close

Вход

Забыли?

вход по аккаунту

?

Патент USA US3082194

код для вставки
_ United States Patent 0 ' ice
'_
3,082,184
Patented Mar. 19, 1963
1
2
3,082,184
most practical purposes acrylic acid, methacrylic acid,
COATING COMPOSITION COMPRISING AN ALCO
HOL-MODIFIED AMINOPLAST RESIN AND A
C 0 P 0 L Y M E R OF, A p-HYDROXYI’ROPYL
or itaconic acid is preferred.
Other monoethylenically unsaturated compounds co‘
ACRYLIC ESTER AND AN ACID, AND METAL
polymerizable with the hydroxyl and acid monomers
which may be used include esters of acrylic acid or
CGATED THEREWITH
methacrylic acid with cyclohexanol, benzyl alcohol, or
_
Dominicv Richard Falgiatore and Allen M. Levantin,
Philadelphia,.Pa., assignors to Rohm & Haas Com
pany, Philadelphia, Pa., a corporation of Delaware
alkanols having 1 to 18 carbon atoms; acrylonitrile or
methacrylonitrile, styrene, vinyltoluene,_a-methyl styrene,
and so on. The hardness, ?exibility, toughness, and
No Drawing. Filed Jan. 9, 1959, Ser. No. 785,798
10 adhesion for various substrates can be varied widely as
19 Claims. (Cl. 260--30.4}
desired by suitably adjusting the proportions of these
‘This invention is concerned with thermosetting coating
various monomers. For example, a copolymer contain
compositions comprising an alkylated aminoplast resin
ing 94% of an ester of acrylic acid such as methyl, ethyl,
forming condensate and a thermoplastic copolymer of
or butyl acrylate with 5% of B-hydroxypropyl acrylate
(1) a ?-hydroxypropyl ester of acrylic, or methacrylic
or methacrylate and 1% of one of the acids mentioned
acid, (2) an tsp-unsaturated carboxylic acid, and (3) one
produces ?lms which are extremely ?exible and adherent.
or more other monoethylenically unsaturated copolym
On the other hand, a copolymer of 96% by Weight of
erizable compounds containing a CHZ=CL= group.
methyl methacrylate with 5% by weight of ?-hydroxy
Frazier et al. in United States Patent 2,681,897 disclose
propyl acrylate or rnethacrylate and 1% of one of the
thermosetting coating compositions comprising an alkyl
acids produces an extremely hard ?lm, which is suitable
ated aminoplast and a thermoplastic copolymer‘ of a
for relatively rigid substrates but is insu?iciently ?exible
hydroxyalkyl ester of acrylic or methacrylic acid, which
to be applied to highly ?exible substrates such as of paper,
copolymer contains primary hydroxyl groups, that is
leather, or textiles.
'
groups of the formula ——CH2OH. It has been found
The copolymers may be prepared in any suitable _.
that coatings obtained from such compositions are un 25 fashion. They should have a molecular weight in ‘the
reliable in respect to the production of gloss. This appar
ently involves instability on standing so that widely
diiferent ‘gloss values or ratings are obtained if the coating
. composition is allowed to stand various'lengths of time
after compounding before application. While a composi
tion made in'accordance with this patent at times may
range of about 10,000 to about 130,000 viscosity average
and for this purpose solution polymerization, particularly
in a solvent which may be employed as the solvent for
- the coating application, is generally preferred. The mon
omers comprising the unsaturated acid, the B-hydroxy
propyl acrylate or methacrylate, and the other mono
produce a certain glossiness, it is ditiieult, if not impos
sible, to reproduce. coatings having 'the same glossiness
ethylenically unsaturated compounds in the proportions
?lms and ‘which are capable of producing even higher
glossiness than those obtainable from the compositions of
oxygen compound, such as t-butyl peracetate, or a perox
discovered that coating compositions comprising an alkyl
ated'aminoplast and a thermoplastic copolymer containing
held at re?ux for a period of 2 to 6 hours or more. There
secondary hydroxyl groups is 30% by weight, produce
coatings having outstanding gloss even when highly pig
mented. Also, the production of highly glossy coatings
‘from 1 to 6 carbon atoms or cyclohexanol, of a con
needed to give the composition hereinabove de?ned are
even though they are made from what was believed to
mixed in the solvent at a concentration. of about 10 to
be the same composition originally. It is an object of 35 60% total monomer in the entire solution and any suit
the present invention to provide compositions which are
able free-radical initiator soluble in the solvent is intro‘
far more reliable in their capacity to produce glossy
duced. The initiator may be an azo catalyst, a per
ide, such as benzoyl peroxide, or a hydroperoxide, such
40 as t-butyl hydroperoxide, or cumene hydroperoxide. The
the patent.
'
In accordance with the-present invention, it has been
solution is heated to re?ux to effect copolymerization and
after, the solution of the copolymer may be cooled and
5 to 30% by weight of ?-hydroxypropyl acrylate or meth
the aminoplast solution prepared as described hereinabove
acrylate, from 1 to 4% of a copolymerizable pap-unsatu 45 may be introduced with adjustment of the solvent con
rated carboxylic acid, and one or more other copolymer-1'2
tent to provide the concentration desired. Pigments,
ablemonoethylenically unsaturated compounds contain
extenders, curing catalysts, and any other adjuvants may
ing a CHZ=C= group which latter compounds are devoid
then be added.
of primary alcoholic hydroxyl groups and in which
The alkylated aminoplasts which may be used include
copolymer the maximum content of units containing 50 those obtained by the alkylation, with an alkanol having
employing the compositions of the present invention is
highly reliable and readily reproducible.
