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Патент USA US2411590

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Patented Nov. 28, 1946
_ 2,411,590
'UNITED STATES PATENT OFFICE
2,411,500
_
vnvrr. aesnz ooarma com'osmos
George M. Powell. 8rd, South Charlesion, W. Va”
‘
arbido and Carbon Chemicals Cor
nation, a corporation of New York
assignortoc
No Drawing. Appliestion July 3, 1848,
Serial No. 498,42‘!
a claims.- (Cl. 148-“)
1
.
compositions
activity on h
2
now Patent No. 2,848,097, March 14, 1944. How
ever, vegetable oils and alkyd resins may be pres
ent in the coating compositions of this invention.
This invention relates to vinyl resin coating
ving a controlled and limited re
.
In addition to improving the
‘ Vinyl resins formed by the copolymerization of
co to water
and solvents of coatings containing the vinyl
halide polymers or copolymers modi?ed with the
alpha. beta-oleiinic carboxylic acids, the urea
formaldehyde and melamine-formaldehyde resins
vinyl compounds with alpha, beta-oleiinic car
boxylic acids are known. Those resins which
contain a relatively large amount of the copoly
merized acid are soluble in dilute alkalies and in
act as heat stabilizers for the vinyl halide resins
many common organic solvents. It has hereto
tore been proposed to insolubilize these resins by 10 in a manner set forth in the above-identi?ed ap
plication of Powell and McKnight.
An important feature of the present inven
esterii'ying them with polyhydric alcohols, such
as glycerine and polyvinyl alcohol. Such alkyd
type condensation products have insumcient re
tion is that the amount of the heat-reactive
aminoplasts employed may becontrolled so as
According to this invention, copolymers of vinyl 15 to improve the softening point and solvent re
sistance to water for many purposes.
sistance of the vinyl resin coatings in accordance
with speci?c requirements, without seriously de
creasing the ?exibility, toughness, and chemical
halides, vinyl esters of lower fatty acids, and
alpha, beta-ole?nic carboxylic acids, as well as
copolymers of vinyl halides with alpha, beta
resistance of the resins. Films of the urea-for
ole?nic carboxylic acids, which are soluble in a
number of common organic solvents, are rendered 20 maldehyde and melamine-formaldehyde resins
alone, usually tend to- be brittle, because of the
more resistant to solvents by an essentially new
extensive three dimensional polymerization or
type of treatment. This treatment involves ap
condensation involved in the thermosetting re
plying such copolymers admixed with alcohol
action. On the other hand, the vinyl resins are
soluble, heat-reactive aminoplasts, such as urea
tormaldehyde or melamine-formaldehyde resins, 25 believed to have essentially one and two dimen
sional molecular structures, which may account
to a surface to be coated, and then baking the
for their ?exibility. However, the three dimen
coating. As a result of the' heat treatment, a
sional aminoplasts in minor amounts, do not
water-resistant coating is obtained which is either
insoluble in the original solvents-for the copoly
mer resins, or which has much enhanced resist
seriously decrease the ?exibility of the vinyl resins
30 and eilect the speci?c improvements mentioned
ance to these solvents. In addition, the heat
treated coating has a higher softening point than
- coatings formed of the original copolymers. Y
above.
'
'
_ In more detail, the types ‘of vinyl resins to
which this invention is applicable are those
formed by the copolymerization of vinyl halides,
The presence of the combined-,carboxylic acid
in the copolymers plays an important part in the 35 such as vinyl chloride or vinyl bromide, with
insolubilization and the improvement in waterf;
resistance which occurs, slnceoomparative tests
have established that these phenomena are not
observed when vinyl halide polymers or copoly
aliphatic, alpha, beta-ole?nic carboxylic acids,
boxylic acids combined in the polymer, are heat
The copolymerization may be carried out in the
or by the copolymerization of vinyl halides, vinyl
esters of lower fatty acids, such as acetic, pro
pionic and butyric acids. and the aliphatic, alpha,
, mers ofvinyl halides with vinyl'fatty acid esters, 40 beta-ole?nic carboxylic acids. In this latter in
stance, three component copolymers are formed.
