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Патент USA US2407623

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2,407,623
Patented Sept. 10, 1946
UNITED‘ STATES PATENT OFFICE
in 2,407,623
-
v ,
1 MODIFIED‘LINSEED on. WRINKLE FINISH _‘
William'ArWaldie, Oakwood, Ohio, assignorjtc
New Wrinkle, 1110., Dayton,- Ohio, a‘ corpora-I
‘
‘
qtion'of Delaware
,No‘; Drawing. Original application‘ ant-W31,“ '
1942, SerialNo]. 42.9;116. Ilivided‘aiid'tliis a'p-g:
plication November‘ 6, 1942; semi-1x19464593’: '
6 Claims.
(Cl. 106-12)‘
'
n
This application ' is a1 division‘ of ‘ copending ' ap
creased ' to " 5401"‘
21
r
.
where Lit-‘is held until a‘ uni'-"
form mixture ‘has been obtained‘as evidenced by
the formatio‘n'oi a clear‘ spot when‘ai drQpTof-the‘
mixture is dropped On' glass‘aiidallow'ed-ftti cool.
plication ‘Serial No.‘ 424,010j ?led. December 22,
, Thereupon the‘ batchis cooled to approximately
1941;
400 to 420° F. and bIOWl'iI'With air until'thedé
This invention relates to wrinkle, varnish’basei
sired or required viscosity has been obtained. A
and the; primary purpose-thereof is'tl'ie prepara
plication Serial, No.‘ 429,116, ?led. January.‘ 31,
1942,: as a1continuation-in-partiof copending ap
tioniof a Wrinkle varnish base» comprising the
satisfactory viscosity or end-point may be con
heat-‘reaction product of modi?ed drying oil, oil
sidered to have been reached-when a drop‘ falls
soluble resin and airy atelevated temperature.
1O from a stirring rodwith a slight thread-jlikel?lé
Hitherto‘ the preparation of wrinkle’ varnish
ament while hot. When this condition has been‘
reached‘ the mixture isR-‘withdrawn from the?re
base has been considered to, require‘th'e use of
andthe hydrocarbon solvent added ther" "of A
China-wood oil, oiticica oiland other ‘similar dry
ing oilscontaining conjugated double bonds, or
suitable liquid drier‘ shb'uld be added: at"the'~'saime
mixtures of them. These-oils, or mixtures, were 15 time. In the case’ of Nuodex cobalt v6%‘ liquid
generally used either in their raw or natural
drier threeefourths to one gallon would‘ be re;
quired' for a batch such as that‘ of ExampleI;
state, or subsequent-to preliminary treatment‘as
by blowing, depending on‘ the particular charac
I
.
Example 11
teristics required in the ?nished wrinklevv‘arnish
20
Ambero1801
___________________
__‘_;‘_-_-lb‘s'_~_ 10'0
base and the nature of the individual oil or’fmi-xl
ture of oils being used.-
-
My ‘copending application Serial No. 424,010 - to
which reference'has been made'hereinb'eiore‘sets
forth a method whereby wrinkle varnish base
can be produced by chemically ‘combining un
Varnish grade linseed oille :~_____gal1ons__ 12
Polyglycerol _____________________ __d0___-
3/1
Mineral spirits"___________ _; ______ __do_~‘___
>5
Solvess'o' #2“ ________ __-_‘;_‘___‘_;-l___do____
i6
25 Nuodex coba1t~6% ________________ -_do____
%
blown drying-type oil with oil soluble resin and
air at elevatedv temperature; the (resulting prod
uct exhibiting excellent wrinkling tendency with
the‘addition of a small-amount of» drier in'the
usual manner.
