USO0804897OB2

(12) United States Patent (10) Patent No.: US 8,048,970 B2

Yahkind et al. (45) Date of Patent: Nov. 1, 2011
(54) REACTION PRODUCT OF MELAMINE (56) References Cited
ALDEHYDE RESIN AND DOL
U.S. PATENT DOCUMENTS
(75) Inventors: Alexander Leo Yahkind, West 2,358,276 A 9/1944 Hodgins et al.
Bloomfield, MI (US); Xueting Qiu, West 3,293,212 A * 12, 1966 Power et al. .................. 528,211
3,966,665 A 6, 1976 Sakata et al.
Bloomfield, MI (US); Dhruv Vrajlal 4,271,286 A * 6/1981 Michel et al. ................. 528,254
Parekh, Troy, MI (US) 4,528,344 A 7/1985 Chang
4,855,165 A 8/1989 Bolgiano et al.
(73) Assignee: Akzo Nobel Coatings International 5,750,627 A * 5/1998 St. Clair ....................... 525,162
B.V., Arnhem (NL) 6,753,386 B1* 6/2004 Yahkind et al. ............... 525/458
2002/0000536 A1 1/2002 Spitz et al.
2003/0050474 A1 3/2003 Ratzsch et al. ................ 544,204
(*) Notice: Subject to any disclaimer, the term of this 2004/0249088 A1 12/2004 Hees et al.
patent is extended or adjusted under 35 FOREIGN PATENT DOCUMENTS
U.S.C. 154(b) by 431 days.
DE 1620217 A * 9, 1966
(21) Appl. No.: 12/066,232 EP 199605 B1 * 10, 1986
FR 1274.670 10, 1961
GB 13O8697 2, 1973
(22) PCT Filed: Sep. 5, 2006 GB 1465426 A * 2, 1977
GB 1597995 A * 9, 1981
(86). PCT No.: PCT/EP2006/066O22 WO WOO3,O29318 A1 * 4, 2003
WO WOO3/091347 A1 * 11, 2003
S371 (c)(1), WO WO 2007/020269 2, 2007
(2), (4) Date: Mar. 7, 2008 OTHER PUBLICATIONS
(87) PCT Pub. No.: WO2007/028792 “Cymel Resins for coatings and specialty applications. Cytec Indus
tries, Inc., 2000, 23 pages.*
PCT Pub. Date: Mar. 15, 2007 “Cymel 325 resin.” Cytec Industries, Inc., 1999, 2 pages.*
“Cymel 303 crosslinking agents.” Cytec Industries, Inc., 2000, 2
(65) Prior Publication Data pages.*
HCAPLUS accession No. 2001:616927 for the Farbe + Lack article
US 2008/O2O785O A1 Aug. 28, 2008 by Schellekens et al., “Polyurethane polyols against acid and
scratches.” vol. 107, No. 8, 2001 and registry No. 382143-36-4 for
Related U.S. Application Data 2-buty-2-ethyl-1,3-propandiol-formaldehyde-isophorone diisocyan
ate-melamine copolymer, 2001, three pages.
(63) Continuation of application No. 1 1/221,129, filed on Hans-Georg Elias, “Macromolecules.” vol. 3, 2008, p. 26.
Sep. 7, 2005, now abandoned. Rompp Chemie Lexikon, 9" Edition, 1995, p. 2424.
(30) Foreign Application Priority Data * cited by examiner
Primary Examiner — Robert Sellers
Sep. 21, 2005 (EP) ..................................... O5108691 (74) Attorney, Agent, or Firm — Kenyon & Kenyon LLP
(51) Int. Cl. (57) ABSTRACT
B05D3/02 (2006.01)
COSL 33/10 (2006.01) Novellow viscosity oligomeric polyols and the use thereof in
C08L 6L/28 (2006.01) coating compositions are disclosed. The novel low viscosity
COSL 63/00 (2006.01) oligomeric polyols may be prepared by reacting at least one
COSL 7L/02 (2006.01) melamine aldehyde resin and at least one of C.f3-diol, C.Y-
COSL 73/04 (2006.01) diol, or mixture thereof. The reaction may occur in the pres
COL 67/02 (2006.01)
ence of an acid catalyst. Coating compositions with a low
VOC able to cure under ambient and forced dry conditions
(52) U.S. Cl. ..................... 525/509; 427/386; 427/388.3: while providing good application and performance character
525/162: 525/406; 525/427: 525/440.01; istics, such as an improved scratch resistance, are also dis
525/440.02; 525/456; 525/510 closed.
(58) Field of Classification Search ........................ None
See application file for complete search history. 10 Claims, No Drawings
 US 8,048,970 B2
1. 2
REACTION PRODUCT OF MELAMINE crosslinker to have acceptable film properties. But scratch
ALDEHYDE RESIN AND DOL and marresistance may be negatively influenced, especially
in 2K coating compositions.
REFERENCE TO RELATED APPLICATION(S) Polyurethane polyols, such as those described in U.S. Pat.
No. 6,753.386, are presently utilized in coating formulations
This application is the U.S. National Phase of PCT/ to improve Scratch resistant coatings.
However, these polyurethane polyols may be expensive to
EP2006/066022 filed on Sep. 5, 2006, which is a continuation produce based on the high cost of polyisocyanates. Further,
of prior U.S. application Ser. No. 1 1/221,129, filed on Sep. 7, although these polyurethane polyols are effective at low tem
2005, now abandoned. 10 peratures, it is desirable to have a polyol which has more
The present invention relates to novel low viscosity oligo reactivity in low bake systems.
meric polyols and the use thereof in coating compositions. Melamine formaldehyde resins are utilized as crosslinkers
The novel low viscosity oligomeric polyols are prepared by in many coating applications. However, due to their reactiv
reacting at least one melamine aldehyde resin and at least one ity, these resins have a predisposition toward self-condensa
C.f3-diol, C.Y-diol, or mixture thereof. 15
tion making them difficult to utilize. Further, melamine form
aldehyde crosslinkers are generally utilized for high bake
BACKGROUND OF THE INVENTION systems.
