U.S. patent application number 11/611987 was filed with the patent office on 2008-06-19 for golf balls comprising (meth)acrylated amine curatives.
Invention is credited to Ronald R. Ambrose, Anthony M. Chasser, Susan Donaldson, Constantine A. Kondos, Jonathan T. Martz, John E. Schwendeman.
Application Number | 20080146381 11/611987 |
Document ID | / |
Family ID | 39387264 |
Filed Date | 2008-06-19 |
United States Patent
Application |
20080146381 |
Kind Code |
A1 |
Kondos; Constantine A. ; et
al. |
June 19, 2008 |
GOLF BALLS COMPRISING (METH)ACRYLATED AMINE CURATIVES
Abstract
Golf balls having a core and a layer disposed about the core are
disclosed. The layer comprises a polyurea formed from the reaction
of an isocyanate and a (meth)acrylated amine. Sports equipment
comprising such a polyurea are also disclosed.
Inventors: |
Kondos; Constantine A.;
(Pittsburgh, PA) ; Ambrose; Ronald R.;
(Pittsburgh, PA) ; Schwendeman; John E.; (Wexford,
PA) ; Martz; Jonathan T.; (Glenshaw, PA) ;
Chasser; Anthony M.; (Allison Park, PA) ; Donaldson;
Susan; (Allison Park, PA) |
Correspondence
Address: |
PPG INDUSTRIES INC;INTELLECTUAL PROPERTY DEPT
ONE PPG PLACE
PITTSBURGH
PA
15272
US
|
Family ID: |
39387264 |
Appl. No.: |
11/611987 |
Filed: |
December 18, 2006 |
Current U.S.
Class: |
473/378 |
Current CPC
Class: |
A63B 37/0054 20130101;
A63B 37/0075 20130101; C08G 18/10 20130101; A63B 37/0074 20130101;
C08G 18/3821 20130101; C08G 18/10 20130101; C08G 18/10 20130101;
C08G 18/5024 20130101; C08G 18/758 20130101; C08G 18/50 20130101;
C08G 18/792 20130101; A63B 37/0003 20130101; C08G 18/3821 20130101;
C08G 18/088 20130101; C08G 18/10 20130101; A63B 37/0058
20130101 |
Class at
Publication: |
473/378 |
International
Class: |
A63B 37/14 20060101
A63B037/14 |
Claims
1. A golf ball comprising: a) a core b) a layer disposed about the
core, wherein the layer comprises a polyurea fanned from the
reaction of an isocyanate and a (meth)acrylated amine.
2. The golf ball of claim 1, wherein the amine comprises
diaminodicyclohexylmethane.
3. The golf ball of claim 1, wherein the amine comprises
3,3'-dimethyl-4,4'-diaminodicyclohexyl methane.
4. The golf ball of claim 1, wherein the amine comprises a
difunctional, amine terminated polypropylene glycol having an
average molecular weight of 4000.
5. The golf ball of claim 4, wherein the amine further comprises a
difunctional, amine terminated polyethylene glycol having an
average molecular weight of 600.
6. The golf ball of claim 1, wherein the (meth)aerylated amine is
prepared by reacting: a) a poly(meth)aerylate; b) an amine; and c)
a mono(meth)aerylate.
7. The golf ball of claim 6, wherein the poly(meth)acrylate
comprises polyacrylated and wherein the mono(meth)acrylate
comprises monoacrylate.
8. The golf ball of claim 7, wherein the amine comprises
diaminodicyclohexylmethane.
9. The golf ball of claim 7, wherein the amine comprises
3,3'dimethyl-4,4'-diaminodicyclohexyl methane.
10. The golf ball of claim 7, wherein the amine comprises a
difunctional, amine terminated polypropylene glycol having an
average molecular weight of 4000.
11. The golf ball of claim 7, wherein the amine further comprises a
difunctional, amine terminated polyethylene glycol having an
average weight of 600.
12. The golf ball of claim 7, wherein the amine comprises IPDA.
13. The golf ball of claim 7, wherein the polyacrylate comprises
hexanediol diacrylate, the amine comprises IPDA, and the
monoacrylate comprises butylacrylate.
14. The golf ball of claim 7, wherein the polyacrylate comprises
hexanediol diacrylate, the amine comprises
3,3'-dimethyl-4,4'-diaminodicyclohexyl methane, and the
monoacrylate comprises methyl acrylate.
15. The golf ball of claim 1, wherein the layer is a cover
layer.
16. The golf ball of claim 15, wherein the cover layer has a
thickness of 0.001 inches to 0.125 inches.
17. The golf ball of claim 1, wherein the golf ball further
comprises at least one intermediate layer disposed between the core
and the layer disposed about the core.
18. The golf ball of claim 1, wherein the polyurea further
comprises a colorant.
19. The golf ball of claim 1, wherein the polyurea has a Shore D
hardness of 55.
20. The golf ball of claim 19, wherein the layer has a Ts of at
least 60, as measured by thermal mechanical analysis.
21. The golf ball of claim 1, wherein the (meth)acrylated amine is
prepared by reacting: a) a (meth)aerylate; b) a polyamine; and c) a
dialkyl maleate and/or dialkyl fumarate.
22. The golf ball of claim 21, wherein the amine comprises
3,3'-dimethyl-4,4'-diaminodicyelohexyl methane and the
(meth)acrylate comprises hexanediol diacrylate and/or methyl
acrylate.
23. Sports equipment comprising a polyurea formed from the reaction
of an isocyanate and a (meth)acrylated amine.
24. The golf ball of claim 1, wherein the golf ball has a Shore D
hardness of 38 to 65.
25. The golf ball of claim 1, wherein the isocyanate comprises a
prepolymer.
26. The golf ball of claim 25, wherein the prepolymer comprises the
reaction product of 4,4'-methylenedicyclohexyl diisocyanate and a
difunctional amine terminated polypropylene glycol.
27. The golf ball of claim 26, wherein the glycol has an average
molecular weight of 2000.
28. The golf ball of claim 26, wherein the glycol has an average
molecular weight of 4000 or greater.
29. The golf ball of claim 1, wherein the (meth)aerylated amine
comprises the reaction product of polyetheramine and acrylate.
30. The golf ball of claim 29, wherein the acrylate comprises
methyl acrylate.
Description
FIELD OF THE INVENTION
[0001] The present invention is directed to golf balls comprising a
core and a layer disposed about the core; the layer comprises
polyurea formed from the reaction of an isocyanate and a
(meth)acrylated amine.
