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Патент USA US2137995

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Patented Nov.
1938’v
-
2,137,995, '
UNI-TED s'r-A'rss jliATENTp OFFICE
2,131,995
, ORGANIC‘ PRODUCT AND PROCESS OF:
'
‘
'
MAKING THE SAME
'
Allen
The D.
Mantle
Whipple,
LampAlexandria,
Company of
Ind.,
America,
aasignor
Chi
cago, I_ii.,'a corporation ofilllnois
.
No Drawing. Application November 30, 1931,
Serial No. 578,191 ,
3 Claims.
(01. 134-69)
,
which requires the application of a less‘ number
of coats to form a deposited ?lm of desired thick
ness, than would otherwise be required.
Wherever in this speci?cation, the terms cel
5 ing materials wherein these synthetic coating lulose nitrate, nitro-cellulose, and pyroxylin are
compositions dissolved by, dispersed in, and com-' used, they should be construed as being synony
,
bined with cellulose esters, impart certain new mous.
As a basis for illustrating the novelty and
and useful characteristics to the lacquers and
This invention relates to synthetic substances,
coating and molding compositionalacquers and
enamels, and ?lms and objects made therefrom,
and particularly to lacquers, enamels, and mold
enamels and molding compounds and to the
m ?lms and objects made therefrom, all as more
particularly hereinafter described.
The invention has as an object, the produc
tion of new synthetic substances of practically
zero volatility at ordinary temperatures, which
15 in, and of themselves combine in a, single ma
terial, many of the properties of resins, gums,
and also solvent softeners of the class which have
come to be known in the plastics and surface
coating industry as plasticizers.
99
.
Another object of the invention is the pro
duction of synthetic lacquers and enamel com
desirability of my invention, in so far as its abil
ity to modify the properties of solutions of cellu- m
lose esters and particularly cellulose nitrate is
concerned, a shortnarration of the development ,
of the use of plasticizing and molding composi
tions is given.
_
_
'
‘
Cellulose nitrate in solution in ether and al- 15
cohol, was used at an early date under the name -
of collodion as a coating to form ‘a protective
sheath over cuts and scratches. The ?lm puck
ered and contracted on drying. For most pur
poses, this property was undesirable by reason st
of its contraction, and its tendency to peel 0d.
'
Tov overcome this fault, various materials such as
positions having the properties of ‘depositing vcamphor,
Canada Balsam, and castor oil were
' ‘?lms and protective coatings possessing the .
incorporated in the collodion, and the ?exible ,
characteristics of great transparency, in, clear collodion of the Pharmacopoeia resulted.
%
291 coatings, of great adhesion to surfaces to be coat
when cellulose nitrate solutions, also'known as
ed, great fullness and body, great permanence of pyroxylin solutions, began to be‘ used for other
lustre, great durability, great‘ resistance to the purposes, the same diillculty was encountered.
3
destructive in?uences of water, light, and weath
er, great toughness and ?exibility, and of being
non-shrinking, and after having been thorough
ly dried, being very resistant to re-psolution and
attack, even by the usual lacquer solvents;
A further object of the invention is to provide
35 such compositions wherein the total content of
solids exclusive of pigments, may be so increased
by additions of the new synthetic substances
herein described, as to give fullness to the ?lms
deposited from lacquers when they have ‘been.
40 thinned down to a viscosity suitable for spraying
or dipping (between 100 and 300 'centipois'es as
The coating bridged away from irregularities of " r
the coated surface, or was too brittle for use on
supple material like leather, or could not endure’,
the warping of woods to which it was applied.
Plasticizers were essential to modify the proper-
ties of- the cellulose nitrate. The literature of the
pyroxylin industry is cumbered with literally ~35
hundreds of compounds that are considered ef
?cacious for that purpose. Of these, only a dozen
or so are of any present practical importance.
‘ The early celluloid lacquers used the camphor
present in celluloid as the plasticizer. It was in ‘40
a measure effective, but in time, they camphor
measured by the Stormer viscometer at 28° (3.),
volatilized and disappeared and the ?lm became
without the necessity of resorting to the use of
brittle.
45 those cellulose esters previously used for. this
,
I Various drying oils, such as linseed oil, have 45
purpose, which have certain speci?c low‘ viscose , been incorporated in ' pyroxylin solutions, but
since these ‘materials absorb oxygen from the
A further object of the invention ‘is to provide ' air, and polymerize to hard resinous bodies, their
ity characteristics.
