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Патент USA US3092514

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IQQ
3,092,594
Patented June 4, 1963
2
It will be seen from the above that the liquid bright
3,092,504
THERMOPLASTIC PRECIOUS METAL DECO
RATiNG COMPOSITIONS
Robert C. Langley, Millington, and David B. Kellam,
Nutley, N..l., assignors, by mesne assignments, to
Engelhard Industries, Inc., Newark, N.J., a corpora
tion of Delaware
No Drawing. Filed Mar. 11, 1960, Ser. No. 14,168
23 Claims. (Cl. 106-1)
precious metal decorating compositions comprise solu
tions of organic precious metal compounds in organic
solvents. Soluble ?uxes are ordinarily included in such
compositions, and compositions including ?uxes are pre
ferred, although for a few limited applications, such as
for application over a previously ?uxed substrate, such
fluxes are not essential.
Thermosetting precious metal decorating compositions
are known and are described in U.S. Patent No. 2,842,457,
This invention relates to precious metal decorating 10 granted to J. E. Morgan and C. W. Wagner. These ther
compositions, and, more particularly, relates to new pre
mosetting compositions are made by dissolving gold res
cious metal decorating compositions which are thermo
inate ‘or terpene mercaptan gold resinate and suitable gold
plastic, i.e., they are solid at room temperature but ?uid
?uxes in a solvent mixture which also dissolves a certain
at moderately elevated temperatures of the order of 120°
15 thermosetting epoxy resin and a certain catalyst for this
F. to 240° F. These precious metal decorating composi
epoxy resin. These thermosetting gold compositions are
tions are suitable for application, While at such moderately
fluid at room temperature; they are applied at room tem
elevated temperatures, to glass, quartz, glazed ceramics,
perature to refractory substrates and upon subsequent
unglazed ceramics, Pyroceram, mica, stainless steel,
heating to temperatures between 167° F. and 392° F., set
aluminum, titanium and other refractory substrates. 20 to hard solid ?lms.
Immediately upon application to such substrates, these
The thermoplastic precious metal decorating composi
thermoplastic precious metal compositions freeze to hard,
tions of this invention di?er from the thermosetting com
tack-free ?lms, having the advantages of ease of handling
positions of the prior art in that the thermoplastic pre
without smearing, freedom from defects due to settling
cious metal decorating compositions of this invention are
dust and permitting immediate subsequent application of 25 solids at room temperature and are heated to moderately
other decorating compositions. Upon ?ring the refractory
elevated temperatures before application to refractory
substrates to temperatures between 750° F. and 2100° F.,
substrates. The thermoplastic precious metal decorating
adherent precious metal ?lms result. These ?lms are use
compositions of this invention set to hard solid ?lms im
ful for their decorative appeal, for their ability to conduct
mediately upon contacting refractory substrates which are
electricity, to transmit particular wavelengths of ultra
at room temperature.
violet and visible light, to re?ect infra-red and other
The thermoplastic precious metal decorating composi
energy, as bases for soldering and for other purposes.
As “liquid bright gold,” precious metal decorating com
tions of this invention have an advantage over all pre
cious metal decorating compositions of the prior art in that
the thermoplastic precious metal decorating compositions
positions have been known for many years. In Boud
niko?, Comp. rend. 196, 1898-9‘ (1933) a method is de 35 of this invention can be handled immediately after appli
scribed for making a gold compound from sulfurized
cation to a substrate without any necessity for an inter
Venetian turpentine. This gold compound is dissolved in
mediate drying operation. This property of immediate
hardening on application to a substrate eliminates costly
essential oils, such as oil of lavender, oil of rosemary and
drying equipment, permits faster production of decorated
aniseseed oil, and when gold ?uxes, such as rhodium
resinate, bismuth resinate and chromium resinate have 40 objects, eliminates the rejects due to smears experienced
been added to the solution in the proper proportions, a
with conventional precious metal decorating compositions
decorating composition known as “liquid bright gold”
and permits unusual decorative eifects not obtainable with
results. The gold compound made in this way is referred
conventional precious metal decorating compositions.
An example of such a decorative effect obtainable only
Another type of gold resinate used in making liquid 45 with the thermoplastic precious metal decorating compo
sitions of this invention is a “wraparound” design screen
bright gold is described in US. Patent No. 2,490,399,
printed on a round object such as a glass cylinder. When
granted to H. K. Ballard. This type of gold resinate is
a thermoplastic precious metal decorating composition
referred to as a terpene mercaptan gold resinate or simply
such as a thermoplastic liquid bright gold is maintained
as gold terpene mercaptide. Still another class of liquid
to in the art as gold resinate.
bright golds contain gold tertiary alkyl mercaptides as 50 in a screen stencil at a moderately elevated temperature
such as 150° F., it can be applied in a “wraparound”
described in copending application Serial No. 727,254,
design to a round object, such as a glass cylinder, which
?led April 9, 1958, now Patent No. 2,984,574.
