Note: Descriptions are shown in the official language in which they were submitted.
The so-called"advancement" of relatively low molecular and low-melting
or liquid epoxide resins by reaction with polyfunctional compounds of
which the functional groups react with epoxide groups, to give
relatively higher molecular, higher melting epoxide resins is known.
Such a so-called "advancement" is above all intended to improve or
modify, in the desired direction, the technical processing proper~ies
for certain end uses. For some end uses, for example in sintering
powders, compression moulding powders and the like, an increase in the
softening point or melting point can be desirable. The so-called
"advancement" produces, in parallel to the increase in size of the
molecule, a lowering of the epoxide group content per kilogra~ of
resin and hence a reduction in the reac~ivity. This has an
atvantageous effect, for example when using the product as a casting
and impregnating resin, in that the shrinkage on reaction becomes less
and reduces the danger of ca~ity formation, above all in the case of
larger castings.
The following represent typical patents which disclose such
advancement products. U.S. ~atents 3,779,949, 3,793,248 and
3,799,894 teach that certain binuclear N-heterocyclic compounds
containing one endocyclic NH group in each nucleus can be employed
for advancement of a number of epoxy resins including non-aromatic
resins such as N,N'-diglycidyl hydantoin products.
U.S. 4,209,516 and U.S. 4,210,744 also ti~close advancement of
diglycidyl hydantoin compounds with binuclear ~is-hydantoin compounds.
It is to be noted that the latter sdvanced products exhibit active
epoxy groups through which curing occurs. U.S. 4,119,595 discloses
adducts of an epoxy resin and a polymerized fatty acid. The latter
materials are non-heterocyclic, require excess strong acid catalyst
and do not provide good weatherability performance characteristics.
. . ,
~lS~
-- 3 --
The sub;ect of the present invention is an advanced addition product
containing hydroxyl groups, which is obtained by heating a mixture
comprising:
(a) one equivalent of a mononuclear hydantoin glycidyl compound
selected from the group consisting of
(1) a compound of the formula I
Rl O
H2C-~HCH2-N ~ N-CH2CH-~H2 (I);
O O O
(2) a compound of the formula II
~:~ O
R4 ~ Rs
H2C-/CHCH2-N ~ N-CH2CH-O-CH2 ~H-~ H2 (II)
O O O
(3) a compound of the formula III
R6
R7 ~ R8
H2C~-~ H-CH2- ~ -CH2CH-OH . (III);
t4) any combination of compounds of the formulae I, II, or III,
wherein Rl, R2, R3, R4, R6 and R7 are independently alkyl of 1 to
8 carbon atoms or cycloalkyl of 5 to 6 carbon atoms or Rl and R2
together, R3 and R4 together and R6 and R7 together are tetra-
~ethylene or pentamethylene, and R5 and R8 independently are hydrogen
'
1~54~
-- 4 --
or methyl;
(b) 0.7 to 2.0 equivalents of a non-aromatic dicarboxylic acid of 9 to
44 carbon atoms; and
(c) O.O. to 0.5 equivalents of a monocarboxylic acid of 6 to 18 carbon
atoms.
The hydantoin of the formula IV
R" O
R' ~ /
. ~ (IV),
wherein R' and R" are independentty alkyl or cycloalkyl or R' and R"
are tetramethylene or pentamethylene, can be prepared by the well-
known Bucherer synthesis employing a given ketone, sodium cyanide and
ammonium carbonate. Hydantoins of the formula IV are known to react
with alkylene oxides in a molar stoichiometry to afford 3-hydroxy-
alkyl hydantoins of tbe formula V
R" a
R'_ ~ R " '
. ~ ~-CH2CHOH (V)
wherein R"' i9 the alkyl radical obtained from removing the epoxide
moiety from the alkylene oxide or hydrogen in the case of ethylene
oxide. Hydantoins o~ the formula IV are also known to react with
epihalohydrins to for~ 1,3-diglycidyl hydantoins of formula I.
Similarly, the glycidylization of hydroxyalkyl hydantoins of the
` .
,
,
l~S~O~;~
-- 5 --
formula V afford, in the addition to diglycidyl hydantoins of the
formula II, monoglycidyl-hydantoins of the formula III.
