Note: Descriptions are shown in the official language in which they were submitted.
.r
CA 02341113 2001-03-16
PHASE CHANGE INKS
BACKGROUND OF THE INVENTION
The present invention is directed to phase change ink
compositions. More specifically, the present invention is directed to phase
change ink compositions particularly suitable for use in acoustic ink jet
printing processes that exhibit improved surface hardness subsequent to
being jetted onto a substrate and cooled. One embodiment of the present
invention is directed to an ink composition comprising (a) an ink vehicle, (b)
a colorant, (c) an anionic surfactant, (d) a cationic surfactant, (e) an
optional nonionic surfactant, (f) an optional conductivity enhancing agent,
(g) an optional antioxidant, and (h) an optional UV absorber, said ink
composition being solid at 25°C and having a melting point of about
60°C or
higher.
Acoustic ink jet printing processes are known. In acoustic ink
jet printing processes, an acoustic beam exerts a radiation pressure against
objects upon which it impinges. Thus, when an acoustic beam impinges on a
free surface (i.e., liquid/air interface) of a pool of liquid from beneath,
the
radiation pressure which it exerts against the surface of the pool may reach
a sufficiently high level to release individual droplets of liquid from the
pool, despite the restraining force of surface tension. Focusing the beam on
or near the surface of the pool intensifies the radiation pressure it exerts
for
a given amount of input power. These principles have been applied to prior
ink jet and acoustic printing proposals. For example, K. A. Krause,
"Focusing Ink Jet Head," IBM Technical Disclosure Bulletin, Vol. 16, No. 4,
September 1973, pp. 1168-1170, the disclosure of which is totally
incorporated herein by reference, describes an ink jet in which an acoustic
1
CA 02341113 2001-03-16
beam emanating from a concave surface and confined by a conical aperture
was used to propel ink droplets out through a small ejection orifice.
Acoustic ink printers typically comprise one or more acoustic radiators for
illuminating the free surface of a pool of liquid ink with respective acoustic
beams. Each of these beams usually is brought to focus at or near the
surface of the reservoir (i.e., the liquid/air interface). Furthermore,
printing conventionally is performed by independently modulating the
excitation of the acoustic radiators in accordance with the input data
samples for the image that is to be printed. This modulation enables the
radiation pressure which each of the beams exerts against the free ink
surface to make brief, controlled excursions to a sufficiently high pressure
level for overcoming the restraining force of surface tension. That, in turn,
causes individual droplets of ink to be ejected from the free ink surface on
demand at an adequate velocity to cause them to deposit in an image
configuration on a nearby recording medium. The acoustic beam may be
intensity modulated or focused/defocused to control the ejection timing, or
an external source may be used to extract droplets from the acoustically
excited liquid on the surface of the pool on demand. Regardless of the
timing mechanism employed, the size of the ejected droplets is determined
by the waist diameter of the focused acoustic beam. Acoustic ink printing is
attractive because it does not require the nozzles or the small ejection
orifices which have caused many of the reliability and pixel placement
accuracy problems that conventional drop on demand and continuous
stream ink jet printers have suffered. The size of the ejection orifice is a
critical design parameter of an ink jet because it determines the size of the
droplets of ink that the jet ejects. As a result, the size of the ejection
orifice cannot be increased, without sacrificing resolution. Acoustic printing
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CA 02341113 2001-03-16
has increased intrinsic reliability because there are no nozzles to clog. As
will be appreciated, the elimination of the clogged nozzle failure mode is
especially relevant to the reliability of large arrays of ink ejectors, such
as
page width arrays comprising several thousand separate ejectors.
Furthermore, small ejection orifices are avoided, so acoustic printing can be
performed with a greater variety of inks than conventional ink jet printing,
including inks having higher viscosities and inks containing pigments and
other particulate components. It has been found that acoustic ink printers
embodying printheads comprising acoustically illuminated spherical focusing
lenses can print precisely positioned pixels (i.e., picture elements) at
resolutions which are sufficient for high quality printing of relatively
complex images. It has also been discovered that the size of the individual
pixels printed by such a printer can be varied over a significant range during
operation, thereby accommodating, for example, the printing of variably
shaded images. Furthermore, the known droplet ejector technology can be
adapted to a variety of printhead configurations, including (1 ) single
ejector
embodiments for raster scan printing, (2) matrix configured ejector arrays
for matrix printing, and (3) several different types of pagewidth ejector
arrays, ranging from single row, sparse arrays for hybrid forms of
parallel/serial printing to multiple row staggered arrays with individual
ejectors for each of the pixel positions or addresses within a pagewidth
image field (i.e., single ejector/pixel/line) for ordinary line printing. Inks
suitable for acoustic ink jet printing typically are liquid at ambient
temperatures (i.e., about 25°C), but in other embodiments the ink is in
a
solid state at ambient temperatures and provision is made for liquefying the
ink by heating or any other suitable method prior to introduction of the ink
into the printhead. Images of two or more colors can be generated by
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CA 02341113 2001-03-16
several methods, including by processes wherein a single printhead launches
acoustic waves into pools of different colored inks. Further information
regarding acoustic ink jet printing apparatus and processes is disclosed in,
for example, U.S. Patent 4,308,547, U.S. Patent 4,697,195, U.S. Patent
5,028,937, U.S. Patent 5,041,849, U.S. Patent 4,751,529, U.S. Patent
4,751,530, U.S. Patent 4,751,534, U.S. Patent 4,801,953, and U.S. Patent
4,797,693, the disclosures of each of which are totally incorporated herein
by reference. The use of focused acoustic beams to eject droplets of
controlled diameter and velocity from a free-liquid surface is also described
in J. Appl. Phys., vol. 65, no. 9 (1 May 1989) and references therein, the
disclosure of which is totally incorporated herein by reference.
In acoustic ink printing processes, the printhead produces
approximately 2.2 picoliter droplets by an acoustic energy process. The ink
under these conditions preferably displays a melt viscosity of from about 1
to about 25 centipoise at the jetting temperature. In addition, once the ink
has been jetted onto the printing substrate, the image thus generated
preferably exhibits excellent crease properties, and is nonsmearing,
waterfast, of excellent transparency, and of excellent fix. The vehicle
preferably displays a low melt viscosity in the acoustic head while also
displaying solid like properties after being jetted onto the substrate. Since
the acoustic head can tolerate temperatures typically up to about
180°C,
the vehicle for the ink preferably displays liquid-like properties (such as a
viscosity of from about 1 to about 25 centipoise) at a temperature of from
about 75 to about 180°C, and solidifies or hardens after being jetted
onto
the substrate such that the resulting image exhibits a hardness value of from
about 0.1 to about 0.5 millimeter (measured with a penetrometer according
to the ASTM penetration method D1321 ).
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CA 02341113 2001-03-16
Ink jet printing processes that employ inks that are solid at
room temperature and liquid at elevated temperatures are known. For
example, U.S. Patent 4,490,731, the disclosure of which is totally
incorporated herein by reference, discloses an apparatus for dispensing solid
inks for printing on a substrate such as paper. The ink vehicle is chosen to
have a melting point above room temperature so that the ink, which is
melted in the apparatus, will not be subject to evaporation or spillage
during periods of nonprinting. The vehicle selected possesses a low critical
temperature to permit the use of the solid ink in a thermal ink jet printer.
In thermal ink jet printing processes employing these phase-change inks, the
solid ink is melted by a heater in the printing apparatus and used as a liquid
in a manner similar to that of conventional piezoelectric or thermal ink jet
printing. Upon contact with the printing substrate, the molten ink solidifies
rapidly, enabling the dye to remain on the surface instead of being carried
into the paper by capillary action, thereby enabling higher print density
than is generally obtained with liquid inks. After the phase-change ink is
applied to the substrate, freezing on the substrate resolidifies the ink.
In phase-change printing processes, the ink preferably
undergoes a change with temperature from a solid state to a liquid state in
a desirably short period of time, typically in less than about 100
milliseconds. One advantage of phase-change inks is their ability to print
superior images on plain paper, since the phase-change ink quickly solidifies
as it cools, and, since it is primarily waxy in nature, it does not normally
soak into a paper medium.
Phase-change inks also preferably exhibit a high degree of
transparency, generally measured in terms of haze value of the ink.
5
CA 02341113 2001-03-16
Transparent, low haze inks exhibit high gloss and high optical density
compared to opaque inks, although both may appear to be evenly colored.
The use of phase-change inks in acoustic ink printing processes
is also known. U.S. Patent 4,745,419 (Quate et al.), the disclosure of which
is totally incorporated herein by reference, discloses acoustic ink printers
of
the type having a printhead including one or more acoustic droplet ejectors
for supplying focused acoustic beams. The printer comprises a carrier for
transporting a generally uniformly thick film of hot melt ink across its
printhead, together with a heating means for liquefying the ink as it nears
the printhead. The droplet ejector or ejectors are acoustically coupled to
the ink via the carrier, and their output focal plane is essentially coplanar
with the free surface of the liquefied ink, thereby enabling them to eject
individual droplets of ink therefrom on command. The ink, on the other
hand, is moved across the printhead at a sufficiently high rate to maintain
the free surface which it presents to the printhead at a substantially
constant level. A variety of carriers may be employed, including thin plastic
and metallic belts and webs, and the free surface of the ink may be
completely exposed or it may be partially covered by a mesh or perforated
layer. A separate heating element may be provided for liquefying the ink,
or the lower surface of the carrier may be coated with a thin layer of
electrically resistive material for liquefying the ink by localized resistive
heating.
U.S. Patent 5,541,627 (Quate), the disclosure of which is
totally incorporated herein by reference, discloses a method and apparatus
for ejecting droplets from the crests of capillary waves riding on the free
surface of a liquid by parametrically pumping the capillary waves with
electric fields from probes located near the crests. Crest stabilizers are
6
CA 02341113 2001-03-16
beneficially used to fix the spatial locations of the capillary wave crests
near the probes. The probes are beneficially switchably connected to an AC
voltage supply having an output that is synchronized with the crest motion.
When the AC voltage is applied to the probes, the resulting electric field
adds sufficient energy to the system so that the surface tension of the liquid
is overcome and a droplet is ejected. The AC voltage is synchronized such
that the droplet is ejected about when the electric field is near is minimum
value. A plurality of droplet ejectors are arranged and the AC voltage is
switchably applied so that ejected droplets form a predetermined image on
a recording surface. The capillary waves can be generated on the free
surface of the liquid by using acoustical energy at a level approaching the
onset of droplet ejection. The liquid used with the invention must also must
be attracted by an electric field.
Phase-change inks used in acoustic ink printing processes also
preferably exhibit a low acoustic-loss value, typically below about 100
decibels per millimeter. In addition, the ink vehicle preferably can fill the
pores of a porous substrate, such as paper, and preferably has a melting
point of from about 80 to about 120°C; this melting point, along with
low
acoustic-loss, enables a minimization of energy consumption. When the
phase-change inks are used in an electric field assisted acoustic ink printing
process, the inks also are sufficiently conductive to permit the transmission
of electrical signals generated by the electric field assisted acoustic ink
jet
printer; the inks preferably exhibit a conductivity of from about 2 to about 9
log(picomho/cm) (measured under melt conditions at about 150°C by
placing an aluminum electrode in the molten ink and reading the resistivity
output on a GenRad 1689 precision RLC Digibridge at a frequency of 1
kiloHertz). In general, the conductivity of a material can be measured in
7
CA 02341113 2001-03-16
terms of the reciprocal of resistivity, which is the capacity for electrical
resistance. Further information regarding electric field assisted acoustic ink
printing processes is disclosed in, for example, Copending Application U.S.
Serial No. 09/280,717, filed March 30, 1999, entitled "Method and Apparatus
for Moving Ink Drops using an Electric Field and Transfuse Printing System
Using the Same," with the named inventors John S. Berkes, Vittorio R.
Castelli, Scott A. Elrod, Gregory J. Kovacs, Meng H. Lean, Donald L. Smith,
Richard G. Stearns, and Joy Roy, the disclosure of which is totally
incorporated herein by reference, which discloses a method of forming and
moving ink drops across a gap between a printhead and a print medium or
intermediate print medium in a marking device. The method includes
generating an electric field, forming the ink drops adjacent to the
printhead, and controlling the electric field. The electric field is generated
to extend across the gap. The ink drops are formed in an area adjacent to
the printhead. The electric field is controlled such that an electrical
attraction force exerted on the formed ink drops by the electric field is the
greatest force acting on the ink drops. The marking device can be
incorporated into a transfuse printing system having an intermediate print
medium made of one or more materials that allow for lateral dissipation of
electrical charge from the incident ink drops.
"Dynamic Mechanical and Spectroscopic Study of lonomer
Blends Based on Carboxylated or Sulfonated Flexible Polystyrene and Rigid
Poly(diacetylenes) with Functional Side Groups," C.D. Eisenbach et al.,
Macromolecules, Vol. 27, p. 3162 (1994), the disclosure of which is totally
incorporated herein by reference, discloses a study wherein the dynamic
mechanical and infrared spectroscopic investigation of ionomer blends of
poly(diacetylene)- and polystyrene-based ionomers has shown that
8
CA 02341113 2001-03-16
miscibility of this usually incompatible polymer pair can be achieved
through ion-ion interactions between the blend components. Microphase
separation is prevented through ionic contacts generated during the blend
formation. A schematic model of mixing in the blends is proposed.
"Statistical Thermodynamics of Mixtures of Rodlike Particles. 5.
Mixtures with Random Coils," Paul J. Flory, Macromolecules, Vol. 11, no. 6,
p. 1138 (1978), the disclosure of which is totally incorporated herein by
reference, discloses a study wherein ternary systems consisting of a solvent,
a rigid rod solute, and a randomly coiled polymer chain are treated
according to a specific model and procedures. Phase equilibria are
calculated for systems specified by (xZx3)=(10,10), (20,20), (20,~), and
(100,100), where x2 and x3 are the molar volumes of the respective solutes
relative to the solvent. Addition of the randomly coiled polymer chain to
the binary system of solvent and solute increases the volume fraction v2' of
the rodlike solute in the anisotropic phase and broadens the biphasic gap.
The preponderance of the randomly coiled polymer chain is retained by the
isotropic phase. Its volume fraction v3' in the anisotropic phase is <10-4 for
all compositions and becomes vanishingly small if v2' is much increased by
raising v3 in the isotropic phase. The isotropic phase exhibits a somewhat
greater tolerance for the rodlike component. For large values of xz and v3,
however, vz becomes negligible. The marked segregation of these
components between the two phases underscores the basic differences in
their mixing tendencies.
Many phase change inks lack surface hardness after deposition
on a substrate and cooling. The resulting images are thus susceptible to
smearing. When addressing this issue, it is also desirable to do so in a way
that does not undesirably affect the bulk viscosity of the ink. Increasing
9
CA 02341113 2001-03-16
bulk viscosity is a major concern for phase change inks because the power
required to eject droplets is strongly dependent on the ink bulk viscosity,
with higher ink viscosities requiring more ejection power.
