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Патент USA US3063883

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States Patent 0
' 3,063,873‘
CC
Patented Nov. 13, 1962 -_ ‘I
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3,063,873
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ALKALI-SENSITIVE COATINGS
5 Claimsn
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hot seawater under pressure somewhere from 90-95%015
.
the radioactive particles are removed alongwith the hot- '
' water-removable top coating in a process of “tactical deg
John ‘R. Saroyan, 1320 Carl Ave., Vallejo, Calif.
No Drawing. Filed Feb. 8,‘ 1960,‘. Ser. No. 7,494
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out. By subjecting the exposed surfaces-of the ship with
DECONTAMINATION PROCESS UTILIZING
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coating consider a shipv at sea trapped in radioactive fall
(Cl. 134—4)
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’
contamination.” After the ship has returned to shipyard
’
(Granted under Title 35, US. Code (1952), see. 266)
' the alkali-sensitive undercoating along with the remaining
contaminants is removed by the application of ,a mild‘.
The invention described‘ herein‘, may be manufactured
alkali solution. In another embodiment a water-sensitive
and used by or for the Government of the United States 10 undercoating is employed._ ‘This water-sens'itive-under
of America for governmental purposes without the pay
coating may vary considerably in adhesive and cohesive .
ment of any royalties thereon or
"
erefor.
properties from the top protective coating. Thistwater~
The present invention‘relatemto a decontamination.
sensitive undercoating is removed,‘ after contamination
process and, more particularly, to one employing either
exposure, at the same'time as the top coating'under the
alkali-solution-removable or hot-water-removable pro 15 action of the pressured hot water or steam and, in fact,
tective coatings.
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usually expedites the removal of the top coating
The protection‘ of surfaces from contaminants ‘has
The invention further contemplates the use ofan alkali- 7
been a continual problem which has received an upsurge
of attention with the advent of atomic weapons and the
sensitive coating as the sole coating to be applied to the I
to-be-protected surfaces. Such a coating may be removed
In addition 20 in whole or in part to meet various degrees of contamina
resulting danger from radioactive particles.
to the more notorious radioactive fallout ‘contamination,
contaminating substances such as dirt, grit, tar, paint,‘
tion.
grease, oil, organic debris, concrete, living'organisms and
facile, and economical method for freeing surfaces from
metal particles have long posed a problem. Most attempts
contaminants, includingvradioactive contaminants.
_
A further object is to provide a decontamlnation‘process ’
which, as one of its steps, provides a normal, durable pro
at, removing these contaminants from surfaces have in
volved ‘the, use of detergents. In addition to the expense
involved‘ this often yields an unsatisfactory removal ‘of
these contaminants. Small particle‘s‘of the contaminant,
such as radioactive particles, for instance, settle into the
pores of the paint covering the'surface and are very dif
?cult to “scrub”fout. To accomplish complete removal
‘
An object of the present invention is to provide a quick,
tective covering for surfaces involved.
'» ,
Another object is to provide a decontamination process
' capable of freeing surfaces from a severe degree of con-,
30-
of the‘contamin‘ant sandblasting or some other equallyv
di?‘lcult and expensive procedure then has been‘ resorted to. .
tamination.
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, An additional object‘is to provide a coating composi
tion which serves as a protective coating under normal...
operating conditions and which easily can be sloughed '1
‘According to the present invention, the surface-to-be-_
oh’ after contamination to free the coated surface of con-: protected is, coated prior {to exposure to contamination 35 taminants.
with a‘ protective coating composition lwhich forms upon
A further object is to provide a protective coating com-’
the surface ‘a dry ?lm of high durability and high weather
position whose dry ?lm can be controllably and easily
ingcapability. ‘The nature of the ycoating composition
removed in whole or to a selected fraction of its original , _
employed is such that the resulting ‘?lm has excellent
wear and weathering-properties and is at the same time 40
Still another objectisv to provide a paint system of
hot-water-removable'. -After the coated surface has been
coatings and undercoatings which join to give protective
exposed to contamination it is then subjected to hot water
coatingvto a surface under normal operating conditions
(fresh, brackish, or seawater) under p'ressure. The coat
and which can be sloughed o? after exposure to severe
ing (dry ?lm), now contaminated, under the action of the ’ contamination to leave the surface contamination-free.
hot water or steam under pressure loses its' adhesive
Other objects and many ofthe attendant advantages of
capability and is stripped from the surface. As an appli
this, invention readily will be appreciated by reference tov
cation, example, such a composition ‘would be applied
the following detailed description.
i _
1 to the skin of a naval vessel to' serve thereon as a durable
The basic coating composition of the invention com
protective coating. ‘After nuclear attack‘ this coating
prises essentially a high polymer plastic of either the
would be washed away by the steam of hot water carrying 50 elastomeric type or the thermoplastic type, or a combi
with it the radioactive particles embedded therein, thereby _ nation of both, formulated with a water-sensitive adhesion ‘
thickness.
freeing the ship from contamination. ‘
To meet situations where a severe ‘degree of contamina- .