BACKGROUND OF THE INVENTION
[0002] The use of amines and polyamines as crosslinkers or
"curatives" is well known. For example, amines are known to
crosslink with isocyanates to form urea compounds. Amines are also
known to be reactive with, and therefore used with, activated
unsaturated groups, epoxy groups, aromatic activated aldehyde
groups, cyclic carbonate groups, and acid and anhydride and ester
groups. Polyamine crosslinkers with primary amino groups can be
quite reactive with some of these functionalities under ambient or
low temperature conditions (i.e. less than 100.degree. C.). This
high reactivity can result in too short a potlife. Certain
aliphatic secondary amines, however, are not reactive enough with
these various functionalities. It is therefore desired to provide
amine curatives that are sufficiently reactive, but that provide an
adequate potlife. Such curatives can be reacted, for example, with
isocyanates to produce polyureas that can be used in the formation
of golf balls.
SUMMARY OF THE INVENTION
[0003] The present invention is directed to golf balls comprising a
core, and a layer disposed about the core, wherein the layer
comprises a polyurea formed from the reaction of an isocyanate and
a (meth)acrylated amine. The present invention is further directed
to sports equipment comprising a polyurea formed from the reaction
of an isocyanate and a (meth)acrylate amine.
DETAILED DESCRIPTION OF THE INVENTION
[0004] The present invention is directed to golf balls comprising a
core and a layer disposed about the core, wherein the layer
comprises a polyurea formed from the reaction of an isocyanate and
a (meth)acrylated amine. These acrylated amines are generally
prepared by reacting a (meth)acrylate and a polyamine. In certain
embodiments, the (meth)acrylated amines are generally prepared by
reacting a (meth)acrylate, a dialkyl maleate and/or dialkyl
fumarate, and a polyamine. Dialkyl maleate and/or dialkyl fumarate
are sometimes referred to herein as "maleate(s)--fumarate(s)", and
like terms. All of these reaction products are referred to
collectively herein as "(meth)acrylated amine", "(meth)acrylated
amine curative" and like terms. Those embodiments in which
maleates-fumarates are also used in the reaction product may
sometimes be referred to herein as a (meth)acrylate/aspartate
amine, a (meth)acrylate/aspartate amine curative and like terms,
but these embodiments are also included in the more general terms
"(meth)acrylated amine" and "(meth)acrylated amine curative" and
like terms.
[0005] The (meth)acrylate can be any suitable mono or poly
(meth)acrylate. In certain embodiments, the polyacrylate comprises
di(meth)acrylate, in certain embodiments the polyacrylate comprises
tri(meth)acrylate, and in certain embodiments the polyacrylate
comprises tetra(meth)acrylate. Suitable monoacrylates include but
are not limited to those having the formula:
##STR00001##
wherein R is H or methyl and R.sup.1 may be, without limitation,
alkyl or hydroxyalkyl, such as methyl, ethyl, 2-hydroxyethyl,
1-methyl-2-hydroxyethyl, 2-hydroxypropyl, propyl, isopropyl,
n-butyl, 2-hydroxybutyl, 4-hydroxybutyl, isobutyl, sec-butyl,
tert-butyl, hexyl, 2-ethylhexyl, cyclohexyl, methylcyclohexyl,
trimethylcyclohexyl, isobornyl, lauryl, stearyl and the like.
Non-limiting examples of mono (meth)acrylates include methyl
(meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl
(meth)acrylate, isobutyl (meth)acrylate, sec-butyl (meth)acrylate,
tert-butyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-ethylhexyl
(meth)acrylate, isooctyl (meth)acrylate, isodecyl (meth)acrylate,
lauryl (meth)acrylate, stearyl (meth)acrylate, isobornyl
(meth)acrylate, hydroxyethyl (meth)acrylate, hydroxypropyl
(meth)acrylate, 2-hydroxybutyl (meth)acrylate, 4-hydroxybutyl
(meth)acrylate, and adducts of hydroxy (meth)acrylates with
lactones such as the adducts of hydroxyethyl (meth)acrylate with
.epsilon.-caprolactone. Suitable diacrylates include ethylene
glycol di(meth)acrylate, 1,3-butylene glycol di(meth)acrylate,
1,4-butanediol di(meth)acrylate, 2,3-dimethylpropane
1,3-di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, propylene
glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate,
tripropylene glycol di(meth)acrylate, tetraethylene glycol
di(meth)acrylate, tetrapropylene glycol di(meth)acrylate,
ethoxylated hexanediol di(meth)acrylate, propoxylated hexanediol
di(meth)acrylate, neopentyl glycol di(meth)acrylate, alkoxylated
neopentyl glycol di(meth)acrylate, hexylene glycol
di(meth)acrylate, diethylene glycol di(meth)acrylate, polyethylene
glycol di(meth)acrylate, polybutadiene di(meth)acrylate,
thiodiethyleneglycol di(meth)acrylate, trimethylene glycol
di(meth)acrylate, triethylene glycol di(meth)acrylate, alkoxylated
hexanediol di(meth)acrylate, alkoxyolated neopentyl glycol
di(meth)acrylate, pentanediol di(meth)acrylate, cyclohexane
dimethanol di(meth)acrylate, ethoxylated bisphenol A
di(meth)acrylate, and mixtures thereof. Non-limiting examples of
tri and higher (meth)acrylates include glycerol tri(meth)acrylate,
trimethylolpropane tri(meth)acrylate, ethoxylated
trimethylolpropane tri(meth)acrylate, propoxylated
trimethylolpropane tri(meth)acrylate, ditrimethylolpropane
tetra(meth)acrylate, pentaerythritol tetra(meth)acrylate,
ethoxylated pentaerythritol tetra(meth)acrylate, propoxylated
pentaerythritol tetra(meth)acrylate, and dipentaerythritol
penta(meth)acrylate. Other suitable acrylate oligomers include
(meth)acrylate of epoxidized soya oil, urethane acrylates of
polyisocyanates and hydroxyalkyl (meth)acrylates and polyester
acrylates. Mixtures of (meth)acrylate monomers may also be used,
including mixtures of mono, di, tri, and/or tetra (meth)acrylates.
(Meth)acrylates higher than di (meth)acrylates (e.g. tri, tetra,
and the like) will typically only be used in minor amounts to avoid
gelling of the product. One skilled in the art can determine what
amount of these (meth)acrylates is suitable.