Decorating compositions containing platinum for use
is maintained at 75° F., by rotating the glass cylinder
on glass and ceramics are known in the art and have been
while in contact with the screen stencil through more than
described by Chemnitius, Sprechsaal 60, 226 (1927); 55 360 degrees relative to a ?xed point on its periphery.
This gives a design which overlaps without smearing; the
CA. 24, 4909. Such compositions contain a platinum
resinate prepared by causing a platinum salt to react with
thermoplastic precious metal composition sets to a hard
?lm immediately upon contact with the glass cylinder
pentine. The platinum resinate is dissolved in vehicle
and does not smear when, after the glass cylinder rotates
such as oils of lavender, rosemary, aniseseed, Sassafras, 60 through more than 360 degrees, the thermoplastic pre
cious metal composition again comes in contact with the
Wintergreen and fennel, turpentine, various terpenes, nitro
a sulfurized terpene such as sulfurized Venetian tur
benzene and the like and is mixed with ?uxes such as salts
and resinates of rhodium, chromium, bismuth, lead, cad
mium, tin, copper, cobalt, antimony and uranium and
screen stencil. While conventional precious metal deco
rating compositions are commonly applied to round ob
jects such as glass cylinders by the screen stencil method,
with resins such as Assyrian asphalt and various rosins to 65 “wraparound” designs are not possible without smearing
form decorating compositions. Such compositions are
since rotation of the decorated object through more than
known as liquid bright platinums.
360 degrees brings a wet design into contact with the
It is well known in the art that a palladium compound
screen stencil. Thus conventional precious metal deem
rating compositions for round objects are limited to use
may be prepared in the same manner as the above-men
tioned platinum resinate. lDecorating compositions made 70 in designs which cover less than 360 degrees of the pe
from a palladium resinate are known as liquid bright
riphe-ry of such objects. Conventional precious metal
palladiums.
decorating compositions for application by brushing or
3,092,504
spraying‘ are subject to defects caused by dust settling on
the wet ?lm after application and prior to ?ring. Dust
causes unsightly voids in the ?red film.
The thermo
plastic precious metal decorating compositions of this
invention eliminates defects due to dust by forming hard,
tack-free ?lms to which dust cannot adhere, immediately
upon application to the substrate.
Thermoplastic ceramic colors have been known for
'4
ester of hydrogenated rosin, the rosin Amine D salt of
naphthenic acid, and an acrylic resin available commer
cially as Catalin Resin A-1l14.
By using both a wax and a thermoplastic resin in vary
ing proportions in a thermoplastic precious metal deco
rating composition, it is possible to vary the viscosity of
the composition to suit different conditions or methods of
application and to allow for variations in temperature of
the substrate to be decorated. Suitable mixtures of ther
many years and are fully described in US. Patents No.
2,682,480 issued to R. Andrews; :No. 2,842,454 to O. A. 10 moplastic resins and Waxes are available commercially,
such as “Dralcotherm #712” and “Drakotherm #744,”
Short; -No. 2,607,701 and No. 2,607,702 to C. C. lessen,
both melting at about 140° F. These compositions include
and No. 2,748,093 to W. C. Morris. These and other
a thermoplastic resin, a thermoplastic wax, a plasticizer
patents describe suspensions of inorganic colors, also
and a solvent, and leave no ash or residue on ?ring. The
known in the art as glass enamel-s, in various waxes,
resins, plasticizers and solvents, such as “Carbowax” 4000, 15 range of total thermoplastic component is preferably 40
to 70 percent by weight of the formulation. It has also
“Abalyn,” “Armeen” 18D stearamide, “Acryloid” SF 100,
been found that the addition of certain organic solids to
“Armid" HT, “Staybelite,” stearic acid, limed wood rosin,
thermoplastic precious metal decorating solutions is useful
“Aeroplaz” 905, Pliolite R-‘l08, paraffin wax, stearyl alco
in controlling their viscosity. These organic solid addi
hol, carnauba wax, aluminum stearate, phosphorated tall
oil, bayberry wax, natural vegetable wax, “Polypale” 20 tives are selected for their insolubility in'the precious
metal decorating composition, for their stability at moder
resin, lecithin, stearyl acid phosphate, various polyethylene
glycols, diphenyl, various esters of hydrogenated rosin,
ate temperatures, such as 125° F. to 240° F., and for their
quality of volatilizing at temperatures above 240° F. with
and polybutene. From this prior art relating to ceramic
out etiect on the precious metal ?lm. Examples of such
colors, it is apparent that precise mixtures of the above
named and other thermoplastic materials are necessary in 25 thermally fugitive organic ?llers are ?nely divided urea
or melamine.
