USOO6433131B1

(12) United States Patent (10) Patent No.: US 6,433,131 B1

Zhou et al. (45) Date of Patent: Aug. 13, 2002

(54) HIGH GLOSS ACRYLIC COATINGS WITH 3,900,682 A 8/1975 Taylor ........................ 427/386
IMPROVED IMPACT RESISTANCE CURED 3,901,752 A 8/1975 Taylor ........................ 156/155
WITH MELAMINE 4,018,727 A 4/1977 Taylor ......................... 260/13
4,533,729 A 8/1985 Newland et al. ............ 528/371
Lichang Zhou; Shelby F. Thames, 5,212,321 A 5/1993 Muller et al. ............... 549/228
(75) Inventors:
5,225,129 A 7/1993 van den Berg ............... 264/85
both of Hattiesburg; Oliver W. Smith, 5,525,670 A 6/1996 Nishi et al. ................. 524/512
Petal, all of MS (US); Thomas Clayton 5,527,879 A 6/1996 Nakae et al. ............... 528/371
Forschner, Richmond, TX (US); Roy 5,849,859 A 12/1998 Acemoglu .................. 528/271
Frank Smith, Pearland, TX (US); FOREIGN PATENT DOCUMENTS
David Eric Gwyn, Houston, TX (US);
Wyndham Henry Boon, North Canton, EP O712873 A2 11/1995 ......... CO8F/220/28
OH (US); Abdulai Mobolaji Dawodu, JP 64-1724 6/1989 ........... CO8G/63/62
Houston, TX (US) JP SOO9434 1/1993
JP 6313149 11/1994
(73) ASSignee: Shell Oil Company, Houston, TX (US) OTHER PUBLICATIONS
(*) Notice: Subject to any disclaimer, the term of this International Search Report of Dec. 5, 2001.
patent is extended or adjusted under 35
U.S.C. 154(b) by 0 days. Primary Examiner Duc Truong
(74) Attorney, Agent, or Firm-Donald F. Haas
(21) Appl. No.: 09/784,376 (57) ABSTRACT
(22) Filed: Feb. 15, 2001 Disclosed is a modified acrylic coating composition cured
Related U.S. Application Data with melamine characterized by improved impact resistance
which comprises: An acrylic polyol dissolved in a Suitable
(60) Provisional
2000.
application No. 60/185,649, filed on Feb. 29, solvent to 40-90% solids; 2 to 50% by weight of said acrylic
7 polyol Substituted with a polytrimethylene carbonate polyol
(51) Int. Cl. .......................... C08G 63/62; B32B 27/36 Selected from a polytrimethylene carbonate diol, a polytri
(52) U.S. Cl. ....................... 528/371; 528/371; 525/461; methylene carbonate triol, or a higher functionality polytri
525/467; 428/412 methylene carbonate polyol; a melamine crosslinking agent;
(58) Field of Search .......................... 528/371; 525/461, optionally a catalyst; and optionally pigments and other
525/467; 428/412 additives commonly used in coatings. Also disclosed in a
related embodiment is a melamine/urea formaldehyde poly
(56) References Cited trimethylene carbonate coating composition that is prepared
U.S. PATENT DOCUMENTS without acrylic.
3.816,162 A 6/1974 Taylor ......................... 117/46 40 Claims, 6 Drawing Sheets

PC329 PC474 PC597 PCS 13 PC 1336

- 30 - 70 10 3O
IEMPERATURE (OC) --
U.S. Patent Aug. 13, 2002 Sheet 1 of 6 US 6,433,131 B1

FIG. 1
PC329 PC474 PC597 PC373 PC1336
- - - - nm - was -- - - - - - - - -

-50 - 30 u
TEMPERATURE (C) --
FIG.2
PT 121 PI217 PT305 PT445 PT573

TEMPERATURE (OC) --
U.S. Patent Aug. 13, 2002 Sheet 2 of 6 US 6,433,131 B1

F/G3
PC328 PC474 PC597 PC 613 PC 1336
10000

100 O

100

-50 - 25 O 25 50
TEMPERATURE (OC) --

FIG 4
PT 121 PI217 PT303 PT445
va mann as
PT573
- - - - - - - - - -

1000

100

TEMPERATURE (OC) --
U.S. Patent Aug. 13, 2002 Sheet 3 of 6 US 6,433,131 B1

FIG.5
CONTROL 20%. PC328 20%. PC474

1
20% PC597
wux won a
20% PC813 20% PC1336

7N,
S. 0. // \\
- 27- - - \
Q
2
S.

OO) :
-50 O 50 100 150
TEMPERATURE (OC) --

CONTROL 20%.PT 12, 20%PT27 FIG.6

20% PT308
onna - a
20% PT45U
- P - tis ur on OP
20% PT573

-50 O 50 100 150

TEMPERATURE (OC) --
U.S. Patent Aug. 13, 2002 Sheet 4 of 6 US 6,433,131 B1

CONTROL 20%. PC328 20%. PC 474.

FIG 7
20%. PC597 20%. PC813 20%. PC 1336
10000

1000

100

f
O 50 - 25 O 25 50 75 100 125 150
TEMPERATURE (OC) --
CONTROL 20% PT2) 20% PT217 F/G, 8
20%. 306 20%. 45U 20%, 573
10000 wip is as a as -------------