Properly plasticized synthetic molding composi» incorporation in pyroxylin solutions which dry
almost entirely by evaporation of solvents, was 59
5o tions.
Other objects of my invention will be appar—
eat as the following description proceeds.
detrimental, ‘and'caused the ?lm to ‘become brit
'tle in a short time.
p
"
,
Non-drying oils gave better results, and castor
oil may beused to illustrate this class of mate
55 “5?: as an ingredient for lacquers. ‘
i
1‘ or enamel having “fullness” is one rials. It is slowdrying, but has the undesirable “
Cellulose nitrate is a cellulose ester commonly
2
2,137,995
habit of making the ?lm too soft.if_.used in
slight excess. Under the in?uence of moderate
heating, it exudes from the coating and the ni
tro-cellulosev ?lm becomes brittle.
Triphenyl phosphate, tricresyl phosphate and
dibutyl phthalate have all been considered use
ful as plasticizers, and have been used as sub
stitutes for camphor, but they all have de?nite
rates of volatilization, and since pyroxylin ?lms
10 deposited with this class of’ plasticizers are plas
tic only by reason-of being very concentrated
solutions, it is evident that as soon as the solvent
has volatilized, the original brittleness of the cel
lulose nitrate asserts itself.
15
'
Practically all lacquers and enamels include
certain amounts of resin. There are several
‘reasons for their inclusion therein. They in
crease the solid content in, the lacquer and en
amels, without raising the viscosity of the solu
20 tion as rapidly as would be the'case if cellulose
nitrate alone were used to produce the solid con
tent of the coating. A high total solids content
gives fullness to the ?lm. Resins also enhance
the gloss ‘of the ?lm deposited from cellulose
nitrate lacquers. Resins also promote the ad
hesion of the lacquer ?lms to surfaces. Resins
are incorporated in lacquers and enamels for the
further purpose of rendering the deposited coat—
ings more or less resistant to water. Heretofore,
30 clear pyroxylin lacquers have found only lim
ited application out of doors by reason of the
_ fact that the short wave lengths of sunlight de
strength and durability in the high-‘viscosity
nitro-cotton.
‘
Certain ?elds of the surface coating industry
have heretofore been largely beyond the reach
of the lacquer and enamel‘ industry by reason 5
of the physical limitations of the lacquers and
enamels of the prior-art. Some of these ?elds
are house paints, railroad and steamship paints,
household paints, varnishes, and enamels usual
ly sold to householders in cans, and intended to 10
be applied to surfaces by means of a brush.
There existed several obstacles to the success
of those brushing lacquers. They had to possess.
a ?owing quality that enabled the user to brush,
cross brush, and lap without leaving ridges or
. brush marks.
'
By the use of alcohols, such as ansol, and
.hexalin, together with higher esters such as
butyl propionate, combined with low viscosity
pyroxylin, and‘the old plasticizers of the prior 20
art, lacquers have been produced that could be
reasonably well applied by means of brushing.
These prior-art brushing lacquers and- en
amels, however, possessed several faults that
have limited their use, although they have been 25
applied to small work such as shelves, chairs,
'and toys with fairly satisfactory results. The
lack of ability of these lacquers and enamels of
the prior-art to withstand the destructive ef
fects of sunlight and the weather, and the fur 30
ther facts that in multiple-coat-work, the ?rst
and succeeding coats were not inert to the sol
stroy the-?lms too quickly by_brin_ging about the
types of failure known as chalking, alligatorlng,
the degraded cellulose of the low-viscosity nitro
amels of the prior-art. depend upon the inclu
cotton did not provide the wear resistance de 35
sired, nor the ability to resist those types of
35 checking or peeling. Pigmented lacquers or en
sion of ?nely-divided ‘pigments to protect the
film from the destructive e?‘ects of light by ab
sorbing the harmful rays of short wave length.
In the manufacture of nitro-cellulose lacquers
and enamels, prior to the discovery of such low
. viscosity nitro-cellulose as that described by‘
vents contained in the following coats, and that
failure of surface coatings known as chalking,
alligatoring, and loss of lustre, prevented these
prior-art lacquers and enamels from realizing
the full scope of useful application that their
quick drying qualities would otherwise have made 40
possible.
several inventors, it was not practicable to make
_
The desideratum, therefore, has been the dis
solutions having a nitro-cellulose content, which,
covery of a means whereby spraying and dipping
after thinning to the extent required for use as
'a dipping or spraying lacquer, namely, 100 to
lacquers and enamels containing the strong,
tough, and relatively stable high viscosity nitro
cotton, and retaining all of the good properties
300 centipoises as measured by the Stormer
viscometer at 28° 0., was of more than about’
6%, since with ordinary nitro-cellulose, more
50 than this proportion rendered the solution too
.55
‘
45
enumerated elsewhere in this speci?cation, can
be
manufactured.