A
.
modi?er. The-polymer plastic is substantially water-in
soluble and may possess various degrees of cohesive or
tion is to be encountered the invention embraces the use
adhesive ‘properties. The elastomeric type‘ commonly
of easily-removed undercoatings to supplement the afore 55 possesses
excellent cohesive properties and is limited to’
mentionedv ‘top protective coating. ‘The undercoating
poor adhesive properties; the thermoplastic types possess
serves as an additional barrier between the contaminants
a range of various degrees of cohesive and adhesive prop
and the 'to-‘be-protected surface. As with the top pro
erties. This water-sensitive adhesion modi?er must'be
tective coating, this undercoating is removed, after con
of a type capable of at least maintaining the adhesive
lamination, front the surface it covers and carries along 60 property of the particular plastic and, preferably, of in-_
with it any contaminants i'which .havepenetrat'ed past the
creasing this adhesive property. The water sensitive ad
top coating. In one embodiment an alkali-removable
hesion modi?er is preferably, but‘not necessarily, a ?lm
undercoating is used. To’ illustrate use of the hot-water
forming material.
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removable top coating and an alkali-removable under~
Among suitable high polymer elastomeric materials are.
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3,063,878
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the natural and synthetic rubbers. Some of the synthetic
In the method employed herein the above-described
rubbers are: styrene-butadiene co-polymers (Buna S or
composition is applied to the surface, which, it is antic
GR-S), the chlorobutadiene polymers (neoprene or GR
M), the butadiene-acrylonitrile polymers (Buna N or
ipated, may later be subjected to contamination, and on "
drying becomes a durable protective coating capable of
withstanding typical weathering. Even though the coat
ing may exhibit some leaching effect during atmospheric
GR-N), iso-butylene copolymers (s-Polymers), butyl
‘
rubber or GR-I, polyisobutylene (Vistanex) and poly
sul?de rubbers ('l‘hiokol).
Among suitable polymer thermoplastics are the follow
. this action is slow and the net durability of the coating is
the bitumins vinyls, polystyrene, polyethylene,
retained for extended periods of months. After the'coated
acrylics and silicones. Among the vinyls are included:
surface has been subjected to contamination hot water or
steam under pressure is applied to the dry ?lm of the com-v
position. The adhesion modi?er reacts to the hot-water
or steam to become mobile by dissolving, dispersing, or
ing:
exposure because of the water-sensitive adhesion modi?er,
vinylidene chloride, polyvinyl butyral, vinyl chloride co
polymers, polyvinyl chloride and polyvinyl acetate.
Other appropriate thermoplastics include celluloses, such
as ethyl cellulose, benzyl cellulose, cellulose acetate, cel
lulose' acetate butyrate, and polyamides, alkyds and 15
swelling, simultaneously lowering the adhesion of the en
tire ?lm. Then the impact of the water or steam under
pressure ruptures the ?lm and separatesthe coating from
the surface with subsequent complete removal of the coat
glyptals.
The water-sensitive adhesion modi?er, sometimes here
7 ing and 'the contaminants it contains.
inafter referred to as an “adhesion modi?er" may include
as a broad class a hydrophilic ?lm-forming material
The rate of re
moval of the ?lm is proportional to the rapidity with
which in waterborne systems embraces latices and water 20 which the adhesion modi?er employed is dissolved, swol
len, or dispersed by the pressured hot water or steam.
emulsions and which is known as a thickener or protec
When reference is made to the make-up of the coating " V
tive colloid. Usually this type of material promotes ad
composition it is to be understood that the constituents of
hesion at ambient conditions and may further be de
the dry ?lm are of primary signi?cance. On the other ‘
scribed as a material which shows physical change in the
hand, the composition of the wet ?lm may vary, partic
manner of ?lm de?ciency when subjected to hot water
ularly in relation to the addition of‘ solvents‘to render
up to 212° F. under pressure. Some typical examples of
the composition applicable to the purpose at hand. It is
suitable water-sensitive adhesion modi?ers are: poly
obvious that, if a solvent paint ‘is too thick to apply, add
amide 115 (General Mills: a reaction product of dimer
ing some solvent will render it more applicable; the
ized and trimerized linolenic and linolenic acids with
ethylene diamine), hide glue, bone glue, gelatin, sodium 30 composition of the dry ?lm will not have been altered
thereby.
alginate, gum arabic ammonium caseinate, sodium
It is obvious to one skilled in the art that certain modi
carboxymethyl cellulose, polyvinyl alcohol, methyl cel
?cations in composition can be made to produce a given
lulose, sodium polyacrylate, polyethylene glycol, car
coating composition in three different forms or types:
bowax polyethylene glycol (Union Carbide and Carbon
Company), Santicizer 9 (Monsanto: mixture of ortho 35 namely as a hot melt, solvent system, or waterborne
system. Examples are:
"
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and para toluene sulfonamides), benzoic acid, acetanilide,
diethylene glycol stearate, sodium stearate, polyvinyl
methyl ether, aryl and alkyl sulfonates, glyceryl esters
Parts by weight
such as glyceryl monostearate and glyceryl mono laurate,
glycol fatty acid esters such as ethylene glycol mono laur 40
Example 1 Example 2
ate and diethylene glycol stearate, polyethylene glycol
fatty acid esters such as carbowax 4000 mono laurate
(1) nor MELT svs'rEM
and polyethylene glycol distearate and other hydrophilic
Ethyl cellulose N-14 (Hercules) _____________ __
70
30
materials commonly classed as wetting agents or emulsi
?ers such as fatty acid amines or derivatives and alkali‘ 4
Polyami'le 115 (General Mills) ...... .'_ ______ ..
