U.S. patent application number 09/078190 was filed with the patent office on 2003-09-04 for isocyanate-derived materials for use in phase change ink jet inks.
Invention is credited to BANNING, JEFFREY H., BUI, LOC V., KING, CLIFFORD R., TITTERINGTON, DONALD R..
Application Number | 20030164116 09/078190 |
Document ID | / |
Family ID | 24700128 |
Filed Date | 2003-09-04 |
United States Patent
Application |
20030164116 |
Kind Code |
A1 |
KING, CLIFFORD R. ; et
al. |
September 4, 2003 |
ISOCYANATE-DERIVED MATERIALS FOR USE IN PHASE CHANGE INK JET
INKS
Abstract
Resins and waxes made by reacting selected nucleophiles,
including alcohols and/or amines, with an isocyanate are disclosed.
The order of addition of the isocyanate and the different
nucleophiles can tailor the distribution of di-urethane, mixed
urethane/urea, and/or di-urea molecules in the final resin product.
The isocyanate-derived resin and wax materials are useful as
ingredients as phase change ink carrier compositions used to make
phase change ink jet inks.
Inventors: |
KING, CLIFFORD R.; (SALEM,
OR) ; BUI, LOC V.; (VALENCIA, CA) ; BANNING,
JEFFREY H.; (HILLSBORO, OR) ; TITTERINGTON, DONALD
R.; (TUALATIN, OR) |
Correspondence
Address: |
WELLS ST. JOHN ROBERTS GREGORY & MATKIN P.S.
601 W. FIRST AVENUE
SUITE 1300
SPOKANE
WA
99201-3828
US
|
Family ID: |
24700128 |
Appl. No.: |
09/078190 |
Filed: |
May 13, 1998 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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09078190 |
May 13, 1998 |
|
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|
08672816 |
Jun 28, 1996 |
|
|
|
5782966 |
|
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Current U.S.
Class: |
106/250 |
Current CPC
Class: |
C08G 18/2815 20130101;
C09D 11/34 20130101; C08G 18/2835 20130101; C08G 18/71 20130101;
C08G 18/283 20130101; C08G 18/2825 20130101; C09B 69/10 20130101;
C08G 18/2865 20130101; C08G 18/285 20130101; C08G 18/38
20130101 |
Class at
Publication: |
106/250 |
International
Class: |
C09D 004/00 |
Claims
What is claimed is:
1. An isocyanate-derived material comprising the solid reaction
product of the following reactants: (a) at least one
non-ethylenically unsaturated monohydric alcohol; (b) an
isocyanate; and (c) at least one amine.
2. The isocyanate-derived material of claim 1 wherein the reaction
further comprises adding a catalyst.
3. The isocyanate-derived material of claim 1 wherein the reaction
further comprises mixing and heating the alcohol and the isocyanate
in an inert atmosphere.
4. The isocyanate-derived resin of claim 1 wherein the alcohol is
selected from the group of monohydric alcohols consisting of an
aliphatic alcohol, an aromatic alcohol, an aliphatic/aromatic
alcohol, a fused ring alcohol, and mixtures thereof.
5. The isocyanate-derived material of claim 1 wherein the
isocyanate is selected from the group consisting of a
monoisocyanate, a diisocyanate, a triisocyanate, a copolymer of a
diisocyanate, and a copolymer of a triisocyanate.
6. The isocyanate-derived material of claim 1 wherein the monoamine
is selected from the group of monoamines consisting of an aliphatic
monoamine, an aromatic monoamine, an aliphatic/aromatic monoamine,
a fused ring system monoamine, and a hydroxyl/amino containing
compound.
7. The isocyanate-derived material of claim 4 wherein the alcohol
is selected from the group consisting of hydroabietyl alcohol,
octylphenol ethoxylate and octadecyl alcohol.
8. The isocyanate-derived material of claim 5 wherein the
isocyanate is isophorone diisocyanate.
9. The isocyanate-derived material of claim 6 wherein the amine is
octadecyl amine.
10. The isocyanate-derived material of claim 1 wherein the resinous
material is an oligomer or a monomer.
11. The isocyanate-derived material of claim 1 wherein the
isocyanate-derived material is a urethane/urea mixture.
12. The isocyanate-derived material of claim 3 wherein the reaction
further comprises mixing and heating the alcohol and the isocyanate
in the presence of a catalyst.
13. The isocyanate-derived material of claim 3 wherein the reaction
further comprises using a nitrogen atmosphere as the inert
atmosphere.
