Ceramics Coating PDF
Ceramics Coating PDF
Ceramics Coating PDF
Example 4
Ingredient Weight Percent
epoxy resin 15.54 Example 9
propylene glycol methyl ether acetate 50.04 Ingredient Weight Percent
methyl ethyl ketoxime-blocked 20.52 50
polyisocyanate epoxy resin 7.28
propylene glycol methyl ether acetate 34.94
solvent naphtha 6.84 methyl ethyl ketoxine-blocked 22.82
n-butyl acetate 6.22 polyisocyanate
fluoropolymer surfactant 0,16 solvent naphtha 7.61
aminopropyl trimethoxy silane 0.31 xylene 14.11
xylene 0.37 55
fluoropolymer surfactant 0.10
dibutyltin dilaurate 37 ppm aminopropyl trimethoxy silane 0.23
benzotriazole 1.94
hindered amine 0.97
dibutyltin dilaurate 28 ppm
Example 5
Ingredient Weight Percent
epoxy resin 6.2 Example 10
propylene glycol methyl ether acetate 47.98
methyl ethyl ketoxime-blocked 21.29 Ingredient Weight Percent
polyisocyanate 65 epoxy resin 7.63
solvent naphtha 7.11 propylene glycol methyl ether acetate 45.13
n-butyl acetate 6.45 caprolactam-blocked polyisocyanate 22.50
fluoropolymer surfactant 0.08 xylene 14.39
n-butanol 0.58 fluoropolymer surfactant 0.11
5,234,983
9 10
-continued tions given above, one skilled in the art would recognize
Example 10 that it would not be mixed with the other ingredients
Ingredient Weight Percent until just prior to application of the formulation to the
aminopropyl trimethoxysilane 0.24 ceramic or other substrate. The nature of all compo
dibutyltin dilaurate 28 ppm nents is such that the preparation of the composition
does not require any particular procedure. All ingredi
ents, with the exception of the adhesion promoter, may
be mixed according to standard laboratory and com
Example 1 10 mercial techniques that are well known to those skilled
Ingredient Weight Percent in the art. The resulting coating compositions are stable
epoxy resin 8.80 at room temperature, inasmuch as the blocked isocya
propylene glycol methyl ether acetate 46.30
caprolactam-blocked polyisocyanate 19.18 nates become deblocked at approximately 300' F. (149
xylene 15.35 C.).
fluoropolymer surfactant
aminopropyl trimethoxy silane
0.11
0.26
15 In use, the coating formulations of this invention are
dibutyltin dilaurate 30 ppm applied to a rigid substrate, such as the surface of a mug,
that is to be imprinted with an image by sublimation or
diffusion transfer. The coating may be applied in any of
20 the ways available for application of thin layers of mate
Example 12 rial to a supporting substrate, most commonly by spray
Ingredient Weight Percent ing or dipping in a liquid bath. As mentioned above,
epoxy resin 17.15 different formulations with different viscosities would
propylene glycol methyl ether acetate 48.75 be used to best suit different methods of application.
caprolactam-blocked polyisocyanate 20.20
xylene 3.52 25 An adhesion promoter, if used, is either mixed with
fluoropolymer surfactant 0.12 the composition or it is instead first applied by itself to
aminopropyl trimethoxy silane 0.26 the substrate immediately prior to application of the
dibutyltin dilaurate 32 ppm
coating. A thin layer of coating is then applied and
30
cured at approximately 400 F. (204' C.) for about 15
minutes to cause the partial polymerization of the mix
- Example 13 ture to obtain a polyurethane coating. This polymer will
Ingredient Weight Percent contain unreacted isocyanate groups that are instrumen
epoxy resin 18.29 tal to the functioning of the invention after the image
propylene glycol methyl ether acetate 43.80 35 transfer has taken place. After cooling, the coating is
methyl ethyl ketoxime-blocked 27.87 stable at normal ambient conditions because a tempera
polyisocyanate
solvent naphtha 9.29 ture of approximately 110 F. (43° C) in 100% relative
xylene
fluoropolymer surfactant
0.34
0.3
humidity is required for the isocyanates to start react
aminopropyl trimethoxy silane 0.28 ing. Thus, the problem of unrefrigerated transportation
dibutyltin dilaurate 34 ppm and storage during the summer is overcome.
