U.S. patent application number 09/736104 was filed with the patent office on 2002-08-22 for sporting goods having a ceramer coating.
Invention is credited to Kang, Soonkun, Martin, Steven J., Norquist, Scott G., Rouser, Forrest J., Rowen, Susan K., Sadlo, James L., Terrazas, Michael S..
Application Number | 20020114959 09/736104 |
Document ID | / |
Family ID | 24958523 |
Filed Date | 2002-08-22 |
United States Patent
Application |
20020114959 |
Kind Code |
A1 |
Kang, Soonkun ; et
al. |
August 22, 2002 |
Sporting goods having a ceramer coating
Abstract
A sporting goods article with a coating on a surface of the
article for abrasion resistance and/or a high gloss appearance. The
outer layer of the surface is a polymer, wood, metal, non-polymeric
ink, non-polymeric colorant, non-polymeric dye, or a combination
thereof. The coating is a cured ceramer composition. The cured
ceramer composition, in its simplest embodiment, is derived from a
composition including inorganic oxide particles and a curable
organic matrix, with the curable organic matrix including at least
one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
Inventors: |
Kang, Soonkun; (Lake Elmo,
MN) ; Rouser, Forrest J.; (Stillwater, MN) ;
Rowen, Susan K.; (Hudson, WI) ; Martin, Steven
J.; (Shoreview, MN) ; Terrazas, Michael S.;
(Prescott, WI) ; Norquist, Scott G.; (St. Paul,
MN) ; Sadlo, James L.; (Round Rock, TX) |
Correspondence
Address: |
Attention: Kimberly S. Zillig
Office of Intellectual Property Counsel
3M Innovative Properties Company
P.O. Box 33427
St. Paul
MN
55133-3427
US
|
Family ID: |
24958523 |
Appl. No.: |
09/736104 |
Filed: |
December 13, 2000 |
Current U.S.
Class: |
428/447 |
Current CPC
Class: |
Y10T 428/259 20150115;
Y10T 428/2998 20150115; Y10T 428/265 20150115; Y10T 428/31663
20150401; A63B 2244/04 20130101; A63B 53/00 20130101; A43B 5/04
20130101; Y10T 428/31507 20150401; A63C 9/00 20130101; A63B 59/50
20151001; Y10T 428/31 20150115; A63B 60/00 20151001; A43B 1/00
20130101; C09D 4/00 20130101; A63B 71/10 20130101; A63C 5/12
20130101; A63B 2102/18 20151001; C09D 4/00 20130101; C08F 226/06
20130101 |
Class at
Publication: |
428/447 |
International
Class: |
B32B 009/04 |
Claims
What is claimed is:
1. A sporting goods article comprising a substrate, and a coating
provided on at least a portion of a surface of said substrate,
wherein said portion of said surface of said substrate has at least
an outer layer comprising a material selected from the group
consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
2. The sporting goods article of claim 1 wherein said coating of
said cured ceramer composition is effective to improve the abrasion
resistance of said portion of said surface of said substrate.
3. The sporting goods article of claim 2 wherein said coating of
said cured ceramer composition is effective to enhance the gloss of
said portion of said surface of said substrate.
4. The sporting goods article of claim 1 wherein said inorganic
oxide particles comprise silica particles.
5. The sporting goods article of claim 1 wherein said inorganic
oxide particles comprise particles selected from the group
consisting of silica, alumina, titania, zirconia, ceria, antimony,
and combinations thereof, which are derived from sols of such
particles.
6. The sporting goods article of claim 1 wherein said
organofunctional silane monomer coupling agent comprises a
hydrolyzable organofunctional silane.
7. The sporting goods article of claim 1 wherein said ethylenically
unsaturated monomer comprises at least one multifunctional
ethylenically unsaturated monomer.
8. The sporting goods article of claim 7 wherein said curable
organic matrix further comprises at least one monofunctional
ethylenically unsaturated monomer.
9. The sporting goods article of claim 8 wherein said
multifunctional ethylenically unsaturated monomer is
pentaerythritol triacrylate, said monofunctional ethylenically
unsaturated monomer is N-vinyl caprolactam, said organofunctional
silane coupling agent is (meth)acryloxypropyl trimethoxysilane, and
said inorganic oxide particles comprise silica.
10. The sporting goods article of claim 1 wherein said sporting
goods article is selected from the group consisting of a ski, a ski
boot, a ski binding, a ski pole, a golf club, a baseball bat, a
helmet, an arrow, a surfboard, an athletic shoe, and a rope.
11. The sporting goods article of claim 1 wherein the thickness of
said coating of said cured ceramer composition is about 1 to about
40 microns.
12. The sporting goods article of claim 1 wherein the thickness of
said coating of said cured ceramer composition is about 2 to about
10 microns.
13. A sporting goods article comprising a substrate, and a coating
provided on at least a portion of a surface of said substrate,
wherein said portion of said surface of said substrate has at least
an outer layer comprising a material selected from the group
consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one multifunctional ethylenically
unsaturated monomer, and at least one organofunctional silane
monomer coupling agent.
14. The sporting goods article of claim 13 wherein said curable
organic matrix further comprises at least one monofunctional
unsaturated ethylenically unsaturated monomer.
15. The sporting goods article of claim 14 wherein said coating of
said cured ceramer composition is effective to improve the abrasion
resistance of said portion of said surface of said substrate.
16. The sporting goods article of claim 15 wherein said coating of
said cured ceramer composition is effective to enhance the gloss of
said portion of said surface of said substrate.
17. The sporting goods article of claim 14 wherein said
multifunctional ethylenically unsaturated monomer is
pentaerythritol triacrylate, said monofunctional ethylenically
unsaturated monomer is N-vinyl caprolactam, said organofunctional
silane coupling agent is (meth)acryloxypropyl trimethoxysilane, and
said inorganic oxide particles comprise silica.
18. A sporting goods article comprising a substrate, graphics, and
a coating provided on at least a portion of a surface of said
substrate, wherein said portion of said surface of said substrate
has at least an outer layer comprising a material selected from the
group consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, wherein said coating
comprises a cured ceramer composition that is derived from
ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
19. The sporting goods article of claim 18 wherein said coating of
said cured ceramer composition is effective to improve the abrasion
resistance of said surface of said portion of said substrate.
20. The sporting goods article of claim 19 wherein said coating of
said cured ceramer composition is effective to protect the visual
appearance of said graphics.
21. A ski comprising a substrate having a top surface, and a
coating on at least a portion of said top surface, wherein said
portion of said top surface of said substrate has at least an outer
layer comprising a material selected from the group consisting of
polymers, woods, metals, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, and combinations thereof, wherein
said coating comprises a cured ceramer composition that is derived
from ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
22. The ski of claim 21 wherein said coating of said cured ceramer
composition is effective to improve the abrasion resistance of said
portion of said top surface of said substrate.
23. The ski of claim 22 wherein said coating of said cured ceramer
composition is effective to enhance the gloss of said portion of
said top surface of said substrate.
24. The ski of claim 21 wherein said inorganic oxide particles
comprise silica particles.
25. The ski of claim 21 wherein said inorganic oxide particles
comprise particles selected from the group consisting of silica,
alumina, titania, zirconia, ceria, antimony, and combinations
thereof, which are derived from sols of such particles.
26. The ski of claim 21 wherein said ethylenically unsaturated
monomer comprises at least one multifunctional ethylenically
unsaturated monomer.
27. The ski of claim 26 wherein said curable organic matrix further
comprises at least one monofunctional ethylenically unsaturated
monomer.
28. The ski of claim 27 wherein said multifunctional ethylenically
unsaturated monomer is pentaerythritol triacrylate, said
monofunctional ethylenically unsaturated monomer is N-vinyl
caprolactam, said organofunctional silane coupling agent is
(meth)acryloxypropyl trimethoxysilane, and said inorganic oxide
particles comprise silica.
29. A golf club comprising a shaft and a head, and a coating
provided on at least a portion of a surface of said shaft, wherein
said portion of said surface of said shaft has at least an outer
layer comprising a material selected from the group consisting of
polymers, woods, metals, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, and combinations thereof, wherein
said coating comprises a cured ceramer composition that is derived
from ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
30. The golf club of claim 29 wherein said coating of said cured
ceramer composition is effective to improve the abrasion resistance
of said portion of said surface of said shaft.
31. The golf club of claim 30 wherein said coating of said cured
ceramer composition is effective to enhance the gloss of said
portion of said surface of said shaft.
32. The golf club of claim 29 wherein said inorganic oxides
particles comprise silica particles.
33. The golf club of claim 29 wherein said inorganic oxide
particles comprise particles selected from the group consisting of
silica, alumina, titania, zirconia, ceria, antimony, and
combinations thereof, which are derived from sols of such
particles.
34. The golf club of claim 29 wherein said ethylenically
unsaturated monomer comprises at least one multifunctional
ethylenically unsaturated monomer.
35. The golf club of claim 34 wherein said curable organic matrix
further comprises at least one monofunctional ethylenically
unsaturated monomer.
36. The golf club of claim 35 wherein said multifunctional
ethylenically unsaturated monomer is pentaerythritol triacrylate,
said monofunctional ethylenically unsaturated monomer is N-vinyl
caprolactam, said organofunctional silane coupling agent is
(meth)acryloxypropyl methoxysilane, and said inorganic oxide
particles comprise silica.
