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Патент USA US2404463

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Patentedluly 23,1946 ‘
' 2,404,463 '
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"PATENT?ames“
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lifelikeinouaousmgonrnm'r
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- Marvin '1‘. Schmidt, Chicago, 111., assignor to
‘United States Gypsum Company, Chicago," 111.,
a corporation of Illinois
‘No Drawing.
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I Application February 23, 1944, ' .
Serial No. 523,581
' ill-Claims. (01. 106-143);
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~ hence cannotibe properly-sized until-:1
‘One
' This invention relates to an improvement in the
art of manufacturing colored» washable emulsion ‘ of‘ the . outstanding :advanta'ges 'of‘v an ' aqueous
paints sometimes referred’ to as resin emulsion
paints and more particularly. to a paint which is
uniform in color and; free from streaking and
blotching when applied to ordinary surfaces.
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__It is. the purpose ofvthis invention to produce
a colored emulsion .paint which is substantially
emulsion'paint is that it can'be applied-to green
walls without previous drying, and to; dry} ‘and
size ‘the wall so that it can be painted would ‘be
i, doing away with one of the big advantages in
using this type'ofpaintr
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It has been discovered that by the simple 1addi-'
tion of certain materials this di?iculty of streak
freefrom blotching and‘streaking when applied
in thin film form, particularly to surfaces which 10 ing and blotching can be practically completely
are high in‘absorption such as plasterboard or a
lime putty ?nish.
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' eliminated. Thus if di?lculty' of this type is en
.
It is well known that colored emulsion paints,
countered in actual ?eld application,‘ it'can be
overcome merely by mixing. a small quantity
of the inhibitingmaterlal into the paint.
other_'?lm forming materials, will sometimes show 15 The materials that accomplish the purpose of
differences in color when ‘applied over surfaces ~ this invention were obtained as a result of a great
number of trials using various types of materials.
exhibiting different degrees of f‘suction" in various
such asthose madev using alkyd resins, as ‘well as
No predictions arising out'of knowledge com
monly known to those skilled in the art could be
color as streaks along the path of the brush when 20 made. No explanations can be made‘ as to why
only certain few materials will work satisfactorily
the paint is appliedover such surfaces. When a
whileea great range of other materials will not.
painted surface exhibits either brush streaks or.
Numerous theories were considered, but no data
blotches a very undesirable condition exists which
to'support them could be evolved. '
is a consistent cause for complaint in the ?eld.
areas, though the paintitselfais uniform; and in _
addition, these paints often show differences 1 of
Unfortunately,
repainting
- the . non-uniform.
colored surface does not always result in an im
provement of the surface, but in many cases mag
ni?es the dif?culty. The exact, cause of these con
ditions is not known but itisv believed due to
irregular absorption of the surface.
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-'In the description of this invention the term
“blotching” is de?ned-‘to mean-the variation in
shade in localized areas different'from the ?eld
colorv when the ‘same shade of ‘paint is used
throughout, and where such di?erence is not ac
countable for by a corresponding difference in»
Only a very limited number of materials can
;be ‘used for the purpose, One classof materials
which has beenv found satisfactory is the fatty
acid esters of polyethylene‘glycols, such as the
type known as and sold under the‘ trade name
of “Carbowax 4000” and manufactured by the
Carbide and CarbonCompany. It has been found
that‘the, esters of saturated or unsaturated fatty
acids of between 12-24, inclusive, carbon atoms,‘
particularly‘ stearic, :formed with a polyethylene‘
glycol'such as “CarbowaxAOOO,” ‘asreferred to
above, are very well suited for carrying out this
Other materials‘ “which ‘prevent’
streaking and blotching form' the subject'of ‘an
color of the surfacebeing painted. Also, by the - ' invention.
term “streaking” ,is meant the color variation
which followsthe path of the brush strokes in
parallel lines like the , ridges and depressions 40
following the brush though there-may not be such
ridges andv depressions.
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dif?culty, ‘of streaking ‘and . blotching can
other application, Serial No. 523,580,\?led Feb-v
ruary 23, 1944.
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In carrying out this invention, it is preferred to ,
add the material tothe-paint'during‘ its ‘formula
tion as a more complete and accurate intermixin'g
can be accomplished; though it is within ithe'scope
ing the surface with a vamishtype of surfacing 45 of this invention, and sometimes necessary; to add
the polyethylene glycol ester to the paint in'the
material. This treatment is expensive when ap-'
?eld. For purpose of’ illustrating the preferred
plied only for this purpose as in general it is not
method‘of carrying out this ‘invention’ in the fol-'‘
ordinarily neededto accomplish any other pur
lowing example, the material will be added during
pose. In fact, many of the walls to which ‘an
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emulsion paint is to be applied are "green” and‘ 50 formulation.
be overcomeby ?rst thoroughly sealing or prim
2,404,463
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The forthcoming example clearly describes a
paint composition which but for the inhibiting
and other ingredients are added and mixed in a
material incorporated therewith will result in
suitable type of mixer. The Carbowax stearate I
is preferably added last.