Accordingly, while known compositions and processes are
suitable for their intended purposes, a need remains for improved phase
change inks. In addition, a need remains for phase change inks particularly
suitable for use in acoustic ink jet printing processes. Further, a need
remains for phase change inks that exhibit improved surface hardness
subsequent to being ejected onto a substrate and cooled. Additionally, a
need remains for phase change inks with desirable bulk viscosities. There is
also a need for phase change inks that exhibit good smear resistance
subsequent to being ejected onto a substrate and cooled. In addition, there
is a need for phase change inks that exhibit low haze subsequent to being
ejected onto a substrate and cooled.
SUMMARY OF THE INVENTION
The present invention is directed to an ink composition
comprising (a) an ink vehicle, (b) a colorant, (c) an anionic surfactant, (d)
a
cationic surfactant, (e) an optional nonionic surfactant, (f) an optional
conductivity enhancing agent, (g) an optional antioxidant, and (h) an
optional UV absorber, said ink composition being solid at 25°C and
having a
melting point of about 60°C or higher. Another embodiment of the
present
invention is directed to a printing process which comprises incorporating
into an ink jet printing apparatus an ink composition comprising (a) an ink
vehicle, (b) a colorant, (c) an anionic surfactant, (d) a cationic surfactant,
(e) an optional nonionic surfactant, (f) an optional conductivity enhancing
agent, (g) an optional antioxidant, and (h) an optional UV absorber, said ink
CA 02341113 2001-03-16
composition being solid at 25°C and having a melting point of about
60°C or
higher, melting the ink, and causing droplets of the melted ink to be
ejected in an imagewise pattern onto a recording sheet. In a preferred
embodiment, the printing apparatus employs an acoustic ink jet process,
wherein droplets of the ink are caused to be ejected in imagewise pattern
by acoustic beams.
DETAILED DESCRIPTION OF THE INVENTION
The inks of the present invention contain an ink vehicle. The
ink vehicle is present in the ink in any desired or effective amount,
typically
at least about 50 percent by weight of the ink, and preferably at least about
60 percent by weight of the ink, and typically no more than about 98 percent
by weight of the ink, preferably no more than about 92 percent by weight of
the ink, and more preferably no more than about 85 percent by weight of the
ink, although the amount can be outside of these ranges. The ink vehicle
typically has a melting point of no less than about 60°C, preferably no
less
than about 65 ° C, and more preferably no less than about 70 °
C, and typically
has a melting point of no more than about 150°C, preferably no more
than
about 135°C, and more preferably no more than about 100°C,
although the
melting point can be outside of these ranges. Preferably, the ink vehicle
has an acoustic-loss value of no more than about 100 decibels per
millimeter, although the acoustic-loss value can be outside of this range.
Typically, the ink vehicle has a hardness value of at least about 60, although
the hardness value can be outside of this range.
Any desired or suitable hot melt ink vehicle can be employed.
Specific examples include low molecular weight polyamides,
polyesteramides, block copolymers of polyamides of polyesteramides,
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CA 02341113 2001-03-16
polyethylene, polypropylene, copolymers and block copolymers of
polyethylene and polypropylene, carbamates and biscarbamates of the
generic formula C"H2~+~ -NHC00-CnHz"+t and
C~H2"+~-OCONH-C"H2"-NHC00-C"H2"+~ wherein n is an integer typically of
from about 5 to about 20 and selected to provide materials that are solid at
room temperature, low molecular weight alkylated ureas and bis-ureas in
which the alkyl groups typically have from about 5 to about 20 carbons with
the number of carbon atoms selected to provide materials that are solid at
room temperature, and the like, as well as mixtures thereof.
Also suitable are primary and secondary monoamides, including
primary mono-amides such as stearamide (KEMAMIDEO S, available from
Witco Chemical Company, Memphis, TN), secondary mono-amides such as
behenyl benenamide (KEMAMIDEO EX--666, available from Witco), stearyl
stearamide (KEMAMIDEO S-180, available from Witco), and the like, as well
as mixtures thereof.
Also suitable are (I) conductive nonpolymeric pyridinium
compounds, such as those of the general formula
R4
Rs / R5
An O
R ~ N R6
n
wherein each of R~, RZ, R3, R4, R5, and R6, independently of the others, can
be (but are not limited to) hydrogen atoms, alkyl and alkoxy groups,
including saturated, unsaturated, branched, linear, and cyclic alkyl and
alkoxy groups (typically with from 1 to about 30 carbon atoms, although the
12
o r CA 02341113 2001-03-16
number of carbon atoms can be outside of this range), including substituted
and unsubstituted alkyl and alkoxy groups, aryl and aryloxy groups (typically
with from 6 to about 30 carbon atoms, although the number of carbon atoms
can be outside of this range), including substituted and unsubstituted aryl
and aryloxy groups, arylalkyl, arylalkyloxy, alkylaryl, and alkylaryloxy
groups
(typically with from 7 to about 30 carbon atoms, although the number of
carbon atoms can be outside of this range), including substituted and
unsubstituted arylalkyl, arylalkyloxy, alkylaryl, and alkylaryloxy groups,
heterocyclic groups (typically with from about 5 to about 10 ring atoms,
wherein the hetero atoms can be (but are not limited to) oxygen atoms,
nitrogen atoms, sulfur atoms, phosphorus atoms, silicon atoms, and the
like), including substituted and unsubstituted heterocyclic groups, hydroxy
groups, amine groups, imine groups, ammonium groups, pyridine groups,
pyridinium groups, ether groups, ester groups, amide groups, carbonyl
groups, thiocarbonyl groups, sulfate groups, sulfonate groups, sulfide
groups, sulfoxide groups, phosphine groups, phosphonium groups, phosphate
groups, mercapto groups, nitroso groups, sulfone groups, acyl groups, acid
anhydride groups, azide groups, and the like, wherein two or more
substituents can be joined together to form a ring, wherein the substituents
on the substituted alkyl, alkoxy, aryl, aryloxy, arylalkyl, arylalkyloxy,
alkylaryl, alkylaryloxy, and heterocyclic groups can be (but are not limited
to) hydroxy groups, amine groups, imine groups, ammonium groups, pyridine
groups, pyridinium groups, ether groups, ester groups, amide groups,
carbonyl groups, thiocarbonyl groups, sulfate groups, sulfonate groups,
sulfide groups, sulfoxide groups, phosphine groups, phosphonium groups,
phosphate groups, mercapto groups, nitroso groups, sulfone groups, acyl
groups, acid anhydride groups, azide groups, and the like, A is any desired
13
- " CA 02341113 2001-03-16
or suitable anion, with examples of anions including (but not limited to) Cl-,
Br , ~ , HS04 , HS03 , SO42 , SO32 , CHZS03 , CH3SO3 , CH3C6H4SO3 , N03 , HC00
,
CH3C00~, HC03-, C032~, HZP04 , HP042-, PO43-, SCN-, BF4 , C104-, SS03-, and
the
like, as well as mixtures thereof, and n is an integer; n typically is 1, 2,
or 3,
but when the anion is polymeric, the value of n is not limited; examples of
suitable conductive pyridinium compounds include (1) 1-propyl pyridinium
salts, such as 1-propyl pyridinium bromide (Aldrich 41,288-0), of the formula
Bra
V
CH2CH2CH3
(2) 1-ethyl-3-hydroxy pyridinium salts, such as 1-ethyl-3-hydroxy pyridinium
bromide (Aldrich 19,264-3), of the formula
OH
~N Bra
CH2CH3
(3) 1-ethyl-4-phenyl pyridinium salts, such as 1-ethyl-4-phenyl pyridinium
iodide (Aldrich 36,208-5), of the formula
/ to
~J
~N
CH2CH3
14
CA 02341113 2001-03-16
(4) 1-ethyl-4-(methoxy carbonyl) pyridinium salts, such as 1-ethyl-4-
(methoxy carbonyl) pyridinium iodide (Aldrich 32,625-9), of the formula
H3C~C~0
I
~ V
CH2CH3
(5) pyridinium 3-nitrobenzene sulfonate (Aldrich 27,198-5), of the formula
o SO3
~J
~N
H ~ N02
(6) pyridinium-p-toluene sulfonate (Aldrich 23,223-8), (7) pyridinium
trifluoroacetate (Aldrich 21,513-9), (8) 1-heptyl-4-(4-pyridyl) pyridinium
salts, such as 1-heptyl-4-(4-pyridyl) pyridinium bromide (Aldrich 37,778-3),
of the formula
CH3(CH2)5CH2-
Br~
(9) cetyl pyridinium salts, such as cetyl pyridinium bromide monohydrate
(Aldrich 28,531-5), of the formula
. , CA 02341113 2001-03-16
/ OH
H2O
Br ~
~H2(CH2)14CH3
and cetyl pyridinium chloride monohydrate (Aldrich 85,556-1), (10) 1-
dodecyl pyridinium salts, such as 1-dodecyl pyridinium chloride hydrate
(Aldrich 27,860-2), of the formula
/ ~ . H2O
CI~
CH2(CH2)1 oCH3
and the tike, as well as mixtures thereof; (II) 1,3-dialkyl ureas, including
those of the general formula CH3(CH2)~NHCONH(CH2)~CH3, wherein n is an
integer typically of from about 5 to about 20, such as 1,3-dioctadecyl urea
(Aldrich 32,803-0), wherein n is 17, and the like; (III) N,N'-ethylene
bisalkylamides, wherein the alkyl groups can be saturated or unsaturated,
including those of the general formula (CH3(CHZ)"CH=CH(CH2)"CONHCH2-)z,
wherein n is an integer typically of from about 5 to about 20, such as N,N'-
ethylene bisoleamide (Atdrich 43,466-3), wherein n is 7, and those of the
general formula (CH3(CHZ)~CHCONHCH2-)2, wherein n is an integer typically
of from about 5 to about 20, such as N,N'-ethylene bisstearamide, wherein n
is 16, and the like; (IV) N-(4-chloro-3-(4,5-dihydro-5-oxo-1-(2,4,6-
trichlorophenyl)-1 H-pyrazol-3-ylamino) phenyl)-2-(1-octadecenyl)
succinimide (Aldrich 38,582-4); (V) 1,3-diamino-5,6-bis(octyloxy) isoindoline
(Aldrich 46,218-7); (VI) N,N-dimethyl alkylamine N-oxides, including those
16
CA 02341113 2001-03-16
of the general formula CH3(CH2)"N(CH3)Z0, wherein n is an integer typically
of from about 5 to about 20, such as N,N-dimethyl heptylamine N-oxide
hydrate (Aldrich 38,250-7), wherein n is 6, N,N-dimethyl octylamine N-oxide
hydrate (Aldrich 36,568-8), wherein n is 7, N,N-dimethyl nonylamine N-oxide
hemihydrate (Aldrich 38,252-3), wherein n is 8, N,N-dimethyl undecyl amine
N-oxide (Aldrich 38,253-1 ), wherein n is 10, N,N-dimethyl dodecyl amine N-
oxide (Aldrich 28,970-1), wherein n is 11, and the like; (VII) alkyl amides,
wherein the alkyl portion can be saturated or unsaturated, including those
of the general formula CH3(CH2)~CH=CH(CH2)mCONH2, wherein m and n are
each integers the sum of which typically is from about 5 to about 20, such as
erucamide (Aldrich 28,057-7), wherein n is 7 and m is 11, and those of the
general formula CH3(CH2)"CONHz, wherein n is an integer typically of from 0
to about 20, such as acetamide (Aldrich 12,263-7), wherein n is 0,
propionamide (Aldrich 14,393-6), wherein n is 1, hexanoamide (Aldrich
29,339-3), wherein n is 4, octadecanamide (Aldrich 0-60-1), wherein n is 16,
or the tike; (VIII) polymeric anhydrides, such as (1 ) poly (sebacic
anhydride)
(Aldrich 45,832-5), (2) poly (azelaic anhydride) (Aldrich 45,831-7), (3) poly
(malefic anhydride-alt-1-tetradecene (Aldrich 45,251-3), (4) polyethylene-
graft-malefic anhydride with 0.5 weight percent malefic anhydride (Aldrich
45,662-4), (5) poly(ethylene-co-butylacrylate-co-malefic anhydride) with 91
weight percent ethylene, 5.5 weight percent butyl acrylate, and 3.5 weight
percent malefic anhydride (Aldrich 43,085-4), (6) poly(maleic anhydride-alt-
a-olefin, wherein the olefin typically has from about 24 to about 28 carbon
atoms (Aldrich 45,262-95), and the like; (IX) aldehyde copolymers,
including copolymers of aldehyde monomers, such as formaldehyde and the
like and other monomers, with specific examples of suitable aldehyde
17
CA 02341113 2001-03-16
copolymers including (1 ) poly ((phenyl glycidyl ether)-co-formaldehyde)
(Aldrich 40,676-7), of the formula
O O O
~H2 I H2 ~H2
\ \ \
CH2 CH2
/ / n /
(2) poly ((o-cresyl glycidyl ether)-co-formaldehyde) (Aldrich 40,551-5), of
the formula
O O O
I H2 I H2 , H2
\ CH3 \ CH3 \
CH2 CH2
n
(3) poly (p-toluenesulfonamide-co-formaldehyde) (Aldrich 28,076-3), and the