14. The isocyanate-derived material of claim 2 wherein the reaction
further comprises adding the catalyst prior to the addition of the
amine.
Description
[0001] This is a continuation-in-part application of U.S. Ser. No.
08/672,816 filed on Jun. 28, 1996.
BACKGROUND OF THE INVENTION
[0002] 1. Field of the Invention
[0003] The present invention relates to resins or waxes made by
reacting isocyanates with selected nucleophiles such as alcohols
and/or amines. The nucleophiles can be used singly or in
combinations to achieve certain desirable properties in the resins.
The present invention also relates to phase change ink
compositions, both generally and in specific compositions,
containing such resins and/or waxes. More particularly, the present
invention employs the use of an isocyanate-derived urethane/urea
resin, which is the condensation reaction product of at least one
alcohol precursor, an isocyanate precursor and at least one amine
precursor. The present invention also covers a phase change ink
carrier composition and the ink formed from the isocyanate-derived
resin, a tackifier resin, a mono-amide and a colorant. Still
further, the present invention relates to the process of using such
phase change ink compositions containing such resins and/or waxes
in a printing device.
[0004] 2. Description of the Relevant Art
[0005] In general, phase change inks (sometimes referred to as "hot
melt inks") are in the solid phase at ambient temperature, but
exist in the liquid phase at the elevated operating temperature of
an ink jet printing device. At the jet operating temperature,
droplets of liquid ink are ejected from the printing device and,
when the ink droplets contact the surface of the printing media,
they quickly solidify to form a predetermined pattern of solidified
ink drops. Phase change inks have also been investigated for use in
other printing technologies such as gravure printing as referenced
in U.S. Pat. No. 5,496,879 and German patent publications DE
4205636AL and DE 4205713AL assigned to Siegwerk Farbenfabrik
Keller, Dr. Rung and Co.
[0006] Phase change inks for color printing generally comprise a
phase change ink carrier composition which is combined with a phase
change ink compatible colorant. Preferably, a colored phase change
ink will be formed by combining the above-described ink carrier
composition with compatible subtractive primary colorants. The
subtractive primary colored phase change inks of this invention can
comprise four component dyes, namely, cyan, magenta, yellow and
black. U.S. Pat. Nos. 4,889,506; 4,889,761; and 5,372,852 teach
that the subtractive primary colorants employed typically may
comprise dyes from the classes of Color Index (C.I.) Solvent Dyes,
Disperse Dyes, modified Acid and Direct Dyes, and a limited number
of Basic Dyes. The colorants can also include pigments as
exemplified in U.S. Pat. No. 5,221,335, assigned to Coates
Electrographics LTD. U.S. patent application Ser. No. 08/381,610,
filed Jan. 30, 1995, and assigned to Tektronix, Inc., is directed
to the use of a specific class of polymeric dyes in phase change
ink compositions.
[0007] Phase change inks are desirable for ink jet printers since
they remain in a solid phase at room temperature during shipping,
long-term storage, and the like. Also, the problems associated with
nozzle clogging due to ink evaporation are largely eliminated,
thereby improving the reliability of ink jet printing. Furthermore,
in the above-noted prior art phase change ink jet printers where
the ink droplets are applied directly onto the printing medium the
droplets solidify immediately upon contact with the substrate,
migration of ink along the printing medium is prevented and dot
quality is improved. This is also true of the processes and ink
compositions described herein.
[0008] In addition to the above-referenced U.S. patents, many other
patents describe materials for use in phase change ink jet inks.
Some representative examples include U.S. Pat. Nos. 3,653,932;
4,390,369; 4,484,948; 4,684,956; 4,851,045; 4,889,560; 5,006,170;
and 5,151,120; as well as EP Application Nos. 0187352 and 0206286.
These materials can include paraffins, microcrystalline waxes,
polyethylene waxes, ester waxes, fatty acids and other waxy
materials, fatty amide-containing materials, sulfonamide materials,
resinous materials made from different natural sources (tall oil
rosins and rosin esters are an example) and many synthetic resins,
oligomers, polymers and co-polymers.
[0009] Separately, PCT Patent Application WO 94/14902, which was
published on Jul. 7, 1994 and is assigned to Coates Brothers PLC,
teaches a hot melt ink containing a colorant and, as a vehicle for
the hot melt ink, an oligourethane having a melting point of at
least 65.degree. C. and obtained by reacting an aliphatic or
aromatic diisocyanate with at least a stoichiometric amount of
either: (i) a monohydric alcohol component; or (ii) a monohydric
alcohol component followed by another different monohydric alcohol
component; or (iii) a monohydric alcohol component, followed by a
dihydric alcohol component, followed by a monohydric alcohol
component.