The composition of the copolymer, as stated, includes
from 5 to 30% of ?~hydroxypropyl acrylate or meth
acrylate which may be represented generically by the
densate of an aldehyde with urea, N,N’-ethyleneurea,
dicyandiamidc, and aminotriazines. Both water-soluble
and water-insoluble alkylated aminoplast condensates
may be employed provided they are soluble in the or
ganic solvent employed in making the coating composi
tions.
Thus, such- water-soluble condensates as the
methylated dimethylolurea condensates can be employed
formula
provided the alkylation with methanol is su?iciently com
60
plete, and preferably substantially 100%, to render the
alkylated condensate soluble in the organic solvents men
tioned hereinafter. In general, the alkylated condensates
in which'n is an integer having avalue of 1 to 2. The
should have at least 80% and preferably 100% of the "
copolymer may contain as much as 30% by weight of
units containing secondary hydroxyl groups which may 65 metnylol groups alkylated with cyclohexanol or an al
kanol having 1 to 6 carbon atoms. Preferably, the alkyla
include units derived from ?-hydroxypropyl vinyl ether
tion products of alcohols having from 3 to 6 carbon
or sul?de. However, the compound is devoid of mon
atoms are employed,and the butylated products are par
omcrs containing'primary hydroxyl groups, that is those
ticularly valuable because of their greater‘compatibility.
having units of the formula -CH2OH.
Any copolymerizable unsaturated acid may be used in 70 with a wide range of copolymers and solvents mentioned
hereinafter.
preparing the copolymer including maleic acid, fumaric
acid, aconitic acid, citraconic acid, crotonic acid; but for
Among the aminotriazines which are suitable are‘v
3,082,184
4
3
melamine, acetoguanamine, benzoguanamine, forrnogua
namine, N-(t-butyl)-n1elamine, N-(t-octyl)-melam1ne in
which the t-octyl group has the formula
of aminoplast condensate. The use of the curing catalyst
may be particularly desirable when lower temperatures
of curing or baking are needed. With such curing cata
lysts, insolubilization can be accomplished simply by dry
ing and ageing at room temperature. Amongst the curing
ammeline, 2-chloro—4,6~diamino-1,3,5-triazine, 2-phenyl-p
oxy-4,6-diamino-1,3,5-triazine, 6-methyl-2,4-diamino-l,3,
5-triazine, 2,4,6-trihydrazine-1,3,5-triazine, 2,4,6—triethyl
catalysts that may be used to cure the composition of the
present invention are any of the acid catalysts and, in
cluded in that group, are the organic and the inorganic
acid catalysts. One may use, for instance, in catalytic
triamino-l,3,5-triazine, and the N,N-di—(C1—C.,)alkyl mel
amines such as N,N-dimethylmelamine. While any ‘alde 10 amounts, sulfuric acid, hydrochloric acid and their acid.
hyde may be employed such as acetaldehyde, crotonalde
salts, such as ammonium sulfate, ammonium chloride, or
hyde, and acrolein, the condensates obtained using formal
the organic acids, such as acetic acid, phthalic acid, ben
dehyde and revertible polymers thereof such as parafor
zoic acid, toluene sulphonic acid, naphthalene sulphonic
maldehyde are preferably employed.
acid, and the mono-salt of maleic acid with triethylamine.
The compositions herein maybe applied for the coating
The copolymer and the aminoplast condensate are 15
of a wide variety of substrates including paper, textiles,
dissolved in an organic solvent in the proportions of 50'
to 95 parts of copolymer to 50 to 5 parts respectively of
leather, wood, ceramics, brick, stone, and concrete sur
faces, as well as metals. They are particularly valuable
the condensate. The proportions in which any particular
for application as ?nishing topcoats for automobiles or
alkylated aminoplast and any particular copolymer are
mixed must also be selected so as to provide compatibility 20 for the decoration of metals in general, such as tin cans
of these two components in the coating solution as well as
or other canisters.
As stated above, the compositions, after application to
in the ?nal ?lm. Any suitable concentration of the
copolymer and aminoplast in the solvent may be em
the substrate to be coated, are dried and cured. If a
curing catalyst is present, such drying and curing may be
ployed such as from 1 to 50% by weight. If a pigment is
present, the total solids concentration in the coating 25 carried out simply at room temperatures. However,
composition may be from 5 to 75% by weight. The
whether or not a catalyst is present, drying may be effected
ratio of pigment to binder (using the latter term to em
at elevated temperatures such as at 140° F. up to 220°
F.; and baking may be effected at temperatures anywhere
brace the copolymer and the aminoplast condensate)
may be from 1:20 to 20:1.