[0006] Any suitable polyamine can be used according to the present
invention. A "polyamine" is an amine with at least 2 primary amino
groups. In certain embodiments, the polyamine is a diamine, and the
amine nitrogens on the diamine are equally reactive; that is, all
of the amine nitrogens are equally likely to react with another
functional group. In certain other embodiments, the amine nitrogens
of the diamine may be unequal in reactivity toward, for example,
(meth)acrylates and/or maleates-fumarates. Examples of suitable
diamines include but are not limited to ethylene diamine,
1,2-diaminopropane, 1,5-diamino-2-methylpentane (DYTEK A, Invista),
1,3-diaminopentane (DYTEK EP, Invista), 1,2-diaminocyclohexane
(DCH-99, Invista), 1,6-diaminohexane, 1,11-diaminoundecane,
1,12-diaminododecane, 3-(cyclohexylamino)propylamine,
1-amino-3,3,5-trimethyl-5-aminomethylcyclohexane, (isophorone
diamine ("IPDA")), 4,4'-diaminodicyclohexylmethane (PACM-20, Air
Products; DICYKAN, BASF), 3,3'-dimethyl-4,4'-diaminodicyclohexyl
methane (DIMETHYL DICYKAN or LAROMIN C260, BASF; ANCAMINE 2049, Air
Products), 3,3'-[1,4-butanediylbis-(oxy)bis]-1-propanamine,
menthanediamine, and diamino functional polyetherpolyamines having
aliphatically bound primary amino groups, examples of which include
JEFFAMINE D-230, JEFFAMINE D-400, JEFFAMINE D-2000, and JEFFAMINE
D-4000, Huntsman Corporation. It will be appreciated that when the
amine is hindered, the reaction time between the (meth)acrylated
amine and the isocyanate will be slower. This gives a longer
pot-life or work processing time in those situations where a longer
processing time is desired.
[0007] In certain embodiments the amine is a triamine. Examples of
suitable triamines include but are not limited to diethylene
triamine, dipropylene triamine, bis(hexamethylene) triamine and
triamino functional polyetherpolyamines having aliphatically bound
primary amino groups (JEFFAMINE T-403, T-3000, T-5000, Huntsman
Corporation). For example, the amine can be an amine terminated
(that is, an amine on each end, thus rendering the amine
difunctional) polyethylene or polypropylene glycol, such as a
polypropylene having an average molecular weight of 4000 or a
polyethylene having an average molecular weight of 600. One skilled
in the art will understand that these types of products are sold
with a mixture of polymers having a relatively wide range of
molecular weight, such as 4000+/-500 or 600+/-200 but that the
average molecular weight is 4000 or 600. In other embodiments the
amine can be a tetraamine or other higher functional amine.
[0008] In certain specific embodiments of the present invention,
the (meth)acrylate is acrylate and the polyamine is
diaminodicyclohexyl methane. In other certain specific embodiments,
the (meth)acrylate is acrylate and the polyamine is
3,3'-dimethyl-4,4'-diaminodicyclohexyl methane. In certain other
specific embodiments, the amine is JEFFAMINE D4000, a difunctional,
amine terminated polypropylene glycol having an average molecular
weight of 4000, and in other specific embodiments the amine is XTJ
500, a difunctional, amine terminated polyethylene glycol having an
average molecular weight of 600, and commercially available from
Huntsman. The amine and acrylate can be reacted in any ratio to
give a suitable product. In certain embodiments, the equivalent
ratio of amine to (meth)acrylate is substantially
stoichiometric.
[0009] In certain other embodiments, both a monoacrylate and a
polyacrylate can be reacted with the polyamine. The polyacrylates,
polyamines, and monoacrylates can be as described above. In
particularly suitable embodiments, the polyacrylate is hexanediol
diacrylate, the amine is 3,3'-dimethyl-diaminodicyclohexyl methane,
and the monoacrylate is methyl acrylate. In other particularly
suitable embodiments, the polyacrylate is HDDA, the amine is IPDA,
and the monoacrylate is butylacrylate.
[0010] The ratio of poly(meth)acrylate to amine to
mono(meth)acrylate can be any suitable ratio to give the desired
properties to the (meth)acrylated amine curative. For example, when
the (meth)acrylate is a diacrylate, the equivalent ratio of
poly(meth)acrylate:amine:mono(meth)acrylate can be 0.20-0.40:
1:0.75-0.55, such as 0.30:1:0.65; 2:3:1; 1:2:1; or 1:3:2. When the
poly(meth)acrylate is a triacrylate, the equivalent ratio of
triacrylate:amine:mono(meth)acrylate can be 1:3:2 or 1:2:1. It will
be appreciated that these ratios are just examples, and that any
other suitable ratio can be used according to the present
invention.
[0011] The (meth)acrylated amines used in the present invention can
be formed, for example, in the manner described in the examples, or
any other suitable manner. When both a mono(meth)acrylate and
poly(meth)acrylate are used, the poly(meth)acrylate and amine can
be reacted first, and then reacted with a mono(meth)acrylate in
sequential steps, or the polyamine can be reacted with the
poly(meth)acrylate and mono(meth)acrylate simultaneously. The
equivalent ratio of (meth)acrylated:polyamine and/or
poly(meth)acrylate:polyamine:mono(meth)acrylate can be any of those
described above or any other suitable ratio; it will be
appreciated, however, that use of a stoichiometrically equivalent
amount of polyamine, or an excess of polyamine, may be desired. In
this manner, the polyamine and poly(meth)acrylate react such that
there is at least some amine termination. The result is a
(meth)acrylated amine that is reactive and thus can function as a
curative.
[0012] Any dialkyl maleates and/or dialkyl fumarates can be used
according to present invention. Examples of maleates and fumarates
include but are not limited to esters of maleic acid and fumaric
acid with monoalcohols such as dimethyl, diethyl, di-n-propyl,
di-isopropyl, di-n-butyl, di-sec-butyl, di-tert-butyl, di-isobutyl,
di-penyl, di-t-amyl, di-hexyl, cyclohexyl and di-2-ethylhexyl
maleates or the corresponding fumarates. In certain embodiments,
dialkyl maleates or dialkyl fumarates with two different alkyl
groups and/or mixtures of dialkyl maleates and dialkyl fumarates
can be used. The alkyl groups of dialkyl maleate and/or dialkyl
fumarate may comprise additional functional groups such as hydroxyl
groups, such as the reaction product of maleic anhydride, an
alcohol, and an epoxy, the reaction product of maleic acid or
fumaric acid with an alcohol and an epoxy, or the reaction product
of maleic acid or fumaric acid with an epoxy. Suitable alcohols
include but are not limited to methanol, ethanol, propanol,
isopropanol, butanol, isobutanol, sec-butanol, tert-butanol,
various isomeric pentanols, various isomeric hexanols,
cyclohexanol, 2-ethylhexanol, and the like. Suitable epoxies
include but are not limited to ethylene oxide, propylene oxide,
1,2-epoxybutane, and glycidyl neodecanoate (an example of which is
CARDURA E10P, Hexion Speciality Chemicals, Inc.).
[0013] It will be appreciated that the (meth)acrylated amine
curatives described above can be reacted with any other
functionality to form, for example, a coating. In a particular
example, the (meth)acrylated amine curative is reacted with an
isocyanate to form a urea. It will be appreciated that the various
polyamines, (meth)acrylates and in certain embodiments
maleates-fumarates as described above can be selected so as to
impart the desired properties to the resulting coating. Certain
desired properties that can be affected through selection of
various polyamines and/or (meth)acrylates and/or maleates-fumarates
include glass transition temperature ("Tg"), softening point
("Ts"), "tack time", and Shore D hardness.
