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Патент USA US2138140

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2,138,140
Patented Nov. 29, 1938 ‘
UNITED STATES PATENT OFFICE
2,138,140
COATING COMPOSITIONS AND METHOD OF
PRODUCING
Irwin C. Clare, Wilmington, DeL, assignor to Her
cules Powder Company, Wilmington, Del., a
corporation of Delaware
7 No Drawing.
Application February 8, 1936,
Serial No. 62,991
'
15 Claims.
(Cl. 134-26)
My invention relates to varnish and enamel col, ‘diethylene glycol, diglycol, triethylene glycol,
compositions and to a method for the preparation glycerol, pentaerythrite, etc.
thereof.
The phenol-formaldehyde type resin used in
Heretofore it has ‘been known to produce var
the preparation of a varnish in accordance with
my invention may be any oil-soluble, phenol
?ed phenol-formaldehyde type resin with a dry
formal'clehyde type resin, of either the oil-reac
ing oil and then thinning the resulting composi- - tive or the oil non-reactive type, produced by the
Cl nish compositions by heating a rosin ester-modi
tion with a volatile solvent.
Such varnishes are
characterized by many desirable properties, 'such
as quick drying, high water and alkali resistance,
and excellent durability. However, they have the
undesirable property of discoloring on exposure
to sunlight or arti?cial light rich in ultraviolet.
This property has restricted the use of the modi
?ed phenol-formaldehyde resins, since they are
example the commercially available phenol—form
aldehyde type resins known as Durez #550, Super
Beckacite 1001, Amberol ST-137, and Bakelite
XR. 3360 are suitable for this purpose. The dry
ing oil used may be any ‘of the usual drying oils
used in the preparation of varnish, such as, for
forthe production of white or light-colored var
example, tung oil, linseed oil, perilla oil, oiticica
nishes, which do not discolor after application.
Now, I have discovered that a modi?ed phenol
formaldehyde resin type. varnish which is highly
oil, etc. The drying oil may be used in the raw
state or itlmay be subjected to the various heat~
bodying, oxidizing or thermolizing processes 20>
known to the art and then used. The drying oil
may be used alone, or in admixture with ‘other
resistant to discoloration on exposure to light and
ties of the prior art modi?ed phenol-formalde
hyde type varnishes, is produced by heating to
gether an oil-soluble phenol-formaldehyde type
.25
resin, a hydrogenated rosin ester and a drying oil,
‘ and then thinning with a volatile solvent.
I The method for the production of my new var-
nish, then, involves the reaction of an oil-soluble,
phenol-formaldehyde resin, hydrogenated rosin
ester and a drying oil. I have found, strangely
enough, that when I produce a hydrogenated
rosin ester modi?ed phenol-formaldehyde.resin,
and then prepare a varnish by reacting this resin
35 with a drying oil and then thin with a volatile
solvent, that the varnish so produced does not
show the advantageous resistance to discoloration
shown by the varnish produced by the reaction of
an admixture of a hydrogenated rosin ester, a
40
tuted phenol with analdehyde, such as, form
aldehyde or one of its homologues. Thus, for 10
unsuited for ?nishing light-colored surfaces ‘and
which has, at the same time, the desirable proper
3O
reaction of a phenol, such as, phenol or a substi
phenol-formaldehyde type resin, and a drying oil.
The hydrogenated rosin ester used in the prep
aration of the varnish in accordance with my
invention, may be any monohydric or polyhydric
alcohol ester of either hydrogenated wood rosin
’ or hydrogenated gum rosin, or it may be a mono
drying oils, or it may be used in admixture with
a semi-drying oil, such as, for example, soya bean
oil, ?sh oil, etc. When using a semi-drying oil
in admixture with the drying oil, the proportion 25
of semi-drying oil must not ‘be su?ici'ently high
7' to affect the drying characteristics adversely.