from 180° to 450° F. As is obvious from the preceding
The solvents that may be employed include such by 30 statement, drying and curing may be considered as part
of one operation, the curing following the drying im
drocarbons as benzene, toluene, xylenes, and aromatic
mediately. The time of curing may vary from a period
naphthas or mixtures of such solvents; esters such as
ethyl, butyl, amyl, ethoxyethyl, or methoxyethyl acetates,
lactates, or propionates; ketones such as acetone, methyl
as short as one-half to two minutes at the upper range of
temperature around 450° F. up to one hour or two at
isopropyl ketone, methyl isobutyl ketone, dioxane, iso~ 35 the lower portion of the temperature range given, namely
180° F. A particularly practical curing operation is
t-butanol, isopropyl alcohol, n-propyl alcohol, amyl alco
effected at 300° F. for a period of 15 to 30 minutes or so.
hols, and cyclohexanol; ethers such as diethyl ether, the
The examples immediately following illustrate the
monoethyl ether of ethylene glycol, the monomethyl
preparation of several aminoplast-type condensates, but
phorone, and cyclohexanone; alcohols such as n-butanol,
ether of ethylene glycol, and the monobutyl ether of 40 it is to be understood that the preparation of such con
ethylene glycol; and miscellaneous solvents including
densates is not in itself part of the present invention since
dimethylformamide, dimethylacetamide, acetonitrile, ni
tromethane, ni-troethane, nitropropane, and nitrobutanc;
conventionally-available alkylated aminoplast conden
sates can be employed. The following resins designated
as well as mixtures of two or more solvent materials
A through D are merely typical of alkylated aminoplast
either from the same group or any or all of the groups 45 resins that can be employed herewith. In these examples,
just listed.
the parts and percentages are by weight unless otherwise
Pigments suitable for use according to the invention
are inorganic pigments such as, for example, chrome yel
lows, Prussian blues and Brunswick greens, titanium pig
ments such as titanium dioxide, extended titanium pig 50
ments (extended with either precipitated or natural ex
tenders, such as alkali earth sulphates for instance cal
cium sulphate, barium sulphate, and the like), tinted
titanium pigments, titanates such as barium, zinc, lead,
magnesium titanates, and the like. Additionally, other
types of inorganic pigments might be included, such as
zinc sulphide pigments, for instance, zinc sulphide, litho
pone, other extended zinc sulphide pigments, such as cal
cium base lithopone, zinc sulphide extended with natural
clearly indicated.
EXAMPLE A (RESIN A)
Preparation of Metlzoxymethyl Melamine in Bulanol
Charge:
Moles
A. 1070.0 g. ?ake paraformaldehyde ______ _- 32.5
B. 2400.0 g. methanol __________________ __ 75.0
C. 630.0 g. melamine ___________________ __ 5.0
D. 5.0 ml. 50% formic acid.
E. 620.0 g. n-butanol for dilution.
Materials A, B, C, and D were charged to a glass
reaction vessel equipped with thermometer, mechanical
extenders, and the like, zinc oxide and antimony oxide, 60 stirrer and re?ux condenser. The mixture was heated
to re?ux and held at re?ux temperature for about 31/2
or organic pigments, that is organic coloring matters
which are devoid of sulphonic, carboxylic, or other water
solubilizing groups. Also, for the purposes of this in
vention, we include within the term “pigment” other
waiter-insoluble organic coloring matters such as, for
example, the calcium or barium lakes of azo lake
dyestuffs.
_
The compositions of the present invention are adapted
to be applied in any suitable fashion to the substrate to
be coated such as by brushing, spraying, dipping, roller
coating, or the like, then dried and ?nally cured by bak
ing. Generally, it is unnecessary to add any other ma
terial to catalyze the reaction but, if desired, an acidic
catalyst may be included. The amount of such a catalyst
may be from 0.1 to 1% by ,weight, based on the weight
hours. At the end of this time, the heat was shut off
and the pH of the system adjusted to 9 to 10 with tri
ethylamine (about 12.0 grams required).
The reaction mixture was then stripped under reduced
pressure (about 20 to 30 mm. Hg) to about 82 to 85%
solids (about 2,400 grams of solvent was distilled off),
then cut back to about 60% solids with butanol “E."
Yield: ~2,320 grams of product at 61.6% solids, viscosity
2.5 poises. The product was ?ltered through Super-Cel.
EXAMPLE B (RESIN B)
126 parts of melamine and 405.5 parts of formalin (a
37% aqueous solution of formaldehyde) and 440 parts
of n-butanol are introduced into a suitable reaction cham
3,082,184
5
her equipped with thermometer, stirrer, re?ux condenser,
and a suitable water trap through which the re?ux con
densate passes on its return to the reaction chamber and
ing and stirring are continued for a total of twelve
hours. The ?nal composition is a clear, viscous solu
in which the essentially aqueous fraction of the conden
sate may be separated from the essentially non-aqueous
fraction. Means are provided so that the former fraction
may be drawn off if desirable. The reaction mixture is
tion of a copolymer of about 36% ‘methyl methacrylate,
36% styrene, 15% ethyl acrylate, 11% of ?-hydroxy
propyl methacrylate, and 2% itaconic acid, having a vis~
cosity of about 10 poises at approximately 50% co
polymer solids in a xylene/2-methoxy-ethanol: 77.6/22.4
re?uxed to a temperature of about 91°‘ to 93° C. at at
(weight ratio) solvent system.
mospheric pressure for 6 to 8 hours. The water is re
movedby azeotropic distillation from the reaction mix 10
ture during the re?ux operation. The vapor temperature
'
EXAMPLE F (COPOLYMER F)
The procedure used for making Copolymer E is re
peated substituting for the 80.3 grams (11.0 weight per
will be about 100° to 105° C. The pressure is lowered
sufficiently to reduce the vapor temperature to about 85°
cent) of ?-hydroxypropyl methacrylate, 80.3 grams (11.0
to“90° C. and the resin solution is concentrated to about
weight percent) of ?-hydroxypropyl acrylate. A similar
50% solids by vacuum distillation.