[0014] For example, when the (meth)acrylated amine curatives
described above are reacted with an isocyanate to form a urea
coating, the urea coating will have different physical properties
as compared with when other amine curatives are used. Any suitable
isocyanate can be reacted with the acrylated amine to form a
polyurea.
[0015] As used herein, the term "isocyanate" includes unblocked
compounds capable of forming a covalent bond with a reactive group
such as a hydroxyl or amine functional group. In alternate
non-limiting embodiments, the isocyanate of the present invention
can be monomeric containing one isocyanate functional group (NCO)
or the isocyanate of the present invention can be polymeric, i.e.
"polyisocyanates", containing two or more isocyanate functional
groups (NCOs). The polyisocyanates can be selected from monomers,
prepolymers, oligomers, or blends thereof. In an embodiment, the
polyisocyanate can be C.sub.2-C.sub.20 linear, branched, cyclic,
aromatic, or blends thereof.
[0016] Suitable isocyanates for use in the present invention may
include but are not limited to isophorone diisocyanate (IPDI),
which is 3,3,5-trimethyl-5-isocyanato-methyl-cyclohexyl isocyanate;
hydrogenated materials such as cyclohexylene diisocyanate,
4,4'-methylenedicyclohexyl diisocyanate (H.sub.12MDI); mixed
aralkyl diisocyanates such as tetramethylxylyl diisocyanates,
OCN--C(CH.sub.3).sub.2--C.sub.6H.sub.4C(CH.sub.3).sub.2--NCO;
polymethylene isocyanates such as 1,4-tetramethylene diisocyanate,
1,5-pentamethylene diisocyanate, 1,6-hexamethylene diisocyanate
(HMDI), 1,7-heptamethylene diisocyanate, 2,2,4-and
2,4,4-trimethylhexamethylene diisocyanate, 1,10-decamethylene
diisocyanate and 2-methyl-1,5-pentamethylene diisocyanate; and
mixtures thereof.
[0017] Examples of aromatic isocyanates for use in the present
invention may include but are not limited to phenylene
diisocyanate, toluene diisocyanate (TDI), xylene diisocyanate,
1,5-naphthalene diisocyanate, chlorophenylene 2,4-diisocyanate,
bitoluene diisocyanate, dianisidine diisocyanate, tolidine
diisocyanate, alkylated benzene diisocyanates,
methylene-interrupted aromatic diisocyanates such as
methylenediphenyl diisocyanate, 4,4'-isomer (MDI) including
alkylated analogs such as 3,3'-dimethyl-4,4'-diphenylmethane
diisocyanate, polymeric methylenediphenyl diisocyanate; and
mixtures thereof.
[0018] In certain embodiments, an excess of polyisocyanate monomer
(i.e., residual free monomer from the preparation of prepolymer)
may be used to decrease the viscosity of the polyurea composition
thereby improving its flowability, and, when used in a coating, may
provide improved adhesion of the polyurea coating to a previously
applied coating and/or to an uncoated substrate. In alternate
embodiments of the present invention, at least 1 percent by weight,
or at least 2 percent by weight, or at least 4 percent by weight of
the isocyanate component comprises at least one polyisocyanate
monomer (i.e. residual free polyisocyanate monomer).
[0019] In a further embodiment of the invention, the isocyanate can
include oligomeric polyisocyanates including but not limited to
dimers, such as the uretdione of 1,6-hexamethylene diisocyanate,
trimers, such as the biuret and isocyanurate of
1,6-hexanediisocyanate and the isocyanurate of isophorone
diisocyanate, and polymeric oligomers. Modified polyisocyanates can
also be used, including but not limited to carbodiimides and
uretone-imines, and mixtures thereof. Suitable materials include
but are not limited to those available under the name DESMODUR from
Bayer Corporation of Pittsburgh, Pa. and include, for example,
DESMODUR N 3200, DESMODUR N 3300, DESMODUR N 3400, DESMODUR XP
2410, and DESMODUR XP 2580.
[0020] In certain embodiments, the isocyanate is in the form of a
prepolymer. As used herein, "prepolymer" means polyisocyanate that
is pre-reacted with polyamine and/or another isocyanate reactive
group such as polyol. Suitable polyisocyanates include those
disclosed herein. Suitable polyamines are numerous and selected
from a wide variety known in the art. Non-limiting examples of
suitable polyamines may include but are not limited to primary, and
secondary triamines and tetraamines, and mixtures thereof, such as
any of those listed above. Amines comprising tertiary amine
functionality can be used provided that the amine further comprises
at least two primary and/or secondary amino groups. In certain
embodiments an isocyanate such as 4,4'-methylenedicyclohexyl
diisocyanate (DESMODUR W) is reacted with JEFFAMINE D4000,
JEFFAMINE D2000, and/or a difunctional, amine terminated
polypropylene glycol having a molecular weight higher than 4000 to
form the isocyanate prepolymer. Suitable polyols are numerous and
selected from a wide variety known in the art. Examples of suitable
polyols may include but are not limited to polyether polyols,
polyester polyols, polyurea polyols (e.g. the Michael reaction
product of an amino functional polyurea with a hydroxyl functional
(meth)acrylate), polycaprolactone polyols, polycarbonate polyols,
polyurethane polyols, polyvinyl alcohols, addition polymers of
unsaturated monomers with pendant hydroxyl groups, such as those
containing hydroxy functional (meth)acrylates, allyl alcohols and
mixtures thereof.
[0021] In certain embodiments, the polyurea compositions of the
present invention can additionally include other amines such as
those known in the art, including but not limited to any polyamines
or combinations thereof listed herein. Other suitable amines
include, but are not limited to, monoamines, secondary
cycloaliphatic diamines, aspartic ester functional materials,
polyoxyalkyleneamines, (meth)acrylate modified amines, reaction
products of materials having primary amines and acrylonitrile, and
oligomers or polymers formed by addition polymerization, such as
free radical or cationic polymerization of unsaturated monomers
that comprise pendant amino groups. Suitable monoamines include but
are not limited to primary amines of the formula R.sub.2--NH.sub.2,
where R.sub.2 is a hydrocarbon radical that may be represented by a
straight chain or branched alkyl group, an aryl-alkyl group, a
hydroxyalkyl group or an alkoxyalkyl group.