like; (X) nonpotymeric aromatic compounds, including (1 ) 4-hexyl resorcinol
(Aldrich 20,946-5), (2) 4-dodecyl resorcinol (Aldrich D22,260-7), (3) 4-(tert-
octyl) phenol (Aldrich 29,082-3), (4) 4-bromo-N-dodecyl-1-hydroxy-2-
naphthalene carboxamide (Aldrich 37,157-2), (5) 2,2-Biphenyl-1,4-diazaspiro-
(4, 5)deca-1, 3-diene (Aldrich 37,146-7), (6) N, N'-dibenzyl-1,4,10,13-
tetraoxa-
7,16-diazacyclooctadecane (Aldrich 29,472-1 ), (7) 1,4-dihydro-9-
isopropylidene-1,4-methanonaphthalene (Aldrich 43,201-6), (8) 1,4,4a,8a-
tetrahydro-endo-1,4-methanonaphthalene (Aldrich 34,180-0), (9) 1, 5-
18
CA 02341113 2001-03-16
dihydroxy-1,2,3,4-tetrahydronaphthalene (Aldrich 10,915-0), (10) 2,5-
difluorophenylhydrazine (Atdrich 32,419-1 ), and the like; (XI) nonpolymeric
ketones, including (a) alkyl alkyl ketones, including those of the general
formula
R-(C=0)-R'
wherein R and R' each, independently of the other, is an alkyl group,
including linear, branched, cyclic, saturated, unsaturated, and substituted
alkyl groups, typically with from 1 to about 25 carbon atoms, although the
number of carbon atoms can be outside of this range, with specific examples
including (1 ) n-octyl-n-propyl ketone (ICN #213357), (2) n-octyl-n-butyl
ketone (ICN #206848), (3) n-decyl-n-ethyl ketone (ICN #204911 ), (4) n-
undecyl-n-propyl ketone (ICN #207355), (5) n-dodecyl-n-ethyl ketone (ICN
#209666), (6) di-n-hexylketone (ICN #215620), (7) di-n-heptylketone (ICN
#209745), (8) di-n-octyl ketone (ICN #204765), (9) di-n-nonyl ketone (ICN
#212765), (10) di-n-decyl ketone (ICN #215139), (11 ) di-n-undecyl ketone
(ICN #203303), (12) di-n-tridecyl ketone (ICN #213235), (13) di-n-heptadecyl
ketone (ICN #201684), (14) di-n-octadecyl ketone (ICN #201684), and the
like, as well as mixtures thereof, (b) alkyl aryl ketones, including those of
the general formula
R-(C=0)-Ar
wherein R is an alkyl group, including linear, branched, cyclic, saturated,
unsaturated, and substituted alkyl groups, typically with from 1 to about 20
carbon atoms, although the number of carbon atoms can be outside of this
range, and Ar is an aryl group, including substituted aryl groups, typically
with from 6 to about 25 carbon atoms, although the number of carbon atoms
can be outside of this range, such as phenyl, naphthyl, anthryl, or the like,
with specific examples including (1 ) n-octyl phenyl ketone (obtained from
19
CA 02341113 2001-03-16
ICN Biomedical; ICN #204935), (2) n-undecyl phenyl ketone (ICN #217796),
(3) n-pentadecyl phenyl ketone (ICN #225428), (4) n-octadecyl phenyl
ketone (available as #00185 from TCI America), and the like, as well as
mixtures thereof, (c) aryl aryl ketones, including those of the general
formula
Ar-(C=0)-Ar'
wherein Ar and Ar' each, independently of the other, is an aryl group,
including substituted aryl groups, typically with from 6 to about 25 carbon
atoms, although the number of carbon atoms can be outside of this range,
such as phenyl, naphthyl, anthryl, or the like, with specific examples
including (1 ) diphenyl acetone (ICN #208157, ICN #206354), (2) 2-naphthyl
phenyl ketone (available as #B0301 from TCI America), and the like, as well
as mixtures thereof, (d) aryl arylalkyl ketones and aryl alkylaryl ketones,
including those of the general formulae
Ar-(C=0)-RAr'
and
Ar-(C=0)-Ar'R
wherein Ar and Ar' each, independently of the other, is an aryl group,
including substituted aryl groups, typically with from 6 to about 25 carbon
atoms, although the number of carbon atoms can be outside of this range,
such as phenyl, naphthyl, anthryl, or the like, and R is an alkyl group,
including linear, branched, cyclic, saturated, unsaturated, and substituted
alkyl groups, typically with from 1 to about 25 carbon atoms, although the
number of carbon atoms can be outside of this range, with specific examples
including (1 ) benzyl phenyl ketone (ICN #202318) and the like, (e) arylalkyl
arylalkyl ketones, arylalkyl alkylaryl ketones, and alkylaryl alkylaryl
ketones,
including those of the general formulae
. CA 02341113 2001-03-16
ArR-(C=0)-Ar'R'
ArR-(C=0)-R'Ar'
RAr-(C=0)-R'Ar'
wherein Ar and Ar' each, independently of the other, is an aryl group,
including substituted aryl groups, typically with from 6 to about 25 carbon
atoms, although the number of carbon atoms can be outside of this range,
such as phenyl, naphthyl, anthryl, or the like, and R and R' each,
independently of the other, is an alkyl group, including linear, branched,
cyclic, saturated, unsaturated, and substituted alkyl groups, typically with
from 1 to about 25 carbon atoms, although the number of carbon atoms can
be outside of this range, with examples of suitable substituents on the
substituted alkyl, aryl, arylalkyl, and alkylaryl groups including (but not
being limited to) hydroxy groups, amine groups, imine groups, ammonium
groups, pyridine groups, pyridinium groups, ether groups, ester groups,
amide groups, carbonyl groups, thiocarbonyl groups, sulfate groups,
sulfonate groups, sulfide groups, sulfoxide groups, phosphine groups,
phosphonium groups, phosphate groups, mercapto groups, nitroso groups,
sulfone groups, acyl groups, acid anhydride groups, azide groups, and the
tike, with specific examples of suitable ketones including (1 ) di-n-benzyl
ketone (obtained from ICN Biomedicals; ICN #208157) and the like; (XII)
polyesters, including homopolymers of ester monomers and copolymers of
ester monomers and other monomers, with examples of suitable polyesters
including (1 ) poly(hexamethylene sebacate) (#124 Scientific Polymer
Products), (2) poly(1,6-hexamethylene adipate) (Aldrich 45,836-8), (3)
polyvinyl acetate) (Aldrich 43,043-9), (4) polyvinyl cinnamate) (Aldrich
18,264-8), (5) polyvinyl stearate) (Aldrich 18,279-68), (6) polyethylene
succinate (Aldrich 18,203-6), (7) polyethylene terephthalate (Vitel 5833,
21
CA 02341113 2001-03-16
available from Shell Chemical Co.), (8) poly(vinylacetate-co-crotonic acid)
(Aldrich 44,467-7), (9) sucrose octaacetate (Aldrich 25,260-3), (10)
poly(di(ethyleneglycol)/cyclohexanedimethanol-alt-isophthalic acid,
sulfonated) (Aldrich 45,871-6), and the like; (XIII) carbamates, such as (1 )
butyl carbamate (Aldrich B9,080-7); (2) tert-butyl carbamate (Aldrich
16,739-8); (3) tert-butyl N-(3-aminopropyl) carbamate (Aldrich 43,699-2);
(4) tert-butyl N-(3-hydroxypropyl) carbamate (Aldrich 41,644-4); (5) tert-
butyl-N-(benzytoxy)-carbamate (Atdrich 40,769-0); (6) tert-butyl-N-
hydroxycarbamate (Aldrich 22,615-7); (7) tert-butyl-N-allylcarbamate
(Aldrich 42,233-9); (8) tert-butyl-N-(tert-butoxycarbonyloxy) carbamate
(Aldrich 41,279-1); (9) tert-butyl-N-(2-hydroxy-2-(hydroxyphenyl)-1-
methylethyl) carbamate (Aldrich 40,429-2); (10) tert-butyl-(2,4-
dinitrophenoxy) carbamate (Aldrich 33,305-0); (11 ) benzyl carbamate (Alfa
Organics #A11569); (12) benzyl N-hydroxycarbamate (Aldrich 32,327-6); (13)
benzyl N-(2-hydroxyethyl)carbamate (Aldrich 40,790-9); (14) benzyl-N,N-
dimethyldithiocarbamate (Aldrich 36,822-9); (15) ethyl N-methyl-N-
phenylcarbamate (Aldrich 30,951-6); (16) ethyldiphenyl carbamate (Aldrich
37,291-9); (17) cyanomethyt-N,N-dimethyt dithiocarbamate (Aldrich 28,054-
2); (18) 4,4'-methylene-bis(dibutyldithio carbamate) (Vanlube 7723,
Vanderbilt Corporation); (19) potassium N-hydroxy methyl-N-methyl-
dithiocarbamate (Busan 40 from Buckman Laboratories Inc.); (20) sodium
dimethyl dithiocarbamate; (21 ) disodium ethylenebis-dithio carbamate; (22)
diethylammonium diethyldithio carbamate (Alfa Organics #A10458); (23)
benzyl(S)-(-)-tetrahydro-5-oxo-3-furanyl carbamate (Aldrich 41,924-9); (24)
diethyldithiocarbamic acid, ammonium salt (Aldrich 35,954-8); (25)
diethyldithiocarbamic acid, diethyl ammonium salt (Aldrich 31,811-6); (26)
diethyldithiocarbamic acid, sodium salt, trihydrate (Aldrich 22,868-0); (27)
22
CA 02341113 2001-03-16
4-bromo-3,5-dimethylphenyl N-methylcarbamate (Aldrich 34,694-2); (XIV)
thioureas, such as (1) 1-allyl-2-thiourea (Aldrich 10,880-41); (2) 1-allyl-3-
(2-
hydroxyethyl)-2-thiourea (Aldrich A3,280-2); (3) 1-methyl-2-thiourea (Aldrich
M8,460-7); (4) 1-methallyl-3-methyl-2-thiourea (Aldrich 19,046-2); (5) 1,3-
dibutyl-2-thiourea (Aldrich D4,959-8); (6) 1,1,3,3-tetramethyl-2-thiourea
(Aldrich 11,516-9); (7) N,N'-di-n-propyl thiourea (Alfa Organics #A17217); (8)
1-benzyl-3-methyl-2-thiourea (Atdrich 27,550-6); and the like; (XV) alcohols,
such as (A) cyclic alcohols, such as (1 ) cycloalkyl alcohols where the number
of carbons in the alkyl chain vary, for example, from 1, preferably from
about 6 to about 12 and more preferably from about 8 to about 10, such as
cyclohexanol (Aldrich 10,589-9), cycloheptanol (Aldrich C9,880-2),
cyclododecanol, (Aldrich C9,740-7); (2) 4-tert-butyl cyclohexanol (Aldrich
89,200-1 ); (3) 3-aminomethyl-3,5,5-trimethyl cyclohexanol (Aldrich 19,479-
4); (4) 2,2,6,6-tetrachloro cyclohexanol, (Aldrich 18,681-3); (5) cycloalkane
methanol where the number of carbons in the alkane chain is for example,
from about 5 to about 12 and preferably between about 8 to about 11, such as
cyclopentane methanol (Aldrich 10,398-5), cyclohexane methanol (Aldrich
C10,580-5), cycloheptane methanol (Aldrich 13,865-7), cyclododecane
methanol (Aldrich 11,224-0); (6) dicyclohexylmethanol (Aldrich 31,772-1 ); (7)
3-cyclohexyl-1-propanol (Aldrich 30,440-9); (8) 2-amino-3-cyclohexyl-1-
propanol (Aldrich 42,161-8); (9) (S)-2-(tert-butoxycarbonylamino)-3-
cyclohexyl-1-propanol (Aldrich 42,169-3); (10) cycloalkane diol where the
number of carbons in the alkane chain is from 5 to about 9 and preferably
between about 6 and 8 such as 1,2-cyclopentanediol (Aldrich 36,144-5), 1,3-
cyclohexanediol (Aldrich C10,110-9), 1,2-cyclohexane diol (Aldrich 36,126-7;
14,171-2), 1,4-cyclohexane diol (Aldrich C10,120-6), cyclooctanediol (Aldrich
17,903-5; 36,223-9); (11) cis-3,5-cyclohexadiene-1,2-diol (Aldrich 36,506-8);
23
CA 02341113 2001-03-16
(12) p-menthane-3,8-diol (Aldrich 38,404-6; 38,405-4); (13) cyclohexane
dimethanol (Aldrich 12,559-8; Aldrich 18,908-1 ); (14) 1,3-dioxane-5,5-
dimethanol (Aldrich 22,062-0); (15) 3-cyclohexene-1,1-dimethanol (Aldrich
16,215-9); (16) piperidine methanol (Aldrich 15,522-5; Aldrich 15,523-3);
(17) 4,4'-trimethylenebis(1-piperidine ethanol) (Aldrich 12,122-3); (B) linear
alcohols, such as (1 ) alkyl alcohols where the number of carbons in the alkyl
chain is for example, from about 1, preferably from about 6 about 22 and
more preferably between about 12 to about 16 such as hexyl alcohol (Aldrich
H1330-3), heptyl alcohol (Aldrich H280-5), octyl alcohol (Aldrich 29,324-5),
nonyl alcohol (Aldrich 13,121-0), decylalcohol (Aldrich 23,976-3), undecyl
alcohol (Aldrich U100-1), 1-dodecanol (Aldrich 12,679-9), 1-tetra decanol
(Aldrich 18,538-8), 1-pentadecanol (Aldrich 41,222-8), 1-hexadecanol
(Aldrich 25,874-1 ), 1-eicosanol (Aldrich 23,449-4), 1-docosanol (Aldrich
16,910-2); (2) alkane diols where the number of carbons in the alkane chain
is about 5 to about 14 and preferably from about 8 to about 12, such as 1, 5-
pentane diol (Aldrich P770-3), 1,6-hexane diol (Aldrich H1,180-7), 1,7-
heptane diol (Aldrich H220-1), 1,2-octane diol (Aldrich 21,370-5), 1,8-octane
diol (Aldrich 0,330-3), 1,9-nonane diol (Aldrich N2,960-0), 1,10-decane diol
(Aldrich D,120-3), 1,2-decane diol (Aldrich 26,032-0), 1,2-dodecane diol
(Aldrich 21,372-1), 1,12-dodecane diol (Aldrich D22,130-9), 1,2-tetradecane
diol (Aldrich 26,029-0), 1,14-tetradecane diol (Aldrich 29,901-4); (3)
di(trimethylol propane) (Aldrich 41,613-4); (4) nitromethane trispropanol
(Aldrich 36,153-4); (5) 11-bromo-1-undecanol (Aldrich 18,413-6); (6) 12-
bromo-1-dodecanol (Aldrich 22,467-7); (7) 2-methyl-2-propyl-1,3-propane
diol (Aldrich M7,520-9); (8) 2,2-diethyl-1,3-propanediol (Aldrich D10,000-5);
(9) (2-(hydroxymethyl)-1,3-propanediol (Aldrich 39,365-7); (10) 2,2,4-
trimethyl-1,3-pentanediol (Aldrich 32,722-0); (11) 2-butyne-1,4-diol (Aldrich
24
CA 02341113 2001-03-16
810,320-9); (12) (~)-3,6-dimethyl-4-octyne-3,6-diol (Aldrich 27,840-8); (13)