15 solution of a copolymer of about 36% methyl meth
EXAMPLE C (RESIN C)
3370 parts of a 37% aqueous formaldehyde solution
are charged into a suitable reaction chamber and neu
acrylate, 36% styrene, 15% ethyl acrylate, 11% of‘
B-hydroxypropyl acrylate, and 2% itaconic acid, is ob
tained.
.
The following examples in which all parts and per
tralized to a pH of 8.6 with 20% sodium hydroxide and 20
centages
are by weight unless otherwise indicated are
there is then added 6 parts of an 85% phosphoric acid
illustrative of the invention.
solution. The mixture is heated to 70° C. and 1200 parts
of urea are added over a one hour period.
The mixture
EXAMPLE 1
is then heated to 85° C. and held at that temperature for
(a) Mix 200 parts of rutile titanium dioxide with 200
approximately one hour. 1340 parts of butanol are 25 parts of the 50% solution of Copolymer E (‘Example
added and the mixture is heated to re?ux and held at
E) on a three-roll mill. Then mix into this paste 155.2
that temperature for approximately one hour. 1550 ad
parts of the 50% solution of Copolymer E with 88.8
ditional partsof butanol are added and the mixture dis
parts of the 50% solution of butylated methylol mela
tilled, while replacing distillate with a feed of dry butanol,
mine (Resin B), 195.8 parts of xylene, and 97.9 parts
until ,the batch temperature reaches about 112° C. The 30 of Z-ethoxyethyl acetate. Adjust to a spray viscosity of
batch is then vacuum concentrated at 90° C. to approxi
22 seconds (No. 4 Ford cup) by adding a mixture of
mately 65% resin solids. This solution is diluted with
xylene and butanol to give a ?nal composition of 20%
xylene, 30% butanol, and 50% resin solids.
xylene and 2-ethoxyethyl acetate (6923.1 weight ratio)
giving a total solids concentration of 45%. Spray the
composition on bonderized steel panels to give a ?lm
35 thickness of 0.0015 inch after a 15-minute air~dry and a
EXAMPLE D (RESIN D)
30-minute bake at 300° F. The glossiness as determined
“1554 parts of a 37% aqueous formaldehyde solution
by a. 60° photovolt glossimeter manufactured by the
with a pH adjusted to about 8 with sodium hydroxide is
_Photovolt Corporation is 90. The same 90 photovolt
introduced. into a suitable reaction chamber. Thereafter,
gloss is obtained whether the coating composition is ap
654 parts of benzoguanamine, 3 parts of magnesium car 40 plied to the panels immediately after compounding or
bonate, 945 parts of n-butanol and 122 parts of benzene
a week or even a month or more after compounding.
are introduced. The reaction is heated under re?ux de
(b) For comparison purposes, a coating composition
cantation until 700 parts of water are drawn o?. Seven
is compounded and applied in the same way as in part
parts of phthalic acid are then added and the heating un
(a) hereof except that the copolymer is substituted by
der decantation is continued until practically all of the 45 a copolymer of 36.1 parts of methyl methacrylate, 36.1
water (1300 parts) has been removed. The reaction
parts'of styrene, 14.8 parts of ethyl acrylate, and 11.0
mass is then cooled to about 70° to 80° C. and then
?ltered. The yield is about 1950' parts of resin solution
containing 61 to 63% solids.
The following examples illustrate the preparation of
copolymers of ,B-hydroxypropyl acrylate or ?-hydroxy
propyl methacrylate, an unsaturated acid, and other co»
‘parts of ?-hydroxyethyl methacrylate.
polymerizable material, the parts and percentages being
by weight unless otherwise noted.
Coatings ob
tained on application immediately ‘after compounding
‘have a photovolt gloss of 90, but coatings obtained on
application of the composition after standing one week
have a photovolt gloss of 10.
EXAMPLE 2
The procedure of Example 1(a) is repeated substi
tuting 416 parts (in 200-part and 2l6-part batches) of
EXAMPLE E (COPOLYMER E)
a 50% solution of copolymer F for the two batches of
A charge comprising_263.5 grams (36,1‘weight per
copolymer E solution and 60 parts of the 61.6% solu
cent) of methyl methacrylate; 263.5 grams (36.1 Weight
tion of methoxymethyl melamine (Resin A) for the
percent) of styrene; 108.1 grams (14.8 weight percent)
butylated methylol melamine. Similar high gloss coat
of ethyl acrylate; 80.3 grams v(11.0 weight percent) of 60 ings are obtained whether the compositions are applied
IS-hydroxyp‘ropyl methacrylate; 14.6 grams (2.0 weight
immediately or a week after compounding.
