вход по аккаунту


Патент USA US2121690

код для вставки
Patented June 21,‘ 1938_ Q
nnsiNoUs COATING don'rrosrrlons’
Donald [Edwards ‘ Edgar, Philadelphia, 'Pa., as‘
signor to E. I. du Pont de Nemours & Company,
Wilmington, Dei._,_ a corporation of Delaware- _
No Drawing.’ Application November 5, 1935, ‘ '
Serial No. 48,44‘!
, 3 Claims.
This invention relates‘ to coating compositions
and more particularly to improved resinous com-_
positions combined with China-wood and similar
(01. 9mm
‘ .
ent state of the art.~ A further object, is the prep
aration of ‘coating compositions which‘ will pro- .
duce?lms that will have excellent adhesion to
sanded steel vor its equivalent. 'A still further. '
Drying oils such as China-wood oil are ‘used , object is the preparation of coating compositions 5
extensively in coating compositions, frequently which can be applied in. extremely heavy .(or
thick) ,coats to produce hard, tough and durable
in combination with, other materials. China
Other objects'will appear hereinafter.
wood oil is used also, for example,'to modify alkyd ?lms.
These objects are accomplished according to
or polyhydric “alcohol-polybasic organic acid res
- m‘ ins to impart'to such. resins certain desirable the present invention by preparing the: China- 10
oil or China-wood on acid modi?ed poiY-.
properties possessed by the China-wood oil. 'wood
Coating compositions prepared from ‘such. "-oil hydric alcohol-polybasic acid resin in the pres;
en'cc of an amount of polyhydric alcohol in ex
modi?ed alkyd type resins when used to prepare cessi'of
that required as the theoretical quantity
enamel-like ?nishes are usually subjected to a‘
15 baking treatment at elevated temperatures in' necessary for -'the reaction-and then’ combining 15
‘the alkyd resin in solution in organic solvent '
order to produce a thoroughly hardened ?lm. with a suspension of urea-formaldehyde resin in
It has been' found, however, that China-wood vorganic‘ solvent. Conveniently I add tothe alkyd
oil composition ?nishes as, for example, China
wood. oil modi?ed alkyd resin coatings produce a resin a suspe'nsionof the urea-formaldehyde res
20 frosted or wrinkled surface in the ?nish on being in in an organic liquid in which the alkyd resin 20
dried and baked unless the China-wood oil has is soluble. If desired the alkyd resin may ?rst ' '
previously been subjected to a heat treatment to be dissolved in the organic solvent and the urea
overcome this tendency: ‘This heat treatment is ,fo'rmaldehyde reaction product added to the solu
known as a “curing” treatment and the oil so tion of the alkyd resin.‘ Although the use cfja
Various treatments of I suspension rather than a solution ofurea-formthe oil to minimize or eliminate the tendency of aldehyde resin is not‘a theoretical requirement,
it is a fact that this resin is generally insoluble
China-wood oil to frost or wrinkle have been sug
' gested but the results have not been satisfactorily in organic liquids and is but soluble only to the
consistent to eliminate the defect with any degree extent of about-10% in water. However, when
the urea-formaldehyde resin is combined, usualqv
- 30 of practical assurance. The heat treatment of
ly with ~heat and agitation, with the. polyhydric
China-wood oil, as well as other treatments sug
gested, to “cure" the oil also add to the cost of alcohol-polybasic acid resin in the presence of
the oil and to the product in which the oil. is organic solvent as. described above there is ob-
25 treated as a “cured” oil.
to be used.
In using China-wood oil ‘or China
35. wood oil modi?ed alkyd resins in coating com
positions there is always present the inherent
tained a homogeneous blend which, for. all'prac- f
tical purposes and as far as visual conception is '_35
concerned, contains the urea-formaldehyde res- _
tendency for the coating to develop a. “frosted” - in in solution.
