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Патент USA US3084139

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3,084,129
Retentetl Apr- .2, 19.63.
2
It is of the essence of this‘invention~ that the meth
acrylate polymer and. monohydroxy alcohol ,beutpresent
3,034,129
BUTYL METHACRYLATE POLYMER AND
GLASS FRIT VEHICLE COWRISING NORMAL
in combination in the vehiclein the aforesaidratip of
7 to .30 parts byvweig'nt of the polymerrand, 63. to‘ 88
parts by weight of the_alcohol. The useofthe meth
acrylate polymerwith?other waxqs andwax-like ma
terialsv in the absence of .thevaboyeratio ‘ofv monohydroxy
alcohol. will fail‘ to produce .a. vehicle that willxbeusatisr
MQNOHYDROXYv ALEPHATIC ALCBHQL
Lewis. CharlesHoifrnan, Scotch. Plains, N.J., assignorto
El 1.. duPont deNelnours and Company, ‘Wiimington,
DeL, a corporation of Delaware
No Drawingo Filed Jan.;29,j1960, Ser. No. 5,345
3 Claims. _ (cram-1 7).
This invention relates to a glass frit vehicle and‘ more
particularly, it relates to. anew and improved composi_
tion of, athermo?uid vehicle for glassfrits or glass colors.
The vehicles of this invention have particular utility- for
therapid super-imposition, of a plurality of colored glass
frits on metal or ceramic surfaces.
10
15
Thermo?uid vehicles have been used for some time in
factorily ¢Qmr>atib1ewithcther commercial thermo?uid
vehicles. On (the otherrhanm, the. use. ofyother resins in
place of n-butyl methacrylatepolymer with, the. mono
hydroxy alcohol will‘fail to produce a vehicle that is
fully satisfactory in respect to carbonaceousresidue upon
?ring.
.Normal butyl methacrylatepolymer is theuonlyacrylic
resin ‘found suitable for thewpurposes vofgthe' present in,
vention- Normal butyl methasrylate Polymers as here:
tofore made ¢omrnercia11y.,f.or. example. “Lucite 44,”
the application of colored glass yfrits on. surfaceaon
which they are to be ?redlfor the production of-enamelled
made and sold by L. du .Pont de Nemours and Com.
surfaces. Such vehicles are available commercially as 20 pany, may haves viscosity ofbetwsen aboutl? and
mixtures of thermoplastic resins and waxes orywax-like
100 secondswfor a, 43% solution of thepolyrner in .tol
materials and arereferred to generally as f‘resin-wax type’?
none at 25° C. when measured in a Parlin cup. By use
thermo?uid vehicles or as mixtures solely of waxes and
of so-called chain stoppers, lower viscosity polymers ‘may
Wax-like materials and are referred tovv as “all-wax type”
be made. Any of such polymers of n-butyl methacrylate
thermo?uid vehicles.
'
25 are suitable for this purpose. Such polymer possesses
Since the various types of thermofluid vehicles func:
the required solubility and solution stability in waxes
tion in substantiallythe same manner, they are some
and. wax-like materials. It is‘ lower in melting point
times mixed in‘ the tradeby users thereof, especially when
than other methacrylate polymers so' that the screen
switching from ‘one. to another type of vehicle.’ Such
stencil used in applying the glass colors can be operated
mixing of vehicles hasiledv to a great deal of ,dil?crulty
at a low temperature, avoiding heat deterioration.
and failure by reason of the incompatibility-With.each
' Any saturated monohydroxy aliphatic alcohol solid at
other utmost of the .thermo?uid vehicles sold on .the
market.
.
_
Another common objection- to many thermo?uidsvee
hides is the. relatively high carbonaceous. residueremain
ing after ?ring of “they glass“ frit colors,
It is, therefore. an object vof‘this,.irlvexnism to Provide
a new and,improvedneornposition .ofth‘ermo?uivdhglass
frit vehicle.’
room temperature can be used. More speci?cally, these
alcohols, having. acarbon'chaim length of;1'2;;to; 32,are
useful foruthispurposeh .The monohydroxy alcohols, may
be single ‘alcohols or mixtures v‘of such alcohols. Mix
.tures of fatty alcohols highly useful for the preparation
ofnvehicle compositions offthis invention are exempli?ed
by thetfol-lowing commercial substances:
(1) “Siponol TX” (a mixed fatty alcohol made and sold
It is another object to provide a‘ compositionzof ther 40 by AmericaniAlcolacvCorp.) containing C12-C14, 8%..and
moiluid glass frit vehicle that will have .a very low car
bonaceous residue upon ?ring of the glass frit.