making thermoplastic ceramic colors which will have de
The invention will be further illustrated by reference
sirable properties in use. These thermoplastic ceramic
to the following speci?c examples:
colors are commonly used in applying decorative ?lms
on glass; they are applied by the screen stencil technique,
Example I
usually with a screen heated electrically to soften the 30
thermoplastic for printing. The use of such thermoplastic
ceramic colors permits overprint-ing with successive colors
immediately and eliminates the need for any intermediate
A thermoplastic liquid bright gold made with a mixture
of waxes, resins, plasticizers and solvents was prepared
as follows:
drying before overprinting.
The thermoplastic precious metal decorating composi 35
Parts by
tions of this invention diifer from the thermoplastic
,
weight
ceramic colors of the prior art in that the latter do not
Gold resinate dissolved in a mixture of essential oils
contain organic precious metal compounds nor are they
400
(24 percent Au)
solutions but rather suspensions of inert inorganic solids
Rhodium
resinate
dissolved
in
a
mixture
of
essential
in thermoplastic vehicles. When ?red on glossy or glazed 40
*oils and hydrocarbons (2 percent Rh) ________ __ 25
substrates, the precious metal decorating compositions of
this invention yield specular, electrically conductive
Bismuth resinate dissolved in a mixture of essential
metallic ?lms.
Chromium resinate dissolved in a mixture of cyclo
hexanone and oil of turpentine (2.05 percent Cr) __ 20
The ?red ?lms obtained from thermo
plastic ceramic colors are non-specular mixtures of oxides,
not electrically conductive.
45
The thermoplastic precious metal decorating composi
oils (9 percent Bi) ________________________ __
Drakotherm #712 __________________________ __ 296
tions of this invention can be made by‘substituting a wax
or waxlike substance for part of the solvent normally
present in conventional precious metal decorating com
positions. Such wax or waxlike substance may be present 50
35
776
This mixture was evaporated with stirring on a steam
bath to
__
560
in the ?nished composition in the amount of from about
20 percent to about 80 percent by weight, depending on
the particular wax used, the method of application and the
degree of hardness sought in the ?lm upon application.
A dark, clear solution when at a temperature of 125 ° F.
These compositions melt in the range of 125° F. to 215° 55 and above, resulted. This set to a hard, wax-like solid
F.
Examples of such waxes are the Armids, which are
primary amides of fatty acids. Armid HT, melting point
on cooling to room temperature. The solution contained
approximately 17 percent Au, 0.09 percent Rh, 0.56 per
cent Bi, and 0.073 percent Cr. When applied to a round
208° F., Armid C, M.P. 174° F., and Armid O, M.P. 154°
glass object by a stainless steel screen heated electrically
F., have been found to be very suitable in thermoplastic
precious metal formulations. Other waxes found to be 60 to 125° F. to 140° F., a. hard, waxy ?lm formed im—
mediately upon contact with the glass object which was
useful are Rosin Amine D stearate and Rosin Amine D
2-ethyl hexoate;
at 75 ° F. > When this glass object was ?red to a tempera
. ture of approximately 1100° F., an adherent gold ?lm
of mat appearance resulted. This film was an excellent
resin can be used to make a thermoplastic precious metal
decorating composition. An example of such thermo 65 conductor of electricity.
Instead of a wax or waxlike substance, a thermoplastic
plastic resin is Staybelite Resin, a hydrogenated rosin de
scribed in the booklet, “Staybelite Resin,” published in
1946. Thermoplastic resins may be present in the ?nished
composition in the amount of from about 20 percent to
Example II
A thermoplastic liquid ibright gold which ?res out
brighter than Example I was prepared as follows:
about 90 percent by weight, giving precious metal decorat-, 70 To 560 parts by Weight of the mixture of Example I
after evaporation was added 260 parts by weight of
ing compositions which melt at somewhat higher tempera
tures, such as 200 to 240° F., than those made with waxes.
