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Патент USA US2121680

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‘
_ 1,121,680
Patented June 21, 1938,
- UNITED STATES! PATENT
OFFICE -
’ 2.121.680
COATlNG COMPOSITIONS
James A. Arvin. Chicago, Ill., assignor ‘to E. I.
du Pont de Nemours vit Company, Wilmington, 'Del., a corporation of Delaware ~_
i
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No Drawing.‘ Application August 1,1935.
'
Serial No. 34,302
“5 Claims. -(c1. 91-68)
This invention relates to the’ art; of coating
and .more particularly to articles of manufac
ture provided with a protective coating which is
highly resistant to acids, alkalis and other deteri
orating
agents.
'
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-
I
This case is a‘ continuation in part of my
Patent No. 2,060,715.
This patent claims new
resins'known as ether resins and discloses valu
able coated products which are claimed here.
This invention has as an object the manufac
10
ture of products having rigid surfaces protected
with a coating which is highly durable upon out
door exposure and which is substantially chemi
cally inert and. practically unaffected bypro
longed _contact with moisture, acids, alkaiis, and
aliphatic hydrocarbon solvents. A further object
is to provide improved metal products of the
kind Just mentioned. A still further object is
toprovidelnew and useful coating compositions
20 particularly adapted for coating metal or other
articles. having rigid surfaces. Other objects will
appear hereinafter.
_
>
‘
In the preferred method of carrying out my
, invention I coat the steel or other article having
a rigid surface‘ with- a solution‘ of polyether resin
and bake the coated object to remove the'last
' traces of solvent from the polyether resin ?lm.
'30
‘toluene solution of the polyether resin described
below, the coated panel allowed to stand for two
hours at room temperature, and then baked for .
one hour at 250° F. ' After one year’s exposure
the panel was examined and the ?lm ‘found to be
in good condition, having aiiorded the steel ex
cellent protection against rusting. Control
panels put out at the same time but ?nished with 10
an oil modi?ed polyhydric alcohol-polycarboxy'lic
acid resin, oil>type varnish, and pyroxylin lac
quer, respectively, showed rusting of the steel
after eight, ?fteen, and twelve weeks’ ‘exposure.
After two years’ exposure, the, polyether resin.
panel was still in good condition, while at. this
time the .controlshad failed.
The resin of the foregoing example was made
as follows:
'
20
'
Parts
Di(4-hydroxyphenyl)dimethylmethane (M.
P. 157° C.)
456 }
B;B'-dich1orodiethy1 ether______ __-_____s___. 286
Water
-
450
Sodium hydroxidei(50% aqueous solution)‘- 326
room
or until a few drops of clear distillate shows that
temperature.
'
'
'
The polyether resins referred to herein, which . 7 there is no remaining‘free halide. The water is
consist essentially of ether linkages, are obtained ' distilled oil? over a period of two hours, the tem
alkaline metal salts, with organic polyhalides
5 .
The above mixture is re?uxed in an atmos
phere of nitrogen for 10-15 hours with stirring
free of ester groups whose halogen atoms are all
attached to different carbon atoms which are in
30'
perature ?nally being carried to 225~230° C. and
maintained at this point for 12 hours The mass
is' now very viscous and pasty. It is poured while 4 5
hot into a steam-jacketed Wemer-P?eiderer
mixer, washed with water, then. withv small por
tions of dilute hydrochloric acid until the wash
ings are acid to Congo red and’?nally with water
again until the washings are substantially free
turn joined to other atoms by, single bonds only..
A preferred type of polyether resin is the alkaline
reaction product of a dihydric polynuclear phenol 'of chloride ion; The'product is then dried by
of the general formula_
heating in vacuo at 120_-125° C. for 16 hours. The
f .
resin is hard, clear, pale-colored and extremely
tough, and is inert to acids, alkalis, water and
R
.45
Example I
The coating may, however, be allowed to dry at
in accordance with the disclosure in the-- above
mentioned patent by reacting in resinifying pro-'
portions substantially unpolymerizable mono
35 mericg polyhydric phenols, or their. alkali and‘
40
.
A sanded steel panel was coated with a 37%
\ 0O a
light“ Itds insoluble in. alcohol and‘ aliphatic
45
alkyl or aryl) and an organic compound having
hydrocarbons, but soluble in toluene, xylene, and
in aromatic esters such as dibutyl phthalate.
