U.S. patent application number 11/426123 was filed with the patent office on 2006-10-19 for method and compositions for applying multiple overlying organic pigmented decorations on ceramic substrates.
Invention is credited to DONALD P. HART, RICHARD W. MORALES, ROBERT H. TANG, ALAN E. WANG, YINGCHAO ZHANG.
Application Number | 20060235111 11/426123 |
Document ID | / |
Family ID | 30000719 |
Filed Date | 2006-10-19 |
United States Patent
Application |
20060235111 |
Kind Code |
A1 |
TANG; ROBERT H. ; et
al. |
October 19, 2006 |
METHOD AND COMPOSITIONS FOR APPLYING MULTIPLE OVERLYING ORGANIC
PIGMENTED DECORATIONS ON CERAMIC SUBSTRATES
Abstract
A pigmented curable composition adapted for decorating ceramic
substrates (e.g., glass bottles) comprises curable organic binder
and solid spherical particles (glass or polymer) having diameters
of 10 to 50 microns for facilitating overprinting of additional
layers. The preferred embodiment comprises: (a) reactive organic
resin component in which epoxy groups comprise the major reactive
functionality; (b) amino-functional curing agent; (c) blocked
polyisocyanate; and (d) 5 to 35 percent solid spherical particles
having diameters of 10 to 50 microns.
Inventors: |
TANG; ROBERT H.;
(Murrysville, PA) ; ZHANG; YINGCHAO; (Murrysville,
PA) ; MORALES; RICHARD W.; (South Milwaukee, WI)
; WANG; ALAN E.; (Gibsonia, PA) ; HART; DONALD
P.; (Pittsburgh, PA) |
Correspondence
Address: |
PPG INDUSTRIES INC;INTELLECTUAL PROPERTY DEPT
ONE PPG PLACE
PITTSBURGH
PA
15272
US
|
Family ID: |
30000719 |
Appl. No.: |
11/426123 |
Filed: |
June 23, 2006 |
Related U.S. Patent Documents
|
|
|
|
|
|
Application
Number |
Filing Date |
Patent Number |
|
|
10465486 |
Jun 19, 2003 |
|
|
|
11426123 |
Jun 23, 2006 |
|
|
|
60391555 |
Jun 25, 2002 |
|
|
|
Current U.S.
Class: |
523/223 ;
257/E21.568; 257/E21.569 |
Current CPC
Class: |
Y10T 428/25 20150115;
H01L 21/76256 20130101; H01L 21/2007 20130101; H01L 21/76254
20130101 |
Class at
Publication: |
523/223 |
International
Class: |
C08K 7/16 20060101
C08K007/16 |
Claims
1. A one-component pigmented curable composition adapted for
decorating ceramic substrates, said composition comprising: curable
organic binder; and 5 to 50 weight percent rigid substantially
spherical organic particles having average diameters of 5 to 50
microns, percentages based upon total weight of the composition,
wherein the curable organic binder comprises polyepoxy-functional
reactive resin wherein the particles are not expanded or
expandable.
2. The composition of claim 1, wherein the polyepoxy-functional
reactive resin contains an average of epoxy groups per molecule
greater than 1.0.
3. The composition of claim 1, wherein the polyepoxy-functional
reactive organic resin comprises polyglycidyl ether of polyhydric
alcohol.
4. The composition of claim 3, wherein the polyhydric alcohol is
bisphenol A.
5. A pigmented curable composition adapted for decorating ceramic
substrates, said composition comprising: curable organic binder,
and 5 to 50 weight percent rigid substantially spherical organic
particles having average diameters of 5 to 50 microns, percentages
based upon total weight of the composition, wherein the curable
organic binder further comprises an amino-functional curing agent
selected from the group consisting of melamine,
2,4,6-tris(alkoxycarbonylamino)-1,3,5-triazine where each alkoxy
independently contains from 1 to 4 carbon atoms, a compound
represented by the formula: ##STR3## wherein: R.sub.1, R.sub.2, and
R.sub.3 each independently represents hydrogen, alkyl containing
from 1 to 3 carbon atoms, or hydroxyalkyl containing from 1 to 3
carbon atoms, R.sub.4 represents hydrogen, phenyl, cyano, acetyl,
or ##STR4## R.sub.5 represents O, S, or NH, and R.sub.6 and R.sub.7
each independently represents hydrogen, alkyl containing from 1 to
3 carbon atoms, hydroxyalkyl containing from 1 to 3 carbon atoms,
or phenyl, and a mixture of two or more thereof and wherein the
particles are not expanded or expandable.
6. The composition of claim 5, wherein the amino-functional curing
agent comprises dicyandiamide.
Description
CROSS-REFERENCE TO RELATED APPLICATION
[0001] This application is a continuation of U.S. patent
application Ser. No. 10/465,486, filed Jun. 19, 2003, which claims
priority under 35 U.S.C. .sctn.119 to U.S. Provisional Application
Ser. No. 60/391,555, filed Jun. 25, 2002, both of which are hereby
incorporated by reference.
BACKGROUND OF THE INVENTION
[0002] This invention relates to decorating ceramic objects,
particularly glass articles such as glass containers. As used
herein "glass" should be understood to refer to a wide range of
ceramic substrates, including glass. Although decorating glass
containers, particularly bottles, is a use for which the invention
finds particular utility, it should be understood that the shape of
the substrate does not affect the utility of the invention.
Decorating may refer to printing discrete words or designs onto the
substrate or onto a previously applied coated areas, or it may
involve applying a coating (colored or clear, opaque or
transparent) onto substantial areas of the substrate. In either
case, the process may be referred to as "printing" and the material
used may be referred to as "ink." Application of brand indicia to
glass bottles is one commercially important example.
[0003] In particular, the present invention deals with the
application of two or more layers of organic decoration having
different colors in which at least a portion of the layers overlap
in direct contact with each other. For example, a colored field may
first be applied to the substrate, and then lettering of a
different color printed onto the first colored field. When a second
decorating layer is printed onto a first decorating layer that has
not been sufficiently hardened by curing, there is considerable
risk that the first layer will be damaged by the second printing
operation. For example, in the screen printing operations typically
used in the ceramic decorating industry, contact by the screen in
the second printing step often causes uncured portions of the first
decorating layer to be lifted from the substrate. A common response
to this problem is to cure or at least partially cure a previous
decorating layer before applying a second layer, either by passing
the articles being decorated through a curing oven or by
specialized intermediate curing means such as ultraviolet curing.
These additional steps disadvantageously add cost, complexity, and
process time to the decorating process. It would be highly
desirable if multi-layered organic decorations could be applied to
ceramic substrates without the inconvenience and cost of added
steps.
[0004] In the past, glass decorations have been applied as
inorganic frits, which required exposure to high temperatures in
order to be fused into a durable film. Ceramic frit decorations,
however, suffer from one or more disadvantages, such as the
presence of heavy metals, low color brilliance, the necessity of
using high temperatures to fuse the frits after application, and
often a requirement to subsequently reanneal the labeled bottles.
Once ceramic frit decorations are fired onto a glass surface,
adhesion is usually excellent, and removal of the decoration is
extremely difficult.
[0005] Organic decorations have been proposed for decorating
bottles to overcome some of these problems, and particularly useful
organic decorating compositions are disclosed in commonly assigned
U.S. patent application Ser. No. 09/617,847 and in U.S. Pat. No.
6,214,414 B1, the disclosures of which are hereby incorporated by
reference. Other organic decorating compositions are disclosed in
U.S. Pat. Nos. 3,468,835; 3,471,312; 3,607,349; 5,346,933; and
5,411,768.
[0006] It is desirable for coatings applied to bottles to be tough
and resistant to marring by abrasion or impact and they should be
resistant to degradation by caustic solutions commonly employed for
cleaning bottles.