'
'
Cellulose esters, and particularly cellulose
viscous. Moreover, in the presence of this maxi - nitrates, are subject to continued polymerization
mum‘ amount of nitro-cellulose, the proportion after manufacture. They slowly and spontane
of the gum used to promote gloss and adhesion, ously change their physical properties with time.
had to be comparatively low, so that, as a rule, Amongst the properties which change, is solu
>
‘it was necessary to limit the total solids content bility.
of these old lacquers and enamels exclusive of
Plasticizers of the prior-art may be divided
pigment when thinned’ to spraying “viscosity,
into three classes.
namely, 100 to 300 centipoises as described above,
(11) Those, like camphor, triphenyl phosphate
and tricresyl phosphate, which possesses some
to‘With
less than
the 13%.
advent of the low-viscosity cotton,
described by Pitman, and others, it became pos
sible to increase the total solids content of
lacquer and enamels, exclusive of pigments,
I
solvent properties for nitro-cellulose before it
has polymerized to such an extent as to be
no longer soluble. These plasticizers have slow
rates of evaporation, and are fugitive con
stituentsf-of the lacquers, enamels and mold
ing compounds in which they are incorpo 65
rated.
_
,
tained oxy-cellulose, and hydro-cellulose, and (b) Those known as drying oils, like linseed oil,
which have'no solvent properties for cellulose
their nitrates in high percentage. As a con
70 sequence, they were unstable, and of poor tensile , esters, but which gradually take up and com
bine with oxygen from the air, and in so
strength. The conditions under which low
doing, resinify. Invtime, the ?lms deposited
viscosity cotton- is made, favor the breaking down
from lacquers and enamels plasticized with
of the cellulose molecule and the degradation
this class of materials, become hard and brit
of ' the cellulose, and lead to a general conces
tle, and in consequence, of little protective
sion by the lacquer trade that there is greater
v?lue.
'
to amarked degree, but in so .doing, the ability
to increase the gum contents was not materially
increased. Also, the low viscosity cotton, con
2,187,995
3.’
_
and permanently-plastic material, is a
(c) Those materials which maybe represented - adhesive
sticky semi-solid, which, at ordinary tempera- ‘ by eastor oil, and which are known as non
tures,.will slowly ?ow. It has no boiling point
.drying oils. These, like class (D) have no sol
vent properties for-cellulose esters. They are
and is'st'able up to the point at which chemical
dissociation begins. Itis insoluble in petroleum
capable of being colloidally dispersed in solu
tions of cellulose esters by reason of their
being miscible with the solvents of lacquer
and enamel, and, by their presence among and
between the particles of cellulose ester, lu
10
.15
or coal tar distillates or other hydrocarbons.‘
This material may be regarded as a solvent sof
tener for nitro-cellulose or nitro-cellulose may
be regarded as a solvent hardener for this new
synthetic material. By putting this new syn
into solution along with nitroé
bricate, and'seem to soften the films deposited
from lacquers and enamels in which they are
incorporated, so long as enough solvent _re
mains to keep them dispersed. When the
true solvents, all of which are fugitive, have
, thetic material
cellulose, a molecular dispersion of one in the
other throughout the mass is e?ectuated, and,
if the volatile solvents should disappear from
the lacquer, enamel or molding compound, there
will remain a composite, non-volatile, perms-4
disappeared, these non-adhesive plasticizers
are squeezed out by the contraction of the
unplasticized ?lm, and exude so that they may
be wiped from the surface. Heat rapidly ex
nently-cohesive, and adhesive .and permanently
plastic film, or object, that is-incapable of the
disintegration which causes chalking, alligator
pels the true solvents,‘ and. therefore, hastens
20
the "exudation of the non-drying oils.
ing, etc.
This '
,
-
20
I
That this new synthetic‘ resinous plasticizer
method of forcing out these materials is so
I desirably promotes
the rapid polymerization of
well recognized in the lacquer and enamel in- . nitro-cellulose to its di?lcultly-soluble, or insolu
dustry, that a technical term has 'been applied
to it.