37. A golf club comprising a shaft and a head, and a coating
provided on at least a portion of a surface of said head, wherein
said portion of said surface of said head has at least an outer
layer comprising a material selected from the group consisting of
polymers, woods, metals, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, and combinations thereof, wherein
said coating comprises a cured ceramer composition that is derived
from ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
38. The golf club of claim 37 wherein said coating of said cured
ceramer composition is effective to improve the abrasion resistance
of said portion of said surface of said head.
39. The golf club of claim 38 wherein said coating of said cured
cermaer composition is effective to enhance the gloss of said
portion of said surface of said head.
40. The golf club of claim 37 wherein said inorganic oxides
particles comprise silica particles.
41. The golf club of claim 37 wherein said inorganic oxide
particles comprise particles selected from the group consisting of
silica, alumina, titania, zirconia, ceria, antimony, and
combinations thereof, which are derived from sols of such
particles.
42. The golf club of claim 37 wherein said ethylenically
unsaturated monomer comprises at least one multifunctional
ethylenically unsaturated monomer.
43. The golf club of claim 42 wherein said curable organic matrix
further comprises at least one monofunctional ethylenically
unsaturated monomer.
44. The golf club of claim 43 wherein said multifunctional
ethylenically unsaturated monomer is pentaerythritol triacrylate,
said monofunctional ethylenically unsaturated monomer is N-vinyl
caprolactam, said organofunctional silane coupling agent is
(meth)acryloxypropyl trimethoxysilane, and said inorganic oxide
particles comprise silica.
45. A ski boot comprising an outer shell, and a coating provided on
at least a portion of a surface of said outer shell, wherein said
portion of said surface of said outer shell has at least an outer
layer comprising a material selected from the group consisting of
polymers, non-polymeric inks, non-polymeric colorants,
non-polymeric dyes, and combinations thereof, wherein said coating
comprises a cured ceramer composition that is derived from
ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
46. The ski boot of claim 45 wherein said coating of said cured
ceramer composition is effective to improve the abrasion resistance
of said portion of said surface of said outer shell.
47. The ski boot of claim 46 wherein said coating of said cured
ceramer composition is effective to enhance the gloss of said
portion of said surface of said outer shell.
48. The ski boot of claim 45 wherein said inorganic oxide particles
comprise silica particles.
49. The ski boot of claim 45 wherein said inorganic oxide particles
comprise particles selected from the group consisting of silica,
alumina, titania, zirconia, ceria, antimony, and combinations
thereof, which are derived from sols of such particles.
50. The ski boot of claim 45 wherein said ethylenically unsaturated
monomer comprises at least one multifunctional ethylenically
unsaturated monomer.
51. The ski boot of claim 50 wherein said curable organic matrix
further comprises at least one monofunctional ethylenically
unsaturated monomer.
52. The ski boot of claim 51 wherein said multifunctional
ethylenically unsaturated monomer is pentaerythritol triacrylate,
said monofunctional ethylenically unsaturated monomer is N-vinyl
caprolactam, said organofunctional silane coupling agent is
(meth)acryloxypropyl trimethoxysilane, and said inorganic oxide
particles comprise silica.
53. A helmet comprising an outer shell, and a coating provided on
at least a portion of a surface of said outer shell, wherein said
portion of said surface of said outer shell has at least an outer
layer of a material selected from the group consisting of polymers,
non-polymeric inks, non-polymeric colorants, non-polymeric dyes,
and combinations thereof, wherein said coating comprises a cured
ceramer composition that is derived from ingredients comprising
inorganic oxide particles and a curable organic matrix, and wherein
said curable organic matrix comprises at least one ethylenically
unsaturated monomer and at least one organofunctional silane
monomer coupling agent.
54. The helmet of claim 53 wherein said coating of said cured
ceramer composition is effective to improve the abrasion resistance
of said portion of said surface of said outer shell.
55. The helmet of claim 54 wherein said coating of said cured
ceramer composition is effective to enhance the gloss of said
portion of said surface of said outer shell.
56. The helmet of claim 53 wherein said inorganic oxide particles
comprise silica particles.
57. The helmet of claim 53 wherein said inorganic oxide particles
comprise particles selected from the group consisting of silica,
alumina, titania, zirconia, ceria, antimony, and combinations
thereof, which are derived from sols of such particles.
58. The helmet of claim 53 wherein said ethylenically unsaturated
monomer comprises at least one multifunctional ethylenically
unsaturated monomer.
59. The helmet of claim 58 wherein said curable organic matrix
further comprises at least one monofunctional ethylenically
unsaturated monomer.
60. The helmet of claim 59 wherein said multifunctional
ethylenically unsaturated monomer is pentaerythritol triacrylate,
said monofunctional ethylenically unsaturated monomer is N-vinyl
caprolactam, said organofunctional silane coupling agent is
(meth)acryloxypropyl trimethoxysilane, and said inorganic oxide
particles comprise silica.
Description
TECHNICAL FIELD
[0001] This invention relates to sporting goods articles that are
coated for abrasion resistance or for both abrasion resistance and
a high gloss appearance. More specifically, the invention relates
to sporting goods article comprising a substrate, and a coating
provided on at least a portion of a surface of said substrate,
wherein said portion of said surface of said substrate has at least
an outer layer comprising a material selected from the group
consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
BACKGROUND
[0002] Sporting goods, by virtue of their use, are subject to rough
treatment. For instance, sporting goods are subject to abrasion
from many different sources. In order to maintain the high
performance and appearance of such sporting goods, it is desirable
to protect them from damage by abrasion. In addition, it is
desirable to protect the graphics, or their appearance, on such
sporting goods from abrasion.
[0003] To protect the surfaces of other articles from abrasion and
scratching, a ceramer layer has been coated onto one or more
portions of the surfaces of such articles. One particularly
excellent ceramer composition is described in WO 99/38034 (Bilkadi
et al.).
[0004] Ceramers have been used on articles for abrasion resistance
and/or a high gloss appearance. Some examples include traffic
signs, pavement markers, lenses for glasses, and microwave oven
doors.
[0005] Currently, some sporting goods are coated with materials,
other than ceramers, to protect their surfaces from abrasion. For
example, the outer surface of some skis are protected with a
polyamide or polyester polymeric layer. Sporting goods can also be
coated with lacquers, which enhance their appearance and offer some
protection. However, the coatings currently used on sporting goods
do not perform as necessary to resist most types of abrasion
normally observed under normal usage.
SUMMARY OF INVENTION
[0006] The present inventors have recognized a need for a coating
on sporting goods articles that will effectively protect the
articles from abrasion, and additionally, if desired, provide a
high gloss appearance. The present invention is a sporting goods
article including a coating that provides effective abrasion
resistance and a high gloss appearance if desired. The coating may
also may protect graphics that are part of the sporting goods
article.
[0007] The present invention relates to, in its simplest
embodiment, a sporting goods article comprising a substrate, and a
coating provided on at least a portion of a surface of said
substrate, wherein said portion of said surface of said substrate
has at least an outer layer comprising a material selected from the
group consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
[0008] The coating of said cured ceramer composition is effective
to improve the abrasion resistance of said portion of said surface
of said substrate that is coated with said cured ceramer
composition. In addition, said coating is effective to enhance the
gloss of said portion of said surface of said substrate.
[0009] The inorganic oxide particles may comprise silica particles.
The particles may also comprise particles selected from the group
consisting of silica, titania, zirconia, ceria, antimony, and
combinations thereof.
[0010] The organofunctional silane monomer coupling agent may
comprise a hydrolyzable organofunctional silane.
[0011] The ethylenically unsaturated monomer may comprise at least
one multifunctional unsaturated monomer. Alternatively, there may
be another, or second, ethylenically unsaturated monomer that may
be at least one monofunctional ethylenically unsaturated
monomer.
[0012] The most preferred cured ceramer composition is derived from
the following ingredients: pentaeryritol triacrylate (the
multifunctional ethylenically unsaturated monomer), N-vinyl
caprolactam (the monofunctional ethylenically unsaturated monomer),
(meth)acryloxypropyl methoxysilane (the coupling agent), and silica
(inorganic oxides particles).
[0013] The thickness of the coating of the cured ceramer
composition is not limited, except that it must be thick enough to
be effective in resisting abrasion, for example. The thickness of
the coating is, however, preferably about 1 to about 40 microns,
and most preferably about 2 to about 10 microns.
[0014] Another embodiment is a sporting goods article comprising a
substrate, and a coating provided on at least a portion of a
surface of said substrate, wherein said portion of said surface of
said substrate has at least an outer layer comprising a material
selected from the group consisting of polymers, woods, metals,
non-polymeric inks, non-polymeric colorants, non-polymeric dyes,
and combinations thereof, wherein said coating comprises a cured
ceramer composition that is derived from ingredients comprising
inorganic oxide particles and a curable organic matrix, and wherein
said curable organic matrix comprises at least one multifunctional
ethylenically unsaturated monomer, and at least one
organofunctional silane monomer coupling agent. The curable organic
matrix of the sporting goods article may further comprise at least
one monofunctional ethylenically unsaturated monomer.