3,6-dithia-1,8-octanediol (Aldrich 23,533-4); (14) 2,4,7,9-tetramethyl-5-
decyne-4,7-diol (Aldrich 27,838-6); (C) amino alcohols such as (1 ) 2-(2-
aminoethoxy)ethanol (Aldrich A5,405-9); (2) 2-(2-amino ethylamino) ethanol
(Aldrich 12,758-2); (3) amino-1-propanol (Aldrich 23,886-4, 29,768-2, 19,217-
1, A7,620-6, 23,984-4); (4) 2-amino-1-butanol (Aldrich A4,380-6); (5) 4-
amino-1-butanol (Aldrich 17,833-0); (6) 2-amino-3-methyl-1-butanol (Aldrich
18,483-7); (7) 5-amino-1-pentanol (Aldrich 12,304-8); (8) 6-amino-1-hexanol
(Aldrich A5,645-0); (9) D,L-2-amino-1-hexanol (Aldrich 23,767-1 ); (10) (S)-(-
)-
N-(tert-butoxycarbonyl) leucinol (Aldrich 44,119-8); (D) aromatic alcohols,
such as (1 ) alkyl benzyl alcohol where the number of carbon atoms in the
alkyl
group is, for example, from 0 to about 8, and preferably between about 4 and
6, such as benzyl alcohol (Aldrich 10,800-6), 3-methyl benzyl alcohol (Aldrich
18,821-2), 4-methyl benzyl alcohol (Aldrich 12,780-9), 2-phenyl benzyl
alcohol (Aldrich 18,882-4), 2-phenethyl benzyl alcohol (Aldrich 18,478-0); (2)
alkoxy and aryloxy benzyl alcohols where the number of carbons in the alkoxy
groups is for example, from about 1 to about 4 such as 2-methoxy benzyl
alcohol (Aldrich M1,080-8), 3-methoxybenzyl alcohol (Aldrich M1,100-6), 4-
methoxy benzyl alcohol (Aldrich 13,690-5), 2-ethoxy benzyl alcohol (Aldrich
19,066-7), 4-ethoxy benzyl alcohol (Aldrich 19,047-0), 4-butoxy benzyl
alcohol (Aldrich 18,424-1 ), and in the aryloxy groups these vary from 6 to 8
such as 3-benzyloxy benzyl alcohol; (3) alkyl alkyl benzyl alcohols where the
number of carbons in each alkyl group varies from about 1 to about 4, such as
2,4-dimethyl benzyl alcohol (Aldrich 18,878-6), 2,5-dimethyl benzyl alcohol
(Aldrich 18,932-4), 3,5-dimethyl benzyl alcohol (Aldrich 19,999-0), 3,4-
dimethyl benzyl alcohol (Aldrich 18,879-4); (4) 2-amino-3-methyl benzyl
alcohol (Aldrich 33,419-7); (5) alkoxy alkoxy benzyl alcohols where the
CA 02341113 2001-03-16
number of carbon atoms in each alkoxy group varies from about 1 to about
4, such as 2,4-dimethoxy benzyl alcohol (Aldrich 15,963-8), 3,5-dimethoxy
benzyl alcohol (Aldrich 19,165-5), 2,3-dimethoxy benzyl alcohol (Aldrich
12,631-4), 3-ethoxy-4-methoxy benzyl alcohol (Aldrich 30,790-4), 4-ethoxy-3-
methoxy benzyl alcohol (Aldrich 18,914-6); (6) 2-hydroxy-3-methoxy benzyl
alcohol (Aldrich 30,596-0); (7) 3,4,5-trimethoxy benzyl alcohol (Aldrich
T7,000-9); (E) phenyl alcohol derivatives such as (1 ) phenylpropanol (Aldrich
P3,080-2; Aldrich 14,085-6); (2) 3-(4-hydroxy phenyl)-1-propanol (Aldrich
19,741-6); (3) (S)-(-)-1-phenyl-1-butanol (Aldrich 31,731-4); (4) 2-amino-1-
phenyl ethanol (Aldrich A7,240-5); (5) 3,4-dimethoxy phenethyl alcohol
(Aldrich 19,765-3); (6) 2-phenyl-1,2-propane diol (Aldrich 21,376-4); (7) 3-
phenoxy-1,2-propane diol (Aldrich 10, 819-7); (8) 3-methoxy catechol (Aldrich
M1,320-3); (9) benzhydrol (Aldrich B,485-4); (10) methyl benzhydrol (Aldrich
18,995-2; Aldrich 18,996-0); (11 ) phenethylalcohol (Aldrich P1,362-2); (12) 4-
methoxy phenethyl alcohol (Aldrich 15,418-0); (13) 2-hydroxy phenethyl
alcohol (Aldrich 18,824-7; Aldrich 19,902-8); (14) 2-amino phenethylalcohol
(Aldrich 19,260-0); and the like; (XVI) oxazolines, such as (1 )
5-(hydroxymethyl)-5'-(methoxy stearate) oxazoline; (2) 2-stearyl-5-
(hydroxymethyl)-5'-(methoxy stearate) oxazoline; and the like; (XVII)
oxime compounds, such as (i) 2,3-butanedione monoxime (Aldrich 11,213-5);
(ii) acetone oxime (Aldrich A1,050-7); (iii) cyclohexanone oxime (Aldrich
C10,220-2); (iv) 4-(trifluoromethoxy) benzamidoxime (Aldrich 42,223-1 ); (v) 2-
nitrobenzaldoxime (Aldrich 24,204-7); (vi) 1-phenyl-1,2-propanedione 2-oxime
(Aldrich 22,009-4); and the like; (XVIII) azoles, such as (a) pyrazole
compounds, such as (1) pyrazole (Aldrich P5,660-7); (2) 1-nitro pyrazole
(Aldrich 39,074-7); (3) 4-iodo pyrazole (Aldrich 21,399-3); (4) 4-bromo
26
CA 02341113 2001-03-16
pyrazole (Aldrich 37,482-2); (5) 3,5-dimethyl pyrazole (Aldrich D18,200-1 );
(6) 4-bromo-3-methylpyrazole (Aldrich 27,823-8); (7) 4-bromo-3,5-dimethyl
pyrazole (Aldrich B6,440-7); (8) 3-amino-5-phenyl pyrazole (Aldrich 39,379-
7); (9) ethyl 4-pyrazolecarboxylate (Aldrich 30,078-0); (10) 1,1'-
cyclopentylidene bis-1-H-pyrazole (Aldrich 39,415-7); (11) a-((2-ethoxy-2-
oxoethoxy)imino)-3-pyrazoleacetic acid (Aldrich 38,971-4); (12) ethyl 5-
amino-1-phenyl-4-pyrazole carboxylate (Aldrich 37,944-1); (13) 1,1'-(1-
ethylpropylidene)bis-1-H-pyrazole (Aldrich 39,414-9); (14) ethyl 3-amino-4-
pyrazolecarboxylate (Aldrich A4,500-9); (15) 3,5-bis(trifluoromethyl)
pyrazole (Aldrich 39,039-9); (16) N-(tert-butoxycarbonyl)-1H-pyrazole-1-
carbox amidine (Aldrich 44,201-1); (17) 3,5-dimethylpyrazole-1-carboxamide
(Aldrich D18,220-6); (18) 3,5-dimethylpyrazole-1-methanol (Aldrich 33,145-
7); (19) 2,3-dimethyl-1-phenyl-3-pyrazolin-5-one, (Aldrich A9,135-3); (b)
imidazole compounds such as (1 ) imidazole (Aldrich 43,615-1 ); (2) 4-methyl
imidazole (Aldrich 19,988-5); (3) 2-ethyl imidazole (Aldrich 23,934-8); (4) 2-
ethyl-4-methylimidazole (Aldrich E3,665-2); (5) 2-propyl imidazole (Aldrich
37,537-3); (6) 2-isopropyl imidazole (Aldrich 37,399-0); (7) 1-acetylimidazole
(Aldrich 15,786-41); (8) 1-benzylimidazole (Aldrich 11,641-6); (9) 2-undecyl
imidazole (Aldrich 40,948-0); (10) 1,5-dicyclohexyl imidazole (Aldrich
31,654-7); (11) 1-(2,4,6-triisopropyl benzene sulfonyl imidazole (Aldrich
40,948-0); (12) 1-(mesitylene sulfonyl) imidazole (Aldrich 24,422-8); (13) 1-
trans-cinnamoyl imidazole (Aldrich 21,904-5); (14) 2-methyl-4-nitro-1-
imidazole propionitrile (15) 1,1'-carbonyl diimidazole (Aldrich 11,553-3);
(16) 1,1'-thiocarbonyl diimidazole (Aldrich 15,605-1); (17) 1,1'-sulfonyl
diimidazole (Aldrich 36,781-8); (18) 1,1'-oxalyldiimidazole (Aldrich 36,643-
9); Aldrich 37,769-4); (19) 5-methyl benzimidazole (Aldrich 30,523-5); (c)
triazole derivatives such as (1) 1,2,4-triazole (Aldrich T4,610-8); (2) 4-
27
CA 02341113 2001-03-16
amino-1,2,4-triazole (Aldrich A8,180-3); (3) benzotriazole (Aldrich B1,140-
0); (4) 1H-benzotriazole carboxaldehyde (Aldrich 44,691-2); (5)
benzotriazole-5-carboxylic acid (Aldrich 30,423-9); (6) 1-(methoxy methyl)-
1 H-benzotriazole (Aldrich 43,802-0); (7) 5-methyl-1 H-benzotriazole (Aldrich
19,630-4); (8) N-(triphenylphosphoranylidene)-1H-benzotriazole-1-methane
amine (Aldrich 44,693-9); (9) 1-aminobenzotriazole (Aldrich 38,637-5); (10)
1-cyanobenzotriazole (Aldrich 38,181-0); (11) (4-morpholinyl methyl)
benzotriazole (Aldrich 46,750-2); (12) (4-morpholinyl phenylmethyl)
benzotriazole (Aldrich 46,926-2); (13) (1-(4-morpholinyl) propyl)
benzotriazole (Aldrich 47,108-9); (d) those with four nitrogens in the cyclic
ring such as (1) 5-mercapto-1-methyltetrazole (Aldrich 35,787-1); (2) 1,5-
pentamethylene tetrazole (Aldrich P,720-7); (XIX) bisamides, including
those of the structure RCONH-R'-NHOCR, where R is an alkyl of from about 2
to about 30 carbon atoms or aryl, R' is an alkylene with from about 2 to
about 30 carbon atoms, as disclosed in U.S. Patent 5,667,568, wherein
examples of bisamides include (a) N,N'-ethylene bis-stearamide; (b) N,N'-
propylene bis-stearamide; (c) N,N'-butylene bis-stearamide; (d) N,N'-
hexylene bis-stearamide; (e) N,N'-heptylene bis-stearamide; (f) N,N'-
octylene bis-stearamide; (g) N,N'-decylene bis-stearamide; (h) N,N'-
dodecylene bis-stearamide; (i) N,N'-stearylene bis-stearamide; (j) N,N'-
ethylene bis-lauramide; (k) N,N'-propylene bis-lauramide; (l) butylene bis-
lauramide; (m) N,N'-hexylene bis-lauramide; (n) N,N'-heptylene bis-
lauramide; (o) N,N'-octylene bis-lauramide; (p) N,N'-decylene bis-lauramide;
(q) N,N'-dodecylene bis-lauramide; (r) N,N'-stearylene bis-lauramide, with
preferred bisamides include N,N'-stearylene bis-stearamide, N,N'-stearylene
bis-lauramide; (XX) organic acid salts, such as (1 ) diethyldithiocarbamic
acid
ammonium salt (Aldrich 35,954-8); (2) diethyldithiocarbamic acid
28
CA 02341113 2001-03-16
diethylammonium salt (Aldrich 31,811-6); (3) L-alanine ethyl ester
hydrochloride (Aldrich 85,566-9); (4) D,L-alanine ethyl ester hydrochloride
(Aldrich 26,886-0); (5) ethyl 4-aminobutyrate hydrochloride (Aldrich 39,066-
6); (6) 2-ethyl-2-thiopseudourea hydrobromide (Aldrich 30,131-0); (7)
formamidine hydrochloride (Aldrich 26,860-7); (8) N-methylhydroxylamine
hydrochloride (Aldrich M5,040-0), and the like, as well as mixtures thereof.
Any desired or effective colorant can be employed in the inks
of the present invention, including dyes, pigments, mixtures thereof, and
the like, provided that the colorant can be dissolved or dispersed in the ink
vehicle, with solvent or alcohol (spirit) soluble dyes being preferred.
Particularly preferred dyes include the Macrolex series available from Bayer
and the Ceres dyes, such as Ceres Blue N, the Savinyl series available from
Clariant, such as Savinyl Yellow RLS, Red 3BL, Blue GLS, Black RLSN, Black
NS, and Duasyn Black A-RG VP280; the Orasol dyes available from Ciba
Geigy, such as Orasol Yellow 4GN, Yellow 2GLN, Yellow 3R, Orange G,
Orange RG, Red 3GL, Red 2B, Red BL, Pink 5BLG, Blue GN, Blue BL, Black
CN, Black RL, and Black RL1; the Neopen Series available from BASF, such as
Neopen Yellow 075, yellow 159, orange 252, red 336, red 335, red 366, blue
808 or 807, black X53, and Black X55. Also suitable are dispersed dyes and
polymeric dyes, such as the Millijet Series available from Milliken.
Examples of suitable pigments include Violet Toner VT-8015
(Paul Uhlich); Paliogen Violet 5100 (BASF); Paliogen Violet 5890 (BASF);
Permanent Violet VT 2645 (Paul Uhlich); Heliogen Green L8730 (BASF); Argyle
Green XP-111-S (Paul Uhlich); Brilliant Green Toner GR 0991 (Paul Uhlich);
Lithol Scarlet D3700 (BASF); Toluidine Red (Aldrich); Scarlet for Thermoplast
NSD PS PA (Ugine Kuhlmann of Canada); E.D. Toluidine Red (Aldrich); Lithol
Rubine Toner (Paul Uhlich); Lithol Scarlet 4440 (BASF); Bon Red C (Dominion
29
~
CA 02341113 2001-03-16
Color Company); Royal Brilliant Red RD-8192 (Paul Uhlich); Oracet Pink RF
(Ciba-Geigy); Paliogen Red 3871 K (BASF); Paliogen Red 3340 (BASF); Lithol
Fast Scarlet L4300 (BASF); Heliogen Blue L6900, L7020 (BASF); Heliogen Blue
K6902, K6910 (BASF); Heliogen Blue D6840, D7080 (BASF); Sudan Blue OS
(BASF); Neopen Blue FF4012 (BASF); PV Fast Blue B2G01 (American Hoechst);
Irgalite Blue BCA (Ciba-Geigy); Paliogen Blue 6470 (BASF); Sudan III (Red
Orange) (Matheson, Colemen Bell); Sudan II (Orange) (Matheson, Colemen
Bell); Sudan Orange G (Aldrich), Sudan Orange 220 (BASF); Paliogen Orange
3040 (BASF); Ortho Orange OR 2673 (Paul Uhlich); Paliogen Yetlow 152, 1560
(BASF); Lithol Fast Yellow 0991 K (BASF); Paliotol Yellow 1840 (BASF);
Novoperm Yellow FGL (Hoechst); Permanent Yellow YE 0305 (Paul Uhlich);
Lumogen Yellow D0790 (BASF); Suco-Yellow L1250 (BASF); Suco-Yellow D1355
(BASF); Suco Fast Yellow D1355, D1351 (BASF); Hostaperm Pink E (American
Hoechst); Fanal Pink D4830 (BASF); Cinquasia Magenta (Du Pont); Paliogen
Black L0084 (BASF); Pigment Black K801 (BASF); and carbon blacks such as
REGAL 330~ (Cabot), Carbon Black 5250, Carbon Black 5750 (Columbia
Chemical), and the like. Additional examples of suitable spirit solvent dyes
include Neozapon Red 492 (BASF); Orasol Red G (Ciba Geigy); Direct Brilliant
Pink B (Crompton F~ Knowles); Aizen Spilon Red C-BH (Hodogaya Chemical);
Kayanol Red 3BL (Nippon Kayaku); Levanol Brilliant Red 3BW (Mobay
Chemical); Levaderm Lemon Yellow (Mobay Chemical); Spirit Fast Yellow 3G;
Aizen Spilon Yellow C-GNH (Hodogaya Chemical); Sirius Supra Yellow GD 167;
Cartasol Brilliant Yellow 4GF (Sandoz); Pergasol Yellow CGP (Ciba Geigy);
Orasol Black RLP (Ciba Geigy); Savinyl Black RLS (Sandoz); Dermacarbon 2GT
(Sandoz); Pyrazol Black BG (ICI); Morfast Black Conc. A (Morton-Thiokol);
Diaazol Black RN Quad (ICI); Orasol Blue GN (Ciba-Geigy); Savinyl Blue GLS
(Sandoz); Luxol Blue MBSN (Morton-Thiokol); Sevron Blue 5GMF (ICI); Basacid
CA 02341113 2001-03-16
Blue 750 (BASF), and the like. Neozapon Black X51 (C.I. Solvent Black, C.I.