It is known as lwsteresis.
ble state, in heretoforegknown solvents, although
'
Of these ‘three cl
of plasticizers, class a
has been most useful. The lacquer or. enamel
after losing its more highly volatile constituents,
‘ it is readily soluble and remains dissolved in my 25;
retains the slowly-volatile solvents for a time,‘
and, therefore,,the solute remains inv a state of
partial solution as long as some of the solvents
remain or retain their solvent properties, oras
long as the cellulose ester remains soluble. This
distinction between the retention of the solvents
‘and the solubility of the celluloseester, depends
upon the fact that cellulose, when nitrated, is
new resinous plasticizer, is‘ indicated by the fact
that, as shown by tests, ?lms deposited from lac
quers compounded of nitro-ceilulose and this new '
resinous plasticizer are, after drying, completely
inert to the solvents contained in succeeding 30
coats, and that coatings of steel panels so lac
quered and enameled and prepared for weath
erometer tests, have failed to be dissolved when
soaked for a week in acetone, which is a power
ful solvent for nitro-cellulose.
'
'
35
‘This property, whereby a deposited and dried
as pointed out above, subject to continued poly
film of lacquer or enamel containing nitro-cellu
merization and, as the polymerization proceeds, lose and this-new synthetic resinous plastieizer
becomes less and less soluble in any heretofore
is inert to the solvents of ‘succeeding coats, ren
known solvent,‘ whereas, unpolymerized and poly
1181's such lacquers and enamels, when properly 40
are
both
soluble
in
the
compounded to give flow characteristics during
. merized nitro'cellulose
_ new plasticizer herein disclosed. It, therefore,
application, suitable for use as brushing lacquers.
appears that lacquers or enamels or molding
An example of such a brushing lacquer will
compounds, plasticized ‘by the old methods, re
be given later in this speci?cation.
>
main plastic for so long a time only as the nitro
Tests have shown that ?lm's, deposited from
‘cellulose remains in "solution in the slowly
lacquers and enamels containing acetyl cellulose
vBlatile solvents, and that as soon as the solvents
and this non-volatile; water-resistant, perma
' disappear,-- which they do in time, or as soon as
nently-cohesive and adhesive and permanently
plastic synthetic resinous plasticizer, are satis
the nitro-cellulose becomes insoluble in those
solvents, it passes out of solution, and the lac
factorily plasticized, although it has not been 60
quers deteriorate with the production of the‘ ‘noted that appreciable solution of acetyl cellulose
faults knownas chalking, alligatoring,.etc.
in this new resinous plasticizer, occurs. How
Furthermo . the adhesion of such lacquers ever, it has been found that by putting this non
as have existed in the past, depends upon the volatile, water-resistant, permanently cohesive
stlckiness‘of such giim's and resins asv are in
and adhesive, and permanently-plastic material 55
55 troduced in order to eiihance the adhesion of the
lacquers to surfaces coated with them.
'
-
into solution containing as its solute, acetyl cel
lulose, or any hard ?lm-forming substance with
In contradistinction to the .old and above de
which it is compatible-and which is soluble in
scribed method of plasticizing, the new method. the same solvents that dissolve this'new resin:
herein revealed, consists in the oduction of a ,ous plasticizer, a molecular dispersionof the 60
into the sub
plasticizer- which when introdu
plasticizer throughout the mass is e?ectuated,
stance to be plasticiaed,
.. ‘_
the properties and that if the volatile solvents should disappear
of a gum or resin, and is a_ strictly non-volatile. from ‘the lacquer or enamel or molding compo
non-oxidizable, water-resisting, permanently sition, there willremain an intermolecular film
plastic and permanently-cohesive and adhesive or cement, which, by reason of itsladhesiveness, Yes
synthetic resinous material.
'
.
not only will bind together the associated mole
Thisi'ion-volatile, water-resistant, permanent
ly-coheslve and adhesive, and permanently-plas
tic material is soluble in usual solvents for nitro
cellulose, and is, itself, a solvent for nitro-eellu
lose, and further --~_--~
; the property of rap
Wh promoting the polymerization of nitro-cellu
Y! to the point at'which it‘ becomes insoluble
other solvents for nitro-cellulose, but remains
It
“is in the new material.
