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Патент USA US3100760

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United States Patent 0 1.
C6
31,100,755
Patented Aug. 13, 1963
2
1
In the preferred embodiment of my invention, I dis~
3,100,755
CGATING CGMPUSITION COMPRISKNG A. VINYL
ACETATE UNSATURATED ‘JARBOXYLIC ACID
COPOLYMER AND AN .ORGANEC BAdE DES
SQLVED IN AN ORGANIC SOLVENT 'AND
ARTICLE THEREWITH
Joseph R. Ehrlich, 17 93 Riverside Drive, New Yorlr, N.Y.
No Drawing. Filed Apr. 13, 1959, Ser. No. 803,793
23 Claims. (Cl. Zebu-29.6)
solve a suitable starting or reactant resin of this class in
an organic solvent, which is substantially "neutral and
which may be polar or non-polar. This solvent may be
anhydrous or substantially anhydrous, preferably with
not more than 5 percent of water by weight or volume.
These organic solvents are exempli?ed by many ‘alcohols,
such as methanol, ethanol; by many esters as ethyl ace
tate, butyl acetate; by many ketonm, such as acetone,
10 methyl ethyl ketone; by many hydrocarbons, such as
toluene, benzene; and by many chlorinated solvents, such
My invention relates to new and improved polymeric
as methylene chloride, perechlor-ethylene.
coating lacquers or coating compositions, new and un
I also dissolve in said preferably anhydrous solvent at
proved polymeric coating layers, and a new and improved
small quantity of an organic nitrogen base, which is sub
method of making said compositions and layers.
There are certain well-known grades of copolymers of 15 stantially non-volatile at 20° C.—-30° C. at ordinary atmos
pheric pressure of 760 millimeters of mercury. The
vinyl-acetate with certain unsaturated acids or anhydride‘s,
quantity of said organic nitrogen base would be insu?i
containing four carbon atoms, such as maleic, furnenc
cient to form a water soluble salt with the co~polymer,
and crotonic or isocrotonic. These grades of said copoly
would it have been reacted vwith the copolymer in the
mers react with aqueous alkalies, ammonia and amines
20 form of an aqueous solution at room temperature and
to form water-soluble salts.
760 mm. mercury pressure and in the absence of a sol
If the ratio of said unsaturated ‘acids or anhydrides in,
the copolymer is kept low, say from 0.5% to 5.0% the
properties and characteristics of said copolymers are much
like those of vinyl acetate homopolymers. Their appear
vent.
>
When the solvent is evaporated, as at 20° C.-30° C.,
and under said normal pressure, the solutes form a coat
ance, solubility in organic solvents, softening or melting 25 ing film on a base object, which may be made of metal,
points, excellent adhesion to all kind of surfaces, ?lm
forming properties, .insolubility in water, etc. are quite
similar to those of polyvinyl acetates. Except that they
can form Water soluble salts, as before mentioned, a
property which the polyvinyl acetates do not possess.
If the aqueous alkaline material which is being reacted
with said copolymers is volatile, such as ammonia or a
low boiling amine, such as methyl- or ethylamine or
morpholine, such salts of the copolymers decompose
glass, plastic, and which may have a smooth surface.
This residual dry ?lm (i.e. the ?lm provided by the
lacquer upon evaporation of the sol-vent) is inert to water
vapor under ordinary atmospheric humidity.
However, if this residual ?lm is wetted with water, I
can easily and very quickly strip the ?lm in shriveled
form from the base object by mild rubbing or wiping
or pulling. The ?lm does not dissolve in water.
If the solution contained a su?‘icient amount of the
again, when exposed for some time to air or when heated, 35 dissolved organic nitrogen base to react su?iciently with
the acidic resin, the wetting with water would form a
and revert to the water-insoluble resin. Thus, by dis
.salt or salt-like compound in the ?lm, which would be
solving the resin e.g. in an ammonium hydroxide solu~
wat‘ersoluble.
tion, it is possible to prepare an aqueous solution e.g.
’ ‘If the solution contains insu?icient dissolved organic
of the ammonium salt of said copolymer which can be
used for casting a ?lm on a surface. After a suf?cient 40 nitrogen base to react completely with the acidic resin,
the resulting ?lm, after wetting with water is quickly and
long drying time or, in a much shorter ‘time, when heated,
easily strippable by mechanical action.
the ammonium salt decomposes into volatile ammonia
The residual ?lm is insoluble in water, at least to any
and the original copolymer resin, which is water insoluble.
practical extent.