30
70
(l)
(1)
fatty acid soaps. Although not typically ?lm formers,
certain alkalimaterials, such as sodium or potassium hy
droxide, have also been utilized. The preferred type of
water-sensitive adhesion modi?er is the ?lm-forming type
although the non-?lm-forming types can be utilized under
(Doenax, antioxidant) (may be added to pre
(1)
(1)
(A- 5 stabilizer) ‘ (carbide chemicals-epoxy
stabilizer). _____________________________ _.
vent rltscoloriug) .......................... .-
Example 3 Example 4
Dry ?lm:
certain non-critical conditions.
Ethyl cellulose (N-H) ___________________ __
70
Polynmlde 1X5 ___________________________ __
30
304
70
' 466
200
150
350
Wet ?lm:
The sought-for goal in the formulation of the high
polymer plastic with the water-sensitive adhesion modi?er
Ethyl cellulose sol. 15% in xylene ........ . .
Polyamlde 115, 20% in xylene _________ ..
is the production of a coating which is sut?ciently co
hesive and adhesive to provide adequate protective cover 55
ing and which at the same time is easily removed by the
application of hot water or steam under pressure. When
a high polymer plastic possessing poor or limited ad
hesion, and unmodi?ed, is applied as ordinary paint over
(2) SOLVENT sYs'rEn
(3) WATERBORNE SYSTEM
Example 5 Example 6
Ethyl cellulose N-14 ________________________ __
Polynmi'le 111...-.. . ____. ___
_
Ammonium caseinate, 16% sol
'I‘n'ethanolamine oleate ..... _.
_
Water _______________________________________ __
70
30
30
70
l8—36
18- 36
3-9
3-9
200-400
200-400
-typical surfaces, such as metal surfaces, painted or un
painted, glass, wood, concrete, asphalt, rubber, etc., it
will show loss of adhesion in a relatively short time as
The above listedformulations based on equal dry ?lm
thickness should produce reasonably similar ?lms of a
evidenced by peeling. Commonly, when increments of
representative composition.
water-sensitive adhesion modi?ers are added to such a
Application techniques may vary from one formula
plastic of low adhesive properties, the adhesion char 65 tion‘ to another. For example, the hot melt formulation
acteristic of the resulting composition increases, each ad
of Example 2 is viscous and best can be applied by
dition of adhesion modi?er promoting up to a point the
adhesive properties of the dry ?lm of the composition.
Generally, as the value of adhesion is increased, the
. troweling or by using high-pressure spray equipment.
However, if the amount of ethyl cellulose is reduced and
replaced by more water-sensitive adhesion modi?er, as
value of cohesion decreases. The value of cohesion, how 70 shown by Example 3, the viscosity is lowered and appli
cation of the coating composition can be done easily
ever, does not decrease to the point that an unsatisfactory
with conventional hot melt equipment.
_ '
?lm will result. Thus, the addition of water sensitive ad
hesion modi?er to the high polymer plastic produces a
composition wherein adhesion is improved and the ?lm
therefrom still retains good cohesive characteristics. _
Some other examples of the hot melt type of coating
composition of the invention are as follows with some
75 physical properties included:
8,068,873
S
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5
HOT MELT FORMULATIONS
It is obvious that the coating composition of the in
' vention- should ‘adhere permanently to the surface to’v
Ethyl cellulose N—14_-
Example 7
Example 8
60 ___________ ._
33 ___________ _.
which it is applied until such time as the contaminant.
has been planted and removal of the contaminant is
Example 9
33.
desired.
Santiclzer 9.
50
66
. 33.
Castorv wax (polym- ______________________________ .. 33.
crized
castor oil
Baker.
.
a previously-applied protective coating by playing hot
Polyamide 115
______ __ r~
...'.
Film ............... __ Sogn?t?exi.
l
y.
Hard ________ --
Flexible.
-.
Viscosity ___________ -. Very viscous._ Lower than
Application _________ __ 'I‘rowel with
istic of the given composition.’ To test the removal
rates of given compositions an automatic traveling de
vice ‘housing a specially arranged jet of hot water at
a ‘predetermined temperature and pressure, at a given
Can tro\vel..__ Spray with
difficulty.
Falrlygood-..
Ethyl cellulose N—14..
water or steam, under pressure, over, said‘surfaees. Ac
10 cordingly, the “removal rate" is an important'character
Lower than
dilheulty.
Adhesion ___________ _-
Feir....'. ____ ..
Example 10
Example 11
25 ___________ __
50 ___________ ..
Fair.
Example 12
15 angle of impact, and at a predetermined distance from
panels coated with the individual compositions was sped
past each part at a given uniform speed. Removal tests
conducted on panels coated with‘ compositions of Ex
amplcs 17 and 18 after 6 Weeks ofoutdoor exposure,
33.
Santicizer 9
'__- 25
.
Castor wax (polym- 25 ___________________________ ..
erized
'
contamination of surfaces by the complete removal of
'
Stearic acid
.
-
As previously stated, this invention relates-to the de
castor
oil-
.
.Baker’s).
25
Polyamide 115
50
Flexible _____ .-
Some ?exibility.
Hard.
Viscosity ___________ _-
Lowest ______ .-
Very visc0us._
Lower than
Application"-.. ____ .- Can spray.-._. Trowcl with
-
the coating is noted in square inches per pass):
_-_ 66.
Film _______________ __
.
Adhesion ___________ -.
for example, showed the following results (removal of
20
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Stearic acid
Table 2
Example 17
Can trowel.
Example 18
dil’u‘culty.