which do not contain alpha, beta-ole?nic car
treated with the heat-reactive urea-formaldehyde
or melamine-formaldehyde resins. Furthermore,
absence of any solvent or diluent, or the mon
omers may be dissolved in solvents or emulsi?ed
water prior to polymerization. The tempera
the urea-formaldehyde and melamine-formalde 45 in
ture of polymerization may be between 30° and
hyde resins are slightly more compatible with
80° 0., and oxygen-yielding catalysts, such as
the copolymers containing combined alpha, beta
hydrogen peroxide, benzoyl peroxide, and potas
ole?nic carboxylic acids. They show much less
sium persulphate may be employed. Certain
tendency towards formation of a prominent retic
ulated pattern in the baked coatings, than they 60 alpha, beta-ole?nic carboxylic acids, such as
maieic acid, copolymerize at a faster rate than the
exhibit in the unmodi?ed vinyl‘halide polymers
vinyl halides or mixtures of vinyl halides and
or copolymers in the absence of a‘, blending in
vinyl aliphatic esters. In such instances, allow
gredient, such as a vegetable oil or alkyd resin as
ance for this can be made by adjusting the
described in an application of vPowell and Mc
Knight, Serial No. 429,112, ?led January 31, 1942, 55 charslns ratio of the monomers, or by adding
2,411,590
-
4
the maleic acid in small amounts during the poly
merization.
.
The aliphatic, alpha, beta-oleilnic carboxylic
acids all contain the resinophoric group,
cause of the obvious diiliculties, this has not been
experimentally established, however, but in any
events. distinct improvement in resistance of
the ?lm to attack by solvents, to softening under
heat, and to thermal decomposition is observed.
The amount of heat reactive resin in such mix
tures may vary from about 5 to 30 parts of such
resin per 100 parts of the modi?ed vinyl resin,
depending, to some extent, on the amount of
and the term "acids" also includes the anhydrides 10 carboxylic acid combined 'in the vinyl resin.
About 10 to 20 parts of the heat-reactive resin
oi’ the acids. The acids may be either monobasic
per 100 parts of the modified vinyl resin are pre
or polybasic and may contain one or more ole?nic
groups in addition to the one which is in a con
ferred.
jugated position with the 0:0 linkage. Ex
The coating composition of this invention may
amples of suitable acids include maleic acid, fu 15 be applied tojany surface which will withstand
maric acid, mono-esters of fumaric and maleic
the heat-treatment required. Thus, it may be
acids, maleic anhydride, acrylic acid, a-meth
applied as a protective coating to foils, sheets,
acrylic acid, crotonic acid, citraconic acid and its
panels, wires, rods and tubes made of metals,
anhydride, itaconic acid and its anhydride, chlor
such as iron, tin plate, zinc, copper, aluminum,
maleic acid, and the like. Examples of mono 20 lead, magnesium, and their alloys; it may also
esters of maleic and fumaric acids include mono- .
methyl fumarate and mono-2-ethyl-hexyl male
serve as a water-resistant coating for cellulosic
sheet material, such as porous papers, glassine
ate, as well as other lower mono-alkyl esters of
paper, waxed papers, and regenerated cellulose
these acids.
sheeting. It may be used to coat textile fabrics
The amount of the alpha, beta-ole?nic car 25 made of yarns composed of cotton, wool, viscous
boxylic acid which need be combined in the vinyl
rayon, cellulose acetate, or linear polyamides. It
halide polymers or copolymers is not large in
may also serve as an oxidation-resistant and
order that insolubilization of the coating may
solvent-resisting coating for natural rubber,
occur on heat-treatment with the urea-formal
butadiene-styrene rubbers, butadiene-acryloni
dehyde
or melamine-formaldehyde resins. 30 trile rubbers, and other synthetic rubbers and
Amounts of combined acid between about 0.5%
rubber substitutes, such as sodium polysul?de
and 20% of the polymer are usually su?flcient,
ethylene dichloride or dichlorethylether conden
and for most purposes, a resin containing from
sation products, gamma polyvinyl chloride and
copolymers of vinyl chloride and vinyl acetate
isfactory. Dibasic acids, such as maleic acid, are 35 having molecular weights above 18,000 and vinyl
usually effective in smaller amounts than mono
chloride contents of about 95%, containing about
basic acids. When vinyl esters are present in
30% to 45% plasticizer. It may be used to apply
the copolymer, in addition to vinyl halides and
a solvent-resistant coating on resinous sheet ma
the carboxylic acids, their amount may vary‘
terial which otherwise may be attacked by sol
from 3.2% or 5% to 15, 20, 35 or 40% by weight 40 vents, such as sheets composed of cellulose ace
of the copolymer. The molecular weight of the
tate, cellulose nitrate and vinyl resins, for in
resins as determined by Staudinger’s method may
stance, copolymers of vinylv chloride and vinyl
vary from 5,000 to 30,000, or higher. The resins
acetate. It may be used to protect wood and con
0.5% to 10% of combined carboxylic acid is sat
described above are insoluble in dilute solutions
crete articles from moisture, or to impart chem
of sodium hydroxide.