Films 'dry to a hard, non-tacky condition in a
very few minutes by simple evaporation of sol
vent; in this respect, theresin resembles cellu 50
two halogen atoms attached to diiierent carbon
atoms, said carbon atoms being joined to other
atoms by single bonds only.
with oils and most cellulose derivatives, but is
compatible with benzyl cellulose. The resin does
/O
.
.
L
(R being hydrogen, alkyl or aryl, and'R' being
lose derivatives. The resin does not mix readily
The following examples illustrate, the practice‘ ' not heat-harden (like a phenol-formaldehyde v
.resin) nor dry by oxidation (like a drying oil 55 .
.56 ‘of my invention:
2
2,121,080
modified polyhydric alcohol-polycarboxylic acid
Patent 1,812,849, made adherent by means of a
resin).
poly-ether resin undercoat.
‘
'
Example II
A 25% solution of the polyether resin described
Example VI
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the coated panel baked for one hour at 149° C.
After 12 months’ exposure the polyether resin
?lm was still in good condition, while controls
10
‘Galvanized iron sheeting was dipped into a 30
xylene solution of the polyether resin described
below, the coated sheeting allowed to stand at
room temperature for 2 hours, and then baked
.for one hour at 149°- C. Over this polyether resin
coating was superposed a coating of the synthetic
15
thetic' drying oil topcoat from the metal sur
below in a 1: 1- ethylene dichloride-chlorobenzene
I solvent mixture was brushed." on sanded steel, and
of 011 type ?nishes, oil modi?ed polyhydric al
cohol-polycarboxylic acid resins, and pyroxylin _ drying 011 Of Example I in U. 8. Patent 1,812,849
and vthe system air-dried. After twelve months’
lacquers had failed.
'
'
The resin of the above example was made as" exposure the ?lm was in good condition, and
there was no evidence of separation of the syn
follows:
Di(4' - hydroxy - 3 - methylphenyl) dimethyle
'
>
20
methane
,
?,p'-dichlorodiethyl
448
ether___~__; ______ __...... 250
Sodium hydroxide (50% aqueous solution)- 286.
Water
-
-
'415
The above mixture isre?uxed and stirred for '
10 hours, or until a few [drops of distillate are
clear upon cooling.’ The re?ux condenser is then
25 replaced bya downward condenser and the water
distilled off over a period of 2 hours, the tem—
perature meanwhile being carried to 225-230° C.
‘ By maintaining in this range for 12 hours, a,
viscous, opaque mass is obtained It is poured
30 while hot into a steam-jacketed Werner
P?eiderer mixer, washed with water, then with
small portions of dilute hydrochloric acid until
15
face, whereas in a similarly prepared panel but
without the intermediate coat of polyether resin
separation of the synthetic drying oil coating
i'rom the metal surface occurred after approxi-.
20
mately two weeks exposure.
7
Example VII .
A pigmented polyether resin varnish of the fol
lowing composition:
.
'
' Parts'by weight
25
Lead chromate ________ ___ ______________ __ 39.1
Asbestine
‘
7. 9
China clay
v
5. 2
Polyether resin of Example I____________ __ 17. 5
Toluene
g
Xylene
30
the washings are acid to Congo red, and ?nally ‘ was prepared by grinding the pigment mixture
with more water until the washings are substan
for24 hours in the solution of polyether resin in
35
tially free ‘of chloride ions. The product is then
dried by heating at 130° C. in vacuo for 16 hours.
A pale, tough resin is obtained which is soluble
the1to1uene-xylene solvent mixture.v This var
nish was brushed on a sandedasteel panel,‘ and
the system allowed to stand at room tempera
in toluene and insoluble in alcohol. Films there- . ture for’24 hours, after which time it was coated
of dry rapidly to a hard non-tacky condition by
40
with a pigmented synthetic drying oil varnish of
simple evaporation of solvent. ‘ ‘
Example III
the following composition:
_
,
‘ To a solution of 100 parts of the resin ofiEx
ample I in 258 parts of xylene was added a mix
ture of 7 parts’ of carbon black and 55 parts of
45 silumite, and the mixture ground in a ball mill
for 48 hours. This paint was brushed on steel
and exposed for one year to corrosive atmos
_ pheres, e. g}, hydrogen chloride, sulfur dioxide,
Parts ‘ by weight
Synthetic drying oil of Example I in U. S.
Patent 1,812,849 _____ .__‘_____________ __
Silca silica
Asbestine
‘
i _
20.0
45.0
_
_
Indigo
v
Solvent naphtha _____________________ __
Turpentine '
,'
15. 0
45
0. 6
5.0
15. 0
chlorine, etc., at the end oi’ which time the steel
_50 showed no evidences of fasting. Controls of oil
modi?ed polyhydric alcohol-polycarboxylic acid
I resins and pyroxylin lacquers exposed at the same
time to the same conditions had completely failed
55 at the end of this period of exposure.