In EP-A-0 199 605, pigment pastes, mainly for use in
paints and ink, comprising a pigment dispersing agent and,
Many of the high solids automotive coatings presently in optionally, an organic solvent are disclosed. The pigment
use are based upon polymeric systems comprised of a binder dispersing agent may be obtained by co-condensing a triaz
comprising either polyester-based or polyacrylic-based poly ine-type amino compound, formaldehyde, a diol, and a mono
ols and crosslinking agents therefor. These coatings are gen hydric alcohol.
erally Supplied as "one-pack” or “two-pack” systems. WO 2003/091347 relates topolymeric dispersion additives
In a typical one-pack system, all of the coating ingredients with hyperbranched structures and the use of modified and
are combined into one storage-stable mixture. Upon applica 25 unmodified hyperbranched polyurethanes.
tion, the polyol component is crosslinked, generally with an WO 2003/029318 relates to polyurethane block copoly
aminoplast resin (such as a melamine resin) or a blocked mers containing one or more hydrophilic groups and the use
isocyanate, usually under heat cure conditions of 120° C. or of such copolymers as crosslinkable dispersion additives for
above. In a typical two-pack system, the polyol component is colorant preparations.
combined with a crosslinking agent, generally an isocyanate, 30 U.S. Pat. No. 4.271,286 relates to a process for the prepa
shortly before application, with curing being conducted at ration of methylolaminotriazines etherified with alkanols
having per mole of the aminotriazine 0.6n to 2n methyol
ambient and/or elevated temperatures. groups to the extent of 30% to 60%, n being the number of
Coatings used for painting motor vehicles and repairing the amino groups in the amino triazine.
original paint are desired to have good physical properties GB patent no. 1465426 relates to low viscosity mixture of
Such as hardness, mechanical strength, and resistance to 35 etherified emthyolaminotriazines with average degree of
water, acids, and solvents. The coatings are also desired to emthylolation substantially 50% to 80% for use with
have good appearance properties, providing Smooth films and hydroxyl containing resins.
a high gloss and high distinctness of image. It is also desirable U.S. Pat. No. 3,293.212 relates to reaction products of
that such coatings have an excellent car wash, Scratch, and hexaalkyl ethers of hexamethylolmelamines and bisphenols.
mar resistance. 40 DE patent no. 1620217 relates to a cleaning process for
A large number of cars and transport vehicles are coated removing residual glycol in melamine mixture.
with a multilayer topcoat System wherein an unpigmented U.S. Pat. No. 4,528.344 discloses an ungelled, crosslink
clearcoat is applied over a pigmented basecoat. Both solvent able, hydroxyl group-containing resin having a molecular
borne and water borne clearcoats and basecoats are in use. weight of less than 4500, which is the reaction product of a
So-called metallic basecoats comprise metallic flakes. 45 nonaromatic polyol having a molecular weight of less than
For environmental reasons, it is becoming increasingly 230, and an aminoplast.
important to develop polymeric systems with low solution It is an object of the present invention to provide low
Viscosities, which permit the formulation of high Solids coat Viscosity oligomeric polyols for use in coating compositions.
ings with low application viscosities suitable for spraying. It is a further object of this invention to provide low vis
High solids coatings (generally 50 wt.% or greater Solids) 50 cosity oligomeric polyols for use in coating compositions that
significantly decrease the amount of volatile organic com will cure under ambient and forced dry conditions while
pounds (VOC) entering the atmosphere upon drying/curing providing good application and performance characteristics.
of the coating. It is also an object of this invention to provide low viscosity
One way to achieve a lower solvent content is to use so oligomeric polyols forusein coating compositions with a low
called high-solids compositions. Such compositions com 55 VOC.
prise a relatively high level of non-volatile materials such as It is additionally an object of this invention to provide low
film forming polymer, pigments, and fillers, and a relatively Viscosity oligomeric polyols for use in coating compositions
low level of organic solvent. A problem when formulating resulting in dried and cured coatings with an improved
high-solids coating compositions is that such compositions scratch resistance in particular compared to coatings prepared
have an unacceptably high viscosity due to the high molecular 60 from a coating composition comprising an acrylic polyol and
weight of the conventional film forming polymer. The high a polyisocyanate compound.
Viscosity gives rise to problems in spray application with poor
paint atomization and poor flow-out and, consequently, low SUMMARY OF THE INVENTION
gloss levels and poor appearance.
The use of low-molecular weight film forming polymers 65 In accordance with the present invention, the low viscosity
results in adequate application viscosities. However, coating oligomeric polyols (hereinafter referred to as melamine poly
composition based on this type of resins generally use the ols) comprises the reaction product of
 US 8,048,970 B2
3 4
(a) at least one melamine aldehyde resin having the formula (iii) distilling the reaction mixture to remove substantially all
(I) residual alcohol,
wherein the diol (b) and the resin (a) are reacted in such
relative amounts that the ratio of the number of hydroxyl
(I) 5 groups from diol (b) to the total number of R to R groups
R6 Rs
n N1 from resin (a) is in the range of 1.25 to 2.25.
The present invention also relates to coating compositions

R s
l Nals R4 10
comprising these novel melamine polyols.
As indicated by resulting molecular weights and hydroxyl
values, it has surprisingly been found that the above
melamine aldehyde resins react with the above diols predomi
nantly single ended, despite the many potential side reactions,
R R3
including the self-condensation of the melamine resins.
15
Further, it was also unexpectedly found that coating com
wherein R to R are each selected from —H, —CHOH, positions prepared from the above diols and the melamine
—CHOR-7, and may be the same or different, wherein R, aldehyde resins in situ result in significant shrinkage in the
is a C to Cs alkyl group, coating, indicating that the present melamine polyols cannot
(b) at least one C.f3-diol, C.Y-diol, or mixture thereof, and, be made in situ in the same ratios.
optionally,
(c) a compound (c) containing a single functional group DETAILED DESCRIPTION OF THE INVENTION
capable of reacting with the melamine aldehyde resin and, Melamine Polyols
optionally, other functional groups,
wherein the diol (b) and the resin (a) are reacted in such The novel melamine polyols of the present invention are of
relative amounts that the ratio of the number of hydroxyl 25 great utility for coating compositions and comprises the reac
groups from diol (b) to the total number of R to R groups tion product of:
from resin (a) is in the range of 1.25 to 2.25. (a) at least one melamine aldehyde resin having the formula
The resulting melamine polyols have a low polydispersity, (I)
e.g. Mw/Mns3.5, or s2.5, or s2.
The melamine polyols of the present invention are pro 30
duced by reacting (I)
(a) at least one melamine aldehyde resin having the formula
(I) above,
(b) at least one C.f3-diol, C.Y-diol, or mixture thereof, and,
optionally,
(c) a compound (c) containing a single functional group
capable of reacting with the melamine aldehyde resin and,
optionally, other functional groups,
35

R s
l Nals R4
in the presence of an acid catalyst. R R3
Further, the present invention relates to a method (A) of 40
preparing melamine polyols comprising reacting at a tem wherein R to R are each selected from —H, —CHOH,
perature between about 50° C. to 130° C. —CHOR-7, and may be the same or different, wherein R,
(a) at least one melamine aldehyde resin having the formula is a C to Cs alkyl group,
(I) above, (b) at least one C.f3-diol, C.Y-diol, or mixture thereof, and,
(b) at least one C.f3-diol, C.Y-diol, or mixture thereof, and, 45
optionally,
optionally, (c) a compound containing a single functional group capable
(c) a compound (c) containing a single functional group of reacting with the melamine aldehyde resin and, option
capable of reacting with the melamine aldehyde resin and, ally, other functional groups,
optionally, other functional groups, wherein the diol (b) and the resin (a) are reacted in such
in the presence of an acid catalyst, wherein the diol (b) and the 50
relative amounts that the ratio of the number of hydroxyl
resin (a) are reacted in Such relative amounts that the ratio of groups from diol (b) to the total number of R to R groups
the number of hydroxyl groups from diol (b) to the total from resin (a) is in the range of 1.25 to 2.25.
number of R to Regroups from resin (a) is in the range of 1.25 The melamine aldehyde resins useful for the present reac
to 2.25.