Mixtures of the mononuclear hydantoin glycidyl compounds may be
prepared in a number of alternative methods. First, mixtures of the
mononuclear hydantoin glycidyl compounds may simply be prepared by
combining the individual mononuclear hydantoin glycidyl compounds.
Secondly, a mixture of the mononuclear hydantoin glycidyl compounds of
the formulae I, II and III, wherein the substituents in the
5,5 position of the hydantoin moiety are the same, can be prepared by
the glycidylization of a mixture of hydantoins of the formula IV, and
hydroxyalkyl hydantoins of the formula V, prepared by the partial
reaction of a hydantoi~ of the formula IV with less than a stoichio-
metric amount of alkylene oxide. Alternative methods of producing
mixtures of the mononuclear hydantoin glycidyl compounds are quite
apparent to the s~illed artisan.
The preferred mononuclear hydantoin glycidyl-:compounds are those
compounds of fonmulae I, II or III wherein Rl, R2, R3, R4, R6 and R7
are independently alkyl of 1 to 8 carbon atoms and R5 and R8 are
independently hydrogen or methyl. The most preferred mononuclear
hydantoin glycidyl compounds are as follows:
1,3-diglycidyl-5,5-dimethylhydantoin;
1,3-diglycidyl-5-ethyl 5-me~hylhydantoin;
1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin;
l-glycidyl-3 (glycidyloxy-2'-propyl)-5,5-dimethylhydantoin;
l-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin; and
mixtures thereof.
The preferred non-aromatic dicarboxylic acids are those containing 17
to 36 carbon atoms. The most preferred non-aromatic dicarboxylic
acids are those selected from the group consisting of aliphatic
dicarboxylic acids, dibasic fatty acids and a dicarboxylic acid of the
formula VI
~15~
-- 6 --
Hl3C6 ~ C7Hl4co2H (VI).
~2 H
Examples of the aliphatic dicarboxylic acids which may be employed in
the instant invention are azelaic acid, sebacic acid, l,10-decanedi-
carboxylic acid, l,ll-undecanedicarboxylic acid and undecanedioic acid.
Examples of dibasic fatty acids are obtained by the dimerization of
olefinic fatty acids employing known synthetic me~hods. The olefinic
fatty acids which may be dimerized to form the dibasic fatty acids
include oleic acid, ricinoleic acid, petroselinic acid, vaccenic acid,
linoleic acid, linolenic acid, eleostearic acid, punicic acid,
licanic acid, parimaric acid and the like or mixtures thereof. The
dibasic fatty acids which are commercially available consist
essentially of the dimerized fatty acids containing 36 carbon atoms
with minor amounts of monobasic fatty acids of 18 carbon atoms and
tribasic fatt~ acids of 51 carbon atoms.
The C21 dicarboxylic acid of the formula VI
Hl3C~ ~ ~ C7Hl4C02H (VI)
C02H
is commercially available from Westvaco Chemical Division,
Chaleston Heights, South Carolina, under the name Westvaco Diacid
1550 and prepared via a Diels-Alder cycloaddition of acrylic acid
with a conjugated mono-acid of the formula
H13C6-CH~cH-cH~cH C7H14 C2
..
~, ~. . .
li5451;~
Examples of the monocarboxylic acid which may be employed with the
non-aromatic dicarboxylic acid in the instant invention include
caprylic acid, lauric acid, myristic acid, palmitic acid, stearic acid,
arachidic acid, decylenic acid, dodecylenic acid, oleic acid,
ricinoleic acid and linolenic acid.
The new adducts of this invention are manufactured by heating the non-
aromatic dicarboxylic acid or a mixture of the non-aromatic dicarboxylic
acid and the monocarboxylic acid with the mononuclear hydantoin
glycidyl compounds at a temperature between 100 and 250C and
preferably 150 to 200C. Preferably, 0.8 to 1.2 equivalents of the
non-aromatic dicarboxylic acid is reacted with one equivalent of the
mononuclear hydantoin glycidyl compound.
The reaction can be accelerated by adding suitable catalysts. Such
catalysts are for example alkali hydroxides such as sodium hydroxide
or alkali halides such as lithium chloride, potassium chloride and
sodium chloride, bromide or fluoride; tertiary amines such as
triethylamine, tri-n-propylamine, benzyldimethylamine, N,N-dimethyl-
aniline and tricthanolamine; quaternary ammonium hydroxides such as
benzyltrimethylammonium hydroxide; quaternary = onium salts such as
tetramethylammonium chloride, tetraethylammonium chloride, benzyl-
trimethylammonium chloride, benzyltrimethylammonium acetate or methyl-
triethylammonium chloride; hydrazines having a tertiary nitrogen atom,
such as l,l-dimethylhytrazine, which can also be employed in th~
quaternized form.