Fair _________ __
Fairly good-.-
Fair.
Water pressure (lbs/sq. 1n.)-.--'.---__ 1
Water temperature (° F.)_-._
---.
Sq. inches removal per pass ........ .-
It. is obvious that all of the above melt coating composi
100
185
100
185
I 170
2-
170
10
170
0
170
1
tions also can be formulated as solvent systems or water
The results of this particular test indicate‘. that. Ex-v
borne systems as known to the art and as illustrated by 30'
Examples 1 through 6.
_
ample 17 coating composition was more readily re
The following compositions were tested by being ape
plied over previously painted metal panels and the prop
erties of adhesion. and cohesion of the resulting ?lms
observed after six weeks of outdoor exposure:
moved than Example 18 coating composition. ' Hence, if f
the requirements were such in this particular series of . .
coating compositions that fast removal were required, Ex
ample 16 or 17 coating compositions would‘ be used
in preference to Example 18 coatingcomposition.
- ‘Table 1
'
Using adhesion modi?ers other than Santicizer 9 ‘faster
removal rates were obtained as indicated by the follow
Example 13
Example 14
Example 15
ing removal test results.
40
Formula-Dry film:
'
Ethyl cellulose, N-14- 100 ........ ._
SanticizerQ _________ --
O_-____.-.>_-_
20.
cellulose 501.
666 ________ ._
533.
15% in xylene. '
Santicizer 9 sol. 20%
0 __________ .-
100.
Example Example
- '
Exposure results:
Poor ______ _-
Cohesion.
Exccllent.__.
Very good.
Dry ?lm ____________ _.
Tough._..__
Alittle
Peeling ____ ._
Some peeling.
Less than 1..
About 1.
Benzoic acid .................... Aeetanilide. .
Fair.
_
Ethyl cellulose, N~14 ........... -
Polyamicle 11 5
?exible.
' Approximate pounds
of pull required to
20
Formule—-Dry ?lm:
-
Adhesion---"
'
Table 3
19
in Cellosolve.
Condition..___‘ _____ .-
.
.
80.
Ethvl
Formula-Wet ?lm:
(Formulas ‘are all by parts by
weight.)
Formula-Wet ?lm:
.
.
Benzoic acid sol. 20% in Cello
solve- ........................ ..
Aeetanilide sol. 20% in Cellosnlve.
Ethyl cellulose N-14 sol. 15% in
strip a 1" pulling
piece.
xylene ........................ __
Example 16
Example 17
Formula-Dry ?lm:
L0
Formula-Wet ?lm:
Ethyl cellulose sol.
15%in xylene.
Santicizer 9 sol. 20%
in Cellosolve.
_
Sq. inches removed per pass ____ -.
_
35
140
12
.
100
140
35
Example
22
60
Good ______ _.
Flexible.
Approximate pounds
of pull required" to
strip a 1" pulling
Water temperature (° F)...
50.
250.
I
dhesion ___________ ..
50.
383.
Cohesion ........... -_ ---do-.
piece.
Removal tests-Formula:
Water pressure (lbs/sq. in.)--.'.-
'
Ethyl cellulose, N-14.
Santicizer 9 _________ ..
Exposure results:
Polyamide 115, 20% in'xylpnp
Example 18
Very good...
Fairly good‘.
Excellent
air.
Formula-Dry ?lm:
..-. Flexiblc....'. Hard;
No peeling._ No peeling__ No peeling;
About 3~5..- About 3—5... About 5-6.
>
Benzoic acid-
I
Anetnnilide
-‘
'
Ethyl cellulose, N—14-. ..................... -_
.
Polyamide 115
-
Formula—-Wet ?lm:
85
Benzoic acid sol. in 20% Cellosolve
_ .
' Aoetanilide sol. 20% in Cellosolvc ........... -
Ethyl cellulose N-14 Sol. 15% in xylene.- ' Polyamide 115, 20% in xylene ............... .
From the results of the above exposure test, it can
clearly be seen ‘that Examples 13, 14 and 15 would be
unsatisfactory as coating composition of the invention for
long periods of outdoor exposure because of the loss of
adhesion and the subsequent peeling of the dry ?lm at
ambient temperatures and conditions. Hence Examples
16, 17 and 18 would be more practical and useful when
' long periods of exposure are anticipated.
Removal tests-*Formula:
Water pressure (lbs/sq?.‘ in.) .................... ..
Water temperature (° J...
.
35
' Sq. inches removed per pass .................... -.
It can clearly be seen that the removal rates of the
dry ?lm' of the coating composition shown in Table 3_
are greater than the removal rates for the type of for
'
75 mulas shown in Table 1.
3,063,873
2
in ethyl cellulose and agitate until dispersed.
By varying the water sensitive adhesion modi?er as
. moval can be effected.
Gain
300° F. and off ?re.
to the hot water sensitivity property, various rates of re
The following coating composi
tions of the invention given in Table 4 showed in gen
eral very fast removal rates.
Table 4
Example 33
(A)
Examples
l
24
Formula-Dry ?lm:
Ethyl cellulose, N-14 (Her
cules) ____________________ __
Polynmide 115 (General
Mills) .................... .-
25
26
27
28
29
30
10
Ethyl cellulose N~l4
5"
Polyvinyl methyl ether _____________________ ._
40
Antioxidant and heat stabilizer may be added
Very viscous. Fluid.
20.
_
80. ‘
1% by weight Deenox and A-5.