After application and curing of the coating, the
coated articles are ready for imprinting according to the
standard procedures used for sublimation and diffusion
Example 14 transfer. When the coating is first exposed to hot water,
Ingredient Weight Percent 45
such as in an automatic dishwasher, the isocyanate
epoxy resin
propylene glycol methyl ether acetate
16.09
24.54
groups react with water, liberating CO2 and freeing
methyl ethyl ketoxine-blocked 24.52 amine groups that form highly cross-linked
polyisocyanate polyisocyanurates as a film along the surface of the
Water
solvent naphtha
21.06
8.17 SO coating. This polymer skin provides protection of the
xylene 5.25 image fixed in the coating and prevents the loss of adhe
fluoropolymer surfactant 0.1 sion that is normally characteristic of polyurethane
aminopropyl trimethoxysilane 0.25 coatings. I found that no appreciable image distortion or
dibutyltin dilaurate 30 ppm
coating damage is visible after 100 dishwasher cycles.
55 Thus, while the invention has been particularly
shown and described with reference to a preferred en
Example 15 bodiment thereof, it will be understood by those skilled
Ingredient Weight Percent in the art that changes in form and detail may be made
epoxy resin 16.03 therein without departing from the spirit and the scope
propylene glycol methyl ether acetate 46.53 of the invention.
caprolactam-blocked polyisocyanate 24.43 I claim:
xylene 12.64
fluoropolymer surfactant 0. 1. A polyurethane coating composition for applica
aminopropyl trimethoxy silane 0.25 tion over the surface of a substrate to be imprinted with
dibutyltin dilaurate 30 ppm 65 an image by means of sublimation transfer, comprising:
(a) an epoxy component in the range from 4 to 30
While the adhesion-promoter component is listed as percent by weight of the total composition and
one of the ingredients of the composition in all formula having a formula corresponding to:
5,234,983
11 12
from the group consisting of polypropylene glycol
methyl ether acetate, ethyl 3ethoxypropionate, or a
O R OH mixture thereof.
/ N 15. The polyurethane coating composition of claim
CH-CHCH o-a--at-o-CH-CH-ch 13, wherein the solvent carrier is diluted with an ingre
R
r dient selected from the group consisting of lower boil
R O
ing esters, aromatic hydrocarbon solvents, n-butanol,
/ N isopropanol, water, or mixtures thereof.
16. The polyurethane coating composition of claim 1,
-o-At--ar-o-CHCH-ch.
R
10 further comprising a urethane polymerization catalyst.
17. The polyurethane coating composition of claim
Aris any aryl group; n may vary between 2 and 18; 16 wherein said urethane polymerization catalyst is
and R and R' consist of a hydrocarby radical with selected from the group consisting of tertiary amines,
1-6 carbon atoms, or of mixtures thereof; and 15 amine-blocked Lewis acids, p-toluenesulfonic acid/
(b) a polyisocyanate component in the range from 3 tris(dimethylaminonethyl) phenol, dibutyltin dilaurate,
to 36 percent by weight of the total composition, and stannous octoate.
wherein the isocyanate groups comprise at least 18. The polyurethane coating composition of claim 1,
two functional groups and are blocked with a further comprising a flow modifier.
blocking group capable of being deblocked upon 20 19. The polyurethane coating composition of claim
heating at about 250 to about 430 F.; 18, wherein said flow modifier is selected from the
wherein the epoxy and isocyanate components are group consisting of silanol-dimethyldiphenylsiloxane,
combined to form a highly crosslinked polyure fluoropolymer surfactants, or mixtures thereof in con
thane polymer. centrations of 0.2 to 1.0 parts per hundred parts by
2. The polyurethane coating composition of claim 1, 25 weight of polyurethane resin.
wherein the epoxy component is present in the range 20. The polyurethane coating composition of claim 1,
from 10 to 25 percent by weight of the total composi further comprising a component capable of screening or
tion.
3. The polyurethane coating composition of claim 1, absorbing ultraviolet radiation.
wherein in may vary between 8 to 14 in the formula for
21. The polyurethane coating composition of claim
the epoxy component. 30 20, wherein said component capable of screening or
4. The polyurethane coating composition of claim 1, absorbing ultraviolet radiation is selected from the
wherein the polyisocyanate component is present in the group consisting of hindered-amine light stabilizers,
range from 6 to 30 percent by weight of the total com hindered phenols, benzotriazoles, cyanoacrylate esters,
position. or mixtures thereof,
5. The polyurethane coating composition of claim 1, 35 22. The polyurethane coating composition of claim 1,
wherein the polyisocyanate groups are blocked with an further comprising an adhesion promoter added to the