Depending on the choice of the starting substances the reaction takes
place, quantitatively, so rapidly that no addition of catalyst is
necessary. Whilst the starting substances may be mixed with one
another at room temperature and then brought to the reaction
temperature, it is advantageous in the case of very viscous and
li~i4()~'~
-- 8 --
reactive components for the non-aromatic dicarboxylic acid or the
mixture of the non-aromatic dicarboxylic acid and the mono-carboxylic
acid to be heated to the requisite reaction temperature and the
nononuclear hydantoin glycidyl compounds gradually added. The progress
of the reaction can be followed by titration of ~he epoxide groups
using samples taken during ~he reaction; the end product will contain
a defined, constant epoxide group content of less than 0.7
equivalent/kg, and preferably 0.0 to 0.5 equivalents/kg.
The advanced addition products of the instant invention have a
molecular weight range from 600 to 15,000, and preferably 800 to 3,000.
The advanced addition products are usually viscous liquids at ambient
temperature but, in the case of the higher molecular weight products,
may be solid. The advanced addition products contain a high content of
hydroxyl groups as evidenced by a hydroxyl number of 80 to 160. The
color of these advanced addition products i8 generally a light
amber.
Because of their high content of free hydroxyl groups, these adeanced
attition protucts react with the usual curing agents for hydroxyl
containing compounds, and can, therefore, be crosslinked or cured by
atting such curing agents~
A preferred curing agent includes the so-called amino resins of amino-
plasts containing -NH2 groups derived ~rom urea and melamine.
Suitable amino-containing resins are prepared by reacting urea or
melamine with formaltehyte under well-known contitions to form a
reaction monomer first and then, by condensation polymerization, a
large number of varying types of polymeric intermediates are formet.
The preparation of urea-formaldehyde and melamine-formaldehyde resins
is well known in the art and forms no part of the present invention.
Their use in crosslinking epoxy resins mostly through methylol groups
is also well known. Accordingly, a large number of amino-plast and
~159~0~2
g
phenol-plast resins, i.e., urea-formaldehyde and melamino-formaldehyde
resins, are commercially available under such trade designations as
Plaskon, Beetle, Cymel, Fiberite, Resimene, Curacron and Beckamine,
among many others.
The amount of curing agent employed to cure the advanced addition
products may vary with respect to the type of advanced addition product
to be cured and the curing agent to be employed. Generally, a weight
ratio of advanced additi~n product to aminoplast resin employed would
be fro~ 95:5 to about 70:30, and preferably from 90:10 to about
75:25.
The above compositions containing the advanced addition product and
curing agent are heat curable at emperatures over 150C, and
preferably cured at temperatures between 180 and 250C.
To accelerate the curing process an acidic curing-accelerator, well
known in the art~ can be added to the heat curable mixture. Examples
for accelarators are strong organic and inorganic acids such as para-
toluene sulfonic acid, sulfuric acid and phosphoric acid or
derivatives thereof such as the = onia or amine salts. The amount of
the curing accelerator may be less than 2 percent by weight of the
advanced addition product, preferably less than 1 percent by weight.
The expression "cure", as used here, denotes the conversion of the
above adducts, containing hydroxyl groups, into insoluble and
infusible crosslinked products, as a rule with simultaneous shaping to
give shaped articles such as castings, pressings or laminates, or
to give two-dimensional structures such as coatings, enamel films or
adhesives bonds.
~lS40~2
- 10 --
The heat curable compositions are employed mainly in ~he field of
surface protection. The resultant cured coatings are suitable for
application areas such as coil, appliance, automotive and metal
decorating. The present coating composit~on?-~may be applied to a
suitable substrate by any suitable means such as spraying, dipping,
brushing~ painting or roller coating. After the desired film thickness
is applied to a suitable substrate, the coated substrate is baked at
temperatures over 150C for sufficient time to cure the films.