A varnish composition, in accordance with my
invention, will contain the drying oil, mixture of
drying oils, or mixture of drying oil or semi-dry
ing oil, in amount within the range of about 10
gallons to about 100 gallons per 100 pounds of
resin contained. The exact proportion of oils
contained will depend on the characteristics de 35
sired of the ?nal ?lm. For the majority of uses
the oils will be within the range of about 10 gal
lons to about 70 gallons per 100 pounds of resin
contained. The total resin content includes the
hydrogenated rosin ester and the phenol-form 40
aldehyde type resin. The phenol-formaldehyde
type resin'or mixture of phenol-formaldehyde
resin may comprise from about 1.0% to about
75% of the total resin content, with a hydro—
genated rosin ester or mixture of hydrogenated
rosin esters making up the remainder. I prefer,
however, to use a. phenol-formaldehyde type resin
or a mixture of different phenpl~fonnaldehyde
type
resins in amount within the range of about
will desirably be hydrogenated to an extent with- '
1% to about 50%‘ of the total resin content. The 50
0 in the range of about 40% to about 90% satura
amount of volatile solvent added to secure the
tion of two double bonds, and preferably within desired consistency for the application of my var
the range of about 60%‘. to about 70% saturation nish composition is controlled by the consistency
of two double bonds. The hydrogenated rosin of the resin and oils used, the conditions of cock
ing, etc., and will usually be added in amount 55
5 ester used may be an ester‘ of a monohydric alco
hol, such as, for example, methyl alcohol, ethyl within the range of about 25% to about 70% of
hydric or polyhydric alcohol ester of either wood
or gum rosin which has been hydrogenated after
esteri?cation. The hydrogenated rosin ester used
alcohol, propyl alcohol, iso-propyl alcohol, butyl
the total varnish composition. Any suitable
alcohol, iso-butyl alcohol, amyl alcohol, iso-amyl . volatile solvent may be used for this purpose, such
alcohol, etc., or it may be an ester of a poly
as, for example, turpentine, benzol, toluol, xylol,
60 hydric alcohol, such as,'£or example, ethylene gly
the commercial xylol mixture known as Hi-?ash 60
I 2
2,138,140
Naphtha, petroleum hydrocarbon mixtures, such
as those known to the trade as, V. M. and P.
Naphtha, Varsol, etc.
The procedure for the preparation of the var
nish composition, in accordance with this inven
tion, involves heating a mixture ‘of a hydro
genated rosin ester, or a mixture of hydro
genated rosin esters, a phenol-formaldehyde
type resin or a mixture of phenol-formaldehyde
10 type resins and a drying oil, a mixture of drying
oils or mixture of drying and semi-drying oils,
The resulting composition was a smooth, white
enamel which dried to a glossy, white ?lm of good
durability and excellent resistance to discolora
tion on exposure to light.
'
An alternate procedure for the production of
varnish compositions in accordance with this
invention, which is especially suitable for use
with certain types of the oil~soluble phenol
formaldehyde type resins, such as, for example,
the resin known in the trade as Durez #550, 10
involves heating a mixture of a drying oil and
to a maximum temperature~ within the range _ a hydrogenated rosin ester to a temperature
of about 320° F. to about 600° F. The exact
temperature used will depend upon the particu
15 lar phenol-formaldehyde resin used. After the
maximum temperature has been. reached the
‘ batch is then maintained at this temperature or
at a temperature not below about 450° F., until
the desired consistency is obtained. The compo
20 sition is then allowed to cool to a temperature
low'enough to avoid excessive evaporation of the
thinning solvent, usually about 440° F., and then
thinned to a consistency suitable for application.
After the addition of drier, this material is suit
.25 able for application as a clear coating.
within the range of about 550° F. to about 600° F.
in a period within the range of about 20 minutes
to about 75 minutes, adding the phenol-‘formalde
hyde type resin to chill back to a temperature
within the range of about 500° F. to about 560° F.
The batch is then held at this temperature for
body, and then further chilled by‘ the addition
of a portion of a drying or semi-drying oil and 20
the hydrogenated rosin ester. The batch is
then thinned by the addition of 'a volatile solvent.
An illustration of this alternate procedure is
given in the following example.
If it is
25
Example III
The following raw material formula was‘used:
desired to produce an enamel, the desired pig
ment or pigments, and the drier are ground into
the varnish after it is thinned with volatile sol
vent, or the desired pigment or pigments may be
-
Raw mammal
30 ground into the clear coating described hereto
fore.
'
The following raw ‘material formula was used:
-
Raw matenal/
Oil reactive phenol-formaldehyde type resin
(Super lleekn'citc 1001, Amberol S'l‘—l37
or Bakelite 3300) ________________________ _.
45 ‘Distilled hydrogenated glycerol ester of rosin
(60% saturated) _______________________ __‘__
50
'
Laboratory
amounts
Plant
amounts
30
.
As a speci?c illustration of the procedure for
the production of varnish compositions, in ac
cordance with this invention, the following ex
35 amples may be cited.
Example I
40
15
Laboratory
amounts
Plant
amounts
Oil
soluble
phenol-formaldehyde
resin
Grams
(Durez #550) ____________________________ __
Distilled hydrogenated glycerol ester of resin
((30% saturated).
Tung oil ........ __
25
25 lbS.
75
75 lbs.
156
Heat-bodied linseed oil _ _ _ _ _ _
. _ . __
20 gals.
_
19.5
2% gals.