[0007] Many earlier bottle decorating compositions were "applied
ceramic labels," that is, they are applied as inorganic frits that
are subsequently exposed to high temperatures. Applied ceramic
labels, however, suffer from one or more disadvantages, such as the
presence of heavy metals, low color brilliance, the necessity of
using high temperatures to melt the frits after application, and
often a requirement to subsequently reanneal the labeled
bottles.
[0008] Organic compositions have been used for bottle decorating,
but resistance to abrasion and impact strength of many of these
coatings were typically low, and resistance to degradation by
caustic bottle-cleaning solutions have often also been lower than
desired. Organic bottle decorating compositions based primarily on
epoxy resins, dicyandiamide curing agent, and siloxane, and usually
containing various additional components, are known. See, for
example, the following U.S. Pat. Nos. 3,468,835; 3,471,312;
3,607,349; 5,346,933; and 5,411,768.
SUMMARY OF THE INVENTION
[0009] A composition adapted for decorating ceramic substrates has
now been found that is based upon organic binder curable by
application of relatively low temperature energy and yet has
sufficient integrity in the uncured state to permit applying an
additional decorating layer directly onto a previously applied
layer before applying the curing energy. The curing energy may
include heat, but at a significantly lower temperature than
required for fusing ceramic frit type decorative composition.
Alternatively, the energy may comprise ultraviolet radiation.
Because of the integrity of the prior-applied layer or layers, the
invention permits two or more layers of decoration, typically
constituting different colors, to be applied without an intervening
energy-applying curing step. After all of the desired layers have
been applied, curing energy may be applied to cure all of the
layers with one step. This results in considerable efficiencies in
an industrial decorating operation, such as glass bottle
decorating.
[0010] The novel composition comprises a curable organic binder
component, a colorant component, and a rigid particle component
comprised of organic or inorganic particles that are substantially
spherical. The particles may be polymeric (e.g., polyacrylamide)
but preferably are inorganic (e.g., glass). The rigid particle
component is characterized by the presence of little or no
spherical particle fraction in which the diameters are
substantially greater than the wet film thickness of the applied
decorating layer. Typically, the wet film thickness when decorating
beverage bottles is no greater than 50 microns, more typically on
the order of 35 microns or less. Therefore, in those cases, the
preferred decorating compositions have no substantial rigid
particle content greater than 50 microns and 35 microns
respectively. Wet film thicknesses for beverage bottle decorating
are most commonly in the range of 15 to 35 microns, and accordingly
that is also the range of average diameters of the spherical
particles that will be most useful in typical commercial ceramic
decorating situations. Spherical particles can also be used with
diameters that are less than the layer thickness, so other
embodiments may employ average diameters as low as one half or less
of the wet film thickness. Although theoretically there may be no
absolute minimum particle diameter that may be useful at some small
film thickness, with typical commercial decorating thicknesses, the
benefit may be very minor at particle diameters less than 5
microns.
[0011] Another aspect of the invention is the method of decorating
a ceramic substrate by applying at least one decorating layer
characterized by the spherical particle content of the compositions
of the present invention. The last layer to be applied may also
contain spherical particles, but since it is not subjected to the
rigors of a subsequent printing operation, the topmost layer need
not include the spherical particle component of the compositions of
the present invention. Energy to complete the cure is utilized only
after all layers have been applied, and yet the method has
permitted maintaining integrity of the uncured layers during the
printing steps. In accordance with this method, a multi-colored
organic decoration can be applied to a ceramic substrate in a
plurality of printing steps in rapid succession, followed by curing
in a single step.
[0012] Screen printing processes generally involve heating the
decorating composition (below the curing temperature) during the
printing step in order to reduce the viscosity of the composition
during printing. In the prior art, when multiple colors were
applied in sequential printing steps, it was considered advisable
to use progressively lower temperatures in each successive printing
step to avoid damaging the previously printed layers. It is another
advantage of the present invention that there is considerably
greater freedom in the selection of screen temperatures in
subsequent printing steps. When using the compositions of the
present invention, it has been found that durability of the
applied, uncured layers is sufficient to permit subsequent printing
steps to be freed of restriction to lower temperatures. This
property provides the operator with the advantage of selecting the
temperature most appropriate for the particular decorating
composition, regardless of its order in a multi-step decorating
process.
DETAILED DESCRIPTION OF THE INVENTION
[0013] It is hypothesized that the beneficial effects of the
present invention attributable to the inclusion of rigid spherical
particles in the decorating composition is at least in part a
physical phenomenon and therefore is independent of the chemical
make-up of the decorating composition. Therefore, the present
invention is applicable to a wide variety of organic compositions
for decorating ceramics known to those of skill in the art. These
are compositions that contain an organic, resinous component that
is capable of being printed onto a ceramic substrate in a
substantially liquid state and thereafter cured to a durable,
hardened state by means of heat, UV radiation, electron beam
radiation or some other form of energy that causes the resinous
component to cure. Included are the prior art organic compositions
disclosed in the patents cited in the Background section herein.
Typically, these may include two organic components that undergo a
curing reaction when the curing energy is applied. A two-component
organic decorating composition employed commercially is the type
employing an epoxy resin and an amine curing agent (e.g.,
dicyandiamide). Due primarily to the presence of the dicyandiamide
curing agent, some crosslinking of prior art organic glass
decorating compositions occurs at application temperatures and such
crosslinking eventually causes the decorating composition to
thicken to the point it cannot be applied. Accordingly, another
problem with the prior coatings has been short pot life, where "pot
life" is the length of time the coating will remain fluid enough to
apply to substrates at application temperatures. Because it
addresses the pot life problem, a particularly preferred type of
decorating composition to which the present invention may be
applied is that disclosed in U.S. Pat. No. 6,214,414 B1 and
copending, commonly owned U.S. patent application Ser. No.
09/617,847, and the specific embodiments disclosed in detail herein
are based upon that type of decorating composition. More
specifically, that type of decorating composition is characterized
by the inclusion of epoxy resin, amine curing agent, and a blocked
isocyanate curing agent, and will be described in detail
hereinbelow. Colored decorating compositions of any type
additionally contain a coloring component, usually one or more
pigments and/or dyes. Many other additives may be included for
improving rheology, opacity, durability, lubricity, color
brightness, and many other functions known to those of skill in the
art.
[0014] The polyepoxy-functional reactive organic resin that may be
used in preferred embodiments of the invention may be widely
varied. As used herein and in the claims, the term
"polyepoxy-functional" means that on a number average molecular
weight basis, the resin contains, on average, more than one epoxy
group per molecule. Preferably the resin contains, on average,
approximately two hydroxyl groups per molecule or more. Of
particular interest are the polyglycidyl ethers of polyhydric
alcohols. Useful polyglycidyl ethers of polyhydric alcohols can be
formed by reacting epihalohydrins, such as epichlorohydrin [CAS
106-89-8], with polyhydric alcohols, especially dihydric alcohols,
in the presence of an alkali condensation and dehydrohalogenation
catalyst such as sodium hydroxide or potassium hydroxide. Inasmuch
as phenolic hydroxyls react with epichlorohydrin in much the same
way as aliphatic alcoholic hydroxyls, compounds having at least two
phenolic hydroxyls are, for purposes of the present discussion,
regarded as polyhydric alcohols. Suitable polyhydric alcohols can
be aromatic, aliphatic or cycloaliphatic.