1000

100

10. 5O - 25 O 25 50 75 100 125 150

TEMPERATURE (OC) --
U.S. Patent Aug. 13, 2002 Sheet 5 of 6 US 6,433,131 B1

FIG.9

20 OC 60 oC FIG. IO

FI- N` PTM D/OL MODIFIERS

U.S. Patent Aug. 13, 2002 Sheet 6 of 6 US 6,433,131 B1

F/G 11
260°F/30nnin 300F/10min 300°F720min
300°F730min 300°F/40min 350°F715min

-50 0 50 100 150

TEMPERATURE (OC) --

2600F/30min 300F/Omin 300°F720min FIG. 12

3OOOF/3Ornin 3000F/4Orin 350°F/15 finin

1000

-50 -25 O 25 50 75 100 125 150

TEMPERATURE (OC) --
 US 6,433,131 B1
1 2
HIGH GLOSS ACRYLIC COATINGS WITH urethane crosslinked bonds, but may also entail certain
IMPROVED IMPACT RESISTANCE CURED drawbacks. In order to prevent premature gelation of the
WITH MELAMINE coating composition, the polyisocyanate must either be kept
Separate from the resin in what is known in the art as a
CROSS REFERENCE two-package or two-pack coating System, or else the highly
This application is related to U.S. patent application Serial reactive isocyanate groups on the curing agent must be
No. 60/185,649, filed of even date Feb. 29, 2000 and blocked (e.g., with an oxime or alcohol). Blocked
incorporated by reference herein in the entirety. polyisocyanates, however, require higher temperatures (e.g.,
150 C., or more) to unblock and begin the curing reaction.
FIELD OF INVENTION The Volatile blocking agents released during curing can
possibly adversely affect coating properties, as well as
This invention relates to acrylic coating compositions increase the Volatile organic content for the composition.
and, in particular, to a high gloSS acrylic coating composition Another curing mechanism utilizes a melamine formal
cured with melamine that demonstrates improved impact dehyde resin curing agent in the coating composition to react
resistance. More particularly, this invention relates to the 15 with hydroxyl groups on the resin. Where suitable, this
incorporation of polytrimethylene carbonate diols and triols curing method provides good cure at relatively low
into acrylic coatings cured with melamine to obtain high temperatures, for example 250 F. or 121 C. with a blocked
gloSS acrylic coatings with improved impact resistance, with acid catalyst, or even lower with an unblocked acid catalyst,
no significant loSS of other properties. however higher curing temperatures can also be effective.
BACKGROUND OF THE INVENTION There are Some advantages in curing with melamine
where Suitable. Melamine can exhibit moisture resistance,
Thermoset or cured coating compositions are widely used cure at lower temperatures, and can be extremely hard, and
in coatings operations on a variety of Substrates, including yet colorless. The moisture resistance feature of melamine
plastic, metal, wood, primed metals, or previously coated or 25
based adhesives, combined with its durability, may provide
painted metals. One type of thermosetting coating is an advantages for exterior applications. Curing temperatures as
acrylic coating composition. In automotive applications, in low as 140 F. have been used for melamine adhesives, with
particular, acrylic coatings provide durable finishes. Acrylic a normal range from 240-260 F. for 2 to 5 minutes,
coating compositions are well known and have been widely depending upon the thickness of the composite assembly.
used to finish automobiles and truckS. Crosslinked melamine-based coatings are colorless, chemi
Automotive coatings include primers and topcoats, which cally resistant and resilient. They provide a tough and
may be single layer topcoats or two layer basecoat/clearcoat durable finish to items that will be repeatedly exposed to
topcoat Systems. The primer may be applied either as a first harsh environments.
coating layer or over another layer, for example over an Few applications experience Such demanding and harsh
electrocoat primer layer. The topcoats are then usually 35
environments over time as automotive paints. In this appli
applied as a protective coat over the primer layer. cation melamine can deliver chemical resistance and dura
In order to make the coating more chip resistant, one bility. Melamine resins also provide the long-term buffabil
recognized Solution is to cover all or parts of the finished ity vehicle owners desire. Melamine-based coatings also
Surface of the automobile with a protective coating, however permit coils of metal sheeting to be prepainted, then Stamped
the acrylic enamel, acrylic lacquer, or nitrocellulose lacquer 40
into the final product, as in the case of appliance and
typically used on vehicles produce coatings which are automotive parts and panels.
difficult to overcoat with protective materials due to prob Another important benefit of high Solids melamine-based
lems with adhesion, yellowing, etc. A useful protective coatings is that they are low in Volatile organic emissions
coating composition should first and foremost be chip- and during application and curing.
abrasion-resistant, have good adhesion to the painted 45 The use of various modifiers to attempt to improve impact
Surface, be clear, Smooth (i.e., without Surface roughness) properties of acrylic coatings has been addressed in the art.
and indistinguishable over the painted Surface when applied Polytrimethylene ether glycol (PTMEG) has been suggested
to the areas being protected. as a modifier, however at the expense of optimum UV
There are a number of considerations regarding the use of resistance. The addition of glycol adipates to improve
thermosetting coating compositions. One consideration 50 impact resistance has been Suggested, but results in the
involves the curing conditions needed to achieve Sufficient reduction of hydrolytic stability. Impact modifiers previ
crosslinking of the film, with higher curing temperatures and ously proposed in the art typically result in the loSS of other
longer times at the curing temperature generally increasing properties.
the manufacturing costs of the coated article. Another con The preparation of trimethylene carbonate is known. U.S.
cern in Some cases is the generation of undesirable 55 Pat. No. 5,212,321 discloses a process for preparing trim
by-products of the curing reaction. For example, blocked ethylene carbonate wherein 1,3-propanediol is reacted with
curing agents may release the blocking agents as volatile diethylcarbonate in the presence of Zinc powder, Zinc oxide,
organic compounds that are emissions regulated by various tin powder, tin halide or organo-tin compound, at an
government regulations. It is also important that the elevated temperature. It is also known in the art to use
crosslinks that are formed by curing thermosetting compo 60 polytrimethylene carbonate in polyester applications. See,
Sitions are Suitable for providing long life to the coating for example, U.S. Pat. Nos. 5.225,129 and 5,849,859.
under the particular conditions to which the coated article The preparation of polycarbonate polyols is known in the
will be exposed. art. U.S. Pat. No. 4,533,729 discloses a process for preparing
Several different crosslinking mechanisms may be amorphous polycarbonate polyols by reacting phosgene, a
employed in thermosetting coatings. Polyisocyanate 65 branched-chain polyhydric alcohol, and a Straight chain
crosslinkers may be reacted with amine or hydroxyl groups polyhydric alcohol in the presence of a Solvent and in the
on the resin. This curing method provides desirable urea or absence of a catalyst at a temperature of from about 60 to
 US 6,433,131 B1
3 4
100° C. The reaction mixture is then contacted with a composition cured with melamine characterized by
catalytic amount of a tertiary amine at reflux temperature for improved impact resistance which comprises:
a period of time of at least about 30 minutes. It is Suggested a) An acrylic polyol dissolved in a Suitable Solvent to
the resulting polycarbonate polyol can be used in coating 40–90% solids;
compositions. In JP 64001724 there is disclosed the prepa b) 2 to 50% by weight of said acrylic polyol substituted
ration of a polycarbonate polyol from (di) allyl-, alkyl- or
alkylene carbonate and a polyhydroxy compound using a with a polytrimethylene carbonate polyol Selected from
titanium catalyst. a polytrimethylene carbonate diol, a polytrimethylene
Polycarbonates have been used in acrylic and polyester carbonate triol, or a higher functionality polytrimeth
coatings. U.S. Pat. No. 5,525,670 describes a coating com ylene carbonate polyol;
position based on either acrylic or polyester resins modified c) A melamine crosslinking agent;
with polycarbonates which are cured by either urethane or d) Optionally a catalyst; and
melamine formaldehyde chemistries. The polycarbonate e) Optionally pigments and other additives known in the
described preferably has a number average molecular weight art and used in coatings.
above 2000. The polycarbonate of this reference is made 15 In the Second embodiment, where no acrylic is
from a mixture of Straight chain diols, branched chain diols, incorporated, the invention comprises:
and polyhydric alcohols and an aliphatic carbonate, where A melamine/urea formaldehyde polytrimethylene carbonate
both the branched chain diols and the polyhydric alcohols coating composition comprising:
are present in at least 10 mol%. It is stated in this reference a) 5 to 80% by weight polytrimethylene carbonate,
that if less than 10 mol % is present, the material crystallizes optionally blended with 0 to 30% glycol;
(branched chain diol), and inferior curing characteristics b) 5 to 70% by weight melamine crosslinking agent;
(polyhydric alcohols) and inferior water resistance
(polyhydric alcohols) are exhibited. Also see U.S. Pat. No. c) 0 to 70% solvent; and
5,527,879. d) Optionally a catalyst
EP 0 712873 A2 describes an acrylic copolymer which is 25 The compositions can be applied over a variety of Sub
an acrylic monomer having a hydroxy alkyl carbonate group StrateS.
and an acid group-containing monomer. The composition is
Said to be crosslinked with melamine to prepare a thermo BRIEF DESCRIPTION OF THE DRAWINGS
Setting water borne coating composition. FIG. 1 is a graph of the tan delta Versus temperature
There does not appear to be any reference in the art that curves of PTMC diol coatings.
discloses or Suggests the use of polytrimethylene carbonate FIG. 2 is a graph of the tan delta Versus temperature
diols and triols and higher functionality polyols in relatively curves of PTMC triol coatings.
Small amounts to provide improved impact resistance in
acrylic melamine coatings. FIG. 3 is a graph of the Storage modulus versus tempera
There is a need in the art for coating compositions with 35 ture curves of PTMC diol coatings.
improved impact resistance. Attempts have been made to FIG. 4 is a graph of the Storage modulus versus tempera
produce tougher, more chip-resistant coatings, particularly ture curves of PTMC triol coatings.
for automobiles, but these have not been completely Satis FIG. 5 is a graph of the tan delta versus temperature
factory. In view of the some of the desirable properties of curves of PTMC diol modified melamine coatings.
melamine as a crosslinking agent, it would be particularly 40
FIG. 6 is a graph of the tan delta Versus temperature
desirable if it were possible to obtain acrylic melamine curves of PTMC triol modified melamine coatings.
coatings with improved impact resistance, with minimal FIG. 7 is a graph of the Storage modulus versus tempera
effect on other properties. ture curves of PTMC diol modified melamine coatings.
SUMMARY OF THE INVENTION FIG. 8 is a graph of Storage modulus verSuS temperature
45
In the present invention it has been found that modified curves of PTMC triols modified melamine coatings.
acrylic melamine coatings with improved impact resistance FIG. 9 is a bar graph of 20° and 60° gloss of PTMC diol
can be achieved through incorporation of polytrimethylene modified melamine coatings.