The present invention also relates to another method (B) of 55
tion have the formula (I):
preparing melamine polyols comprising
(i) reacting at a temperature between about 50° C. to 80°C. R6 R5 (I)
(a) at least one melamine aldehyde resin having the for
mula (I) above,
(b) at least one C.f3-diol, C.Y-diol, or mixtures thereof, and,
optionally
(c) a compound containing a single functional group
capable of reacting with the melamine aldehyde resin
and, optionally, other functional groups, in the presence
60

R s
l Nals R4
of an acid catalyst, 65
(ii) increasing the temperature of the reaction mixture to
between 85°C. and 130° C., and
 US 8,048,970 B2
5 6
wherein R to R are each selected from —H, —CH2OH. alcohols are branched, primary monofunctional alcohols that
—CHOR, and may be the same or different, wherein R, is have two linear carbon chains with the branch point always at
a C to Cs alkyl group. In one embodiment, R, is selected the second carbon position. Guerbet alcohols are chemically
from —CH or—CH. In another embodiment, R to R are described as 2-alkyl-1-alkanols. Examples of Guerbet alco
each —CHOCH. hols include 2-ethyl-1-hexanol, 2-hexyl-1-decanol, 2-octyl
Melamine aldehyde resins of formula (I) are known in the 1-decanol, 2-octyl-1-dodecanol, 2-hexyl-1-dodecanol, and
art and many are commercially available. Examples of Suit mixtures thereof. Guerbet alcohols are commercially avail
able commercially available melamine aldehyde resins able from Sasol Chemie GmbH as Isofolo (R) alcohols.
includebut are not limited to hexamethoxymethyl (HMMM)- When a compound (c) is used, the melamine aldehyde
type melamine resins such as Cymel 303 and Cymel 303LF, 10 resin, the diol, and compound (c) are reacted together in an
available commercially from Cytec Industries Inc., and Res amount Such that the ratio of hydroxyl groups and the single
imene 747 and Resimene CE7103, available commercially functional group capable of reacting with the melamine alde
from Surface Specialties. hyde resin of compound (c) to the total number of R to R.
The melamine aldehyde resin is reacted with an O.B-diolor groups is typically in the range of 0.5 to 3, or 1 to 2.5, or 1.25
C.Y-diol, or a mixture thereof. 15 to 2.25.
In one embodiment, the C.B-diol or C.Y-diol has from 2 to In one embodiment the melamine polyols of the present
18 carbonatoms. In another embodiment it has 2 to 15 carbon invention have a number average molecular weight between
atoms. A further embodiment has 2 to 10 carbon atoms. 700 and 4000; in another embodiment between 1500 and
Examples of suitable diols include but are not limited to 3000. Within these ranges, the molecular weight of the
ethylene glycol. 1.2 propanediol. 1,3-butanediol, 2-methyl melamine polyol may be customized through the choice of
butane-1,3-diol, cyclopentene-1,3-diol. 1.2-hexanediol. the diol utilized for the reaction. In one embodiment, the
2-ethyl-1,3-hexanediol (EHDO), 2,2,4-trimethyl-1,3-pen melamine polyols have a low polydispersity, Such as
tanediol. 1,2-octanediol, 2-butyl-2-ethyl-1,3-propane diol Mw/Mns3.5, s2.5, or s2. The melamine polyols of the
(BEPD), 2,4,4-trimethyl-hexane-3,4-diol. 1,2-decanediol, present invention have a hydroxyl equivalent weight of 75 to
2,3,4,5-tetramethyl-hexane-3,4-diol, and 1.2-octade 25 350, in one embodiment in the range of 100 to 300.
canediol. Preparation of the Melamine Polyols
Optionally, a third compound (c) can be used to prepare the The melamine aldehyde resin and C.B-diol or C.Y-diols
novel melamine polyols. These compounds contain a single may be reacted in the presence of an acid catalyst. The acid
functional group capable of reacting with the melamine alde catalyst may be blocked or unblocked. Examples of suitable
hyde resin (c1) or these compounds contain a single func 30 catalysts include but are not limited to mineral acids, such as
tional group capable of reacting with the melamine aldehyde hydrochloric acid, nitric acid, and Sulphuric acid, dodecyl
resin and other functional groups (c2). benzene sulphonic acid (DDBSA), dinonylnaphthalene sul
Examples of compounds (c 1) are mono-alcohols. phonic acid (DNNSA), oxalic acid, hexamic acid, phosphoric
Examples of the other functional groups from compounds acid, alkyl phospahate esters, phthalic acid, copolymerized
(c2) include carboxyl-functional groups, ethylene oxide 35 acrylic acid, and metal salt catalysts. Such as magnesium
functional groups, ethylenically unsaturated groups, mer bromide. Zinc or magnesium nitrates may also be utilized,
capto functional groups, acetoacetate functional groups, and although discoloration may occur at temperatures greater
mixtures thereof. Also, mixtures of compounds (c 1) and (c2) than about 120° C. Sulphonic acids such as paratoluene sul
can be used. phonic acid (PTSA) is less corrosive to equipment as the
For example, stable low molecular weight hydrophilic 40 mineral acids may negatively influence the coating proper
melamine polyols for water reducible application can be pro ties. Of course, the particular choice of catalyst type and
duced by reacting carboxyl- or ethylene oxide functional amount will be dictated upon a number of factors such as the
compounds with the melamine aldehyde resin and the diol. chosen components being reacted and the chosen reaction
An example of such a compound is 2.2-bis(hydroxylmethyl) conditions. These and other factors are well-known to those
propionic acid. For UV curing applications, ethylenically 45 skilled in the art, who can make proper choices accordingly.
unsaturated compounds such as anhydride functional com The skilled person may also choose catalyst type and amount
pounds, such as maleic anhydride, or hydroxyl functional that will limit the amount of residual diol in the reaction
(meth)acrylate monomers may be reacted with the melamine mixture. Further, due to the tendency of melamine resin to
aldehyde resin and the diol. A mercapto functional melamine self-condense, the catalyst should be chosen based on the
polyol can be designed by reacting the melamine aldehdyde 50 reaction temperature being utilized.
resin and the diol with a mercapto functional compound. A In one embodiment, the acid catalyst is present in an
coating composition comprising a mercapto functional amount ranging from 0.001 to 5 wt.% on solids; in another
melamine polyol may react with polyisocyanate and epoxy 0.01 to 7.5 wt.%, in yet another 0.1 to 5 wt.%.
resins at low temperature. For applications requiring good Optionally, solvents may be added to the present reaction.
adhesion and corrosion resistance. Such as primers, and even 55 Suitable solvents include but are not limited to ketones, ester
lower viscosity, acetoacetate monomers can be incorporated acetates, alcohols and aromatics. Water-miscible solvents
into the melamine polyol. An example of such a compound is may be used such as N-methyl-2-pyrrolidone and dipropy
methoxyacetate. lene glycol dimethyl ether. In one embodiment the solvent is
In one embodiment, compound (c) is a monoalcohol. butyl acetate.