[0022] The polyurea composition disclosed above may be used to
form, in whole or in part, one or more portions of a layer of a
golf ball, such as a cover layer, an intermediate layer, a barrier
layer, a coating layer, and the like. The golf ball cover layer or
at least one sub-layer thereof (such as an inner cover layer and/or
an outer cover layer) may preferably be formed from one of the
compositions disclosed herein; that is, a polyurea formed from the
reaction of an isocyanate and a (meth)acrylated amine curative as
described herein. The layer can have a thickness from 0.001 inches
to 0.125 inches, such as from 0.005 inches to 0.1 inches, or from
0.015 inches to 0.04 inches, like 0.035 inches. Alternatively, the
thickness of the layer can be 0.5 inches or less, such as 0.05
inches to 0.2 inches, or 0.5 inches to 0.1 inches. The layer may
have a flexural modulus of 1,000 to 100,000 psi, such as 1,000 psi
to 80,000 psi, 1,000 to 50,000 psi, 1,000 psi to 30,000 psi, 2,000
psi to 25,000 psi, or 10,000 psi to 80,000 psi. The Shore D
hardness of the layer may be 90 or less, such as, 20 to 70, 20 to
60, 25 to 55, 30 to 55, or 40 to 55. The layer may have a WVTR of 2
g/(m.sup.2.times.day) or less. The layer can have a Ts of
55.degree. C. to 110.degree. C., such as 85.degree. C. In certain
embodiments, the layer has a Shore D hardness of 15 to 80. Ts and
Tg can be measured by methods known in the art, such as
differential scanning calorimetry (DSC) and thermal mechanical
analysis (TMA). Shore D and WVTR are also measurable by methods
known in the art. The golf ball itself can have a Shore D hardness
of 38 to 65; this will vary depending on the material(s) used in
the outer layer as well as the material(s) used in any other layers
of the golf ball, such as the core.
[0023] The core of the golf ball may be solid, fluid-filled,
gel-filled, or gas-filled, having a single-piece construction or a
multi-piece construction that includes a center and one or more
outer core layers. Non-limiting examples of materials and
compositions suitable for forming the core or one or more layers of
the core will be known to those skilled in the art, and are
described in U.S. Publication No. 2006/0014923 and the references
cited therein, all of which are hereby incorporated by reference.
Suitable compositions for solid cores include a base rubber (such
as polybutadiene rubbers having a 1,4-cis content of at least about
40%), a crosslinking agent (such as ethylenically unsaturated acids
having 3 to 8 carbon atoms and metal salts thereof), an initiator
(such as peroxides, carbon-carbon initiators, and blends of two or
more thereof) and, optionally, one or more additives (such as
halogenated organsulfur compounds).
[0024] The golf ball core may have a diameter of 0.5 inches or
greater, such as 1 inch or greater, or 1.5 inches of greater, 1.54
inches or greater, 1.545 inches or greater, or 1.55 inches or
greater, typically about 1.65 or less, or about 1.6 inches or
less.
[0025] The golf balls of the present invention may have a variety
of constructions, typically comprising at least a core and a layer
disposed about the core. The layer can be a cover layer. One or
more intermediate layers may be disposed between the core and the
cover; an intermediate layer can include, for example, a moisture
barrier layer. The core may be a single solid mass, or include a
solid, liquid-filled, gel-filled or gas-filled center and one or
more outer core layers. The cover may include an outer cover layer
and one or more inner layers. Any of the outer core layers, the
intermediate layers, or the inner cover layers may be a continuous
layer, a discontinuous layer, a wound layer, a molded layer, a
lattice network layer, a web or net, an adhesion or coupling layer,
a barrier layer, a layer of uniformed or non-uniformed thickness, a
layer having a plurality of discrete elements such as islands or
protrusions, a solid layer, a metallic layer, a liquid-filled, a
gas-filled layer, or a foamed layer.
[0026] The compositions for golf balls as disclosed herein may be
used in sporting equipment in general. "Sports equipment" includes
but is not limited to game balls, golf club shafts, golf club head
inserts, golf shoe components, and the like.
[0027] Any standard additives can be used with the polyurea
according to the present invention. Such additives include, for
example, catalysts, rheology modifiers, flow additives, thickeners,
fillers, antistatic agents, stabilizers, adhesion promoters,
antioxidants, UV absorbers, hindered amine light stabilizers, and
colorants.
[0028] As used herein, the term "colorant" means any substance that
imparts color and/or other opacity and/or other visual effect to
the composition. The colorant can be added to the coating in any
suitable form, such as discrete particles, dispersions, solutions
and/or flakes. A single colorant or a mixture of two or more
colorants can be used in the coatings of the present invention.
[0029] Example colorants include pigments, dyes and tints, such as
those used in the paint industry and/or listed in the Dry Color
Manufacturers Association (DCMA), as well as special effect
compositions. A colorant may include, for example, a finely divided
solid powder that is insoluble but wettable under the conditions of
use. A colorant can be organic or inorganic and can be agglomerated
or non-agglomerated. Colorants can be incorporated into the
coatings by use of a grind vehicle, such as an acrylic grind
vehicle, the use of which will be familiar to one skilled in the
art.
[0030] Example pigments and/or pigment compositions include, but
are not limited to, carbazole dioxazine crude pigment, azo,
monoazo, disazo, naphthol AS, salt type (lakes), benzimidazolone,
condensation, metal complex, isoindolinone, isoindoline and
polycyclic phthalocyanine, quinacridone, perylene, perinone,
diketopyrrolo pyrrole, thioindigo, anthraquinone, indanthrone,
anthrapyrimidine, flavanthrone, pyranthrone, anthanthrone,
dioxazine, triarylcarbonium, quinophthalone pigments, diketo
pyrrolo pyrrole red ("DPPBO red"), titanium dioxide, carbon black
and mixtures thereof. The terms "pigment" and "colored filler" can
be used interchangeably.
[0031] Example dyes include, but are not limited to, those that are
solvent and/or aqueous based such as pthalo green or blue, iron
oxide, bismuth vanadate, anthraquinone, perylene, aluminum and
quinacridone.
[0032] Example tints include, but are not limited to, pigments
dispersed in water-based or water miscible carriers such as
AQUA-CHEM 896 commercially available from Degussa, Inc., CHARISMA
COLORANTS and MAXITONER INDUSTRIAL COLORANTS commercially available
from Accurate Dispersions division of Eastman Chemical, Inc.
[0033] As noted above, the colorant can be in the form of a
dispersion including, but not limited to, a nanoparticle
dispersion. Nanoparticle dispersions can include one or more highly
dispersed nanoparticle colorants and/or colorant particles that
produce a desired visible color and/or opacity and/or visual
effect. Nanoparticle dispersions can include colorants such as
pigments or dyes having a particle size of less than 150 nm, such
as less than 70 nm, or less than 30 nm. Nanoparticles can be
produced by milling stock organic or inorganic pigments with
grinding media having a particle size of less than 0.5 mm. Example
nanoparticle dispersions and methods for making them are identified
in U.S. Pat. No. 6,875,800 B2, which is incorporated herein by
reference. Nanoparticle dispersions can also be produced by
crystallization, precipitation, gas phase condensation, and
chemical attrition (i.e., partial dissolution). In order to
minimize re-agglomeration of nanoparticles within the coating, a
dispersion of resin-coated nanoparticles can be used. As used
herein, a "dispersion of resin-coated nanoparticles" refers to a
continuous phase in which is dispersed discreet "composite
microparticles" that comprise a nanoparticle and a resin coating on
the nanoparticle. Example dispersions of resin-coated nanoparticles
and methods for making them are identified in United States Patent
Application Publication 2005-0287348 A1, filed Jun. 24, 2004, U.S.