45 ical resistance to articles molded from phenol
The heat-reactive urea-formaldehyde resins
formaldehyde resins.
or melamine-formaldehyde resins are well known.
They are usually formed by heating urea or
The metal sheets may already contain a dec
orative or primer coating before the composition
melamine with a molar excess of formaldehyde.
of this invention is applied, and such coatings
The initial heating is under non-acidic condi 50 may consist of solid color coatings, varnishes,
tions, and the ?nal heating is in the presence
lacquers, or lithographic prints. Similarly, the
of an acidic catalyst, and a solvent, such as
plastic sheets to be protected may have press
butanol. Water is removed during the latter
polished, matte or embossed surfaces.
stage, and the reaction is stopped while the
The coating composition exhibits good adhesion
resin is still soluble in alcohol. The resins may 55 to various types of surfaces, but it ?nds its most
be modi?ed during manufacture with other in
useful adaptation in applications where the
gredients such as ethylene glycol phthalate resins
chemical inertness; acid, alkali, oil, and grease
having unreacted hydroxyl groups. polyhydric
resistance; ?exibility; abrasive resistance, and
alcohols, vegetable oils, and the like. In addi
toughness of the vinyl resins are desired, but a
tion, both urea and melamine may be used in 60 coating. of higher softening point and greater
the same resin if desired, or other nitrogen de
rivatives, such as dicyandiamid, thiourea, and the
various diazine and triazine derivatives, may be
resistance to solvents and boiling water is re
quired. Thus, the coating composition of this
invention gives excellent service as an adherent,
used alone or in combination with other start 65 non-toxic lining for food or beverage containers
ing materials. In general, resins of these types
magic of metal, in which the food or beverage is
are capable of undergoing insolubilization reac
packaged at temperatures of 212° F. or higher
tions after deposition in film form, and are char
to insure sterility. Also, many of the present
acterized by the relative speed of these ther
vinyl
resin coatings for paper do not have a suf
mosetting reactions even at baking temperatures
70 ficiently high softening temperature to prevent
“blocking" at summer temperatures, especially in
warehouses exposed to the sun.v However, paper
blended with the acid modi?ed vinyl resin and
coatings containing the modi?ed vinyl resin heat
films are deposited from such mixtures and
treated in situ with the heat-reactive urea-form
baked, it is possible that some degree of reaction
as low as 200° F.
When such heat reactive aminoplasts are
between the two resinous ingredients occurs. Be
75 aldehyde or melamine-formaldehyde resins have
2,411,500
5
' In this manner, damage to the heat-sensitive a!’
ticle can be minimized or avoided.
at temperatures'of 180° 1'‘.