Monofunctional alcohols can be linear or branched, cyclic or 60 A neutralizing agent may be added after the reaction to
acyclic, and the alcohols can be primary, secondary or ter neutralize the acid catalyst. Examples include triethylamine,
tiary. In one embodiment, aliphatic C-2 monoalcohols are 2-(dimethylamino)-2-methyl-1-propanol, 2-amino-2-me
used; in another Co monoalcohols are used. Examples thyl-1-propanol, 2-imino-a-phenyl-3-thiazolidine ethanol,
include methanol, ethanol, butanol, 2-ethylhexanol, cyclo diethylene triamine, dimethylethanolamine, isophoronedi
hexanol, benzyl alcohol, stearyl alcohol, 4-tert, butyl cyclo 65 amine, morpholine, N,N-diethyl-p-phenylenediamine,
hexanol, and mixtures thereof. Compound (c) can be N-ethylmorphonoline, piperidine, pyridine, triethanolamine,
branched monoalcohols, such as Guerbet alcohols. Guerbet and trimethylhexanediamine.
 US 8,048,970 B2
7 8
The preparation may be carried out under a nitrogenblan avoided. Examples of readily available amino crosslinkers of
ket. the kind described above include: hexamethoxymeth
The novel melamine polyols of the present invention may ylmelamine, such as Cymel 303, available from Cytec Indus
be produced at least by one of three processes depending upon tries, Inc., mixed ether methoxy/butoxy methylmelamine,
the desired molecular weight and Solids content characteris such as Cymel 1135, also available from Cytec; polymeric
tics of the resulting melamine polyol. butoxy methylmelamine, such as M-281-M, available from
Method A Cook Composites and Polymers; and high imino polymeric
In one embodiment, the melamine aldehyde resin(s) is fed methoxymethylmelamine, such as Cymel 325, available from
into the diol component(s), in the presence of the catalyst, at Cytec. This list could include many other crosslinkers which
a temperature range between about 50° C. and about 130°C. 10 differ by degree of polymerization, imino content, free
during a two to three hour time period and held for an addi methylol content, and ratios of alcohols used for etherifica
tional time period after Such feeding is complete. Subse tion.
quently, a neutralizing agent may be added to neutralize the These aminoplast crosslinking agents can be utilized in
acid catalyst. In one embodiment, the reaction is carried out at widely varying weight ratios of melamine polyol to amino
temperatures between about 95° C. and 130° C.; in another 15 plast, generally ranging from about 90:10 to 40:60, and in one
embodiment between 115° C. and 120° C. The resulting embodiment about 90:10 to 50:50.
melamine polyols have, relative to other melamine polyols The polyisocyanate compound is a cross-linker which
according to this invention, high number average molecular reacts with hydroxy groups. Polyisocyanates are compounds
weights between about 2000 to 3000. Such melamine polyols with two or more isocyanate groups per molecule, and are
also have low viscosities, e.g. between about 25 cps and 700 well-known in the coating art. Suitable polyisocyanates are
cps, i.e. Brookfield viscosity measured at 40% solid content at aliphatic polyisocyanates Such as trimethylene diisocyanate,
25°C., spindle #4 and 20 RPM, which makes them particu 1.2-propylene diisocyanate, tetramethylene diisocyanate,
larly useful for spray applied coating compositions. 2,3-butylene diisocyanate, hexamethylene diisocyanate,
Method B octamethylene diisocyanate, 4-isocyanatomethyl-1,8-octane
In another, embodiment, the melamine aldehyde resin(s) is 25 diisocyanate, 2,2,4-trimethyl hexamethylene diisocyanate,
fed into the diol component(s)at a temperature between about 2,4,4-trimethylhexamethylene diisocyanate, dodecamethyl
50° C. and about 80°C., typically for 2-3 hours, followed by ene diisocyanate, C.C.'-dipropyl ether diisocyanate, and trans
acid catalyst neutralization and alcohol distillation at a tem vinylidene diisocyanate; alicyclic polyisocyanates, such as
perature about 85°C. to about 130° C. Subsequently, another 1.3-cyclopentylene diisocyanate, 1.2-cyclohexylene diisocy
amount of neutralizing agent may be added to neutralize the 30 anate, 1,4-cyclohexylene diisocyanate, 4-methyl-1,3-cyclo
acid catalyst further. Melamine polyols that are the reaction hexylene diisocyanate, 4,4'-dicyclohexylene diisocyanate
product of this process B will have, relative to other melamine methane, 3,3'-dimethyl-4,4'-dicyclohexylene diisocyanate
polyols of the present invention, a low number average methane, norbornane diisocyanate, and isophorone diisocy
molecular weight, e.g. between about 1500 to 2000. Such anate; aromatic polyisocyanates such as m- and p-phenylene
melamine polyols have Brookfield viscosities, between about 35 diisocyanate, 1.3- and 1,4-bis(isocyanate methyl)benzene,
1500 cps and 1800 cps at 25°C., measured as mentioned 1,5-dimethyl-2,4-bis(isocyanate methyl)benzene, 1,3,5-tri
above at 70% solid content. isocyanate benzene, 2.4- and 2,6-toluene diisocyanate, 2.4.6-
Method C toluene triisocyanate, C.C.C.'.C.'-tetramethyl o-, m-, and p-Xy
Alternatively, the process can be carried out under vacuum. lylene diisocyanate, 4,4'-diphenylene diisocyanate methane,
Then, the melamine aldehyde resin(s) is fed into the diol 40 4,4'-diphenylene diisocyanate, 3,3'-dichloro-4,4'-diphe
component(s) at a temperature between about 50° C. and nylene diisocyanate, and naphthalene-1,5-diisocyanate; and
about 80° C. under a vacuum of 50 to 100 mbar, in one mixtures of the aforementioned polyisocyanates.
embodiment for 2-3 hours, followed by acid catalyst neutral Also, such compounds may be adducts of polyisocyanates,
ization and alcohol distillation at a temperature about 50° C. e.g., biurets, isocyanurates, allophonates, uretdiones, pre
and about 80° C. under a vacuum of 50 to 100 mbar. Subse 45 polymers of polyisocyanates, and mixtures thereof.