Other thermoplastic resins found to be useful are Stay
belite Ester No. l, the ethylene glycol ester of hydro
the Rosin Amine D salt of naphthenic acid. Rosin Amine
D is a primary amine made from a-modi?ed rosin. It
is fully described in the booklet “Rosin Amine D and Its
genated rosin, Staybelite Ester No. 2, the diethylene glycol 75 Derivatives,” published in 1950. Rosin Amine D has an
3,092,50s
approximate molecular weight ‘of 318 and when reacted
by warming with a naphthenic acid of approximately
molecular weight of 252, in the proportion of one mole of
captide, prepared as described in Example 7b of copend
ing application Serial Number 727,254, of Howard M.
Fitch. The printing properties and ?red appearance of
the amine to one mole of the acid, a thermoplastic com
Example III were duplicated in every way with the sub
pound results. This Rosin Amine D salt of naphthenic 5 stituted gold tertiary dodecyl mercaptide.
acid is a clear yellow solid at room temperature, but
changes to a ?uid when warmed to approximately 175° F.
Example VI
A thermoplastic liquid bright gold comprising only
The addition of 260 parts by weight of the Rosin
Amine D salt of naphthenic acid to 560 parts by weight
liquid bright gold and a wax was prepared as follows:
of Example 1 resulted in a product which was a clear 10
dark solution when warmed by an infra-red source to
a temperature of 125° F. to 140° F. While warmed
Parts by
in this manner, the solution was stenciled through a silk
weight
screen on to a round glass object maintained at 75° F.
Gold tertiary dodecyl mercaptid-e dissolved in a mix
Immediately upon contact with the glass, the solution of 15
ture of essential oils (24 percent Au) _______ __ 75
liquid bright gold set to a hard, waxy ?lm. When the
Rhodium resinate ‘dissolved in a mixture of essential
glass object was ?red to approximately 1100° R, an
oils (2 percent Rh) _______________________ __
adherent decorative bright gold ?lm resulted.
Armid HT
Example 111
_____
_
10-5
20
‘185
A thermoplastic liquid bright gold suitable for over
printing with a ceramic color was prepared as follows:
This mixture was evaporated with stirring on a steam
bath to ____
_
1150
25
Parts by
Armid HT is a synthetic wax and is composed of ‘amides
of hexadecane, octadecane and octadecene, mp. about
208° F. After evaporation, the dark brown solution con
664
30 tained 70 percent Armid HT, 12 percent Au and 0.066
percent Rh, and was ?uid at 215° F. and above. When
44.7
warmed to 240° F., the solution was transferred by means
weight
Gold resinate dissolved in a mixture of essential
oils (24 percent Au) ____________________ __
Rhodium resinate dissolved in a mixture of essen
tial oils and hydrocarbons (2 percent Rh) ____
Bismuth resinate dissolved in a mixture of essen
tial oils (9 percent Bi) __________________ __
cent Cr)
of ‘a brush to a ‘glass cylinder. Immediately upon contact
with the glass, the solution set to ‘a hard, waxy solid.
58.1
Chromium resinate dissolved in a mixture of cyclo
~hexanone and oil of turpentine (2.05 per
35 Upon subsequent ?ring to 1100° F., a bright electrically
33.2
Drakotherrn #712 ________________________ __
600
Rosin Amine D salt of naphthenic acid ______ __
Finely divided melamine powder ____________ __
450
810
conductive gold ?lm resulted.
Example VII
A thermoplastic liquid bright gold suitable for screening
40 and melting at approximately 200° F. was prepared ‘as
follows:
2660
Parts by
weight
This mixture was evaporated with stirring on a
Gold resinate dissolved in a mixture of essential
steam bath to __________________________ .... 2300
oils (24 percent Au) ___________________ __
664
Rhodium resinate dissolved in a mixture of essen
tial oils and hydrocarbons (2 percent Rh) ___
The mixture contained approximately 7 percent Au
44.7
Bismuth resinate dissolved in a mixture of essen
and when warmed to approximately 140° F. on an elec—
tial oils (9 percent Bi) __________________ __
trically heated stainless steel screen, printed sharply 'on 50 Chromium resinate dissolved in a mixture of cy~
to a round glass bottle maintained at 75° F. The print
clohexanone and oil of turpentine (2.05 per
on the bottle was hard and tack-free immediately after
cent Cr) _____________________________ __
printing and was overprinted with a ceramic color sus
pended in squeegee oil, a mixture well known in the art
as squeegee glass enamel. This overprinting was accom
Armid HT _____________________________ __
58.1
33.2
600
Rosin Amine D salt of naphthenic acid ______ __
450
Finely divided melamine powder __________ __'_
461
plished without smearing or detracting ‘from the gold
print in any way. When ?red to approximately 1100° F.,
2311.0
an appealing design of adherent bright gold overprinted
with adherent glass enamel resulted. The ?nely divided
This mixture was evaporated with stirring on a
melamine powder in this example serves as an inert or 60
steam bath to _________________________ __ 1971
ganic diluent which volatilizes during ?ring without af
fecting the ?red appearance of the bright gold.