The resultant cured coatings are void-free and possess excellent
physical properties and chemical resistance. Specifically, the coatings
are highly resistant to chalking, salt spray ~nd humidity. The cured
coating also exhibit excellent weather resistance.
The following examples are illustrative of the instant invention. All
parts are based on parts by weight.
TABLE OF GLYCIDYL 50MP0UNDS
A - 1,3-diglycidyl-5,5-dimethylhydantoin
~ - 1,3-diglycidyl-5-ethyl-5-methylhydantoin
C - 1,3-diglycidyl-5-sec-amyl-5-ethylhydantoin
D - l-glycidyl-3-(glycidyloxy-2'-propyl)-5,5-dimethylhydantoin
E - l-glycidyl-3-(2'-hydroxypropyl)-5,5-dimethylhydantoin
A. Preparation o~ ad~anced additlon products
Example 1
The dicarboxylic acid of the formula VI (415.6 parts) was charged into
a one li~er, 3 neck round bottom flask equipped with a thermometer,
nitrogen inlet tube, ant a mechanical stirrer. The acid was heated ~o
a temperature of 175 - 183~C with stirring in a nitrogen atmosphere.
~lS40~
A mixtu~e of glycidyl compound C (199.3 parts), glycidyl compound D
(135.5 parts) and glycidyl compound E (58.1 parts) was added portion-
wise over a period of 20 minutes to the heated acid (0.83 equivalents
of acid to 1.0 equivalent of glycidyl compounds). After the addition
was complete, the reaction was monitored by periodic epoxy value
determination. rhe reaction was essentially complete after 16 minutes
when the epoxy value of 0.57 equiv./kg was obtained. The resulting
advanced addition product (Adduct J) had an acid number of 8 and a
hytroxyl number of 117. Adduct J (80 parts) was dissolved in methyl
ethyl ketone (20 parts) to afford a coating composition.
Exam ~
Adduct K, Adduct L and Adduct M were prepared employing 0.83
equivalents of the dicarboxylic acid of the formula VI with 1.0
equivalents of the glycidyl compounds in the following table according
to Example 1.
Glycidyl Epoxy Value Hydroxyl Acid
Compound Adduct Equiv. Number Number
--~
B K 0.45 152 8
D (70 parts) L 0.56 91 --
E (30 parts)
A (70 parts)
D (21 parts) M 0.62 125 2
E (9 parts)
Example 3
Adduct N was prepared according to Example l except a dihasic fatty
acid of 36 carbon atoms (578 parts) was employed in place of the
dicarboxylic acid of formula VI (0.83 equivalents of acid to 1.0
equivalent of glycidyl compounds). Adduct N had an epoxy value of
0.63 equiv.~kg, an acid number of 9 and a hydroxyl number of 95.
.
. : ~
11540~
- 12 -
Example 4
The dicarboxylic acid of the formula VI (187.0 parts) and oleic acid
(28.3 parts) were combined in a one liter , 3-neck round bottom flask
equipped with a thermometer, a nitrogen inlet tube, and a mechanical
stirrer. The mixture was heated to a temperature of 170-175C with
stirring in a nitrogen atmosphere.
A mixture of glycidyl compound C (83.1 parts) and glycidyl compound D
(80.7 parts) was added portion-wise over a period of 20 minutes to the
hea~ed acid (1Ø equivalent of acid to 1.0 equivalent of glycidyl
compounds). After the addition was complete, the reaction was
monitored by periodic epoxy value determination. The reaction was
essentially complete after 32 minutes when the epoxy value of 0.32
equiv./kg was attained. The resulting advanced addition product
(Adduct 0) had an acid number of 26.6 and a hydroxyl number of 148.
Adtuct 0 (80 parts) was dissolved in methyl ethyl ketone (20 parts)
to af~ord a coating comRosition.
Example 5
The dicarboxylic acid of the formula VI (270.8 g) was charged to a
one liter, 3-neck round bottom flask equipped with a thermometer, a
nitrogen inlet tube, and a mechanical stirrer. The acid was heated to
a temperature of 175-183C with stirring in a nitrogen atmosphere.
A mixture of glycidyl compound A (127.5 parts), glycidyl compound D
(38.3 parts) and glycidyl compound E (16.4 parts) was added
portionwise at this temperature over a period of 28 minutes
(1.0 equivalent of acid to 1.0 equivalent of glycidyl compunds).