My present application- deals
with an ‘improved method in which chemically
modi?ed drying type oil is substituted for the un
blown'drying type oil-(0r theoil is modi?ediin
situl and a substantial-‘reduction is madein the
‘
Example IV
cooking time for the varnish.‘
35 Amberol F7 _______ __; ____________ __1bs;_'100
As typical examples‘ of formulations and-‘pro
Varnish‘ ‘grade linseed “oil; _______ “gallons; 15
cedures according to my present invention, but
Polyglycercl ‘_‘______' ______________ __do'____
without thereby limiting myself. to the speci?c
Mineral spirits '_ __________________ __do____
5
details. of procedure and proportions indicated,
S‘olvessd #2 l ____________________ __do'____ 16
the. following illustrative‘ examples :are: given:
40 Nu‘odex‘ cobalt 6%; _______________ __do____ %’
Example'l'
Wrinkling, resin _______________ __1bsl_- 100-125
Vegetable dryingoil ____ _____-_gallonsls 10-35
Polyglycerol _________________ __do_-___- 0.5-2
Hydrocarbon' solvent _________ “dollar
5-40
In preparing the'varnish base-from: the aiored
mentioned; components approximately ‘one-half
of the oil and all of the; resin are placed in a-‘ket
Example ‘VI
‘
tle and heated rapidlyto400° F-. to obtain-ather 50 Amberol 801 ______________________ __lbs__ 100
ough dispersion of the resin in the oil; Of course,
Soya bean ‘oil __________________ "gallons; 12"
ifvit‘iislso desired,‘ it, is‘ possible'to' disperse ‘the
resin in the entire quantity ofoil by following
Polyglyc'erol _________________ _.~____do___l
Mineral spirits __________________ __do____
the same ‘ procedure; The polyglycerol "is then‘ ‘ Solve'ss0“#‘2V___.‘__l _______________ _._do____
added’ to: the » batch“ and-‘the temperature ‘in 55 Nuodexcobalt 6%"; _______________ "an---
1Y5‘
5
16
%
2,407,628
3
Example VII
As will be noted from the examples, maleic
acid resin, as well as phenol-aldehyde resin, may
be used satisfactorily in the practice of my in
vention. Maleic acid resin of the type com
mercially available and sold under trade names
Amberol 801 ______________________ __lbs__'100
Perilla oil _____________________ __gallons__ 12
Polyglycerol _____________________ __do____ %
Mineral spirits ____,/._
5
Solvesso‘#2 __"____:_‘_>_
‘
‘
,
such as 'Amb‘erolj801, Beckacite 1110,, B'eckacite
~16
1111 and ‘Beckacite 1114'_may» be employed, but,
Nuodex cobalt "6% __________ _'_____’_clo____ " 3/;
of course, other alkyd-resins made from combina
The procedure followed in preparing the? I'tions of rosin, ipolyhydric alcohols and polycar
wrinkle varnish base of my vinvention from the 1o boxylic acids or anhydrides prove suitable. Like
components given in Examples II to
is sub?" 'wise,"oil soluble‘and non-reactive phenol-alde
stantially the same as that followedin Example , .,hyde resins may ,be ,used in the practice of my
I, although minor changes-in temperature and , "invention; :These-include resins known by trade
time of cooking are at times advantageous de
namesII-such' as'Beckacite, Durez, Para-dura,
pending on the nature of the oil, being used.
It will be noted that in Examples‘: to."
Durite, Locto, Paranol, Varcum, etc. In every
< {case anoil'soluble'land non-reactive quality must
the
polyglycerol was incorporated gin the mixture ,-"_'_";be.'emp10y7ed__.j- ’ l .
of oil and resin and cooked therein; This ‘pro
It willbe understood by those skilled in the art
that by “mineral spirits” is meant that grade of
cedure is entirely satisfactory and economical l
and represents one wherein the oil is modi?ed
in, situ; however, ingthe practice of my invention
petroleum product of . .either
I ;,have obtained, equally. satisfactory‘ results by
the trade as turpentine substitute; while Solvesso
#Zlis av hydrogenated naphtha having a vola
tility similar to that .of xylol and manufactured
by Standard Oil Company. Nuodex cobalt_'6%
is a cobaltnaphthenate drier solution, in which
separately heating a mixture of ‘drying oil and
polyglycerol and using the mixture in the varnish
formulation; The'procedure followed was sub‘
stantially as given below:
-
‘
‘I
~ .
Ezrmn‘ple-VI'IIv
"
-
_
'
’
~
'
~‘
I
a paraf?nic or
naphthenic origin which‘is commonly ,known'jin
the metallic cobalt amounts to about 6%. , H ,
‘
‘The end-point of the blowing step employed
Gallons
in the practice of my invention may be deter;
1 30 mined as previously mentioned herein; how-.
Vegetable drying oil ________ _r __________ __'__ 20
Polyglycerol ____V___>_____'_> ____ _‘___r__-___'_____
ever,¢it may also be determinedhby other means,
as, for instance, by withdrawing test samples
from time to time during the blowing operation,"
adding a predetermined amount of thinner to” a
de?nite weight of sample, and comparing the
Theabove mixture was heated to a tempera
ture of approximately ‘500 vto 520° Fiand held
at substantially that, temperature until a sample
withdrawn from the‘ batch. did not show any
substantialseparation of polyg'lycerol 1 and oil
viscosity I of the resulting solution__ with» the
on coolingifanduntil a drop deposited on glass
showed complete’ homogeneity. 'The resulting
Gardner-Holdtvviscosity standards.