The alkyd resins with which-the present in
or wrinkled surface even though the oil may have
been subjected to a preliminary treatment to vention is concerned arepolyhydric alcohols hav
m “cure" it. This defect often develops into what 1 ing some of their hydroxyl groups esteri?ed with 40
is known in the ?nishes" industry as "crowsfoot" polybasic acid radicals and some‘ esteri?ed with - '
which results in a very. unsatisfactory ?nished 1 the acid radicals of oil acids derived from. China
vwood oiland similar'oils subject to .frosting'in
This inventionhas as an object the preparation " the film. These frosting oil modi?ed resins may
45 of coating compositions which‘ contain polyhydric
alcohol-ypolybasic‘ acid resins combined with
China-wood and similar oils but which produce
?lms substantially free from the frosting, wrin
kling, checking, etc., which takes place in the
be made by‘ reacting simultaneously'with- heath?
treatment polyhydric .alcohol, polybasic acid and
the acids derived from the oil. Or the polyhydric
alcohol may be ?rst reacted in the presence of_ .
an alcoholysis catalyst with the oil itself and‘ the
50 ?lms of ‘ such oils. A further object is the prepa- ’ resulting polyhydric ' alcohol partially‘ acylated 50
ration of coating. compositions which will pro ,with the. on acid reacted with polybasic acid '
duce ?lms which are hard and tough and which until resini?catio-n takes place. .
The new resinous combinations may be illusé "
can be dried and baked at relatively low temper
atures and for relatively short periods of time as _~trated by the following examples'inv which the
understood, 55
55 compared with similar compositions of the pres-n . 'partsare by weight, but it is-to
however, that the invention is not limited there
to except as indicated in the appended claims.
positions appearing below may be replaced with
oiticica oil, as indicated in the following example,
for the production of ?lms which are substantial
Example I
I ly free from frosting as compared to the ?lms
China-wood.,oil 488: parts, glycerol 96 parts,
from compositions formulated with the oil itself
or with alkyd resin modi?ed with this 011.
and 0.5 part of sodium hydroxide were‘ heated
' with agitation to a temperature of 220-,2540° C.‘
and the ‘mixture maintained in this temperature
range until, a sample removed therefrom is clear
Example IV
40.7'parts of oiticica oil and 8.0 parts of glyc
erine were heated with 0.04 part of sodium hy
and homogeneousand ‘soluble in approximately
2 parts of methyl ‘alcohol. 493‘grams phthalic
droxide to a temperature of 220-240° C. and held
at this temperature until a sample was clear and
anhydride and 166 grams of glycerol were then
addedv and. the temperature again raised to
homogeneous and soluble in 2 parts of methyl
alcohol. 41.1 parts of phthalic anhydride and 20
,220-225° c. and heating continued with agita
15 tion
at this temperature until the‘ material - partsof glycerine were added. The temperature 15
was raised to 220-225° C. andheld at that point
until a sample on analysis showed an acid num
ing 45% of combined China-wood oil was added ber of 50-60.
One part of the above resin was dissolved in
to a suspension of the reaction product of urea
20 and formaldehyde in two parts ethyl ether of
two parts of the monoethyl ether of ethylene 20
glycol and one part of reaction product of urea
ethylene glycol and the mixture heated with agi
and formaldehyde was added to this solution and
tation at approximately .100" c. until substan
tially all of the solid material disappeared. The the temperature was raised to 90-100° C. and
material was allowed to cool and then strained or maintained until substantially all of the solid
25 ?ltered to remove any extraneous material. This
material was dissolved.
Undissolved material 25
resinous combination forms the basis for the may be removed by ?ltration, centrifuging or
possessed’an acid number of approinmately 45.
One part of the resin thus prepared contain
preparation of the pigmented coating composi
other suitable manner.
The following are examples of enamels formu
tions or enamels described later.