[0015] Another embodiment is a sporting goods article comprising a
substrate, graphics, and a coating provided on at least a portion
of a surface of said substrate, wherein said portion of said
surface of said substrate has at least an outer layer comprising a
material selected from the group consisting of polymers, woods,
metals, non-polymeric inks, non-polymeric colorants, non-polymeric
dyes, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
[0016] Yet another embodiment is a ski comprising a substrate
having a top surface, and a coating on at least a portion of said
top surface, wherein said portion of said top surface of said
substrate has at least an outer layer comprising a material
selected from the group consisting of polymers, woods, metals,
non-polymeric inks, non-polymeric colorants, non-polymeric dyes,
and combinations thereof, wherein said coating comprises a cured
ceramer composition that is derived from ingredients comprising
inorganic oxide particles and a curable organic matrix, and wherein
said curable organic matrix comprises at least one ethylenically
unsaturated monomer and at least one organofunctional silane
monomer coupling agent.
[0017] A further embodiment is a golf club comprising a shaft and a
head, and a coating provided on at least a portion of a surface of
said shaft, wherein said portion of said surface of said shaft has
at least an outer layer comprising a material selected from the
group consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
[0018] An additional embodiment is a golf club comprising a shaft
and a head, and a coating provided on at least a portion of a
surface of said head, wherein said portion of said surface of said
head has at least an outer layer comprising a material selected
from the group consisting of polymers, woods, metals, non-polymeric
inks, non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
[0019] Yet another additional embodiment is a ski boot comprising
an outer shell, and a coating provided on at least a portion of a
surface of said outer shell, wherein said portion of said surface
of said outer shell has at least an outer layer comprising a
material selected from the group consisting of polymers,
non-polymeric inks, non-polymeric colorants, non-polymeric dyes,
and combinations thereof, wherein said coating comprises a cured
ceramer composition that is derived from ingredients comprising
inorganic oxide particles and a curable organic matrix, and wherein
said curable organic matrix comprises at least one ethylenically
unsaturated monomer and at least one organofunctional silane
monomer coupling agent.
[0020] Another embodiment is a helmet comprising an outer shell,
and a coating provided on at least a portion of a surface of said
outer shell, wherein said portion of said surface of said outer
shell has at least an outer layer of a material selected from the
group consisting of polymers, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, and combinations thereof, wherein
said coating comprises a cured ceramer composition that is derived
from ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
[0021] In this application:
[0022] "Ceramer," "cured ceramer composition" or "inorganic/organic
composite" mean a coated dispersion comprising substantially
non-aggregated, colloidal inorganic oxide particles dispersed in a
cured organic binder or matrix composition, wherein the binder
being cured is understood to mean in a broad sense the
solidification (hardening) of the binder brought about by a
suitable approach such as cooling of a molten thermoplastic
material, drying of a solvent-containing composition, chemical
cross-linking of a thermosetting composition, radiation curing of a
radiation curable composition, or the like;
[0023] "Curable" means that a coatable material can be transformed
into a solid, substantially non-flowing material by means of
radiation cross-linking, or the like;
[0024] "Cured" means a coatable material has been transformed into
a solid, substantially non-flowing material by means of heat,
ultraviolet radiation, electron beam radiation, or the like;
[0025] "Gloss" refers to shininess or luster of a surface;
[0026] "Graphics" refers to text, letters, pictures, drawings,
logos, insignias, trademarks, service marks and the like, that
comprise polymers, non-polymeric inks, non-polymeric colorants,
non-polymeric dyes, or combinations thereof, or the like, and that
are used to decorate or identify the articles that they are
attached to, adhered to, embedded in or placed on;
[0027] "Helmet" refers to a head covering of a hard material
designed to protect the head;
[0028] "Ski" refers to one (which could be one of a pair of skis)
long, relatively flat runner of wood, metal, polymer, or
combinations thereof, of varying length that curves upward in front
and may or may not be attached to a boot(s) or shoe(s), or a
binding(s) used to attach a boot(s) or a shoe(s), for gliding or
traveling over snow or water; and is meant to include alpine
(otherwise known as "downhill" or "slalom") skis, water skis,
cross-country skis, snowboards and the like;
[0029] "Ski boot" refers to a piece of foot gear covering the foot
and part of the leg, which may be attached to a ski and used for
skiing (including downhill skiing (otherwise known as "alpine" or
"slalom"), and cross-country skiing and the like); and
[0030] "Sporting goods articles" refers to articles that are used
in or are appropriate for sports.
DETAILED DESCRIPTION
[0031] The embodiments of the present invention described below are
not intended to be exhaustive or to limit the invention to the
precise forms disclosed in the following detailed description.
Rather the embodiments are chosen and described so that others
skilled in the art may appreciate and understand the principles and
practices of the present invention. The present invention relates
to coating sporting goods articles with a ceramer to protect them
from abrasion. The ceramer also provides a high gloss appearance if
desired. In its simplest embodiment, the present invention is a
sporting goods article comprising a substrate, and a coating
provided on at least a portion of a surface of said substrate,
wherein said portion of said surface of said substrate has at least
an outer layer comprising a material selected from the group
consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, and combinations
thereof, wherein said coating comprises a cured ceramer composition
that is derived from ingredients comprising inorganic oxide
particles and a curable organic matrix, and wherein said curable
organic matrix comprises at least one ethylenically unsaturated
monomer and at least one organofunctional silane monomer coupling
agent.
[0032] Sporting Goods Article
[0033] The sporting goods article of the present invention
comprises a substrate wherein at least a portion of a surface of
said sporting goods article has an outer layer comprising a
material selected from the group consisting of polymers, woods,
metals, non-polymeric inks, non-polymeric colorants, non-polymeric
dyes, and combinations thereof. The sporting goods article also
comprises a coating of a cured ceramer composition on said outer
layer of said portion of said substrate, said layer of cured
ceramer composition being effective to improve the abrasion
resistance of said surface of the sporting goods article and may
additionally be effective to enhance the gloss of the portion of
the surface of the article that is coated. One, or more than one,
surface on the sporting goods article may be coated. The surface of
the sporting goods article can be completely coated, or just a
portion of the surface can be coated with said layer of the cured
ceramer composition.
[0034] The cured ceramer composition adheres to substrates such as
polymers, metals, and woods. Polymers include paints, inks, dyes
and colorants. In addition, the cured ceramer composition adheres
to non-polymeric inks, non-polymeric dyes and non-polymeric
colorants. The polymers, non-polymeric inks, non-polymeric dyes and
non-polymeric colorants may comprise the graphics that may be part
of some sporting goods articles. The curable ceramer composition
may also be applied to leather, printed surfaces, and textiles for
abrasion resistance.
[0035] Some examples of sporting goods articles of the present
invention include, but are not limited to, skis (which include
alpine (otherwise known as "downhill" or "slalom") skis,
cross-country skis, water skis and snowboards), skis poles, ski
boots, ski bindings, helmets, golf clubs, baseball bats, ropes,
surf boards, athletic shoes and arrows. The sporting goods articles
listed herein are not, however, an exhaustive list of the sporting
goods articles of the present invention. Any sporting goods article
that has at least one surface with an outer portion comprising
polymers, metals, woods, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, leather, textiles or combinations
thereof, is included in the present invention.
[0036] Only certain surfaces of the sporting goods articles may be
desired to be coated. For example, just the shaft of a golf club
may be coated, or just the head of the golf club. It may be
desirable, however, to coat both the head and the shaft of the golf
club. In addition, only certain portions of the surface may be
desired to be coated by a cured ceramer composition.
[0037] The sporting goods articles of the present invention may
include graphics, which are discussed in more detail below.
[0038] Ceramer Composition
[0039] The cured ceramer composition of the present invention is
derived from ingredients comprising an organic matrix and inorganic
oxide particles. The cured ceramer composition has inorganic
particles dispersed within the organic matrix.
[0040] The organic matrix can include a variety of monomers,
oligomers, and/or polymers that form the cured matrix for the
inorganic oxide particles. The organic matrix may comprise at least
one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent. Optional
initiators, photosensitizers and additives may also further
comprise the curable composition from which the cured organic
matrix of the cured ceramer composition is derived, which are
discussed in more detail below.
[0041] The cured ceramer composition also includes inorganic oxide
particles, which are also discussed in more detail below.
[0042] Ethylenically Unsaturated Monomer
[0043] The organic matrix comprises at least one ethylenically
unsaturated monomer and at least one coupling agent. The
ethylenically unsaturated monomer(s) of the organic matrix may be
at least one multifunctional ethylenically unsaturated monomer, or
a combination of at least one multifunctional ethylenically
unsaturated monomer and at least one monofunctional ethylenically
unsaturated monomer.
[0044] The multifunctional ethylenically unsaturated monomer may be
an ester of (meth)acrylic acid. It is more preferably selected from
a group consisting of a difunctional ethylenically unsaturated
ester of acrylic or methacrylic acid, a trifunctional ethylenically
unsaturated ester of acrylic or methacrylic acid, a tetrafunctional
ethylenically unsaturated ester of acrylic or methacrylic acid, and
combinations thereof. Of these, trifunctional and tetrafunctional
ethylenically unsaturated esters of (meth)acrylic acid are more
preferred.