carbonate diols and triols, and higher functionality polytri FIG. 10 is a bar graph of 20° and 60 gloss of PTMC triol
methylene carbonate polyols. Furthermore, these improve 50 melamine coatings.
ments were observed while maintaining high gloSS, weather
resistance, and overall durability. It has Surprisingly been FIG. 11 is a graph of the effect of curing conditions on T.
found that to have both high impact resistance and high of 20% PC597 modified melamine coatings.
gloSS, polytrimethylene carbonate diols and triols, and FIG. 12 is a graph of the effect of curing conditions on
higher functionality polytrimethylene carbonate polyols 55 modulus of 20% PC597 modified melamine coatings.
within a Specific molecular weight range provide the best DETAILED DESCRIPTION OF THE
results. INVENTION
In a related embodiment of the present invention it has
also been found that a new baked coating composition can In the present invention poly(trimethylene carbonate)
be prepared without acrylic from poly 60 polyols (hereafter referred to as PTMC polyols) were exam
(trimethylenecarbonate), optionally Substituted with a ined as modifiers for acrylic melamine coatings and, in a
glycol, and a melamine/urea formaldehye which provides a Second embodiment, for coatings where no acrylic was used.
number of formulating options for coatings manufacturers. Typically when PTMC polyols are incorporated into
Various formulations have been demonstrated to have desir acrylic polyols as potential coatings modifiers, problems can
able levels of adhesion, mar resistance, and low haze. 65 be observed with phase Separation, hazy coating appearance,
In accordance with the foregoing, the present invention in and reduced gloSS. In the present invention we have discov
the first embodiment comprises: A modified acrylic coating ered that the compatibility of PTMC with acrylic copoly
 US 6,433,131 B1
S 6
mers can be greatly improved by lowering the carbonate thermosetting crosslinking type. Suitable alkyl esters of
molecular weight and increasing PTMC polyol functional acrylic acid or methacrylic acid include methyl
ity. In addition, it has Surprisingly been found that the use of methacrylate, ethyl methacrylate, butyl methacrylate, ethyl
lower percentages of polytrimethylene carbonate diols and acrylate, butyl acrylate, and 2-ethylhexyl acrylate. Suitable
triols provides the desired improvements in key properties of 5 other copolymerizable ethylenically unsaturated monomers
the cured compositions. Furthermore, it has been found that include vinyl aromatic compounds Such as Styrene and Vinyl
to have both high impact resistance and high gloSS, the toluene, nitrites Such acrylonitrile and methacrylonitrile;
poly(trimethylenecarbonate) must be within a specific vinyl and vinylidene halides such as vinyl chloride and
molecular weight range. PTMC polyols used in the first Vinylidene fluoride and vinyl esterS Such as Vinyl acetate.
embodiment of the invention had molecular weights from Acrylic polymers can be prepared via aqueous emulsion
about 360 to about 2700, with molecular weights below polymerization techniqueS or can be prepared via organic
2000 more suitable. Overall performance, particularly with Solution polymerization techniques. Generally, any method
respect to coating gloSS and appearance, was found to be a of producing Such polymers that is known to those skilled in
function of molecular weight, with PTMC polyols having the art utilizing art recognized amounts of monomers can be
molecular weights less than 1500 providing very good 15 used.
results. It was found that coating performance improved Suitable functional monomers may be used in addition to
with increasing PTMC polyol molecular weight until incom the other acrylic monomers mentioned above for crosslink
patibility adversely impacted the gloSS and overall appear ing purposes and include, for example, acrylic acid, meth
ance. Examples demonstrate that PTMC polyols having acrylic acid, hydroxyalkyl acrylates, and hydroxyalkyl
molecular weights less than 1000 are very compatible as methacrylates. Preferably, the hydroxyalkyl group of the
modifiers and result in no loSS of gloSS. latter two types of compounds contains from about 2 to 4
In the examples 2 to 50 wt %, preferably 5 to 20 wt % carbon atoms. Examples thereof are hydroxyethyl acrylate,
poly(trimethylenecarbonate)polyol, comprising preferably hydroxyethyl methacrylate, hydroxypropyl acrylate,
PTMC diols with equivalent weights ranging from 324 to hydroxypropyl methacrylate, 4-hydroxybutyl acrylate and
1336 and triols with equivalent weights ranging from 121 to 25 4-hydroxybutyl methacrylate and the like. Also, the acrylic
573(Table 2) were incorporated into an acrylic polyol and polymer can be prepared with N-(alkoxymethyl)acrylamides
crosslinked by a melamine crosslinking agent. and N-(alkoxymethyl)methacrylamides.
The effect of curing conditions, PTMC polyol molecular The polymeric film-forming resin for the composition can
weights, and level used in the formulation on coating also be Selected from Suitable polyesters. Such polymers
properties were evaluated. DMA analysis revealed a pre may be prepared in a known manner by condensation of
ferred molecular weight range for the PTMC polyols. polyhydric alcohols and polycarboxylic acids. Suitable poly
Higher molecular weight PTMC polyols resulted in incom hydric alcohols include ethylene glycol, propylene glycol,
patible coatings with hazy appearance and reduced gloss butylene glycol, 1,6-hexylene glycol, neopentyl glycol,
compared to the control. In comparison with higher molecu 35
diethylene glycol, glycerol, trimethylol propane,
lar weight PTMC polyols, PTMC diols and triols with lower pentaerythritol, 1,3-propanediol, and 2-methyl-1,3-
molecular weights were more compatible with the acrylic propanediol.
polyol, provided cured coatings with the desired properties, Suitable dicarboxylic acids are known to those skilled in
and had less tendency to crystallize. For example, at 20 wt the art and include terephthalic acid, isophthalic acid, Suc
% PTMC diol, improved impact resistance with high gloss 40 cinic acid, adipic acid, azelaic acid, Sebacic acid, maleic
is obtained when the equivalent weight is equal to or leSS acid, fumaric acid, phthalic acid, tetrahydrophthalic acid,
than 328, when applied to polished iron phosphated Steel hexahydrophthalic acid, dodecanedioic acid, and trimellitic
panels. For PTMC triols, improved impact with high gloss acid. In addition to the polycarboxylic acids mentioned
is obtained for equivalent weights up to 308. above, functional equivalents of the acids, Such as
The PTMC polyol modifiers of the present invention 45 anhydrides, where they exist, or lower alkyl esters of the
exhibited additional improvements compared with the con acids, Such as the methyl esters, may be used.
trol or at least maintained desirable properties. The PTMC Acrylic polyols are preferred for good results. Suitable
polyol modifiers provided improved flexibility for the acrylic polymers have an equivalent weight of about 300 to
melamine coatings. The PTMC modifiers also provided a 1300 and a hydroxyl value of 43 to 187. Preferably, the
Significant improvement in coating adhesion. Under UV 50 acrylic polymer has an equivalent weight of about 400 to
testing improved non-yellowing properties were observed. 700 and a hydroxyl value of 80 to 140.
Incorporation of the carbonate polyols had no appreciable Suitable acrylic polyols are, for example, SCX902, SCX
effect on pencil hardness, chemical and Stain resistance, or 912, and JoncrylF) 587, commercially available from S. C.
MEK double rub resistance. All fully cured coatings exhib Johnson Polymer. The acrylic polyol used in the examples to
ited good humidity resistance. 55 demonstrate the benefits of the PTMC diols and triols was
The acrylic melamine coating composition of the present Joncryl(R) 587 polyol. Joncryl(R) 587 typically has a hydroxyl
invention requires a polyol, a PTMC diol, triol, or higher number of 94, an equivalent weight of 600, an acid
functionality PTMC polyol, a solvent, optionally a number<5, and a glass transition temperature of 50° C.
co-Solvent, a melamine crosslinking agent, and optionally an Joncryl(R587 is a solid flaked acrylic polyol designed for use
acidic catalyst. 60 in thermosetting coatings at conventional Solids. Jon
A variety of polyols can be used, including, but not cryl(R587 allows the formulator to select the solvent and the
limited to, polyether polyols, polyurethane polyols, acrylic optimized equivalent weight of this product results in Suf
polyols, and polyester polyols. ficient crosslink density to provide good chemical and
The acrylic polymers are copolymers of one or more alkyl Solvent resistance.
esters of acrylic acid or methacrylic acid optionally together 65 The melamine resin used for the curing agent of the
with one or more other polymerizable ethylenically unsat present invention may be the resin obtained by addition
urated monomers. These polymers are generally of the condensation of an amine compound Such as melamine,
 US 6,433,131 B1
7 8
guanamine, and urea with formaldehyde by art-known Nacure(R) 155, and commercially available from King
methods, or the resin obtained by further addition Industries, Inc. Where an acid catalyst was employed, an
condensation of Such resin with alcohol. For instance, it may effective amount was 0.1 to 3.0% based on the total weight
be methylated melamine, butylated melamine, methylated of the resin. The preferred amount of catalyst was about 0.5
benzoguanamine, butylated henzoguanamine, etc. to 2.0%, most preferably about 1.0%.
Particularly Suitable crosslinking agents are fully or par The composition can be applied over a wide variety of
tially methylolated melamine resins, Such as hexamethylol Substrates Such as plastic, metal, wood, primed metals, or
melamine, pentamethylol melamine, tetramethylol previous coated or painted metals. If used on an existing
melamine, etc. These are made by reacting 6 or leSS moles finish, the composition is usually applied over an acrylic
of formaldehyde with each mole of melamine. The reaction primer Surfacer. The composition can be applied directly to
causes the addition of hydroxymethyl groups to the amine
groups of the melamine resin. The fully or partially methy an acrylic lacquer or enamel finish that has been Sanded and
lolated melamine may also be fully or partially alkylated by cleaned with an aliphatic hydrocarbon Solvent. The compo
reacting with an alcohol, Such as methanol. In acid envi Sition can be applied as an original finish over an epoxy
ronments (pH preferably less than 5) at elevated tempera primer or other conventional primerS or can be applied
15 directly to bare metal. It is preferred to have the metal
tures (preferably about 250 F.), these melamine
formaldehydes react with the hydroxy groups of the resin to Surface treated with a phosphate.
form complex crosslinked polymer Structures. The coating composition may contain, in addition to the
Suitable melamine resins include those hydrophilic above components, about 0.5-5% by weight, based on the
melamines and/or hydrophobic melamines, Such as, for weight of the binder, of ultraviolet light stabilizers, prefer
example, CYMEL(R)303, CYMEL(R325, CYMEL(R) 1156, ably a derivative of benzophenone, Such as, for example,
manufactured by Cytec; YUBAN 20N, YUBAN 20SB, benzotriazole.
YUBAN 128, manufactured by Mitsui Toatsu Chemicals, Other useful ultraviolet light stabilizers are: Benzophe
Inc.; SUMIMAL(RM-50 W, SUMIMAL(RM-40N, nones Such as hydroxydodecycl benzophenone, 2,4-
SUMIMACRL M-30W, manufactured by Sumitomo Chemi 25
dihydroxybenzophenone, hydroxybenzophenones contain
cal Co. Ltd, and the like, used alone or in combinations. ing Sulfonic acid groups, 2,4-dihydroxy-3',5'-di-t-