12195) (BASF), Sudan Blue 670 (C.I. 61554) (BASF), Sudan Yellow 146 (C.I.
12700) (BASF), and Sudan Red 462 (C.I. 26050) (BASF) are preferred.
The colorant is present in the ink in any desired or effective
amount to obtain the desired color and hue, typically at least about 0.5
percent by weight of the ink, preferably at least about 1 percent by weight,
and more preferably at least about 2 percent by weight of the ink, and
typically no more than about 10 percent by weight of the ink, preferably no
more than about 7 percent by weight of the ink, and more preferably no
more than about 6 percent by weight of the ink, although the amount can
be outside of these ranges.
The inks of the present invention also contain both a cationic
and an anionic surfactant. While not being limited to any particular theory,
it is believed that at the temperatures at which the ink is jetted from the
printhead (typically at least about 125 and typically no more than about
170°C, although the temperature can be outside of this range), the
cationic
and anionic surfactants are partly or fully thermally dissociated. When the
ink cools to ambient temperature (typically from about 20 to about
25°C),
however, the cationic and anionic surfactants can become strongly
associated by Coulomb attractions. This strong association is believed to
form a hard shell at the surface of the ink drop, thereby producing images
that are smear resistant and possibly also with increased surface hardness.
Although some of the surfactant molecules are dissolved in the bulk of the
ink, the ink bulk viscosity is not undesirably affected because the overall
concentration of surfactant in the ink is usually relatively small. The
addition of the optional neutral surfactant provides a method of controlling
31
~
~ CA 02341113 2001-03-16
the amount of association by diluting the surface concentration of the
charged surfactants.
Any anionic surfactant can be employed. Examples of suitable
anionic surfactants include alkyl carboxylic acids of the general formula
RCOOH, wherein R is an alkyl group, typically with at least about 5 carbon
atoms, and typically with no more than about 20 carbon atoms, although the
number of carbon atoms can be outside of these ranges, including those of
the formula CH3(CH2)XCOOH wherein x is an integer representing the number
of repeat -CH2- units, typically being at least about 5, and preferably at
least about 10, and typically being no more than about 20, and preferably
no more than about 18, although the value of x can be outside of these
ranges. Salts of these acids can also be used. Specific examples of anionic
surfactants of this formula include palmitic acid, wherein x=14, lauric acid,
wherein x=10, stearic acid, wherein x=16, and the like. Branched,
unsaturated, and cyclic acids can also be used in addition to linear acids.
Also suitable are alkyl dicarboxylic acids of the general formula
HOOC-R-COOH, wherein R is an alkyl group, typically with at least about 10
carbon atoms and typically with no more than about 20 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
including those of the formula HOOC(CH2)xC00H wherein x is an integer
representing the number of repeat -CHZ- units, typically being at least about
10, preferably at least about 12, and more preferably at least about 16, and
typically being no more than about 20, although the value of x can be
outside of these ranges. Branched, unsaturated, and cyclic acids can also
be used in addition to linear acids. Specific examples of anionic surfactants
of this formula include undecanedioic acid and the like. Also suitable are
alkyl sulfates, salts of sulfonated naphthalene-formaldehyde condensates,
32
~
~ CA 02341113 2001-03-16
salts of lignosulfonate, poly(methyl vinyl ether/maleic anhydride) salts, and
those of the formula ROS03-B+ wherein R is an alkyl group, typically with at
least about 5 carbon atoms, preferably with at least about 10 carbon atoms,
and more preferably with at least about 16 carbon atoms, and typically with
no more than about 20 carbon atoms, although the number of carbon atoms
can be outside of these ranges, and B is a cation. Any desired or suitable
cation can be employed, including monovalent, bivalent, trivalent, and
polyvalent cations. Examples of suitable cations include, but are not
limited to, alkali metal cations, such as Li+, Na+, and K+, alkaline earth
metal cations, such as Mg2+ and Caz+, ammonium and quaternary amine
cations such as NH4+, N(CH3)4+, and the like, as well as mixtures thereof.
Specific examples of anionic surfactants of this formula include sodium
lauryl sulfate and the like. Also suitable are alkyl ether sulfates, of the
formula R(OCH2CH2)nOS03-B+ wherein n is an integer with an average value
of from about 1 to about 4, R is an alkyl group, typically with at least about
12 carbon atoms and typically with no more than about 15 carbon atoms,
although the number of carbon atoms can be outside of this range, and B is
a cation as defined above for the formula ROS03-B+. Specific examples of
anionic surfactants of this formula include sodium lauryl ether sulfate (also
known as sodium laureth sulfate) and the like. The anionic surfactant is
present in the ink in any desired or effective amount, typically at least
about 0.01 percent by weight of the ink, preferably at least about 0.1
percent by weight of the ink, and more preferably at least about 1 percent
by weight of the ink, and typically no more than about 50 percent by weight
of the ink, preferably no more than about 40 percent by weight of the ink,
and more preferably no more than about 20 percent by weight of the ink,
although the amount can be outside of these ranges.
33
CA 02341113 2001-03-16
Any cationic surfactant can be employed. Examples of suitable
cationic surfactants include those of the general formula N(R~)X(R2)y(R3)Z+A-
wherein R~ and R2 each, independently of the other, are hydrogen atoms,
alkyl groups, typically with at least about 1 carbon atom, and typically with
no more than about 25 carbon atoms, preferably with no more than about
20 carbon atoms, and more preferably with no more than about 18 carbon
atoms, although the number of carbon atoms can be outside of these
ranges, or a mixture thereof, R3 is an alkyl group, typically with at least
about 1 carbon atom, and preferably with at least about 10 carbon atoms,
and typically with no more than about 25 carbon atoms, and preferably with
no more than about 18 carbon atoms, although the number of carbon atoms
can be outside of these ranges, an aryl group, typically with at least about 5
carbon atoms, and preferably with at least about 6 carbon atoms, and
typically with no more than about 25 carbon atoms, preferably with no more
than about 20 carbon atoms, and more preferably with no more than about
18 carbon atoms, although the number of carbon atoms can be outside of
these ranges, an alkylaryl group or arylalkyl group, typically with at least
about 6 carbon atoms, and preferably with at least about 7 carbon atoms,
and typically with no more than about 30 carbon atoms, preferably with no
more than about 25 carbon atoms, and more preferably with no more than
about 22 carbon atoms, although the number of carbon atoms can be
outside of these ranges, or a mixture thereof, x, y, and z are integers
representing the number of R~, R2, and R3 groups, wherein x is at least one
and z is at least one and the sum of x+y+z=4, and A is an anion. Any desired
or suitable anion can be employed, including monovalent, bivalent,
trivalent, and polyvalent anions. Examples of suitable anions include, but
are not limited to, Cl-, Br-, I-, HS04-, HS03-, 5042-, 5032-, CH2S03-, CH3S03-
,
34
CA 02341113 2001-03-16
CH3C6H4SO3 , N03 , HC00 , CFi3C00 , IiC03 , CO32~, HZP04 , HP042 , P043 , SCN
,
BF4-, C104~, SS03-, or the like, as well as mixtures thereof. Specific
examples
of cationic surfactants of this formula include benzyl cetyl dimethyl
ammonium chloride, wherein R~ is methyl, x is 2, R2 is benzyl, y is 1, R3 is
cetyl dimethyl (-(CH2)~5(CH3)2), z is 1, and A is chloride, hexadecyl
trimethyl
ammonium bromide, wherein R~ is methyl, x is 3, RZ is hexadecyl, y is 1, and
A is bromide, tetraheptyl ammonium bromide, wherein R~ is heptyl, x is 3,
R3 is heptyl, z is 1, and A is bromide, and the like. Also suitable are
octadecylamine, acetic acid salts of n-alkyl amines wherein the alkyl groups
typically have at least about 1 carbon atom and typically have no more than
about 25 carbon atoms, although the number of carbon atoms can be
outside of this range, stearamido amine, stearamido morpholine, palmitic
amidoalkyl dimethyl amine, stearic amido alkyl dimethyl amine, substituted
imidazoline from oleic acid, alkyl dimethyl benzyl ammonium saccharinate,
dihydydrogenated tallow dimethyl ammonium chloride, dialuryl dimethyl
ammonium bromide, n-octyl decylamine, and the tike, as well as mixtures
thereof. The cationic surfactant is present in the ink in any desired or
effective amount, typically at least about 0.1 percent by weight of the ink,
preferably at least about 0.5 percent by weight of the ink and more
preferably at least about 1 percent by weight of the ink, and typically no
more than about 50 percent by weight of the ink, preferably no more than
about 40 percent by weight of the ink, and more preferably no more than
about 20 percent by weight of the ink, although the amount can be outside
of these ranges.
One particularly preferred pair of anionic and cationic
surfactants is that of stearic acid and octadecylamine.
CA 02341113 2001-03-16
Any nonionic surfactant can be employed as the optional
nonionic surfactant. Preferably, the nonionic surfactant has a melting point
of at least about 70°C, and more preferably of at least about
100°C, with no
necessary upper limit, although the melting point can be outside of these
ranges. Examples of suitable nonionic surfactants include ethoxylated
lanolin alcohol (typically having at least about 5 ethylene oxide repeat units
and typically having no more than about 75 ethylene oxide repeat units),
polyethylene glycol monostearate (typically having at least about 200 repeat
ethylene glycol units and typically having no more than about 1,500 repeat
ethylene glycol units), and the like, as well as mixtures thereof. The
optional nonionic surfactant, when present, is present in the ink in any
desired or effective amount, typically at least about 0.1 percent by weight
of the ink, and preferably at least about 1 percent by weight of the ink, and
typically no more than about 20 percent by weight of the ink, preferably no
more than about 10 percent by weight of the ink, and more preferably no
more than about 5 percent by weight of the ink, although the amount can
be outside of these ranges.
The inks of the present invention further optionally contain a
conductivity enhancing agent when conductive inks are desirable, as in
applications such as electric field assisted hot melt acoustic ink printing
processes. Any desired or effective conductivity enhancing agent can be
employed. Specific examples of suitable conductivity enhancing agents
include complexes of dianilines, including dianiline and bis dianiline
compounds, such as (1 ) 2,2'-dithio dianiline (Aldrich 16,676-6), (2) 4,4'-
dithiodianiline (Aldrich 36,946-26), (3) 3,3'-methylene dianiline (Aldrich
37,826-7), (4) 4,4'-methylene dianiline (Aldrich 13,245-4), (5) N-methyl-4,4'-
methylene dianiline (Aldrich 42,282-7), (6) 4,4'-methylene bis(2,6-diethyl
36
CA 02341113 2001-03-16
aniline) (Aldrich 36,078-3), (7) 4,4'-methylene bis(2,6-diisopropyl-N,N-
dimethylaniline) (Aldrich 40,353-9), (8) 4,4'-methylene bis (N,N-
dimethylaniline) (Aldrich M4,445-1 ), (9) 4,4'-methylene bis (2,6-
dimethylaniline) (Aldrich 36,079-1 ), (10) 4,4'-methylene bis (3-chloro-2,6-
diethylaniline) (Aldrich 42,660-1), (11) 3,3'-(sulfonyl bis(4,1-
phenylene))dianiline (Aldrich 44,095-7), (12) 4,4'-(1,3-phenylene
diisopropylidene) bisaniline (Aldrich 45,048-0), and the like, as well as
mixtures thereof, said dianilines being complexed with, for example,
conductivity inducing phosphorous compounds such as phosphorus-containing
acid compounds, with specific examples including (1 ) phenylphosphinic acid
(Aldrich P2,880-8), (2) dimethylphosphinic acid (Aldrich 32,829-4), (3) methyl
phosphonic acid (Aldrich 28,986-8), and the like, as well as mixtures thereof.
Additional suitable conductivity enhancing agents include (1 ) (diethyl-(4-
aminobenzyl) phosphonate (Aldrich 33,847-8), (2) diethyl-
(phthalimidomethyl) phosphonate (Aldrich 36,622-6), (3) diethyl-(2,2,2-
trifluoro-1-hydroxyethyl) phosphonate (Aldrich 43,982-7), (4) Biphenyl
succinimidyl phosphate (Aldrich 45,061-8), (5) dihexadecyl phosphate
(Aldrich 27,149-7), (6) undecylenic acid zinc salt (hardness value 68; Aldrich
32,958-4), (7) zinc bis(2,2,6,6-tetramethyl-3,5-heptanedionate) (Aldrich
41,773-4), (8) zinc cyclohexanebutyrate (Aldrich 22,841-9), (9) zinc stearate
(Aldrich 30,756-4), (10) methyl-1-adamantane sulfonate (Aldrich 40,956-1 ),
(11 ) octadecyl-4-chlorobenzene sulfonate (Aldrich 47,799-0), (12)
tetrabutylammonium trifluoromethanesulfonate (Aldrich 34,509-1), (13) S,S'-
ethylene-p-toluene thiosulfonate (Aldrich 23,257-2), (14) pyridinium-3-
nitrobenzene sulfonate (Aldrich#27,198-5), (15) p-toluene sulfonyl chloride
(Aldrich 24,087-7), (16) o-toluene sulfonyl chloride (Aldrich 15,971-9), (17)
1-(p-toluene sulfonyl) imidazole (Aldrich 24,424-4), (18) 1-(p-toluene
37
CA 02341113 2001-03-16
sulfonyl)-3-vitro-1,2,4-triazole (Aldrich 24,417-1), (19) 2,4,6-triisopropyl
benzene sulfonyl chloride (Aldrich 11,949-0), (20) 1-(2,4,6-triisopropyl
benzene sulfonyl) imidazole (Aldrich 40,948-0), (21) 1-(2,4,6-triisopropyl
benzene sulfonyl)-3-vitro-1,2,4-triazole (Aldrich 40,948-0), (22) 4-
nitrobenzene sulfonyl chloride (Aldrich 27,224-8), and the like, as well as
mixtures thereof. The conductivity enhancing agent, when present, is
present in the ink in any desired or effective amount, typically at least
about 1 percent by weight of the ink, and typically no more than about 20
percent by weight of the ink, preferably no more than about 10 percent by
weight of the ink, and more preferably no more than about 5 percent by
weight of the ink, although the amount can be outside of these ranges.