The mixture contained ‘approximately 8.1 percent Au,
0.045 percent Rh, 0.26 percent Bi and 0.034 percent Cr,
Example IV
Example III was repeated, substituting for gold resinate, 65 and when warmed to approximately 200° F. on an elec
trically heated stainless steel screen, printed sharply on
to a round glass bottle maintained at 100° F. The print
a 24 percent Au solution of gold pinene mercaptide‘, pre
pared as described in Example I of Us. Patent No.
2,490,399. The printing properties and ?red appearance
of Example III were duplicated in every way with the
substituted gold pinene mercaptide.
on the bottle was hard and tack-free immediately after
printing, and was overprinted with squeegee glass enamel
70 without smearing. When the bottle was ?red to 1100” R,
Example V
Example III was repeated, substituting for gold resinate,
a 24 percent Au solution of gold tertiary dodecyl mer 75
an appealing design of adherent bright gold overprinted
with adherent glass enamel resulted.
Example VIII
A thermoplastic liquid bright gold suitable for screen
3,092,504
7
8
ing ‘and melting at approximately ‘170° ‘F. was prepared
Parts by
220° F., the clear dark solution was applied to the edge
of a glazed earthenware dinner plate. Almost immedi
ately upon contact with the dinner plate, the gold solu—
weight
,tion set to a medium-hard ?lm having very little tack.
654
bright gold in its ability to resist smears caused by han
as follows:
'
This ?lm proved greatly superior to conventional liquid
Gold resinate dissolved in a mixture of essential
oils (24 percent Au) __________________ __
Rhodium resinate dissolved in a mixture of essen
tial oils and hydrocarbons (2 percent Rh) ___
Bismuth resinate dissolved in a mixture of essen
44.7
tial oils (9 percent Bi) _________________ __
58.1
dling or imperfections due to dust settling on a wet ?lm.
When ?red to 1375° R, an adherent bright gold ?lm
resulted.
Example XII
A thermoplastic liquid bright platinum was prepared
Chromium resinate dissolved in a mixture of cy
clohexanone and oil of turpentine (2.05 per
cent Cr)
as follows:
_____________________________ __
Armid HT
__
-
33.2
__
600
Rosin Amine D salt of naphthenic acid ______ __
450
Stearic acid _____________________________ __
188
Finely divided melamine powder ___________ __
461
Parts by
a
Weight
15 Gold resinate dissolved in a mixture of essential oils
(24 percent Au) _________________________ __
oils (12 percent Pt) ______________________ __
_
_
300
Rhodium resinate dissolved in a mixture of essential
2499.0
This mixture was evaporated with stirring on a
100
Platinum resinate dissolved in a mixture of essential
20
steam bath to __________________________ __ 2159
oils and hydrocarbons (1 percent Rh) _______ __
50
Bismuth 'resinate dissolved in a mixture of ‘essential
The mixture contained approximately 7.4 percent Au,
0.041 percent Rh, 0.24 percent Bi and 0.032 percent Cr,
oils (4.5 percent Bi) _____________________ __
70
Chromium resinate dissolved in a mixture of cyclo
hexanone and oil of turpentine (2.05 percent Cr)
20
and When warmed to approximately 170° F. on an elec
trically heated stainless steel screen, printed sharply on 25 Drakotherm #712 _________________________ __ 405
Rosin Amine D salt of naphthenic acid ________ __ 300
to a round glass bottle maintained at 75° F. The print
{Finely divided melamine powder _____________ __
on the bottle was hard and tack-free immediately after
195
printing and was overprinted with squeegee glass enamel
When the bottle Was ?red to 1100°
1440
prepared as described in Example I of US. Patent No.
ed' stainless steel screen, printed sharply on to a round
glass bottle maintained at 75° F. The print on the bottle
was hard and tack-free immediately after printing. When
without smearing.
F., ‘an appealing design of adherent bright gold over 30
The above mixture was evaporated with stirring on
printed with adherent glass enamel resulted.
a steam bath to
_
__
1200
Example IX
This mixture contained 2 percent Au, 3 percent Pt, 0.04
Example VIII was repeated, substituting for gold res
percent Rh, 0.26 percent Bi, 0.034 percent Cr, and when
inate, a 24 percent solution of gold pinene mercaptide, 35 ‘warmed to approximately 140° F. on an electrically heat
2,490,399. The printing properties and ?red appearance
of Example VIII were duplicated in every way ‘with the
substituted gold pinene mercaptide.