In the examples, good results were achieved using butylbenzophenone, 2,2',4'-trihydroxybenzophenone esters
CYMEL(R303, a hexamethoxymethylmelamine resin, com of dicarboxylic acids, 2-hydroxy-4-
mercially available from Cytec. Melamine resins of this type acryloxyethoxybenzophenone, aliphatic monoesters of 2.2,
may be produced as set forth in U.S. Pat. Nos. 2,906,724; 4-trihydroxy-4'-alkoxyben Zophenone, 2-hydroxy-4-
2,918,452; 2,998.410; 2,998.411; 3,107,227; 3,422,076, all methoxy-2-carboxybenzophenone; triazoles Such as
of which patents are incorporated herein by reference in the 2-phenyl-4-(2-4'-dihydroxybenzoyl)triazoles, substituted
entirety. benzotriazoles Such as hydroxyphenyltriazoles Such as 2-(2-
Suitable solvents for use in the invention include a hydroxy-5'-methylphenyl)benzo triazole, 2-(2'-
number of conventional Solvents, however PTMC diols 35 hydroxyphenyl)benzo triazole, 2-(2'-hydroxy-5'-
were not Soluble in aliphatic or aromatic hydrocarbon octylphenyl)naphthotriazole; triazines Such as 3,5-dialkyl
Solvents, Such as, for example, hexane, toluene, Xylene, etc. 4-hydroxyphenyl derivatives of triazine, Sulfur-containing
Examples of Solvents which are generally Suitable include, derivatives of dialkyl-4-hydroxyphenyltria Zine S,
but are not limited to, esterS Such as butyl acetate, n-propyl hydroxypheny-1,3,5-triazines and Such triazines containing
acetate, and ethylene glycol diacetate, ketones Such as 40
Sulfonic acid groups, aryl-1,3,5-triazines, orthohydroxyaryl
methyl ethyl ketone, methyl n-propyl ketone, and methyl S-triazine, and benzoates Such as dibenzoate of
amyl ketone, etherS Such as propylene glycol methyl ether diphenylolpropane, t-butylbenzoate of diphenylolpropane,
acetate and ethylene glycol methyl ether acetate; and nonyl phenylbenzoate, octyl phenylbenzoate, and resorci
alcohols, Such as butanol and diacetone alcohol. The pre nol dibenzoate.
ferred Solvents were glycol ethers and/or esters, particularly 45 The coating may also optionally contain color pigments or
propylene glycol methyl ether acetate (PGMA), which is metallic pigments known to those skilled in the art. Suitable
also a good Solvent for acrylic polyols. It was also desirable metallic pigments include, for example, aluminum flake,
to incorporate a co-Solvent to improve the Solubility and copper bronze flake, and metal oxide coated mica. The
evaporation rate for coatings applications. coating may also include nonmetallic colored pigments
Suitable co-solvents include, but are not limited to, 50 conventionally used in Surface coating compositions, includ
methyl ethyl ketone, methyl n-propyl ketone, acetone, ethyl ing inorganic pigments Such as titanium dioxide, iron oxide,
acetate, methyl isobutyl ketone, and tertiary butyl acetate. chromium oxide, lead chromate, carbon black, and the like,
The preferred co-solvent was methyl ethyl ketone (MEK). and organic pigments Such as phthalocyanine blue and
About 0 to 40% of the primary solvent used in the formu phthalocyanine green.
lations was substituted with co-solvent, preferably from 55 In general, pigment is incorporated in amounts of about 1
about 10 to 30%. to 80 percent by weight based on weight of coating Solids.
The coatings can be cured without the use of catalyst. Metallic pigmentation is employed in amounts from about
However, a catalyst can optionally be used to promote the 0.5 to 35 percent by weight of the aforesaid aggregate
crosslinking reaction of the melamine crosslinking agent weight. If desired, the coating composition may additionally
with the acrylic polyols. Suitable catalysts include acid 60 contain other materials well known in the art of formulating
catalysts, Such as, for example, p-toluenesulfonic acid, Xyle Surface coatingS Such as Surfactants, flow control agents,
neSulfonic acid, dodecyl benzene Sulfonic acid, didodecyl thixotropic agents, fillers, anti-gassing agents, and other
naphthalene Sulfonic acid, didodecyl naphthalene Sulfonic Similar auxiliary additives.
acid, dinonyl naphthalene Sulfonic acid, dinony naphthalene In order to formulate the modified coatings, the acrylic
disulfonic acid, their amine blocks, phosphoric acid, etc. 65 polyol was dissolved in a suitable solvent to about 40-70%,
The catalyst used to demonstrate the invention is dinonyl preferably 50–60% solids. The PTMC diols and triols were
naphthalene disulphonic acid, Sold under the name of typically dissolved in PGMA and a co-solvent to improve
 US 6,433,131 B1
10
Solubility and evaporation rate for the coating composition, coatings gloss, however no loss of 20 or 60 gloss was
to about 40-70%, preferably 50–60% solids. The PTMC observed in coatings modified with low molecular weight
diols and triols were incorporated into the formulation at 5, PTMC polyols such as PC328 diol and PT 217, PT121, and
20, and 50% levels, based on the weight of total polyols. The PT308 triols (FIGS. 9 and 10). Gloss generally decreased
resulting polyol Solutions were then blended in a high-speed with increasing PTMC molecular weights. Therefore, the
mixer. A weight ratio of polyols to melamine of about incompatibility of the PTMC modifier with acrylic polyol
65–90/10–35, preferably 70–80/20–30, and more preferably resulting in the loSS in gloSS is attributed to phase Separation
about 75/25, was used to provide crosslinked coatings. An consistent with DMA data.
acid catalyst was used to provide acceptable cure rates for Humidity Resistance Test
the coatings. Dynamic mechanical analysis (DMA) showed that the T.
Where the film was cured, the desired results were and Storage modulus increased when the curing tempera
obtained using temperatures in the range of from about 120 tures and/or the curing time increased (FIGS. 11 and 12).
Modification of Pigmented Coatings
C. to 240° C., more often from about 140° C. to 200 C., The effect of PTMC polyols on the performance of the
with curing temperatures at or above 150° C. providing pigmented acrylic melamine coatings can be Summarized by
better results. For example, all PTMC polyol modified 15 the following observations:
melamine coatings baked at 150° C. for 30 minutes exhib 1. PTMC polyol modifiers improved the flexibility of
ited excellent humidity resistance. pigmented melamine coatings.
Dynamic Mechanical Analysis of the Modified Acrylic 2. PTMC polyol modifiers had no effect on the ultimate
Coatings hardness, acid, caustic, mustard, and gasoline resis
Dynamic mechanical analysis confirmed that the glass tance.
transition temperature (T) of the PTMC polyol modified 3. Pigmented PTMC polyol modified coatings had good
acrylic melamine coatings decreased with increasing PTMC gloSS retention compared to the control and to modified
molecular weights, likely a function of crosslink density. clear top coatings.
PTMC triols provided a wider range of T values than the 4. The PTMC polyol modified melamine coatings exhib
diols over the molecular weight range investigated. TS for 25 ited equivalent resistance to UV radiations as indicated
the triol coatings decreased from 76 to 25 C. with increas by gloSS and color change compared to the control.
ing the triol molecular weights, while the T range for the Polytrimethylene Carbonate Melamine/Urea Formaldehyde
diol coatings varied from 25 to 9 C. The damping Baked Coatings
temperature curves of pure PTMC diol and triol cured films In the related embodiment of the invention in which new
with melamine formaldehyde are given in FIGS. 1 and 2, melamine/urea formaldehyde polytrimethylene carbonate
while their moduli variation with temperature are given in coating composition is prepared, a polycarbonate, optionally
FIGS. 3 and 4, respectively. Substituted with a glycol, is reacted in the presence of a
Two separate peaks were clearly visible for both of the Solvent, and optionally a co-solvent, with one or more of
diols and triols with higher molecular weight modified Several melamine/urea formaldehyde precursors.
coatings when Tan delta was plotted vs. temperature for 20% 35 The polycarbonate is preferably polytrimethylene
PTMC diol and triol modified melamine coatings (FIGS. 5 carbonate, which can be used alone, or Substituted with a
and 6). DMA properties of polymers are primarily Sensitive glycol. The glycol can be blended in an amount of 0-30%,
to the microStructure of the materials. For a two component preferably about 5-20%.
System only one relaxation is shown in the damping The glycol component may be Selected from aliphatic,
temperature curve when the two polymers are compatible. A 40 alicyclic, and aralkyl glycols. Examples of Such glycols
two-phase System shows two peaks. Hence, DMA Studies include ethylene glycol, propylene glycol, 1,3-propanediol;
indicate that the higher molecular weight PTMC polyols 2,4-dimethyl-2-ethylhexane-1,3-diol; 2,2-dimethyl-1,3-
were incompatible with the acrylic copolymer. propanediol, 2-ethyl-2-butyl-1,3-propanediol, 2-ethyl-2-
The two peaks in the damping-temperature curves corre isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-butanediol;
spond to the T of the crosslinked acrylic polyol exhibiting 45 1,5-pentanediol, 1,6-hexanediol, 2,2,4-trimethyl-1,6-
the main relaxation at higher temperature, and the hexanediol; thiodiethanol, 1,2-cyclohexanedimethanol; 1,3-
crosslinked PTMC modifiers providing the relaxation at low cyclohexanedimethanol, 1,4-cyclohexanedimethanol; 2,2,4,
temperature. The data also indicated that incorporation of 4-tetramethyl-1,3-cyclobutanediol; and p-xylylenediol. The
PTMC polyols resulted in reduced Ts for the modified examples demonstrate the effectiveness of 1,3-propanediol.
coatings, i.e., the main relaxation at the high temperature 50 Suitable solvents and co-solvents include those listed for
(FIGS. 5 and 6). Therefore, DMA studies confirm that higher use with the modified acrylic coatings. Good results were
molecular weight PTMC diols and triols are essentially obtained using methyl isobutyl ketone.
immiscible with the acrylic polyol, thereby giving rise to a Suitable catalysts may be Selected from the acidic cata
hazy appearance and reduced gloSS. lysts listed for use with the modified acrylic coatings.
The Storage modulus was also affected with incorporation 55 Example 11 demonstrates the usefulness of p-toluene Sul
of the PTMC polyol modifiers. The storage modulus phonic acid.
temperature curves of 20% carbonate diols and triols modi The baked coatings are prepared by adding polytrimeth
fied coatings resulted in slightly reduced modulus at room ylene carbonate, optionally Substituted with a glycol,
temperature compared with the control (FIGS. 7 and 8). melamine/urea formaldehyde, and Solvent, and optionally
Appearance and GloSS 60 co-Solvent, into a kettle and heating at a temperature of
The immiscibility effect of the acrylic polyol and PTMC about 80–130° C., preferably 100 to 110° C., for about 1 to
polyol modifiers on coating appearance was generally obvi 10 hours, preferably about 3 to 5 hours under nitrogen gas.
ous over polished iron phosphated Steel panels. For instance, The Solution obtained at the end of the reaction, as noted in
the low molecular weight PTMC polyols modified coatings Examples 11 and 12, is clear. These compositions illustrate
and the control were clearly transparent, while the higher 65 a few of the formulating options for coatings manufacturers.
molecular PTMC polyol modified coating exhibited visual The following examples will serve to illustrate specific
haze. This hazy appearance had a detrimental affect on the embodiments of the invention and related embodiments
 US 6,433,131 B1
11
disclosed herein. These examples are intended only as a
means of illustration and should not be construed as limiting TABLE 1.
the scope of the invention in any way. Those skilled in the P1 P2 P3
art will recognize many variations that may be made without
departing from the Spirit of the disclosed invention. 5 STARTING
MATERIALS