percent) of itaconic acid; 10.95 grams (1.5% of total
EXAMPLE 3
' monomer charge) of benzoyl peroxide; and 164.0 grams
of the monomethyl ether of ethylene glycol, is added in
the course of two hours to a glass reaction vessel con
taining 566.0 grams of xylene maintained at 105°. to
107° "C. by means of external heating. The mixture in
the flask is stirred during the addition and subsequent
reaction and maintained at‘ 105° to 107° -C. under a
(a) The procedure of Example 1(a) is repeated sub
stituting 416 parts (in 200-part and 2l6-part batches) of
a 50% solution (in a 77.6:22.4 ratio mixture of xylene/
Z-methoxymethanol) of a copolymer of 44 parts of meth
yl methacrylate, 44 parts of styrene, 10 parts of ?-hy
droxypropyl methacrylate, and 2 parts of methacrylic
nitrogen atmosphere. Two and a half hours after the 70 acid for the copolymer solution there used and substi
start of the polymerization, the reaction is recatalyzed
tuting 60 parts of the 61.6% solution of methoxymethyl
with 0.73 gram of additional benzoyl peroxide and the
melamine (Resin A) for the butylated methylol ‘mela—
temperature, maintained at 109° to 110° C.
At the
mine.
‘Coatings obtained ‘by application immediately
end of the fourth hour, the reaction is again recatalyzed
after compounding have a gloss of 90 photovolts. Coat
with an. additional 0.73 gram of benzoyl peroxide. Heat~
ings obtained by application of the composition after
3,082,184
8
standing one week after compounding also have a 90
of a mixture of monomers consisting essentially of 5 to
photovolt gloss.
30% by weight of a compound of the formula
(b) Part (a) hereof is repeated except that the co
polymer is replaced with the same amount of a copoly
mer of 45 parts methyl methacrylate, 45 parts of styrene,
wherein n is an integer having a value of l to 2, 1 to 4%
and 10 parts of B-hydroxyethyl methacrylate. Coatings
obtained by application of the composition immediately
by weight of a copolymerizable monoethylenically (1,6
unsaturated acid selected from the group consisting of
after compounding show a photovolt gloss of 44. Coat
acrylic acid, methacrylic acid, itaconic acid, and aconitic
ings obtainedfrom the composition allowed to stand one
week after compounding show a photovolt gloss reading 10 acid, and the balance, to make 100%, of at least one other
copolymerizable monoethylenically unsaturated com
of i0.
pound selected from the group consisting of esters of
EXAMPLE 4
acrylic acid with a member selected from the group con
Example 1(a) is repeated using as the copolymer a
sisting of cyclohexanol, benzyl alcohol and (Cl-Cm)
copolymer of 78 parts of methyl methacrylate, 15 parts 15 alkanols, esters of methacrylic acid with a member se
of ethyl acrylate, 5 parts of IS-hydroxypropyl meth
lected from the group consisting of cyclohexanol, benzyl
acigllate, and 2 parts of acrylic acid and using as the
alcohol and (C1—C18)-alkanols, styrene, vinyltoluene, a
aminoplast, Resin D (Example D). Similar results in
methylstyrene, acrylonitrile and methacrylonitrile, and
glossiness are obtained whether the compositions are ap
(B) 5 to 50% by weight of a thermosetting alcohol
plied immediately, or a week, after compounding.
20 modi?ed aminoplast resin condensation product of formal
dchyde with a member selected from the group consist
EXAMPLE 5
ing of urea, N,N'-ethyleneurea, dicyandiamide, and
aminotriazines, alkylated by an alcohol selected from the
Example 1(a) is repeated using as the copolymer a
group consisting of cyclohexanol and alkanols having 1
copolymer of 14 parts of methyl methacrylate, 14 parts
of vinyltoluene, 50 parts of ethyl acrylate, 24 parts of 25 to 6 carbon atoms.
3. A composition suitable for coating purposes com
?-hydroxypropyl acrylate, and 1 part of aconitic acid
prising a solution in an organic solvent of l to 50% by
and using Resin C (Example C) as the aminoplast.
weight of a compatible mixture of (A) 50 to 95% by
Similar results in glossiness are obtained whether the
weight of a thermoplastic copolymer, having a viscosity
compositions are applied immediately, or a week, after
30 average molecular weight of about 10,000 to 130,000, of
compounding.
a mixture of 5 to 30% by weight of a compound of the
EXAMPLE 6
formula
Example 1(a) is repeated using as the copolymer a
copolymer of 20.5 parts of acrylonitrile, 20.5 parts of a
rnethylstyrene, 45 parts of ethyl acrylate, 10 parts of
?-liydroxypropyl methacrylate, and 4 parts of acrylic acid.
wherein n is an integer having a value of l to 2, l to 4%
by weight of a copolymerizable monoethylenically a,?~
unsaturated acid selected from the group consisting of
Similar results in glossiness are obtained whether the com
positions are applied immediately, or a week, after com
pounding.
acrylic acid, methacrylic acid, itaconic acid, and aconitic
-
acid, and the balance, to make 100%, of at least one other
it is to be understood that changes and variations may 40 copolymerizable monoethylenically unsaturated com
’ be made without departing from the spirit and scope of
pound selected from the group consisting of esters of
the invention as de?ned by the appended claims.