quently, another amount of neutralizing agent may be added Examples of such adducts are the adduct of two molecules of
to neutralize the acid catalyst further. hexamethylene diisocyanate or isophorone diisocyanate to a
Coating Compositions Comprising Melamine Polyols diol such as ethylene glycol, the adduct of 3 molecules of
The invention also relates to coating compositions com hexamethylene diisocyanate to 1 molecule of water, the
prising at least one melamine polyol and at least one 50 adduct of 1 molecule of trimethylol propane to 3 molecules of
crosslinker. isophorone diisocyanate, the reaction product of 3 moles of
There are numerous kinds of hydroxyl group-reactive m-O.C.C.'.C.'-tetramethylxylene diisocyanate with 1 mole of
crosslinkers which can be used with the melamine polyols, trimethylol propane, the adduct of 1 molecule of pentaeryth
Such as polyisocyanates, blocked polyisocyanates and/or ritol to 4 molecules of toluene diisocyanate, the isocyanurate
aminoplast resins. 55 of hexamethylene diisocyanate, available from Bayer under
The aminoplast resins are generally speaking aldehyde the trade designation DesmodurRN3390 and DesmodurR)
condensation products of melamine, urea, benzoguanamine LS2025, the uretdione of hexamethylene diisocyanate, avail
or similar compounds. The most commonly used aldehyde is able from Bayer under the trade designation DesmodurR)
formaldehyde. These condensation products contain methy N3400, the allophonate of hexamethylene diisocyanate,
lol or similar alkylol groups, and these alkylol groups are 60 available from Bayer under the trade designation DesmodurR)
commonly at least partly etherified with an alcohol. Such as LS 2101, the adduct of 3 moles of toluene diisocyanate to 1
methanol or butanol, to form alkylated ethers. The crosslinker mole of trimethylol propane, available from Bayer under the
resin can be substantially monomeric or polymeric depending trade designation Desmodur R. L., and the isocyanurate of
on the desired final properties of the cured coating. Mono isophorone diisocyanate, available from Hills under the trade
meric melamine resins allow the formulation of coatings with 65 designation Vestanat(RT1890. Furthermore, (co)polymers of
higher Solids contents. Polymeric melamines are useful in isocyanate-functional monomers such as C.C.'-dimethyl-m-
coatings where the use of a strong acid catalyst should be isopropenylbenzyl isocyanate are Suitable for use.
 US 8,048,970 B2
9 10
The above-mentioned isocyanates and adducts thereof The coating composition of the present invention may be
may be present in the form of blocked isocyanates, as is applied to any Substrate. The Substrate may be, for example,
known to the skilled person. The blocking agents for the metal, plastic, wood, glass, ceramic, or another coating layer.
blocked polyisocyanate can be ketoximes, alcohols, phenolic The other coating layer may be comprised of the coating
compounds, malonic esters or acetoacetates. 5 composition of the current invention or it may be a different
The polyisocyanate compound is used in an amount Such coating composition. The coating compositions of the current
that the ratio of isocyanate groups to the total number of invention show particular utility as clearcoats, basecoats, pig
hydroxy groups in the coating composition is in the range 0.5 mented topcoats, primers, and fillers. One embodiment of the
to 3, and in one embodiment 0.8 to 2. current invention is the use of the coating composition of the
The coating composition can also comprise catalysts. 10 present invention as clearcoat. In the case of the coating
Examples of catalysts for the isocyanate-hydroxy reaction composition being a clearcoat, the basecoat may be a conven
include dibutyl tin dilaurate, triethyl amine, and the like. tional basecoat known in the coating art. The clearcoat com
Generally, 0.1 to 5 percent by weight of the active catalyst is position is then applied to the Surface of a basecoat and then
used, based on the coating formulation nonvolatile content. cured. An intermediate curing step for the basecoat may be
introduced.
Acid catalysts are used to increase the rate of the crosslink 15 The coating compositions can be applied by conventional
ing reaction in melamine-cured compositions. Generally, 0.1 means such as by spray gun, brush, or roller. Curing tempera
to 5 percent by weight of the active catalyst is used, based on
the coating formulation nonvolatile content. These acids may tures are in one embodiment between 0 and 200° C., and in
be blocked by a suitable compound, so that the catalyst is another embodiment between 20 and 100° C.
inactive until the coating is baked. Optionally, the catalyst The compositions are particularly Suitable in the prepara
may be used in an unblocked form, which may necessitate the tion of coated metal Substrates, such as in the refinish indus
formulation of a two-component coating. Examples of acids try, such as in the body shop, to repair automobiles and
which may be used include phosphoric acid, alkyl acid phos transportation vehicles and in finishing large transportation
phates, Sulfonic acid and Substituted Sulfonic acids, and vehicles Such as trains, trucks, buses, and aeroplanes. The
maleic acid or alkyl acid maleates. Examples of readily avail coating compositions comprising the novel melamine polyols
able catalysts include: para-toluenesulfonic acid (PTSA) 25 are also well in the preparation of coated plastics. Plastics are
such as Cycat 4040, available from Cytek; dodecylbenzene used in an increasing number of interior and exterior appli
sulfonic acid (DDBSA) such as Bio-Soft 5-100, available cations in the automotive industry, such as airbag covers,
from Stepan; phenyl acid phosphate (PAP); amine blocked bumpers, fascias, fenders, wing mirrors, door panels, panel
DDBSA, such as Nacure 5226 and Nacure XP-158, available hoods, panel roofs, and panel trunk lids. In another embodi
from King Industries, amine blocked PTSA, such as VP-451, 30
ment, coating formulations according to the present invention
available from Byk-Mallinckrodt; dinonylnaphthalene disul also can be used for a wide range of industrial coating appli
fonic acid (DNNDSA); and maleic acid. This list could cations including coil and wood.
include numerous additional catalysts (blocked and The foregoing description is further illustrated by the fol
unblocked) known to those skilled in the art. The type of lowing examples.
Methods
catalyst used is determined by the desired bake schedule. In the Examples set forth below the following methods
The coating compositions may also contain pigments. were used.
Inorganic as well as organic pigments can be used. The com
position can further comprise conventional additives, such as The Brookfield viscosity (CPS) was measured at 25°C.,
stabilizers, surfactants, fillers, UV-absorbers, catalyst block spindle #4, and 20 RPM.
ers, anti-oxidants, pigment dispersants, flow additives, rheol The number average and weight average molecular
ogy control agents, levelling agents, and solvents. The solvent 40 weights were measured using polystyrene standard 1940.
can be any solvent known in the art, i.e. aliphatic and/or The solid content was measured using ASTM 2D2369.
aromatic hydrocarbons. Examples include Solvesso(R) 100, The heat stability was tested at 120°F (50° C.) for 6 weeks.
toluene, Xylene, butanol, isopropanol, butyl acetate, ethyl Adhesion was tested as crosshatch according to ASTM D
acetate, acetone, methyl isobutyl ketone, methyl isoamyl 3359-95, Standard Test Methods for Measuring Adhesion by
ketone, methyl ethyl ketone, ether, ether alcohol, and ether 45 Tape Test.
ester, or a mixture of any of these. Persozhardness was tested according to ASTM D 4366-95,
In addition to the melamine polyols and the crosslinker Standard Test Methods for Hardness of Organic Coatings by
other compounds may be present in the coating composition Pendulum Damping Tests, test method B. PersoZ Pendulum
according to the present invention. Such compounds may be Hardness Test.
main binders and/or reactive diluents. Examples include 50 Tukon hardness was tested according to ASTM 1474.
hydroxyl-functional binders, e.g., polyester polyols, poly The MEK double rub test is a standard test known in the art
ether polyols, polyacrylate polyols, polyurethane polyols, for determining solvent resistance. The test involves saturat
cellulose acetobutyrate, hydroxyl-functional epoxy resins, ing a cloth with methyl ethyl ketone and rubbing the coating
alkyds, and dendrimeric polyols. These hydroxyl-functional panels with one complete forward and backward motion over
binders can be utilized in widely varying weight ratios of 55 the coating Surface.
melamine polyol to hydroxyl-functional binders, generally
ranging from about 10:90 to 90:10, and in one embodiment Film thickness was measured with a Fisher Permascope.
from about 25:75 to 75:25.