product was then used in-formulations such as
the
following;
,
H
,
'
'
40
_
~
Example IX
'
I
’
Amberol 8'01 ______ __<_'_____"__ '__“_____'__lbsv_l_ 100
Productof Example VIII ________ "gallons; _ '12
Mineral-spirits _____ -g _______ __'_-_'__'''_,_do____'
5
Solvesso‘ #2 ______ ._._r '_I___ 1.,_____ __‘do____'. w 16 45
Nuodex cobalt 6%__r___1___;___r___do____ %
‘In preparing the wrinkle varnish base of my
invention- from the components of Example ‘IX
the resin and modi?ed drying» oil were heated
together at a temperature of approximately
400° C. until thelvresin became thoroughly dis
persed-inthe ‘oil. The temperature .was then
increased to approximately v540° F. and held at
that temperature until a clear spot formed when
a drop was deposited on glass. The batch was
then allowed to cool to approximately 400°'F.
and blown with air until the proper degree of vis
cosity was obtained,‘ whereupon the drier and
solvents vwere added to produce a coating compo‘
sition possessing suitable spraying characteristics
and adapted to yield a wrinkled ?lm of uniform
texture and satisfactory hardness and toughness
when applied onasurface and baked.'
- vThepolyglycerol used in the various examples
hereinbeforeset forth was producedv by treat
ing glycerin with sodium acetate or sodium hy
droxide, or other suitable ‘dehydrating agent. A
typical procedure was as follows:
h
7
Example}!
4
V
, _-
' ._
od'of my ,invention, as disclosed; herein, andthe
method disclosed and claimed in mycopending
application Serial No. 424,010,; ?led December 22,
1941, is that according to my present improved
procedure, I am able toreduce the blowing time
required to produce any ‘predetermined body‘by,
approximately one-half; therefore, ,the improved
procedure which isthe subject matter .of. ‘the
present invention makes it possible ‘ to‘ effect
economies; in manufacture and substantially. in-,
crease the'output of the varnish kettles in any
given plant.‘
,
i
,
v
The coatings produced with; the wrinkle var
nish'base of the present invention yield ‘hard,
tough ?lms, and since I employ unblown oils in
the practice of my invention, I do notencounter
the di?iculties and inconveniences which chars
I acterize the use of such oils. It. is well known
that blown oils commonly used in thew prior art
exhibit auto-oxidizing tendencies due to the fact
that they contain intermolecularly dispersed air,
69 which results in gradual andcontinuous oxidation and also leads to separation of part of the
oil as an insoluble gel, thus rendering the prod
uct-valuelessforuse in a varnish, and particu
larly so when the varnish is 'part of a sprayable
composition.
''
>
a
-
r
'
~
"
In 'con-tradistinction, the product of my‘ in
vention will preserve its homogeneous nature and
- will show no separation for an inde?nite period
of time. It will be noted that according to-my
v
70,, inventionv the oil, as such,‘ is not ‘submitted to
‘I
Glycerin‘v _'; _____________________ __gallons__
4
Sodium acetate _____________________ __lbs__ %
‘I The above mixture was heated slowly to 500° F.
(‘in 30 minutes) and then allowed to‘cool.
_
,The fundamental di?erence between the meth-'v
.
aeration and that it is the cooked varnish that
is blownwith air. I am unable to o?eriproof
as to, the mechanism of the reaction which the
oil undergoes when treated with?ipolyglycerol.
Likewise, Iam'unable to o?er proof as ‘to the,
2,407,623
5
mechanism of. the reaction which the modi?ed
oil? undergoes when-treated with air at elevated
6
‘ enamels,‘ and-texture modifying ingredients‘ of
various“ sorts maybe incorporated; therein.
temperature in ‘the presence of the synthetic resin
as hereinbefore set forth. However, with'resp'ect
able to give- any explanation ‘or set forth the
to the latter, it is my opinion that due to the
mechanics of the reactions which take place when
comparatively high temperature used in the blow
ing operation only that air which is chemically
1 As has been mentioned hereinbefore‘,‘ ‘I am uné
dehydrated» 'gly'ceroll or rpolyglycerol?is reacted
with the drying oil, but it is reasonable to assume
that there is esteri?cation of the oil with the
formation of di-glycerides and perhaps of mono
taken up by the mixture of modi?ed oil and resin
remains therein, since the temperature of treat
ment is suf?ciently high to expel any uncombined 10 glycerides.
The most signi?cant thing about the present
air. This prevents the intermolecular dispersion
invention is that I make use of oils which are
of air which appears to be present in blown oils
plentifully available from domestic sources and
and leads to their continuous oxidation during
which are characterized by substantial stability
storage.