EXAMPLE 1. Trimethylene 55 7B 85
Carbonate parts
Trimethylol 45 25 15
1O Propane
CALCULATED
Preparation of PTMC Triols PROPERTIES

Equivalent 1OO 18O 3OO

The preferred results were obtained using PTMC diols Weight
and triols. Polytrimethylene carbonate triols were prepared 15 Molecular 3OO 540 900
Weight
by reacting trimethylene carbonate with trimethylol pro TMC units 1.6 4 7.5
pane. The trimethylene carbonate and trimethylol propane
were weighed and measured into a three-necked flask
equipped with a stirring bar. Then the mixture was heated EXAMPLE 2
slowly to 120° C. and held at that temperature for about
three hours. The contents were then analyzed by GC and A number of diol and triols were prepared. The diols were
NMR for unreacted starting materials. The reaction can be prepared by reacting PTMC with 1,3-propanediol and the
represented by the following: triols were prepared by the procedure discussed in Example
25 1. Although no catalyst was used in Example 1, the diols and
triols can be prepared using, for example, dibutyl tin dilau
O
us O +
tion
CHCH2C-CH-OH C
rate or Sodium acetate as a catalyst, as discussed in copend
ing U.S. patent application Ser. No. 09/671,572. In the case
of Sodium acetate, an effective amount is about 50 ppm,
Nu CH2OH based on Sodium. The physical properties of these diols and
O triols are presented in Table 2. All the diols and triols have
very low glass transition temperatures (T,), which increase
as the polyol molecular weights increase. The triols pro
duced a slightly higher T, than the diols at similar molecular
35 weights. Depending on the molecular weight, PTMC diols
CHCHC-CH-O-(C-OCH2CH2CH2O).H were Semisolid or very low melting Solids that produced a
clear liquid upon melting. Differential Scanning Calorimetry
(DSC) indicated that the degree of crystallinity increased
X=0 to total of TMC units
O with increasing molecular weights. Also, the Speed of
Y=O to total of TMC units 40 recrystallization was faster as the molecular weight
Z= 0 to total of TMC units
X-Y + Z = Total of TMC units
increased for the molecular weights Studied.
In comparison with the PTMC diols, the triols were clear
liquids at room temperature. This characteristic provides the
triol Solutions with an extra degree of Stability, hence it is an
Table 1 shows the amounts of Starting materials used to 45 additional advantage with respect to the Suitability of triols
make the PTMC triols and the calculated properties: for coating formulations.

TABLE 2
Properties of Polytrimethylene Carbonate Polyols
PC PC PC PC PC PT PT PT PT PT
PTMC 328 474 597 813 1336 121 217 3O8 445 573

Functionality Diol Dio Diol Diol Dio Triol Triol Triol Triol Triol
Molecular 656 948 1194 1626 2672 363 651 924 1336 1718
weight
Equivalent 328 474 597 813 1336 121 217 3O8 445 573
weight
Tg ( C.) -46.4 -40.9 -35.6 -30.2 -25.7 -48.9 -38.8 -35.9 -28.3 -26.3
Melting Point 33.3 33.4 34.8 38.4 41.7
( C.)
Fusion Heat O.3 7.0 17.8 32.3 39.0
 US 6,433,131 B1
13 14
EXAMPLE 3
TABLE 4-continued
The purpose of Example 3 was to investigate the Solu
bility of the PTMC diol, PC813 with various solvents. The Compatibility of Polytrimethylene Carbonate Polyols with an
selection of solvents for the PTMC diols was restricted due 5 Acrylic Polyol
to the Susceptibility of them to crystallize. The results are PTMC
shown in Table 3. In Table 3 the symbol “S” means soluble, Content PTS73 PT445 PT308 PT217 PT121
and that a clear Solution was formed. It was determined that 5% Hazy Clear Clear Clear Clear
propylene glycol methyl ether acetate (PGMA) solubilized 10% Hazy Hazy Clear Clear Clear
PTMC polyols well and was likewise a good solvent for 10 3. E. E. Sirt la la
acrylic polyols. Consequently, a mixture of PGMA and o paque paque E. y ea ea
methyl ethyl ketone (MEK) was chosen as solvent for the
acrylic melamine coatings.