In one embodiment the coating composition comprises less EXAMPLES
than 500 g/l of volatile organic solvent based on the total
composition; in another embodiment less than 480 g/l, in yet 60 Preparation of Melamine Polyols
another embodiment less than 420 g/l. The solid content in
one embodiment is higher than 50 wt.%; in another embodi Examples 1 to 3 and Comparative Examples A and B
ment higher than 52 wt.%; and in yet another higher than 58
wt.%. Method A
The coating compositions are formulated in a 1-, 2-, or 65
3-component system, depending on the choice of crosslinker A HMMM-type melamine resin was reacted with an O.B-
and catalyst in the system. diol or C.Y-diol (examples 1, 2 and 3) and with 1,4- and
 US 8,048,970 B2
11 12
1,6-diols (comparative examples A and B). For all tests, 105.7 phonic acid. Then, the temperature was raised to 105° C. to
g of Resimene CE 7103 was fed at 120° C. into a suitable distil the methanol until a yield of 85% was reached
reactor containing the 1.67 times equivalents of the below The resulting melamine polyol has a Mn of 1997, a Mw of
specified diol (the ratio of the number of OH groups from the 5372, and a dispersity of 2.69. The solid content was 70%.
diol to the number of OCH groups from the resin the The Brookfield viscosity was 1570 cps. The experimental OH
OH:OCH ratio thus was 1.67), 40 wt.% n-butyl acetate on equivalent weight is 225.
total, and 0.5 wt.% of paratoluene sulphonic acid, based on Examples 7 to 10
solids, for 2 to 3 hours and held for an additional hour after
feeding. The use of the 1,4- and 1,6-diols, as compared to the 10 Melamine polyols were prepared and tested for heat sta
C.f3-diols and C.Y-diols, resulted in gellation during the reac bility. The Solid content, Viscosity, and molecular weights
tion. The Brookfield viscosity at 40 wt.% solid content and were measured for four polyols both initially (Table 2-A) and
the molecular weights of the melamine polyols according to after six weeks (Table 2-B).
the present invention were determined and are listed in Table The melamine polyol according to example 7 was prepared
1. 15 in a similar way as the method described in example 5
TABLE 1.
(Method A).
The melamine polyol according to example 8 was the
EX. Type of Diol Viscosity Mw Mn D (Mw/Mn) melamine polyol according to example 7, but triethylamine
was added as a neutralizer after the reaction was completed
1 Ethylene glycol 1OO 2003 817 2.45 (Method A).
2-butyl-2-ethyl-1,3- 45 3361 1802 1865
propanediol The melamine polyol according to example 9 was prepared
3 1,3-butanediol 60 5575 1723 3.23 in a similar way as the method described in example 6
A 14-butanediol Gelled n.d. n.d. n.d. (Method B).
B 16-hexane diol Gelled n.d. n.d. n.d. The melamine polyol according to example 10 was the
25 melamine polyol according to example 9, but triethylamine
was added as a neutralizer after the reaction was completed
Example 4 (Method B).
Method A TABLE 2-A
30
Initial
A melamine polyol was prepared by adding 130g of Cymel
Brookfield
303 LF to a mixture of 322 g of 2-butyl-2-ethyl-1,3-pro Ex. No. Solid content (%) Viscosity Min Mw Dispersity
panediol, 100 g butyl acetate, and 2.5 g of paratoluene Sul
phonic acid over 2 to 3 hours under 120 to 130° C. The 35
7
8
60.8
60.4
690
660
2121,7290
2121,7290
3.43
3.43
OH:OCH ratio was 2:1. The reaction was held for an addi 9 68.2 1545 1858,5962 3.2
tional hour after the feed was finished. 10 68.0 1540 1858,5962 3.2
The resulting melamine polyol has a Mn of 2167, a Mw of
5680, and a dispersity of 2.62. The solid content was 43%.
The Brookfield viscosity was 38 cps. The theoretical OH 40
equivalent weight is 160. TABLE 2-B
Six Weeks
Example 5
Brookfield
Method A Ex. No. Solid content (%) Viscosity Mn/MW Dispersity
45
7 61.8 1420 3366,10998 3.27
A melamine polyol was prepared by adding 720g of Cymel 8 59.7 590 2369,7542 3.2
303 to a mixture of 1200 g of 2-butyl-2-ethyl-1,3-pro 9 68.7 1735 2260,8074 3.57
panediol. 690 g butyl acetate, and 9.6 g of paratoluene sul 10 68.1 1510 1964,6016 3.06
phonic acid over 2 hours under 115 to 120° C. The OH:OCH 50
ratio was 1.34:1. The reaction was held for an additional hour
after the feed was finished. Example 11
The resulting melamine polyol has a Mn of 2680, a Mw of
8043, and a dispersity of 3. The solid content was 60%. The Monoalcohol Modified Melamine Polyol (Method
Brookfield viscosity was 445 cps. The experimental OH 55 B)
equivalent weight is 240.
A monoalcohol modified melamine polyol was prepared
Example 6 by adding 1365 g of Cymel 303 to a mixture of 1512 g of
2-butyl-2-ethyl-1,3-propanediol, 530 g butyl acetate, 591.5 g.
Method B
60
of 2-ethyl-1-hexanol, and 17.4 g of paratoluene Sulphonic
acid over 1-3 hours under 90°C. The reaction was held for an
A melamine polyol was prepared by adding 853 g of Cymel additional 30 minutes at 90° C. after the feed was finished.
303 to a mixture of 1409 g of 2-butyl-2-ethyl-1,3-pro Then 12.5 g of N,N-dimethyl benzyl amine was added to
panediol. 200 g butyl acetate, and 11 g of paratoluene Sul neutralize the paratoluene Sulphonic acid before raising the
phonic acid over 2 hours under 70° C. The OH:OCH ratio temperature to 105° C. A total of 350g distillates were col
was 1.34:1. The reaction was held for an additional hour at 65 lected.
70° C. after the feed was finished. 7.8 g of N,N-dimethyl The resulting melamine polyol has a Mn of 1673, a Mw of
benzyl amine was added to neutralize the paratoluene Sul 4520, and a dispersity of 2.7. The solid content was 72.2%.
 US 8,048,970 B2
13 14
Example 12 After the addition of the Cymel 303 mixture was com
pleted, the reaction mixture was held for one hour at 70° C.