The inks of the present invention further optionally contain an
antioxidant. The optional antioxidants of the ink compositions protect the
images from oxidation and also protect the ink components from oxidation
during the heating portion of the ink preparation process. Specific examples
of suitable antioxidants include (but are not limited to) (1 ) 2,6-di-tert-
butyl-
4-methoxyphenol (Aldrich 25,106-2), (2) 2,4-di-tert-butyl-6-(4-methoxybenzyl)
phenol (Aldrich 23,008-1), (3) 4-bromo-2,6-dimethylphenol (Aldrich 34,951-8),
(4) 4-bromo-3,5-didimethylphenol (Aldrich B6,420-2), (5) 4-bromo-2-
nitrophenol (Aldrich 30,987-7), (6) 4-(diethyl aminomethyl)-2,5-
dimethylphenol (Aldrich 14,668-4), (7) 3-dimethylaminophenol (Aldrich
D14,400-2), (8) 2-amino-4-tert-amylphenol (Aldrich 41,258-9), (9) 2,6-
bis(hydroxymethyl)-p-cresol (Aldrich 22,752-8), (10) 2,2'-methylenediphenol
(Aldrich B4,680-8), (11) 5-diethylamino)-2-nitrosophenol (Aldrich 26,951-4),
(12) antimony dialkyl phosphorodithioate (commercially available from
Vanderbilt), (13) molybdenum oxysulfide dithiocarbamate (commercially
available from Vanderbilt), (14) (nickel-bis(o-ethyl(3,5-di-tert-butyl-4-
38
CA 02341113 2001-03-16
hydroxybenzyl) phosphonate (commercially available from Ciba Geigy), (15)
4,4'-methylene-bis(dibutyldithiocarbamate) (commercially available as
Vanlube 7723 from Vanderbilt), (16) tetrasodium-N-(1,2-dicarboxyethyl)-N-
octadecyl sulfosuccinamate (commercially available from American
Cyanamid), (17) 2,6-di-tert-butyl-a-dimethylamino-4-cresol (commercially
available as Ethanox-703 from Ethyl Corporation), (18) 2,2'-isobutylidene-
bis(4,6-dimethyl phenol) (commercially available as Vulkanox NKF from
Mobay Chemicals), (19) 2,2'-methylenebis(6-tert-butyl-4-methylphenol)
(commercially available as Cyanox-2246, Aldrich 41,315-5), (20) 2,2'-
methylenebis(6-tert-butyl-4-ethylphenol) (commercially available as
Cyanox-425, Atdrich 41,314-3), (21) N-isopropyl-N'-phenyl-phenylene
diamine (commercially available as Santoflex-IP from Monsanto Chemicals,
(22) N-(1,3-dimethylbutyl)-N'-phenyl-phenylene-diamine (commercially
available as Santoflex-13 from Monsanto Chemicals), (23) N,N'-di(2-octyl)-4-
phenylene diamine (commercially available as Antozite-1 from Vanderbilt),
(24) N,N'-bis(1,4-dimethylpentyl)-4-phenylene diamine (commercially
available as Santoflex-77 from Monsanto Chemicals), (25) 2,4,6-tris-(N-1,4-
dimethyl pentyl-4-phenylenediamino)-1,3,5-triazine (commercially available
as Durazone-37 from Uniroyal), (26) D-raffinose pentahydrate (Aldrich
20,667-9), (27) 2,2'-methylene bis(6-tert-butyl-4-methyl-phenol) (Aldrich
41,313-5), (28) 2,6-di-tert-butyl-4-(dimethylaminomethyl) phenol (Aldrich
41,327-5), (29) 4-dodecylresorcinol (Aldrich D22,260-7), and the like, as well
as mixtures thereof. When present, the optional antioxidants are present in
any desired or effective amount, typically at least about 0.01 percent by
weight of the ink, preferably at least about 0.05 percent by weight of the
ink, and more preferably at least about 0.1 percent by weight of the ink,
and typically no more than about 2 percent by weight of the ink, and
39
CA 02341113 2001-03-16
preferably no more than about 0.5 percent by weight of the ink, although
the amount can be outside of these ranges.
The inks of the present invention further optionally contain a
UV absorber. The optional UV absorbers in the inks of the present invention
primarily protect the images generated therewith from UV degradation.
Specific examples of suitable UV absorbers include (but are not limited to) (1
)
2-amino-2',5-dichlorobenzophenone (Aldrich 10,515-5), (2) 2'amino-4',5'-
dimethoxyacetophenone (Aldrich 32,922-3), (3) 2-benzyl-2-(dimethylamino)-
4'-morpholino butyrophenone (Aldrich 40,564-7), (4) 4'-benzyloxy-2'-hydroxy-
3'-methylacetophenone (Aldrich 29,884-0), (5) 4,4'-bis(diethylamino)
benzophenone (Aldrich 16,032-6), (6) 5-chloro-2-hydroxy benzophenone
(Aldrich C4,470-2), (7) 4'-piperazinoacetophenone (Aldrich 13,646-8), (8) 4'-
piperidinoacetophenone (Aldrich 11,972-5), (9) 2-amino-5-
chlorobenzophenone (Aldrich A4,556-4), (10) 2-bromo-2',4-
dimethoxyacetophenone (Aldrich 19,948-6), (11) 2-bromo-2',5'-
dimethoxyacetophenone (Aldrich 10,458-2), (12) 2-bromo-3'-
nitroacetophenone (Aldrich 34,421-4), (13) 2-bromo-4'-nitroacetophenone
(Aldrich 24,561-5), (14) 3',5'-diacetoxyacetophenone (Aldrich 11,738-2, (15) 2-
phenylsulfonyl) acetophenone (Aldrich 34,150-3), (16) 3'-aminoacetophenone
(Aldrich 13,935-1 ), (17) 4'-aminoacetophenone (Aldrich A3,800-2), (18) 1 H-
benzotriazole-1-acetonitrile (Aldrich 46,752-9), (19) 2-(2H-benzotriazol-2-yl)-
4,6-di-tert-pentylphenol (Aldrich 42,274-6), (20) 1,1-(1,2-ethane-
diyl)bis(3,3,5,5-tetramethylpiperazinone) (commercially available from
Goodrich Chemicals), (21 ) 2,2,4-trimethyl-1,2-hydroquinoline (commercially
available from Mobay Chemical), (22) 2-(4-benzoyl-3-hydroxy
phenoxy)ethylacrylate, (23) 2-dodecyl-N-(1,2,2,6,6-pentamethyl-4-
piperidinyl) succinimide (commercially available from Aldrich Chemical Co.,
~
CA 02341113 2001-03-16
Milwaukee, WI), (24) 2,2,6,6-tetramethyl-4-piperidinyl/~,~,~',~3'-tetramethyl-
3,9-(2,4,8,10-tetraoxo spiro(5,5)-undecane) diethyl)-1,2,3,4-butane
tetracarboxylate (commercially available from Fairmount), (25) N-p-
ethoxycarbonylphenyl)-N'-ethyl-N'-phenylformadine (commercially available
from Givaudan), (26) 6-ethoxy-1,2-dihydro-2,2,4-trimethylquinoline
(commercially available from Monsanto Chemicals), (27) 2,4,6-tris-(N-1,4-
dimethylpentyl-4-phenylenediamino)-1,3,5-triazine (commercially available
from Uniroyal), (28) 2-dodecyl-N-(2,2,6,6-tetramethyl-4-piperidinyl)
succinimide (commercially available from Aldrich Chemical Co.), (29) N-(1-
acetyl-2,2,6,6-tetramethyl-4-piperidinyl)-2-dodecyl succinimide
(commercially available from Aldrich Chemical Co.), (30) (1,2,2,6,6-
pentamethyl-4-piperidinyl/ ~, ~~', ~'-tetramethyl-3,9-(2,4,8,10-tetraoxo-spiro-
(5,5)undecane)diethyl)-1,2,3,4-butane tetracarboxylate (commercially
available from Fairmount), (31 ) (2,2,6,6-tetramethyl-4-piperidinyl)-1,2,3,4-
butane tetracarboxylate (commercially available from Fairmount), (32) nickel
dibutyl dithio carbamate (commercially available as UV-Chek AM-105 from
Ferro), and the like, as well as mixtures thereof. The optional UV absorber,
when present, is present in the ink in any desired or effective amount,
typically at least about 0.01 percent by weight of the ink, preferably at
least about 0.05 percent by weight of the ink, and more preferably at least
about 0.1 percent by weight of the ink, and typically no more than about 2
percent by weight of the ink, and preferably no more than about 0.5
percent by weight of the ink, although the amount can be outside of these
ranges.
Other optional additives to the inks include clarifiers, such as
UNION CAMP~ X37-523-235 and UNION CAMPO UC-235 (commercially
available from Union Camp), in an amount typically of at least about 5
41
CA 02341113 2001-03-16
percent by weight of the ink, and preferably at least about 10 percent by
weight of the ink, and typically no more than about 40 percent by weight of
the ink, and preferably no more than about 25 percent by weight of the ink,
although the amount can be outside of this range, tackifiers, such as
FORAL~ 85, a glycerol ester of hydrogenated abietic (rosin) acid
(commercially available from Hercules), FORALO 105, a pentaerythritol
ester of hydroabietic (rosin) acid (commercially available from Hercules),
CELLOLYNO 21, a hydroabietic (rosin) alcohol ester of phthalic acid
(commercially available from Hercules), ARAKAWA KE-311 Resin, a
triglyceride of hydrogenated abietic (rosin) acid (commercially available
from Arakawa Chemical Industries, Ltd.), synthetic polyterpene resins such
as NEVTACO 2300 and NEVTAC~ 80 (commercially available from Neville
Chemical Company), WINGTACKO 86, a modified synthetic polyterpene resin
(commercially available from Goodyear), and the like, in an amount
typically of at least about 1 percent by weight of the ink, and preferably at
least about 3 percent by weight of the ink, and typically no more than about
40 percent by weight of the ink, preferably no more than about 20 percent
by weight of the ink, and more preferably no more than about 10 percent by
weight of the ink, although the amount can be outside of this range,
adhesives, such as VERSAMIDO 757, 759, 744, and 963 (commercially
available from Henkel), in an amount typically of at least about 0.5 percent
by weight of the ink, preferably at least about 5 percent by weight of the
ink, and more preferably at least about 10 percent by weight of the ink, and
typically no more than about 50 percent by weight of the ink, preferably no
more than about 40 percent by weight of the ink, and more preferably no
more than about 20 percent by weight of the ink, although the amount can
be outside of this range, plasticizers, such as UNIPLEXO 250 (commercially
42
CA 02341113 2001-03-16
available from Uniplex), the phthalate ester plasticizers commercially
available from Monsanto under the trade name SANTICIZERO, such as dioctyl
phthalate, diundecyl phthalate, alkylbenzyl phthalate (SANTICIZERO 278),
KP-1400, a triphenyl phosphate (commercially available from MC
Corporation), MORFLEXO 150, a dicyclohexyl phthalate (commercially
available from Morflex Chemical Company, Inc.), trioctyl trimellitate
(commercially available from Eastman Kodak Co.), and the like, in an
amount typically of at least about 0.5 and typically no more than about 20
percent by weight of the ink, and preferably no more than about 10 percent
by weight of the ink, although the amount can be outside of this range, and
the like.
The ink compositions of the present invention typically have
melting points no tower than about 60°C, preferably no lower than about
70 ° C, and more preferably no lower than about 80 ° C, and
typically have
melting points no higher than about 160°C, preferably no higher than
about
140°C, and more preferably no higher than about 120°C, although
the
melting point can be outside of these ranges.
The ink compositions of the present invention generally have
melt viscosities at the jetting temperature (typically no lower than about
75 ° C, preferably no lower than about 100 ° C, and more
preferably no lower
than about 120°C, and typically no higher than about 180°C,
preferably no
higher than about 150°C, and more preferably no higher than about
130°C,
although the jetting temperature can be outside of these ranges) typically
of no more than about 25 centipoise, preferably no more than about 20
centipoise, and even more preferably no more than about 10 centipoise, and
typically of no less than about 2 centipoise, preferably no less than about 5
centipoise, and even more preferably no less than about 7 centipoise,
43
CA 02341113 2001-03-16
although the melt viscosity can be outside of these ranges. Since image
hardness tend to drop with lower viscosities, it is preferred that the
viscosity be as low as possible while still retaining the desired degree of
image hardness.
Hardness is a property of solids and plastics that is defined by
their solidity and firmness as measured by their resistance to indentation by
an indenter of fixed shape and size under a static load. The hardness of
images can be measured with a Digital-Pencil style Durometer, Model 211 B-
00 PTC, obtained from Pacific Transducer Corporation, using ASTM Standard
specifications D2240 for resistance to penetration with a conical (30 degrees
included angle) indenter and applying a 1 kilogram load. The hardness
range for materials as measured with this instrument is from about 1 to
about 100, the latter being the highest measurable value. It is believed that
the images generated with the inks of the present invention, after cooling to
ambient temperature (typically from about 20 to about 25°C, although
ambient temperature can be outside of this range) will exhibit hardness
values of at least about 60 or more, with no necessary upper limit (although
practical upper limits may be around 90).
The inks of the present invention typically undergo, upon
freezing on the print substrate, a change from a liquid state to a solid state
in a period of less than about 100 milliseconds, preferably less than about 50
milliseconds, and more preferably less than about 10 milliseconds, although
the time can be outside of these ranges. There is no necessary lower limit
on this period of time for the inks; it is believed that practically
achievable
lower limits are around 5 milliseconds, although, if practically achievable,
lower periods of time are acceptable.