Provisional Application No. 60/482,167 filed Jun. 24, 2003, and
U.S. patent application Ser. No. 11/337,062, filed Jan. 20, 2006,
which is also incorporated herein by reference.
[0034] Example special effect compositions that may be used in the
coating of the present invention include pigments and/or
compositions that produce one or more appearance effects such as
reflectance, pearlescence, metallic sheen, phosphorescence,
fluorescence, photochromism, photosensitivity, thermochromism,
goniochromism and/or color-change. Additional special effect
compositions can provide other perceptible properties, such as
opacity or texture. In a non-limiting embodiment, special effect
compositions can produce a color shift, such that the color of the
coating changes when the coating is viewed at different angles.
Example color effect compositions are identified in U.S. Pat. No.
6,894,086, incorporated herein by reference. Additional color
effect compositions can include transparent coated mica and/or
synthetic mica, coated silica, coated alumina, a transparent liquid
crystal pigment, a liquid crystal coating, and/or any composition
wherein interference results from a refractive index differential
within the material and not because of the refractive index
differential between the surface of the material and the air.
[0035] In certain non-limiting embodiments, a photosensitive
composition and/or photochromic composition, which reversibly
alters its color when exposed to one or more light sources, can be
used in the coating of the present invention. Photochromic and/or
photosensitive compositions can be activated by exposure to
radiation of a specified wavelength. When the composition becomes
excited, the molecular structure is changed and the altered
structure exhibits a new color that is different from the original
color of the composition. When the exposure to radiation is
removed, the photochromic and/or photosensitive composition can
return to a state of rest, in which the original color of the
composition returns. In one non-limiting embodiment, the
photochromic and/or photosensitive composition can be colorless in
a non-excited state and exhibit a color in an excited state. Full
color-change can appear within milliseconds to several minutes,
such as from 20 seconds to 60 seconds. Example photochromic and/or
photosensitive compositions include photochromic dyes.
[0036] In a non-limiting embodiment, the photosensitive composition
and/or photochromic composition can be associated with and/or at
least partially bound to, such as by covalent bonding, a polymer
and/or polymeric materials of a polymerizable component. In
contrast to some coatings in which the photosensitive composition
may migrate out of the coating and crystallize into the substrate,
the photosensitive composition and/or photochromic composition
associated with and/or at least partially bound to a polymer and/or
polymerizable component in accordance with a non-limiting
embodiment of the present invention, have minimal migration out of
the coating. Example photosensitive compositions and/or
photochromic compositions and methods for making them are
identified in U.S. application Ser. No. 10/892,919 filed Jul. 16,
2004 and incorporated herein by reference.
[0037] In general, the colorant can be present in the coating
composition in any amount sufficient to impart the desired visual
and/or color effect. The colorant may comprise from 1 to 65 weight
percent of the present compositions, such as from 3 to 40 weight
percent or 5 to 35 weight percent, with weight percent based on the
total weight of the compositions.
[0038] As used herein, unless otherwise expressly specified, all
numbers such as those expressing values, ranges, amounts or
percentages may be read as if prefaced by the word "about", even if
the term does not expressly appear. Also, any numerical range
recited herein is intended to include all subranges subsumed
therein. Singular encompasses plural and vice versa. For example,
although reference is made herein including the claims to "a"
(meth)acrylated amine curative, "a" (meth)acrylate, "a" polyamine,
"a" layer, "a" polyurea, "an" isocyanate and the like, one or more
of any of these compounds or things can be used. As used herein,
the term "polymer" refers to oligomers and both homopolymers and
copolymers, and the prefix "poly" refers to two or more.
EXAMPLES
[0039] The following examples are intended to illustrate the
invention, and should not be construed as limiting the invention in
any way.
Example 1
[0040] An acrylated amine curative was prepared as follows:
TABLE-US-00001 Ingredients Parts By Weight Charge 1
.sup.1DIMETHYLDICYKAN 60.6% Charge 2 Methyl acrylate 39.4%
.sup.1DIMETHYLDICYKAN, available from BASF Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 40.degree. C. under a nitrogen
blanket and Charge #2 was added over 15 minutes. The reaction was
heated to 60.degree. C. and held for 6 hours. The temperature was
increased to 70.degree. C. and held an additional 5 hours.
Examples 2-4
[0041] Acrylated amine curatives were prepared as follows:
TABLE-US-00002 Parts By Weight Ingredients Example 2 Example 3
Example 4 Charge 1 DIMETHYLDICYKAN 57.0% 56.6% 56.2%
.sup.2Hexanediol diacrylate 16.2% 18.8% 21.4% Methyl acrylate 26.8%
24.6% 22.4% 4-methoxy phenol 0.024% 0.024% 0.024% % residual MA
(HPLC) 0.74% Not tested 0.40% .sup.2Available from Sartomer
Corporation
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 71-75.degree. C. and held
until residual methyl acrylate was <2.0% (HPLC).
Example 5
[0042] An acrylated amine curative was prepared as follows:
TABLE-US-00003 Ingredients Parts By Weight Charge 1
.sup.3Polyetheramine 91.0% Methyl acrylate 4.2% 4-methoxy phenol
0.024% Charge 2 Methanol 4.8% % residual MA 0.7% (HPLC)
.sup.3XTJ-510, available from Huntsman Petrochemical
Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. Charge 2
was added at a rate to keep the temperature <75.degree. C. The
contents of the flask were heated to 71-75.degree. C. and held
until residual methyl acrylate was <1.0% (HPLC).
Example 6
[0043] An acrylated amine curative was prepared as follows:
TABLE-US-00004 Ingredients Parts by Weight Charge 1 .sup.4polyether
triamine 59.2% 4-methoxy phenol 0.023% Charge 2 Methyl acrylate
36.0% Charge 3 Methanol 4.8% % residual MA 2.8% (HPLC)
.sup.4JEFFAMINE T403, available from Huntsman Petrochemical
Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. Charge 2
was added over 15 minutes. Charge #3 was added at a rate to keep
the temperature <75.degree. C. The contents of the flask were
heated to 71-75.degree. C. and held until residual methyl acrylate
was <3.0% (HPLC).
Example 7
[0044] An acrylated amine curative was prepared as follows:
TABLE-US-00005 Ingredients Parts by Weight Charge 1 .sup.5Polyether
amine 86.9% Methyl acrylate 8.3% 4-methoxy phenol 0.024% Methanol
4.8% % residual MA 0.4% (HPLC) .sup.5XTJ-502, available from
Huntsman Petrochemical Corporation.