acrylic acid with a member selected from the group con
We claim:
1
sisting of cyclohexanol, benzyl alcohol and (Cl-Cm)
l. A composition comprising a compatible mixture of
(A) 50 to 95% by weight of a thermoplastic copolymer
alkanols, esters of methacrylic acid with a member se
lected from the group consisting of cyclohexanol, benzyl
of a mixture of 5 to 30% by weight of a compound of
the formula
alcohol and (C1—C1B)-alkanols, styrene, vinyltoluene, a
‘
methylstyrene, acrylonitrile and methacrylonitrile, and
Gila-:C-(CHzh-JI
(B) 5 to 50% by weight of a thermosetting alcohol- ,
modi?ed aminoplast resin condensation product of form
aldehyde with an aminotriazine alkylated by an alcohol
O O OHzCH(OH) CH3
having 3 to 6 carbon atoms.
4. A composition suitable for coating purposes com
prising a solution in an organic solvent of l to 50% by
weight of a compatible mixture of (A) 50 to 95% by
weight of a thermoplastic copolymer of a mixture of
wherein n is an integer having a value of 1 to 2, 1 to 4%
by weight of a copolymerizable monoethylenically (1,13
unsaturated acid selected from the group consisting of
acrylic acid, methacrylic acid, itaconic acid, and aconitic
acid, and the balance, to make 100%, of at least one other
methyl methacrylate, ethyl acrylate, a vinylaromatic com
pound having from 8 to 9 carbon atoms, 5 to 30% by
weight of a compound of the formula
copolymerizable monoethylenically unsaturated com
pound selected from the group consisting of esters of
acrylic acid with a member selected from the group con
sisting of cyclohexanol, benzyl alcohol and (Cl-C13)
alkanols, esters of methacrylic acid with a member se
00
O O CIIICII(0H) CH;
lected from the group consisting of cyclohexanol, benzyl
wherein n is an integer having a value of 1 to 2, and l
alcohol and (C1—C18)-alkano1s, styrene, vinyltoluene, w
to 4% by weight of a copolymerizable monoethylenically
earl-unsaturated acid selected from the group consisting
methylstyrene, acrylonitrile, and methacrylonitrile, and
(B) 5 to 50% by weight of a thermosetting alcohol-modi
?ed aminoplast resin condensation product of formalde
hyde with a member selected from the group consisting of
urea, N,N'-ethyleneurea, dicyandiamide, and aminotri
azines, alkylated by an alcohol selected from the group
consisting of cyclohexanol and alkanols having 1 to 6
carbon atoms.
2. A composition suitable for coating purposes com
prising a solution in an organic solvent of 1 to 50% by
weight of a compatible mixture of (A) 50 to 95% by
weight of a thermoplastic copolymer, having a viscosity
average molecular. weight of about 10,000 to 130,000,
CHFC-(CIIZ) NH
of acrylic acid, methacrylic acid, itaconic acid, and
aconitic acid, and (B) 5 to 50% by weight of a thermo
setting alcohol-modi?ed aminoplast resin condensation
product of formaldehyde with an aminotriazine alkylated
by an alcohol having 3 to 6 carbon atoms.
70
5. A composition comprising a compatible mixture of
(A) 50 to 95% by weight of a thermoplastic copolymer
of a mixture of 5 to 30% by weight of ?-hydroxypropyl
methacrylate, 1 to 4% by weight of itaconic acid, and the
balance, to make 100%, of at least one other copolym
erizable monoethylenically unsaturated compound se»
3,082,184
10
lected from the group consisting of esters of acrylic acid
with a member selected from the group consisting of
from the group consisting of cyclohexanol, benzyl alcohol
and (C1-C18)-alkanols, styrene, vinyltoluene, (Jr-methyl
styrene,'acrylonitrile and methacrylonitrile, and (B) 5 to
50% by weight of a thermosetting alcohol-modi?ed amino
plast resin condensation product of formaldehyde with an
cyclohexanol, benzyl alcohol and (C1—C18)—alkanols,
esters of methacrylic acid with a member selected from
the vgroup consisting of cyclohexanol, benzyl alcohol and
(C1~C1a)-a1kanols, styrene, vinyltoluene, a-methylstyrene,
aminotriazine alkylated by an alcohol having 3 to 6 car
acrylonitrile, and methacrylonitrile, and (B) 5 to 50% by
weight of a thermosetting alcohol-modi?ed aminoplast
bon atoms.
10. A composition comprising a compatible mixture of
' resin condensation product of formaldehyde with an
- (A) 50 to 95 % by weight of a thermoplastic copolymer
aminotriazine alkylated by an alcohol having 3 to 6 carbon 10 of a mixture of 5 to 30% by weight of ?-hydroxypropyi
atoms. “
methacrylate, 1 to 4% by weight of itaconic acid, and the
balance, to make 100%, of a mixture of methyl meth
’
6. A composition comprising a compatible mixture of
(A) 50~to 95% by weight of a thermoplastic copolymer
of a mixture of ,5 to 30% by weight of ?-hydroxypropyl
acrylate, styrene, and ethyl acrylate, and (B) 5 to 50%
by weight of a thermosetting alcohol-modi?ed aminoplast‘
methacrylate, 1 tov4% by weight of acrylic acid, and the 15 resin condensation product of formaldehyde with an ami
balance, to‘make 100%, of at least one other copolym
notriazine alkylated by an alcohol having 3 to 6 carbon
erizable monoethylenically unsaturated compound se
_, lected from the group consisting of esters of acrylic acid
with a member selected from the group consisting of cyclo
atoms.