Process-Heat polyvinyl ether to 275° F. Sprinkle in
ethyl cellulose and agitate until dispersed. Gain 300° F. 5
80
70
60
5O
40
30
20
20
80
40
50
60
70
80
Formula-Wet ?lm:
Ethyl cellulose, N-14 15%
and oil ?re.
.
s0l.ln xylene ............. _. 533
466
400
333
266
200
133
100
150
200
250
300
350
400
It has bcenfound that the removal rate is sui?ciently
rapid to be practical only if a minimum of 10% by weight
of water-sensitive adhesion modi?er is used, this 10%
being ?guredon the total weight of the ?lm-forming con
Example 34
15
Santicizer 9 ____ .._
_
66
Polyvinyl acetate ____________________________ __ 33
Polyamide 115 20% sol. in
xylene ___________________ __
(B)
Process.—Heat Santicizer 9 to melt. At 280° F. add
20 polyvinyl acetate.
Continue agitation until dispersed; '
When uniform, take off ?ve. Do not exceed 350° F.
' Example 35
' stituents of the dry ?lm of this composition.
25
There also appears to be a lower limit to the quantity
of high polymer plastic required for a satisfactory com
position, this amount being about 10% of the total weight
of the ?lm-forming constituents of the dry ?lm of the
composition.
A
B
C
D
40
33
25
33. 3
Glyceryl monostearate _________________ a’... 40 33 25
Castor wax (Baker's polymerized castor oil). _.._ _.-_ 25
22. 2
22.2
22.2
Santicizer 9 ________________________________ ._
Ethyl cellulose N~14 ______________________ -_ 20
The invention contemplates the use of supplementary
33
25
E
22. 2
33. 3
22.2
22.2
30
Process.--Heat to melt all ingredients except ethyl cel
lulose. Gain 280° F. Then with agitation slowly sprinkle.
in ethyl cellulose. Continue agitation until ethyl cellulose
materials usually are economical and their use in combi
nation with the high polymer plastic and the adhesion 35 is uniformly dispersed. Gain 300° F. and off ?re.
modi?er would greatly reduce costs and yet not seriously
Example 36
materials in addition to the high polymer plastic and the
water-sensitive adhesion modi?er. These supplementary
' alter the required ?lm characteristics of adhesion and
cohesion. Such supplementary materials usually are wa
Glyceryl monostearate ..___; __________________ __ 25
As a speci?c example, the stearic acid and castor wax of
with agitation disperse Vistanex. When uniform, gain
Example 10 greatly reduce the viscosity of the molten
coating composition thus permitting ease of application.
300° F. and off ?re.
Santicizer 9
25
ter-insoluble and comprise natural and synthetic resin,
_-_
25
vegetable, mineral and petroleum wax, synthetic wax, 40 Castor wax
Polyisobutylene (Vistanex LM-MS, Enjay Co.) ___._ 25.
metallic soap, plasticizer or fatty acid. Said supplemen
tary materials may perform certain functions such as, for
Pr0cess.—-Heat glyceryl monostearate, Santicizer 9 and
example, reducing the viscosity of a hot melt composition.
castor wax to around 250° F. Add Vistanex LM-MS and
'
-.
SOLVENT ‘ SYSTEMS
The amount of supplementary materials used can be var
ied up to about 60% by weight based on the ?lm form
ing constituents of the dry ?lm of the coating composi
tion. The basic composition may be loaded with a variety 50
of pigments.
The following are further representative examples of
the invention along with the mixing processes involved:
HOT MELT
Example 31
Santicizer 9 (Monsanto) ______________________ __ 25
Example 37
A
Glyceryl monostearnte ...... .-
B
10
C
10
D
10
E
10
F
10
>
10
Vlstanex 13-100 solids) ..... __ (4. 4) (5. 3) (8. 8) (9. 7) (13. 2) (17.6)
istanex B-IOO. 8.8% sol. in
mineral spirits ............ __
Mineral spirits.’ ____ __
._
5O
40
60
40
100
40
110
40
150
40
200
40
Magnesium silicate.-."
___
12
12
16
16
20
24
Titanium calcium __________ ..
6
6
8
8
10
12
Stearic acid _________________________________ __ 25
Glyceryl monostearate (Aldo 33 Glyco Co.) _____ _.. 25
Ethyl cellulose (N-l4, Hercules) _______________ __ 25
Pr0cess.—Heat Santicizer 9, stearic acid and glyceryl
monostearate together and gain 280" F.. Slowly with
agitation sprinkle in ethyl cellulose. Continue to agitate
until ethyl cellulose is dispersed and gain 300° F. and oil
?re.
Process.--Heat glyceryl monostearate to melt.~ At
00 250° F. slowly add Vistanex 3-100 solution.
Then add .
mineral spirits. Then add magnesium silicate and tita
nium calcium and grind or run through colloid mill.
Example 38
A.
B
O
D
E
F
G
70
60
50
40
05
55
200' 250
300
175'. 255
275
400
266
433
300
Example 32
Dry film:
(A)
Glyceryl monostearate (Aldo
(B)
Ethyl cellulose, N~14 ........................ ..
60 __________ ._' 20.
Polyarnide 115 _______________________________ -.
40 .......... -_
Antioxidant and heat stabilizer may be added
1% by weight Deenax and A-5.
Very viscous. Fluid.
_
33-Glyeo Co. .._'. ....... __
70
80.
E t hyl cellulose (N-14 Her
es ....................