It is well to reiterate that in the practice of 15 of quality and cost. In addition, these oils have
never been considered suitable for use in the
my invention the oil, as such, is not aerated for
production of wrinkling varnishes without ‘first
it will be remembered that the modi?ed oil and
blowing them in view of the fact that the un
resin are conjointly aerated.
blown oils have always produced smooth, glossy
The selection of thinners to be used in the
practice of my invention is not critical although 20 ?lms such as those which characterize linseed
oil. It may be said, therefore, that according to
preference should be given to those products of
my invention it is possible to produce wrinkling .
high volatility such as toluol, xylol, light naphtha,
varnishes from unblown drying oils which hith
etc. Of course, a small quantity of low volatility
erto have been considered unsuitable for the pur
solvent may prove of value to bring about a sud
den chilling of a batch in order to check the 25 pose without prior blowing thereof and which
have been hitherto considered inhibitors of
bodying thereof in the event it should have been
wrinkle formation. Therefore, the substance of
blown a tri?e too long.
my invention is that I have obtained an unex
Many different driers may be used but pref
pected result contrary to the teachings and skill
erence should be given to those commonly known
as “top driers” and which are characterized by 30 of the art.
a tendency to form the surface skin which is
so desirable in wrinkle compositions. The res
Wrinkle coating compositions produced using
the Wrinkle varnish base of my invention are
adapted to be sprayed and then baked at tem
inate, linoleate and naphthenate type of drier,
peratures of from 200 to 250° F. for approxi
characterized by ready solubility, proves very
35 mately one hour to produce a wrinkle ?nish
suitable for this purpose.
characterized by its toughness and hardness.
It will be understood that while I have given
It will be understood that while I have set
typical examples using certain oils, it is not my
forth certain speci?c embodiments of my inven
intention to limit myself to the use of such oils
tion, it is not my intention to have it limited to
in view of the fact that other drying oils are
or circumscribed by the speci?c details of pro
susceptible to the same treatment and may be
cedure and proportions indicated in view of the
used in the practice of my invention. The choice
fact that my invention is adapted to changes
of oil will depend primarily on availability and
according to individual preference and conditions
cost. Those skilled in the art will understand
without departing from the scope thereof as de
that the Castung Z-3 used in Example III is a
'
commercial grade of dehydrated castor oil.
45 ?ned in the appended claims.
I claim:
_
The choice of resin will depend on the desired
1. The method of making wrinkle varnish base
characteristics of the wrinkle varnish base. As
consisting in heating glycerine with a dehydrat
has been noted hereinbefore, rosin modi?ed alkyd
ing agent from the group consisting of sodium
resin such as maleic acid resin may be used sat
isfactorily and it will be understood that other 50 acetate and sodium hydroxide to approximately
500° F. for about 30 minutes, adding non-con
polycarboxylic acids or their anhydrides includ
jugated double-bonded drying oil and heating to
ing phthalic, tartaric, citric and malic may be
approximately 500° to 520° F.; adding natural
substituted for the maleic acid or anhydride, al
resin and heating to approximately 540° F., and
though the rosin modi?ed maleic acid resin is
preferred from among the alkyd resins. Like 65 blowing the reaction mixture with air at about
400° to 420° F.
wise, other phenol-aldehyde resins may be used
2. The method of making wrinkle varnish base
in place of that mentioned in the examples.
consisting in heating approximately 4 gallons of
Furthermore, natural resins such as Congo,
glycerine with % lb. of a dehydrating agent from
Kauri, Batu, Zanzibar, oil soluble Manila, Ponti
anak, etc. may be employed, but where such resins 60 the group consisting of sodium acetate and sodi
um hydroxide to approximately 500° F. for about
are used they should ?rst be “run” to make them
30 minutes; adding per one part by volume of
oil soluble and the ?rst step of the process here
the
mixture thus obtained 20 parts by volume
inbefore described would have to be altered ac
of non-conjugated double-bonded drying oil and
cordingly. In such case, for example, the resin
heating the mixture to approximately 500 to 520°
would ?rst be fused and then added to the heated 65 F.; thereafter adding oil soluble natural resin and
oil and the temperature raised to a point su?i
heating to approximately 540° F.; and then blow
cient to dissolve the resin in the oil. The neces
ing the reaction mixture with air at about 400°
sity for pretreating the natural resin will be fully
to 420° F.
appreciated by those skilled in the art.
3. A pro-duct obtained by the process of claim 1.
70
The products resulting from the practice of
4. A product obtained by the process of claim 2.
my invention are adapted for use as clear wrinkle
5. The method of making wrinkle varnish base
?nishes without further treatment. They may
consisting in heating approximately 4 gallons of
glycerine with 5/8 pound of dehydrating agent
be further compounded with pigment ground in
oil vehicle for the purpose of producing wrinkling 75 from the group consisting of sodium acetate and
2,407,628
sodium hydroxide to approximately 500° F. for
oil soluble» natural resin and heating to approxi-:
about; 30 minutes; adding to 0.5 to 2 gallons of
mately 540° F.; and then blowing the'reaction
the mixture thus obtained 10 to 35 gallons “of
mixture with air at about 400 to 420°. F.
_
non-conjugated double-bonded drying oil and
6. A product obtained by the process of claim 5.
heating the mixture to approximately 500 to 5
520° F.; thereafter adding 100 to 125 pounds of
.WILLIAM A. WALDIVEL
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