Petroleum hydrocarbon thinner (Varso1)-___
279. 5
43 gals.
35
A mixture of 60 grams of the distilled hydro
genated glycerol‘ ester of rosin and 156 grams of
tung oil were heated to 585° F. in a period of 40.
about 30 minutes. 25 grams of the oil-soluble,
phenol-formaldehyde resin was then added to
this mixture and the temperature allowed to drop
Grams
25
25 lbs.
75
75 lbs.
Tung oil (China-wood oil) ________________ _.
Heat-bodied linseed oil ____________________ __
. 156
19.5
20 gals.
2% gals.
Petroleum hydrocarbon thinner (Varsol) __..
279. 5
43 gels.
The phenol-formaldehyde resin, the hydro
genated rosin ester, and 39 grams (laboratory
amount) of tung oil were heated to 450° 1"‘. The
to 540° F. The mixture was then held at this
temperature until a suitable body was attained; 45
The linseed oil and 15 grams of the distilled hy- -
drogenated glycerol ester of rosin were then
added and the temperature allowed vto drop.
When the temperature had dropped to 440° F.
the Varsol was stirred in to thin the mixture.'
The varnish prepared in Example III is suit 50
able .for use as a protective or decorative coat
remainder of the tung oil (117 grams) was then
added and the temperature raised to 540° F.
55 The linseed oil was then added to chill the batch
and the temperature then maintained at 510°
515° F. to produce a body such that the compo
sition will give a 30 inch string from a cold glass
ing or may be made into a white enamel as illus
65 preparation of a.white enamel.
The product was a white enamel which dried 65
to a glossy white ?lm of gooddurability and ex
trated in Example II. The following example
illustrates the preparation of another white 55
enamel:
'
‘
Example IV
The following ingredients were ground together
plate. The composition is then cooled to 440° F. in a ball mill:
‘
.
60 and thinned with Varsol.
60
The varnish made according to Example I Titanium oxide pigment _________ __av.oz__ 2
may be used as a clear protective and decorative Varnish (Example III) __________ __liq.oz__ 8
6% cobalt naphthenate drier _____ __gram__ 1k
coating or it may be made the basis of an enamel
as illustrated by the following example of the 24% lead naphthenate drier ______ __grams__-2
.‘
.
I Erample II
The following ingredients were ground to
gether in a ball mill:
70 Titaium dioxide __________________ __av.o-z__ 2
15% titanated lithopone ____ ___ _____ __do____ 1
Varnish (from Example I) ________ __liq.oz__ 8
6% cobalt naphthenate drier______ __gram__ 0.4
75 24% leadnapththenate drier______ __do___.. 1.7
cellent light resistance.
The excellent resistance of my new composi
tions to discoloration on exposure to ultraviolet
_ light and their unusual durability was exempli?ed
‘ by the following: A series of thirty-three var
nishes were prepared from a‘ number of oil sol
uble phenol-formaldehyde type resins, including
both oil-nonreactive and oil-reactive resins, tung
oil and various gradesof hydrogenated glycerol
3
9,188,140
ester, a drying oil and an unmodi?ed oil-soluble,
oil-reactive phenol-formaldehyde type resin at a
maximum temperature of at least about 320°~F.
esters of rosin, similar to those illustrated in Ex
amples I and III given above. Several varnishes
of compositions recognized by the art to be out
standing in resistance to discoloration and de
cidedly superior to the prior art rosin ester modi
?ed phenol-formaldehyde varnishes, were then
prepared from well-known commercial modi?ed
maleate resins. Enamels from each of these var
7. A protective coating composition including
as ingredients, a drier, and the product of the
simultaneous reaction of a hydrogenated rosin
ester, a drying oil and an unmodi?ed oil-soluble,
oil-nonreactive, phenol-formaldehyde type resin
ggoa maximum temperature of at least about
nishes were then prepared in such a way that the
10 only di?erences in the ?nished enamels were in
'8'. A protective coating composition including
the resin or combination of resins contained.
Panels were then prepared of each of these enam
as ingredients, a drier, and the'product oi the
ultraviolet are, at a distance of 12 inches, for a
maximum temperature of at least about 320° F.
period of 4 hours.' A visual comparison of the
panels so exposed, clearly demonstrated the su
as ingredients a drier, and the product of the
els by spraying two coats on steel, with 48 hours simultaneous reaction of hydrogenated glycerol
drying between coats. These panels were then ester of rosin, a drying oil, and an unmodi?ed
exposed to the radiation of a low-pressure type oil-soluble phenol-formaldehyde type resin at a 15
9. A protective vcoating composition including
simultaneous reaction of hydrogenated glycerol
periority of the hydrogenated rosin esterphenol
- ester of rosin, tung oil, and an unmodified, oil 20
20 formaldehyde type enamels made in accordance soluble, phenol-formaldehyde type resin at a
with this invention, over the glycerol maleate
type enamels in resistance to discoloration. A maximum temperature of at least about 320° F.