-
-
‘his nm-vola?lt. permanently-cohesive and
cules of the acetyl cellulose, but will also cement
the entire mass to the surface upon which the
lacquer or enamel ‘has been applied, with the I
result that, no matter how polymerization of
the acetyl cellulose may subsequently- proceed,
and no matter how hard andhorny the acetyl
cellulose may become, when considered in'its
state of molecular division,.its particles are still
bound together by a permanently-plastic, pliable,
2,187,995
adhesive material which, because of its complete
lack of volatility, and its permanent adhesive
ness, remains permanently in place upon and in
sures an extremely long life to the lacquered or
enameled surface, thus completely preventing
the disintegrations which are known as chalking,
alligatoring, etc.
It will beapp'arent from the foregoing descrip
tion, that this non-volatile, water-resistant, per
10 manently cohesive and adhesive and permanent
ly plastic material will act as an efficient and
desirable binder for the segregated molecular or
colloidal particles, of any coating material, lac
quer, enamel or molding compound, to which
'15 particles it will permanently adhere. ‘
>
It will also be apparent from the‘ foregoin
coating, lacquers, enamel or molding compound
and are therefore fugitive.
The process of plasticizing herein described is
of importance to the lacquer industry in that it
provides, in one lacquer, the properties required
for a “primer” coat, that is, the ?rst coat applied
for the purpose of obtaining adhesion to the object
or surface being lacquered, and at the same time
provides a ?nishing coat by producing a. superior
gloss and producing within the lacquer the ability 10
to permanently resist the effects of ageing that
have heretofore so quickly destroyed lacquered
surfaces.
General experience in the surface-coating in
dustries, has shown that organic surface coatings
exposed to the weather, and particularly to sun
light, deteriorate rapidly. and tests, conducted
to disclose the reasons therefor, have established
that this resinous plasticizer herein described is
a non-fugitive component of coating materials,
lacquers, enamels, and molding compounds in
which it may be effectively incorporated, and, as ‘ the fact that the short wave-length radiations in
the ultra-violet end of the spectrum of sunlight, 20
such, permanently conserves the essential prop
are the principal cause of the deteriorations noted.
erties of those substances; whereas, coating ma
terials, lacquers, enamels and molding com
- pounds, as now made, initially include substances
such as cellulose esters which are bound together
by other substances, which other substances in
time fail to effectuate the binding of said par
ticles, either because they evaporate, or because
of some alteration in the solute, regardless of
80 whether it is intro-cellulose or some other sub-'
stance.
The new resinous plasticizer is, therefore, one
which, in and of itself, is stable, is non-volatile,
and is permanently adherent to other constitu
ents of any coating material, lacquer, enamel
or molding compound, whatever they may be,
Much work has been done along that line of in
vestigation, and it is generally conceded that no
organic coating, whether it be oil and resin
varnish or a pyroxylin lacquer or enamel, is proof 25
against the destructive in?uence of the short
wave-length radiations, unless it be so thoroughly
pigmented that the solid pigment particles will
absorb and prevent the passage of these short
wave-length radiations into and through the coat 30'
ing or ?lm.
However, no radiations having a
wave length longer than 315 millimicrons, are
'known to have a destructive in?uence -on surface ‘
coatings. Tests,‘conducted to determine the light
transmission characteristics of my new synthetic 35
in which it-may be effectively incorporated. It _ resinous plasticizer, reveal the fact that while this
material is highly transparent to the light radia
is therefore evident that the longevity of a lac
quer or varnish is entirely dependent upon the tions in the visible range, and, therefore, can be
used to make so-‘called water-white clear lacquers,
character of its plasticizer, and that the deterio
rations of these substances, as heretofore pro ' it is opaque to all radiations having a wave length
shorter than 317_ millimicrons. "The practical as
duced, is chie?y due to the elimination, the in
pect of this property of the new resinous plasti
activity or the lack of stability of their plastic
cizer, is that clear lacquers may now'be manu
Lacquered panels, exposed for breakdown tests factured with my invention, which, when exposed
to the weather and sunlight, are more fully pro 45
in a weatherometer, have demonstrated the lon
gevity of lacquers compounded with ‘the new tected against the , destructive .effects of short
plasticizer, herein described, as compared with wave-length radiations than were the lacquers of
the prior art when pigmented.
. commercial lacquers compounded with plastic
Other tests have shown that ?lms of applicant's
izers such as castor oil, triphenyl phosphate, tri
resinous plasticizer having a thickness of one
cresyl phosphate, and dibutyl phthalate.