[0045] Preferred multifunctional ethylenically unsaturated esters
of (meth)acrylic acid can be described by the formula: 1
[0046] wherein R.sup.4 is hydrogen, halogen or a
(C.sub.1--C.sub.4)alkyl group (preferably R.sup.4 is hydrogen or a
methyl group); R.sup.5 is a polyvalent organic group, which can be:
a cyclic, branched, or linear aliphatic moiety; a cyclic, branched
or linear heteroaliphatic moiety; an aromatic moiety; or a
heteroaromatic moiety; Y is hydrogen, (C.sub.1--C.sub.4)alkyl, or a
protic functional group; m is an integer designating the number of
acrylic or methacrylic groups in the ester and has a value of at
least 2; and n has a value of the valence of R.sup.5 minus the
value of m. Referring to this formula, preferably, R.sup.5 has a
molecular weight of about 12-100, m has a value of 2-6 (more
preferably m has a value of 2-5, most preferably m has a value of
3-4, or where a mixture of multifunctional acrylates and/or
methacrylates are used, m has an average value of about 2.05-5),
and n is an integer having a value of 1 to 3. Preferred protic
functional groups are selected from the group consisting of --OH,
--COOH, --SH,--PO(OH).sub.2, --SO.sub.3H and --SO(OH).sub.2.
[0047] Examples of suitable multifunctional ethylenically
unsaturated esters of (meth)acrylic acid are the polyacrylic acid
or polymethacrylic acid esters of polyhydric alcohols including,
for example, the diacrylic acid and dimethylacrylic acid ester of
aliphatic diols such as ethyleneglycol, triethyleneglycol,
2,2-dimethyl-1,3-propanediol, 1,3-cyclopentanediol,
1-ethoxy-2,3-propanediol, 2-methyl-2,4-pentanediol,
1,4-cyclohexanediol, 1,6-hexamethylenediol, 1,2-cyclohexanediol,
1,6-cyclohexanedimethanol; the triacrylic acid and trimethacrylic
acid esters of aliphatic triols such as glycerin,
1,2,3-propanetrimethanol, 1,2,4-butanetriol, 1,2,5-pentanetriol,
1,3,6-hexanetriol, and 1,5,10-decanetriol; the triacrylic acid and
trimethacrylic acid esters of tris(hydroxyethyl) isocyanurate; the
tetraacrylic and tetramethacrylic acid esters of aliphatic triols,
such as 1,2,3,4-butanetetraol, 1,1,2,2-tetramethylolethane,
1,1,3,3-tetramethylolpropane, and pentaerythritol tetraacrylate;
the pentaacrylic acid and pentamethacrylic acid esters of aliphatic
pentol such as adonitol; the hexaacrylic acid and hexamethacrylic
acid esters of hexanols such as sorbitol and dipentaerythritol; the
diacrylic acid and dimethacrylic acid esters of aromatic diols such
as resorcinol, pyrocatecol, bisphenol A, and bis(2-hydroxyethyl)
phthalate; the trimethacrylic acid ester of aromatic triols such as
pyrogallol, phloroglucinol, and 2-phenyl-2,2-methylolethan- ol; and
the hexaacrylic acid and hexamethacrylic acid esters of dihydroxy
ethyl hydantoin; and mixtures thereof. Other examples include, but
are not limited to, poly-ethoxylated or -propoxylated
di-(meth)acrylate (that is, poly(ethylene/propylene oxide)
di-(meth)acrylate) macromers (that is, macromolecular
monomers).
[0048] Preferably, the multifunctional ethylenically unsaturated
ester of (meth)acrylic acid is a nonpolyetheral multifunctional
ethylenically unsaturated ester of (meth)acrylic acid. More
preferably, the multifunctional ethylenically unsaturated ester of
(meth)acrylic acid is selected from the group consisting of
pentaerythritol triacrylate (PETA), pentaerythritol
trimethacrylate, and a combination thereof. Most preferably, the
multifunctional ethylenically unsaturated ester of (meth)acrylic
acid is pentaerythritol triacrylate.
[0049] In addition to the multifunctional ethylenically unsaturated
esters of acrylic acid, the curable composition, from which the
cured organic matrix is derived, may include at least one
monofunctional ethylenically unsaturated monomer. The
monofunctional ethylenically unsaturated monomer may be a
monofunctional ethylenically unsaturated ester of (meth)acrylic
acid (that is, an alkyl and/or aryl acrylate or methacrylate).
Preferably, the alkyl group of the (meth)acrylate has about 4 to 14
carbon atoms (on average). The alkyl group can optionally contain
oxygen atoms in the chain thereby forming ethers, for example.
Preferably, the aryl group of the (meth)acrylate has about 6 to
about 20 carbon atoms (on average).
[0050] The monofunctional ethylenically unsaturated monomer may be
selected from a group consisting of a monofunctional (meth)acrylic
acid ester, a (meth)acrylamide, an alpha-olefin, a vinyl ether, a
vinyl ester, a vinyl amide and combinations thereof.
[0051] The monofunctional acrylate monomer may be an
N,N-disubstituted (meth)acrylamide monomer or an
N-substituted-N-vinyl-amide.
[0052] Further examples include, but are not limited to,
2-hydroxyethyl acrylate, 2-hydroxymethylacrylate, 2-methylbutyl
acrylate, isooctyl acrylate, lauryl acrylate, 4-methyl-2-pentyl
acrylate, isoamyl acrylate, sec-butyl acrylate, n-butyl acrylate,
n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl
acrylate, isodecyl acrylate, isodecyl methacrylate, and isononyl
acrylate. Other examples include, but are not limited to,
poly-ethoxylated or -propoxylated methoxy (meth)acrylate (that is,
poly(ethylene/propylene oxide) mono-(meth)acrylate) macromers (that
is, macromolecular monomers), polymethylvinyl ether
mono(meth)acrylate macromers, and ethoxylated or propoxylated
nonyl-phenol acrylate macromers. The molecular weight of such
macromers (that is, macromolecular monomers) is typically about 100
grams/mole to about 600 grams/mole, and preferably, about 300
grams/mole to about 600 grams/mole. Preferred monofunctional
(meth)acrylates that can be used include 2-methylbutyl acrylate,
isooctyl acrylate, lauryl acrylate, and methoxy-capped
poly(ethylene glycol) mono-methacrylate.
[0053] The monofunctional ethylenically unsaturated monomer may
also be selected from the group of a (meth)acrylamide, an
alpha-olefin, a vinyl ether, a vinyl ester, a vinyl amide and a
combination thereof. Examples include, but are not limited to,
acrylamides, such as acrylamide, methacrylamide, N-methyl
acrylamide, N-ethyl acrylamide, N-methylol acrylamide,
N-hydroxyethyl acrylamide, diacetone acrylamide, N,N-dimethyl
acrylamide, N,N-diethyl acrylamide, N-ethyl-N-aminoethyl
acrylamide, N-ethyl-N-hydroxyethyl acrylamide, N,N-dimethylol
acrylamide, N,N-dihydroxyethyl acrylamide, t-butyl acrylamide,
dimethylaminoethyl acrylamide, N-octyl acrylamide (normal and
branched), and 1,1,3,3-tetramethylbutyl acrylamide. Other examples
include acrylic acid, methacrylic acid, itaconic acid, crotonic
acid, malieic acid, fumaric acid, 2,2'-(ethoxyethoxy)ethyl
acrylate, 2-hydroxyethyl acrylate or methacrylate, 2-hydroxypropyl
acrylate or methacrylate, 3-hydroxypropyl acrylate or methacrylate,
t-butyl acrylate, n-butyl methacrylate, isobornyl acrylate,
2-(phenoxy)ethyl acrylate or methacrylate, biphenylyl acrylate,
t-butylphenyl acrylate, cyclohexyl acrylate, dimethyladamantyl
acrylate, 2-naphthyl acrylate, phenyl acrylate, N-vinyl
pyrrolidone, and N-vinyl caprolactam. Preferred monofunctional
acrylic monomers include acrylic acid, t-butyl acrylate,
N,N-dimethyl acrylamide, 1,1,3,3-tetramethylbutyl acrylamide,
N-octyl acrylamide, 2-(phenoxy) ethyl acrylate, 2-hydroxypropyl
acrylate, 3-hydroxypropyl acrylate, isobronyl acrylate, and
2-(phenoxy)ethyl acrylate. A particularly preferred monofunctional
unsaturated monomer is N-vinyl caprolactam (NVC).
[0054] In general, the acrylamide compounds have the following
formula: 2
[0055] wherein: R.sup.1 and R.sup.2 are each independently
hydrogen, a (C.sub.1--C.sub.8)alkyl group optionally having
hydroxy, halide, carbonyl, and amido functionalities, a
(C.sub.1--C.sub.8)alkylene group optionally having carbonyl and
amido functionalities, a (C.sub.1--C.sub.4)alkoxymethyl group, a
(C.sub.4--C.sub.18)aryl group, a
(C.sub.1--C.sub.3)alk(C.sub.4--C.sub.18)aryl group, and a
(C.sub.4--C.sub.18)heteroaryl group; with the proviso that only one
of R.sup.1 and R.sup.2 is hydrogen; and R.sup.3 is hydrogen, a
halogen, or a methyl group. Preferably, R.sup.1 is a
(C.sub.1--C.sub.4)alkyl group; R.sup.2 is a (C.sub.1--C.sub.4)
alkyl group; and R.sup.3 is hydrogen, a halogen, or a methyl group.
R.sup.1 and R.sup.2 can be the same or different. More preferably,
each of R.sup.1 and R.sup.2 is CH.sub.3, and R.sup.3 is
hydrogen.