44
CA 02341113 2001-03-16
The inks of the present invention typically exhibit acoustic-loss
values of no more than about 100 decibels per millimeter, preferably no
more than about 60 decibels per millimeter, and more preferably no more
than about 40 decibels per millimeter, although the acoustic-loss value can
be outside of these ranges. There is no necessary lower limit on acoustic-
loss value for the inks; it is believed that practically achievable lower
limits
are around 10 decibels per millimeter, although, if practically achievable,
lower acoustic-loss values are acceptable. Acoustic-loss can be measured by
placing a sample of the material to be measured between two transducers
with the temperature set at about 150°C. The samples are allowed to
equilibrate at 150°C for five minutes. The two transducers are then
brought
together to maximize the acoustic signal. The amplitude and the position of
the signals are recorded. The two transducers are then separated by a
distance varying from about 25.4 microns to about 125.4 microns, recording
each time the amplitude and the position of the signal. Preferably, each
measurement is performed three times, and three samples of the same
material are measured. The attenuation decibels per millimeter is then
calculated by ratioing the amplitude values obtained at different separation
distances.
The inks of the present invention typically exhibit a
conductivity of no less than about 2 log(picomho/cm), preferably no less
than about 6 log(picomho/cm), more preferably no less than about 6.5
log(picomho/cm), and even more preferably no less than about 7
log(picomho/cm), although the conductivity can be outside of these ranges.
While there is no upper limit on conductivity, typical conductivity values
generally do not exceed about 9 log(picomho/cm). Conductivity can be
measured under melt conditions (typically at about 150°C) by placing an
CA 02341113 2001-03-16
aluminum electrode in the molten ink and reading the resistivity output on a
GenRad 1689 precision RLC Digibridge at a frequency of 1 kiloHertz). The
conductivity of the material is measured in terms of the reciprocal of
resistivity, which is the capacity for electrical resistance.
The ink compositions of the present invention can be prepared
by any desired or suitable method. For example, the ink ingredients can be
mixed together, followed by heating, typically to a temperature of from
about 100 to about 140°C, although the temperature can be outside of
this
range, and stirring until a homogeneous ink composition is obtained,
followed by cooling the ink to ambient temperature (typically from about 20
to about 25°C). The inks of the present invention are solid at ambient
temperature.
The present invention is also directed to a process which
entails incorporating an ink of the present invention into an ink jet printing
apparatus, melting the ink, and causing droplets of the melted ink to be
ejected in an imagewise pattern onto a recording sheet. In one preferred
embodiment, the printing apparatus employs an acoustic ink jet process,
wherein droplets of the ink are caused to be ejected in imagewise pattern
by acoustic beams. In a particularly preferred embodiment, the printing
apparatus employs an acoustic ink jet printing process wherein droplets of
the ink are formed by acoustic beams without imparting a substantial
velocity component toward the print medium, using a droplet forming force
that is sufficient only to form the ink droplets, and the printing process
further comprises generating an electric field to exert an electrical force
different from the droplet forming force on the ink droplets to move the ink
droplets toward the print medium, and controlling the electrical force
exerted on the formed complete ink droplets by the electric field.
46
CA 02341113 2001-03-16
Any suitable substrate or recording sheet can be employed,
including plain papers such as Xerox~ 4024 papers, Xerox~ Image Series
papers, Courtland 4024 DP paper, ruled notebook paper, bond paper, silica
coated papers such as Sharp Company silica coated paper, JuJo paper, and
the like, transparency materials, fabrics, textile products, plastics,
polymeric films, inorganic substrates such as metals and wood, and the like.
In a preferred embodiment, the process entails printing onto a porous or ink
absorbent substrate, such as plain paper.
Specific embodiments of the invention will now be described in
detail. These examples are intended to be illustrative, and the invention is
not limited to the materials, conditions, or process parameters set forth in
these embodiments. All parts and percentages are by weight unless
otherwise indicated.
SYNTHESIS I
Synthesis of C,$-C,6 Carbamate Vehicle
A carbamate vehicle of the formula
O
H3CCH2C)~ ~
I
H
was prepared as follows. In a 500 milliliter Erlenmeyer flask with a
magnetic stirrer, 82 grams of 1-hexadecanol and 0.1 gram of 1,4-
diazabicyclo(2.2.2)octane (catalyst) were mixed with 200 grams of toluene
and the resultant mixture was heated to 80°C. To this heated solution,
100
grams of octadecyl isocyanate was slowly added. The mixture was heated
47
CA 02341113 2001-03-16
for 3 hours at 80°C, after which the mixture was allowed to cool to
room
temperature. The product precipitated out of solution, and was filtered
and recrystallized from isopropyl alcohol to yield the white solid product
with a melting point of 83°C.
SYNTHESIS II
Synthesis of C~$-C4 Urea Vehicle
A urea vehicle of the formula
O
H3CCH2C)pN~
I I
H H
was prepared as follows. In a 500 milliliter Erlenmeyer flask with a
magnetic stirrer, 39 grams of n-butyl amine were mixed with 200 grams of
toluene and the resultant mixture was heated to 80°C. To this heated
solution, 150 grams of octadecyl isocyanate was slowly added. The mixture
was heated for 3 hours at 80°C, after which the mixture was allowed to
cool
to room temperature. The product precipitated out of solution, and was
filtered and recrystallized from isopropyl alcohol to yield the white solid
product with a melting point of 98°C.
SYNTHESIS III
Synthesis of C~8-C$ Urea Vehicle
A urea vehicle of the formula
48
' CA 02341113 2001-03-16
I
H3CCH2C)~ yN~yN
I I
H H
was prepared as follows. In a 500 milliliter Erlenmeyer flask with a
magnetic stirrer, 36.7 gams of octyl amine were mixed with 200 grams of
toluene and the resultant mixture was heated to 80°C. To this heated
solution, 80 grams of octadecyl isocyanate was slowly added. The mixture
was heated for 3 hours at 80°C, after which the mixture was allowed to
cool
to room temperature. The product precipitated out of solution, and was
filtered and recrystallized from isopropyl alcohol to yield the white solid
product with a melting point of 98°C.
SYNTHESIS IV
Synthesis of Stearylcarbamoyl Alkanoate Vehicles
In a 100 milliliter round bottom flask fitted with a reflux
condensor and nitrogen purge were placed 14.78 grams (0.05 mole) of
octadecylisocyanate, 50 milliliters of toluene, and 10 milligrams of a
catalyst 1,4-diazabicyclo(2.2.2)octane. Stearyl alcohol (13.53 grams; 0.05
mole) was then rapidly added and the mixture heated to reflux.
Precipitation was evident at completion of the alcohol addition. The
reaction mixture was heated at reflux for 5 hours, cooled, and filtered to
secure stearylcarbamoyl stearate as a white solid melting at 85°C in 85
percent yield. Other stearylcarbamates were prepared in an analogous
fashion by varying the alcohol component of the reaction mixture as shown:
Carbamate Alcohol mp (°C)
Stearylcarbamoyl octoate 1-octanol 66
49
' CA 02341113 2001-03-16
Stearylcarbamoyl dodecanoate 1-dodecanol 72
Stearylcarbamoyl hexadecanoate1-hexadecanol 83
INK SAMPLE PREPARATION AND TESTING
All ink samples were prepared by adding to an aluminum dish
the most viscous compounds first, followed by the less viscous ones (other
than the dye). The aluminum dish was then placed on a hot plate set at
130°C. The sample was covered by a glass slice and heated for about an
hour to melt all of the components. A magnetic stirrer was used at the end
of this cycle to mix the melted sample. A weight was used to keep the dish
stable. The appropriate amount of dye was then added to the sample. The
covered sample was stirred for 1.5 hour and then poured into a brass mold.
The sample was left to stand overnight before evaluation was done.
HARDNESS TEST
A PTC Durometer stand Model 476 211 B-00 was used to
determine the hardness of the samples.
SMEAR TEST
A draw-down of each of the samples was made on XeroxO
Color Xpressions0 paper using a #5 rod (Consler Scientific Design, Inc.) to
obtain a coated film about 12 microns thick. The smear was determined 18
to 24 hours later as follows: The coating was rubbed with a Pink PearlO 100
eraser (Dixon) for 1 rub, 5 rubs, and 10 rubs at three different places along
the draw-down coating. The optical density of the original drawdown, the
smeared area, and the paper background was determined with an X-Rite
Model 428 Density Meter. The smear percent was calculated by taking the
' ° CA 02341113 2001-03-16
ratio of the optical density of the smeared area over the optical density of
the drawdown, both corrected for paper background for each of the
smeared areas.
HAZE TEST
The haze was determined with a Haze-Bard plus-Byk Gardner-
Folio Co. using recommended testing conditions. The samples tested were
prepared by the method described for the smear test except that a MylarO
film was used instead of paper.
CREASE TEST
The crease was determined by the method developed for
xerographic print evaluation. More specifically, crease values were
measured on solid area ink sample images on paper by (a) folding inwards the
printed area of the image, (b) passing over the folded image a standard
TEFLON~ coated copper roll 2 inches in width, 3 inches in outer diameter,
2.25 inches in inner diameter, and weighing 860 grams, (c) unfolding the
paper and wiping the loose ink from the creased imaged surface with a cotton
swab, and (d) measuring the average width of the ink free creased area with
an image analyzer.
CYA11D1 C 1
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.4 gram of VERSAMIDO 963
(adhesive; amine terminated polyamide copolymer; obtained from Henkel),
1.12 grams of FORALO F-105 (tackifier, obtained from Hercules), 1.75 grams
of UNION CAMPO UC-235 (clarifier, obtained from Union Camp), and 6.18
51
' ' CA 02341113 2001-03-16
grams of KEMAMIDE~ S-180 (ink vehicle; obtained from Witco). The mixture
was heated to 130°C for one hour until all of the components were
melted.
While stirring with a magnetic stirrer, 0.55 gram of Duasyn Black A-RG VP280
black dye (obtained from Clariant) was added to the molten mixture. The
covered sample was further heated and stirred for an hour and a half. It
was then poured in a brass mold of 35 millimeters in diameter and 6.3
millimeters in thickness. The hardness, haze, crease, and smear resistance
after 1, 5, and 10 rubs for this ink were as follows:
hardness: 75.3
haze: 27.6
crease: 11
smear resistance after 1 rub: 0.93
smear resistance after 5 rubs: 3.06
smear resistance after 10 rubs: 3.70
EXAMPLE II
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.5 gram of VERSAMIDO 757
(adhesive; amine terminated polyamide copolymer; obtained from Henkel),
1.10 grams of FORALO F-105 (tackifier, obtained from Hercules), 1.63 grams
of UNION CAMPO UC-235 (clarifier, obtained from Union Camp), and 6.21
grams of KEMAMIDEO S-180 (ink vehicle; obtained from Witco). The mixture
was heated to 130°C for one hour until alt of the components were
melted.
While stirring with a magnetic stirrer, 0.56 gram of Duasyn Black A-RG VP280
black dye (obtained from Clariant) was added to the molten mixture. The
covered sample was further heated and stirred for an hour and a half. ft
was then poured in a brass mold of 35 millimeters in diameter and 6.3
52
' ' CA 02341113 2001-03-16
millimeters in thickness. The hardness, haze, crease, and smear resistance
after 1, 5, and 10 rubs for this ink were as follows:
hardness: 74.6
haze: 36.3
crease: 20
smear resistance after 1 rub: 0.96
smear resistance after 5 rubs: 3.85
smear resistance after 10 rubs: 6.38
EXAMPLE III
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.25 gram of VERSAMIDO 963
(adhesive; amine terminated polyamide copolymer; obtained from Henkel),
0.25 gram of VERSAMIDO 757 (adhesive; amine terminated polyamide
copolymer; obtained from Henkel), 1.10 grams of FORALO F-105 (tackifier,
obtained from Hercules), 1.63 gram of UNION CAMPO UC-235 (clarifier,
obtained from Union Camp), and 6.21 grams of KEMAMIDEO S-180 (ink
vehicle; obtained from Witco). The mixture was heated to 130°C for one
hour until all of the components were melted. While stirring with a
magnetic stirrer, 0.56 gram of Duasyn Black A-RG VP280 black dye (obtained
from Clariant) was added to the molten mixture. The covered sample was
further heated and stirred for an hour and a half. It was then poured in a
brass mold of 35 millimeters in diameter and 6.3 millimeters in thickness.
The hardness, haze, crease, and smear resistance after 1, 5, and 10 rubs for
this ink were as follows:
hardness: 75.3
haze: 60.7
53
' CA 02341113 2001-03-16
crease: 20
smear resistance after 1 rub: 2.44
smear resistance after 5 rubs: 3.60
smear resistance after 10 rubs: 7.69
EXAMPLE IV
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.25 gram of VERSAMIDO 963
(adhesive; amine terminated polyamide copolymer; obtained from Henkel),
0.25 gram of VERSAMIDO 744 (adhesive; amine terminated polyamide
copolymer; obtained from Henkel), 1.10 grams of FORALO F-105 (tackifier,
obtained from Hercules), 1.63 gram of UNION CAMPO UC-235 (clarifier,
obtained from Union Camp), and 6.21 grams of KEMAMIDEO S-180 (ink
vehicle; obtained from Witco). The mixture was heated to 130°C for one
hour until all of the components were melted. While stirring with a
magnetic stirrer, 0.56 gram of Duasyn Black A-RG VP280 black dye (obtained
from Clariant) was added to the molten mixture. The covered sample was
further heated and stirred for an hour and a half. It was then poured in a
brass mold of 35 millimeters in diameter and 6.3 millimeters in thickness.