[0010] This PCT patent application defines the monohydric alcohol
component as either a monohydric aliphatic alcohol (e.g. C.sub.1 to
C.sub.22 alcohols), an etherified dihydric aliphatic alcohol (e.g.
propylene glycol methyl ether (PGME), dipropylene glycol methyl
ether (DPGME), ethylene glycol butyl ether (EGBE), diethylene
glycol butyl ether (DPGBE), tripropylene glycol butyl ether (TPGBE)
and propylene glycol phenyl ether (PPL); esterified dihydric
aliphatic alcohol (e.g. the esterifying acid may be an
ethylenically unsaturated acid (such as acrylic acid or methacrylic
acid), thereby introducing ethylenic unsaturation into the
oligourethane and rendering it suitable for eventual further
additional polymerization (curing) after having been applied to a
substrate by hot melt printing), or dihydric polyalkylene glycol.
This PCT Application further defined the dihydric alcohol component
as a dihydric aliphatic alcohol or a dihydric polyalkylene glycol
(e.g. ethylene glycol, polyethylene glycol (PEG 1500),
polypropylene glycol (PPG 750, 1000 and 1500), trimethylene glycol,
dipropylene glycol, methylpropanediol and 1,6-hexanediol).
[0011] Also, PCT Patent Application WO 94/04619, assigned to the
General Electric Company, teaches the use of ionomeric materials in
combination with image forming agents to form a hot melt ink jet
ink. The ionomeric materials can include many different types of
copolymeric or polymeric ionomers, including carboxyl-functional
polyurethanes prepared from a diol or polyol and a hydroxyl acid.
Many other carrier materials and colorants for the image forming
agent of the invention are included in this PCT application.
[0012] U.S. Pat. No. 4,665,146 discloses the use of
monoethylenically unsaturated monomers that are polymerizable
precursors used to produce aqueous coating compositions by reacting
a diisocyanate, a monoamine and a monoalcohol. The reaction product
is reactive and is disclosed as being in a solution.
[0013] There is still a need for new materials for novel and
different applications of phase change inks. There is a also a need
for relatively low viscosity resins, including non-polymeric
resins, and waxes designed for phase change ink jet and other forms
of phase change ink printing. These needs are solved by the present
invention by providing a means to tailor the properties of a resin
or an isocyanate-derived material for specific applications.
BRIEF SUMMARY OF THE INVENTION
[0014] It is an aspect of the present invention that urethane
compounds comprising the reaction product of selected isocyanates
with selected alcohols or mixtures of selected alcohols are
obtained.
[0015] It is another aspect of the present invention that urea
compounds comprising the reaction product of selected isocyanates
with selected amines or mixtures of selected amines are
obtained.
[0016] It is still another aspect of the present invention that
urethane/urea compounds comprising the reaction product of selected
isocyanates with mixtures of selected alcohols and amines are
obtained.
[0017] It is still a further aspect of the present invention that a
reaction product of a selected alcohols or mixtures of selected
alcohols, an isocyanate, and a monoamine is obtained that can be
used in a phase change ink composition.
[0018] It is a feature of the present invention that the reaction
product is an isocyanate-derived material.
[0019] It is another feature of the present invention that the
colorless isocyanate derived material or resin reaction product of
the selected isocyanates with selected alcohols or mixtures of
selected alcohols and/or selected amines or mixtures of selected
amines obviates the need for the use of a separate plasticizer when
the material or resin is employed in an ink formulation because the
resulting ink is sufficiently malleable and ductile on its own.
[0020] It is an advantage of the present invention that the
isocyanate-derived material or resin reaction product can be design
engineered to obtain desired properties for specific printing
platforms and architectures.
[0021] It is another advantage of the present invention that the
isocyanate-derived materials or resins are very pure, being free of
salts and other insoluble contaminants.
[0022] It is still another advantage of the present invention that
the isocyanate-derived materials or resins can be used in
combinations with other phase change ink carrier materials to
obtain ink compositions that display improved yield stress versus
temperature curves over prior art ink compositions.
[0023] It is still another advantage of the present invention that
the isocyanate-derived materials or resins are nonethylenically
unsaturated stable solids.
[0024] It is yet another advantage of the present invention that
the isocyanate-derived materials or resins are transparent.
