coating on both sides of the sheet


- should preferably not exceed 0.00004-0.00005 of
,an inch. The coated sheet is glass-clear, ?exi

Pyroxylin

' 2.5.

1.0

Alcohol _____________ __-____. ________ __

20.0

The method 01' applying the coating composition

123.5

and drying the coated sheet are the same as de

19.0

scribed under 1(a) . The coated and dried sheet

Low ?ash naphtha____.'. ___________ __-___..\ 47.5

is ?exible, non-tacky and glass-clear. The coat


ing thickness (both sides) may be about

The method lofapplying the coating and dry


ing is the same as in I(a). The properties of the
coated sheet are also the same as given in 1(a).

0.00005-000006 of an inch.

'

(0) Para?in wax (M. P. 60 C.62 c.)____ _ 7.5

(b) Amberol, grade 38-1, is substituted for


the hydrogenated rosin in Example 11(a). The
resulting coated sheet is transparent, ?exible and

non-tacky.-

Parts by weight
Spermaceti wax ______ -1 ___________ __

2.0

Pyroxylin (283 seconds) ___________ ____

2.5 I

Alcnh'nl

(Note: Spermaceti is used here as a blending

(d) Para?in wax (M. P. 60 (L-62 C.)'____

9.0

Pyroxylin (283 seconds) ______ _..'_____

1.0

1,7

~ The coating composition is applied and dried


as previously described. The coating thickness
is approximately about. 0.00001 of an inch. The

the same as those described under 1(a). ~

3.0

Methyl butyl ketone'__'_-.. ___________ __ 195.0

Low ?ash naphtha ________________ __ 50.0

'
Parts byweight

6.0
4.0 60

W Rosin

20.0

The process for applying the coating composi


tion and the properties of the ?nished sheets are
agent.)

Parts by weight

(c) Para?ln wax (M. P. 60 C.-62 C.)____


Pyroxylin

140 C.-180 C.) _____- ____________ __ 125.0

does not smear when handled.

Parts by weight

(d) Paraffin wax (M. P. 60 C.-62 C.)____


Pyroxylin

'

5.0

W rosin ______________ _,____-______

Amyl acetate ____________ ..; ________ __ 123.5

Low ?ash naphtha ________________ __

20.0

47.5

70

5.0

Alcohol-

VI ' The method of application and drying of the

as

coated sheet is non-tacky, ?exible, glass-clear and

Amyl acetate______ .._- ______________ __ 123.5

55

'

Acetic acid esters of high molecular


weight synthetic alcohols (B. P.
Alcohol __________________ _.. _______ __

45

Toluol ____________________________ ___. v4.7.5

Parts by weight

Alcohol ____________________ _._'_________ __

____

rosin _______________ __

Amyl acetate7 _________________ _'..___ 123.5

(b) The above solids may be used with the fol

m1 acetate

_____

Hydrogenated

ble, non-taclw and moistureproof.


.

2.0

The spermaceti wax in this formula acts in the


capacity of a blending agent. The coating thick 35
ness is about 0.00001 of an inch. The resulting
sheet is ?exible, non-tacky and vglass-clear. '

' "

lowing solvent composition:

78.0

Alcohol ____________________________ __

moves traces of residual solvents and also incor


porates a suitable amount of moisture into the
base sheet.

2.0 30

Spermaceti wax ______________ _;____..

Ethcxy ethylacetate _______________ __ 117.0

4.0

Almmhnl

201)

Toluol

47.5 75

v4.

2,094,771

The coating composition is applied and dried

Example IV-Waz-mroxylimresin-plasticizer

gn'pgigigilsgndescribed. The properties are the


'

'

'

Parts by weight

Pyroxylin (283 seconds) ____________ __

2.5

A W

1,0.
L0

Tricresyl phosphatef -------- -/.---2-O


Methyl butyl ketone_.__' _______ __'__-_ 200.0

123.5

main

'

Alpnhn]

2'0

Alcohol; _____________________ -__--.-_

20-0

The coating is applied and dried as previously

Low ?ash naphtha ________________ __

47.5

described. The product is ?exible, non-tacky

The coating composition is applied. and dried

as previously described. The coating thickness


may
be from 0.00005 to 0.00006 of an inch. The
15 properties are the same as 11(a) . '

and glass-clear, and the surface'is substantially


non-smearing.

*\

to abrasion.

'

'

Since it is obvious that various changes and


modi?cations may be made in the above descrip

7.5

Pyroxylin (283 seconds).7 __________ __ g


Dixylyl ethane ________ ____ _____ _;___-

Formula IV(a) with the result that a slightly


harder coat is obtained which is more resistant

Parts by weight

(a) Para?lnwax (M. P. 60 C.62 C.) _..__

(b) 2 grams or candelilla wax are added to

Example IIIWa:c-py'ro:cylin-plasticizer
2.5
2.0

tion without departing from the nature or spirit

Butyl acetate"; __________ __' ____ __'__ 117.0

thereof, this invention is not restricted thereto

Toluol ____________________________ __

78.0

except as set forth in the appended claim.

A1Coh01-__r______________ __'________ .._.

2.0

The coating composition is applied and dried


as previously described. The coating thickness
is of the order of 0.00001 to 0.00004 of an inch.

30

Parts by weight
(b) Paramn wax (M. P. 60 C.-62 C.) ___

7.5

Pyroxylin (283 seconds) ___________ __

2.5

2 ~ Methyl - hexa - hydro - benzyl -

'

phthalate ________ ..._ _____________ __

2.0

Acetic acid esters of.high molecular


weight synthetic alcohols (B. P.
140 C.-l80 C.) _________________ ..- 123.5
Alcohol _____________________ __' ____ __

20.0

Low ?ash naphtha....__e ___________ -4 v

47.5

The coating and drying is the same as pre


viously described.

The ultimate sheet is ?ex

ible, non-tacky and transparent.

We

claim:

'

'

"

A liquid coating composition consisting essen

tially of the.following ingredients and approxi


mate proportions by weight:
. .-

The properties are the same as II(a) .

4.0

3-8

7.5

Amyl acetate

25

6.0

Pymxylm ---------------- -,,-----

(e) Para?ln wax (M. P. 60 C.-62 c.)____


Hydrogenated rosin ________________ __
.Candemla wax ____________________ __

20

Parts by weight

(a) Para?ln wax (M. P. 60 Chi-62 C.) ____

>
'

Parts by weight

Parailin (M. P. 60 C.-62 C.) _..;__' ____ __

- 7.5

Pyroxylin _____________________ __ ______ _-

Hydrogenated

Amyl

_/ 1.0

acetate ____ _'_ ____________ _.'. _____ __

123.5

Alcohol _______ __

Tolunl

2.5

rosin ________ __' ____ ..v___..__

20.0

__'I._-..

V 47.5

said composition depositing a glass-clear, ?ex


ible, moistureproof coating uponvthe evapora
tion of the solvent at a temperature at least equal
to the melting point of the wax in the composi

tion.
WILLIAM HALE CHARCH.

ALBERT HERSHBERGER.