The hardness, haze, crease, and smear resistance after 1, 5, and 10 rubs for
this ink were as follows:
hardness: 72.2
haze: 31.2
crease: 17
smear resistance after 1 rub: 0.44
smear resistance after 5 rubs: 3.15
smear resistance after 10 rubs: 5.02
54
" CA 02341113 2001-03-16
rveum r t7
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of stearic acid, 4.62
grams of EP700 (ink vehicle; polyethylene wax; obtained from Baker Hughes,
Petrolite), and 3.08 grams of VYBARO 103 (V-103) (ink vehicle; polyethylene
wax; obtained from Baker Hughes, Petrolite). The mixture was heated to
130°C for one hour until all of the components were melted. While
stirring
with a magnetic stirrer, 0.30 gram of Ceres Blue N dye (obtained from Bayer
Co. ) was added to the molten mixture. The covered sample was further
heated and stirred for an hour and a half. It was then poured in a brass
mold of 35 millimeters in diameter and 6.3 millimeters in thickness. The
hardness, haze, and smear resistance after 1, 5, and 10 rubs for this ink
were as follows:
hardness: 70.4
haze: 53.3
smear resistance after 1 rub: 0.78
smear resistance after 5 rubs: 5.43
smear resistance after 10 rubs: 11.5
EXAMPLE VI
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of octadecylamine, 4.62
grams of EP700 (ink vehicle; polyethylene wax; obtained from Baker Hughes,
Petrolite), and 3.08 grams of VYBARO 103 (V-103) (ink vehicle; polyethylene
wax; obtained from Baker Hughes, Petrolite). The mixture was heated to
' " CA 02341113 2001-03-16
130°C for one hour until all of the components were melted. While
stirring
with a magnetic stirrer, 0.30 gram of Ceres Blue N dye (obtained from Bayer
Co.) was added to the molten mixture. The covered sample was further
heated and stirred for an hour and a half. It was then poured in a brass
mold of 35 millimeters in diameter and 6.3 millimeters in thickness. The
hardness, haze, and smear resistance after 1, 5, and 10 rubs for this ink
were as follows:
hardness: 68.2
haze: 99.7
smear resistance after 1 rub: 5.56
smear resistance after 5 rubs: 6.42
smear resistance after 10 rubs: 9.57
EXAMPLE VII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 1.0 gram of stearic acid, 1.0 gram
of octadecylamine, 4.62 grams of EP700 (ink vehicle; polyethylene wax;
obtained from Baker Hughes, Petrolite), and 3.08 grams of VYBARO 103 (V-
103) (ink vehicle; polyethylene wax; obtained from Baker Hughes,
Petrolite). The mixture was heated to 130°C for one hour until all
of the
components were melted. While stirring with a magnetic stirrer, 0.30 gram
of Ceres Blue N dye (obtained from Bayer Co.) was added to the molten
mixture. The covered sample was further heated and stirred for an hour
and a half. It was then poured in a brass mold of 35 millimeters in diameter
and 6.3 millimeters in thickness. The hardness, haze, and smear resistance
after 1, 5, and 10 rubs for this ink were as follows:
hardness: 69.8
56
' CA 02341113 2001-03-16
haze: 36.8
smear resistance after 1 rub: 5.22
smear resistance after 5 rubs: 10.66
smear resistance after 10 rubs: 13.33
As the data indicate, haze is substantially reduced when the octadecylamine
and stearic acid are used in combination, compared to the inks containing
only stearic acid (Example V) and only octadecylamine (Example VI).
EXAMPLE VIII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of the C~$-C~6 ink vehicle
prepared in Synthesis I, 4.62 grams of EP700 (ink vehicle; polyethylene wax;
obtained from Baker Hughes, Petrolite), and 3.08 grams of VYBARO 103 (V-
103) (ink vehicle; polyethylene wax; obtained from Baker Hughes,
Petrolite). The mixture was heated to 130°C for one hour until all
of the
components were melted. While stirring with a magnetic stirrer, 0.30 gram
of Ceres Blue N dye (obtained from Bayer Co. ) was added to the molten
mixture. The covered sample was further heated and stirred for an hour
and a half. It was then poured in a brass mold of 35 millimeters in diameter
and 6.3 millimeters in thickness. The hardness, haze, and smear resistance
after 1, 5, and 10 rubs for this ink were as follows:
hardness: 71.5
haze:43.0
smear resistance after 1 rub: 5.3
smear resistance after 5 rubs: 12.3
smear resistance after 10 rubs: 13.7
57
' CA 02341113 2001-03-16
EXAMPLE IX
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 1.0 gram of the C~8-C~6 ink vehicle
prepared in Synthesis I, 1.0 gram of stearic acid, 4.62 grams of EP700 (ink
vehicle; polyethylene wax; obtained from Baker Hughes, Petrolite), and 3.08
grams of VYBARO 103 (V-103) (ink vehicle; polyethylene wax; obtained from
Baker Hughes, Petrolite). The mixture was heated to 130°C for one
hour
until all of the components were melted. While stirring with a magnetic
stirrer, 0.30 gram of Ceres Blue N dye (obtained from Bayer Co.) was added
to the molten mixture. The covered sample was further heated and stirred
for an hour and a half. It was then poured in a brass mold of 35 millimeters
in diameter and 6.3 millimeters in thickness. The hardness, haze, and
smear resistance after 1, 5, and 10 rubs for this ink were as follows:
hardness: 71.8
haze: 52.0
smear resistance after 1 rub: 6.8
smear resistance after 5 rubs: 11.5
smear resistance after 10 rubs: 14.4
EXAMPLE X
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of octadecylamine, 2.0
grams of stearic acid, 3.45 grams of EP700 (ink vehicle; polyethylene wax;
obtained from Baker Hughes, Petrolite), and 2.25 grams of VYBARO 103 (V-
103) (ink vehicle; polyethylene wax; obtained from Baker Hughes,
58
' ' CA 02341113 2001-03-16
Petrolite). The mixture was heated to 130°C for one hour until all
of the
components were melted. White stirring with a magnetic stirrer, 0.30 gram
of Duasyn Black A-RG VP280 (obtained from Clariant) was added to the
molten mixture. The covered sample was further heated and stirred for an
hour and a half. It was then poured in a brass mold of 35 millimeters in
diameter and 6.3 millimeters in thickness. The hardness, haze, and smear
resistance after 1, 5, and 10 rubs for this ink were as follows:
hardness: 69.6
haze: 59.0
smear resistance after 1 rub: 3.1
smear resistance after 5 rubs: 4.8
smear resistance after 10 rubs: 6.3
rvAUm r V1
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.5 grams of octadecylamine, 2.5
grams of stearic acid, 2.70 grams of EP700 (ink vehicle; polyethylene wax;
obtained from Baker Hughes, Petrolite), and 1.80 grams of VYBARO 103 (V-
103) (ink vehicle; polyethylene wax; obtained from Baker Hughes,
Petrolite). The mixture was heated to 130°C for one hour until all
of the
components were melted. While stirring with a magnetic stirrer, 0.30 gram
of Duasyn Black A-RG VP280 (obtained from Clariant) was added to the
molten mixture. The covered sample was further heated and stirred for an
hour and a half. It was then poured in a brass mold of 35 millimeters in
diameter and 6.3 millimeters in thickness. The hardness, haze, and smear
resistance after 1, 5, and 10 rubs for this ink were as follows:
hardness: 69.0
59
' CA 02341113 2001-03-16
haze: 57.2
smear resistance after 1 rub: 2.4
smear resistance after 5 rubs: 6.1
smear resistance after 10 rubs: 11.2
EXAMPLE XII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of stearic acid and 7.5
grams of EPOLENEO N-14 (ink vehicle; polyethylene, molecular weight about
4,000; obtained from Eastman). The mixture was heated to 130°C for one
hour until all of the components were melted. While stirring with a
magnetic stirrer, 0.50 gram of Duasyn Black A-RG VP280 (obtained from
Clariant) was added to the molten mixture. The covered sample was further
heated and stirred for an hour and a half. It was then poured in a brass
mold of 35 millimeters in diameter and 6.3 millimeters in thickness. The
hardness, haze, and smear resistance after 1, 5, and 10 rubs for this ink
were as follows:
hardness: 69.3
haze: 59.6
smear resistance after 1 rub: 2.9
smear resistance after 5 rubs: 32.6
smear resistance after 10 rubs: 32.6
EXAMPLE XIII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 2.0 grams of octadecylamine and
' ' CA 02341113 2001-03-16
7.5 grams of EPOLENEO N-14 (ink vehicle; polyethylene, molecular weight
about 4,000; obtained from Eastman). The mixture was heated to 130°C
for
one hour until all of the components were melted. While stirring with a
magnetic stirrer, 0.50 gram of Duasyn Black A-RG VP280 (obtained from
Clariant) was added to the molten mixture. The covered sample was further
heated and stirred for an hour and a half. It was then poured in a brass
mold of 35 millimeters in diameter and 6.3 millimeters in thickness. The
hardness, haze, and smear resistance after 1, 5, and 10 rubs for this ink
were as follows:
hardness: 66.9
haze: 98.0
smear resistance after 1 rub: 0.81
smear resistance after 5 rubs: 17.96
smear resistance after 10 rubs: 32.3
EXAMPLE XIV
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 1.0 gram of stearic acid, 1.0 gram
of octadecylamine and 7.5 grams of EPOLENEO N-14 (ink vehicle;
polyethylene, molecular weight about 4,000; obtained from Eastman). The
mixture was heated to 130°C for one hour until all of the components
were
melted. While stirring with a magnetic stirrer, 0.50 gram of Duasyn Black A-
RG VP280 (obtained from Clariant) was added to the molten mixture. The
covered sample was further heated and stirred for an hour and a half. It
was then poured in a brass mold of 35 millimeters in diameter and 6.3
millimeters in thickness. The hardness, haze, and smear resistance after 1,
5, and 10 rubs for this ink were as follows:
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' CA 02341113 2001-03-16
hardness: 71.4
haze: 44.3
smear resistance after 1 rub: 2.0
smear resistance after 5 rubs: 8.6
smear resistance after 10 rubs: 14.4
As the data indicate, haze is substantially reduced and smear
resistance is substantially improved when the octadecylamine and stearic
acid are used in combination, compared to the inks containing only stearic
acid (Example XLI) and only octadecylamine (Example XIII).
EXAMPLE XV
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 1.5 grams of stearic acid and 8.0
grams of the C~$-C~6 ink vehicle prepared in Synthesis I. The mixture was
heated to 130°C for one hour until all of the components were melted.
While stirring with a magnetic stirrer, 0.50 gram of Duasyn Black A-RG VP280
(obtained from Clariant) was added to the molten mixture. The covered
sample was further heated and stirred for an hour and a half. It was then
poured in a brass mold of 35 millimeters in diameter and 6.3 millimeters in
thickness. The hardness, haze, and smear resistance after 1, 5, and 10 rubs
for this ink were as follows:
hardness: 74.0
haze: 63.7
smear resistance after 1 rub: 2.7
smear resistance after 5 rubs: 12.5
smear resistance after 10 rubs: 16.9
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CA 02341113 2001-03-16
EXAMPLE XVI
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 1.5 grams of octadecylamine and
8.0 grams of the C,$-C~6 ink vehicle prepared in Synthesis I. The mixture
was heated to 130°C for one hour until all of the components were
melted.
While stirring with a magnetic stirrer, 0.50 gram of Duasyn Black A-RG VP280
(obtained from Clariant) was added to the molten mixture. The covered
sample was further heated and stirred for an hour and a half. It was then
poured in a brass mold of 35 millimeters in diameter and 6.3 millimeters in
thickness. The hardness, haze, and smear resistance after 1, 5, and 10 rubs
for this ink were as follows:
hardness: 65.7
haze: 90.7
smear resistance after 1 rub: 1.9
smear resistance after 5 rubs: 14.4
smear resistance after 10 rubs: 17.8
EXAMPLE XVII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.75 gram of octadecylamine, 0.75
gram of stearic acid, and 8.0 grams of the C~$-C~6 ink vehicle prepared in
Synthesis I. The mixture was heated to 130°C for one hour until all
of the
components were melted. While stirring with a magnetic stirrer, 0.50 gram
of Duasyn Black A-RG VP280 (obtained from Clariant) was added to the
molten mixture. The covered sample was further heated and stirred for an
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' CA 02341113 2001-03-16
hour and a half. It was then poured in a brass mold of 35 millimeters in
diameter and 6.3 millimeters in thickness. The hardness, haze, and smear
resistance after 1, 5, and 10 rubs for this ink were as follows:
hardness: 72.6
haze: 53.5
smear resistance after 1 rub: 3.8
smear resistance after 5 rubs: 9.6
smear resistance after 10 rubs: 12.5
As the data indicate, haze is substantially reduced and smear
resistance is substantially improved when the octadecylamine and stearic
acid are used in combination, compared to the inks containing only stearic
acid (Example XV) and only octadecylamine (Example XVI).
EXAMPLE XVIII
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.5 gram of stearic acid, 0.5 gram
of the C~$-C$ urea ink vehicle prepared in Synthesis III, 5.97 grams of
KEMAMIDEO S-180 (ink vehicle; obtained from Witco), 1.016 grams of
FORALO F-105 (tackifier, obtained from Hercules), 1.335 grams of
X37-523-235 (clarifier, obtained from Union Camp), and 0.126 gram of
VERSAMIDO 963 (adhesive; amine terminated polyamide copolymer;
obtained from Henkel). The mixture was heated to 130°C for one hour
until
all of the components were melted. While stirring with a magnetic stirrer,
0.554 gram of Duasyn Black A-RG VP280 (obtained from Clariant) was added
to the molten mixture. The covered sample was further heated and stirred
for an hour and a half. It was then poured in a brass mold of 35 millimeters
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in diameter and 6.3 millimeters in thickness. The haze and smear resistance
after 1 rub for this ink were as follows:
haze: 35.2
smear resistance after 1 rub: 5.5
EXAMPLE XIX
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.5 gram of stearic acid, 0.5 gram
of EPOLENEO N-14 (ink vehicle; polyethylene, molecular weight about
4,000; obtained from Eastman), 5.97 grams of KEMAMIDE~ S-180 (ink
vehicle; obtained from Witco), 1.016 grams of FORAL~ F-105 (tackifier,
obtained from Hercules), 1.335 grams of X37-523-235 (clarifier, obtained
from Union Camp), and 0.126 gram of VERSAMID~ 963 (adhesive; amine
terminated polyamide copolymer; obtained from Henkel). The mixture was
heated to 130°C for one hour until alt of the components were melted.
While stirring with a magnetic stirrer, 0.554 gram of Duasyn Black A-RG
VP280 (obtained from Clariant) was added to the molten mixture. The
covered sample was further heated and stirred for an hour and a half. It
was then poured in a brass mold of 35 millimeters in diameter and 6.3
millimeters in thickness. The haze and smear resistance after 1 rub for this
ink were as follows:
haze: 57.1
smear resistance after 1 rub: 5.3
" ' CA 02341113 2001-03-16
EXAMPLE XX
A 10 gram sample of ink was prepared by adding to an
aluminum dish (diameter 5 centimeters) 0.5 gram of stearic acid, 0.5 gram
of the C~$-C4 urea ink vehicle prepared in Synthesis II, 5.97 grams of
KEMAMIDEO S-180 (ink vehicle; obtained from Witco), 1.016 grams of
FORALO F-105 (tackifier, obtained from Hercules), 1.335 grams of
X37-523-235 (clarifier, obtained from Union Camp), and 0.126 gram of
VERSAMID~ 963 (adhesive; amine terminated polyamide copolymer;
obtained from Henkel). The mixture was heated to 130°C for one hour
until
all of the components were melted. While stirring with a magnetic stirrer,
0.554 gram of Duasyn Black A-RG VP280 (obtained from Clariant) was added
to the molten mixture. The covered sample was further heated and stirred
for an hour and a half. It was then poured in a brass mold of 35 millimeters
in diameter and 6.3 millimeters in thickness. The haze and smear resistance
after 1, 5, and 10 rubs for this ink were as follows:
haze: 54.7
smear resistance after 1 rub: 3.1
smear resistance after 5 rubs: 3.8
smear resistance after 10 rubs: 5.8
Other embodiments and modifications of the present invention
may occur to those of ordinary skill in the art subsequent to a review of the
information presented herein; these embodiments and modifications, as
well as equivalents thereof, are also included within the scope of this
invention.
66