[0015] Examples of suitable aliphatic polyhydric alcohols include,
but are not limited to, aliphatic dihydric alcohols such as: [0016]
ethylene glycol [CAS 107-21-1], [0017] neopentyl glycol [CAS
126-30-7], [0018] diethylene glycol [CAS 111-46-6], [0019]
triethylene glycol [CAS 112-27-6], [0020] tetraethylene glycol [CAS
112-60-7], [0021] dipropylene glycol [CAS 110-98-5], [0022]
1,2-propanediol [CAS 57-55-6], [0023] 1,3-propanediol [CAS
504-63-2], [0024] 1,2-butanediol [CAS 26171-83-5], [0025]
1,3-butanediol [CAS 107-88-0], [0026] 2,3-butanediol [CAS
513-85-9], [0027] 1,4-butanediol [CAS 110-63-4], [0028]
1,2-pentanediol [CAS 5343-92-0], [0029] 1,4-pentanediol [CAS
626-95-9], [0030] 2,4-pentanediol [CAS 625-69-4], [0031]
1,5-pentanediol [CAS 111-29-5], [0032] 1,6-hexanediol [CAS
629-11-8], [0033] 3-hydroxy-2,2-dimethylpropyl
3-hydroxy-2,2-dimethylpropanoate [Ester Diol 204; CAS 1115-20-4],
[0034] poly(ethylene oxide) [CAS 25322-68-3], and [0035]
poly(propylene oxide) [CAS 25322-69-4].
[0036] Examples of suitable aliphatic polyhydric alcohols having
more than two alcoholic hydroxyl groups include, but are not
limited to: [0037] sorbitol [CAS 50-70-4], [0038] mannitol [CAS
69-65-8], [0039] glycerol [CAS 56-81-5], [0040] 1,2,6-hexanetriol
[CAS 106-69-4], [0041] erythritol [CAS 149-32-6], [0042]
pentaerythritol [CAS 115-77-5], [0043] dipentaerythritol [CAS
126-58-9], [0044] tripentaerythritol [CAS 78-24-0], [0045]
1,1,1-trimethylolethane [CAS 77-85-0], and [0046]
1,1,1-trimethylolpropane [CAS 77-99-6].
[0047] Examples of suitable aromatic polyhydric alcohols include:
[0048] pyrocatechol [CAS 120-80-9], [0049] resorcinol [CAS
108-46-3], [0050] hydroquinone [CAS 123-31-9], [0051]
4,4'-(1-methylethylidene)bis [phenol] [bisphenol A; CAS 80-05-7],
[0052] 4,4'-(1-methylethylidene))bis[2,6-dibromophenol]
[tetrabromobisphenol A; CAS 79-94-7], [0053]
4,4'-(1-methylethylidene))bis[2,6-dichlorophenol]
[tetrachlorobisphenol A; CAS 79-95-8], [0054]
4,4'-(1-methylpropylidene)bis[phenol] [bisphenol B; CAS 77-40-7],
[0055] 4,4'-(1-methylethylidene)bis(2-methylphenol] [bisphenol C;
CAS 79-97-0], [0056] 4,4'-(1,2-ethanediyl)bis[phenol] [bisphenol E;
CAS 6052-84-2], [0057] 2,2'-methylenebis[phenol] [bisphenol F; CAS
2467-02-9), [0058]
4,4'-(1-methylethylidene)bis[2-(1-methylethyl)phenol] [bisphenol G;
CAS 127-54-8], [0059]
4,4'-[1,3-phenylenebis(1-methylethylidene)]bis [phenol] [bisphenol
M; CAS 13595-25-0], [0060]
4,4'-[1,4-phenylenebis(1-methylethylidene)]bis [phenol] [bisphenol
P; CAS 2167-51-3], [0061] 4,4'-sulfonylbis[phenol] [bisphenol S;
CAS 80-09-1], [0062] 4,4'-cyclohexylidenebis[phenol] [bisphenol Z;
CAS 843-55-0], [0063]
4,4'-(2,4,8,10-tetraoxaspiro[5.5]undecane-3,9-diyldi-2,1-ethanedi-
yl)bis[phenol] [bisphenol PA; CAS 3616-75-9], [0064]
4,4'-(1-phenylethylidene)bis [phenol] [bisphenol ACP; CAS
1571-75-1], [0065] 4,4'-methylenebis[phenol] [HDM; CAS 620-92-8],
[0066] 2,2'-methylenebis[4-methyl-6-(1-methylethyl)phenol]
[bisphenol 2246; CAS 24742-47-0], [0067] 3,3-bis(4-hydroxyphenyl)-1
(3H)-isobenzofuranone [phenolphthalein; CAS 77-09-8], [0068]
4,4'-ethylidenebis[phenol] [CAS 2081-08-5], [0069]
4,4'-propylidenebis[phenol] [CAS 1576-13-2], [0070]
4,4'-(1-ethylpropylidene)bis[phenol] [CAS 3600-64-4], [0071]
4,4'-(1,4-cyclohexanediyl)bis[phenol] [CAS 10466-91-8], [0072]
4,4'-(1,3-cyclohexanediyl)bis[phenol] [CAS 55418-36-5], [0073]
4,4'-(1,2-cyclohexanediyl)bis[phenol] [CAS 55418-39-8], [0074]
4,4'-(phenylmethylene)bis[phenol] [CAS 4081-02-1], [0075]
4,4'-(2,2,2-trichloroethylidene)bis[phenol] [hydroxychlor; CAS
2971-36-0], [0076] 4-hydroxy-a-(4-hydroxyphenyl)benzeneacetic acid,
butyl ester [CAS 71077-33-3], [0077]
4,4'-(diphenylmethylene)bis[phenol] [bisphenol TP; CAS 1844-01-5],
[0078] 4,4'-thiobis[phenol] [CAS 2664-63-3], [0079]
1,2-dihydroxynaphthalene [CAS 574-00-5], [0080]
1,3-dihydroxynaphthalene [CAS 132-86-5], [0081]
1,4-dihydroxynaphthalene [CAS 571-60-8], [0082]
1,5-dihydroxynaphthalene [CAS 83-56-7], [0083]
1,1,3-tris(4-hydroxyphenyl)propane, [0084] phenol-formaldehyde
novolac, and [0085] o-cresol-formaldehyde novolac.
[0086] Many ethylene oxide or propylene oxide extended aromatic
polyhydric alcohols are known and may be used when desired.
[0087] Examples of suitable cycloaliphatic polyhydric alcohols
include, but are not limited to: [0088] 1,2-cyclohexanediol [CAS
931-17-9], [0089] 1,3-cyclohexanediol [CAS 504-01-8], [0090]
1,4-cyclohexanediol [CAS 556-48-9], [0091]
1,2-cyclohexanedimethanol [CAS 3971-29-7], [0092]
1,3-cyclohexanedimethanol [CAS 3971-28-6], [0093]
1,4-cyclohexanedimethanol [CAS 105-08-8], [0094]
4,4'-(1-methylethylidene)bis[cyclohexanol] [hydrogenated bisphenol
A; CAS 80-05-7].
[0095] Another useful class of polyepoxy-functional resins
containing at least two epoxy groups per molecule, are those
containing, on average, at least two epoxycycloaliphatic groups per
molecule. These resins may be made by epoxidation of the
cycloalkene group using a peracid such as peracetic acid.
[0096] An example of a resin that contains one epoxycycloalkyl
group and a pendent epoxy group is
1-(epoxyethyl)-3,4-epoxycyclohexane [CAS 106-87-6].
[0097] Examples of epoxy-functional resins containing two or more
epoxycycloalkyl groups include, but are not limited to: [0098]
bis(2,3-epoxycyclopentyl)ether [CAS 2386-90-5], [0099]
3,4-epoxycyclohexylmethyl 3',4'-epoxycyclohexanecarboxylate [CAS
2386-87-0], [0100] bis(3,4-epoxycyclohexyl) adipate [CAS
83996-66-1], and [0101] bis(3,4-epoxycyclohexylmethyl)
4,5-epoxycyclohexane-1,2-dicarboxylate [CAS 21678-82-0].