It has also been found that the presence in the
Another illustration of the utility of the new
coating of phosphoric acid or acid esters of
coatings in this respect is as a top or ?nishing
phosphoric acid, such as the mono- or dialkyl
coating for cloth coated with a highly plasticized
acid phosphates, will accelerate the curing reac
vinyl resin, such as a copolymer of vinyl chloride
tion, and result in more insoluble and adherent
with vinyl acetate or a plasticized polyvinyl par
coatings of higher softening point and better re
tial butyral resin, which may itself be of a ther
sistance to boiling water. The amount of the
mosetting or heat-curing type. Upon heat-treat
phosphoric acid or organic acid phosphate may
ment, the top coating is converted to‘ its insoluble
be varied from less than 1% to over 30% by weight
form and insures that the coated cloth does not
of the urea or melamine resin. About 10% of
block at temperatures of 180° F. or higher. An
such compounds appears preferable because of
other advantage is that such top coatings tend to
the increasing incompatibility of higher propor
prevent excessive loss of plasticizer by evapora
tion, and prevent plasticizer exudation or "sweat 15 tions. Suitable alcohols for making the mono
and dialkyl phosphoric acid esters include methe
out,” both 'where this is caused by the underly
anol, ethanol, isopropanol, butanol, 2-ethyl bu
ing resin absorbing water, as is sometimes the
tanol and 2-ethyl hexanol. The phosphoric acid
case with highly plasticized base coatings of
may also be spread over the surfaceof ferrous
thermoplastic polyvinyl partial butyral resins, or
where “sweat-out" iscaused by diffusion of the 20 metals to be coated, but better results are. ob
tained“ the surface of the iron or steel is lightly
plasticizer to the surface. For coating cloth, it is
phosphatized by any of the known chemical .or
desirable that the top coating also be plasticized,
higher softening points and do not "block" even
electrochemical treatments, such as the “Bond
but not necessarily to such an extent as to equal
erizing process,” to form a coating which does not
the ?exibility of the base coating. To prevent
crack on subsequent forming operations. The
the plasticizer of the base coating from penetrat
composite coating of this invention is then ap
ing the‘clotb, a primer coating of the modified
plied and baked for 10 to 15 minutes at 325° to
vinyl~ resin and heat-reactive vresin may be ap
400° F.
plied tothe cloth.
In many instances, copolymers of vinyl chlo
Composite coatings prepared in this manner
o?er advantages not easily obtainable by other 30 ride and vinyl acetate containing from 60% to
95%, and preferably from 85% to 88% of vinyl
methods. Thus coated fabrics of very good ?ex
chloride may be included in the coating. These
ibility can be prepared by using high proportions
resins may be blendedwith the other resinous
of plasticizer in the intermediate coats, while the
ingredients of the coating in amounts of 10, 20,
less soluble top coat and base coat, based upon
composit‘ons of heat reactive‘ aminoplasts 35 30, 40, 50, 60, 70, 80 or 90% depending on the
solvent resistance and softening point which is
blended with the modi?ed vinyl resins, prevent
‘required for the particular application. Where
escape of the excess plasticizer, which otherwise
the larger amounts of the vinyl acetate-vinyl
would occur and make the surface "tacky” at
chloride oopolymers are employed, it is usually
temperatures of l50°~200° F.
_
The coating composition in combination with 40 necessary to include a small amount of a vegeta
ble oil, an alkyd resin, or a vegetable oil-modi
suitable plasticizers may also be applied in dilute
?ed alkyd resin in the composite coatinglto avoid
solution to impregnate cotton fabrics of the type
difficulties from “checking” of the film after bak
used in shirts, collars and overalls, whereby
ing. Castor oil or a castor oil-modi?ed glyceryl
about 1% to 5% of the composition by weight of
phthalate resin are preferred for this purpose.
The usual ketone solvents for vinyl resins may
of the cloth to improve the wearing qualities of
be employed in the coating compositions, but a
the cloth and its resistance to abrasion. The-un
coupling or blending solvent in addition to the
plasticized coating composition may also be used
hetone solvent is frequently desirable in order to
to improve the sti?ness and crease-resistance of
fabrics, such as curtain fabrics, or pile fabrics by 50 obtain clear solutions of the vinyl resins and mel
amine or urea resins. Suitable coupling agents
spreading a dilute solution of the composition
include aloohol-ethers, such as ethylene glycol
over the fabric, and subjecting it to a heat-treat
the cloth is deposited as a coating over the ?bers
rnégnoethyi ether and ethylene. glycol monoethyl
ment. Such fabrics are adapted to resist discol
oration and deterioration on exposure to light
and oxygen.
'
The temperature and duration of the heat
e
55
er.