Such resin ?lms adhere strongly to surfaces of glass,
The ?nal dry ?lm is hydrophilic or waterseusitive in
metal, etc. and cannot be removed with water. They 4-5
each case, without being necessarily watersoluble.
can be removed with solvents or aqueous alkalies. Aque
The coating composition or lacquer may be free from
ous solutions of the salts of said co-polymers which are
coloring materials, or it may include pigments, and it
formed with non-volatile alkaline materials, such as
may also include a \dye or dyes which are soluble in
sodium hydroxide can also be used to cast a ?lm on a
surface, however, such ?lms, ‘after drying, are completely 50 the solvent’vehicle of the coating lacquer and in the
material of the residual coating ?lm. The residual ?lm
Watersoluble.
of the new polymeric ?lm or coating may be light
Resins of this class can be dissolved in various volatile
permeable or opaque. The coating composition may
anhydrous amines, and the solvent can be evaporated
also include a light-?ltering agent which is soluble in
to deposit the original resin in the original form, showing
that many amines do not react with these resins, in the 55 said solvent. 'I‘his light-?ltering agent becomes part of
the residual coating ?lm. I can thus form a residual ?lm
absence of water. These anhydrous amine solvents in
of the new polymeric material which is transparent and
clude morpholine, pyridine, and mono-iso-propylamine.
susbtantially colorless; or which is transparent and has
Hence I believe that the salt formation takes place only
any desired color; or which blocks any selected range
in the presence of water.
I use resins of this class which do not hydrolyze in 60 of visible or invisible light, such as ultra-violet light in
water. This stability to hydrolyzation in water is an im
any selected range thereof; or any monochromatic visible
portant feature. I use resins of this class which can
light; or which is opaque. The coating lacquer may be
supplemented with wetting agents. If the coating com
react with an alkaline material in the presence of Water,
position has a pigment or pigments, said‘composition may
to provide a water-soluble salt.
3,100,755,.
3
.
ll
be supplemented with dispersing agents. I can alsoadd
coming cars.
‘For such applications organic nitrogen
dichroic staining materials such as eg iodine and obtain
an oriented ?lm by stretching as will be outlined later on
bases can also be used which have a very slow evapora
tion rate at room temperature of 20° C.—30° C. and
in the speci?cation.
ordinary atmospheric pressure, instead of being com
pletely non-volatile. In such cases a slightly larger
amount of nitrogen base might be added to the coplymer
duce a highly adherent, residual thermoplastic surface
?lm upon a smooth and impervious surface of many
than needed to make the residual ?lm strippable after
contact with water, in order to allow for slight evapora~
materials, such as glass, metal, stone and plastics. This
thermoplastic ?lm is inert to water under ordinary con
tion losses of the dry ?lm.
ditions, in the absence of mechanical stripping action, 10 If to such a lacquer type solution iodine is added,
such as rubbing, wiping and pulling. The ?lm may be
which completely dissolves in the solvent or solvents, a
wettable by water. It is su?icient if the ?lm is‘ hydro
?lm layer can be cast from such a lacquer on a smooth
philic, namely, sensitive to water. The coating lacquer
surface, such as glass, cellophane etc. When said ?lm,
As one important ‘feature of my invention, I can prod
may contain a dissolved water-proo?ng agent, such as
after the‘ solvents have completely evaporated, is moist
a silicone oil. In such case, if water is applied to the 15 ened with water, it becomes detachable from its base.
' By stripping said ?lm from its base and simultaneously
dry residual ?lm, the water forms drops on said ?lm,
instead of forming a continuous ?lm of water, as in
stretching it to one and a half to three times its original
other cases. Still, such a ?lm can be removed after short
length, said stretched ?lm becomes oriented and, while
contact with water, andvmechanical stripping action.
keeping it under tension can be transferred to another,
Such a ?lm can also be removed in one piece, with slight
transparent base where it is allowed to dry while kept
shriveling, by ?owing water upon it, without dissolving
in a stretched position. After the stretched ?lm has
dried and all water has evaporated the ?lm adheres
the ?lm.
Such lacquer, made with the use of a water
proo?ng agent, and the resultant ?lm, are within the
?rmly to the new base. If the new base is a thin trans
scope ‘of this invention. Said resultant ?lm, like the other
parent plate or sheet the resulting lamination product
?lms, is soluble in an aqueous solution of sodium 25 polarizes light. The original copolymer Without the small
hydroxide or other alkali, if the aqueous solution
quantity of alkaline organic material does neither exhibit
such stretchability nor such detachability ‘from a base
is of sufficient concentration. If the coated, body is
kept in a humid atmosphere, which results in condensing
on which it was cast.
a
' a thin surface ?lm or drops of water on the exposed
It is of course well-known to provide removable coat
surface of the coating ?lm, said coating ?lm remains ad 30 ings of water-soluble polyvinyl alcohol ‘and other mate
herent and stable in all respects, in the absence of
rials which are applied by means of aqueous coating
rubbing or wiping tor pulling or ?owing water upon it.
, compositions or to use ‘so-called strip coatings which are
The exposed surface of the coating ?lm may even be
either applied by hot-melt dipping ‘or spray or from sol
wetted with a thin ?lm of water at 20° C.—30° C., or by
vent solution. However, they all have certain disad
condensing steam thereon ‘from boiling water which is 35 vantages so that they cannot be used for most of the
at 100° C.
In such case, the coating ?lm remains ad- '
herent and stable in all respects, and the applied water
can be evaporated by air-drying, without weakening the
adherence or changing any property of the original coat
ing ?lm, in the absence of rubbing or wiping or pulling.