[0025] It is yet further advantage of the present invention that
the isocyanate-derived materials or resins may be substituted for
one or more components in prior fatty amide containing phase change
inks, such as the tetra-amide, mono-amide, tackifier, or
plasticizer components.
[0026] These and other aspects, features and advantages are
obtained by the use of reaction products of selected isocyanates
with selected alcohols and amines to produce isocyanate-derived
material or resins. These materials are suitable for use in phase
change inks that may be employed in direct or indirect printing
applications.
BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The aspects, features, and advantages of the invention will
become apparent upon consideration of the following detailed
disclosure of the invention; especially when it is taken in
conjunction of the accompanying drawing wherein:
[0028] FIG. 1 is a graphical illustration of the yield stress
versus temperature curve of ink from Example 20 compared to a prior
art phase change ink, wherein the test ink from Example 20 is
represented by small squares and the prior art ink is shown by
small diamonds.
DESCRIPTION OF THE PREFERRED EMBODIMENTS
[0029] The term "nucleophile" in the present specification and
claims is used as defined on page 179 of "Advanced Organic
Chemistry", 3rd Edition by Jerry March, .COPYRGT.1985 by John Wiley
and Sons, to describe a reagent that brings an electron pair to a
reaction to form a new bond. The preferred nucleophiles of this
invention are alcohols or amines, but it is understood that other
nucleophilic functional groups that are capable of reacting with
the isocyanate moiety could also be used in the invention.
[0030] The term "oligomer" in the current specification and claims
is used as defined on page 7 of "Polymer Chemistry--The Basic
Concepts" by Paul Hiemenz, .COPYRGT.1984 by Marcel Dekker, Inc., to
describe a term coined to designate molecules for which n
(representing the number of repeating monomer units) is less than
10.
[0031] The term "isocyanate-derived material or resin" as used in
the present specification and claims is defined as any monomeric,
oligomeric or non-polymeric resinous material derived from the
reaction of mono-, di-, or poly-isocyanates with suitable
nucleophilic molecules.
[0032] The term "isocyanate-derived wax" as used in the present
specification and claims is defined as any crystalline or
semicrystalline waxy material derived from the reaction of a fatty
isocyanate with a suitable nucleophile, or the reaction of a fatty
nucleophile with a suitable isocyanate, or the reaction of a fatty
nucleophile with a fatty isocyanate.
[0033] Any suitable reaction condition for making urethane or urea
compounds by condensing alcohols and/or amines with isocyanates may
be employed in the practice of the present invention. Preferably,
the reaction is carried out at elevated temperatures (e.g. about
60.degree. C. to about 160.degree. C.) in the presence of a
urethane reaction catalyst such as dibutyltindilaurate, bismuth
tris-neodecanoate, cobalt benzoate, lithium acetate, stannous
octoate or triethylamine. The reaction conditions preferably are
conducted in an inert atmosphere, such as argon or nitrogen gas or
other suitable atmosphere, to prevent oxidizing or yellowing the
reaction products and to prevent undesirable side reactions. The
mole ratio of reactants is adjusted so that the isocyanate
functionalities are completely consumed in the reaction with a
slight molar excess of alcohol or amine typically remaining.
Conceptually the reactants can be added together in any order
and/or added to the reaction as physical mixtures. However, in the
preferred embodiments of the invention, reaction conditions and the
order of the addition of reactants are carefully controlled for
several reasons. First, reaction conditions and reactant additions
are chosen to provide a controlled exothermic reaction. Secondly,
when reacting mixtures of alcohols and/or amines with diisocyanates
such as isophorone diisocyanate (IPDI), the order of addition of
the isocyanate and the different nucleophiles to the reaction is
chosen to tailor the distribution of diurethane molecules, and/or
mixed urethane/urea molecules, and/or diurea molecules in the final
resin. When doing this, the different reactivities to isocyanates
of alcohols versus amines are employed, as are the different
reactivities of the two separate isocyanate groups on IPDI. See J.
H. Saunders and K. C. Frisch's "Polyurethanes Part I, Chemistry"
published by Interscience of New York, N.Y. in 1962 and Olin
Chemicals' Luxate.RTM. isophorone diisocyanate technical product
information sheet which provide further explanation of this
chemistry. This control of the reaction conditions and order of
addition of the reactants is done to specifically tailor or
customize the different types of molecular species in the finished
resin so that the resin will:
[0034] (1) have a controlled viscosity that is designed for a
specific application,
[0035] (2) have a controlled glass transition temperature and/or
melting point, and
[0036] (3) have consistent properties from batch to batch.