.
cul)
-_
Wet ?lm:
Glyceryl 1 monostenrate,
20%dlspersloninnaphtha._ 150
Ethyl cellulose, 15% solution
innaphtha _______________ _- 466
Process.—-Heat Polyamide to about 275° F. Sprinkle 75
45
333
366
3,063,873
10..
Pr0cess.-'—Heat glyceryl monostearate to melt. Add
naphtha, stlr untll cool. Grlnd. Dlssolve ethyl cellulose
in ‘naphtha. Stir the glyceryl monostearate dispersion
mto thelethyl-cellulose solution. _»
.
.
.
.
.
,
WA
I
Drysml?l
.
gh
A. B I .C ' D I E I F IG
.
_WetPé)1lyviny1 methyl ether ____ __
20
70
60
50 v ~ 40
so
40
so
l
30
60 V70
B-
so -
3 Vfé?gg“ gjfig; eggl?gf?l- poly.
‘ Y
"
_
(‘I
.
'
'
'>
Y
'
y
1
.i
'
7.
_
PTOCeS-Y-—-DISSOIVC ethyl‘ cellulose 111 xylene.
-
‘
20
""
10
’
"""""""" "
g: i?yggy?tgfi??iilii oeuulose"'::""' 20 1° -.--
'
'
\
'9"
'
""""""""""""" "'
Gum arabic___.
-
Wet ?lm:
_
8°
vmyl acetate emqlsion)"'."-j" "'" ""'
.
-
‘
9°
E
8Q .
B‘ lvagfdgeggm “has?” mmh?e’“
mtoluonotunt ________ -__°'_ 100 150 200 250 300 ‘350 400 _
I
D
‘
2 ' Bkso' 11a"sallas‘zsnsllee‘ilaly'
"
.
'
Pl? xyleliené?nln51.66;. 533 466 400 333 266 200 133 1
y
8°
Haas. polyaerylate water emul-
20
'
157
o
1. RhoplexA —33,sollds(Rohm&
v
Ethyl cellulose (N44)
- B
l l
‘ 1 8-5‘ti 0!
poymel'
l 10
DryE?ghm
ylce 11*
u’ se( 1;,—14 ) __..-_.. ' B0
A
FORMULA
I
h
H18
M
5
Example 39
oyvmy
ORNE SYSTE S
Emmi)!“
'
m:
TERB
,
4
Rhoplex, so-sa, 46%. __________ -'. ____ __ .174,
Dlssolve-
{lvkél
_-_-_ --._
“
195
174
195
____
all)? ---------------------------------------------- - - v
polyvinyl methyl ether in toluene. Add‘the ethyllcellu- 20
1.11degm'e,2fé%,_,quemj_________________ " '
I:
lose solution to the polyvinyl methyl‘ ether solution._
(Note: A is too thick. Requires more solvent?)
$303393ailgfggsé?§_g?éaaénn
Gm’); 8.51m, 50%, aqueousuau?_____ -IIII
-idb
-
l
Example 50
‘
,A
Dry ?lm:
\
B
25
D
E
F_
G
'
'
‘Villyllto VAGH (Bakelite
70
60
50‘
40.
go
20
'30
40
50
60
'0
so
266
200
133
_
.
'
methyl lsobul'yl
.
ketone) __________________ _- 533
r
,
100
vlnylaceme emulsion); _____________________ __
.
-
400
'
333
-
(20% in T01l1er1E)_-_ ...... _-
150
200
>
250 .300
I
'-
'
'
t
350
'
_P>r cess
'
'
'egue _______________________ __
_-_
35
400
.___
1O
7 Gum mm
wet mm:
_ '
>
"""""""""" "
""
Rhop'lex’ A6433’ 45%_____‘_________________ __ 174
'
Bks. 114, 40% _______ __
'
'
l
'
'
'
‘
225
Dissolve vmyllte in methyl lsobutyl' ketone.
195 __.___ ____
_____________ __.___
_
133
galcluélwifiu??usny
0 yv
y met y e
Ql'
""""
aqueous‘
Gummb‘c' 50%3‘411801“;________________ __
Dissolve polyamlde 1n toluene. Add the polyamlde solu- 40
-
'
4o
20 _____ >____
m...
l
B
C
'
..
.
D
_
E
l
F
>
G
Y
»
b
Polyvinyl acetate AYAT_.._
so
70
so
5o
4o
30
20
20
30
40
50
60
70
80
15%
.,
'
'Folyvlnyl
‘én’l'fffs‘ion g?lgimylgte,
________________ __
to
m
50 wet ?lm;
..
100
150
v20o
u
l.
250
300
350
.
‘B
'
'
l
M’
“as
-
________ __
2o. 80
- so- 20
so- 20
'
'a. Latex Bks. 114,407., _________ __
gy?igtlgllt; water, 10% by 533 466 400 33,) 666 200 1.";
_
.
o. Adhesion modi?er emulsion,
AYA . In lsvpropyll 90%
20% SantlcizerQinCellosol
R...
Sauticizer 91 (Monsanto), solids-
acetate
'
- A
45 Dry m'm: ’
FORMULA
_
a. Latex Bks. 114, 40% (Bakellte's) polysty-
santlclzeril ---------------- __
We! ?1m=
4
Example“
Example 41 '
A
,
'
'
v50-200 ________ __
- b. Latex Rhoplex A9453, 46%.-
Rh
_
400
'
1
e‘
3
° sanmiwg .em“ “on 0%
I
________________ __
"5:35:65.
zétlgg
-
l
55
amides).