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 71.degree. C. and held until
residual methyl acrylate was <1.0% (HPLC
Example 8
[0045] An isocyanate functional prepolymer was prepared as
follows:
TABLE-US-00006 Parts By Weight Example 8 Ingredients (05-201-038)
Charge 1 .sup.6Polyisocyanate 25.1% Charge 2 Dibutyltin dilaurate
0.02% Charge 3 .sup.7Polyetherpolyamine 67.5% NCO equivalent weight
after ~805 Charge #3 (theory) Charge 4 .sup.8Polyisocyanate 7.0%
Charge 5 .sup.9p-Toluenesulfonyl Isocyanate 0.4% Final NCO
equivalent weight (theory) ~652 .sup.6DESMODUR W, available from
Bayer Material Science LLC. .sup.7JEFFAMINE D2000, available from
Huntsman Petrochemical Corporation. .sup.8DESMODUR N 3300A,
available from Bayer Material Science LLC. .sup.9p-Toluenesulfonyl
Isocyanate, available from Aldrich.
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 50-60.degree. C. with stirring
under a nitrogen blanket. Charge #2 was added at an appropriate
rate to keep the temperature <75.degree. C. Upon completion of
Charge #2, the reaction temperature was set to 70.degree. C. and
Charge #3 was added. The reaction was held at temperature until the
NCO equivalent weight was close to the theory indicated in the
table. Charge #4 was added and the batch was mixed for 15 minutes.
Charge #5 was added and the reaction was held at temperature until
the desired final NCO equivalent weight was reached.
Example 9
[0046] An isocyanate functional prepolymer was prepared as
follows:
TABLE-US-00007 Parts By Weight Ingredients Example 9 Charge 1
DESMODUR W 24.9% Charge 2 Dibutyltin dilaurate 0.02% Charge 3
JEFFAMINE D2000 63.3% NCO equivalent weight after Charge #3
(theory) ~750 Charge 4 .sup.10IPDI Trimer 11.8% NCO equivalent
weight after Charge #4 (theory) ~600 .sup.10VESTANAT T 1890,
available from Degussa Corporation.
[0047] Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 50-60.degree. C. with stirring
under a nitrogen blanket. Charge #2 was added at an appropriate
rate to keep the temperature <75.degree. C. Upon completion of
Charge #2, the reaction temperature was set to 70.degree. C. and
Charge #3 was added. The reaction was held 2.5 hours and the
temperature set point was raised to 85.degree. C. The reaction was
held at temperature until the NCO equivalent weight was close to
the theory indicated in the table. Charge #4 was added, and the
temperature was increased to 115.degree. C. to melt the solid. The
temperature was then reduced to 100.degree. C. and held until the
desired final NCO equivalent weight was reached.
Examples 10-17
[0048] Isocyanate functional prepolymers were prepared as
follows:
TABLE-US-00008 Parts By Weight Example Example Example Example
Ingredients 10 11 12 13 Charge 1 DESMODUR W 38.1% 36.1% 36.1% 34.4%
Charge 2 Dibutyltin dilaurate 0.02% 0.02% 0.02% 0.02% Charge 3
JEFFAMINE D2000 61.9% 63.9% -- 39.2% XTJ-502 -- -- 63.9% -- XTJ-510
26.4% NCO equivalent ~454 ~494 ~494 ~494 weight (theory) Parts By
Weight Example Example Example Example Ingredients 14 15 16 17
Charge 1 DESMODUR W 31.6% 28.7% 30.1% 29.6% Charge 2 Dibutyltin
dilaurate 0.02% 0.02% 0.02% 0.02% Charge 3 XTJ-510 68.4% 71.3%
69.8% 70.4% NCO equivalent ~494 ~560 ~525 ~538 weight (theory)
Charge #1 was added to an appropriate sized, 4-necked flask
equipped with a motor driven stainless steel stir blade,
water-cooled condenser, and a heating mantle with a thermometer
connected through a temperature feedback control device. The
contents of the flask were heated to 50-55.degree. C. with stirring
under a nitrogen blanket. Charge #2 (melted if necessary) was added
at an appropriate rate to keep the temperature <75.degree. C.
Upon completion of Charge #2, the reaction temperature was set to
70.degree. C. and Charge #3 was added. The reaction was held at
temperature until the desired final NCO equivalent weight was
reached.
Examples 18-28
[0049] Various polyurea cast samples (Examples 18-28) were prepared
using the acrylated amine curatives and isocyanate prepolymers
prepared as described above and indicated in the table below.
Generally, for each sample, approximately 80 grams of the
isocyanate prepolymer were measured into a paper cup. The amine
curative was measured into a FlackTek cup (FlackTek Inc., Landrum
S.C.) along with a pigment paste and in some cases Dibutyl Tin
Dilaurate. This mixture is referred to as "curative blend", below.
The curative blend was then placed into a FlackTek SpeedMixer
(FlackTex SpeedMixer DAC 400FVZ, from FlackTek Inc.), and allowed
to spin for 1 minute at 2,500 rpm.
[0050] The isocyanate prepolymer was placed in the microwave oven
and heated for 15 seconds on high power. Immediately after the
microwave oven stopped, the curative blend was placed in the oven,
together with the isocyanate prepolymer, and heated for 15 seconds
on high power. These two materials were then transferred to the
degassing chamber, where both materials were degassed until minimal
bubbling occurred in the two samples. Once minimal to no bubbling
had occurred, the materials were transferred into the microwave for
an additional heating for 15 seconds on high power.
[0051] The curative blend was placed on the balance (Mettler
PG5002), tared, and the isocyanate prepolymer in the amount in
grams indicated in the table below was added. This mixture was
sealed with a lid and was then placed into the FlackTek SpeedMixer,
and allowed to spin for 5 seconds at 2,500 rpm. The sample was
immediately removed from the mixer, the lid was quickly removed,
and the mixed sample was poured into the Teflon mold cavity
(6''.times.6''.times.1/8'', from Accrotool, Inc., New Kensington,
Pa.).
[0052] The "Pour Time" was measured by a stopwatch. When the sample
was placed in the mixer and started, the stopwatch was started.
When the cast sample no longer flowed freely from the cup, the
stopwatch was stopped. This gave a "Pour Time" range as shown in
the table below.
[0053] A flat metal lid covered with Tedlar film (1.4 mil, from
DuPont) was placed over the Teflon cavity containing the polyurea
casting. This mold assembly was then transferred to a Carver Press
(Hydraulic Unit Model #3912, from Carver, Inc., Wabash, Ind.), and
heated to 150.degree. F. Force between 10,000 lb.sub.f to 15,000
lb.sub.f was applied to the mold assembly. The sample was then
cured for 15 minutes under these conditions. After 15 minutes, the
Carver Press was opened, the mold assembly was removed, the metal
lid with the Tedlar film was removed. An article of approximately 6
inch by 6 inch by 1/8 inch thick article was removed from the
Teflon mold, and placed in a 150.degree. F. electric oven for 120
minutes to complete curing.