10. A method for the preparation of a protec
duplicate set of panels was placed on exterior
exposure,‘ at an angle of 45° to vertical, for a tive coating composition which includes simul- I
taneously reacting together a hydrogenated rosin .25
25 period of ?ve months. Periodic examination of ester, an unmodi?ed, oil-soluble phenol-formalde
these panels demonstrated that the varnishes
hyde type resin and a ‘drying oil at a maximum
' made in accordance with this invention, were de
cidedly superior in durability to .the prior art temperature of at least about 320° F. and then
thinning the mixture with a volatile solvent.
varnish compositions.
.It will be understood that the details and exam- " . 11. A method for the preparation of a protec
30
ples herei'nbefore set forth are illustrative only,
and that the invention as herein broadly described
> is in no way limited thereby.
What I claim and desire to protect by Letters
35
Patent is:
»
I
1. A protective coating composition including
as an ingredient the product or the simultaneous
reaction of-a hydrogenated ‘rosin ester, a drying
oil, and an unmodi?ed, oil-soluble resin 01 the
30
tive coating composition which includes simul
taneously heating together a hydrogenated rosin
ester, an unmodi?ed, oil-soluble phenol-formalde
hyde type resin and a drying oil to a temperature
above about 320° F., and then thinning the mix 35
ture with a volatile solvent.
'
12. A method for the preparation of a protec- -
tive coating composition which includes simul
taneously'heating together a hydrogenated rosin
phenol~formaldehyde type at a maximum tem _ ester, an unmodi?ed, oil-soluble phenol-formalde 40
hyde type resin, and a drying- o? to a tempera
perature of at least about 320° F.
2. A protective coating composition including as ture within the range of about 320° F‘. to about
ingredients a drier, and the product of the simul- ' 600° F., and then thinning the mixture with a
taneous reaction of a hydrogenated rosin ester, a
volatile ‘solvent.
.
--
,
.
drying oil, and an unmodi?ed, oil-soluble resin > 13. A method for the preparation of a protec
45 of the phenol-formaldehyde type at a maximum tive coating composition which includes simul
taneously heating together a. hydrogenated rosin
temperature of at least about 320° F.
'
3; A protective coating composition‘ including ester, an unmodi?ed, oil-soluble phenol-formalde
as ingredients a drier, a volatile solvent and the hyde type resin, and a drying oil to a tempera-.
ture within the range of about 320° F. to about 50
product 01’ the simultaneous reaction of a hy
drogenated rosin ester, a drying oil and an un-_ 600° F., holding the mixture at a temperature
within said range for a period of time su?icient
modi?ed, oil-soluble resin of the phenol-iormal
dehyde type at a maximum temperature of at least to produce an increase in the viscosity of the
'mixture and then thinning the mixture with a
about 320° F.
‘
'
4. A‘ protective coating composition including
55 as ingredients a pigment, a drier, a volatile sol
vent and the product or the simultaneous reaction
volatile solvent.
'
'
-
'
14., A method for- the preparation of a protec-.
55
tive coating composition which includes'simul
of a hydrogenated rosin ester, a- drying oil and
taneously heating together a hydrogenated rosin -
an unmodi?ed oil-soluble resin or the phenol-tor
maldehyde type at a maximum temperature of
about 320° F., adding an unmodi?ed.‘ oil-soluble 00
at least about 320° F.
-
5. A protective coating composition including
as ingredients a drier, a volatile solvent and the
pro“ ‘oi the simultaneous reaction or a hy
dromted rosin ester, a drying oil, a semi-dry
05 ing oil and an unmodi?ed oil-‘soluble resin of the
phenol-formaldehyde. type at a malimum'tem
perature oi’ at least about 320° F.
'
6. A protective coating composition including
as ingredients a drier, and the product of the
10 simultaneous reaction of a hydrogenated rosin
ester and a dryingv oil tona temperature above
phenol-formaldehyde resin to the hot mixture
and thinning the mixture with a volatile solvent.
15. A method tor the preparation or a protec
tive coating composition which includes simul
taneously heating together'a hydrogenated rosin
ester and a drying o? to a temperature within-the
range or about 550° F. vto about 600° F. adding an
unmodi?ed oil-soluble phenol-formaldehyde resin
to the hot' mixture, and thinning the mixture
with a volatile solvent.
70
IRWIN O. GL1 . v
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