It is another object to provide a‘ composition“ of ther
mofluid ‘glass frit- vehicle that will be compatible with
“resin-wax” and_“all-wax’.’ commercial thermo?uid ve 45
hicles.
by Archer-Daniels-Mihdland Corp.) containing C18, 24.3%,
Other objects of the invention will, appear hereinafter.
The objects of this invention will beachieved bythe
provision of a composition of thermoiluid vehicle .for
(4) “Lorol 28” (made and sold by E. I. du_ Pont_ de
Nemours and Company as technical grade lstearyln alco
GIG-C18,
C. ‘ ‘ _.
(2) “Adol; 64” (a mixed vfattyralcohol. made and sold
C18,
C20, 7-1%-
'
i
r
(3) “Dytol E446?” (made and sold..by Rohm and Haas
Corp.) containing C14, 1.2%, C16, 34.4%, C18, 64.4%.
hol)’, melting point 58° C.
1
‘ ‘,
use in glass frit application containing, in combination, 50
l-dodecano'l,
melting
point
2~4"-,v
or‘any
similarfatty
polymerized normal butyl methacrylate and a saturated
alcohol to and including l-dotriacontanol (C32) may be
monohydroxy alcohol of 12 to 32 carbon chain length.
used. In order that the vehicle be su?icient-ly stable at
These two materials should be present in a ratio of 7
least 37% by weight of the vehicle has to be composed
to 30 parts by weight of the poly n-butyl methacrylate
of fatty alcohol. Lange amounts of para?in', stearic acid,
and 63 to 88 parts by weight of the saturated mono 55 microcrystalline waxes, carnauba wax or the like either
hydroxy alcohol.
do not fully dissolve the n-butyl methacrylate polymer
In many instances it will be preferred to add a small
amount of ethyl cellulose as a levelling agent and an
anionic surface-active agent composed of the reaction
allowing separation of the components to take place.
of this invention consist substantially entirely of the
aforesaid methacrylate polymer and monohydroxy alco
active agent composed of the reaction product of P0013
and a saturated monohydroxy aliphatic alcohol having 8
or the solutions are unstable at or near the melting point
Ethyl cellulose is an optional component in the ve
product of POCls and a saturated monohydroxy alcohol 60 hicle. It is added only where it is particularly desirable
having 8 to 18 carbon atoms. The ethyl cellulose may
to have an improvement in levelling of the applied glass
advantageously be present in an amount of up to 5% by
color composition during ?ring. The low viscosity (5%
weight and the anionic surface-active agent may be present
solution in toluene-ethanol 9~11 centipoises or lower)
in an amount up to 7% by Weight.
is preferred for reasons of better solubility.
Although it is preferred that the therrno?uid vehicle 65
The other optional ingredient is the anionic surface~
hol, with or without the ethyl cellulose and anionic sur
to 18 carbon atoms.
These surface-active agents are
face-active agent, up to 40% by Weight of the vehicle
used as dispersants and may be obtained, for example,
may be comprised of other resin-wax or all-wax thermo 70 by reacting 28.4 parts of 1,6-hexanediol and 34.5 parts
?uid vehicles or other known resins or waxes as used
of 3,3,5~trimethylhexanol-l with 37.1 parts P0013 at a
in thermo?uid vehicles.
temperature of 70° C. until gas evolution ceases, and
3,034,129
3
then neutralizing with alkali; or by reacting 70 parts
3,3,5-trimethylhexanol-1 with 30 parts POCls at 70° C.