The Carbowax stearate can be made by react
ing polyethylene glycol. i. e., Carbowax 4000, with
pronounced streaking and blotching when applied
to many types of surfaces.
Emulsion
stearic acid or it can be purchased already pre
.Pounds
pared from the Carbide and Carbon Chemicals
0011)., as well as other sources. It ‘is preferred
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j 340 10 to ‘add this material as a waterpaste, and con
taining about 25% of the solid material. This is
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Ester gum-linseed oil binder __________ __
166
6% cobalt drier_--__'_1_ _______________ .._
Casein solution, 20% so1ids-___.._. _____ __
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Paste paint
Emulsion-
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additional water if necessary, the dry pigments
514.0 _
prepared by heating 25'parts of the Carbowax
stearate in 75 parts of water. Various modifica
tions of the Carbowax, such as Carbowax 1500,
Phthalocyanine blue _________________ _-
31.6
Cadmium yellow _____________________ __
31.6
Bone black
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4.75
under different trade names. Any of the poly
Titanium dioxide ____________________ _-
900
ethylene glycols can be used as long as the prop
erties are such as to accomplish substantially the
same results as with Carbowax 4000. It is not
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Fine mica _________________ _; ________ __
60
Pine oil
25
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Water approx _______________________ __
.
350
15 can be used as well as equivalent materials sold
2o, intended to limit this application to the addition
Carbowax ester 25% solids ____________ .._ 35-280
of the stearatein paste form to the paint already
prepared for it may be added in any manner and
at any time during the formulation or use of the
The ester gum-linseed oil binder is prepared by
heating to a temperature of 580 degrees F. for
paint as long as the effective result of this mate
about one hour, 41.5 lbs. of ester gum. with 124.5 25 rial is obtained.
lbs. of heat bodied linseed oil. The cobalt drier
Neither is it the intention to limit the scope of
is then added. The drier can be of the naph
" this invention to a neutral ester of a fatty acid;
thenate type. This mixture, while in liquid form,
for the polyethylene glycol need not all be ester-,
is emulsi?ed, by any of the well known methods
i?ed, though a mere solution of the glycol in the
of preparing an emulsion. with the casein solu 30 fatty type of acid is not enough. The mixture
tion to form a binder. Most any type of casein
must be heated to effect some type of reaction;
solution can be used. A suitable casein solution
between the two which need not 'be an entirely
is one which is described in U. S. Patent No.‘
pure ester in itself. There can be an excess of
2,154,362. This can be used to advantage as it is
the acid over that of the polyethylene glycol and
stable for a. considerable length of time to (18561710! 35 excellent results will. still be obtained. Hence.
ration due to aging. However, the preparation of
throughout the speci?cations and claims of this
casein or other protein solutions using alkalies
invention the word “ester" is intended to mean a
such as borax for use in emulsion paints is well
mixture of a fatty acid and a polyethylene glycol
established in the art and a detailed descrip
solution, in stoichiometrical quantities or other
tion of a procedure for making them need not be 40 wise, which has been heated or treated to effect
included in the description of this invention. ‘
' For the sake of convenience for those who may
a reaction between a portion or all of the constit
not be familiar with this art and with U. S. Pate
ent No. 2,154,362, the following procedure, which
uents. Also it is not necessary that the ester be
prepared from the acid alone for other esters
can be used, such as the glyceride as long as the
is based upon the above patent can be used in 45 fatty acid radical can be‘made to react with the
preparing a casein solution. Following this pat-1
ent the casein solution can be prepared by mix
ing 55 lbs. of commercial casein with 24 gallons
of water with thorough stirring for a su?icient
words, an ester interchange can be used to pre
length of time until a smooth mixture of thor-1 50
oughly soaked casein results. About 3 pounds
and 61/2 ounces of sodium stannate are dissolved;
in about 31/2 gallons of water, while in a. separate
container about 10 lbs, of borax are likewise dis
solved in about 21/2 gallons of hot water. The .55
sodium stannate solution is then added to'the
casein mixture, with constant agitation, and as
soon as all of it has been added, the borax solu
tion is then run into the mixture. An additional
amount of, say, 3 gallons’ of water may then be
a 60
the mixture gradually to about 150 to 160 degrees
F. or higher. The mixing. is continued at the
desired temperature until a smooth solution re
sults. Using the proportion above given, the so- .
lution will ‘be found to exhibit an alkaline reaction ‘
equivalent to from about pH 8.0 to pH 9.0. The
ratio of casein to sodium stannate in the above ‘
formula "is substantially 10026.2. The sodium
stannate used has the following formula:
Na2SnOa.3H2O. While casein is' the preferred
type of protein, other proteins may be used in- ‘
When the emulsion has been prepared, using
pare the polyethylene glycol ester if , desired as
well as other methods.