40 ?red to approximately 1100° R, an adherent bright plati
Example X
num ?lm resulted. This bright platinum film had con
siderable decorative appeal, was electrically conductive
and served as a base for the attachment of copper wires
Example VIII was repeated, substituting for gold res
inate, a 24 percent solution of gold tertiary dodeeyl mer
Iby solder.
I
captide, prepared as described in Example 7b of copend~
A
thermoplastic
liquid
‘brig-ht
palladium
can
be
made
ing application Serial No. 727,254, of Howard M. Fitch. 45 by substituting palladium resinate solution for the platinum
The printing properties and ?red appearance of Example
resinate solution of this example.
VIII were duplicated in every way with the substituted
Example XIII
gold tertiary dodecyl mercaptide.
'
A thermoplastic luster color was produced as follows:
Example Xl
A thermoplastic liquid bright gold comprising only
‘liquid bright gold and a thermoplastic resin was prepared
as follows:
Parts by
:Weight
Gold resinate dissolved in a mixture *of essential oils
(24 percent Au) ____________________ __.,___ 400
Rhodium resinate dissolved in a mixture of essential
oils and hydrocarbons (2 percent Rh) ________ __
Bismuth resinate dissolved in a mixture of essential
'oils (9 percent Bi) __________________ ._'_..___..
Chromium resinate dissolved in a mixture of cyclo
(25
50
Parts by
a
a
weight
Gold resinate dissolved in a mixture of essential oils
(24percent Au) _________________________ __
100
55 Titanium resinate dissolved in a mixture of essential
oils and hydrocarbons (3.6 percent Ti) ______ __
400
Bismuth resinate dissolved in a mixture of essential
oils (4.5 percent Bi) ______________________ __
300
Drakotherm #712 _________________________ __
600
Rosin Amine D salt of naphthenic acid ________ __ 450
3s 60 Finely divided melamine powder _____________ __ 910
hexanone and oil of turpentine (2.05 percent Cr)__ 20
2760
Stabelite Resin, a hydrogenated rosin described in
the booklet “Staybelite Resin,” published in
-1946
_ 300
780
This mixture was evaporated with stirring on a steam
65 The above mixture was evaporated with stirring on
a steam bath to _________________________ __ 2400
The mixture then contained 1 percent Au, 0.6 percent
Ti and 0.56 percent Bi. . When warmed to approximately
150° F. on an electrically heated stainless steel screen,
70 the mixture printed sharply on to a round glass bottle
maintained at 75° F. ‘The ?lm on the bottle was hard
and then contained about 16 percent gold, 0.08 percent.
and tack-free. When ?red to 1100° R, an attractive
Rh, 0.53 percent Bi, and 0.068 percent Cr. '
'
adherent ?lm resulted. This ?lm was blue in transmitted
When placed in the metal well of a roller coating ma
light and had a high metallic sheen when viewed in re?ect
chine and heated by an infra~redsource to approximately 75 ed light. This mixture was placed in a glass container
bath to
____ 600
3,092,504.
9
10
‘and warmed to ‘approximately 170° F., then transferred
3. A liquid bright gold ‘decorating method, which com—
by means of a camel’s hair brush to an earthenware dinner
prises applying as a liquid to a refractory substrate main
tained substantially at room temperature a thermoplastic
plate maintained at 75° F. The brushed ?lm set almost
immediately to a hard, tack-free ?lm. When ?red to
1375 ° R, an adherent, highly iridescent blue luster decora
tion resulted.
liquid bright gold composition comprising a ‘soluble liquid
bright gold and as an organic solvent for the liquid bright
gold, a thermoplastic medium selected from the group
Example XIV
consisting of thermoplastic resins, thermoplastic waxes
A thermoplastic mat ‘gold was produced as follows:
and mixtures thereof, the thermoplastic medium con
stituting from about 20 percent to about 80 percent by
Parts by
weight
10
composition having a melting point within the range of
125° F. to 240° F., maintained liquid by heating at an
elevated temperature above its melting point, a hard,
Gold resinate dissolved in a mixture of essential oils
v“(24 percent Au) ________________________ __
400
Rhodium resinate dissolved in a mixture of essential
oils and hydrocarbons (1 percent Rh) _______ __
Bismuth resinate ‘dissolved in a mixture of essential
oils (4.5 percent Bi) _____________________ __
tack-free ?lm being formed substantially immediately
50 15 upon contact of the composition with the refractory sub
strate.