The following examples will serve to illustrate
the invention:
'
treatment will vary depending on the surface to
Example 1
be protected. For metal coatings, a baking pe
riod of 10 to 15 minutes at temperatures of 350°
Two clear lacquers of the following composi
to 400° F‘. is usually su?icient to convert the coat 60
tion were prepared:
ing to its insoluble form. At lower temperatures,
longer baking periods are usually required. For ,
cloth orpaper coatings, temperatures of 200° to
300° F. areusually the maximum the cloth or pa
per will withstand for prolonged periods, and,_ at 65
these temperatures, baking times of about 30 to
~60 minutes are usually necessitated to obtain
coatings of .improved softening point. For wire
coatings,’ temperatures up to about 800° F., for
A
Vin lohloride(8ii ). vinyl acetate 15
M'olecularwe
2%1 ,
co
1
B
er. Parts Parts
........
_
______ -.
Vinyl chloride (86%), vinyl acetate (14%), maleic
acid (1%), oopolymer.
.
Molecular weight 10,000 ......... _ .
Heat-reactive
nrea-iormaldelgde
resin (50% solution
iii-butanol, 2
, eapryl cohol, 1 part) __________ __
4
20
4
aci
0.10l
0.10l
periods ofabout 1 to 2 minutes may be employed. 70 Phosphoric
Iiltliyl one glycol monomethyl ether __________________ -.
Met ylisobutyl ketone _____________________________ __
60
60
Where the surface to be protected is sensitive
Toluene
00
60
to heat, thin, films of the composite coating can
be cured by exposureof the coated side to intense
Two coats of each lacquer were sprayed over
radiant heat for a brief period, as for instance,
in an. even having a continuous conveyor belt. 75 sanded steel panels, and each panel was baked at
2,411,090
.
with coating A exhibited a prominent reticulated
pattern or checks and cracks, whereas the panel
with coating 13 was smooth. After 45 minutes
heating, coating 3 exhibited better heat stability
than coating A. After baking, coating 3 did not
soften appreciably in contact with acetone, where
as coating A was distinctly softened and swollen.
,
A clear lacquer was prepared as follows:
.
Parts
Vinyl chloride (95%), vinyl acetate (3.2%),
10
Example 2
8
iron panels, coating 1" was somewhat better than.
coating 1:.
Example 4
375' 1". After baking for 15 minutes, the panel
nasal: acid (1.8%). Molecular weight about
Heat-reactive, alkyd modi?ed melamine-form
aldehyde resin, 50% solids in solvent mix
ture consisting of 30% butanol, 20% capryl
Two clear lacquers of the following composi
tion were prepared:
alcohol, and 50% mineral spirits ________ _-
6
15 Phosphoric acid, 10% solution in ethylene
glycol monomethyl ether _______________ __
1
Ethylene glycol monomethyl ether_______ -_ 13
Methyl isobutyl ketone ___________________ _- 50
Vinyl chloride (85.0%), vinyl acetate (13.3%), maleic Parts
acid (L7 a) copolymer ____________ .2 ............... _.
Heat-react ve urea-formaldehyde resin (25% solution
in ethylene glycol monoethyl ether, 5 parts, butanol,
20
Ethy
2.8 ne
rtsglycol
and capryl
monomethyl
alcoho ,ether.
1.4 parts
. __..... ._
Toluene
50
Two coats of the lacquer were applied by spray
ing to black iron panels and to tin plated steel
panels having a primer coating of baked oleo
resinous varnish. All panels were baked at 375°
F. for 15 minutes. The resultant ?nishes were
25 amber in color and very tough and adherent.
Two- coats of each lacquer were sprayed onto
They did not soften appreciably on soaking the
brightly sanded steel panels, and then baked for
panels in methyl ethyl ketone, nor did they blush
one hour at 350° F. Coating D showed better
or lose any of their adherent qualities after im- _
resistance to acetone than coating C, but both
mersion
of the panels in boiling water for one
were distinctly better than coating A of Ex 30 hour.
‘
ample 1. The softening point of coating D was
Phosphoric acid
'lil‘loelthyl isobutyl ketone .......... _ _
Example 5
somewhat higher than coating 0, but the soften
ing points of both coatings were about 30° to
Example 4 was repeated with equivalent re
40° F. higher than that of coatings which con
tain only the modi?ed copolymer of vinyl chlo 85 sults using monobutyi phosphoric acid in place of
phosphoric acid.
ride, vinyl acetate and maleic acid, which have
a softening point of about 170° F. The softening
points are determined by placing a piece of cheese
Example 6
cloth on the baked film under a one pound per
Example 4 was repeated employing a copoly
mer of vinyl chloride (84%), vinyl acetate (14%)
and methacrylic acid (1%), and a ?nish was ob
tained which was resistant to solvents and to
water.
square inch weight. The softening point is taken 40
at the temperature at which the ?bers of the
cloth will print on the ?lm after the pressure is
applied for 30 minutes.