Water Reducible Melamine Polyol (Method A) Subsequently, 18.07 g of dimethyl ethanolamine was added
and the temperature was increased to 105° C. Methanol dis
A water reducible melamine polyol was prepared by add 5 tillation began at +95°C. The temperature was kept at 105°C.
ing 245.7g of Cymel 303 to a mixture of 350 g of 2-butyl-2- until the desired amount of methanol was collected (the theo
ethyl-1,3-propanediol, 46.9 g of 2.2-bis(hydroxyl methyl) retical amount of methanol that can be collected is 98.5 g).
propionic acid, 50 g of N-methyl-2-pyrrolidione, 10 g of This took one to two hours. The batch was cooled downto 60°
dipropylene glycol dimethyl ether, and 3 g of paratoluene C. Dimethyl ethanolamine was added to neutralize the acid
sulphonic acid over 1.5 hours under 95°C. The reaction was 10 based on measured acid value (100% acid neutralization).
held for an additional 30 minutes at 95°C. after the feed was The resulting melamine polyol has a Mn of 1518, a Mw of
finished. The batch was cooled and 35 g of triethylamine was 3912, and a dispersity of 2.6.
added to neutralize the paratoluene Sulphonic acid. Examples 16 to 19
The resulting melamine polyol has a Mn of 2037, a Mw of 15
7691, and a dispersity of 3.78. The solid content was 60.1%. Melamine polyols were prepared and tested for heat sta
Example 13 bility. The molecular weights were measured for four polyols
after three weeks (Table 3).
The melamine polyol according to example 16 was pre
Acetoacetate Modified Melamine Polyol (Method B) pared according to Example 15 except that the acid was not
neutralized after the reaction (0% acid neutralization).
An acetoacetate modified melamine polyol was prepared The melamine polyol according to example 17 was pre
by adding 856.6 g of Cymel 303 to a mixture of 1057 g of pared according to Example 15 except that the acid was
2-butyl-2-ethyl-1,3-propanediol, 143 g butyl acetate, 255 g of neutralized for 50% after the reaction.
methoxy acetate, and 10.9 g of paratoluene Sulphonic acid 25 The melamine polyol according to example 18 was pre
over 1.5 hours under 90 to 95°C. The reaction was held for an pared according to Example 15.
additional 30 minutes at 90° C. after the feed was finished. The melamine polyol according to example 19 was pre
Then 7.5 g of N,N-dimethyl ethanol amine was added to pared according to Example 15 except that the acid was
neutralize the paratoluene Sulphonic acid before raising the neutralized for 150% after the reaction.
temperature to 105°C. Methanol was collected until a yield of 30 The initial molecular weights were: Mn 1518 and Mw
about 80% was reached 3912.
The resulting melamine polyol has a Mn of 1636, a Mw of
4859, and a dispersity of 2.97. The solid content was 64.5%. TABLE 3
Ex. No. Mn/Mw Dispersity
Example 14 35
16 O% acid neutr. 1659,4535 2.73
Preparation of Melamine Polyol Under Vacuum 17
18
50% acid neutr.
100% acid neutr.
1615,4290
1571,4086
2.66
2.6
(Method C) 19 150% acid neutr. 1559,406S 2.6

A melamine polyol was prepared by adding 170.6 g of 40

Cymel 303 to a mixture of 281.8 g of 2-butyl-2-ethyl-1,3- Coating Compositions
propanediol and 2.2 g of paratoluene Sulphonic acid over
about 3 hours under 55-60° C. at 80 mbar. The OH:OCH Examples 20 and 21 and Comparative Example C
ratio was 1.49. The reaction was held for an additional hour at
65° C. after the feed was finished. The batch was cooled and 45 Two melamine polyols prepared according to examples 4
1.8g of N,N-dimethylbenzylamine was added to neutralize and 5 were used to prepare a 1K coating composition with
the paratoluene Sulphonic acid. Then, the temperature was Cymel 303 as a crosslinker in an amount of 80 wt.%
raised to 60° C. at 80 mbar to distil the methanol. melamine polyol and 20 wt.% crosslinker based on total
The resulting melamine polyol has a Mn of 2534, a Mw of solids and 1% based on total solids of a catalyst, i.e. dodecyl
9995, and a dispersity of 3.94. The solid content was more 50 benzene sulfonic acid. Comparative Example C utilized a
than 95%. polyurethane polyol prepared from 2-butyl-2-ethyl-1,3-pro
panediol and DesmodurRN3300 ex Bayer in an equivalent
Example 15 ratio of OH:NCO of 2:1 (PUPO). All three coating formula
tions of less than 420 g/1VOC were coated onto cold roll steel
Preparation of Melamine Polyol (Method B) 55 and cured at 250°F. for 30 minutes. The Tukon hardness was
measured after 72 hours and the MEK Double Rubs were
In a 121 flask equipped with mechanical stirrer, thermo tested after 24 hours.
couple with thermowatch, heating mantle, dean Stark trap,
and an additional port fitted with a masterflex pump and #16 TABLE 4
Viton tubing, under a nitrogen blanket, a mixture of 4931.5 g. 60
Ex. No. Type of Polyol Tukon Hardness MEK Double Rubs
of 2-butyl-2-ethyl-1,3-propanediol, 700 g of n-butyl acetate,
and 38.5 g of paratoluene sulphonic acid was loaded. The 2O Ex. 4 10.8 100+
mixture was heated to 70° C. and held until the diol was 21 Ex. S 13.0 100+
C PUPO 16.9 100+
melted and formed a homogeneous Solution. At a mixing
speed of 150 RPM and at 70° C. a mixture of 2985.5g Cymel 65
303 and 850 g of n-butyl acetate was added drop wise over a As can be seen in the above Table 4, all of the test panels
1 to 2 hours period using the masterflex pump. were unchanged after 100 double rubs. Thus, the melamine
 US 8,048,970 B2
15 16
polyols of the present invention produced 1K coatings that TABLE 7
had good chemical resistance and good film hardness.
Ambient Curing
Examples 22 and Comparative Example D Ex. No. Film Thickness (mills) Hardness (Persoz). MEK (Double Rub)
26 2.02 241 100+
A melamine polyol prepared according to example 5 was
used to prepare a 2K coating composition with Desmodur R.
N3300 as a crosslinker in an equivalent ratio of NCO:OH of As can be seen above, the 2K coating formulation demon
1.2:1. No catalyst was utilized. Comparative Example Duti 10
strated excellent properties at ambient temperature cure.
lized the above-mentioned PUPO. The two coating formula Examples 27 and 28 and Comparative Example E
tions (less than 420 g/1 VOC) were coated onto cold roll steel
and cured at 180° F (80° C.) for 30 minutes. The dry film
thickness was 1.4-1.5 mils. The Tukon hardness was mea Three 420 g/l VOC clear coat formulations were prepared
sured after 1 hour, 24 hours, and 72 hours and the MEK as set forth in the Table 8 below.
15
Double Rubs were tested after 72 hours.