[0056] Examples of suitable (meth)acrylamides are
N-(3-bromopropionamidome- thyl)acrylamide, N-tert-butylacrylamide,
N,N-dimethylacrylamide, N,N-diethylacrylamide,
N-(5,5-dimethylhexyl)acrylamide,
N-(1,1-dimethyl-3-oxobutyl)acrylamide, N-(hydroxymethyl)acrylamide,
N-(isobutoxymethyl)acrylamide, N-isopropylacrylamide,
N-methylacrylamide, N-ethylacrylamide, N-methyl-M-ethylacrylamide,
N-(fluoren-2-yl)acrylamide- , N-(2-fluorenyl)-2-methylacrylamide,
2,3-bis(2-furyl)acrylamide, N,N'-methylene-bis acrylamide. A
particularly preferred acrylamide is N,N-dimethyl acrylamide.
[0057] Organofunctional Silane Monomer Coupling Agent
[0058] The curable organic matrix composition, in addition to at
least one ethylenically unsaturated monomer, comprises an
organofunctional silane monomer coupling agent. A wide variety of
organofunctional silane monomers may be used in the practice of the
present invention. The preferred organofunctional silanes are
hydrolyzable organofunctional silanes, also known in the art as
"coupling agents" for coupling silica particles to organic
materials. Representative examples include methyl trimethoxysilane,
methyl triethoxysilane, phenyl trimethoxysilane, phenyl
triethoxysilane, (meth)acryloxyalkyl trimethoxysilanes, such as
methacryloxypropyl trimethoxysilane, (meth)acryloxypropyl
trichlorosilane, phenyl trichlorosilane, vinyl trimethoxysilane,
vinyl triethoxysilane, propyl trimethoxysilane, propyl
triethoxysilane, glycidoxypropyl trimethoxysilane, glycidoxypropyl
triethoxysilane, glycidoxypropyl trichlorosilane, perfluoroalkyl
trimethoxysilane, perfluoroalkyl triethoxysilane,
perfluoromethylalkyl trimethoxysilanes, such as
tridecafluoro-1,1,2,2-tetrahydrooctyl trimethoxysilane,
perfluoroalkyl trichlorosilanes, trifluoromethylpropyl
trimethoxysilane, trifluoromethylpropyl trichlorosilane, and
perfluorinated sulfonimido ethyl trimethoxysilane (available from
the Minnesota Mining and Manufacturing Company, St. Paul, Minn.,
under the trade designation FC 405), combinations of these, and the
like. Most preferably, the organofunctional silane monomer is
(meth)acryloxypropyl trimethoxysilane.
[0059] Optionally, the inorganic oxide particles may be surface
treated with a silane coupling agent and, in such embodiments, the
coupling agent may be the same or different from the silane
monomers used to form the bulk of the organic binder of the ceramer
composition.
[0060] Inorganic Oxide Particles
[0061] In the present invention, the cured ceramer composition also
includes inorganic oxide particles. The inorganic oxide particles
are dispersed within the cured organic matrix. The preferred
inorganic oxide particles are silica, however others may be
used.
[0062] Silica sols useful for preparing ceramer compositions can be
prepared by methods well known in the art. As used herein, "sol"
shall refer to a colloidal dispersion of substantially
non-aggregated, inorganic oxide particles in a liquid medium.
Colloidal silicas dispersed as sols in aqueous solutions are also
available commercially under such trade names as LUDOX (E. I.
DuPont de Nemours and Co., Wilmington, Del.), NYACOL (Nyacol Co.,
Ashland, Mass.), and NALCO 2327 and 1042 (Nalco Chemical Co., Oak
Brook, Ill.). Nonaqueous silica sols (also called silica
organosols) are also commercially available under the trade names
NALCO 1057 (a silica sol in 2-propoxyethanol, Nalco Chemical Co.),
MA-ST, IP-ST, and EG-ST (Nissan Chemical Ind., Tokyo, Japan) and
HIGHLINK OG Silica Organosols (Clariant Corporation, Charlotte,
N.C.). The silica particles preferably have an average particle
diameter of about 5 nm to about 1000 nm, and more preferably, about
10 nm to about 50 nm. Average particle size can be measured using
transmission electron microscopy or light scattering techniques to
count the number of particles of a given diameter. Additional
examples of suitable colloidal silicas are described in U.S. Pat.
No. 5,126,394 (Bilkadi).
[0063] Preferably, the silica particles are functionalized with a
coupling agent. More preferably, the silica particles are
(meth)acrylate functionalized. Herein "(meth)acrylate
functionalized" means the silica particles are functionalized with
a (meth)acrylate terminated organofunctional silane. The
functionalized particles bond intimately and isotropically with the
organic matrix. Typically, the silica particles are functionalized
by adding a (meth)acrylate functionalized silane to aqueous
colloidal silica. Examples of (meth)acrylate functionalized
colloidal silica are described in U.S. Pat. Nos. 4,491,508 (Olsen
et al.), 4,455,205 (Olsen et al.), 4,478,876 (Chung), 4,486,504
(Chung), and 5,258,225 (Katsamberis).
[0064] In addition to silica, or in place of silica, the colloidal
inorganic particles may be colloidal articles of higher refractive
index than silica. Examples of such higher index colloidal
particles include, but are not limited to, alumina, titania,
zirconia, ceria, and antimony oxide sols, all of which are
available commercially from suppliers such as Nyacol Co., Ashland,
Mass., and Nalco Chemical Co., Oak Brook, Ill.
[0065] It is highly desirable that the colloidal inorganic
particles of the coating be derived from a sol rather than a
powder, which can result in an intractable mass that is unsuitable
for coating. The addition of additives, such as high molecular
weight polymers, may enable compositions derived from colloidal
powder to be cast onto inorganic polymeric substrates. However, it
is believed that the use of compositions containing colloidal
powder will result in coatings having relatively poor optical
transparency and poor flow properties for coating. Therefore, the
use of colloidal powders is not preferable in the coatings of the
present invention. The colloidal silica particles are employed in
the coating at 10% to 50% by weight, and more preferably, at 25% to
40% by weight, and most preferably, at 30% to 33% by weight.
[0066] A cured ceramer composition of the present invention
preferably includes a cured organic matrix and colloidal inorganic
particles that at least include silica. Preferably, the cured
organic matrix is prepared from a curable organic binder, or
curable composition, that includes an ethylenically unsaturated
monomer selected from the group of at least one multifunctional
ethylenically unsaturated ester of (meth)acrylic acid, optionally
at least one monofunctional ethylenically unsaturated monomer (for
example, an ester or amide), and combinations thereof; and at least
one organofunctional silane coupling agent.
[0067] The ceramer composition preferably includes no greater than
about 80 percent by weight (wt. %) of at least one ethylenically
unsaturated monomer and at least about 20 wt. % colloidal inorganic
oxide particles, based on the total weight of the ceramer
composition. Preferably, it includes at least about 40 wt. % of at
least one ethylenically unsaturated monomer, and no greater than
about 60 wt. % of colloidal inorganic oxide particles.
[0068] If the ethylenically unsaturated monomers used include a
mixture of multifunctional and monofunctional ethylenically
unsaturated monomers, the multifunctional monomer is preferably
used in an amount of at least about 20 wt. %, and the
monofunctional monomer is preferably used in an amount of at least
about 5 wt. %. Preferably, the multifunctional monomer is used in
an amount of no greater than about 60 wt. %, and the monofunctional
monomer is used in an amount of no greater than about 20 wt. %.
[0069] If used, an organofunctional silane coupling agent is
preferably used in an amount of no greater than about 80 wt. %,
more preferably, no greater than about 70 wt. %, and most
preferably, no greater than about 60 wt. %, based on the total
weight of the ceramer composition. It is preferably used in an
amount of at least about 5 wt. %, more preferably, at least about
10 wt. %, and most preferably, at least about 15 wt. %, based on
the total weight of the ceramer composition.
[0070] It is the combination of the organic matrix with the
colloidal inorganic oxide particles (with a coupling agent) that
results in unexpected and improved properties as an abrasion
resistant coating for sporting goods. The multifunctional
ethylenically unsaturated esters of (meth)-acrylic acid tend to
increase the hardness of the coating, whereas the monofunctional
ethylenically unsaturated monomer tends to "toughen" the coating
without significant loss in abrasion resistance. Along with the
toughness property, it is also a flexible coating.
[0071] In many instances, the abrasion resistant coating can adhere
directly to the polymeric substrate without the need for an
additional primer or adhesion promoter, which is advantageous at
least because this results in a labor and material savings.
[0072] Optional Initiators and Photosensitizers
[0073] During the manufacture of abrasion resistant coatings, the
uncured ceramer composition can be exposed to an energy source, for
example, heat or ultraviolet (UV) radiation or electron beam
(e-beam) radiation, which initiates a curing process of the curable
composition. This curing process typically occurs via a free
radical mechanism, which can require the use of a free radical
initiator (simply referred to herein as an initiator, for example,
a photoinitiator or a thermal initiator). If the energy source is
an electron beam, the electron beam generates free radicals and no
initiator is required. When the initiator is exposed to one of
these energy sources, the initiator generates free radicals, which
then initiates the polymerization and cross-linking.