45
Example 3
Two clear lacquers were prepared as follows:
Vinyl chloride (85%), vinyl acetate (14%), malelc
acid (1%). Molecular weight 10,000 _______________ _.
Heat-reactive alkyd modi?ed melamine-formalde
h do resin, 50% solids in solvent mixture consisting
o 30% butanol, 20% capryl alcohol, and 60% min
eral spirits
Ethy
Example 7
The following lacquer was prepared:
Parts
50 Vinyl chloride (92%), maleic acid (8%), co
polymer. Molecular weight about 20,000-- 20
Heat-reactive alkyd modi?ed melamine
formaldehyde resin, 50% solids in solvent
mixture consisting of 30% butanol, 20%
capryl alcohol, and 50% mineral spirits"
Phosphoric acid, 10% solution in ethylene
6
glycol monomethyl other.
.
Methyl isobutyl ketone .......... . _
_ _.
glycol monomethyl ether ______________ _-
l
Toluene _____________________________________________ __
Ethylene glycol monomethyl ether ________ _-
l3
Cyclohexanone _________________________ .... 100
Two coats of each lacquer were applied to tin 60
Two coats were applied by spraying to steel
plated steel panels which contained a baked oleo
panels,
and the coating baked for 15 minutes at
resinous varnish of the type used for priming
375° F. The resultant ?nish showed good re
cans for packaging beverages, such as beer. Du
sistance to ketone solvents and to boiling water.
plicate coats were also applied to black iron panels
.
and both sets of panels were baked for 15 min 65
Example 8
utes at 275° F. Coating F had somewhat better
resistance to solvents than did coating E, and
This example illustrates a cloth coating in
it showed better adhesion after immersion in
which the partially heat-reactive vinyl resin
boiling water for 15 minutes. However, both coat
ings were much superior in these respects to 70 composition is employed as a solvent-resistant,
non-blocking, finishing coating over a highly
coatings of unmodi?ed copolymers of vinyl chlo
plasticized base coating containing a copolymer
ride and vinyl acetate, irrespective of whether
of vinyl chloride and vinyl acetate of relatively
such coatings contained urea or melamine resins.
low molecular weight which has good ?exibility
The heat stability of both coatings E and F was
satisfactory, although in the tests on the black 75 but exhibits a tendency to “block” at tempera
8,411,590 .
0
turescfiwlltoiwl'. 'i‘hebaseeoatinghad
thefollowing composition:
'
'
Per-cent
Vinyl chloride (88%). vinyl acetate
(14%) copolymer. Average molecular
weight 10,000 ............. -'_ ....... --
'pliedtotheclothbyusingadoctorkniiafolr
lcwedbyonecostoftbetopcoating.'1‘heilnal
coatingwasbakedforwtowminutesatml'.
The coating did not "block” when sterilised with '
steam under 15 pounds per square inch pressure.
21.2
In determining this, samples of the coated cloth
Yellow iron oxide pigment............ -Black iron oxide pigment. ............ ..-
1. 43
1. 84
Lead titanate ....................... __
1.09
Whiting
8.44 .10
Dloctyl phthalate.................... __
4. 75
were placed face to face under a pressure of one
.pound per square inch. .
Dicapryl phthalate __________________ __
7.78
water-repellent, treatment.
3.19
Light hydrocarbon distillate __________ ..
25. 3
Methylethyl ketone __________________ __
12.8
Methyl isobutyl ketone _______________ __
12. 8
The coated cloth is useful for raincoats, tar
paulins, tents, ski clothing, gun coverings and the
like. The cloth may be coated on both sides with
the composition, or the uncoated side given a
Butyl ester of acetylated polymerized
ricinoleic acid-__-. _________________ ..-
10'
Beveraicoatsofthebasecompositionwereap
15
100.00
Several coats of this composition were applied
to cloth and then a ilnishing coating of the fol
The above composition without the pigments is
useful for coating paper and rubber articles. and
may be applied by conventional methods. For
instance, the paper may be coated employing a
reverse roller machine, and the rubber articlesv
may be coated by a spraying technique, after suit
able thinning of the composition.
lowing composition was applied:
‘
_
Modi?cations of the invention other than as
Per cent
specifically described in the examples will be ap
Vinyl chloride (85%). vinyl acetate
parent to those skilled in the art, and are in
(14%), maleic acid (1.0%) copolymer.
cluded within the scope of the invention.