TABLE 3
Solubility of PCS13 in some Conventional Solvents
Propylene Ethylene
Methyl Glycol Glycol
- Diace- Methyl - Methyl Methyl Methyl Ethylene
Sol- Butyl Propyl tone Ethyl propyl Amyl Ether Ether Glycol Tol
went Acetate Acetate Alcohol Ketone ketone Ketone Acetate acetate Diacetate uene
Room I I I S I I S S S I
Temp.
60° C. S S S S S I S S S I
After I S S S S I S S S I
Cooling
*Concentration of solutions was 33%.
Abbreviation:
I, insoluble:
S, soluble

EXAMPLE 4 EXAMPLE 5
35
In Example 4, levels of PTMC polyols of 5, 10, 20, and
50% were added to the acrylic polyol and observed for
homogeneity. Hazy solutions of acrylic and PTMC polyols Example 5 demonstrates the formulation of the acrylic
indicated polymer immiscibility. The data confirmed that melamine coatings. Joncryl(R) 587, a 100% solids acrylic
compatibility increased as the PTMC polyol molecular 40
polyol from S. C. Johnson was Selected as the commercial
weights decreased. For example, the blend Solution of acrylic polyol for formulation studies. Joncryl(R587 and the
acrylic polyol with as low as 5% PC1336 was hazy, while PTMC polyols were dissolved in propylene glycol methyl
the solution containing even 50% of PC328 diol was still
clear. For the triol system, the blend containing 5% higher ether acetate (PGMA) and methyl ethyl ketone (MEK) to
45 50% solids (Table 5). The resulting polyol solutions were
molecular weight PT573 was hazy, whereas the solutions
containing 50% of PT121 and PT217 were still clear. The then blended in a high-speed mixer. A 75/25 weight ratio of
data also revealed that the compatibility of PTMC diol or polyols to Cymel(R303, a hexamethoxymethylmelamine
triol with acrylic polyol decreased as the modifier content in resin Sold by Cytec Industries, Inc., was used to provide
the formulations was increased. However, the polytrimeth 50 crosslinked coatings. A 1% acid catalyst, dinonyl naphtha
ylene carbonate triols are more compatible than the diols at lene disulphonic acid, from King Industries, Inc., Sold under
similar molecular weights, i.e. PC474 and PT308 triol.
Results are shown in Table 4: the name of Nacure(R155, based on resin weight, provided
acceptable cure rates for the coatings.
TABLE 4 55

Compatibility of Polytrimethylene Carbonate Polyols with an

Acrylic Polyol Solutions containing higher molecular weight PTMC diol
PTMC or triol were hazy, indicating incompatibility with the acrylic
Content PC1336 PC813 PC597 PC474 PC328
60 polyol (Table 6). However, the solution of pure PTMC
5% Hazy Hazy Slightly Clear Clear polyols with melamine crosslinking agent was totally clear,
Hazy demonstrating that the polycarbonates themselves were
10% Opaque Hazy Hazy Slightly Clear
Hazy compatible with the crosslinking agent. Coating properties
20% Opaque Opaque Opaque Hazy Clear were evaluated after casting films on cold-rolled (Q panel
50% Opaque Opaque Opaque Opaque Clear 65
S-36) and iron phosphated steel panels (Q panel S-36-I) and
curing for 30 minutes at 150° C.
 US 6,433,131 B1
15 16
TABLE 5
Formulation of PTMC Diol Modified Melamine Coatings
Resin Control PC1 PC2 PC3 PC4 PC5 PT1 PT2 PT3 PT4 PTS

50% (PGMA)
PC328, - 15
50% (MEK)
PC474, - 15
50% (MEK)
PC 597, - - 15
50% (MEK)
PC813, - - - - 15 - - - - - -
50% (MEK)
PC1336, - - - - - 15 - - - - -
50% (MEK)
PT121, - - - - - - 15 - - - -
50% (MEK)
PT217, 15
50% (MEK)
PT308, 15
50% (MEK)
PT445, 15
50% (MEK)
PT573, 15
50% (MEK)
MEK 3.0 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75
PGMA 3.0 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75 3.75
Cymel (R) 303 1O 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5 12.5
Nacure (E) O.73 0.91 O.91 O.91 O.91 O.91 O.91 O.91 O.91 O.91 O.91
155, 55%
Solid 53%. 53%. 53%. 53%. 53%. 53%. 53%. 53%. 53%. 53%. 53%

EXAMPLE 6
TABLE 6
In Example 6 all of the PTMC polyol modified melamine
Appearance of coating Solutions Before Application 35 coatings, prepared as described in Example 5, were baked at
Coating 150° C. for 30 minutes and tested for humidity resistance.
Composition PC1336 PC813 PC597 PC474 PC328 All exhibited excellent humidity resistance. The coatings
passed over 500 hours without failure in the ASTM D2247
20% PTMC Opaque Hazy Hazy Near Clear Clear 94 test conducted in a chamber with a heated tank at 40 C.
40
Coating
Composition PT573 PT445 PT308 PT217 PT121 EXAMPLE 7
20% PTMC Opaque Hazy Clear Clear Clear In Example 7, the modified acrylic melamine coatings,
prepared as described in Example 5, were examined for
various properties. Data are shown in Table 7:
TABLE 7
Properties cf Cured Coatings
Control PC1 PC2 PC3 PC4 PCS PT1 PT2 PT3 PT4 PTS

Film Thickness 1.1 1.1 1.O 1.2 1.O 1.1 1.1 1.1 1.1 1.1 1.2
(mil)
(F/R.) Impact 2Of &2 34/5 34/5 34/5 36/5 34/5 28/4 32/5 38/6 40/6 40/6
(in. Ib.)
Adhesion 1B 3B 4B 5B 5B 5B 3B 3B 3B 5B 5B
Pencil Hardness 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H 2H

10% HCI NE NE NE NE NE NE NE NE NE NE NE
10% NaOH NE NE NE NE NE NE NE NE NE NE NE
Spot Tests
Mustard NE NE NE NE NE NE NE NE NE NE NE
Gasoline NE NE NE NE NE NE NE NE NE NE NE
Color B 6.37 6.28 5.98 6.15 5.86 6.08 6.06 6.10 6.10 5.9 6.31
Yellowness Index 14.45 14.12 13.64 13.86 1342 13.7 13.65 13.73 13.74 13:46 14.33
 US 6,433,131 B1

TABLE 7-continued
Properties cf Cured Coatings
Control PC1 PC2 PC3 PC4 PC5 PT1 PT2 PT3 PT4 PTS

Q-UV Test
Gloss 96% 92% 92%
Ren. 20
Gloss 98% 98% 98%
Ren. 60
Color 1.59 O.43 O.42
B
YI 1.35 O.93 O.86
Change

Flexibility, Hardness and Adhesion UV Resistance and Color Evaluation

PTMC polyols improved the front and reverse impact The UV resistance of PTMC polyol modified melamine
resistance of the acrylic melamine coatings. All the diols coatings was evaluated after 500 hours exposure in a Q-UV
afforded Similar improvements in the coating flexibility, cabinet using UVA 340 light bulbs at 60° C. with no
while the triols with higher molecular weight provided more humidity cycle according to ASTM D4587-91. The results
flexibility. The ultimate pencil hardness of the modified
coatings was not affected with incorporation of the PTMC confirmed that color changes for the modified coatings were
polyols. Similar to the control after UV-exposure. A slight gloSS
Incorporation of the PTMC polyol modifiers provided 25 reduction was observed at 20 for the PTMC modified
great improvement in the coating adhesion for melamine coatings. In addition, the PTMC polyol modifiers provided
cured coatings. The control melamine coatings performed improved yellowing resistance compared to the control.
poorly with a value of 1B according to the Standard testing
method ASTM D3359-95. As shown in Table 7, higher EXAMPLE 8
molecular weight PTMC polyol modified melamine coat
ings passed the cross-hatch tape adhesion with a value of 5B, In Example 8 white topcoats based on Joncryl 587 modi
i.e., without failure (Table 7). fied with 20% PC597 and TiO, were formulated to a
Chemical, Stain, and MEK-Rub Resistance pigment to binder ratio of 0.7/1 and a resin/melamine ratio
Control and PTMC polyol modified coatings provided
excellent acid, caustic, and Stain resistance after 24 hours 35 of 75/25 by weight and cured at 149° C. for 30 minutes. The
exposure. Modified coatings had good gasoline resistance modified PTMC polyol melamine coatings were tested for a
compared with the control. All the modified and control number of properties. The tests showed improvements in
coatings passed over 200 MEK double rubs without failure adhesion and impact, with other properties being essentially
(Table 7). unaffected. Results are shown in Table 8:

TABLE 8
Properties of PTMC Modified Pigmented Melamine Coatings
Front Reverse Humidity
Pencil Impact Impact Resistance 24-Hour Spot Test
Sample Hardness Adhesion (in-pl) (in-pl) (hours) HCl NaOH Gasoline Mustard
Control 3H 1B 16 <2 >5OO 1O 1O 9 1O
20% 3H 5B 25 2 >5OO 1O 1O 9 1O
PC597