[0037] The isocyanate-derived materials or resins from these
reactions are generally transparent solids having melting points in
the range of about 20.degree. C. to about 150.degree. C.,
viscosities in the range of about 10 cPs to about 5000 cPs at
150.degree. C. and T.sub.g's of about -30.degree. C. to about
100.degree. C. The isocyanate-derived waxes from these reactions
are generally opaque waxy solids having sharp melting points from
about 50.degree. C. to about 130.degree. C., and viscosities of
about 1 cPs to about 25 cPs at 140.degree. C. The
isocyanate-derived materials or resins and waxes display properties
such that the higher the T.sub.g and the melting point, the higher
is the viscosity. While the structural activity relationships are
not fully understood, it is known that the T.sub.g of the
isocyanate-derived resins is controlled by the proper choice of the
mixture of nucleophiles in the reaction as illustrated in Table 3
below. Varying one or more of the readily available commodity
chemicals used as chemical precursors will permit custom-tailoring
of the properties of the isocyanate-derived resin and wax
materials. The isocyanate-derived materials or resins that are the
reaction product of selected isocyanates with selected alcohols or
mixtures of selected alcohols and selected amines or mixtures of
selected amines are nonethylenically unsaturated stable solids.
[0038] Preferred alcohols to react with difunctional and higher
isocyanates to make the isocyanate-derived materials or waxes and
resins of this invention include any monohydric alcohol. For
instance, the monohydric alcohol could be any aliphatic alcohol
[e.g., a C.sub.1-C.sub.22 or higher linear alcohol, any branched
alcohol or any cyclic aliphatic alcohol such as methanol, ethanol,
(n- and iso)-propanol, (n-, iso-, t-) butanol, (n-, iso-, t-, and
the like) pentanol, (n-, iso-, t-, and the like) hexanol, (n-,
iso-, t-, and the like) octanol, (n-, iso-, t-, and the like)
nonanol, (n- and branched) decanols, (n- and branched) undecanols,
(n- and branched) dodecanols, (n- and branched) hexadecanols, (n-
and branched) octadecanols, 3-cyclohexyl-1-propanol,
2-cyclohexyl-1-ethanol, cyclohexylmethanol, cyclohexanol, 4-methyl
cyclohexanol, 4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the
like]; an aliphatic/aromatic alcohol [e.g., benzyl alcohol, octyl,
nonyl, and dodecylphenol alkoxylates of octyl, nonyl, and
dodecylphenol, and alkoxyphenol]; aromatic alcohols such as phenol,
naphthol, and the like, and their derivatives; fused ring alcohols
(e.g., rosin alcohols, hydroabietyl alcohol, cholesterol, vitamin
E, and the like) and other suitable alcohols (e.g.,
N,N-dimethyl-N-ethanolamine, stearamide-monoethanolamine,
tripropyleneglycol monomethylether, hydroxybutanone, menthol,
isoborneol, terpineol, 12-hydroxy stearyl stearamide, and the
like). It will be obvious to those skilled in the art that small
amounts (on a molar basis) of polyols could also be incorporated
into the reaction mixture to produce oligomeric species in the
resins if so desired. The preferred alcohols are hydroabietyl
alcohol, octylphenol ethoxylate and octadecyl alcohol.