After the addition was complete, the reaction was monitored by
periodic epoxy value determination.
-
l~S9~
- 13 -
The reaction was essentially complete after 25 minutes when the epoxy
value of 0.62 was attained. The resulting advanced addition product
~Adtuct P)~had an acid number which was undetectable and a hydroxyl
number of 125. Adduct P (80 parts) was dissolved in methyl ethyl ketone
(20 parts ) to afford a coating composition.
Example 6
The dicarboxylic acid of the formula VI (498.8 parts) was charged to a
one liter, 3-neck round bottom flask equipped with a thermometer, a
nitrogen inlet tube and a mechanical stirrer. The acid was hea~ed to
175-180C with stirring in a nitrogen atmosphere.
Glycidyl compound B (267.4 parts) was added pro~ionwise over a 20
minute period to the heated acid (1.2 equivalents of acid to 1.0
equivalent of glycid-~l compound). After the addition was complete, the
reaction was continued for 85 minutes further. The advanced addition
product (Adduct Q) had an epoxy value of 0.07 eq./k~., an acid number
of 37 and a hydroxyl number of 147. Adduct Q (80 parts) was dissolved
in methyl ethyl ketone t20 parts) to afford a coating composition
having a Gardner bubble viscosity of Z3-Z4.
Example 7
The dicarboxylic acid of formula VI (311.7parts)was charged to one liter,
3-neck round bottom flask equipped with a thermometer, a nitrogen inlet
tube, and a mechanical stirrer. The acid was heated to a temperature of
185-190C with 9tirring in a nitrogen.atmo9phere.
A mixture of glycidyl compound D (112.9 parts) and glycidyl compound E
(48.4 parts) was added portionwise at this temperature over a period
of 33 minutes (0.75 equivalents of acid to 1.0 equivalent of
glycidyl compounds). The reaction was essentially complete after a
period of 2 hours when an epoxy value of 0.27 eq./kg was attained. The
resulting advanced addition product (Adduct S) had an acid number of
60 and a hydroxyl number of 119.
~154~
Example 8
Adduct T was prepared according to Example 7 except glycidyl
compound B (133.7 parts) was employed in place of the mixture of
glycidyl compounds (0.75 equivalents of acid to 1.0 equivalent of
glycidyl compound). The reaction was essentially complete after a
period oEone hour when an epoxy value of 0.26 equiv./kg was attained.
Adduct T had an acid number of 60 and a hydroxyl number of 126.
Example 9
The dicarboxylic acid of formula VI (415.6 parts) was heated to a
temperature of 175-180C. The equipment and condition used were the
same as those o~ Example 5.
A mixture of glycidyl co;mpound A (99.6 parts) glycidyl compound D
(30.0 parts) and glycidyl compound E (13.1 parts) was then added
portionwise over a period of 21 minutes to the heated diacid
(2.0 equivalents of acid to 1.0 equivalent of glycidyl compounds).
After the addition was complete, the reaction was monitored by
periodic epoxy value determination. The reaction was essentially
complete after 70 minutes when an epoxy value of 0.02 equiv./kg was
attained. The resulting advanced addition product (Adduct M) had an
acid number of 92 and a hydroxyl number of 95.
Exa~pl_ 10
Adduct V was prepared according to Example 9 except glycidyl
compound C (166.1 parts) was employed in place of the mixture of
glycidyl compounds (2.0 equivalents of acid to 1.0 equivalent of
glycidyl compound). Adduct V has an epoxy value of 0.02 equiv./kg~
.
an acid number of 89 and a hydroxyl number of 95.
Exam~ e 11
Adtuct W was prepared according to Example 9 except a mixture of
llS40~2
- 15 -
glycidyl compound D (112.9 parts) and glycidyl compound E (48.8 parts)
was employed in place of the mixture of glycidyl compounds A and D
(2.0 equivalents of acid to 1.0 equivalent of glycidyl compound).
Adduct W had an epoxy value which was undetectable, an acid number of
88 and a hydroxyl number of 97.