[0102] Poly(primary amino)-functional and poly(secondary
amino)-functional compounds may be used to chain-extend the
polyepoxy-functional resins.
[0103] Suitable polyepoxy-functional resins usually have an epoxide
equivalent weight (i.e., molecular weight of resin per epoxide
group) in the range of from 100 to 4000, as measured by titration
with perchloric acid using methyl violet as an indicator. Often the
polyepoxy-functional resins have an epoxide equivalent weight in
the range of from 170 to 700. Preferably the epoxide equivalent
weight is in the range of from 250 to 600. Other useful
polyepoxides are disclosed in U.S. Pat. No. 5,820,987 at column 4,
line 52 through column 6, line 59. The disclosure of U.S. Pat. No.
5,820,987 is, in its entirety, incorporated herein by
reference.
[0104] Many of the polyepoxy-functional organic resins formed by
reacting diols with epichlorohydrin also contain
polyhydroxy-functionality. In the case of reaction of bisphenol A
with epichlorohydrin, ideal reaction products having number average
molecular weights of greater than 624 theoretically have, on
average, two epoxy groups and more than one hydroxyl group per
molecule. Examples of suitable commercially available
polyepoxy-functional and polyhydroxy-functional resins are
EPON.RTM. 828, 836, and 880 epoxy resins. If the number average
molecular weight is 908 or greater, ideal reaction products of
bisphenol A and epichlorohydrin theoretically have, on average, two
epoxy groups and at least two hydroxyl group per molecule. Examples
of such polyepoxy-functional and polyhydroxy-functional resins
which are commercially available are EPON.RTM. 1001F, 1002, 1004,
1007, and 1009. The EPON.RTM. resins are available from Resolution
Performance Products, Houston, Tex., USA.
[0105] The polyepoxy-functional resin may be reacted with various
terminating agents, as for example amino-functional siloxane, to
convert some, or even all, of the terminal epoxy groups to terminal
groups of other functionality. In most instances, the consumption
of the epoxy groups during the termination reaction is accompanied
by the generation of hydroxy groups on the resin.
[0106] Reactive waxes are included in some embodiments of
decorating compositions and may optionally be included in the
composition of the present invention. These are long-chain
aliphatic substances which have at least one reactive group having
an active hydrogen, usually selected from hydroxyl, amido,
ureylene, carbamyl, and carbamyloxy, and which have the physical
characteristics commonly associated with waxes. The reactive waxes
comprise many different classes of compounds. Examples of reactive
waxes include normal primary alkanols having from 12 to 20 carbon
atoms, normal primary amines having from 12 to 20 carbon atoms,
normal saturated monocarboxylic acids having from 8 to 20 carbon
atoms, and normal saturated monocarboxylic amides having from 8 to
20 carbon atoms. Although the normal (that is, straight chain)
structures are preferred, some branching may be present, as for
example isostearyl alcohol. Other examples of reactive waxes
include the poly(ethylene oxides) having normal molecular weights
of at least 1000, the poly(propylene oxides) having normal
molecular weights of at least 5000; these may be terminated with
two hydroxyl groups or with one hydroxyl group and one lower alkoxy
group. Saturated long chain aliphatic diols or saturated long chain
dicarboxylic acids having waxy characteristics may also be used.
While saturated compounds are preferred, a small amount of
unsaturation may be present, as for example oleic acid. Similarly
more than one reactive group may be in the molecule, as for example
12-hydroxystearic acid and sebacic acid. Of the reactive waxes, the
normal primary alkanols having from 12 to 20 carbon atoms are
preferred. Stearyl alcohol is especially preferred.
[0107] Organic isocyanates react with organic compounds containing
at least one "active hydrogen", i.e., a hydrogen atom replaceable
by sodium. Substantially all organic compounds containing a
hydrogen atom attached to oxygen or nitrogen will react with
isocyanates under the proper conditions. An organic compound
containing active hydrogen is suitable as a blocking agent if the
product of its reaction with an isocyanate is unreactive with
hydroxyl, amino, amido, ureylene, carbamyl, carbamyloxy, or other
groups containing active hydrogen at room temperature, but reacts,
by intermediate unblocking or otherwise, with one or more such
groups of other compounds at an elevated temperature, usually in
the range of from 90.degree. C. to 325.degree. C., to form desired
products. The reaction product of a blocking agent and an
isocyanate is known as a "blocked isocyanate." Although it is not
desired to be bound by any theory, it is believed that the reaction
to form the blocked isocyanate is reversed at the elevated
temperature to regenerate isocyanato-functionality which then
reacts with other compounds containing active hydrogen to form the
desired products. In most instances the blocking agent contains
active hydrogen attached to an oxygen atom or a nitrogen atom.
[0108] Any suitable aliphatic, cycloaliphatic, aromatic-alkyl
monoalcohol or phenolic compound may be used as a blocking agent in
accordance with the present invention. Examples include but are by
no means limited to methyl alcohol, ethyl alcohol, chloroethyl
alcohol, propyl alcohol, isopropyl alcohol, butyl alcohol, amyl
alcohol, hexyl alcohol, heptyl alcohol, octyl alcohol, nonyl
alcohol, 3,3,5-trimethylhexanol, decyl alcohol, lauryl alcohol,
cyclopentanol, cyclohexanol, phenylcarbinol, methylphenylcarbinol,
ethylene glycol monoethyl ether, ethylene glycol monobutyl ether,
phenol, cresol, xylenol, nitrophenol, chlorophenol, ethylphenol,
tert-butylphenol, 2,5-di-tert-butyl-4-hydroxytoluene, tertiary
hydroxylamines such as diethylethanolamine, oximes such as methyl
ethyl ketone oximes, acetone oxime, and cyclohexanone oxime.
[0109] Any suitable compound containing amine, amide, urea,
urethane, or other groups having an active hydrogen attached to a
nitrogen atom may be used. Examples of such compounds include, but
are not limited to, dibutylamine, diisopropylamine,
2-phenylimidazoline, benzotriazole, benzyl methacrylohydroxamate,
and .epsilon.-caprolactam.
[0110] Polyfunctional blocking agents may be used when desired.
Examples include, but are not limited to ethylene glycol,
propropylene glycol, poly(ethylene glycol), poly(propylene glycol),
Pluronic type polypropylene, poly(tetrahydrofuran),
trimethylolpropane, ethoxylated trimethylolpropane, and poly(vinyl
alcohol).
[0111] Procedures for blocking isocyanato groups are well known in
the art. Blocking is often accomplished by reacting the isocyanato
groups of the isocyanato-functional compound with blocking agent at
temperatures in the range of from 25.degree. C. to 120.degree. C.,
although other temperatures may often be used. The organic blocked
isocyanate is formed by reacting a sufficient quantity of blocking
agent with the organic polyisocyanate to insure that substantially
no unreacted isocyanato groups are present in the product.
[0112] It should be noted that blocked isocyanato functionality
does not contain the isocyanato group; rather it contains a group
which is the reaction product of the isocyanato group and the
blocking agent. For example, an isocyanato group blocked with an
alcohol contains a urethane group, while an isocyanato group
blocked with a primary amine contains a urea group.
[0113] In the preparation of the blocked organic polyisocyanates,
any suitable organic polyisocyanate may be used. Examples of
classes of organic polyisocyanates include, but are not limited to,
the aliphatic polyisocyanates, the cycloaliphatic polyisocyanates,
the aliphatic-cycloaliphatic polyisocyanates, the aromatic
polyisocyanates, and the aliphatic-aromatic polyisocyanates. The
polyisocyanates may be diisocyanates, triisocyanates,
tetraisocyanates or higher order isocyanates.