[0039] Preferred amines to react with difunctional and higher
isocyanates to make the isocyanate-derived waxes and resins of this
invention include any monofunctional amine, with the exception of
tertiary amines void of other nucleophilic functional groups (e.g.,
triethylamine). For instance, the monoamine could be any aliphatic
primary or secondary amine (e.g., a C.sub.1-C.sub.22 or higher
linear amine, any branched amine or any cyclic aliphatic amine)
such as methyl amine, ethyl amine, (n- and iso-)propyl amine, (n-,
iso-, and t-) butyl amine, (n-, iso-, t-, and the like) pentyl
amine, (n-, iso-, t-, and the like) hexyl amine, (n-, iso-, t-, and
the like) octyl amine, (n-, iso-, t-, and the like) nonyl amine,
(n- and branched) decyl amine, (n- and branched) undecyl amines,
(n- and branched) dodecyl amines, (n- and branched) hexadecyl
amines, (n- and branched) dodecyl amines, dimethyl amine, diethyl
amine, di(n- and iso-)propyl amines, di(n-, iso-, t-)butyl amine,
di(n-, iso-, t-, and the like)pentyl amine, di(n-, iso-, t-, and
the like)hexyl amine, di(n-, iso-, t-, and the like)cyclohexyl
amine, di(n-, iso-, t-, and the like)heptyl amine, di(n-, iso-, t-,
and the like)octyl amine, di(n-, iso-, t-, and the like)decyl
amine, di(n-, iso-, t-, and the like)dodecyl amine, di(n-, iso-,
t-, and the like)octadecyl amine, cyclohexyl amine,
2,3-dimethyl-1-cyclohexylamine, piperidine, pyrrolidine, and the
like; an aliphatic/aromatic amine (e.g., benzyl amine or analogues
with longer or additional alkyl chains); aromatic amines such as
aniline, anisidine, and the like; fused ring amines such as rosin
amine, dehydroabietyl amine, dihydroabietyl amine, hydroabietyl
amine, and the like; and miscellaneous amines (e.g., adamantyl
amine, isonipecotamide, polyoxyalkylenemonoamines- , such as
M-series Jeffamines available commercially from Huntsman Chemical
Company of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine, and
the like. It will be obvious to those skilled in the art that small
amounts (on a molar basis) of polyamines could also be incorporated
into the reaction mixture to produce oligomeric species in the
resins if so desired. The preferred amine is octadecyl amine.
[0040] Preferred alcohols to react with monofunctional isocyanates
to make the isocyanate-derived waxes and resins of this invention
include any monohydric alcohol. For instance, the monohydric
alcohol could be any aliphatic alcohol [e.g., a C.sub.1-C.sub.22 or
higher linear alcohol, any branched alcohol or any cyclic aliphatic
alcohol such as methanol, ethanol, (n- and iso-)propanol, (n-,
iso-, and t-) butanol, (n-, iso-, t-, and the like) pentanol, (n-,
iso-, t-, and the like) hexanol, (n-, iso-, t-, and the like)
octanol, (n-, iso-, t-, and the like) nonanol, (n- and branched)
decanols, (n- and branched) undecanols, (n- and branched)
dodecanols, (n- and branched) hexadecanols, (n- and branched)
octadecanols, 3-cyclohexyl-1-propanol, 2-cyclohexyl- 1-ethanol,
cyclohexylmethanol, cyclohexanol, 4-methyl cyclohexanol,
4-ethylcyclohexanol, 4-t-butylcyclohexanol, and the like]; an
aliphatic/aromatic alcohol (e.g., benzyl alcohol, octyl, nonyl, and
dodecylphenol alkoxylates or octyl, nonyl, and dodecylphenol,
alkoxyphenol); aromatic alcohols such as phenol, naphthol, and the
like, and their derivatives; fused ring alcohols (e.g., rosin
alcohols, hydroabietyl alcohol, cholesterol, vitamin E, and the
like) and other suitable alcohols (e.g.,
N,N-dimethyl-N-ethanolamine, stearamide-monoethanolamine,
tripropyleneglycol monomethylether, hydroxybutanone, menthol,
isoborneol, terpineol, 12-hydroxy stearyl stearamide, and the
like), as well as multifunctional alcohols such as ethylene glycol,
diethylene glycol, triethylene glycol, dimethylolpropionic acid,
sucrose, polytetramethylene glycol (MW<.about.3000),
polypropylene glycol (MW<.about.3000), polyester polyols
(MW<.about.3000), polyethylene glycol (MW<.about.3000),
pentaerythritol, triethanol amine, glycerin, 1,6-hexanediol,
N-methyl-N,N-diethanol amine, trimethylol propane,
N,N,N',N'-tetrakis(2-hydroxypropyl)ethylenediamine, and the like.
The preferred alcohol is octadecanol.