However, if the exposed surface of the coating ?lm
is wetted with water, and the wetted coating ?lm is then
rubbed, wiped or pulled, the coating '?lm loses its ad
herence to‘ the applied smooth and impervious surface
of the base body so that the coating ?lm can be easily 45
stripped from the base body of glass, metal, stone, plastic.
In such case, if not stretched, the coating ?lm may shrivel
into a string-like shape. This easy stripping of the coat.
ing ?lm from a smooth and impervious surface is an
important advantage.
special applications which the present invention intends
to provide for. Aqueous coating compositions dry slow
' 1y whereas the improved coating compositions of this in
vention are of the quick-drying lacquer type and op
tionally and preferably of low viscosity, so that the im
proved liquid coating composition dries to provide the
improved residual coating ?lm vas quickly as the usual
nitro-cellulose lacquer, and deposits a very thin ?lm which
is not water soluble, and which can be made transparent
and completely nonJdistorting for use on optical lenses.
When a ?lm of ordinary water-soluble material such as
polyvinyl ‘alcohol, gelatin or water-soluble cellulose ethers
is formed they change their properties with the change of
atmospheric conditions. They become sticky and/or soft
under high humidity and brittle when dry. What is
50
‘It is thus possible, as one use, to coat the glass lenses .
worse, they blister and even lose their adherence when
of eyeglasses or glass photographic lenses with a thin
dry. To remove them, when not brittle they have to be‘
transparent ?lm of any selected color, said ?lm being
washed off with water, and when a water soluble dye
formulated to block any selected portion of the visible
stuif was dissolved in such ?lm, undesired staining and
light spectrum or any portion of the ultra-violet light 55 bleeding of the dye is unavoidable when such ?lm is re
spectrum. Prescription eye-glasses can be thus easily
moved by washing and dissolving.
converted into sun-glasses of any selected color and light
The so-called strip coatings are based on the fact that
blocking effect. The coating is stable and adherent under
?lm-forming compositions are being used which have
ordinary conditions, but it can be easily removed or
very little or no adherence at all to their base, so that
replaced by wetting and mechanical action or by alkaline 60 they can be pulled og easily. There are certain hot-melt
aqueous solution, or by ?owing water upon it in a
compositions, containing certain types of cellulose acetate
stream. Under ordinary atmospheric conditions, the ?lm
butyrate ‘or cellulose acetate which are quite viscous and
remains dry and adherent and stable, so that the unwetted
_ form layers ‘which are comparatively thick. If such a
?lm can‘ be wiped to remove dust without stripping said
?lm. The coating ?lm may be formed on glass windows, 65 hot-melt gets in contact with a cold surface, as by dipping
in order to ?lter out any selected intensity or range of
sunlight. It may also be applied as a protective or
or spraying, the chilling effect causes a spontaneous
V shrinking effect on the contact face of the coating which
prevents adhesion. Strip coatings from solvent solutions
ornamental coating to glass, metal, plastics and all other
can only be made with ?lm-forming materials of poor
materials, and for many other purposes. Though such
coatings may be of permanent nature they lend them 70 adhesion, such as certain unplasticized types of cellulose
acetate; such coatings are necessarily very brittle and
selves particularly tfor temporary use. Tinted coatings
have a tendency to ?ake off.
I
on eye-glasses, car window shields etc. might often be
The improved ?lms of this invention, compared with
desirable only for a short period, such as for the day
the before mentioned removable ?lms known to the pres
time hours to cut out the sun glare, or during night
Idriving to .diminish the glare of the headlights of on 75 ent art, are inert to changes in the humidity of the atmos—
>
3,100,755
5
6
phere; they can be produced in very thin layers, e.g. in a
thickness of one mil, or thicker or thinner, and the layer
will adhere ?rmly to smooth surfaces when ‘dry, and will
not loosen when wet, runless pulled or rubbed; when the
?lm is stained with dyestuffs, which necessarily have to be
water-insoluble, such idyes will neither stain nor bleed
when the ?lm is being wetted for removal. The ?lm can
be removed easily at will land in undissolved form and
will not get loose unvoluntarily through unfavorable at
disclosure copolymers are being used which are obtained
mospheric conditions.
‘
The organic alkaline material which is added to the
copolymer solution may be any nitrogen base; the limita
tions being only that said nitrogen base is soluble in or
ganic solvents and is substantially non-volatile at 20° to
by reacting equimolar quantities of the monomers. The
amines with which said copolymers are reacted are satu
rated primary and secondary aliphatic higher amines con
taining from 8 to 18 carbon atoms, in particular, an aver
age of 14 carbon atoms. ‘One to two moles of aliphatic
primary or secondary amine are reacted with one mole of
the unsaturated polybasic ‘acid or anhydride in the co- .
polymer. Expressed in ratios of amine to copolymer, as
10 given by the examples in US. Patent 2,698,316, said
ratios are from 200 to 285 parts per weight of amine to
100 parts of copolymer. The reaction between amine
and copolymer takes place in \a suspension of toluene or
xylene at temperatures between 100° C. to 200° C. under
30° C. at a pressure of 760 mm. mercury; or, for tem 15 re?ux and the reaction time is from 1 to 5 hours. The
reaction products, after the solvents have been removed,
porary coatings which are needed only over a relatively
are mostly oils, are all soluble in mineral oils‘ and are
short period the boiling point being sufficiently high and
being used as pour point depressants and viscosity index
the vapor pressure being suf?cient-ly low, so that a suffi
improvers for lubricating oils.