The reaction product of urea and formalde
hyde may be made according to any procedure
well-known in the art although it is preferred
to use the material made according to the pro
lated with’ the ‘resinous compositions described
cedure described in co-pending application, Ser
Carbon black _________________________ __
ial Number 34,300, ?led August 1', 1935. >
Solid resin of Example I _____ __'____ ____ ..
Volatile solvent _______________________ __
Example II
A 35% China-wood 011 modi?ed polyhydric'al- I
acting the following ingredients:
Parts by weight
China woodoil
bined. with two parts by weightof the reaction
product of urea and formaldehyde with the ex
ception that the ethyl ether of ethylene glycol
50 of the previous example was replaced by butyl
solvent____ _______ __- ___________ __
Example VI}
oxide ____________ _,_V_ _________ .._
Solid resin of Example I____' ___________ __
Volatile solvent
. The pigment in, each case was dispersed in the
a 55% China-wood 011 modi?ed resin was preé
pared by heating the following ingredients:
Example III
' Solidresin of Example I _______________ .._
in the manner described under Example I. VOne
part by-weight of the resin was likewise com
7 alcohol.
. Toluidine toner _______________________ __
Litha'rge.v _____________________ __,_____ .._
Example VI
cohol-polybasic acid‘ resin was prepared by re
grinding, roller mill grinding, etc.
Parts by weight
oil ___________ _..‘_'_ _______ __
Glycerine ____________________ _'_____.._....
60 Sodium hydroxide; ___________________ __
resinous vehicle by any means well known to
those skilled in the art as by ball or pebble mill
The enamels thus prepared mayj'be applied to
suitable surfaces by any of the well known
means as for example spraying, brushing, etc.
0.05 - If desired the coating may be allowed to air dry
according to the directions given in Example I.
After a homogeneous mass was obtained 8.48
in ‘which instance the ?lm will be tack-free in 60
approximately four hours and will have dried'to
a hard ?lm in from 24 hours-to several days. The
parts by weight of phthalic anhydride and 7.5 ' coating is preferably dried by subjecting it to a
parts by weight of glycerol were added to com
short period of air drying if desired and then
65 plete the resinification. The resinand urea
baking at an elevated temperature of for example
formaldehyde were then combined as described in 200° F. for-a period of 30 minutes after which
Example I.
treatment a hard, tough and durable ?lm is
China-wood oil has been referred to speci?cal
formed. The coating may be baked at a lower
, ly in the foregoing examples because it is the temperature e. g. 140-150" F. with a correspond
70 most representative and widely used of the drying ing increase in time or at a higher temperature
oils subject tofrosting in the ?lm. The present e. g. 300° F. with a corresponding decrease in time.
invention,‘‘ however, is likewise advantageously
In the examples of the pigmentedlcompositions
- practiced with other wood oils and with all drying . or enamels the resinous combinations of China- .,
oils which yield ?lms'which wrinkle upon drying. '\ wood oil modi?ed alkyd resin and the reaction -
75. Thus, the resin in the examples of coating com-
product of urea and formaldehyde are noted as
being the sole constituent of the vehicle. Com
for producing coatings for decorative and pro
binations of the various percentage. China-wood
oil or oil acids modi?ed alkyd resins may be used,
the choice depending on the properties desired
tective purposes.
adapted for use as ‘decorative and protective coat- '
in the ?nished composition.
ings for various types of rigid or semi-rigid sur
The alkyd resin may_ be modi?ed with China
wood oil or oil acids to the extent of from 30 to
60% although the preferred range lies between
35 and 55%.
faces such as wood, metal, etc. The pigmented
compositions may be used to produce enamel-like
?nishes on various metal articles where a smooth,
‘hard, tough and ‘durable ?nish .is desired or
.The pigmented compositions are not limited
, to the use of any special pigments since any pig
The procedure described herein makes possible
ment which will not react deleteriously with the . the production of enamel-like compositions'con- '
resin vehicle'fmay be used.’ Enamels in various taining those. fatty oils or oil acids subject to _
colors and shades may be produced'by blending
15 pigments according to vprocedures well known in
the art.