[0041] Preferred amines to react with monofunctional isocyanates to
make the isocyanate-derived waxes and materials or resins of this
invention include any monofunctional amine, with the exception of
tertiary amines void of other nucleophilic functional groups (e.g.,
triethylamine). For instance, the monoamine could be any aliphatic
primary or secondary amine [e.g., a C.sub.1-C.sub.22 or higher
linear amine, any branched amine or any cyclic aliphatic amine such
as methyl amine, ethyl amine, (n- and iso-)propyl amine, (n-, iso-,
and t-) butyl amine, (n-, iso-, t-, and the like) pentyl amine,
(n-, iso-, t-, and the like) hexyl amine, (n-, iso-, t-, and the
like) octyl amine, (n-, iso-, t-, and the like) nonyl amine, (n-
and branched) decyl amine, (n- and branched) undecyl amine, (n- and
branched) octadecyl amine, (n- and branched) hexadecyl amine, (n-
and branched) dodecyl amine, dimethyl amine, diethyl amine, di(n-,
and iso-)propyl amine, di(n-, iso-, t-)butyl amine, di(n-, iso-,
t-, and the like)pentyl amine, di(n-, iso-, t-, and the like)hexyl
amine, di(n-, iso-, t-, and the like)cyclohexyl amine, di(n-, iso-,
t-, and the like)heptyl amine, di(n-, iso-, t-, and the like)octyl
amine, di(n-, iso-, t-, and the like)decyl amine, di(n-, iso-, t-,
and the like)octadecyl amine, di(n-, iso-, t-, and the like)dodecyl
amine, cyclohexyl amine, 2,3-dimethyl-1-cyclohexylamine,
piperidine, pyrrolidine, and the like]; any aliphatic/aromatic
amines (e.g., benzyl amine or analogues with longer or additional
alkyl chains); aromatic amines such as aniline, anisidine, and the
like; fused ring amines such as rosin amine, dehydroabietyl amine,
dihydroabietyl amine, hydroabietyl amine, and the like; and
miscellaneous amines (e.g., adamantyl amine, isonipecotamide,
polyoxyalkylenemono-, di-, or triamines, such as M-, D-, and
T-series Jeffamines available commercially from Huntsman Chemical
Company of Austin, Tex.; 3,3'-diamino-N-methyl-dipropylamine, and
the like, as well as multifunctional amines such as polyethylene
imine; ethylene diamine; hexamethylene diamine; isomers of
cyclohexyldiamines; 1,3-pentadiamine; 1,12-dodecanediamine;
3-dimethylaminopropylamine; 4,7,10-trioxa-1,13-tridecanediamine;
diethylene triamine; 3,3-diamino-N-methyldipropylamine;
tris(2-aminoethyl)amine, and the like. The preferred amine is
octadecylamine.
[0042] Additionally, hydroxyl/amino containing compounds can be
employed (with di- and higher functionality isocyanates taking
advantage of the difference in reactivity of the amine over the
hydroxyl group, or with monoisocyanates reacting with the amine
preferentially or with both the amine and the hydroxyl groups).
Examples of this include ethanolamine, diethanolamine, and the
like.
[0043] Additionally amides or other nucleophile containing
compounds can be reacted with the isocyanates (mono, di, and the
like). Some examples include: urea, oleamide, stearamide, or the
like.
[0044] Preferred precursors to the isocyanate-derived resins and
waxes of the present invention include mono-, di- and other
poly-isocyanates. Examples of monoisocyanates include
octadecylisocyanate; octylisocyanate; butyl and t-butylisocyanate;
cyclohexyl isocyanate; adamantyl isocyanate;
ethylisocyanatoacetate; ethoxycarbonylisocyanate; phenylisocyanate;
alphamethylbenzyl isocyanate; 2-phenylcyclopropyl isocyanate;
benzylisocyanate; 2-ethylphenylisocyanate; benzoylisocyanate; meta
and para-tolylisocyanate; 2-, 3-, or 4-nitrophenylisocyanates;
2-ethoxyphenyl isocyanate; 3-methoxyphenyl isocyanate;
4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;
2,6-dimethylphenylisocyante; 1-naphthylisocyanate; (naphthyl)
ethylisocyantes; and the like. Examples of diisocyanates include
isophorone diisocyanate (IPDI); toluene diisocyanate (TDI);
diphenylmethane-4,4'-diisocyanate (MDI); hydrogenated
diphenylmethane-4,4'-diisocyanate (H.sub.12MDI); tetra-methyl
xylene diisocyanate (TMXDI); hexamethylene-1,6-diisocyanate (HDI);
hexamethylene-1,6-diisocyanate; napthylene-1,5-diisocyanate;
3,3'-dimethoxy-4,4'-biphenyldiisocyanate;
3,3'-dimethyl-4,4'-bimethyl-4,4- '-biphenyldiisocyanate; phenylene
diisocyanate; 4,4'-biphenyldiisocyanate; trimethylhexamethylene
diisocyanate; tetramethylene xylene diisocyanate;
4,4'-methylenebis(2,6-diethylphenyl isocyanate);
1,12-diisocyanatododecan- e; 1,5-diisocyanato-2-methylpentane;
1,4-diisocyanatobutane; and cyclohexylene diisocyanate and its
isomers; uretidione dimers of HDI; and the like. Examples of
triisocyanates or their equivalents include the trimethylolpropane
trimer of TDI, and the like, isocyanurate trimers of TDI, HDI,
IPDI, and the like, and biuret trimers of TDI, HDI, IPDI, and the
like. Examples of higher isocyanate functionalities include
copolymers of TDI/HDI, and the like, as well as MDI oligomers.