'
'
Pr0cess.—-Stir the emulsion together, avoidingv
sive beating of air into the mix.
SANTICIZER 9 EMULSION
90% isopropyl alcohol and 10% water. Dissolve San
ticizer' 9 in Cellosolve. Mix the two solutions.
Santicizer
9
-
exces- ’
p
100
15% aqueous sol.—Ammonium casein'ate _____ __
Example 42
A‘
B .
C
D
E
F
-
Polyvinyl acetate (AYA'1‘)__
80
70
60
50
40
30
20 65
20
30
40
5O
60 '
70
80
>
> ,
15% S01. polyvinyl acetate
in
ethyl alcohol-
_
,
1
_
31200
to boiling; Add the mixture of ammonium caseinate,
triethanolamine oleate and -( 1) 44 parts water. Stir
vigorously. Grind or run through homogenizer.
’
-
wow-(25:1) ______________ __ 533
466
400
333
266.
200
133
20%polyamide115intoluene_ 100
150
200
250
300
350
400
Resin base: '
Example 45
‘
o
';
v Santicizer 9 (Monsanto) '- ______________ _-=
Stearie acid
1
4
i
65.5
65.5
Glyceryl monostearate (Aldo 33,'Glyco Co.)_> 65.5
' Processo-Dissolve polyvinyl acetate in ethyl alcohol
Ethyl cellulose (N-l4, Hercules) ________ ..
water mix (25:1). Dissolve polyamide 115 in‘ toluene.
Stir the two solutions together.
6
44
Process. "Heat Santicizer 9 and (2) 200parts of water
,
pPulyamlde 115 ............. __
AYA'I‘
Water
(2) Water
G
y
et ?lm:
36
Triethanolamine oleate ____o..'.___..._____‘ ______ ___
(1)
1
v -
-1 Santlcizer 9 Emulsion 30% (mlxture'ot ortho and para toluene sulion
Process-l-Dissolve polyvinyl acetate in a mixture of’
Dry ?lm:
.150
_ . _ _ . _ _.'-_'‘166*
tion to the vinylite solution slowly with constant stirring.
'
90
'6, Polyvinyl methyl ether _________ __
wo~1so 60%; _________ __
__
g0
"""""""" "."" “""1'
5. Sodium carboxymethyl cellulose__
-
466
Polyomide 115 (Gereral Mills)
0
I
B. livaltfil'lsenlsltlve adhesion modi?er:
'
Vmyme. VAGH '(Bakehm)
"
I
' 3. wo~1ao, solids (Bakelite, ‘poly
'80
Z0
_-
H
‘2' “all:“?gliisegtgglgtffi
"1"!" "Sm-Wm‘ high P0P
centuge acetate) .......... --
(15% “1
O
30
wetPffll‘lg’?mlde n5 ------ —-' ----- -.
G
myfhixfl
11' p0 l ymer-pl 88 ll C1
'' '
.
g
" ,
1. Rhoplex lac-33, solids (Rohm &
Haas, polyacrylate water emul
'
. C
n
I
FORMULA .
75
65.5
262.0
3,063,878
11
12
Resin base ___________________________ _..
262
15% aqueous sol. ammonium cascinate ____ ._..
90
Triethanolamine oleate _________________ __
8
(1) H2O ________________________ __Y_____
44
(2) H2O“ _
I
__
_
1,000
ASP 100 ?ller, 64% aqueous slurry _______ __
’‘Add more water for application if required.
155
'
pressured hot water or steam application. When the
water-sensitive undercoating is used a dual removal ac
tion results. The removability of the water-sensitive top
Emulsion:
coating is'acceleratcd by the fast loss of adhesion caused
(a
by the water-sensitive undercoating giving way. Typical ~
of water-sensitive materials which may be used’ in the
undercoating are methyl cellulose, sodium alginate, and.
polyvinyl methyl ether. The alkali-sensitive coating may
employ certain carboxylated polyvinyl acetate polymers ~
such as Shawinigan’s C3Vl0M or others of this series.
Process.—Resin base to 250° F. Add slowly to mix in
Waring Blender of ammonium caseinate, triethanolamine
oleate and (1) 44 water. Add ASP 100 slurry and water.
A typical formulation for one such alkali-sensitive under
coating is as follows:
Example 46
Example 48'
>
Parts by weight
Resin base:
Glyceryl monostearate (Aldo 33) ________ _...
65.5
C3Vl0M polymer (Shawinigan) __.'. ___________ __
90
Santicizer 9 __________________________ __
65.5
Butanol _______________ __-_ _______________ ....'__
105
Xylol -
105
Ethyl cellulose, N—l4 __________________ __ 131.0
Emulsion:
Resin base ______________ -.., ___________ __
Cellosolve (ethylene glycol monoethyl ether) _
15% aqueous solution ammonium caseinate-..
Triethanolamine oleate _______ _-. ________ __
(1) Water ___________________________ ....
(2) Water ___________________________ .._
_
___
For some applications a mild alkali-soluble coating
262
26 20 composition may be used as the sole coating applied over
the surface to be protected. If such a coating is sut?»
45
ciently
thick (several thousandths of‘an inch for ex
8
ample) mono-molecular layers of the dry ?lm may be
44
1344
Titanium calcium pigment _________ ._s._._.._'
100
Magnesium silicate extender ____________ ..