B. Application and Testin~
Example I
Adduct J was formulated into a high solids enamel by blending on a
paint shaker: Adduct J (160.00 parts) (80 % weight solids in methyl
ethyl ketone); Cymel 303, an alkylated melamine-formaldehyde resin
from American Cyanamid (32.00 parts); FC 430, flow control agent from
3M Company (0.06 parts); Curing Agent "C", morpholine salt of
p-toluene sulfonic acid from American Biosynthetics; and me~hyl ethyl
ketone (8.00 parts). The above formulation (200.40 parts) was
combined with Titanox 2060 (80.00 parts), a titanium dioxide
pigment from NL Industries, and ground with sand to Hegman Gauge of 8.
The pigmented formulation was then let down with additional methyl
ethyl ketone (39.40 parts).
The above high solids enamel possessed the following properties:
Fo = lation Propert-'es
Hardener Cymel 303
Resin~Hardener Ratio 80/20
Binder/Pigment Ratio ' 2:1
% Solids in MEK (by Weight~ 75
Viscosity, sec.(~4'F'ord Cup)l 28
Curing Agent "C" 0.5 %
Determined according to ASTM 1200.
1154V~;~
- 16 -
The formulated material was drawn into films on Alodine 12002
treated aluminum and cured at a peak metal temperature ~PMT) of
232C~for 50 seconds. The resulting films possessed the following
properties:
Film properties obtained
Industry
Requirements
Pencil Hardness F F (HB minimum)
"T" Bend 2-3T 2T maximum
MEK P~ubs, double 50 50
Cross-Cut Adhesion ~xcellent Excellent
Reverse Impact (C~ ~g)- i7-23- - -- 34-57 (18 minimum)
Cure Schedule,
P.M.T., 232GC 50 sec. 45-60 sec.
Dry Film Thickness 1-1.2 mils 0.8-l mil
Fuming Factor 3Z~ 5
Chromium oxide conversion coating.
3 Test utilized to determine degree of deformation of a coated sheet
of metal coil Test described in Paint Testing Manual, ed. G.G.
Sword, p. 334, Section 5.4.4.2.
Continental Can Company, Inc. procedure for determining percent
1088 of solids due to non-solvent volatilization when enamel baked
at 232C.
ResiRtance to yellowing
These films were tested for color stability exposure to accelerated
weathering studies in a commercial dew cycle~ carbon arc
Weatherometer.
: .
:- :
l-lS4~)~Z
17 -
C_lor difference readingsl
Hydantoin-Based Acrylic-Based Bisphenol A Epo~7
Resin Resin Resin
... . -- -- --
Rd 2) b Rd b Ra b
Initial 79.6 +0.9 75.0 +1.3 84.0 +0.9
3 Months 80.5 ~0.8 75.4 +0.9 82.8 +1.9
6 Months 79.9 +1.1 74.9 +1.1 80.7 +4.2
Tested according to ASTM D2244-68
+ ~ Rd = Lighter
- ~ Rd ' Darker
+ ~ b - Yellower (less Blue)
: - A b - Bluer (less Yellow)
Accelerated weatheri~g study
The films were also subjected to an accelerated weathering study in a
commercial dew cycle Weatherometer using a carbon arc light source.
Controls were a commercially available acrylicl and a conventional
bisphenol A-base epox~ system.
60 ~
Substrate Initial 500 Hrs 1000 Hrs
(1) Hydantoin-Baset AA 81 75 74 68
Resin R-37 86 82 79 78
(2) Acrylic-BasedM 72 69 45 65
Resin B-37 79 76 67 65
(3) Bisphenol A Epoxy AA 85 25 20 9Resin B-37 89 30 21 8
No chal~ing or yellowing was observed with resins 1 and 2.
Heavy chalking and noticeable yellowing was obser~7ed with resin 3.
.
- , - ., , , .-
- . . -- -,, - . , :
- . : . -
- : . ' ~ ' :
' - . : ' ': : ~
- . . :
.- - : ' - ~
1154~
- 18 -
Acryloid oL-42 from Rohm and Haas
M - Alodine 1200 Aluminum
B-37 - Bonderite Steel ~37
Salt spray and humidity resistance testing
The films were tested for salt spray tASTM B117) and humidity
resistance (ASTM D 2247); results are tabulated in Table I, above~
Acryloid OL-42 from Rohm and Haas ~erved as the control.
Except where noted, no blistering, chalking or peeling occurred.
Table I
Test
. . ~
Hydantoln Based Resin (1)
. _ __ . . .