Example IV
A paint was made by grinding 5 parts of car
bon black in 109 parts of a 36% xylene solution
60 of the resin of Example I, and sprayed both over
wood and over'primed steel. At the end of one'
year’s exposure the panels were examined and.
the ?lms found to
65
in goodcondition.
. 100.6
50
The pigmented synthetic drying oil coating
was allowed to dry for four hours at room tem
perature, and then an unpigmented coating of
the synthetic drying oil of Example I in U. S.
Patent 1,812,849 applied by brushing from a
61.54% solution thereof in a solvent mixture '
comprised of 23.08% turpentine and 15.38% sol
vent naphtha, and after drying overnight at room
temperature exposed’ outdoors.
After twelve
60
month's exposure there was no evidenceof sep
aration o! thesynthetic drying oil coatings from
the substrate, whereas in a similarly prepared
panel but without the polyether resin priming
Example V
coat the synthetic drying oil coatings separated 65
‘A paint was made by grinding ‘31 parts of‘ti- ' from the metal after approximately two weeks’
tanium oxide in- 114 parts of a 35% xylene solu
tion of the resin of Example I, and sprayed both
over steel and over wood.
After one ‘year’s ex
posure to the weather the panels were examined,
exposure.
'
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Any of the resins disclosed in the previously
identi?ed patent, or in Patents Nos. 2,060,716,
2,057,676, and 2,058,510, may replace those men
and found to be in good condition.
tioned in the examples.
.
Another. particularly useful application of ‘my ' 'In place of -,the steel substrate of the examples,
invention is the manufacture of metal products I may'use other substrates such as galvanneal,
provided with a top coating of synthetic drying brass, copper, aluminum, Dow metal, stainless
75 011, e. g., that disclosed and claimed in U. 8.‘ steel, Dural, terneplate, bonderized steel, mar
3
£121,680, '
ble, stone,‘ plaster, glass, ‘or ‘molded synthetic , and other cellulose derivative ?nishes, durable
resins.-
‘
A
5
clears over oil varnish and oil modi?ed polyhydric
alcohol-polycarboxylic acid resin‘ coatings, clear
?nishes for the protection of decorative metal
surfaces, as wellas for marble ‘and polished stone
surfaces, single coat, air-dry, or baking enamels
of high solids and high hiding power for general
industrial use, alcohol‘ resistantfurniture lac
qulers, linoleum ?nishes, ?nishes for vitreous
.
Organic solvents such as benzene, chloroform,
beta,beta'-dichlorodiethyl ether, monoethylether
of ethylene glycol, ethoxy-ethyl-acetate, propyl
ene oxide, cyclohexanone, benzyl alcohol, meth
ylal, etc., may be used as partial or total substi
tutes for the solvents of the examples.
'
vWhile in the vexamples polyether resins have
enamels, protective coatings for glass, P°rceiain, 10
etc., nail polishes, ship bottom paints, as water
proo?ng coatings for plaster, concrete, and gran
10 been used, in some cases there may be employed
coatings containing in addition tothe polyether
resin one or more of the following ingredients:
15
phenol-aldehyde resins, chlorinated diphenyls,
ite, clears over sheet steel to prevent rusting
cellulose ,ethers and esters, cumar, rosin, chlori
prior to fabrication, asr-anticorroslve paints for
nated naphthalenes, damar, methyl methacrylate'
resin, acrylic ester polymers, oil modi?ed poly
hydric alcohol-polycarboxylic acid resins, bitu
quired, gasoline-resistant paints for‘ the interior
mens, etc.v
.
--
chemical containers, for general industrial use 16
where resistance to acids and alkalis, etc., is re-v
of gasoline tanks,‘ as sealer coatings for porous
_
Pigments and ?llers may be added to the poly
ether resin coatings of this invention as needed
and desired. Among suitable pigments and ?ll
building blocks, etc.
.
,
r
The superiority of the products of the present
20
-
invention over those of similar type ?nished with ‘
ers for use are the chrome-greens, iron blues, oleoresinous varnishes or other usual metal pro
chrome yellows, zinc oxide, titanium oxide. china- - tective ?nishes is particularly evident in applica
clay,‘ asbestine, silica,.etc.