Nos. 2,607,701, 2,607,702, 2,682,480, 2,617,740, and
until gas evolution ceases and neutralizing; or by reacting
70 parts cetyl alcohol with 30 parts POCla in the same
manner and neutralizing with an alkali. Commercially
available materials of this type include “Alipal GB 520"
2,823,138. The thermo?uid vehicles of the above ex
amples also exhibited the many essential characteristics
of thermo?uid vehicles for use in glass colors. These
vehicles exhibited good levelling and quick melting With
(a product made and sold by Antara Chemicals Co.
comprising the sodium hydroxide alkalinized POCla re
action product of a higher alcohol).
out running, were operable at varying room tempera
tures, had good aherence to glass and metal surfaces,
10
To the same dispersant e?ect is the addition of the re
action product of H3i>O4 and tall oil neutralized with
NaOH, for example, “Tallicin 120” (a product made and
sold by P?aumer Brothers Company comprising "the NaOH
neutralized reaction product of H3PO4 and tall oil).
The following examples are vgiven to illustrate several
preferred embodiments of this invention, it being under
maintained glass frit in good dispersion, and did not gel
upon melting.
Throughout the speci?cation and claims, any reference
to parts, proportions and percentages refers to parts,
proportions and percentages by weight unless otherwise
speci?ed.
' Since it is obvious that many changes and modi?cations
can be made in the above/described details without de
stood that the details of these examples are in no way
limitative of the scope of the invention.
parting from the nature and spirit of the invention, it is
to be understood that the invention is not to be limited
Thermo?uid glass color compositions are prepared by
thoroughly mixing
to said details except as set forth in the appended claims.
I claim:
1. A thermo?uid vehicle for glass color compositions
at least 60% of which consists essentially of normal
the following ingredients in the pro- -,
portions tabulated while applying suf?cient heat to melt
the several ingredients except, of course, the glass frit
colors. The glass frit colors are composed of 90% by
weight of colorless glass frit having the following com
position and 10% of ceramic color pigments:
butyl methacrylate polymer having a parlin cup viscosity
of between about 20 and 100 seconds for a 43% solution
in toluene at 25° C. and a saturated monohydroxy ali
Percent
52.00
phatic alcohol solid at room temperature and having 12
to 32 carbon atoms, said constituents being present in
the ratio of 7 to 30 parts polymer and 63 to 88 parts
alcohol.
2. The thermoiluid vehicle of claim 1 containing, based
on the weight of polymer and alcohol, up to 5% of ethyl
cellulose and up to 7% of a reaction product of POCI3
6.15
31.00
0.95
3.65
1.98
4.27
with a saturated monohydroxy aliphatic alcohol having 8
to 18 carbon atoms.
100.00
3. A glass color composition consisting essentially of
Any glass frit color other than that set forth in the
above speci?c example can be used equally well.
a ?nely divided glass frit color and a thermo?uid ve
hicle at least 60% of which consists essentially of nor
mal butyl methacrylate polymer having a parlin cup vis
40 cosity of between about 20 and 100 seconds for a 43%
solution in toluene at 25° C. and a saturated monohy
droxy aliphatic alcohol solid at room temperature and
having 12 to 32 carbon atoms, said constituents being
present in the ratio of 7 to 30 parts polymer and 63 to
45 88 parts alcohol.
Examples
Example No ______________ __
Ingredient:
“Lucite 44” ___________ __
“Lorol 28” ____________ -_
Ethyl Cellulose _______ __
Reaction
Product
of
P001: and Lauryl
Alcohol _____________ __
Glass Frit Color (in parts
per 100 parts vehicle) .... _
1
05b:ON
7
O
0
0
0
450
450
400
450
450
parts
parts
parts
parts
4
glycol thermo?uid compositions or “resin-wax” or “all
wax” vehicles of the types exempli?ed in US. Patents
References Cited in the ?le of this patent
UNITED STATES PATENTS
parts
50
The glass color compositons of the examples had a
very low carbonaceous residue after ?ring and were com
patible with at least 40% of known polyethylene ether
2,045,979
2,316,274
2,682,480
2,823,138
Crawford ___________ __ June 30,
Mitchell ______________ .._ Apr. 13,
Andrews ____________ -_ June 29,
Hoffman ____________ __ Feb. 11,
1936
1943
1954
1958
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