this type.
frosting or wrinkling in the-?lm such as China
wood oil or China-wood oil fatty acids which will
form hard, tough and ‘durable ?lms free from
The volatile solvents used in the enamels may
be such as are commonly usedin preparations of
The products of the invention are especially
“frost”, wrinkles, or “crowsfoot”. The enamel
like compositions such as those indicated by the
examples have excellent adhesion when applied
To disperse the reaction product of urea and
formaldehyde in combining it with the fatty oil
or fatty -oil acid modi?ed polyhydric alcohol
polybasic acid resin other liquids than those de
to such’ materials as sanded steel and suitably 20
dried. A still further advantage-is the provision
of compositions which can be applied to a surface
to produce a film in- extremely heavy applications
scribed in the examples may be used as for ex‘-‘ with a resulting ?lm which is smooth and free
25 ample the methyl ether of ethylene glycol, ethyl from surface imperfections. The present inven 25
alcohol, amyl alcohol, butyl alcohol, isobutyl tion also presents as an additional advantage the
alcohol and similar materials.
‘ '
provision of enamel-like compositions which can
Although the amount of glycerol in excess of be baked to hard and tough ?lms at temperatures
that theoretically required for complete esteri?
considerably lower than is practical with resinous
.30 cation of the acid reactants in the preparation compositions of the present art. The economic 30
of polyhydric alcohol-polybasic acid resins of the‘ advantages of the use'of lower temperatures and
examples is between approximately 10% and 22% a shorter periods of baking are obvious.
this may conveniently vary‘between 5% and 30%,
As many apparently widely different embodi
amounts less than 5% not yielding the optimum ments of this invention may be made without
35 results and amounts over 30% being in excess of departing from the spirit and scope thereof, it is
the‘maximum required. Glycerol is noted in the
examples as the polyhydric alcohol used-in the
to be understood that I do not limit myself to
the specific embodiments thereof except as de
preparation of the alkyd resin.
Other polyhydric . ?ned in the appended claims.
alcohols as ethylene glycol, propylene glycol, di
I claim:
ethylene and triethylene glycol may also be used,
1. An article ‘of manufacture coated with a 40
the same or a different polyhydric alcohol being non-frosted and unwrinkled film of a baked
used for the excess quantity over, that necessary
for the theoretical reaction. The choice of the
,polyhydric alcohol will depend to a large extent
45 on the type of alkyd resin it is desired to combine
with the reaction product of urea and formalde
hyde and will be apparent to those skilled in the
art of preparing such resins. Polybasic- acids
other than phthalic, such as 'succinic, maleic, etc.,
50 known to be useful for making alkyd resins may
likewise be used in the practice‘ of the present
In theexamples the ratio of the 'polyhydric
alcohol-polybasic acid resin oil modi?ed resin to
the reaction product of urea and formaldehyde
for the resinous combination is given as 1:1.
This ratio may vary over rather wide limits al
though it is preferred not to have the ratio greater
than 2:1 where the compositions are to be used
resinous composition" comprising urea-formalde
hyde reaction product and substantial amount of
polyhydric alcohol-polybasic acid resin modi?ed
with a substantial quantity of drying oil subject 45
to frosting and wrinkling in the ‘film which nor
mally causes frosting and wrinkling in the ?lms
of such resins‘said resin containing polyhydric
alcohol in combined form in excess of from 5%
to 30% of that required for complete esteri?ca
tion of the acid reactants.
2. The article set forth in claim 1 in which said
film is pigmented.
3. The article set forth in claim 1 in which said
drying oil is China-wood oil, the polyhydric'
‘alcohol-polybasic acid resin is glyceryl phthalate
resin, and in which the excess of said polyh'ydric
alcohol is from 10% to 22%.
Без категории
Размер файла
469 Кб
Пожаловаться на содержимое документа