50
These tests have shown that, whereasthe best millimeter will pass 70% of spectral emanations
obtainable commercial lacquers compounded with of a wave length of 400 millimicrons; but, if the
fugitive plasticizers were completely destroyed substances from which said resinous plasticizer is
55 in from 250 to 300 hours’ exposureiin‘the weath produced ‘should contain contaminations of vari
erometer, those lacquers that were compounded ous kinds, or are, otherwise, variable, the per 55
centage of transmitted spectral emanations will
with the plasticizer herein described as’ non
volatile and non-fugitive suffered no detectable vary, and, in some instances‘, maybe as low as
.
= .
2
change after 718 hours of exposure, under the 49%.
60 same conditions, even though the effort to de
Test conducted in a weatherometer, in which
izers.
.
.
.
tect a change was conducted with the aid of a
powerful microscope.
'
,
.
The product, thus produced, is a permanently
plastic and non-brittle semi-?uid resin that is
suitable for use in coating materials, lacquers,
' enamels and molding compounds, and capable of
imparting desirable plastic properties thereto. It
differs from ?uent substances such as castor oil,
which, blended with coating materials, lacquers,
70 enamel and molding compounds, merely acts as
a non-adhesive lubricant for the other constitu
ents and readily exudes therefrom by hysteresis.
It differs from‘such substances‘ as camphor, tri
phenyl phosphate, vtricresyl phosphate and di
u butyl: phtalate which in time disappear from the
>
coated panels are subjected to as close an ap 60
proach to sunlight as can at present be achieved
arti?cially, and including a larger percentage of
short-wave radiations than does sunlight, even on
high mountains, alternated with high and ‘low
temperatures and rain, have shown that lacquers 65
manufactured according to my invention, have
produced coatings which indicate that they resist
these destructive agencies over three times as
long as the best commercial lacquers of the prior
art. These new lacquers and enamels can, there—
fore, bevsuccessfully used for coating objects sub 70
jected to outdoor exposure. Furthermore, these
coatings are unaffected by grease, oil, gasoline,
benzol, toluol, naphtha, or petroleum.
'
' I have made ?lms composed of nitrocellulose‘
and
2,187,996
As the acid number is reduced, the freezing.
synthetic resinous plasticlzer. Such ?lms
point
of the synthetic resinous plasticizer is
properties that excel the properties of
- exhibit
- celluloid. They may be made transparent. They
may be colored as desired.
They may have pig- I -
, ments incorporated in them to render them
opaque. , Such films are elastic, ?exible, odorless,
= of great tensile strength and maybe
raised. That is to say, at any given temperature,
resins of this series'having higher acid ‘numbers ‘ l
' will be more liquid or plastic than those resins of
lower acid numbers. It will, therefore, be seen
that; where lacquers or enamels are to be sub
jected to very low temperatures, use may advan
tangeously be made of resins having acid num-. -,
10
bers higher than 24.
folded and unfolded without cracking or suffering
' any apparent damage. vThey may be molded ac-'
10 cording to the well-known methods used for mold
_The condensation and ‘polymerization- above
ing celluloid.
Because of the permanence of this plasticizer, outlined are preferably e?ectuated'by me in alue
minum vessels, although vessels made of 'other
these ?lms will retain these properties for an in
materials which will not be attacked by the‘ in"- .- de?nite length of time.
to
describe
in
detail
the
‘
.gr'edients
may be employed.
I shall now proceed
ll
Small batches of. material may be condensed
manufacture of my new synthetic substance and and
without the necessity of con
give examples of its use in lacquers, enamels and stantpolymerized
agitation, although it is my practice ‘to thor
molding materials. ' It is to be understood that the oughly and continuously agitate. the ,material '
examples given are illustrative of my invention, during the entire'period of heating.
20 which, of course, is not limited thereto, since
_ The product resulting from the condensation
. many changes may be made therein without de
and polymerization of phthalic anhydride and
parting from the spirit and scope ofv the inven- I
diethylene glycol, if producedas above described,
tion.
and __without other attention or modification, will
The process of manufacturing this non-vola
produce a‘ synthetic resin havingv the plasticizing
tile,
water-resistant,
permanently-cohesive
and
25
properties above described, but, by reason of the
adhesive and permanently-plastic synthetic mate
heat required for polymerization producing sis
multaneously objectionable discoloring dissocia
rial, may be carried into effect by subjecting a
mixture in substantially the proportion of one
molecule each of diethylene glycol‘ and phthalic. tion compounds, it will be of dark color and, so
‘far as visual inspection of the sticky mass sofpro
30 anhydride, to_a temperature of from 110 to ‘150 ‘ duced is concerned, it will be unattractive to one
degrees centrigrade, but preferably 130_degrees
not aware of its extraordinary usefulness as a
centigrade, and continuing the heating and con
plasticizer, and even to one conversant with-its
sequent condensation and polymerization until.
the desired product has an acid number between plasticizing properties, the dark color is likely
112 and zero, but preferably just below 24'.