[0074] Examples of suitable free radical thermal initiators
include, but are not limited to, peroxides such as benzoyl
peroxide, azo compounds, benzophenones, and quinones. Examples of
photoinitiators that generate a free radical source when exposed to
visible light radiation include, but are not limited to,
benzophenones. Examples of photoinitiators that generate a free
radical source when exposed to ultraviolet light include, but are
not limited to, organic peroxides, azo compounds, quinines,
benzophenones, nitroso compounds, acryl halides, hydrozones,
mercapto compounds, pyrylium compounds, triacrylimidazoles,
bisimidazoles, chloroalkyltriazines, benzoin, benzoin methyl ether,
benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl
ethers and methylbenzoin, diketones such as benzil and diacetyl,
phenones such as acetophenone, 2,2,2-tri-bromo-1-phenylethanone,
2,2-diethoxyacetophenone, 2,2-dimethoxy-2-phenylacetophenone,
2,2,2-tribromo-1(2-nitrophenyl) ethanone, benzophenone, and
4,4-bis(dimethylamino-benzophenone. Examples of commercially
available ultraviolet photoinitiators include those available under
the trade designations IRGACURE 184 (1-hydroxycyclohexyl phenyl
ketone), IRGACURE 361 and DAROCUR 1173 (2-hydroxy-2-methyl-1-pheny-
l-propan-1-one) from Ciba-Geigy, Hawthorn, N.Y. Typically, if used,
an amount of an initiator is included in the precursor composition
to effect the desired level and rate of cure. Preferably, the
initiator is used in an amount of about 0.1 wt. % to about 10 wt.
%, and more preferably about 2 wt. % to about 4 wt. %, based on the
total weight of the curable composition without solvent. It should
be understood that combinations of different initiators can be used
if desired.
[0075] In addition to the initiator, the curable composition of the
present invention can include a photosensitizer. The
photosensitizer aids in the formation of free radicals that
initiate curing of the precursor composition, especially in an air
atmosphere. Suitable photosensitizers include, but are not limited
to, aromatic ketones and tertiary amines. Suitable aromatic ketones
include, but are not limited to, benzophenone, acetophenone,
benzil, benzaldehyde, and o-chlorobenzaldehyde, xanthone,
tioxanthone, 9,10-anthraquinone, and many other aromatic ketones.
Suitable tertiary amines include, but are not limited to,
methyldiethanolamine, ethyldiethanolamine, triethanolamine,
phenylmethyl-ethanolamine, dimethylaminoethylbenzoate, and the
like. Typically, if used, an amount of initiator is included in the
precursor compositions to effect the desired level and rate of
cure. Preferably, the amount of photosensitizer used in the
compositions of the present invention is about 0.01 wt. % to about
10 wt. %, more preferably about 0.05 wt. % to about 5 wt. %, and
most preferably, about 0.25 wt. % to about 3 wt. %, based on the
total weight of the ceramer composition (that is, the abrasion
resistant precursor composition without solvent). It should be
understood that combinations of different photosensitizers can be
used if desired.
[0076] The preferred methods of curing include heat, UV and e-beam.
However, other methods may be used. If thermal (or heat) curing is
used, however, the temperature must not be so high that it will
melt the sporting goods article, or substrate.
[0077] Optional Solvent
[0078] In addition to the other components of the curable ceramer
composition, it may further include a solvent or solvents. The
curable ceramer composition (or curable composition) may include a
solvent or solvents to reduce the viscosity of the curable ceramer
composition in order to enhance the ceramer coating
characteristics. The appropriate viscosity level depends upon
various factors such as the coating thickness, application
technique, and the type of substrate material onto which the
ceramer composition is applied.
[0079] The organic solvent(s) should be selected such that they are
compatible with the components in the ceramer composition. As used
in this context, "compatible" means that there is minimal phase
separation between the solvent and the curable organic binder or
matrix of the ceramer composition. Additionally, the solvent or
solvents should be selected such that they do not adversely affect
the cured coating properties. Furthermore, the solvent(s) should be
selected such that they have an appropriate drying rate. That is,
the solvent(s) should not dry too slowly, which would slow down the
process of making a coated sporting goods article, nor too quickly,
which could cause defects such as pin holes or craters in the
coating. Examples of suitable solvents include alcohols, preferably
the lower alcohols such as isopropyl alcohol, n-butanol, methanol,
ethanol, and ketones such as methyl ethyl ketone, glycols, and
combinations thereof.
[0080] Optional Additives
[0081] The ceramer composition can also preferably include a
leveling agent to improve the flow or wetting of the curable
ceramer composition on the substrate (before it is cured). The
leveling agent can be a solvent that is used to adjust the
viscosity of the ceramer composition. If the ceramer composition
does not properly wet the substrate, this can lead to visual
imperfections (for example, pin holes and/or ridges) in the
coating. Examples of leveling agents include, but are not limited
to, alkoxy terminated polysilicones such as that available under
the trade designation DOW 57 (a mixture of dimethyl-, methyl-, and
(polyethylene oxide acetate)-capped siloxane) from Dow Corning,
Midland, Mich.; and fluorochemical surfactants. The ceramer
composition can include an amount of a leveling agent to impart the
desired result. Preferably, the leveling agent is present in an
amount up to about 3 wt. %, and more preferably, about 0.5 wt. % to
about 1 wt. %, based on the total weight of the ceramer
composition. It should be understood that combinations of different
leveling agents can be used if desired.
[0082] Because organofunctional silane monomers are used, it may be
desirable in some instances to add about 1 wt. % to about 3 wt. %
glacial acetic acid or similar carboxylic acids as a catalyst for
hydrolysis of the organofunctional silane.
[0083] Polymeric materials are known to degrade by a variety of
mechanisms. Common additives that can offset this are known as
stabilizers, absorbers, antioxidants, and the like. The ceramer
compositions of the present invention can include one or more of
the following: ultraviolet stabilizer, ultraviolet absorber, ozone
stabilizer, and thermal stabilizer/antioxidant.
[0084] An ultraviolet stabilizer and/or ultraviolet absorber for
improving weatherability and reducing the "yellowing" of the
abrasion resistant coating with time. An example of an ultraviolet
stabilizer includes that available under the trade designation
TINUVIN 292 (bis(1,2,2,6,6-pentamet- hyl-4-piperidinyl)sebacate)
and an example of an ultraviolet absorber includes that available
under the trade designation TINUVIN 1130 (hydroxyphenyl
benzotriazole), both of which are available from Ciba-Geigy. The
ceramer composition can include an amount of either an ultraviolet
stabilizer and/or an ultraviolet absorber to impart the desired
result. Preferably, the ultraviolet stabilizer or absorber is
present in an amount up to about 10 wt. %, and more preferably,
about 1 wt. % to about 5 wt. %. based on the total weight of the
ceramer composition. It should be understood that combinations of
different ultraviolet stabilizers and absorbers can be used if
desired.
[0085] An ozone stabilizer protects against degradation resulting
from reaction with ozone. Examples of ozone stabilizers include,
but are not limited to, hindered amines such as that available
under the trade designation IRGANOX 1010 available from Ciba-Geigy
and phenoltriazine commercially available from Aldrich Chemical
Company, Inc., Milwaukee, Wis. The ceramer composition can include
an amount of an ozone stabilizer to impart the desired result.
Preferably, the ozone stabilizer is present in an amount up to
about 1 wt. %, more preferably about 0.1 wt. % to about 1.0 wt. %,
and most preferably about 0.3 wt. % to about 0.5 wt. %, based on
the total weight of the ceramer composition.
[0086] A thermal stabilizer/antioxidant reduces the amount of
yellowing as a result of weathering. Examples of such materials
include, but are not limited to, low melting hindered phenols and
trimesters. Specific examples include
2,6-di-tert-butyl-4-methylphenol commercially available under the
trade designation ULTRANOX 226 antioxidant from Borg Warner
Chemicals, Inc., Parkersburg, N.Y.; octadecyl
3,5-di-tert-butyl-4-hydroxy- cinnamate commercially available under
the trade designations ISONOX 132 antioxidant (Schnectady
Chemicals, Inc., Schnectady, N.Y.) or VANOX 1320 antioxidant
(Vanderbilt Co., Inc. Norwalk, Conn.). The ceramer composition can
include sufficient thermal stabilizer/antioxidant to impart the
desired result. Preferably, the thermal stabilizer/antioxidant is
present in an amount up to about 3% by weight, and more preferably
about 0.5 to about 1%, based on the total weight of the ceramer
composition without solvent. It should be understood that
combinations of different thermal stabilizers/antioxidants can be
used if desired.
[0087] Other optional additives to the curable composition, that
eventually forms the cured organic matrix after curing, are
thermosetting resins. These resins may be used to impart their
specific properties to the ceramer composition of the present
invention. Such properties may be desired for particular sporting
goods articles or portions of sporting goods articles. Some
examples of such resins include acrylic, acryl-melamine,
acryl-epoxy, acryl-urethane, melamine-alkyld, epoxy,
epoxy-phenolic, phenolic or silicone resin. These resins are easy
to obtain commercially.
[0088] Some other optional additives may be corrosion reducers or
friction reducers.
[0089] Method of Coating
[0090] To make the curable ceramer composition of the invention,
which results in the cured ceramer composition after it is cured,
all the components are mixed together including the inorganic
particles and the organofunctional coupling agent. Certain
components may be premixed if that is advantageous.