_
ciently large amount of said nitrogen base remains in
The coating compositions of my invention are entirely
the ?lm for the needed period to make the coating de 20
different from the above mentioned products- which are
tachable after wetting with water, without making it nec
presently known to the art. The copolymers which I use
essary to add so much nitrogen base that the coating
‘ for the purpose of my invention contain only from 0.5 to
might become water-soluble. That is normally true for
5.00% of an unsaturated acid containing four carbon
bases with a boiling point of 250° C. or more at 760 mm.
atoms, exempli?ed by crotonic acid, isocro-tonic' acid,
mercury pressure. The substantially non-volatile nitro
fumaric acid and maleic acid; their respective anhydrides
gen bases are solids, or liquids with boiling points of 300°
for the purpose of this invention being considered equiv
' to 360° C. at atmospheric pressure of 760 mm. mercury.
alent to the acids. I prefer to use a copolymer of 97%
Biases which are even sparingly soluble in organic sol
vents may be used, ‘as only very small quantities are
vinyl acetate and 3% crotonic acid. I can use such 00
needed. Such nitrogen bases can be primary, secondary 30 polymers with a molecular weight ranging from 22,000
or tertiary amines, and they may be aliphatic, aromatic
to 60,000 with a preferred range of 25,000 to 40,000, and
or heterocycl-ic compounds, including hydroxyl amines
particularly of ‘around 28,000.
and hydrazines, and they may contain 'alky-l, aryl, hy
I can use any nitrogen base with a basic character, from
mild to strong bases, which are solid, or liquid and sub
stantially non volatile at temperature of 20° C. to 30° C.
more than one amino group or they may be quarternary
at an atmospheric pressure of 760 mm. mercury, and
ammonium bases. All these classes are repeatedly ex
empli?ed by the following compounds which have been
which are su?iciently soluble in organic solvents; su?i
oiently soluble in organic solvents for the purpose of this
‘found to be operable:
Triethylene tetramine; tetnaethvlenepentamine; poly 40 invention means a solubility of not less than 1 part in
glycolamine H-l63
100 parts solvent at 20° C. Such nitrogen bases are not
limited to primary or secondary amines, neither to ali
droxyl or other groups or radicals; they may contain
(HO.CI-I3CH2OCHzCHzOl-izCHzCHzNHz)
tetradecylamine; dioctylamine; didecy-lamine; S-isopro
pylamino-l-pentanol; di(2-ethylhexyl) amine; diethanol—
amine; diisopropanolamine; triisooctylamine; triethanol
amine; di(2-ethylhexyl) ethanolamine; triisopropanol
amine; bu-tyldiethanolamine; meta-amino phenyl methyl
oarbinole; kylidine; u-naphthylamine; IS-naphthylamine;
p-phenylenediarnine; benzidine; phenylhydrazine; aceto
phatic compounds. Of many hundreds of nitrogen bases
which I can use and which ‘are within the given limita~
tions, 52 examples have been listed to represent at least
45 the most important classes of such nitrogen bases.
I dissolve said copolymers and nitrogen bases at room
temperature of 20° C. to 30° C. and under normal atmos
pheric pressure in organic solvents, preferably‘ blended to
provide for a quick drying lacquer which deposits a
acetanilide; iaceto acet ortho anisidide; aceto acet ortho 50 smooth, non-blushing, residual coating. The ratio of such
toluidide; aceto racet ortho xylidide; diphenylamine; N,N
nitrogen base might be from 0.5 part to 10 parts by weight
dibutyl aniline; amine 220
to 100 parts of copolymer; however, the average will be
about 1 to 2 parts nitrogen base to 100 parts by weight
(017E330 :NC2H4NC 2H4OH)
of copolymer. No heating takes place to react the
55 components. After evaporation of the solvent the residue
phenyldiethanolamine; phenyl ethyl ethanolamine; tri
is a ?lm forming resin which is substantially insoluble in
methylphenyl ammonium hydroxide; diphenyl hydrazine;
water and mineral oil. However, the properties of the
tetraethyl tetrazine; amylaniline; N~phenyl morpholine;
hexamethylenetetnamine; phenazine; aminophenazine; di
aminophenazine; naphthazine; antihrazine
original copolymer have changed in the residual resin.
Though the amount of nitrogen base is insu?ioient to
60 possibly form a watersoluble salt with the copolymer in
the presence‘of water it might be that a fraction of co
iminazol or glyoxalin; 1,2,4 triazole; S-amino tetrazole;
quinaldine; ot-hydroxyquinoline; quinine; quinidine; papa
ven'ne; narcotine; antipyrine, etc. etc.
It is well known that copolymers of vinylacetlate with
crotonic acid or maleic acid, copolymerized in the before
polymer has arranged itself with the nitrogen base to
form a latent compound which is uniformly dispersed in
the solvent solution; after evaporation of the solvent such
“latent” particles might be uniformly dispersed in the
remaining “unreacted” part of the copolymer to react in
contact with water to form a water-soluble salt which is
sparingly, but uniformly interspersed in the water insolu
tions of alkalies, ammonia ‘or certain Water soluble
amines, to form water soluble salts.