After the Carbowax stearate paste has been
added and the mixing operation has been com
pleted, the paste is then passed through a roller
mill to insure complete dispersion of the pig-_,
ments into the vehicle and to form a paint com
pletely free from lumps.
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Various types of pigments, ?llers and other
?nely divided inorganic material can be used in
the preparation of paints which can be bene?ted
added and the mixing continued while heating 5
eluding those derived from vegetable sources, for
example alpha protein derived from soya beans.
polyethylene glycol in same manner. 'In other
by this invention. However, it is necessary that
some coloring material be present as streaking
and blotching have not been observed to any great
extent in white paints.
Since water is the thin- ’
her, it is possible to use a wide variety of low in
dex of refraction materials such as clays, mica,
etc., known in the trade as ?ller or extenders
to replace a certain amount of the more expen
sive higher index of refraction materials known
as pigments, such as lithopone and titanium di
oxide, as required in an oil type of paint. ' Since
both types of material can be used, in order to
de?ne these two types of material generically, the
word “pigment-?llers” will be used in the forth- .7
coming claims. '.
Paint prepared in the above manner will not
exhibit the streaking and blotching effects com
tactics
f5,
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nishes. natural.
This is done: without any
. sacrifice
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in the desir
able'properties'ofthistype of
onlyaslightincreaseincost.
and with
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waterjinsolubl'e ?lm forming ‘materials;- theseare
preferably
. ,byi'the . use
'caseinwor -
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Although there
been disclosed av practical
embodiment of thistinvention and vspecific exam
pies and uses, which are .given to, insurea clear
understanding ofthe essence of this invention,
added per gallon.~ Other esters, of polyethylene ‘ it is not the intention tobe, limited thereby. for
If the painthas alreadybeenprepared and it
isdesired to prevent streaking and blotching,
then about 4‘ to 32 ‘ounces of the __25%,Qarbowax
stearate ester paste, mentioned. above,
be
glycol canbe
‘Also it is not necessary
that the ester be added'in pas'teiorm.‘ It may be
expedient in manycases notto add the inhibiting
material until actual trouble is experienced as the
obviously many variations may be made by those
‘skilled in- the art and still be within thescope .
of this invention which is only limited in extent
‘ by the forthcoming claims.
It is claimed:
Examples of the‘ saturated and unsaturated 15 emulsion
1. A non-streaking,
paint comprising
non-blotching,
a protein selected , _
difficulty is only occasionally encountered.
,
fatty acids besides stearic between 12 andr24 _
carbon atoms inclusive which can be used in.
forming an ester with polyethylene glycol, such
as Carbowax stearate 4000 to accomplish the
purpose of this invention are myristic, palmitic,
from the group consistingof casein and an al
kali dispersible vegetable protein derived from
soybean,_a solvent for said protein, water, a
water insoluble ?lm forming material, colored
pigment, and a streaking and blotching inhibit
elaeostearic, dehydrated castor oil fatty acids,
ing material comprising an ester ‘formed from
oleic, linolenic and linoleic. Other acids in this
the reaction of a polyethylene glycol and a fatty
group will readily occur to those skilled in the
acid of from 12 to 24 carbon atoms per molecule.
art in which this invention is a part. The pure
2. A non-streaking, non-blotching, aqueous
acids need not be used as the naturally occur 25
emulsion paint comprising a protein selected
ring mixed acids are just as e?ective. In most
from the group consisting of casein and an al
cases the ester can be prepared by simply heating
kali dispersible vegetable protein derived from
the polyethylene glycol with the fatty acid. In
soybean, a solvent for said protein, water, a»
30 water insoluble ?lm forming material, pigment
of the acid.
iillers, at least one of which is colored, and a
In the above example a mixture of ester gum
streaking and blotching inhibiting material com
and heat bodied linseed oil is used. It is not the
prising an ester formed from' the reaction of a
intention to limit this invention to any of the
' some cases it may be desirable to add an excess
polyethylene glycol and saturated and unsat
ingredients used in the preferred embodiment set
forth, for any water resistant ?lm forming sub 35 urated fatty acids of from 12 to 24 carbon atoms
per molecule.