TABLE 8
TABLE 5 clear coat formulations
Tukon Hardness Comparative
Example 27 Example 28 Example E
Ex. No. Type of Polyol 1 hr 24hr 72 hr MEK Double Rubs Raw material % by weight % by weight % by weight
22 Ex. S 2.3 7.2 12.3 100+
Melamine polyol from 16.14 17.60
D PUPO S.42 9.73 10.1 100+ Example 6
Polyacrylate polyol 29.43 49.33
25 Setalux 27-9712
As can be seen in the above Table 5, all of the test panels Polyester polyol
Setal 26-9552
30.12
were unchanged after 100 double rubs. Thus, the melamine Arylic flow control O45 O.SO O.45
polyol of the present invention produced a 2K coating that had agent Coroc A 620
good chemical resistance and good film hardness. ex CCP
30 10% dibutyl tin O.OS O.O6 O.OS
dilaurate solution
Examples 23 to 25 1.2-Propane diol 2.74 2.97 2.73
methyl acetate
Butyl acetate 27.24 22.69 27.31
A melamine polyol prepared according to example 5 was isocyanurate of 23.95 26.06 20.13
utilized to produce a 2K coating formulation with Desmo 35 hexamethylene
durRN75 ex Bayer as a crosslinker in an equivalent ratio of diisocyanate
NCO:OH of 1.1:1. No catalyst was utilized. Steel panels were (Desmodur N3390)
coated with the 2K formulation (less than 420 g/1 VOC) and total 1OOOO 100.00 100.00
Subject to curing at different temperatures. The panels were
tested after 24 hours for film thickness, hardness, MEK, and 40
adhesion. Steel panels were coated with a black two component Akzo
Nobel AT 331 basecoat at a dry film thickness of about 20
TABLE 6 microns. The clear coat compositions as prepared above were
applied by spray gun over the basecoat in a wet-on-wet appli
Temperature Effects cation. The coatings were baked at 180° F (82° C.) for 30
45 minutes. The properties of the coating compositions were
Curing Film MEK compared to the control system where the clear coat had no
Ex. Conditions Thickness Hardness (Double Adhe melamine polyol.
No. Temp. Time (mils) (Persoz) Rub) sion All systems performed similar in terms of cure response as
measured by Tukon hardness and MEK double rubs.
23 Ambient 24hr 2.16 65 62 10 50 One test where the compositions according to the invention
24
2S
140 F.
180 F.
10 min
10 min
2.39
2.56
55
1OO
90
100-
10
10
performed Superior to the control coating composition was
the gloss retention by the Car Wash test. The ability of a
coating to perform against Scratches encountered during car
As can be seen in the above Table 6, 2K coatings compris wash is simulated in the Car wash bench tester, approved as
ing melamine polyols according to the present invention pro 55 test equipment in OEM specification. The % gloss loss after
the test is a measurement of Scratch resistance. How much
vided excellent properties at a range of curing temperatures. lower the number, how much better the scratch resistance.
In duplicate testing for this test, the coating composition of
Example 26 Example 27 based on acrylic polyol showed about 50% less
60
reduction in gloss than the control E. The coating composi
tion of Example 28 based on polyester polyol showed about
A melamine polyol prepared according to example 4 was 30% less reduction in gloss than the control E.
utilized to produce a 2K coating with DesmodurR N75 ex
Bayer as a crosslinker in an equivalent ratio of NCO:OH of Example 29 and Comparative Example F
1.1:1. No catalyst was utilized. A steel panel was coated with
the 2K formulation (less than 420 g/l VOC) and subject to 65 A melamine polyol prepared according to example 2 was
curing at ambient temperature. After one week, film thick evaluated in a 1K clear coat along with a coating composition
ness, hardness and MEK of the coating were measured. comprising the reactants Cymel 303 and 2-m-butyl-2-ethyl-1,
 US 8,048,970 B2
17 18
3-propanediol in the same ratio as used to prepare the (a) at least one melamine aldehyde resin having the
melaminepolyol. The 1K coating composition comprises the formula (I)
melamine polyol or its reactants and Cymel 303 as a
crosslinker in an amount of 80 wt.% melamine polyol and 20
wt.% crosslinker based on total solids and 0.5 wt.% based on (I)
total solids of a catalyst, i.e. blocked dodecylbenzene sulfonic R6 Rs
n N1
acid.
Although both these coating compositions had cure
response in a pot, according to ASTM 2369 (1 hour, 110°C.)
comparative Example F showed a drop by about 14% in
non-volatiles when compared to its theoretical%. This indi
cates that some 2-n-butyl-2-ethyl-1,3-propanediol has vola
10
R l Nals R4 s
tilized during the curing process. In contrast, a coating com R R3
position based on the melamine polyol according to the
invention showed no significant difference (less than 3%) 15
between the theoretical and experimental values in % non wherein R to R are each selected from —H,
volatiles. —CH2OH. —CHOR-7, and may be the same or
Example 30 different, wherein R, is a C to Cs alkyl group
(b) at least one C.Y-diol, wherein the C.Y-diol is 2-butyl
A clear coat composition was prepared with a polyacrylate 2-ethyl-1,3-propane diol
polyol prepared according to Example A4 disclosed in non wherein the diol (b) and the resin (a) are reacted in such
published patent application EP 05107563.8 and a melamine relative amounts that the ratio of the number of
polyol according to the present invention. The clear coat hydroxyl groups from diol (b) to the total number of
composition was prepared as set forth in the Table 9 below R to R groups from resin (a) is in the range of 1.25 to
25 2.25, and
TABLE 9 ii) a crosslinker which is a blocked or unblocked polyiso
cyanate.
clear coat formulations
2. The coating composition according to claim 1, wherein
Example 30 R to R are the same.
Raw material % by weight 30 3. The coating composition according to claim 1, wherein
Melamine polyol from Example 15 (83% s.c.) 52.1 R to R are each —CHOCH.
Polyacrylate polyol (Example A4) (74% s.c.) 32.2 4. The coating composition according to claim 1, wherein
Byk 331 (12% s.c.) 1.1
Benzoic acid (12% s.c.) 14.1 the melamine polyol has a number average molecular weight
10% dibutyl tin dilaurate solution 1.5 between 700 and 4000.
35
Tinuvin 292
Tinuwin 1130
1.2
0.7
5. The coating composition according to claim 1, wherein
Butylglycol acetate 4.5 the melamine polyol is the reaction product of further:
Butyl acetate 42.1 (c) a compound (c) containing a single functional group
Tolonate HDTLV 52.9 capable of reacting with the melamine aldehyde resin.
40 6. The coating composition according to claim 5, wherein
The clear coat formulation had a NCO: OH ratio of 1:1. The the compound (c) further contains other functional groups.
Solid content of the coating composition was 61.4%. The 7. The coating composition according to claim 1 further
VOC was 389 g/l. comprising a hydroxyl functional binder.
A steel panels was coated with a dark grey metallic water 8. The coating composition according to claim 1, wherein
based basecoat composition. The clear coat as prepared above 45
the composition is a clear coat composition.
was applied by spraygun over the basecoat. The bottom of the
panel received an additional layer to check pinhole sensitiv 9. A method of coating an automobile, said method com
ity. The coatings were cured at 60° C. The properties of the prising applying a coating composition according to claim 1
coating compositions are listed in Table 10. to at least a portion of the Surface of an automobile.
TABLE 10

Viscosity
(sec, DC4) Curing 60° C. Persoz Hardness

Ex. 40 90 15 25 2 1 7
No. Start min. min. min. min. hrs day days Appearance

30 13.8 16.7 22.4 FTH, FTH, 22 70 87 7, no defects

very tacky (no pinholes)
tacky

The invention claimed is:

65
10. The method according to claim 9, wherein the method
1. A coating composition comprising is implemented for repairing the automobile.
i) a melamine polyol comprising the reaction product of k k k k k