70
4. A thermoplastic, normally solid precious metal deco
rating composition comprising a soluble organic precious
Chromium resinate dissolved in ‘a mixture of cyclo
hexanone and oil of turpentine ‘(2.05 percent Cr)
20
Drakotherm #712 _________________________ __
600
Rosin Amine D salt of naphthenic acid ________ __
Finely divided melamine powder _____________ __
200
400
metal compound, and as an organic solvent for the com-.
20 pound, a thermoplastic medium selected from the group
consisting of thermoplastic resins, thermoplastic waxes
and mixtures thereof, said thermoplastic medium con
stituting from ‘about 20 percent to about 80 percent by
1740
This mixture was evaporated with stirring on a steam
bath to
weight of the composition, the thermoplastic precious
25 metal composition having a melting point within the range
of 125° F. to 240° F.
__ 1400
The mixture then contained approximately 6.9 percent
Au, 0.04 percent Rh, 0.23 percent Bi, ‘and 0.029 percent
Cr.
weight of the composition, the thermoplastic bright gold
5. A thermoplastic, normally solid precious metal deco_
rating composition comp-rising a soluble organic precious
metal compound, a soluble ?ux for the precious metal,
The above mixture was spread in a thin ?lm on a 30 and as an organic solvent for the compound and ?ux, a
?at steel plate maintained at 170° F.
When transferred
by means of a rubber stamp to an earthenware dinner
thermoplastic medium selected ‘from the group consisting
of thermoplastic resins, thermoplastic waxes and mix
plate maintained at 75° 'F., the mixture set almost im—
tures thereof, said thermoplastic medium constituting
mediately to a hard, tack-free ?lm. Upon ?ring to 1375"
from about 20 percent to about 80 percent by weight
35 of the composition, the thermoplastic precious metal
R, an attractive mat gold decoration resulted.
It will be apparent from the ‘above examples that varia
composition having a melting point within the range of
tions in the ‘formulations are possible ‘depending on the
125° F. to 240° F.
_
method of application used and the use for which the un
6. A method of making a thermoplastic organic prec
?red or ?red ?lm is intended. For example, with heated
ious metal composition comprising a soluble organic
spraying equipment, it would be possible to spray a liquid 4.0 precious metal compound, and a thermoplastic medium
bright gold formulation which would set immediately
upon contacting an object at room temperature, thus elim
inating the problem of dust settling on the wet ?lm en
as an organic solvent therefor, which comprises, liquefy
ing the thermoplastic medium by heating, and dissolv
ing the organic precious metal compound in the lique?ed
countered with conventional liquid bright golds.
thermoplastic medium present in amount sut?cient to
It will be obvious to those skilled in the art that many 45 constitute from about 20 percent to about 80 percent by
modi?cations may be made within the scope of the present
weight of the product thermoplastic organic precious
invention without departing (from the spirit thereof, and
metal composition, the product thermoplastic precious
the invention includes all such modi?cations.
What is claimed is:
metal composition having a melting point within the
1. A thermoplastic precious metal decorating compo-si 50
tion comprising a soluble organic precious metal com
pound and a thermoplastic medium as an organic solvent
therefor, said composition being proportioned to be solid
at normal temperature and meltable at a temperature
within the range of 120° F. to 240° F. to prepare the
composition for application to the surface to be decorated,
the composition solidifying substantially immediately upon
‘contact with the surface to form a hard tack-free ?lm
thereon.
2. A precious metal decorating method which com
prises applying as a liquid to a refractory substrate main
tained substantially at room temperature a thermoplastic
range of 125° F. to 240° F.
7. A thermoplastic, normally solid precious metal deco
rating composition comprising a soluble organic precious
metal salt, a soluble flux for the precious metal, and as
an organic solvent for the salt and ?ux, a thermoplastic
medium selected from the group consisting of thermo
plastic resins, thermoplastic waxes and mixtures thereof,
said thermoplastic medium constituting from about 20
percent to about 80 percent by Weight of the composi
tion, the thermoplastic precious metal composition hav
ing a melting point within the range of 125° F. to 240° F.
8. A composition according to claim 4 further char
acterized by containing a thermally fugitive organic ?ller.
9. A composition according to claim 4, in which the
precious metal composition comprising a soluble organic
precious metal compound is a precious metal resinate.
precious metal compound and a thermoplastic medium
10. A composition according to ‘claim 4, in which the
as an organic solvent therefor, said composition being 65
precious metal compound is ‘a precious metal mercaptide.
proportioned to be solid at normal temperature and melt
11. A composition according to claim 4, in which the
precious
metal compound is a gold resinate.