>
It is to be understood that during the heatiniL.
condensation and polymerization of- the above
mixture, the‘ acid number gradually reduces from
to create the belief that it will ‘be objectionable as
a material to be used in the manufacture of clear
water-white lacquers and in the manufacture of
white pigmented lacquers, by reason of the pres
ence of the objectionable coloring compounds
above 180 to zero, depending upon the length or
as above‘ described.
duration of the continuation of the heating.‘ At - formed
, I discovered that the inclusion of ray-control
?rst, that is, in the very early stages of the con
densation, the ingredients seem. to be in solution ling substances, the principles of the effects of
in each other, ‘but the solution is water-soluble. ' which are fully set forth in'myco-pending patent
As the condensation followed by polymerlza- - application ?led‘ August 20, 1931, Serial No. 558,
329, was e?ective in preventing the formationof
_-tion,'proceeds, ‘the solution becomes water-inét undesirable
color characteristics during the con
soluble, at an acid number of‘ approximately 112.
At that time, it isv a liquid resin, and greater dens'ation and polymerization of this resinous
and that the much-desired light color
‘quantities of cellulose ester are required to harden plasticizer,
of 'the resin and its transparency in the visible‘ ‘
it, andovercome itstackiness, than would ‘be re— range
could-be so produced. ' I‘ prefer, therefore,
quired if the polymerization had proceeded to. still
50
when making this plasticizer, to‘ include in the
As
an
opposite
‘extreme,
the.
lower acid numbers.
solution polymerized to an acid number of zero, batch at the time of beginningthe heating, a ray- '
:is a plastic solid ‘at‘normal temperatures, and controlling substance‘v as described inthe above
requires comparatively little cellulose ester to cited co-pending application, and speci?cally in _
‘this case I prefer touse .0005 per cent-of copper
. overcome its tackiness, and produce satisfactory
-
coatings, him and objects. It willbe seen, there
fore, that between the acid numbers of 112‘ and
zero, thereis agradual transition in the stateof
being of the condensed and polymerized material,
and it may therefore be said that an in?nitenum;
‘to ber
of plastic resins exist in the above-indicated
range. ’ All of them are useful, and are comprised
nitrate.
-
.
Throughout this specification emphasishasbeen
the fact that nitrocellulose of high
viscosity characteristics is entirely suitable‘for
the manufacture of’lacquers and-enamels having
a high total solids content, providing this .res-_
- placed upon
‘inous plasticizer be employed in sufficient quan- - -
tity to provide the body characteristics in the
fer to stop transition ‘at an’ acid number slightly , lacquer without unduly raising the viscosity of
‘
‘_>
below 24,‘ because of the fact that the plastic the lacquer.
properties of the synthetic resinous plastlciz'er, as - It is not intended to‘ disclaim the use of nitro
cellulose havingv low viscosity, characteristics, such
‘ above made, and stopped at an acid number just 'as that produced by Pitmanand others, because 7
below it, are such as to give excellent results with such low-viscosity nitrocellulose is satisfactorily
within the scope of this invention, although I pre
nitrocellulose of high viscosity characteristics.
otherv cellulose esters, and other hard ?im
"W' substances capable‘ of being plasticized
, jzyatheticresinous plasticizers of thistype,
rm ‘
plasticized
by my new_ resinous material, and by 70
its use lacquers having suitable viscosity for
spraying and dipping may be produced. Such
made with the low-viscosity nitrocellu
18y well require that the transitlon'be . lacquers
l'os'e can be notably improved beyond the limits
oftbcpriorartbybeinlsimatotalsolibconr
' flav‘uatotheracidnumbei'stl'lanthatwhich];v
I!
c-
.
6
2,187,995
tent and consequent fullness far greater than
ever before possible. . ‘
'
ing and employing my invention, the following
is cited:
>
Solids
.
'
ethyl lactate, H. I. F. naphtha, amyl acetate and
ethyl oxy-butyrate.