oxime group. composition immediately prior to its use for coating a
6. The polyurethane coating composition of claim 1, substrate surface.
wherein the polyisocyanate groups are blocked with 23. The polyurethane coating composition of claim
methyl ethyl ketoxime. 22, wherein said adhesion promoter is selected from the
7. The polyurethane coating composition of claim 1, group consisting of aminopropyltrimethoxysilane,
wherein the polyisocyanate groups are blocked with aminopropyltriethoxysilane, aminoethylaminopropyl
caprolactam. trimethoxysilane, aminoethylaminopropylethoxysilane,
8. The polyurethane coating composition of claim 1, or mixtures thereof in concentrations of 0.2 to 2.0 parts
wherein the isocyanate groups have an aliphatic back 45 per hundred parts by weight of polyurethane resin.
bone. 24. A highly crosslinked polyurethane coating com
9. The polyurethane coating composition of claim 1, position applied over the surface of a substrate to be
wherein the isocyanate groups have a cycloaliphatic imprinted with an image by means of sublimation trans
backbone. fer, comprising the following ingredients in the speci
10. The polyurethane coating composition of claim 1, SO fied concentrations expressed as weight percentages of
wherein the epoxy and isocyanate components are com total composition:
bined in an equivalent-weight ratio in the range from 0.6
to 1.2.
11. The polyurethane coating composition of claim 1, Ingredient Weight Percent
wherein the epoxy component is diluted with an ingre 55 epoxy resin 18.33
dient selected from the group consisting of polyesters, ethyl 3-ethoxy propionate 43.75
polyethers, polyacrylic polyols, and mixtures thereof. melanine resin 3.23
polyarylate polyol. S.80
12. The polyurethane coating composition of claim 1, methyl ethyl ketoxime-blocked 7.76
wherein the polyisocyanate component is diluted by polyisocyanate
substituting 10 to 20 percent of polyisocyanate equiva fluoropolymer surfacant 0.11
lents with equivalents of melamine resin. n-butano
n-butyl acetate
.94
7.96
13. The polyurethane coating composition of claim 1, propylene glycol methyl ether acetate 5.58
further comprising a solvent carrier consisting of a solvent naphtha 2.54
mixture of glycolether esters and aromatic hydroca xylene 0.80
brons. 65 p-toluenesulfonic acid 0.65
14. The polyurethane coating composition of claim 1, isopropanol 0.43
aminopropyltrimethoxysilane 1.08
wherein the solvent carrier consists of an aromatic hy
drocarbon in combination with an ingredient selected
13
5,234,983
14
25. A highly crosslinked polyurethane coating com
position applied over the surface of a substrate to be
imprinted with an image by means of sublimation trans O
/ N
R OH
fer, comprising the following ingredients in the speci
fied concentrations expressed as weight percentages of 5 CH-CHCH o-ar--ar-o-ch-ch-ch
R"
total composition: r
r R O
Ingredient Weight Percent / N
epoxy resin 17.42
O -o-a--at-o-CHCH-CH.
R'
propylene glycol methyl ether acetate 40.91
methyl ethyl ketoxime-blocked 23.00
polyisocyanate wherein Ar is an aryl group; n may vary between
solvent naphtha 7.67 2 and 18; and R and R' consist of a hydrocarbyl
xylene 10.79 5 radical with 1-6 carbon atoms; or of mixtures
fluoropolymer surfactant 0.04 thereof; and the polyisocyanate component being
aminopropyl trimethoxy silane 0.17 in the range from 3 to 36 percent by weight of total
dibutyltin dilaurate 34 ppm composition, wherein the isocyanate groups com
prise at least two functional groups and are blocked
26. A method of coating the surface of a substrate to 20 with a blocking group capable of being deblocked
be imprinted with an image by means of sublimation upon heating at about 250 to about 430' F.;
transfer, comprising the following steps: (b) adding an adhesion promoter to the polyurethane
(a) providing a polyurethane composition comprising composition;
a mixture of an epoxy component and a polyisocya (c) coating the surface of the substrate with the poly
nate component, the epoxy component being in the 25 urethane composition; and
(d) curing the coating at approximately 400 F. for
range from 4 to 30 percent by weight of total com about 15 minutes to cause a highly crosslinked
position and having the formula corresponding to: partial polymerization of the mixture.
k k x k
30
35
45
50
55
65