25'
'
tions where the ?nish is either under continuous
.
exposure to corrosive atmospheres or to the ac 25
tion of weak acids, alkalis, petroleum oils,‘ gaso- '
Softeners and plasticizers may be added to
these polyether resin coating compositions as
typi?ed by the following: diamyl phthalate, di
line, alcohol, etc. Under these conditions poly
butyl phthalate, diamyl tart'rate, cyclohexyl butyl : ether resin ?nishes remain substantially .un
phthalate, dicyclohexyl phthalate, cyclohexyl'tar- > changed after prolonged‘ exposure, whereas the
30 trate, benzyl butyl phthalate, hexahydrobenzyl’ usual metal protective ?nishes soon disintegrate
and leave the metal surface. completely unpro
phthalate, dibutyl succinate, dicyclohexyl suc
oinate, tricy'clohexyl phosphate, tricresyl phos-' tected. Another very important advantage of
_ phate,-dixylylethane, butyl benzoyl benzoate, etc. polyether resin coatings over the usualtype of met
The coatings of this invention may be applied a1 protective ?nishes is their remarkable water
35 by any well known method, 'e. g., dipping, spraying, ‘ resistance, as evidenced by the fact that they are
spreading, and roller coating. A particularly substantially unaffected by prolonged soaking in
water, whereas the usual type of metal protective
advantageous way of applying these coatings is
bymeans of preformed ?lms of the resin in which - ?nish is generally softened and lifted under these
a precast polyether resin ?lm is superposed on conditions.-' As .metal primers polyether‘. resins
the object to be coated, and the ?lm laminated give stronger and more permanent bonds than
to the substrate by means of heat and pressure. '_ the usual type of metal primer, particularly over
1
.
V
.
In this manner coatings of any desired thickness galvanized iron.As many apparently widely diiferent'embodi
1 and ‘of remarkable uniformity are obtained. As
be 'majde'without
disclosed in my ‘previously mentioned patent, the. 'ments- of this invention
. resins in thin ‘sheets are vnot only self-supporting departing from the spirit and scope thereof, it is
but are remarkably tough, tear resistant,‘ and .to be understood that I do not limit myself to the - speci?c embodiments thereof except as de?ned
‘l The polyether resin coatings of‘this‘invention
inthe appended claims.
, may be used in single or two coat systems, and in
50 the latter instance the other coating may be an
_
.
'
‘1.1m article of manufacture which comprises
tion com
‘oleoresinous varnish, asphalt varnish, cellulose ~ a rigid body coated with a
resin consisting '
derivative lacquer, etc._ I generally prefer to prising a ‘non-heat
bake the polyether resin coating whenit forms ‘essentially of ether linkages,’ said resin com
prising'the reaction product of a- substantially
the topcoating, because otherwise optimum re
unpolymerizable monomeric polyhy'dric phenol
sults with respect to- durability, adhesion, mois
ture-resistance,’ and resistance to weak acids, ' - and an vorganic. polyhalide free of‘ ester group‘
alkalis, and aliphatic bydrocarbons'is not-ob .whose halogen atoms are all attached to different
carbon atoms which are in turn ioined to other
-'
1 By means of the present
highly use - atoms by single bonds only.
so
tained.
-
-
'
ful' products are made
-
either 'a' single
. 2. An article 'offmanufacture having a rigid
coat of the polyether resin Tci- provided with a‘ surface carrying a
two coat system in whichthe topcoat or under
coat is the polyether resin, the other coat ‘being
any other‘ suitable coating material. Speci?c‘
applications in which polyether resin coatings -
are particularly. useful include protective ?nishes
,
v
i4. As an article of-manufacturé metal having 65
anadherent ?lm of the resinvde?ned in claim -1
and/‘atop coat compriaingahardened?lmofc"
divinyl acetylene
lacquers for
pyrolylin'. .
-,
z
5. vGalvaniaiul iron havinggm'fadherent under
coat of resin-de?ned
1v and a top 70H
comprising abardmed ?lm'of divlnyl acety
resisting paints for metal containers, alkali re- -
> sistant?nishes for condenser boxes and ‘motors;
waterproo?ng shot‘ shell
food containers, durable
,
.3. Asan articleofmanufacturemetalcarrying .>
a coating comprislngtheresin defined in claim 1. t ,
for steel beer barrels, refrigerator ?nishes (both .
as primers and topcoats),.coatings ‘for the in
terior of fountain'pensto protect ‘the barrel from
70 the action of alkali contained in the ink,'acid
comprising the
de?nedinclaimi.
lene
polymer‘.
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I JAIN A. LEVIN.‘
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