Average molecular weight about 10,000- 22. 5
I claim:
Heat-reactive alkyd modified melamine1. A vinyl resin coating composition of a lim
formaldehyde resin, 50% solids in sol
ited heat-reactive type comprising an acid-react
vent mixture consisting of 30% butanol,
ing vinyl resin of the group consisting of a co
20% capryl alcohol and 50% mineral
polymer of vinyl chloride, a vinyl ester of a lower
30
spirits
' 4. 53
saturated fatty acid, and an aliphatic, alpha,
Yellow iron oxide pigment ____________ __
1. 52
beta-ole?nic carboxylic acid, in which from 3.2%
Black iron oxide pigment_____________ __
1. "('1
to 40% of said ester and from 0.5% to 20% of
Lead titanate ______________________ -_'_
1. 18
acid, by weight of the copolymer, are combined
Whiting
8. 94
35 therein, and a copolymer of vinyl chloride and an
Dioctyl phthalate __________________ __
1.76
aliphatic, alpha, beta-ole?nic carboxylic acid, in
Butyl ester of acetylated polymerized
ricinoleic acid _____________________ __
Dicapryl phthalate __________________ __
Light hydrocarbon distillate__________ .._
Methylethyl ketone __________________ _Methyl isobutyl ketone ______________ .._
30% by weight of said ‘acid-reacting vinyl resin
of a heat-reactive, alcohol-soluble resin of the
group consisting of urea-formaldehyde and mel
amine-formaldehyde resins, the composition be
ing dispersed in an organic solvent.
2. A vinyl resin coating composition of a lim
Each coat was baked for a few minutes at 210° 45 ited heat-reactive type comprising an acid-react
ing vinyl resin of the group consisting of a co
F. to remove solvents and the ?nal cost was
polymer of vinyl chloride, a vinyl ester of a lower
baked 30 minutes at 230° F.
The total coating weight was -3.5Ito 4.2 ounces ' saturated fatty acid, and an aliphatic, alpha,
beta-ole?nic carboxylic acid, in whichfrom 3.2%
per square yard. The coating was ?exible at
0° 1". and it did not block at a temperature of 50 to 40% of said ester and from 0.5% to 20% of
acid, by weight of the copolymer, are combined
210° F.
therein, and a copolymer of vinyl chloride and an
Example 9
aliphatic, alpha, beta-ole?nic carboxylic acid, in
To obtain coated cloth of better resistance to
which from 0.5% to 20% of acid by weight of the
solvents and boiling water, it is preferable to em
is combined therein, from 5% to 30%
ploy the heat-reactive vinyl resin composition in 55 copolymer
by weight of said acid-reacting vinyl resin of a
Synthetic wax ______________________ _.
'
3. 00
1.18
15. 82
40
18. 48
18.48
which from 0.5% to 20% of acid by weight of the
copolymer is combined therein, and from 5% to
0.84
100. 00
both the base coating and the top coating. The
following compositions are suitable for this
purpose:
-
Base coat- Top coat
in:
Vinyl chloride (85% , vinyl acetate (14%),
his
Per cm!
22.
maleic acid (1.0%) copolymer. Average
molecular weight about 10,000 __________ _ .
Heat-reactive melamine-formaldehyde
resin solution of Example 8_____________ A
titanate ___________ __
Methyl isobutyl keione ...... __
Metbylethyl ketone __________ _
60 weight of said heat-reactive resin of one of the
group consisting of phosphoric acid and acid es
ters of phosphoric acid, the composition being
dispersed in an organic solvent.