[0114] Only one polyisocyanate or a mixture of two or more
polyisocyanates may be used. When mixtures are used, the
constituent polyisocyanates may be from the same class or from
different classes.
[0115] Representative examples of suitable polyisocyanates include,
but are not limited to, 1,2-diisocyanatopropane, [0116]
1,3-diisocyanatopropane, [0117] 1,2-diisocyanato-2-methylpropane,
[0118] 1,2-diisocyanatobutane, [0119] 1,3-diisocyanatobutane,
[0120] 1,4-diisocyanatobutane, [0121] 1,5-diisocyanatopentane,
[0122] 1,6-diisocyanatohexane, [0123] ethylidine diisocyanate,
[0124] butylidene diisocyanate, [0125]
1,2-diisocyanatocyclopentane, [0126] 1,3-diisocyanatocyclopentane,
[0127] 1,2-diisocyanatocyclohexane, [0128]
1,3-diisocyanatocyclohexane, [0129] 1,4-diisocyanatocyclohexane,
[0130] bis(4-isocyanatocyclohexyl) ether, [0131]
1-(isocyanatomethyl)-5-isocyanato-1,3,3-trimethylcyclohexane,
[0132] 1-(isocyanatomethyl)-1-(3-isocyanatopropyl)cyclohexane,
[0133] bis(4-isocyanatocyclohexyl)methane, [0134]
1,2-diisocyanatobenzene, [0135] 1,3-diisocyanatobenzene, [0136]
1,4-diisocyanatobenzene, [0137] 4,4'-diisocyanatobiphenyl, [0138]
1,4-diisocyanatonaphthalene, [0139] 1,5-diisocyanatonaphthalene,
[0140] bis(4-isocyanatophenyl)methane, [0141]
2,4-diisocyanatotoluene, [0142] 2,6-diisocyanatotoluene, [0143]
1,3-bis(isocyanatomethyl)benzene, [0144]
1,4-bis(isocyanatomethyl)benzene, [0145] bis(4-isocyanatophenyl)
ether, [0146] 3,3'-diisocyanatobiphenyl, [0147]
4,4'-diisocyanatobiphenyl, [0148]
4,4'-diisocyanato-2,2'-dimethylbiphenyl, [0149]
4,4'-diisocyanato-3,3'-dimethylbiphenyl, [0150]
4,4'-diisocyanato-2,2'-dimethoxybiphenyl, [0151]
4,4'-diisocyanato-3,3'-dimethoxybiphenyl, [0152]
tris(4-isocyanatophenyl)methane, [0153]
tris(4-isocyanatocyclohexyl)methane, [0154]
1,3,5-triisocyanatobenzene, [0155] 2,4,6-triisocyanatotoluene,
[0156] bis(2,5-diisocyanato-4-methylphenyl)methane, [0157]
bis(2,5-diisocyanato-4-methylcyclohexyl)methane, polymeric
polyisocyanates such as dimers and trimers, and prepolymers which
are derived from a polyol, including a hydrocarbon polyol, a
polyether polyol, and a polyester polyol. An example is an adduct
(approximately 3:1, molar) of
1-isocyanatomethyl-5-isocyanato-1,3,3-trimethylcyclohexane [CAS
4098-71-9] and 1,1,1-trimethylolpropane [CAS 77-99-6].
[0158] The rigid spherical particles incorporated into the
decorating compositions of the present invention may be organic or
inorganic. Suitable inorganic microspheres are available
commercially as inert filler materials, and include glass and
ceramic microspheres. "Rigid" in the expression "rigid spherical
particles" herein means that they are not readily compressible. In
other words, the particles have greater structural integrity that
the uncured composition in which they are contained. "Solid" as
used herein refers to particles that are substantially void-free.
Either "solid" or hollow microspheres can be used and are
encompassed by the term rigid spherical particles. Inorganic
microspheres are commercially available, and may comprise ceramics
or glasses, including borosilicate glass and soda lime silica
glass. Organic microspheres are available made from polyurethanes,
acrylics, polyamides and other polymeric materials. The very high
rigidity of inorganic microspheres have been found to yield the
best results. Relatively spherical shapes, as opposed to irregular
granular shapes, have been found to be a factor in achieving good
results in accordance with the invention. Crushed materials, such
as crushed glass, and granulated materials have been found to be
ineffective in achieving the results of the present invention.
Absolutely spherical shapes do not appear to be essential, and it
should be understood that the presence of some granular material
does not defeat the advantages of the present invention.
[0159] The relatively small sizes and amounts of microspheres used
in the compositions of the present invention do not produce
perceptible reflectivity as in some compositions of other types
that contain microspheres. The spherical particle content of the
compositions here is in the range of about 5 to 50 weight percent,
preferably 10 to 35 percent, most preferably 15 to 30 percent.
Particle sizes vary in accordance with the thickness of the
decoration layer being produced, and typically are at least 5
microns and no more than 50 microns, most typically 10 microns to
30 microns.
[0160] The relative proportions of the components of the pigmented
decorating composition may be widely varied.
[0161] The reactive organic resin which is polyepoxy-functional
usually constitutes from 20 to 80 percent by weight of the
pigmented decorating composition. Often such reactive organic resin
constitutes from 40 to 70 percent by weight of the pigmented
decorating composition. From 30 to 60 percent by weight of the
pigmented decorating composition is preferred.
[0162] Reactive wax may optionally constitute from 0 to 20 percent
by weight of the pigmented decorating composition. In some
embodiments reactive wax may constitute from 0.5 to 15 percent by
weight of the pigmented decorating composition. From 1 to 10
percent by weight of the pigmented decorating composition is
preferred.
[0163] The color-imparting pigment ordinarily constitutes from 1 to
45 percent by weight of the pigmented decorating composition.
Frequently the color-imparting pigment constitutes from 3 to 40
percent by weight of the pigmented decorating composition. From 5
to 35 percent by weight of the pigmented decorating composition is
preferred.
[0164] When present, blocked polyisocyanate may constitute from 0.5
to 15 percent by weight of the pigmented decorating composition.
Frequently the blocked polyisocyanate constitutes from 1 to 10
percent by weight of the pigmented decorating composition. From 1.5
to 8 percent by weight of the pigmented decorating composition is
preferred.
[0165] Illustrative amino-functional curing agents which may be
used include melamine,
2,4,6-tris(alkoxycarbonylamino)-1,3,5-triazine (also known as
"TACT") where each alkoxy independently contains from 1 to 4 carbon
atoms, and compounds represented by the formula: ##STR1## wherein:
[0166] R.sub.1, R.sub.2, R.sub.3 each independently represents
hydrogen, alkyl containing from 1 to 3 carbon atoms, or
hydroxyalkyl containing from 1 to 3 carbon atoms, [0167] R.sub.4
represents hydrogen, phenyl, cyano, acetyl, or ##STR2## [0168]
R.sub.5 represents O, S, or NH, and [0169] R.sub.6 and R.sub.7 each
independently represents hydrogen, alkyl containing from 1 to 3
carbon atoms, hydroxyalkyl containing from 1 to 3 carbon atoms, or
phenyl.
[0170] When any of R.sub.1, R.sub.2, R.sub.3, R.sub.6, and R.sub.7
is alkyl containing from 1 to 3 carbon atoms, it is independently
methyl, ethyl, propyl, or isopropyl. The alkyl groups may be the
same or some may be different from the others. The preferred alkyl
group is methyl.
[0171] When any of R.sub.1, R.sub.2, R.sub.3, R.sub.6, and R.sub.7
is hydroxyalkyl containing from 1 to 3 carbon atoms, it usually is
independently hydroxymethyl, hydroxyethyl, or hydroxypropyl. The
hydroxyalkyl groups may be the same or some may be different from
the others. The preferred hydroxyalkyl group is hydroxymethyl.