200
removed byacljusting the alkali concentration of the
solution used to wash away the contaminated portions of
the dry ?lm. In this manner all of the coating need not
be removed at one time; removal of only that portion
Pr0cess.-Resin base to 250° F. Add Ce‘losolve. Then
add mix slowly to mix in Waring Blendor of ammonium
necessary to eliminate the contamination can thus be
etfectuated. Portraitive of suitable formulations for this
alkali-removable coating. composition are they
caseinate, triethanolamine oleate, and (l) 44 water. > Add 30 sole
titanium calcium and magnesium silicate‘ alternately
with remainder of water.
following:
_
I
Grind or run through
_
homogenizer.
35
Example 47
Example 49
Water base formulation (clear): ,
Parts by_ weight .
C3Vl0M polymer resin (Shawinigan) ____ __'__. 100
28% NH4OH
B
-
O
'
_
Pine oil
'
3
Example 50
_
88
»tute emulsion, solids _____ ..
Polyvinyl methyl ether ____ ..
Wet ?lm:
Lacquer-phase poly v i n yl
acetate emulsion 1 (46%
solids) ................... ..
152
130
108
100
150
200
250
_
Parts by weight I
C3Vl0M polymer resin (Shawinigan) _-____ .._ 100
28% NH4OH __________________________ __"
Water
174
20% aqueous sol. polyvinyl
methyl ether ............. _.
_
Water base formulation (clear):
Lacquer-phase polyvinyl ac
3
230
FORMULA
Dry ?lm:
_
Water
Pine
400
..__
oil
I
' v
‘
_.._->
_--
228
'
3
_
Pigments may be addedto Examples 49 and 50 to pro—
duce camou?age or decorative colors.
l Lacquer- hase polyvinyl acetate (AYAA) emulsion:
(A) 82% lacquer phase:
Polyvinyl acetate AYAA ............................. ._
7
Various modi?cations falling within the scope of normal
skill in the art obviously may. be resorted to and are
50.
Tricresylphosphats
5.
Toluene. -
3.
contemplated by this invention.
What is claimed is:
Oleic acid _______________________ .._. ............ -.'.---_.
p
1. A process for protecting surfaces liable to be sub
100. 0
jected to contamination which comprises applying to said
(B) 18% water phase:
92. 0
8. 0
28% ammonium hydroxide ........................... ..
surfaces, prior to exposure of the surfaces to contamina
tion, a relatively substantial layer of an alkali-sensitive
100. 0
coating composition whose dry ?lm is removable by an
alkali-solution in proportion to the degree of alkalinity of
the removing solution and washing said alkali-sensitive
Distilled water ....................................... ._
Process-Prepare phase A and B separately. To 18
parts' by weight of water phase B add with stirring 82
parts by weight of lacquer phase A. If both phases are
warmed emulsi?cation takes place easier. Mix the
coating, after exposure of said surfaces to contamination,
with an alkali .solution whose alkalinity is adjusted to re
move the contaminated portion of the coating but leave.
on the surfaces the uncontaminated portion of the coating.‘
2. The process of claim 1 wherein the composition of
lacquer-phase emulsion and- the aqueous polyvinyl methyl '
ether solution.
I
Where an excessive degree of contamination is to be
encountered, removable undercoatings are used to supple 65 said alkali-sensitive coatingcomprises, by weight, about
29.7% polymer resin, about 0.9% ammonium hydroxide, '
ment the composition described above. Thisunderooat
about 68.5%‘ water, and about 0.9% pine oil.
ing may be alkali-sensitive or, like the topcoating, also be
3. The process of claim 1 wherein the-composition of
v water-sensitive.
In the ?rst instance, after the water
said alkali-sensitive coating comprises, by weight, about
29.7% polymer resin, about 1.5% ammonium hydroxide,
sensitive top-coating has been removed by the application
of pressured hot water or steam, a mild alkali solution,
such as soapy water or hot Weak sodium hydroxide solu
about 67.9% water, and about 0.9% pine oil.
tion, is applied to remove the undercoating along with the
balance of contaminants. not carried off by the previously
removed top-coating ?lm. In the second instance the top
coating and undercoating are removed together at the
proportion to. the degree of alkalinity of vthe. removing
solution comprising, by weight, about 29.7% polymer
4. An alkali-sensitive protective coating composition
whose dry ?lm is removable by an alkali solution in
75
-
l
1
V
>
'
V
13
1
‘
3,063,878
,
’
resin, about 0.9% ammonium hydroxide, about 68.5%; -V
‘water and about 0.9% pine oil.
’
,
-
'
'
v
I
14,
~
References Cited in theme of this patent
_
UNITED STATES PATENTS
5. An alkali-‘sensitive protective coating composition
whose dry ?lm is removable by an alkali-Solution in pro-
-
.
>
2,936,938
Hess ___._-__~_,_______ _;_l ]u]y 13', 1937
portion to the‘degree of alkalinity of ‘the removing solu- 5
- 2,563,537
_ Mam _____ __.____ ____ _-__ Aug 7, 1951
tion comprising, by weight, about 29.7% polymer resin,
about 1.5% ammonium hydroxide, about 67.9% water,v '
2,577,514
2,377,131
Mém _ ________________ ___ Dec_ 4, 1951
- Ova-bolt, et 31 _________ __vM-a'n 10, 1959‘
and about 0.9% pine oil. I
-
_
-
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