70 ble residue. However, I do not known whether this
theory is right or whether a new compound has been
In the US. Patent No. 2,698,316 it has also been dis
formed. There are a number of considerations which are
closed to react certain amines with the copolymeric re
for and against either one of those theories and a con
action products of alpha, beta-unsaturated polycarboxylic
mentioned ratios dissolve in an excess of aqueous solu
?rmation will have to wait until additional investigations
acids, in particular, maleic ‘acid, with aliphatic vinyl com
pounds, in particular, vinyl acetate. According to said 75 will produce new facts.
3,100,755
7
8
However, whatever the correct explanation might be,
It would lead unduly far to give examples of every
the new product is a truly new and useful product. It
possible or even desirable or useful variation of these
fhas been established that ?lms cast from this solution
new and improved coating compositions. The following
‘onto smooth, inert surfaces, after being brought into short
few examples shall therefore serve only as a sample
contact with water, loose temporarily their strong bond 5 demonstration as to how such coating compositions can
‘with the base surface‘and can be easily removed by wipbe made. However, the scope of this invention is by
iug, pulling, stripping etc. They become temporarily
no means limited to the examples, and it is emphasized
‘soft and extremely stretchable.‘ They do not dissolve in
that virtually hundreds of di?erent nitrogen bases as
Water. When the coating solution is poured into water or
previously, described can be combined with any one of
carefully cast onto the surface of the water a precipita- 10 the ‘described acid eepelvmers- Likewise, the solvents
tion takes place; the same soft, stretchable material forms
may greatly vary, depending on the end use of the coat
striugs in the water or a ?lm on the surface of the water,
ring solutions, and the addition of additives is optional
respectively. A number of practical applications of these
in any individual case. Such additives can be any one
properties have already been described,
of suitable commercial Wetting or dispersing agents, pig
The choice of the solvent vehicle also in?uences the 15 ments, dye-stuffs Or other Organic 01‘ inorganic Staining
detachability of the ?lm fnom certain base materials.
agsms, ?ltering agents for any band of the spectrum, per
Thus, if the base material which is to be coated, is inert
fumes, Plasticilers ei'd-
to organic solvents, such as glass, metal, stone, poly-
Example 1
ethylene, the ?lm is easily detachable by applying water,
_
combined with mechanical stripping action, irrespective 20
,
v of the organic solvent vehicle.
_
Tile Solve?“ PI soil/ant veinde 15 as follows; tha Pro"
. portions of its ingredients being by volume:
However, if the basematerial is sensitive to certain
Percent
organic solvents, such as base materials which are made
Methanol —————————————————————————————————— -— 20
of polystyrene, methyl methacrylate, cellulose acetate,
lsopmpanol -------------------------------- -— 50
nitrocellulose, polyvinyl acetate, polyvinyl chloride, and 25M6thy1 ethyl ketone ———————— —-.—————.— —————————— ~~ 15 .
other plastics tor resins, the single ‘or mixed solvent vehicle
n'Buty1 acetate —————————————————————————————— ~- 15
' 0f the Coating lacquer QT composition may. Optionally be
free fnom solvent to which said base material is sensitive.
The solvents which attack plastics, especially thermo-
This solvent is anhydrous or substantially anhydrous.
Theeoating composition, in parts by weight, consists of
the following;
plastic plastics, are usually esters, ketones, aromatic hy- 30
_
.
'
drocarb‘ons, and chlorinated hydrocarbons. Most'plas-
(A) 890% 0; Sald Solvent
tics are inert to alcohols and to straight-chain hydrocar-
(B) 10%’ OI iopolymer .
bons. Hence if the base material is a plastic, alcohols
" and straight-‘chain hydrocarbons can be- used as solvents
(C) 9'15?’ methanola‘mme
(P) 035/0 31,6110“, dyesiu?
' in the coating compositions, or as diluents therein. The 35" (n) 050% blue dyestu?
solvent vehicle of the coating composition may consist in
The copolymer (B) is made of 97% vinylacetate and
' whole or in part of alcohols. It is undesirable for some
' purposes to use a coating composition whose solvent
3% crotonic acid and has an approximate molecular
- weight of 28,000; this copolymer is hydrophobic and does
attacks the base material if a str-ippable ?lm is desired, 40 not hydrolyse in Water;
because this prevents easy removal of the ?lm. Also, in
The yellow dyestutf (D) is manufactured and sold by
such case, if the coating composition includes a dissolved
the National Aniline Division of Allied Chemical and
dye, such dye will stain the base material. However, the
Dye Corporation New York, N.Y., under the name of
' invention is not limited to any solvent vehicle or to 21
'strippa'ble ?lm,
Oil Yellow 3 G; this is a disaZO dye, C010111‘ IHdeX 2nd
45 edition, number 21,230, also known as Colour Index
If the solvent vehicle is a mixture which has a major
proportion by volume or weight, or both by volume and
OH
' Solvent Yellow 29;
I
Its formula is given in the Colour Index as ‘follows:
H30
CH;
110
<:>—N=N<:>-@-C>N=NC>
|
1120
CH:
i
130-03
HzC\
oH-oHe
/CH2
>H2C~CH2 '
weight, of an alcohol or alcohols, said solvent vehicle
may have a minor proportion of ketones, esters, aromatic
hydrocarbons ‘or chlorinated hydrocarbons. In such case,
H20
OH:
0H2
V
'
HzC\
'
0H,
nic——-o?,
'The blue dyestuif (E) is a 1,4 dialkyl amino anthra
quinone derivative which is described in U.S.P. 2,211,943;
it is known as Brilliant Oil Blue BMA and manufactured ,
there is no substantial effect on a plastic which is inert to
by the Natl. Aniline Div. Allied Chem. & Dye Corp.