MEK Q-UV Test

Yellow- Gloss Gloss Double Gloss Gloss Color B YI
Sample Color B Ness 20° 60° Rubs 20° 60° Change Change
Control -0.81 -1.28 36 82 >2OO 33 79 O.24 O.38
20% -O-88 -1.42 34 81 >2OO 32 79 O.18 O.32
PC597
 US 6,433,131 B1
19 20
EXAMPLE 9
Example 9 demonstrates the formulation of 5% and 50% TABLE 9-continued
PTMC polyols modified acrylic melamine coatings. Joncryl
587 and the PTMC polyols were dissolved in propylene Formulations of 5% and 50% PTMC modified melamine coatings
glycol methyl ether acetate (PGMA) and methyl ethyl 5
ketone (MEK) to 50% solids. The resulting polyol solutions
were then blended in a high-speed mixer. A 75/25 weight Joncryl 50% 50%
ratio of polyols to melamine resin was used to provide Resin 587 5% PC328 5% PT217 PC328 PT217
crosslinked coatings. A 1% acid catalyst, dinonyl naphtha
lene disulphonic acid, based on resin weight, provided Cymel 303 1O.OO 10.53 10.53 11.OO 11.OO
acceptable CUC rates for the coatings. Nacure 155, O.73 O.77 O.77 O.80 O.8O
Coating properties were evaluated after casting films on 55%
cold-rolled (Q panel S-36) and iron phosphated steel panels
(Qpanel S-36-I) and curing for 30 minutes at 150° C. PTMC Weight 79.33 83.51 83.51 82.68 82.68
polyols improved the front and reverse impact resistance and
the adhesion of the melamine coatings. The ultimate pencil
TABLE 10
Properties of 5% and 50% PTMC modified melamine coatings
Joncryl 5% 5% 5% 5% 5% 50% 50% 50% 50% 50%
587 PC328 PC474 PT217 PT308 PT445 PC328 PC474 PT217 PT308 PT445
Film 1.1 1.1 1.1 1.1 1.1 1.1 1.2 1.2 1.1 1.2 1.1
Thickness
(mil)
(F/R.) 2Ofs2 24/4 22/3 22f&2 22/3 24/4 80/60 7Of 40 34f6 4.8/10 50/30
Impact (in. lb.)
Adhesion 1B 3B 3B 3B 2B 4B 4B 4B 4B 4B 5B
Pencil 2H 2H 2H 2H 2H 2H H-2H 2H 2H 2H 2H
Hardness
MEK Rubs >2OO >2OO >2OO >2OO >2OO >2OO >2OO >2OO >2OO >2OO >2OO
24-hour Spot Tests
10% HCI NE NE NE NE NE NE NE NE NE NE NE
10% NaOH NE NE NE NE NE NE NE NE NE NE NE
Mustard NE NE NE NE NE NE NE NE NE NE NE
Gasoline NE NE NE NE NE NE NE NE NE NE NE
2O Gloss 92 92 91 94 91 92 90 47 84 82 75
60 Gloss 12O 12O 121 12O 12O 119 112 84 116 114 96

hardness of the modified coatings was not affected with 40

EXAMPLE 10
incorporation of the PTMC polyols. The control and modi Example 10 demonstrates the related alternative embodi
fied coatings provided excellent acid, caustic, and Stain ment comprising the formulation of a melamine/urea form
resistance after a 24 hour exposure. Modified coatings had aldehyde polytrimethylene carbonate coating composition.
good gasoline resistance compared with the control. All the In this example a coating composition is made from PTMC,
modified and control coatings passed over 200 MEK double 45 CYMEL(R)327, MIBK as the solvent, and p-toluene Sul
rubs without failure. Data are shown in Tables 9 and 10: phonic acid (PTSA) solution as catalyst. In a 500 ml resin
TABLE 9
kettle, the following were added: PTMC (number-average
MW 3400, 53.2 gm), CYMEL(R)327 (106.2 gm) and MIBK
Formulations of 5% and 50% PTMC modified melamine coatings (81.8 gm) and PTSA solution (1:99 PTSA: MIBK, 12.6 g).
50 This mixture was heated at 100° C. for 5 hrs. under Nagas,
Resin
Joncryl
587 5%. PC328 5% PT217
50%
PC328
50%
PT217
using a reflux condenser. The Solution obtained at the end of
the reaction, designated 23720-184, was clear. Samples of
Joncryl 587, 48.OO 54.OO 54.OO 21.00 21.00 23720-184(20-grams) were made up into blends as shown
50% in below in Table 11. Some of the blends had FC430 added to
PGMA
Joncryl 587, 12.OO 6.OO 6.OO 12.00 12.OO
55 help improve wetness, in order to obtain a Smooth coat. Each
50% in MEK Sample was aged by rolling its container at 23° C. over one
PC328, 3.16 33.OO or two nights as indicated. The Sample was then cast on a
50% in QD412 stainless steel panel using Rod #42 and the panel
PGMA
PT217, 3.16 33.OO
coating cured 20 minutes at 175 C. Panels were cooled for
50% in
60 one hour to approximately room temperature, Visually
PGMA examined for clarity, and tested for mar and adhesion. Mar
MEK 1.33 4.72 4.72 1.15 1.15 test was by attempting to damage with the nylon guide bar
PGMA 5.33 2.30 2.30 1.60 1.60 of an adhesion test cutter. Adhesion testing was according to
ASTM D-3359-95, method B.
 US 6,433,131 B1
22
TABLE 11
Sample 23720- PTSA, 1% Aged ADHE- APPEAR- Substrate
identification 184 PDO in MIBK (hrs) SION MAR ANCE Material
23720-184-1 20gm. 1.2 gm 40 2 POOR HAZY QD 412 (SS)
23720-184-2 20 gm 2.4 gm 40 O POOR HAZY QD12 (SS)
23720-184-3 20 gm 4.8 gm 40 O FAIR HAZY QD412 (SS)
23720-184-4 20 gm 8.4 gm 40 O FAIR HAZY QD412 (SS)
23720-184-5 20 gm 1 gm Ogm 40 4 POOR HAZY QD412 (SS)
23720-184-6 20 gm 2 gm 0.6 gm 40 2 POOR HAZY QD412 (SS)
23720-184-A 20 gm Ogm 16 4 FAIR CLEARQD412 (SS)
23720-184-B 20 gm 1.2 gm 16 3 GOOD SLIGHTLY QD412 (SS)
HAZY
23720-184-2B 20 gm 1.2 gm 16 4 GOOD CLEAR QD412 (SS)
15
EXAMPLE 11 under N, using a reflux condenser. The Solution obtained at
Example 11 also demonstrates the alternative embodi Samplethe end of the reaction, identified as 23720-181, was clear.
ment comprising the formulation of a coating from PTMC, blends were made and evaluated Similarly to
1,3-propanediol, CYMEL(R)327, and MIBK as the solvent, 20 Example 11, except that all aging was for 16 hours. The only
without a catalyst. In a 500 ml resin kettle, the following difference among samples was the amount of PTSA solution
were added: PTMC (number-average MW 3400, 41.75gm), (if any) added to 20 g of 23720-181 before aging. Unlike
1,3-PDO (41.75 gm), CYMEL(R)327 (83.5 gm) and MIBK Example 10, a variety of Substrates were used. Details and
(142.8 gm). This mixture was heated at 110° C. for 3 hrs. results are in Table 12:

TABLE 12
Sample PTSA, 1% Substrate
Identification in MIBK Material Adhesion Mar Appearance
23720-18 None QD-412 (SS) POOR CLEAR
23720-181-1 1.1 gm QD-412 (SS) GOOD CLEAR
23720-181-2 2.2 gm QD-412 (SS) GOOD CLEAR
23720-181-3 3.3 gm QD-412 (SS) GOOD CLEAR
23720-181-4 4.4 gm QD-412 (SS) GOOD CLEAR
23720-181-5 5.5gm QD-412 (SS) POOR HAZY
23720-181-6 6.6 gm QD-412 (SS) POOR HAZY
23720-181-7 7.7gm QD-412 (SS) POOR HAZY
23720-18 None Epoxy-primed POOR HAZY
steel
23720-181-1 1.1 gm Epoxy-primed 2 POOR HAZY
steel
23720-181-2 2.2 gm Epoxy-primed GOOD CLEAR
steel
23720-181-3 3.3 gm Epoxy-primed GOOD CLEAR
steel
23720-18 None A-412 GOOD HAZY
(Aluminum)
23720-181-1 1.1 gm A-412 FAIR SLIGHTLY HAZY
(Aluminum)
23720-181-2 2.2 gm A-412 GOOD HAZY
(Aluminum)
23720-181-3 3.3 gm A-412 GOOD HAZY
(Aluminum)
23720-181-4 4.4 gm A-412 GOOD HAZY
(Aluminum)
23720-181-5 5.5 gm A-412 POOR HAZY
(Aluminum)
23720-181-6 6.6 gm A-412 POOR HAZY
(Aluminum)
23720-181-7 7.7 gm A-412 POOR HAZY
(Aluminum)
23720-18 None Galvanized POOR SLIGHTLY HAZY
Stee
23720-181-1 1.1 gm Galvanized POOR SLIGHTLY HAZY
Stee
23720-181-2 2.2 gm Galvanized GOOD SLIGHTLY HAZY
Stee
23720-181-3 3.3 gm Galvanized GOOD CLEAR
Stee
 US 6,433,131 B1
23 24
We claim: acid, Xylene Sulfonic acid, dodecyl benzene Sulfonic acid,
1. Acrylic melamine coating compositions characterized didodecyl naphthalene Sulfonic acid, didodecyl naphthalene
by improved impact resistance comprising: Sulfonic acid, dinonyl naphthalene Sulfonic acid, dinonyl
a) a polyol having an equivalent weight of about naphthalene disulfonic acid, their amine blocks, and phos
300-1300; phoric acid and combinations thereof.
b) said polyol having incorporated therein 5 to 20% by 18. The composition of claim 17 wherein said acid
weight of a polytrimethylene carbonate polyol; catalyst is used and comprises dinonyl naphthalene disul
c) a melamine crosslinking agent; phonic acid.
d) optionally a catalyst; and 19. The composition of claim 18 wherein an acid catalyst
e) optionally pigments and other additives commonly is used in an amount of 0.1 to 3.0% based on the total weight
of the resin.
used in coatings. 20. The composition of claim 19 wherein an acid catalyst
2. The composition of claim 1 wherein the polytrimeth is used in an amount of 0.5 to 2.0%, based on the total
ylene carbonate polyol is Selected from polytrimethylene weight of the resin.
carbonate diol, polytrimethylene carbonate triol, and a 21. The composition of claim 1 wherein the melamine
higher functionality polytrimethylene carbonate polyol. 15 crosslinking agent is a resin obtained by addition
3. The composition of claim 1 (a) wherein the polyol is condensation of an amine compound Selected from the
Selected from the group consisting of polyester polyols and group consisting of melamine, guanamine, and urea with
acrylic polyols. formaldehyde by art-known methods.
4. The composition of claim 3 wherein the acrylic polyol 22. The composition of claim 21 wherein Said amines
is Selected from the group consisting of copolymers of one condensed with formaldehyde are further condensed with
or more alkyl esters of acrylic acid or methacrylic acid alcohol.
optionally together with one or more other polymerizable 23. The composition of claim 22 wherein the melamine
ethylenically unsaturated monomers. crosslinking agent is Selected from the group consisting of
5. The composition of claim 4 wherein the suitable alkyl methylated melamine, butylated melamine, methylated
esters of acrylic acid or methacrylic acid are Selected from 25 benzoguanamine, and butylated benzoguanamine.
the group consisting of methyl methacrylate, ethyl 24. The composition of claim 1 wherein the melamine
methacrylate, butyl methacrylate, ethyl acrylate, butyl crosslinking agents are Selected from fully or partially
acrylate, and 2-ethylhexyl acrylate. alkylated methylolated melamine resins.
6. The composition of claim 4 wherein the copolymeriz 25. The composition of claim 24 wherein the melamine
able ethylenically unsaturated monomers are Selected from crosslinking agent is Selected from the group consisting of
the group consisting of vinyl aromatic compounds, nitrites, hexamethylol melamine, pentamethylol melamine, and tet
Vinyl and Vinylidene halides, and vinyl esters. ramethylol melamine, or mixtures of two or more thereof.
7. The composition of claim 6 further comprising the use 26. The composition of claim 1 wherein the melamine
of Suitable functional monomers for crosslinking purposes resin is Selected from hydrophilic melamines and hydropho
Selected from the group consisting of acrylic acid, meth 35 bic melamines individually, or in combinations.
acrylic acid, hydroxyalkyl acrylates, and hydroxyalkyl 27. The composition of claim 26 wherein the melamine
methacrylates. resin is hexamethoxymethylmelamine resin.
8. The composition of claim 3 wherein the polyol is 28. The composition of claim 1 wherein a pigment is used
Selected from acrylic polyols having an equivalent weight in Selected from those known in the art.
the range of 300 to 1300. 40 29. The composition of claim 28 wherein the pigment is
9. The composition of claim 8 further comprising an titanium dioxide.
acrylic polyol having a hydroxyl number in the range of 30. An acrylic melamine coating composition character
80-140 and an equivalent weight in the range of 400 to 700. ized by higher impact resistance and high gloSS which
10. The composition of claim 1 further comprising the comprises:
acrylic polyol dissolved in a Solvent Selected from the group 45 a) An acrylic polyol having an equivalent weight in the
consisting of esters, ketones, glycol ethers and esters, and range of 300 to 1300 dissolved in a suitable solvent to
alcohols. 40–70% solids;
11. The composition of claim 10 wherein the solvent is b) Said acrylic polyol having substituted therein 5 to 20%
Selected from the group consisting of butyl acetate, n-propyl by weight of a polytrimethylene carbonate polyol
acetate, methyl ethyl ketone, methyl n-propyl ketone, 50
Selected from a polytrimethylene carbonate diol and
methyl amylketone, propylene glycol methyl ether acetate, polytrimethylene carbonate triol, and higher function
ethylene glycol methyl ether acetate, and ethylene glycol ality trimethylcarbonate polyols,
diacetate.
12. The composition of claim 11 wherein the solvent is c) A methyl Substituted melamine;
Selected from glycol ethers and glycol esters and combina 55
d) Optionally a catalyst; and
tions thereof. e) Optionally pigments and other additives known in the
art.
13. The composition of claim 12 wherein the solvent is 31. Any article coated with the composition of claim 30.
propylene glycol methyl ether acetate. 32. A melamine/urea formaldehyde polytrimethylene car
14. The composition of claim 10 further comprising the bonate coating composition comprising:
use of a co-Solvent. 60
15. The composition of claim 14 wherein the co-solvent a) 5 to 80% by weight polytrimethylene carbonate,
is methyl ethyl ketone (MEK). optionally blended with 0 to 30% glycol;
16. The composition of claim 1 wherein a catalyst com b) 5 to 70% by weight melamine crosslinking agent;
prising an acid catalyst is used to accelerate the formation of c) 0 to 70% solvent; and
the composition. 65 d) Optionally a catalyst.
17. The composition of claim 16 wherein the acid catalyst 33. The composition of claim 32 wherein the melamine
is Selected from the group consisting of p-toluenesulfonic crosslinking agent is a partially alkoxylated melamine resin.
 US 6,433,131 B1
25 26
34. The composition of claim 33 wherein the melamine propanediol, 2,4-dimethyl-2-ethylhexane-1,3-diol, 2,2-
crosslinking agent is hexamethoxymethylmelamine. dimethyl-1,3-propanediol, 2-ethyl-2-butyl-1,3-propanediol;
35. The composition of claim 32 wherein a catalyst is used 2-ethyl-2-isobutyl-1,3-propanediol, 1,3-butanediol, 1,4-
and comprises an acid catalyst. butanediol, 1,5-pentanediol, 1,6-hexanediol, 2,2,4-
36. The composition of claim 35 wherein the acid catalyst trimethyl-1, 6-hexane diol; thiodie thanol; 1,2-
is Selected from the group consisting of p-toluene Sulfonic cyclohexanedimethanol; 1,3-cyclohexanedimethanol; 1,4-
acid, Xylene Sulfonic acid, dodecyl benzene Sulfonic acid, cyclohexane dime thanol; 2,2,4,4-tetramethyl-1,3-
didodecyl naphthalene Sulfonic acid, didodecyl naphthalene
Sulfonic acid, dinonyl naphthalene Sulfonic acid, dinonyl cyclobutanediol; and p-Xylylene, and combinations thereof.
naphthalene disulfonic acid, their amine blocks, and phos 39. The composition of claim 38 wherein the diol is
phoric acid and combinations thereof. 1,3-propanediol.
37. The composition of claim 32 wherein the glycol is 40. The composition of claim 39 wherein 1,3-propanediol
Selected from aliphatic, alicyclic, and aralkyl glycols. is blended in an amount of 5-25%.
38. The composition of claim 37 wherein the glycol is
Selected from ethylene glycol, propylene glycol, 1,3-