[0172] Preferably, all of R.sub.1, R.sub.2, R.sub.3, R.sub.6, and
R.sub.7 are hydrogen.
[0173] Examples of suitable amino-functional curing agents include
melamine [0174] [CAS 108-78-1],
2,4,6-tris(methoxycarbonylamino)-1,3,5-triazine [0175] [CAS
150986-36-0], 2,4,6-tris(butoxycarbonylamino)-1,3,5-triazine [0176]
[CAS 150986-45-1], dicyandiamide [CAS 461-58-5],
1,3-diphenylguanidine [0177] [CAS 102-06-7], urea [CAS 57-13-6],
thiourea [CAS 62-56-6], acetylurea [0178] [CAS 591-07-1], biguanide
[CAS 56-03-1], heptamethylbiguanide [0179] [CAS 91446-22-9],
2-ethyl-4-methylimidazole [CAS 931-36-2], and diaminodiphenyl
sulfone [CAS 80-08-0].
[0180] The amino-functional curing agent may comprise one
amino-functional curing agent compound or it may comprise a mixture
of two or more amino-functional curing agent compounds.
[0181] The amino-functional curing agent usually constitutes from 1
to 25 percent by weight of the decorating composition in which it
is employed. The amino-functional curing agent may constitutes from
1 to 20 percent by weight of the pigmented decorating composition
in which it is employed. From 1 to 10 percent by weight of the
pigmented decorating composition in which it is employed is
preferred for some commercial bottle decorating embodiments.
[0182] One or more organo-functional siloxanes as are known in the
art may be included in some decorating compositions and may
optionally be included in the compositions of the present
inventions. When present in a pigmented decorating composition, the
organo-functional siloxane may constitute from 0.01 to 15 percent
by weight of the pigmented decorating composition. In embodiments
the organo-functional siloxane constitutes from 2 to 10 percent by
weight of the pigmented decorating composition. Preferred
commercial bottle decorating embodiments of the present invention
do not include silane constituents.
[0183] When present in the substantially clear overcoating
composition, the organo-functional siloxane usually constitutes
from 0.01 to 15 percent by weight of the substantially clear
overcoating composition. In many instances the organo-functional
siloxane constitutes from 2 to 10 percent by weight of the
substantially clear overcoating composition. From 4 to 6 percent by
weight of the substantially clear overcoating composition is
preferred.
[0184] Color-imparting constituents used in formulating the
pigmented decorating compositions may include finely divided solid
powders, insoluble but wettable under the conditions of use. They
confer substantial color (which includes white, black and gray) to
the pigmented decorating compositions of the invention and to
coatings formed from such pigmented decorating compositions. Finely
divided solid powders which do not impart substantial color to the
decorating compositions and to coatings formed therefrom are, for
purposes of the present invention, considered not to be pigments,
but rather, they are considered to be substantially colorless
fillers.
[0185] The color-imparting constituents may be widely varied. They
may be organic or inorganic. It is preferred to use color-imparting
pigments which do not contain heavy metals although some heavy
metals such as copper which are not very toxic in the
concentrations employed, may be present. In general it is preferred
to use titanium dioxide as a white pigment and carbon in one of its
forms as a black pigment, and to use organic pigments for imparting
colors other than white, black, or gray. Examples of
color-imparting pigments include, but are not limited to: [0186]
Carbon Black [0187] Lampblack [0188] Furnace Black [0189] Thermal
Decomposition Black [0190] Vegetable Black [0191] Animal Black
[0192] Bone Black [0193] Impingement Carbon Black [0194] Graphite
[0195] Rutile [CAS 1317-80-2] [0196] Anatase [CAS 1317-70-0] [0197]
Clay [0198] Aluminum Hydroxide [0199] Pigment Black 6 [CAS
1333-86-4] [0200] Pigment Black 7 [CAS 1333-86-4] [0201] Pigment
Black 10 [CAS 7282-42-5] [0202] Pigment White 6 [CAS 13463-67-7]
[0203] Pigment Blue 1 [CAS 1325-87-7], [0204] Pigment Blue 15 [CAS
147-14-8], [0205] Pigment Blue 19 [CAS 58569-23-6], [0206] Pigment
Blue 24 [CAS 6548-12-5], [0207] Pigment Blue 60 [CAS 81-77-6],
[0208] Pigment Green 4 [CAS 61725-50-6], [0209] Pigment Green 7
[CAS 1328-53-6], [0210] Pigment Green 36 [CAS 14302-13-7], [0211]
Pigment Yellow 3 [CAS 6486-23-2], [0212] Pigment Yellow 12 [CAS
6358-85-6], [0213] Pigment Yellow 13 [CAS 5102-83-0], [0214]
Pigment Yellow 74 [CAS 6358-31-2], [0215] Pigment Yellow 83 [CAS
5567-15-7], [0216] Pigment Yellow 93 [CAS 5580-57-4], [0217]
Pigment Yellow 96 [CAS 5280-80-8], [0218] Pigment Yellow 110 [CAS
5590-18-1], [0219] Pigment Yellow 138 [CAS 56731-19-2], [0220]
Pigment Yellow 139 [CAS 36888-99-0], [0221] Pigment Yellow 154 [CAS
63661-O.sub.2-9], [0222] Pigment Yellow 168 [CAS 71832-85-4],
[0223] Pigment Yellow 191 [CAS 129423-54-7], [0224] Pigment Orange
5 [CAS 3468-63-1], [0225] Pigment Orange 13 [CAS 3520-72-7], [0226]
Pigment Orange 36 [CAS 12236-62-3], [0227] Pigment Orange 43 [CAS
4424-06-0], [0228] Pigment Red 2 [CAS 6041-94-7], [0229] Pigment
Red 3 [CAS 2425-85-6], [0230] Pigment Red 5 [CAS 6410-41-9], [0231]
Pigment Red 17 [CAS 6655-84-1], [0232] Pigment Red 23 [CAS
6471-49-4], [0233] Pigment Red 38 [CAS 6358-87-8], [0234] Pigment
Red 52 [CAS 17852-99-2], [0235] Pigment Red 57 [CAS 5281-04-9],
[0236] Pigment Red 112 [CAS 6535-46-2], [0237] Pigment Red 122 [CAS
980-26-7], [0238] Pigment Red 123 [CAS 24108-89-2], [0239] Pigment
Red 144 [CAS 5280-78-4], [0240] Pigment Red 170 [CAS 2786-76-7],
[0241] Pigment Red 177 [CAS 4051-63-2], [0242] Pigment Red 179 [CAS
5521-31-3], [0243] Pigment Red 202 [CAS 68859-50-7], [0244] Pigment
Red 254 [CAS 122390-98-1], [0245] Pigment Violet 19 [CAS
1047-16-1], and [0246] Pigment Violet 23 [CAS 6358-30-1].
[0247] Only one color-imparting pigment or a mixture of two or more
color-imparting pigments may be used.
[0248] Substantially colorless fillers are materials which may
optionally be present in one or more of the pigmented decorating
compositions, in the substantially clear overcoating composition,
or in both the pigmented decorating compositions and in the
overcoating composition. Such fillers are finely divided
particulate solids which impart little or no color to the final
coatings. These are in addition to the rigid spherical particle
content. The fillers usually have a maximum dimension of less than
500 nanometers. Often the fillers have a maximum dimension of less
than 100 nanometers. Frequently, the maximum dimension is less than
50 nanometers. In many instances the maximum dimension is less than
20 nanometers. Often the maximum dimension is in the range of from
5 to 20 nanometers. Preferably the fillers are hydrophobic.