,
11. A composition comprising acompatible mixture of
(A) 50 to 95% by weight of a thermoplastic copolymer of
hexanol, benzylalcohol and (C1-C18)‘-alkanols, esters of 20 a mixture of 5 to 30% by weight of a compound of the
methacrylic acid with .a member selected from the group
formula
\
‘
'
'
consisting of cyclohexanol, benzyl alcohol and (Cl-C18)
alkanols, styrene, vinyltoluene, a-methylstyrene', acrylo
nitrile andwmethacrylonitrile, and (B) 5 to 50% by weight
of a‘ thermosetting:alcohol-modi?ed aminoplast resin con_ 25 wherein n is an integer having a value of 1 to 2, l to 4%
densation product oi formaldehyde with an aminotriazine
by weight of a copolymerizable monoethylenically (MS-un
.alkylated by an alcohol having 3 to 6 carbon atoms.
7. A composition‘ comprising a compatible mixture of
acid, methacrylic acid, itaconic acid, and aconitic acid,
saturated acid selected from the group consisting of acrylic
and the balance, to make ‘100%, of at least one other co
(A) 50 to 9.5%» by weight of a thermoplastic copolymer,
having a viscosity average molecular weight of about 30 polymerizable monoethylenically unsaturated compound
selected from the group consisting of esters of acrylic acid
10,000‘to 130,000, of a mixture of 5 to 30% by weight of
with a member selected from the group consisting of cyclo
?-hydroxypropy-l methacrylate, 1 to 4% by weight of
hexanol, benzyl alcohol and (C1-C18)-alkanols, esters of
methacrylic acid, and the balance to make 100%, of at
methacrylic acid with a member selected-from the group
least one other copolymerizable monoethylenically un_
saturated compound selected‘from the group consisting of 35 consisting of cyclohexanol, benzyl alcohol and (Cl-Cm)
alkanols, styrene, vinyltoluene, a-methylstyrene, acrylo
nitrile and methacrylonitrile, and (B) 5 to 50% by weight
group consisting of cyclohexanol, benzyl alcohol and
esters vof acrylic 'acid with a member selected from the
of a thermosetting butylated melamine-formaldehyde con
(Q-Cmyalkanols, .esters of methacrylic acid with a
densate.
,
member selected ‘from the group consisting of cyclohex
12. A composition comprising ‘a compatible mixture of
anol, benzyl alcohol and (C1—C‘1a)-alkanols, styrene, vi 40
(A) 50 to 95% by weight of a thermoplastic copolymer
nyltoluene,a-methylstyrene, acrylonitrile and methacrylo
of a mixture of 5 to 30% by weight of B-hydroxypropyl
nitrile, and (B) 5 to 50% by weight of a thermosetting
methacrylate, 1 to 4% by weight of i-taconic acid, and
alcohol-modi?ed aminoplast resin condensation product
the balance, to make 100%, of at least one other co
of formaldehyde with an aminotriazine alkylated by an
alcohol. having 3 to 6 carbon atoms.
8. 'A composition comprising a compatible mixture of
(A) 50 to~95% by weight of a thermoplastic copolymer,
having ‘a viscosity vaverage molecular weight of about
10,000 to 130,000, of a mixture of '5 to 30% by weight of
?-hydroxypropyl acrylate, l to 4% by weight of itaconic
acid,iand the balance to make 100%, of at least one
other copolymerizable monoethylenically unsaturated com
pound selected from the group consisting of esters of
acrylic acid with a member selected from the group con
sisting of cyclohexanol, benzyl alcohol and (Cl-C18)
alkanols, esters'of methacrylic acid with a member selected
from theigroup consisting of cyclohexanol, benzyl alcohol
and (C1~C18)-alkanols, styrene, vinyltoluene, a-methyl
styrene,.acrylonitrile and methacrylonitrile, and (B) 5 to
45
polymerizable' monoethylenically unsaturated compound
selected
acid withfrom
a member
the group
selected
consisting
from theofgroup
esters
consisting
of acrylic
of '
cyclohexanol, benzyl alcohol and (C1-—C18)-alkanols,
esters of methacrylic acid with a member selected from
the group consisting of- cyclohexanol, benzyl alcohol and
(C1-Cm)-alkan0ls, styrene, vinyltoluene, u-methylstyrene,
acrylonitrile and methacryloni-trile, and (B) 5 to 50%
'by weight of a thermosetting butylated melamine-formal~
dehyde condensate.
13. A composition comprising a compatible mixture of
(A) 50 to 95 % by weight of a thermoplastic copolymer
of a mixture of 5 to 30% by weight of B-hydroxypropyl
methacrylate, 1 to 4% by weight of itaconic acid, and
the balance, to make 100%, of a mixture of methyl
50% by weight .of ‘a thermosetting alcohol-modi?ed amino 60 methacrylate, styrene, and ethyl acrylate, and (B) 5 to
50% by weight of a thermosetting butylated melamine
plast resincondensation product of formaldehyde with an
formaldehyde condensate.