As an example of a lacquer suitable for spray
Ounces
Dry weight R. S. nitrocellulose, 60 to 80'
Add half of the above mixture to the wetted
nitrocellulose and mix thoroughly until the nitro-Y
cellulose is completely dissolved.
batch.
seconds viscosity ____ ___ _______________ __
3
10 My resinous plasticizer_________________ __ 20%
Solvent Mixture
_ As another example of a brushing lacquer, the '
following is presented:
Solids
Toluol
50
Denatured ethyl alcohol, 188 proof______ __
15
Ounces
Dry weight R. S. nitrocellulose of 20 to 30
20
My resinous plasticizer_________________ _.. 20%
5
Solvent Mixture
Same as ?rst example of-brushing lacquer.
15 Ethyl acetate (85 to 88% ester and balance
seconds viscosity_____________________ .._' 4%
ethyl alcohol) _______________________ __
Amyl acetate
15
Ethyl lactate ‘
Mono ethyl ether of ethylene glycol____'___ 20
Butyl mono ethyl ether of ethylene glycol.._
3
Procedure
Dissolve the resin in the ethyl acetate.
Wet the nitrocellulose with the toluol and the
denatured alcohol.
_
.
Mix the amyl acetate, ethyl lactate, mono ethyl
ether of ethylene glycol and butyl mono ethyl
ether of ethylene glycol.
Add half of the above mixture to the wet nitro
cellulose and mix thoroughly.
Add the solution of resin and the remaining
As another example of spraying lacquer, I may
.
'
a
seconds viscosity____ _‘_ _____ .._'_..___x____
4%
My resinous plasticizer_________________ __ 20%
Solvent mixture and procedure
_
Ounces
seconds vviscosity _____________________ __
3
My resinous plasticizer_________________ .._ 20%
Solvent Mixture
'
.
Denatured ethyl alcohol, 188 proof______ .._
15
Mono ethyl ether of ethylene glycol _____ __
. 32
J
8
E71. F. naphtha (H. I. F. means high ?ash '
'
Amyl acetate
10
_ 15
Ethyl oxy-butyrate_____________________ __
5o Ethyl acetate
contrast to'the practice of the prior art, my new
resinous plasticizer may be incorporated in lac
quers and enamels in such manner that the cellu
lose ester constitutes less than 50% of the-total
solids, other than pigment, and that said new 40
‘
'
The reason for this remarkable improvement, is I
,
.
point)
25% of the total solids, the resulting ?lms lacked 1
and still produce lacquers having great cohesive
Dry weight R. S. nitrocellulose of 60 to 80 '
'
solids; that, if the resin or gum, which was the 31)
weakest component of any prior-art lacquer, be
included in the lacquer to an extent greater than
ness.
Solids
Ethyl lactate
be so proportioned that the cellulose ester con
total solids, and, in some cases, as much as 87%,
‘
.Zylol
It will be noted,_from the illustrative formulae
given above, that my new resinous plasticizer
reverses the practice of the prior art in the fol
lowing manner. In the prior art, it was found
that the production of useful lacquers required
that the total solids, other than pigment, should
plasticizer constitutes more than 50% of the said
Same as in the ?rst example above given.
As an example of a brushing lacquer, the fol
-
20
‘ or gum made this defect more prominent; but, in
Ounces
Dry weight R. S. nitrocellulose of 20 to 30
lowing is presented:
‘
coherency, and that the further increase of resin
'
Solids
‘1'
Procedure
Same as in previous examples.
stituted 50% or more than 50% of such total
glixcii
solvent and thoroughly mix the entire
at
.
use:
5
Add the solution of the resin and the remain
ing mixed solvent and thoroughly mix the entire
8
10
Procedure
Dissolve the resin in the ethyl acetate.
Wet the nitrocellulose with the zylol and the
' g5 denatured jalcohol.
Mix the mono ethyl ether of ethylene glycol,
that small quantities of high-viscosity cellulose
esters act effectively to so harden my new plas
ticizer that it constitutes the major coherent and
adhesive portion of the total solids of the lacquer.
Having thus described my invention, what I 50'
claim is:
l. The process of producing a resinous plas
ticizer, which consists in subjecting phthalic an
hydride and diethylene glycol to a temperature of
approximately 130 degrees centigrade until a de
' sired condensation product is produced.
2. An organic nitro~ce1lulose coating material
including, as a component, a plasticizer which is
the polymer of diethylene glycol and phthalic an
hydride produced at a temperature approximat
ing 130 degrees centigrade.
3. A fusible, water~resistant phthalic anhy
dride-diethylene glycol resin condensed and poly
merized at a temperature approximating 130° C.
and having an acid number between 112 and 0.
'
ALLEN D. WHIPPLE.
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