[0054] After the sample was removed from the oven, the sample was
allowed to equilibrate for greater than 12 hours. The sample
hardness was measured by an Instron Shore D probe (Shore
Instruments, Norwood, Mass.). Shore D was measured initially, when
the probe hit the sample, and recorded again after two seconds.
[0055] The sample was measured for thermo-mechanical performance on
a TMA 2940 Thermomechanical Analyzer (TA Instruments, New Castle,
Del.). The test parameters were to start testing at 25.degree. C.,
apply a temperature ramp of 10.degree. C./min, and finish testing
at 125.degree. C. The applied force load was 0.7 lb.sub.force. The
initial softening point ("Ts") is reported in the table below.
[0056] QUV exposure testing was performed as follows. Plaques
approximately 2'' by 3'' were cut from the cast samples prepared as
described above and placed into aluminum holders. A QUV Weathering
Tester, Model QUV/se, from Q-Lab Corporation, Cleveland Ohio, was
used with a UVA 340 bulb. The testing procedure employed a 4 hour
UV light cycle at a temperature of 60.degree. C. followed by a 4
hour humidity cycle at a temperature of 50.degree. C. The UV
irradiance on the samples was 1.00W/m.sup.2. Results are given in
DE*ab in the table below.
[0057] Example 18 reflects a control, using a non-acrylated amine.
The other examples, using an acrylated amine according to the
present invention, have a greater thermal stability as compared to
example 18, as illustrated by the greatly increased Ts values.
Examples 25-28 had a markedly increased Ts as compared with the
control. In addition, the TMA graphs of temperature (y axis) and
dimension change (%) (x axis) (not shown) demonstrated that the
rate of softening was much slower for the compositions according to
the present invention than that of the control.
[0058] For purposes of QUV comparison and light stability
evaluation, another control sample was prepared following the
format outlined above using two commercially available products,
namely 53.7 g of S28804 isocyanate prepolymer (from PPG Industries)
and 10.0 g of S28774Q curative (from PPG Industries). No other
ingredients were used. The Shore D of this second control was
approximately 46D (initial) and approximately 44D (two seconds) and
the Ts was 101.degree. C. The DE*ab values were 49.6001 (48 hours)
and 45.2553 (120 hours), demonstrating the superior QUV resistance
of the present samples as compared with a commercially available
product.
Examples 18-28
TABLE-US-00009 [0059] 18 19 20 21 22 isocyanate Ex. 8 Ex. 8 Ex. 9
Ex. 9 Ex. 10 prepolymer.sup.11 65.78 65.78 60.14 60.14 45.51
Curative(g).sup.12 CLEARLINK1000.sup.13 Ex. 1 Ex. 2 Ex. 2 Ex. 2
16.42 18.89 18.89 21.52 21.52 Pigment (g).sup.14 3.87 3.99 3.72
3.85 3.16 Dibutyl Tin -- -- -- -- 0.07 Dilaurate (g) Pour Time 37
45 37 45 37 45 37 45 47 53 (seconds) Shore D ~50D ~53D ~56D ~60D
~59D (initial) Shore D ~47D ~49D ~52D ~58D ~57D (2 seconds) Ts
(.degree. C.) 51.0 50.6 81.0 89.0 89.0 DE*ab 1.3958(60) 0.7025(104)
1.6539(104) 0.739(48) 1.19(48) (hours) 1.6198(104) 1.2128(120)
1.8592(120) 23 24 25 26 27 28 isocyanate Ex. 12 Ex. 13 Ex. 14 Ex.
15 Ex. 17 Ex. 15 prepolymer 50.13 49.70 49.82 55.03 53.97 56.74
Curative(g) Ex. 2 Ex. 2 Ex. 2 Ex. 2 Ex. 2 Ex. 21.52 21.52 21.52
21.52 21.52 21.52 Pigment (g) 3.38 2.67 2.59 2.78 2.74 2.84 Dibutyl
Tin 0.07 0.07 0.07 0.07 0.07 0.07 Dilaurate (g) Pour Time 50 55 47
53 49 54 57 62 52 57 56 62 (seconds) Shore D ~57D ~63D ~58D ~51D
~54D ~52D (initial) Shore D ~55D ~60D ~55D ~48D ~50D ~49D (2
seconds) Ts (.degree. C.) 84.6 86.0 97.2 95.0 95.5 95.5 DE*ab
2.054(48) 1.8894(48) 2.6678(48) 2.7317(40) 3.0582(48) 2.8302(48)
(hours) 3.0748(120) 2.8976(120) 4.1173(120) 4.441(120) 4.0066(120)
.sup.11Prepared as described in the Examples above, as indicated.
.sup.12Prepared as described in the Examples above, as indicated,
unless indicated otherwise. .sup.13CLEARLINK 1000, cycloaliphatic
diamine, from Dorf-Ketal Chemicals, Mumbai, INDIA. .sup.14STAN-TONE
IOET03 WHITE tint paste, from Poly One Corporation, Avon Lake,
OH.
Examples 29-30
[0060] The examples above were repeated, but the STAN-TONE paste
was replaced with a white pigment dispersion made as described
below, and the acrylated amine of Example 5 was used in addition to
the acrylated amine curative indicated in the table below. The
pigment dispersion was prepared by placing 100 parts of the
acrylated amine of Example 5 and 127.3 parts of R-960 TiO.sub.2
pigment (DuPont Titanium Technologies, Mississauga, Ontario) into a
FlackTek SpeedMixer for 5 minutes at 2,500 rpm.
Examples 29-30
TABLE-US-00010 [0061] 29 30 isocyanate Ex. 16 Ex. 16
prepolymer.sup.15 Curative(g).sup.16 Ex. 2 Ex. 2 15.92 15.84
Dibutyl Tin 0.07 0.07 Dilaurate (g) Curative from 0.21 0.90 Ex. 5
(g) Pigment 2.72 2.75 dispersion (g) Pour Time 63 68 62 67 (sec)
Shore D ~52D ~51D (initial) Shore D ~49D ~48D (2 seconds) Ts
(.degree. C.) 100 100 DE * ab 1.9174 (48) 1.8027 (48) (hours)
2.7999 (120) 2.7367 (120) .sup.15Prepared as described in the
Examples above, as indicated. .sup.16Prepared as described in the
Examples above, as indicated, unless indicated otherwise.
[0062] This example illustrates that by increasing the amount of
"soft segment" in the product (that is, the acrylated amine of
Example 5) the Shore D can be lowered without affecting the Ts.
[0063] Whereas particular embodiments of this invention have been
described above for purposes of illustration, it will be evident to
those skilled in the art that numerous variations of the details of
the present invention may be made without departing from the
invention as defined in the appended claims.
* * * * *