_
'
aminotriazine alkylated by an alcohol having 3 to 6 carbon
14. A composition comprising a compatible mixture of
atoms.
(A) 50 to 95% by weight of a thermoplastic copolymer
9. A composition comprising a compatible mixture of
(A) 50 to 95% by weight of a thermoplastic copolymer, 65 of a mixture of 5 to 30% by weight of a compound of
the formula
‘ ,
having .a viscosity average molecular weight of about
‘10,000 ‘to “130,000, of a mixture of 5 to 30% by weight
of f34hydroxypropyl acrylate, l to 4% by weight of meth
acrylic acid, and the balance to make 100%, of at least
one other‘copolymerizable monoethylenically unsaturated
compound vselectedtrom the group consisting of esters
of acrylic .acid with a‘member selected from the group
consisting of cyclohexanol, benzyl alcohol and (Cl-Cm)
alkanols,» esters of methacrylic acid with a member selected
wherein n is an integer having a value of 1 to 2, 1 to 4%
by weight of a copolymerizable monoethylenically 0a,}?!
unsaturated acid selected from the group consisting of
acrylic acid, methacrylic acid, itaconic ‘acid, and aeonitic
acid, and the balance, to make 100%, of at least one other
copolymerizable monoethylenically unsaturated com
3,082,184
11
pound selected from the group consisting of esters of
acrylic acid with a member selected from the group con
12
molecular weight of about 10,000 to 130,000, of a mixture
of 5 to 30% by weight of a compound of the formula
sisting of cyclohexanol, benzyl alcohol and (Cl-C18)
alkanols, esters of- methacrylic acid with a member
selected from the group consisting of cyclohexanol, benzyl
alcohol and (C1-C18)-alkano1s, vstyrene, vinyltoluene, a
methylstyrene, acrylonitrile and methacrylonitrile, and
(B) 5 to 50% by weight of a thermosetting butylated
‘benzoguanamine-formaldehyde condensate.
wherein n is an integer having a value of 1 to 2, 1 to
4% by weight of a copolymen'zable monoethylenically
cap-unsaturated acid selected from the group consisting
of acrylic acid, methacrylic acid, itaconic acid, and
15. A composition comprising a compatible mixture of 10 aconitic acid, and the balance, to make 100%, of at least
one other copolymerizable monoethylenically unsaturated
(A) 50 to 95% by weight of a thermoplastic copolyrner
compound
selected from the group consisting of esters of
of a mixture of 5 to 30% by weight of B-hydroxypropyl
acrylic acid with a member selected from the group con~
methacrylate, 1 ‘to 4% by weight of itaconic acid, and ' sisting
of cyclohexanol, =benzyl alcohol and (Cr-Cm)
the balance, to make 100%, of a mixture of methyl
alkanols,
esters of methacrylic acid with a member
methacrylate and ethyl acrylate, and (B) 5 to 50% by
selected from the group consisting of cyclohexanol, benzyl
weight of a thermosetting butylated aminotriazine-formal
alcohol and (C1~C18)-alkanols, styrene, vinyltoluene, a
dehyde condensate.
methylstyrene, acrylonitrile and methacrylonitrile, and
16. A composition comprising a compatible mixture of
(B) 5 to 50% by weight of a thermosetting alcohol-modi
(A) 50 to 95 % by weight of a thermoplastic copolymer
?ed aminoplast resin condensation product of formalde
of a mixture of 5 to 30% by weight of B-hydroxypropyl 20 hyde with a member selected from the group consisting
methacrylate, 1 to 4% by weight of methacrylic acid, and
of urea, N,N’-ethyleneurea, dicyandiarnide, and amino_
the balance, to make 100%, of at least one other co—
triazines, alkylated by an alcohol selected from the group
polymerizable monoethylenically unsaturated compound
consisting of cyclohexanol and alkanols having 1 to 6
selected from the group consisting of esters of acrylic acid
carbon atoms.
with a member selected from the group consisting of
18. An article as de?ned in claim 17 in which ‘the sub
cyclohexanol, benzyl alcohol and (Cx-Cm)-alkanols,
strate is a metal.
esters of methacrylic acid with a member selected from
19. An article as de?ned in claim 17 in which the
the group consisting of cyclohexanol, benzyl alcohol and
substrate
is of steel.
(Crcmyalklanols, styrene, vinyltoluene, a-methylstyrene,
acrylonitrile and methacrylonitrile, and (B) 5 to 50% by 30
weight of a thermosetting butylated melamine-dormalde
hyde condensate.
References Cited in the ?le of this patent
UNITED STATES PATENTS
1.7. As an article of manufacture, a solid substrate
having a surface thereof coated with and adhered to a
2,147,1542,681,897
Fikentscher et a1 _______ .._ Feb. 14, 1939
Frazier et a1 ___________ .._ June 22, 1954
baked compatible mixture of (A) 50 to 95% ‘by weight
of a thermoplastic copolymer, having a viscosity average
2,787,603
2,923,653
Sanders ______________ .._ Apr. 2, 1957
Matlin et al. __________ -_ Feb. 2, 1960
Документ
Категория
Без категории
Просмотров
0
Размер файла
1 023 Кб
Теги
1/--страниц
Пожаловаться на содержимое документа