Examples of suitable hydrophobic fillers include AEROSIL.RTM. fumed
silicas designated R972, R974, R812, R812S, R805 (Degussa
Corporation, Ridgefield Park, N.J., USA). Only one substantially
colorless filler or a mixture of two or more substantially
colorless fillers may be used when desired.
[0249] When present in a pigmented decorating composition, the
substantially colorless filler ordinarily constitutes from 0.01 to
20 percent by weight of the pigmented decorating composition. In
many instances the substantially colorless filler constitutes from
1 to 10 percent by weight of the pigmented decorating composition.
From 2 to 5 percent by weight of the pigmented decorating
composition is preferred.
[0250] Many other additional materials may be optionally present in
decorating compositions. Among these are dyes, antioxidants,
degassing aids, flow modifiers, and fluorescent whitening agents.
These are only exemplary; others may be used as desired. When
present, the additional optional materials are ordinarily present
in a pigmented decorating composition and/or in the substantially
clear overcoating composition in their customary amounts for their
customary purposes. In many instances the additional optional
materials, when present, will constitute from 0.01 to 15 percent by
weight of the substantially clear overcoating composition or the
pigmented decorating composition. Frequently, the additional
optional materials, when present, will constitute from 0.01 to 10
percent by weight of the substantially clear overcoating
composition or the pigmented decorating composition.
[0251] The pigmented decorating compositions may be formed by
admixing the respective ingredients at temperatures below those
which would cause significant reaction.
[0252] The pigmented decorating compositions of the present
invention can be applied directly to ceramic substrates and/or to
one or more previously applied coatings of the same or similar
pigmented decorating compositions. Usually they are applied at
elevated temperatures so that the chilling effect of the cooler
substrate will quickly substantially solidify the coating. Such
solidification is helpful in maintaining fine-line definition, in
permitting application of multiple coatings without impairing the
definition of any previously applied coating, and in permitting
multiple coating while avoiding energy-inefficient crosslinking
between coating applications. Although the present invention
lessens the need, when multiple decorating layers are applied to
the same area, it is advantageous for the application temperature
of a subsequently applied coating to be lower than the temperature
at which a previously applied coating will liquefy or unduly
soften. This will enhance preservation of the fine-line definition
and resolution of the previously applied coating.
[0253] Since most of these pigmented decorating compositions
substantially instantly solidify to the touch after application,
they can be advantageously used in decorating lines operating at
high speeds where bottles or other ceramic substrates are
sequentially coated.
[0254] After the coatings have been applied, the coated ceramic
substrate is heated to elevated temperatures to cure, i.e.,
crosslink, the coatings.
[0255] As used herein and in the claims, "ceramic substrate" is
used in its broadest sense, unless otherwise more restrictively
qualified. Examples of ceramic substrates include, but are not
limited to, unglazed pottery, glazed pottery, unglazed earthenware,
glazed earthenware, unglazed porcelain, glazed porcelain, coffee
cups, tea cups, wall tiles, Christmas tree ornaments, promotional
ware, and glass substrates. Examples of glass substrates include,
but are not limited to, window glass, automotive glass, drinking
glasses, glass bottles, glass jugs, glass jars, glass pitchers, and
glass jewelry.
[0256] Application of the decorating compositions can be by any
technique known to the art. Decorating compositions which are
applied at elevated temperatures because they are substantially
solids at room temperature are usually applied using screen
decorating techniques. Decorating compositions which are liquids at
room temperature can be applied by spraying, curtain coating,
roller application, printing, and brushing. These techniques are
only exemplary; others may be used as desired.
[0257] After all decorating layers or coatings have been applied,
the decorated substrate is heated to elevated temperatures to cure,
i.e., crosslink, the coatings substantially simultaneously. Curing
of one or more of the applied decorating compositions is
accomplished at temperatures higher than those at which the
polyisocyanates were blocked. In most instances the curing
temperature is at least 150.degree. C. The curing temperature
should not be so high as to cause unwanted coloration or other
thermal degradation of the coatings. In typical commercial bottle
decorating line, the curing temperature is in the range of from
150.degree. C. to 200.degree. C.
[0258] The invention is further described in conjunction with the
following examples which are to be considered illustrative rather
than limiting, and in which all parts are parts by weight and all
percentages are percentages by weight unless otherwise specified.
Examples 1, 2, 3, 4, 5, 6, 7 and 11 are embodiments in accordance
with the present invention containing glass microspheres (of which
Examples 1, 2, 3, 4, 5, 8 and 11 are white compositions, Example 6
is a red composition, and Example 7 is a blue composition). Example
8 is a white embodiment of the present invention containing
polymeric microspheres. Example 9 is a white comparative example
without microspheres which was tested in direct comparison to
Example 11 using the blue top print ink composition of Example 10.
Except where noted otherwise, the ingredients and procedures of
each of the examples was the same as that described for Example
1.
EXAMPLE 1
[0259] TABLE-US-00001 Weight % EPON 880 .sup.1 25.22 EPON 1001F
.sup.1 25.22 Stearyl alcohol 5.04 VESTAGON B1400 .sup.2 5.04
TiO.sub.2 .sup.3 11.35 NEO GEN DGH .sup.4 4.03 SPHERICEL 110P8
.sup.5 16.67 MODAFLOW Powder III (65%) .sup.6 1.89 UVITEX OB .sup.7
0.50 BYK 405 .sup.8 0.46 DYHARD 100M .sup.9 3.42 AEROSIL R974
.sup.10 1.16 Total 100.00 .sup.1 EPON .RTM. 880 bisphenol A
diglycidyl ether; EPON .RTM. 1001F bisphenol A diglycidyl ether
[CAS 25068-38-6], Resolution Performance Products, Houston, Texas,
USA. .sup.2 VESTAGON .RTM. B 1400, blocked polyisocyanate believed
to be an adduct of isophorone diisocyanate [CAS 4098-71-9],
1,1,1-trimethylolpropane [CAS 77-99-6], and .epsilon.-caprolactam
[CAS 105-60-2] in a 3:1:3 molar ratio, Degussa AG, Coatings and
Colorants, Marl, Germany. .sup.3 TI-PURE .RTM. R-706 titanium
dioxide pigment, E. I. du Pont de Nemours & Co., Wilmington,
Delaware, USA. .sup.4 NEO GEN .TM. DGH aluminum silicate, Dry
Branch Kaolin Co., Dry Branch, Georgia, USA. .sup.5 SPHERICEL 110P8
hollow borosilicate glass microspheres, 11.7 microns mean diameter,
Potters Industries, Inc., Valley Forge, Pennsylvania, USA. .sup.6
MODAFLOW .RTM. Powder III flow modifier - ethyl
acrylate-2-ethylhexyl acrylate copolymer [CAS 26376-86-3] with
silicon dioxide [CAS 7631-86-9], Solutia Inc., St. Louis, Missouri,
USA. .sup.7 UVITEX OB whitening agent,
2,2'-(2,5-thiophenediyl)bis[5-(1,1-dimethylethyl)]-benzoxazole [CAS
7128-64-5], Ciba Specialty Chemicals, Basil, Switzerland. .sup.8
BYK .RTM.-405 rheology control agent, solution of
polyhydroxycarboxylic acid amides, BYK-Chemie, Wesel, Germany.
.sup.9 DYHARD .RTM. 100M dicyandiamide, micronized 98% <40
microns, SKW Trostberg Aktiengesellschaft, Trostberg, Germany.
.sup.10 AEROSIL .RTM. R974 hydrophobic fumed silica [CAS 68
611-44-9; 60 842-32-2], Degussa AG, Frankfort am Main, Germany.