[0091] The mixture is then stripped, e.g., heated under vacuum to
remove substantially all of the water. The resultant dried ceramer
composition is a clear liquid. It may be preferred to filter the
ceramer composition prior to application to a substrate in an
effort to remove gel particles or other agglomerated materials.
[0092] The ceramer composition is applied to the outer portion of
at least one surface of a sporting goods article as a flowable
liquid. It is coated on the surface for which it is desired to
improve the abrasion resistance. The composition may be applied by
many possible methods of application. The method depends upon the
nature of the substrate, the viscosity of the ceramer composition
and the like. Some possible methods of application include, but are
not limited to, spray coating, knife coating, dip coating, flow
coating, roll coating and the like. In spray coating, the ceramer
is atomized and then applied to the outer surface of the substrate.
In dip coating, the substrate is immersed into the ceramer and then
the excess coating drips off the substrate. In flow coating, the
substrate is held in a vertical position and the ceramer is applied
across the top of the substrate. The ceramer then flows down the
substrate. In roll coating, the ceramer is applied to the substrate
by a roll coater.
[0093] The ceramer composition can be applied over the entire
surface of the sporting goods article, one surface if there are
more than one surface, or a portion of one surface. The coating
thickness of the ceramer composition will depend upon the
formulation and the amount of solvent. The thickness of the cured
ceramer composition is such that the coating is effective in
resisting abrasion. Generally, the coating of curable ceramer
composition can be most any thickness that is effective. However,
the thickness is preferably between 1 and 40 microns, and most
preferably between 2 and 10 microns.
[0094] It may be desired to apply more than one layer of curable
ceramer composition to the substrate. Successive layers of curable
ceramer composition may be applied to the outer portion of a
surface of a sporting goods article.
[0095] After the curable ceramer composition is applied to the
substrate, or the outer portion of at least one surface of the
sporting goods article, the solvent is evaporated, or flashed off.
This can be done by using heat to remove the solvents. The
temperature used to remove the solvents depends upon the solvents
that were used. It is typically accomplished at a temperature of
about 15 to 75 degrees Celsius. The flashing unit used can be a
forced-air oven or an infrared heat source, for examples.
[0096] The curable ceramer composition should be applied to the
substrate in a manner to eliminate or minimize any imperfections.
To minimize the formation of such defects, the actual temperature
and humidity conditions may be controlled in a clean room
environment, or a particle-free, filtered room, for examples. The
actual temperature and humidity conditions are dependent upon the
chemistry of the ceramer composition.
[0097] Once the solvent is removed, if used, the layer of ceramer
composition is exposed to an energy source to initiate curing. The
ceramer composition is then cured and forms a coating. The
preferred methods of curing include electron beam, ultraviolet
light and heat. The type of energy source used to cure the ceramer
depends upon the chemical composition of the curable ceramer
composition. The amount of energy required to cure the curable
ceramer composition is also dependent upon the chemistry of the
composition, as well as thickness and density of the coating.
Electron beam radiation can be used at an energy level of about 0.1
megarad to about 10 megarad (Mrad). Ultraviolet radiation refers to
nonparticulate radiation having a wavelength within the range of
about 200 to 400 nanometers. Upon curing, that is, polymerizing
and/or cross-linking, the ceramer composition is solidified to form
a coating.
[0098] It is to be understood that the method of application of the
curable ceramer composition to the sporting goods article is meant
to be an illustration of one process. It is within the scope of
this invention to have many variations on the process of
application of the ceramer. The Examples below describe in more
detail processes that may be used.
[0099] Graphics
[0100] Another embodiment of the present invention is a sporting
goods article comprising a substrate, graphics, and a coating
provided on at least a portion of a surface of said substrate,
wherein said portion of said surface of said substrate has at least
an outer layer comprising a material selected from the group
consisting of polymers, woods, metals, non-polymeric inks,
non-polymeric colorants, non-polymeric dyes, wherein said coating
comprises a cured ceramer composition that is derived from
ingredients comprising inorganic oxide particles and a curable
organic matrix, and wherein said curable organic matrix comprises
at least one ethylenically unsaturated monomer and at least one
organofunctional silane monomer coupling agent.
[0101] "Graphics," in this application, refers to text, pictures,
drawings, logos, insignias, trademarks, service marks and the like,
that comprise polymers, non-polymeric inks, non-polymeric
colorants, non-polymeric dyes, or combinations thereof, and that
are used to decorate or identify the articles that they are
attached to, adhered to or placed on.
[0102] It is important to protect the visual appearance of the
graphics on sporting goods for aesthetic reasons. In addition, the
companies that sell the sporting goods want the appearance of the
graphics to remain good on the articles as, for example,
advertisement for the companies' articles.
[0103] The graphics in the present invention may be on the top of
the outer portion of the surface of the body of the sporting goods
article. The cured ceramer composition may then be used to protect
the graphics from abrasion. However, the graphics may also be
underneath another layer of polymer or other clear material. If
that is the case, then the cured ceramer composition may be used to
protect the visual appearance of the graphics at the same time as
protecting the outer portion from abrasion, since it is necessary
for the outermost layer of polymer or other material of the
sporting goods article to maintain its optical clarity to allow the
graphics to be seen through the outermost layer of clear polymer or
other material.
[0104] Advantages
[0105] Besides the abrasion resistance of the cured ceramer
composition, the cured ceramer composition also offers other
advantages. For instance, the cured ceramer composition can result
in a higher gloss appearance than the base substrate. This adds to
the aesthetics of the sporting goods. The cured ceramer composition
also offers optical clarity, which allows the appearance of the
graphics under the composition to be unaffected by the cured
ceramer layer. The cured ceramer composition also does not require
that a primer be applied for it to adhere to the polymers, metals,
woods, non-polymeric inks, non-polymeric colorants, non-polymeric
dyes, and combinations thereof, on the sporting goods article. The
cured ceramer composition used also results in uniform coating of
the substrate. In addition, an important advantage of the cured
ceramer composition is that it is flexible in a broad range of
temperatures. This allows the ceramer coating to be used on areas
of sporting goods that need to flex, and on sporting goods that are
subject to wide temperature ranges or extremes. Yet another
advantage is that the cured ceramer layer is compatible with dyes,
inks and colorants, which allows graphics to be incorporated into
the sporting goods article.
[0106] Objects and advantages of this invention will now be
illustrated by the following Examples, but the particular materials
and amounts thereof recited in these Examples, as well as other
conditions and details, should not be construed to unduly limit
this invention.
EXAMPLES
[0107] Preparations
Preparation of Curable Composition (A)
[0108] (Aldrich Chemical Co.; Milwaukee, Wis.), 31.2 g (0.13 moles)
of 3-(trimethoxysilyl)propyl methacrylate (Dow Coming; Midland
Mich. product, Z-6030), 19.5 g (0.14 moles) of N-vinylcaprolactam
(Aldrich Chemical Co.; Milwaukee, Wis.), 17.5 mg
(8.78.times.10.sup.-5 moles) of phenothiazine (Aldrich Chemical
Co.; Milwaukee, Wis.) and 15.9 mg (7.22.times.10.sup.-5 moles) of
butylated hydroxytoluene (2,6-di-tert-butyl-4-methylphenol (Aldrich
Chemical Co.; Milwaukee, Wis.). The mixture was stirred for
approximately 30 minutes until all reagents were completely
dissolved. Upon addition of 312.4 g of NALCO.TM. 2327 (40% aqueous
dispersion of colloidal silica with a pH of 9.3; particle size=20
nm; ammonium stabilized, available from Nalco Chemical Co., Oak
Brook, Ill.), the solution became a milky white suspension. The
resin flask was sealed and a 24 cm distillation column and 500 mL
receiving flask, cooled to -78.degree. C. with a dry ice/acetone
bath, were attached. A thermocouple was placed in the reaction
mixture to monitor the reaction temperature. Vacuum was slowly
applied to the apparatus through the distillation head until
reaching a pressure of 10 torr. The temperature of the mixture was
slowly increased, causing the distillation of water from the
suspension. As the distillation proceeded and the distillation of
water was nearly complete the mixture changed from a milky white
suspension to an opaque yellow, nearly clear solution. Water
distillation ceased from the solution when the mixture reached
approximately 50.degree. C. Approximately 195 g of the curable
composition product were recovered from the resin flask. The
curable composition product was diluted to 50% solids by adding 195
g of isopropyl alcohol. The ensuing mixture is curable composition
(A).
Coating Methods
[0109] Coating Method 1
[0110] The coating method 1 was done in three steps:
[0111] (1) Spray coating of curable composition: To 4 kg of curable
composition (A) was added 1.8 kg of n-butanol and 2.2 kg of
isopropyl alcohol and n-butanol to yield a 25% mixture of curable
composition mixture. This 25% curable composition mixture was
charged to the 20 liter tank of a spray coater and sprayed through
a SATA LP 90 NZ nozzle fitted with a 0.5 mm orifice. The following
pressures were used:
[0112] Pot pressure: 12.5 psi
[0113] Gun pressure: 46.0 psi
[0114] Fan air: 50.0 psi
[0115] Atomizing air: 16.0 psi
[0116] Sufficient coating was applied to achieve a coating
thickness in the range of 7-10 microns.