Hours: Substrate Initial500 1000 2000 3000
Salt Spray
(5 Z Solution) M 82 85 83 80
B-37 84 90 86 - -
tSlight (Haavy
Blis- Blis-
tering) tering)
Humidity
Cabinet AA 83 87 87 79 74
B-37 85 88 89 85 84
11~4~ Z
-- 19 --
Acrylic Bas~ Resin (2)
~ . . . _. .
Hours: Substrate Initial 500 lOOG 2000 3000
Salt Spray
(5 % Solution)AA 61 72 72 75
B-37 77 67 82 - -
(Sligh~ (Heavy
Blis- Blis-
tering) tering)
~umidity AA 55 67 65 72 66
Cabinet B-37 82 91 86 83 72
(Surface
covered
with tiny
blisters)
Example II
Adduct L was formulated into a high solids formulation according to
the procedure followed in Example I of the testing section. The
resulting formulation possessed the following properties:
Formulation pro~_rties
Hardener ~ - Cymel 303
Resin/Hardener Ratio 80/20
Binder/Pigment Ratio 2:1
2 Solids in MEK (by weight~ 75.3
Viscosity, ~ec. (~4 Ford Cup) 31
Curing Agent "C" 0.34 2
The formulated material was drawn into films on Alodine 1200
treated aluminum and cured at a peak metal temperature (PMT~ of
232C for 60 sec. The resulting films possessed the following
properties:
~ - - - . . . .
-
.
~54~
- 20 -
Film properties obtained
Pencil Hardness HB
"T" Bend 0-l T
MEK Rubs, Double 50
Cross-Cut Adhesion Excellent
Reverse Impact, (cm kg) 23
Cure Schedule, P.M.T., (232C) 60 sec.
Dry Film Thickness 0.9-1.0 mil (22.5-25.0 ~m)
Fuming Factor 5-6%
Example III
Adduct J (74.38 parts) (80 ~ weight solids in methyl ethyl ketone)
was combined with Cymel (10.50 parts), methyl ethyl ketone
~15.12 parts) and Curing Agent "C" (0.1 parts) to produce a one
component, clear high solids formulat;on. This was placed in
stability testin~ at 25C. The formulation exhibited an initial
Gardner viscosity of H and vi~cosity of I-J after 10 months.
A similar formulation containing glycidyl compound A exhibited an
initial Gardner viscosity of K-l anl a viscosity of N-0 after
10 months.
Example IV
Gloss retention and chalk resistance
. . _ . _ _ . _ _ . . .
The adduct S was formulated with Cymel 303 according to Example 1
and cured at a PMT of 232C. for 50 second~. The substrate was
Alodine 1200 aluminum.
.
The cured films were tested for gloss retention and chalk resistance
after exposure in a dew cycle, carbon arc ~eatherometer.
~lS~ 2
- 21 -
_ 60 ~ Gloss Readings
Initial _ 96213 453 525785_ _ _ _
(1) Hydantoin-Based81 82 8082 76 79 71
Resin
(3) Bisphenol A Epoxy 90 89 86 78 47 23 20
Resin
Chalking was observed after 453 hours with the bisphenol A epoxy
resin. None was observed with the hydantoin-based material.
Resistance to yellowing
Adduct S was formulated with Cymel 303 according to Example 1 and
cured at a temperature of 450F for 50 seconds. The substrate was
Alodine 1200 aluminum.
The cured films were tested for resistance to-yellowing after
Weatherometer exposure.
Color difference readings*
Hydantoin-Based Bisphenol A Epoxy
Resin Resin
_
Exposure Time ~Hours) Rd b Rd b
_ . _
Initial 79 +1.1 84 +0.9
24 81 -0.2 84 +0.9
96 80 -0.2 84 ~1~0
213 81 -0.2 84 +1.1
453 80 -0.5 83 +1.4
525 80 -0.1 83 +1.6
785 80 -0.4 82 +1.9
1409 82 -0.4 80 +3.6
~ . -
1154V;~
- 22 -
*Tested according to AST~ D2244-68
~ ~ Rd = Lighter
- ~ Rd = Darker
+ Q b = Yellow r (less Blue)
- ~ b = Bluer (less Yellow)
Summarizing, it is seen that this invention provides advanced
addition products which afford cured compositions exhibiting
excellent weathering characteristics, color stability and chalking
resistance. Variations may be made in proportion materials and
procedures without departing from the scope of the invention as
defined in the following claims.