3. A coating composition of a limited heat-re
active type comprising a copolymer of vinyl
chloride, vinyl acetate and maleic acid, in which
from 3.2% to 40% of vinyl acetate and from
0.5% to 10% of maleic acid, by weight of the
copolymer, are combined therein. from 5% to
70 30% by. weight of said copolymer of a heat-re
active, alcohol-soluble resin of the group con
uy as r o ace
ym m...
surrenders-am.
pwlel?tiidngm
heat-reactive, alcohol-soluble resin of the group
consisting of urea-formaldehyde and melamine
formaldehyde resins, and from 1% to 30% by
‘3o""""" "
Dlcapryrphtbalate.................... ..I:
§8
5. e
sisting of urea-formaldehyde and melamine
i’ormaldehyde resins, and an organic solvent.
4. A coating composition of a limited heat-re
75 active type comprising a copolymer of vinyl
2,411,590
l1
chloride, vinyl acetate and maleic acid, in which
from 3.2% to 40% of vinyl acetate ‘and from
0.5% to 10% of maleic acid, by weight of the co
polymer, are combined therein, from 5% to 30%
by weight of said copolymer of a heat-reactive,
alcohol-soluble resin of the group consisting of
urea-formaldehyde and melamine-formaldehyde
resins, a copolymer oi! vinvl chloride with vinyl
acetate containing irom 60% to 95% vinyl chlo
ride, and an organic solvent.
5. A coating composition oi’ a limited heat
12
on said surface by baking the coating at tem
peratures between 200' 1". and 800' 1".. and heat
treating said acid-reacting vinyl resin with said
heat-reactive resin to form a coating on said
article which is resistant to water and solvents.
'1. Process for coating metals which comprises
applying a primer coating comprising an oleo
resinous varnish, baking said primer coating, and
then applying a composition comprising a dis
10 persion in an organic solvent of a copolymer of
vinyl‘chloride, vinyl acetate and maleic acid, in
reactive type comprising a copolymer of vinyl
which from 3.2% to 40% of vinyl acetate and
chloride and maleic acid, the amount of maleic
from 0.5% to- 10% of maleic acid, by weight of
acid combined in the copolymer being from 0.5%
the copolymer, are combined therein, and from
to 10% by weight of the copolymer, from 5% to 15 5% to 30% by weight 01' the copolymer 0! an
30% by weight of said copolymer oil a heat-re
alcohol-soluble, heat-reactive resin of the group
active, alcohol-soluble resin 0! the group consist
consisting of urea-formaldehyde resins and me]
ing of urea-formaldehyde and melamine form
amine-formaldehyde resins, baking said compo
aldehyde resins, and an organic solvent.
sition at a temperature of 325° F. to 400° F.. and
6. Process for coating smooth and extended 20 i'orming a coating on the metal which is resist
surfaces which comprises applying to said sur
ant to solvents and to water.
faces a coating composition of a limited heat
8. Process for coating ferrous metal which
reactive type comprising a dispersion in an or
comprises phosphatizing the metal surface. and
ganic solvent of an acid-reacting vinyl resin of
then applying a composition comprising a dis
the group consisting of a copolymer of vinyl chlo
persion in an organic solvent of a copolymer of
ride, a vinyl ester of a lower saturated fatty acid,
vinyl chloride, vinyl acetate and maleic acid, in
and an aliphatic, alpha, beta-ole?nic carboxylic
which from 3.2% to 40% of vinyl acetate and
acid, in which from 3.2% to 40% of said ester
from 0.5% to 10% of maleic acid, by weight oi’
and from 0.5% to 20% of acid, by weight of the
the copolymer, are combined therein, and from
copolymer, are combined therein. and a copoly 30 5% to 30% by weight of the copolymer of an
mer of vinyl chloride and an aliphatic, alpha,
alcohol-soluble, heat-reactive resin 01 the group
beta-ole?nic carboxylic acid, in which from 0.5%
consisting of urea-formaldehyde resins and mel
to 20% of acid by weight of the copolymer is
amine-formaldehyde resins. baking said com
combined therein, and from 5% to 30% by weight
position at a temperature of 325° F. to 400° I-..
of said acid-reacting vinyl resin 0! a heat-re 36 and forming a coating on the metal which is re
active, alcohol-soluble resin 01 the group con
sistant to solvents and to water.
sisting oi’ urea-formaldehyde and melamine
iormaldehyde resins, forming a continuous ?lm
GEORGE ll. POWELL, 3RD.
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