the alcohol or alcohols, so that the ?lm can be easily 60
Ingredients (B) (C) (D) (E) are added in 511606851011
stripped by applying‘ aqueous soap solution with com-‘
to Ingredient (A), as at 20°—3O° C” With Proper Stirring~
bined mechanical action, if an easily strippable ?lm is
It is‘noted that the weight of the triethanolamine is 1.5%
desired. In such case, part of the alcohol or alcohols
can be replaced by straight-chain hydrocarbons to which
. of the Weight of the Ieeetent resin (B)tion of the reactant amine is 0.15%.
The concentra
a
the plastic is inert. The color, gloss and other surface 65
This Coating Composition may be ?ltsfsd, if necessary
characteristics of the plastic are thus unaffected by the
It Provides a transparent ?nalrthin film of uniform thick
application of the ?lm and its removal,
,
ness, which has a green color.
This coating composi
-If a larger amount of nitrogen base is dissolved than
i101] ‘may be applied by brushing, dipping, spraying, etc
necessary to make the residual ?lm strippable by apt0 an Object made of 616311 glass and other nonporous
plication of Water, without dissolving said ?lm in water, 70 materials, at 20° C-—30° C- The miXed Solvent is al
there is also a latent reaction product formed in the
organic solvent solution. In that case, the latent re<
. action product in said residual ?lm will become water
lowed ‘[0 evaporate at 20° C-——30° C- in air at said normal
atmcspheric pressure- This ?lm has good adherence to
a clear surface of glass, metal, stone, plastics and other
soluble and will dissolve after staying immersed in water
non-porous materials.
for some time.
1
v75
When this ?lm is ‘wetted with water the ?lm absorbs
3,100,755
- 10
methane Cl. No. 42,5633 (Solvent Blue 2) with the fol
lowing formula:
water, because the ?lm is now hydrophilic. However,
the wetted ?lm remains stable and adherent in the absence
of mechanical stripping action. Light rubbing, wiping
or pulling, easily strips the ?lm.
After a short redrying
period, the dry ?lm cannot be stripped by mechanical
UK
C _,
action. The ?lm is substantially insoluble in water at
210° C.—30° C.
Example 2
.,_
\\
>=§r<ornmoi
The ultraviolet absorber (N) is 2,4 dihydroxy benzo
The solvent vehicle or solvent is as follows, the pro
phenone. The method of preparation is as in Example
portions being by volume:
’ 10 1. This composition can be used to form a ?lm on
Percent
any non~porous surface, including many plastics. In this
n-Butanol
Xylene
__________________________________ __
example, the weight of the nitrogen base is about 5.4%
17
of the acid resin.
____________________________________ __ 15
Cellosolve (glycol nionoethyl ether) _____________ __ 38
Methanol
____________________________ __' ____ __
Isopropanol
Isobutanol
Example N0. 4
10
The solvent vehicle or solvent is as follows, the pro
________________________________ __ 10
_________________________________ __
portions of its ingredients being by volume:
10
Percent
The solvent is anhydrous or substantially anhydrous.
n~Butyl alcohol ______________________________ __ 17
The coating composition in parts by weight consists of 20
the following:
..
Xylene
Percent
Methanol
(F) Solvent ______________________________ __ 91.0
(G) Co-polymer __________________________ ..
8
(H) Tetraethylenpentamine _________________ __
0.1
(1) Orange dyestuff ________________________ __
0.9
____________________________________ __ 15
Cellosolve (glycol mono ethyl ether) ___________ __ ‘38
__________________________________ __
Isopropanol
________________________________ __
Isobutylalcohol
10
l0
____ __; ______________________ __ 10
The solvent is anhydrous or substantially anhydrous.
The coating composition, in parts by weight, consists of
the following:
The co-polymer (G) is made of 98.5% vinyl acetate and
1.5% maleic acid; its molecular weight is approximately
Percent
40,000.