[0117] (2) IR Heating: The freshly spray coated item was placed on
a 6.1 meter conveyor belt traveling at 1.2 meters/minute and
exposed to IR irradiation in a 3.7 meter oven with three heating
stages. The first 1.2 meter long stage was set at 60.degree. C.,
the second 1.2 meter long stage was set at 82.degree. C. and the
final 1.3 meter long stage was set to 65.degree. C., respectively.
These temperatures were recorded at the surface of the conveyor
belt. Only minimal cooling of the coated item was allowed prior to
the UV curing step.
[0118] (3) UV Curing: A UV curing station (2 mercury H lamps, each
118 watts/cm and 15.2 cm long; available from Fusion UV Systems,
Inc; Rockville Md.) yielding an output of 750 mJ/cm.sup.2 at the
conveyor surface, fitted with a conveyor traveling at 3.7
meters/min was used to achieve UV curing of the spray-coated
curable composition on the surface of the substrate. The surface
temperature of the substrate upon entering the UV curing chamber
was 54.degree. C.
[0119] Coating Method 2
[0120] To 1 kg of curable composition (A) was added 1 kg of
isopropyl alcohol to achieve a 25% solids curable composition
mixture. 1.8 kg of the ensuing mixture was charged to a 2000 mL
graduated cylinder. The item to be coated was slowly lowered into
the mixture in the graduated cylinder and withdrawn. The coated
item was vertically suspended in an oven with an internal
temperature of 70.degree. C. for a period of 5 minutes. The
resulting dried, coated item was then horizontally placed on a
cradle which allowed it to be conveniently subjected to UV curing
on a conveyor traveling at 7.6 meters/minute (2 UV lamps @ 236
watts/cm each and 22.9 cm long; Fusion UV Systems, Inc, Rockville,
Md.). The item was subjected to four passes under the UV curing
system, each time being rotated 90 degrees with respect to the long
axis of the shaft, to assure complete UV exposure, and thus curing
all of the curable composition on the item.
Test Methods
[0121] Test Method 1. The surface of the material to be tested was
taped off to mark the area to be evaluated. Three initial gloss
angles (20.degree., 60.degree. and 85.degree.) using a glossmeter
(ASTM D 523-89) and initial pencil hardness values (PH; ASTM D
3363-92a) were measured. Cross cut adhesion (Cross Cut Adh; ASTM
D-3359) measurements were made on treated surfaces. 15 g of 0000
steel wool was placed directly onto the surface of the test item
followed by a 1246 g weight of dimensions 7.6 cm.times.8.9 cm. The
weight was manually passed back and forth over the area to be
evaluated without applying additional hand pressure to the weight.
When the appropriate number of passes were executed, additional
gloss and hardness readings are taken. In addition, coating
appearance was visually rated using the following scale:
[0122] 1=extreme abrasion
[0123] 2=heavy abrasion
[0124] 3=moderate abrasion
[0125] 4=slight abrasion
[0126] 5=no abrasion
[0127] Test Method 2. Initial gloss angles were measured on the
surface of the item using a glossmeter (ASTM D 523-89) and initial
pencil hardness values (ASTM D 3363-92a). Approximately 15 g of
0000 steel wool was rubbed with equal pressure over the untreated
and treated surface of the test item at medium hand pressure. The
resulting surface of the item was visually rated using the
following scale:
[0128] 1=extreme abrasion
[0129] 2=heavy abrasion
[0130] 3=moderate abrasion
[0131] 4=slight abrasion
[0132] 5=no abrasion
Example 1
[0133] A hard coat ceramer coating was applied to a PROCARV.TM.
5.20 snow ski (from Atomic, Austria) using curable composition (A)
and coating method 1. Test method 1 was used to evaluate the
surface coating. The test results listed in Table A show that the
ceramer coating exhibits superior visual rating, gloss and pencil
hardness values over the untreated substrate. In addition, the
cured ceramer coating shows no loss of adhesion to the substrate,
as exhibited by the cross cut adhesion values.
Example 2
[0134] A hard coat ceramer was applied to an X CARVE.TM. 3.0 snow
ski (from Elan, Begunje, Slovenia) using curable composition (A)
and coating method 1. Test method 1 was used to evaluate the
surface coating. The test results listed in Table B show that the
ceramer coating exhibits superior visual rating, gloss and pencil
hardness values over the untreated substrate. In addition, the
cured ceramer coating shows no loss of adhesion to the substrate,
as exhibited by the high cross cut adhesion values.
Example 3
[0135] A hard coat ceramer was applied to an Junior Z-BUBBLE.TM.
hockey stick (from Easton) using curable composition (A), and
coating method 1. Test method 1 was used to evaluate the surface
coating. The test results listed in Table C show that the ceramer
coating exhibits superior visual rating, gloss and pencil hardness
values over the untreated substrate. In addition, the cured ceramer
coating shows no loss of adhesion to the substrate, as exhibited by
the high cross cut adhesion values.
Example 4
[0136] A hard coat ceramer was applied to a M49V.TM. ski binding
(from Marker USA, Salt Lake City, Utah) using curable composition
(A) and coating method 1. Test method 2 was used to evaluate the
surface coating. The test results listed in Table D show that the
ceramer coating exhibits superior visual rating, gloss and pencil
hardness values over the untreated substrate. In addition, the
cured ceramer coating shows no loss of adhesion to the substrate,
as exhibited by the high cross cut adhesion values.
Example 5
[0137] A hard coat ceramer was applied to a LS snow board binding
(from Preston) using curable composition (A) and coating method 1.
Test method 2 was used to evaluate the surface coating. The test
results listed in Table E show that the ceramer coating exhibits
superior visual rating, gloss and pencil hardness values over the
untreated substrate. In addition, the cured ceramer coating shows
no loss of adhesion to the substrate, as exhibited by the high
cross cut adhesion values.
Example 6
[0138] A hard coat ceramer was applied to a HH 4000L helmut (from
Bauer) using curable composition (A) and coating method 1. Test
method 2 was used to evaluate the surface coating. The test results
listed in Table F show that the ceramer coating exhibits superior
visual rating, gloss and pencil hardness values over the untreated
substrate. In addition, the cured ceramer coating shows no loss of
adhesion to the substrate, as exhibited by the high cross cut
adhesion values.
Example 7
[0139] A hard coat ceramer was applied to an AIR ATTACK.TM. golf
club shaft (from True Temper Sports, Inc.) using curable
composition (A) and coating method 2. Test method 2 was used to
evaluate the surface coating. The test results listed in Table G
show that the ceramer coating exhibits superior visual rating
values over the untreated substrate.
Example 8
[0140] A hard coat ceramer was applied to a A/C 3-71/300 arrow
shaft (from Easton) using curable composition (A) and coating
method 2. Test method 2 was used to evaluate the surface coating.
The test results listed in Table H show that the ceramer coating
exhibits superior visual rating values over the untreated
substrate.
1TABLE A Atomic PROCARV .TM. 5.20 ski Cross Gloss angle Visual Cut
20.degree. 60.degree. 85.degree. Rating PH Adh Initial treated 77.1
93.8 95.8 2B 5B untreated 48.1 73.3 88.3 4B 50 treated 84.2 94.4
96.6 5 passes untreated 9.3 44.2 86.5 1 100 treated 84.9 94.4 97.1
5 passes untreated 6.7 39.1 84.9 1
[0141]
2TABLE B Elan X CARVE .TM. 3.0 ski Cross Gloss angle Cut 20.degree.
60.degree. 85.degree. Rating PH Adh Initial treated 56.4 92.9 89.1
2B 5B untreated 48.6 84.1 86 6B 50 treated 56.8 93.1 86.8 5 passes
untreated 24.9 69.8 77.6 2 100 treated 56.1 93.7 88.5 5 passes
untreated 22 68.6 85.2 2
[0142]
3TABLE C Easton Junior Z-BUBBLE .TM. hockey stick Cross Gloss angle
Visual Cut 20.degree. 60.degree. 85.degree. Rating PH Adh Initial
treated 17.2 66.2 37.6 5B untreated 16 61.5 65.1 50 treated 17.1
67.5 66.9 5 passes untreated 8.3 47.7 58.9 3 100 treated 17.6 67.6
67.0 5 passes untreated 6.8 40.4 54.7 3
[0143]
4 TABLE D Marker M 49V .TM. ski binding Cross Visual Cut Rating PH
Adh Initial treated 2H 5B untreated 2B 50 treated 3 passes
untreated 1 100 treated 3 passes untreated 1
[0144]
5 TABLE E Preston LS Ride snowboard binding Cross Visual Cut Rating
PH Adh Initial treated H 5B untreated 2B 50 treated 5 passes
untreated 2 100 treated 5 passes untreated 2
[0145]
6 TABLE F Bauer HH-4000L Helmet Cross Visual Cut Rating PH Adh
Initial treated HB 5B untreated 6B 50 treated 5 passes untreated 3
100 treated 5 passes untreated 3
[0146]
7TABLE G True Temper AIR ATTACK .TM. golf shaft Visual Rating 50
treated 5 passes untreated 1 100 treated 5 passes untreated 1
[0147]
8TABLE H Easton A/C 3-71/300 arrow shaft Visual Rating 50 treated 4
passes untreated 1 100 treated 4 passes untreated 1
[0148] Various modifications and alterations of this invention will
be come apparent to those skilled in the art without departing from
the scope and spirit of this invention.
* * * * *