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stance which will have utility in a colored emul
3. The composition of claim 1 in which said
sion paint may be used. It is not necessary that ‘r
water insoluble ?lm forming material is capable
the material be a resin, though most of the emul
of drying by oxidation and polymerization.
sion paints in common use contain a resinous
4. The composition of claim 1 in which said
or polymerizable material, usually oleoresinous.
water insoluble ?lm forming material is a res
Examples of some of the materials which can be
inous material selected from the group consist
incorporated are: treated or untreated oils hav
ing of synthetic resins and natural resins, and a
ing drying properties, alkyd resin, phenol form
solvent for said resin.
aldehyde resins, the various esters of rosin, syn
5. The composition of claim 1 in which said
thetic and natural resins, such as congo gum, 45
water insoluble ?lm forming material is an ester
copal gum and manila gum. These can be used '
of resin acids.
alone, in combination or with solvents; the par
6. An aqueous resin emulsion paint substan~
ticular manner in which they are used as well
tially free from streaking and blotching, com
as the addition of other materials such as driers
and the like are all within the skill of the art of so prising a water insoluble ?lm forming material,
colored pigment, an emulsifying agent, water,
which this'invention is a part and need not be
and a streaking and blotching inhibiting ma
further described.
terial comprising an ester formed from the re
While it is preferred to use casein or some other
action of a polyethylene ‘glycol and saturated
protein material, such as Alpha protein derived
from soya beans, as the emulsifying agent, it is 6.5 and unsaturated fatty acids of from 12 to 24
inclusive carbon atoms per molecule.
not the intention to limit this invention thereby,
'7. A non-streaking, non-blotching, colored,
for other emulsifying agents which are com
aqueous emulsion paint comprising a protein
patible can be employed. The volatile alkali soaps
selected from the group consisting of casein and
are especially suitable for the purpose.
It will be found that paints prepared in ac 60 an alkali dispersible vegetable protein derived
from soybean, a solvent for said protein, water,
cordance with the principle set forth in this im
a
water insoluble ?lm forming material, pigment
vention can be applied over practically any sur
?llers, at ‘least one of which is colored, and an
face without danger of forming an appreciable
ester formed from the reaction of stearic acid
amount of streaks or blotches. A uniform colora
tion will be obtained. Water paints applied over 85 and a polyethylene glycol.
8. A non-streaking, non-blotching, aqueous
a lime putty ?nish and over wallboard are par
emulsion paint comprising a protein selected
ticularly liable to give trouble, yet no difficulty
from the group consisting of casein and an alkali
will be encountered if the paint'is prepared fol
dispersible vegetable protein derived from soy
lowing the principles set forth in this invention.
By way of summary this invention pertains to 70 bean, a solvent for said protein, water, pigment
?llers, at least one of which is colored, a water in- '
the prevention ‘of color blotching or streaking in
a colored aqueous emulsion paint by incorporat- " soluble ?lm forming material and from about 1 to
about 8 ounces of an ester, formed from the reac
ing therein a polyethylene glycol ester of fatty
tion of a polyethylene glycol and a fatty acid con-' acids from 12 to 24, inclusive, carbon atoms. The
non-aqueous vehicle may consist of oils, var 75 taining from 12 to 24, inclusive, carbon atoms '
9,404,468
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per molecule, to each gallon of said aqueous
ture of polyethylene glycol and a saturated and
emulsion paint.
unsaturated fatty acid containing from ‘1,2 to 24 '
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9. A vnon-streaking, non-blotching, aqueous
emulsion paint comprising casein,v a solvent for
said casein, a water insoluble ?lm' forming oleo
resinous material containing an alkyd'resin, pig
inclusive carbon atoms per molecule.
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11. An aqueous emulsion paint substantial]
free from streaking and blotching comprising a
protein selected vfrom the group consisting oi’
ment-?llers, at least one of which is colored, and > casein and an alkali dispersibleyegetable pro
an estervformed by the reaction of polyethylene
tein derivedi'rom ‘soya beans. a ‘solvent for‘ said
glycol ‘and ‘a fatty acid selected from the group
protein, a water insoluble ?lm forming resinous
consisting of stearic, palmitic and oleic acids.
10 binder comprising the resulting product formed
10. An aqueous emulsion paint substantially
by heating an oil'capablej of drying by oxidation
free from streaking and blotching comprising a
and polymerization witha resin selected vfrom
water insoluble ?lm forming oleoresinous binder
the group consisting oi’ synthetic resins and nat
comprising the resulting product formed by heat
ural resins, water, pigment-?llers at least one
ing an oil capable of drying by oxidation and ll 01' which is colored, and the ester formed by heat
"polymerization with a resin selected from the‘
ing a mixture of a polyethyleneglycol and a fatty
group consisting of synthetic resins and natural
acid containing from 12 to 24 carbonlzfatoms per
resins,'a volatile alkali’soap emulsifying agent,
‘water, pigment-?llers, at least one of which is
colored, and the ester formed'by heating a mix- '0
molecule.
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MARVIN T. SCHMIDT. -
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