[0260] The EPON 880, EPON 1001F, stearyl alcohol and VESTAGON 1400
were placed in a container, heated in a 120.degree. C. oven and
stirred till homogenous. The mixture was cooled to
.about.100.degree. C. The remainder of the materials were combined
in a separate container, then added to the homogenized mixture in
the first container. The combined mixture was stirred well and
maintained at .about.100.degree. C. until the following step. The
combined ingredients were placed in a DISPERSATOR high shear mixer
from Premier Mill, Reading, Pa., USA, with a HI-VIS head, and high
shear mixing was applied for 5 minutes at <100.degree. C.
EXAMPLE 2
[0261] TABLE-US-00002 Weight % EPON 880 24.21 EPON 1001F 24.21
Stearyl alcohol 4.84 VESTAGON B1400 4.84 TiO.sub.2 10.89 NEO GEN
DGH 3.87 SPHERICEL 110P8 20.01 MODAFLOW powder III (65%) 1.81
UVITEX OB 0.48 BYK 405 0.45 DYHARD 100M 3.28 AEROSIL R974 1.11
Total 100.0
EXAMPLE 3
[0262] TABLE-US-00003 Weight % EPON 880 24.24 EPON 1001F 24.24
Stearyl alcohol 4.85 VESTAGON B1400 4.85 TiO.sub.2 10.91 SPHERICEL
110P8 23.76 MODAFLOW powder III (65%) 1.81 UVITEX OB 0.48 BYK 405
0.45 DYHARD 100M 3.28 AEROSIL R974 1.12 Total 100.0
EXAMPLE 4
[0263] TABLE-US-00004 Weight % EPON 880 24.24 EPON 1001F 24.24
Stearyl alcohol 4.85 EPON 1001F 4.85 TiO.sub.2 10.91 SPHERICEL
110P8 23.76 MODAFLOW powder III (65%) 1.81 UVITEX OB 0.48 BYK 405
0.45 DYHARD 100M 3.28 AEROSIL R974 1.12 Total 100.0
EXAMPLE 5
[0264] TABLE-US-00005 Weight % EPON 880 23.12 EPON 1001F 23.12
Stearyl alcohol 9.25 EPON 1001F 4.62 TiO.sub.2 10.41 SPHERICEL
110P8 22.66 MODAFLOW powder III (65%) 1.73 UVITEX OB 0.46 BYK 405
0.43 DYHARD 100M 3.13 AEROSIL R974 1.06 Total 100.0
EXAMPLE 6
[0265] TABLE-US-00006 Weight % EPON 880 26.49 EPON 1001F 26.49
Stearyl alcohol 5.30 VESTAGON B1400 5.30 INTERPROME 4049 .sup.11
3.18 SPHERICEL 110P8 4.24 SPHERICEL 110P8 21.72 MODAFLOW powder III
(65%) 1.98 BYK 405 0.49 DYHARD 100M 3.59 AEROSIL R974 1.22 Total
100.0 .sup.11 INTERPROME 4049 azo based naphthol red pigment from
Sino, P.R. China.
EXAMPLE 7
[0266] TABLE-US-00007 Weight % EPON 880 25.94 EPON 1001F 25.94
Stearyl alcohol 5.19 VESTAGON B1400 5.19 Palomar Blue B4714 .sup.12
5.19 SPHERICEL 110P8 25.42 MODAFLOW powder III (65%) 1.94 BYK 405
0.48 DYHARD 100M 3.51 AEROSIL R974 1.19 Total 100.0 .sup.12 Palomar
Blue phthalocyanine blue pigment, Bayer Corporation, Pittsburgh,
Pennsylvania, USA.
EXAMPLE 8
[0267] TABLE-US-00008 Weight % EPON 880 24.24 EPON 1001F 24.24
Stearyl alcohol 4.85 VESTAGON B1400 4.85 TiO.sub.2 10.91 ORGASOL
Polyamide 1002D Nat 1 .sup.13 23.76 MODAFLOW powder III (65%) 1.81
UVITEX OB 0.48 BYK 405 0.45 DYHARD 100M 3.28 AEROSIL R974 1.12
Total 100.0 .sup.13 ORGASOL .RTM. 1002 D NAT polyamide
microspheres, 20 micron particle diameter, Atofina Chemicals,
Philadelphia, Pennsylvania, USA.
EXAMPLE 9
[0268] TABLE-US-00009 (Comparative white ink without spherical
particles) Weight % EPON 1001F 30.60 EPON 880 30.60 Stearyl Alcohol
6.12 VESTAGON B 1400 6.12 TiO.sub.2 13.77 MODAFLOW Powder III 2.29
UVITEX 0.61 NEO GEN DGH 4.90 BYK 405 0.55 DYHARD 100M 3.06 AEROSIL
R-974 1.39 Total 100.00
[0269] The EPON 880, EPON 1001F, stearyl alcohol and VESTAGON 1400
were placed in a container, heated in a 120.degree. C. oven and
stirred till homogenous. The mixture was cooled to
.about.100.degree. C. The remainder of the materials were combined
in a separate container, then added to the homogenized mixture in
the first container. The combined mixture was stirred well and
maintained at .about.100.degree. C. until the following step. The
combined ingredients were placed in a DISPERSATOR high shear mixer
from Premier Mill, Reading, Pa., USA, with a HI-VIS head, and high
shear mixing was applied for 5 minutes at <100.degree. C.
EXAMPLE 10
[0270] TABLE-US-00010 (Colored ink for top print) Weight % EPON 880
35.39 EPON 1001F 35.39 Stearyl alcohol 7.08 GEODE V-9250
Blue.sup.14 15.01 CROMOPHTAL Violet GT.sup.15 0.28 TiO.sub.2 1.34
MODAFLOW Powder III 2.51 BYK 405 0.35 DYHARD 100M 1.77 AEROSIL R974
0.87 Total 100.00 .sup.14GEODE V-9250 Blue pigment from Ferro
Corporation. .sup.15CROMOPHTAL Violet GT dioxazine type pigment
from Ciba.
EXAMPLE 11
[0271] TABLE-US-00011 (White ink in accordance with invention)
Weight % EPON 880 23.28 EPON 1001F 25.61 Stearyl alcohol 4.66
VESTAGON B1400 2.33 TiO.sub.2 14.90 SPHERICEL 110P8 22.81 MODAFLOW
Powder III (65%) 1.74 UVITEX OB 0.47 BYK 405 0.28 DYHARD 100M 3.24
AEROSIL R974 0.70 Total 100.0
[0272] The white compositions prepared in Examples 9 and 11 were
printed as a design on glass bottles using a Strutz GP-4
Semi-Automatic General Purpose Decorator. A stainless steel screen
of 180 mesh was used and the white decorating compositions were
printed at temperatures in the range of from 80.degree. C. to
85.degree. C. A portion of the blue ink composition prepared in
Example 10 was substantially immediately printed as a design,
partially on each of the white coatings previously applied to the
glass bottles, using a second screen printing pass of the same
decorating machine. For printing the blue composition, a stainless
steel screen of 230 mesh was used at temperatures in the range of
from 58.degree. C. to 63.degree. C. The printed bottles were
subsequently cured in a forced air oven at 180.degree. C. for one
hour. With the bottles printed with the white composition of
Example 9, white areas had been lifted from most of the bottles
during the blue printing step. The removal was sufficient in most
cases to make small lettering illegible. With the white composition
of Example 11, a run of 1000 bottles showed no damage to the white
design cased by the blue printing step. All lettering was
substantially intact with the composition of Example 11.
[0273] Other than in the operating examples, or where otherwise
indicated, all numbers expressing quantities of ingredients or
reaction conditions used herein are to be understood as modified in
all instances by the term "about".
[0274] Although the present invention has been described with
reference to specific details of certain embodiments thereof, it is
not intended that such details should be regarded as limitations
upon the scope of the invention except insofar as they are included
in the accompanying claims.
* * * * *