(F) Solvent
_______________________________ __
78
The orange dyestu?i' is a xanthene dye, Colour Index
Number (2nd Ed.) 45,456; it is also known as C & D
orange No. 14. Its formula is given in the Amer. Journ.
of Pharm. Sept. 1942 as follows:
(B) Co~polymer ___________________________ __
(C) Triethanolamine _______________________ __
(G) Co-polymer ___________________________ __
11
1
5
Br
HO
H000
(O) Dibutyl phthalate _______________________ __ 2.5
(P) ‘Iodine ________________________________ __. 2.5
Br
O————
—-—-C\—
Br
Copolymer (B) is the same as in Example 1; Co-polymer
OH
(G) is the same as in Example 2. The preparation is the
same as in Example 1.
COOH
.
If this solution is cast on a clean glass plate and the
0\CO
/
40
solvent is allowed to evaporate, the remaining dry ?lm
is transparent and has a light brown color. If said ?lm
is wetted ‘with water it can be lifted from the glass plate
and at the same time be stretched. When stretched to
about 21/2 times of its original length the stretched, soft
?lm can be transferred to another glass plate. It dries
within a short time while kept in the stretched position
and now adheres ?rmly to the transferred glass plate.
This composition is prepared as in Example No. 1. In
this case, the weight of the nitrogen base is 1.25% of
the weight of the acid resin (G). The concentration
of the basic reactant is 0.1% of the Weight of the coating
The ?lm is still transparent and the color has changed
to a light, pinkish yellow. This film now polarizes light.
If two such ?lms are superimposed with the stretched
dimensions parallel to each other incident light can
‘If one ?lm is rotated gradually
up to 90 degrees incident light is gradually extinguished;
Example 3
the light extinction reaches a maximum when the ?lms
The solvent vehicle or solvent is ‘as follows, the pro 55 are crossed at 90 degrees. ‘Instead of transferring the
composition.
, pass through both ?lms.
Properties and applications same as in Example 1.
portions of its ingredients being by volume:
Percent
Xylene __________________________________ _;__
Toluene
7
___________________________________ __
Isopropanol
35
________________________________ __ 30
n-Propanol _________________________________ __
2
n-Butanol
__________________________________ __
1
Methanol
__________________________________ __ 25
stretched ?lm to ‘glass, it can be transferred to a trans
parent plastic sheet, and the stretched ?lm can also be
sandwiched between two transparent sheets. Instead of
using two different co~polymers I can use only one in
60 the above formulation.
Example 5
The solvent vehicle or solvent is as follows, the pro
The solvent is anhydrous or substantially anhydrous. 65 portions of its ingredients being by volume:
The coating composition, in parts by weight, consists of
the following:
Percent
(J) Solvent _______________________________ __
(B) Co~polyrner __________________________ __
11
0.6
2
iso-Amylacetate _____________________________ __
3
n-Butyl acetate ______________________________ __ 12
Methyl ethyl ketone ________ _; ________________ __ 12
86
(L) Meta-amino phenyl methyl carbinol _______ __
Percent
Ethyl acetate ________________________________ __
70
(M) Blue dyestuff __________________________ __ 1.25
(N) Ultraviolet absorber ____________________ __ 1.15
Methyl iso-butyl-ketone"; ____________________ __
Methanol
3
__________________________________ __
8
Ethanol ____________________________________ ..
10
llsobutyl alcohol _____________________________ -_ 10
The co-polyrner (B) is the same as in Example 1.
The
blue dyestuif (M) is Victoria Blue 4R base, a triaryl 75
Isopropanol
________________________________ __ 30
Secondary butyl alcohol ______________________ __ 10
3,100,755
1i.
The solvent is anhydrous or substantially anhydrous.
The coating composition, in parts by weight, consists of
the following:
Percent
(Q)
Solvent"; ____________________________ __ 87.0
(B) (Io-polymer _______________ -7 ___________ __
(S)
3. A coating composition according to claim 1, in
which said resin is a co-polymer of vinyl acetate and iso
crotonic acid.
4. A coating composition according to claim 1, in
5 which said resin is a co-polymer of vinylacetate and male
ic acid.
10.0
l-amino tetradecane_.; __________________ __
0.2
(T) Blue dyestuif __________________________ __
(U) Black pigment ________________________ __
0.4
2.4
.
5. A coating composition according to claim 1, i
which said resin is a co-polymer of vinyl acetate and
fumaric acid.
6. A coated object, said object having a coating which
The 10 is a ?lm formed from a composition according to claim 1.
blue dyestuff (T) Calcogas Blue NA, an anthroquinone
7. A coated object, said object having a coating which
dyestu? made by the Calco Chem. Division of the Ameri
is a ?lm formed from a composition according to claim 2.
can Cyanam-id Corp. of New York. C. I. No. 61555, also
8. A coat-ed object, said object having a coating which
C. I. Solvent Blue 14, also known as D & C Blue No. 5.
is a ?lm formed from a composition according to claim 3.
The formula is as follows:
9. A coated object, said object having a coating which
The co-polymer (VB) is the same as in Example 1.
is a ?lm formed from a composition according to claim 4.
10. A coated object, said object having a coating which
is a ?lm formed from a composition according to claim 5.
11. A transparent coated sheet, said sheet having a
'dichroicly stained coating or layer which is a ?lm pro
vided by a lacquer of a composition according to claim
1, said coating being oriented by stretching said coating
while in the water-moistened, detached state, said coated
The pigment (U) is carbon black.