240° F. to prepare the composition for application to
12. A composition according to claim 4, in which the
the ‘substrate to be decorated, the composition solidifying
substantially immediately upon contact with the substrate 70 precious metal compound is a platinum resinate.
13. A composition ‘according to claim 4, in which the
to form a hard tack-free ?lm thereon, maintained liquid
precious metal compound is a palladium resinate.
by heating at an elevated temperature above its melting
14. A composition according to claim 4, in which the
point, a hard, tack-free ?lm being formed substantially
precious metal compound is a gold terpene mercaptide.
immediately upon contact of the composition with the
15. A composition according to claim 4, in which the
75
refractory substrate.
able at a temperature within the range of 120° F. to
3,092,504r
l1
precious metal compound is a gold tertiary alkyl mercap
with a thermally fugitive organic ?ller, the Wax and ther
moplastic resin together constituting from about 20 per
cent to about 80 percent by weight of the composition,
the thermoplastic bright gold composition having a melt
tide.
16. A thermoplastic bright gold composition com
prising a solution of a gold resinate and a gold ?ux in a
wax and ‘a thermoplastic resin, in admixture with a ther 5 ing point within the range of 125° F. to 240° F.
mally fugitive organic ?ller, the wax and thermoplastic
resin together constituting from about 20 percent to
about 80 percent by weight of the composition, the ther
21. A thermoplastic bright gold composition comprising
a solution of a gold tertiary dodecyl mercaptide and a
gold ?ux in a wax and a thermoplastic resin, in admixture
with a thermally fugitive organic ?ller, the wax and
moplastic bright gold composition having a melting point
within the range of 125 ° F. to 240° F.
17. A thermoplastic bright gold composition compris
10 thermoplastic resin together constituting from about 20
ing a solution of a gold terpene mercaptide and a gold
?ux in a wax and a thermoplastic resin, in admixture
percent to about 80 percent by weight of the composition,
the thermoplastic bright gold composition having a melt
ing point within the range of 125° F. to 240° F.
22. A thermoplastic bright platinum composition com
thermoplastic resin together constituting from about 20 15 prising a solution ‘of a gold resinate, a platinum resinate
percent to about 80 percent by weight of the composi
and a ?ux in a wax and a thermoplastic resin, in admix
tion, the thermoplastic bright gold composition having‘ a
ture with a thermally fugitive organic ?ller, the wax and
melting point within the range of 125° F. to 240° F.
thermoplastic resin together constituting from about 20
18. A thermoplastic bright gold composition compris
percent .to about 80 percent by weight of the composi
ing a solution of a gold pinene mercaptide and a gold 20 tion, the thermoplastic bright platinum composition hav
with a thermally fugitive organic ?ller, the wax and
flux in a wax and a thermoplastic resin, in admixture
with a thermally fugitive organic ?ller, the wax and ther
moplastic {resin together constituting from about 20
percent to about 80 percent by weight of the composi
tion, the thermoplastic bright gold composition having a
melting point within the range of 125° F. to 240° F.
19. A thermoplastic bright gold composition compris
inga melting point within the range of 125 ° F. to 240° F.
23. A thermoplastic bright platinum composition com
prising a solution of a platinum resinate and a ?ux in
a Wax and a thermoplastic resin, in admixture with a
thermally fugitive organic ?ller, the wax and thermoplas
tic resin together vconstituting from about 20 percent to
about 80 percent by Weight of the composition, the
ing a solution of a gold tertiary mercaptide and a gold
thermoplastic bright platinum composition having a melt
flux in a wax and a thermoplastic resin, in admixture
ing point within the range of 125° F. to 240° F.
with a thermally fugitive organic ?ller, the wax and ther 30
moplastic resin together constituting from about 20
percent to about 80 percent by weight of the composition,
the thermoplastic bright gold composition having a melt
References Cited in the ?le of this patent
UNITED STATES PATENTS
ing point Within the range of 125° F. to 240° F.
2,682,480
2,807,555
2,842,454 a
Short ________________ __ July s, 1958
ing a solution of a gold tertiary alkyl mercaptide and a
gold ?ux in a wax and a thermoplastic resin, in admixture
2,842,457
Morgan et a1. ________ __ July 8, 1958
2,965,509
Hoifman ___________ __ Dec. 20, 1960
20. A thermoplastic bright gold composition compris 35
Andrews ___________ __ June 29, 1954
Short ______________ __ Sept. 24, 1957
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