25 sheet having light-polarizing properties.
The addition of a commercial dispersing agenti-s optional.
12. A coating composition according to claim 1, in '
The soluble ingredients (R) (S) (T) are added to
which the weight of said resin is 10 to 100' times the
and dissolved in the solvent (Q) in the above-named
Weight of said nitrogen base.
succession. The pigment (U) is then dispersed in the
13. A liquid coating composition which is a lacquer
solution;
30 characterized in that the ?lm provided thereby upon
The residual ?lm is_ translucent to opaque, depending
evaporation of the solvent thereof is insoluble in water
V on its thickness.
Like the other films, it can be stripped
and after contact with water is strippable by mechanical
action from a surface protected thereby, said composition
The improved ?lms can be thus used to provide colorless
comprising, as the lacquer solvent, a volatile organic
or colored protective ?lms for storing and shipping vari 35 solvent containing less than 5% water, a resin dissolved
ous'articles and materials.
in said solvent and an organic nitrogen base dissolved
As one illustration, a glass lens which had a dry coat
in said solvent, said resin being a co~polymer of vinyl
ing made according to Example No. 1, was immersed in
acetate and an unsaturated carboxylic acid containing a
water at 20° C.—30° C., under normal atmospheric pres—
total of four carbon atoms and selected from the group
sure of 760 millimeters of mercury. No perceptible solu 40 consisting of rn'aleic, fumaric, crotonic, and isocrotonic
after being wetted with water.
'
tion of said ?lm in the water was ‘observed at the end
acid, and being non-hydrolyzable in water, said resin con- I
of an immersion period of one hour.
taining from 95 % to 99.5% vinylacetate groups and
from 0.5 to 5% of the carboxylic acid groups, said nitro
gen base being 0.5 part to 10 parts by weight to 100 parts
'
The thickness of the ?lm may be from one micron to
eighteen microns, with a preferred range of nine microns
to fourteen microns. Thicker ?lms may be formed by 45 by weight of said co-polymer, said organic nitrogen base
increasing the solid content and viscosity of the lacquer.
being substantially non-volatile at 20° C. to 30° C. under
I have described preferred embodiments of my inven
normal atmospheric pressure of 760 millimeters of mer
tion, but numerous changes, omissions, additions and
cury, and being soluble in said solvent in amount of at
substitutions can be made without departing from its
least 1 part of nitrogen base in 100 parts of solvent.
scope.
V
.
50
This application is a continuation-in-part of my appli
cation Serial No. 503,034, ?led April 21, 1955.
14. A coating composition according to claim 13, in
which said resin is a co-polymer of vinyl acetate and
crotonic acid.
15. A coating'composition according to claim 13, in
I claim:
1. A liquid coating composition which is a lacquer
characterized in that the ?rm provided thereby upon
which said resin is a co-polymer of vinyl acetate and
isocrotonic acid.
evaporation of the solvent thereof is insoluble in water
and after contact with water is strippable by mechanical
16. A coating composition according to claim 13, in
which said [resin is a co-polymer of vinyl acetate and
maleic acid.
action from rasurface protected thereby, said composition
comprising, as the lacquer solvent, a volatile organic and
117A coating composition according to claim 13, in
substantially anhydrous solvent, a resin dissolved in said 60 which said resin is a co-polyrner of vinyl acetate and fu
solvent, and an organic nitrogen base dissolved in said
rnaric acid.
solvent, said resin being a ‘co-polymer of vinylacetate and
18. A coated object, said object having a coating which’
an unsaturated carboxylic acid containing atotal of four
carbon atoms and selected from the group consisting of
is a ?lm formed from a composition according to claim 13.
19. A coated object, said object having a coating which
maleic, fumaric, crotonic and isocrotonic acid, said resin 65 is a ?lm formed from a composition according to'claim
containing from 95% to 99.5% vinylacetate groups and
14.
from 0.5% to 5% of said carboxylic acid groups, said
20. A coated object, said object having a coating which
organic nitrogen base being substantially non-volatile at
is a ?lm formed from a composition according to claim
20° C. to 30° C. under normal atmospheric pressure of
760 millimeters of mercury said nitrogen base being 0.5 70
15 . >
21. A coated object, ‘said object having a coating which
part to 10 parts by weight to 100 parts by weight of said
is a ?lm formed from a composition according to
co-polymer.
claim 16.
2. A coating composition according to claim 1, in
which said resin is a co-polymer of vinylacetate and cro
tonic acid.
'
22. A coated object, said object having \a coating which
is a ?lm formed from a composition according to
75 claim 17.
3,100,755
13
'
14
-.
23. A transparent coated sheet, said sheet having a dichroicly stained coating or layer which is a ?lm provided
by a lacquer composition according to claim 13, said
coating being oriented by stretching said coating while
References Cited in the ?le of this patent
UNITED STATES PATENTS
2,562,852
in the water-moistened, detached state, said coated sheet 5
2,698,316
Giammaria ___________ _._ Dec. 28, 1954
having light-polarizing properties.
2,806,020
Scott et a1. ___________ __ Sept. 10, 1957
Baer ________________ __ July 31, 1951
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