[0045] Phase change inks of this invention contain a phase change
carrier system or composition. The phase change carrier composition
is generally designed for use in either a direct printing mode or
use in an indirect or offset printing transfer system. In the
direct printing mode, the phase change carrier composition is
generally made up of one or more chemicals that provide the
necessary properties to allow the phase change ink (1) to be
applied in a thin film of uniform thickness on the final receiving
substrate when cooled to the ambient temperature after printing
directly to the substrate; (2) to be ductile while retaining
sufficient flexibility so that the applied image on the substrate
will not fracture upon bending; and (3) to possess a high degree of
lightness, chroma, transparency and thermal stability. In an offset
printing transfer or indirect printing mode, the phase change
carrier composition is designed to possess not only the above
mentioned properties, but certain fluidic and mechanical properties
necessary for use in such a system, as described in U.S. Pat. No.
5,389,958 which is hereby incorporated by reference in pertinent
part. The phase change inks of the current invention incorporate
isocyanate-derived waxes and isocyanate-derived resins as all or as
part of the carrier composition and can be a supplemental
ingredient or supplemental ingredients to the existing commercial
phase change carrier composition. The isocyanate-derived materials
of the current invention are tailored to have the desirable
properties mentioned above when used in the carrier composition of
the inks of the present invention by varying one or more of the
readily available commodity chemical precursors.
[0046] The phase change carrier compositions of the current
invention may be used in combination with conventional phase change
ink colorant materials such as Color Index (C.I.) Solvent Dyes,
Disperse Dyes, modified Acid and Direct Dyes, Basic Dyes, Sulphur
Dyes, Vat Dyes, and/or polymeric dyes such as those disclosed in
U.S. patent application Ser. No. 08/381,610, and/or pigments. They
may also be used in combination with the isocyanate-derived colored
resins of co-pending U.S. patent application Ser. No. 08/672,617
and assigned to the assignee of the present invention, to produce a
phase change ink.
[0047] Prior art phase change inks for use in direct and indirect
transfer printing systems are described in U.S. Pat. Nos. 4,889,560
and 5,372,852. These inks consist of a phase change ink carrier
composition comprising one or more fatty amide-containing
materials, usually consisting of a mono-amide wax and a tetra-amide
resin, one or more tackifiers, one or more plasticizers and one or
more antioxidants, in combination with compatible colorants. A
preferred tetra-amide resin is a dimer acid based tetra-amide that
is the reaction product of dimer acid, ethylene diamine, and
stearic acid. A preferred mono-amide is stearyl stearamide. A
preferred tackifier resin is a glycerol ester of hydrogenated
abietic (rosin) acid and a preferred antioxidant is that provided
by Uniroyal Chemical Company under the tradename Naugard 524. The
isocyanate-derived resins and/or isocyanate-derived waxes of the
present invention replace one or more of the ingredients in the
above phase change ink carrier composition or the inks of the
present invention can have all of the above ingredients replaced by
the isocyanate-derived resins and/or waxes of the present
invention. The advantages of inks formulated with
isocyanate-derived resins and/or isocyanate-derived waxes over the
prior art phase change inks are:
[0048] (1) The isocyanate-derived resins and waxes of this
invention are very pure, being free of salts and other insoluble
contaminants. This makes the inks made from these materials easy to
filter and provides for high reliability in ink jet printing
devices. This is a major advantage.
[0049] (2) The isocyanate-derived resins and waxes of this
invention are specifically tailored to give certain physical
properties that optimize the performance of the inks of this
invention in ink jet printing devices and on the output substrate.
These desirable ink properties include melting point, viscosity,
transparency and the dynamic mechanical properties referenced in
the aforementioned U.S. Pat. No. 5,389,958.
[0050] (3) The isocyanate-derived resins of this invention can be
used in certain combinations with other phase change ink carrier
materials to give ink compositions that display an improved yield
stress versus temperature curve over prior art ink compositions.
This enables ink droplets to be spread and fused at elevated
temperatures during the fusing and transfer steps in an indirect
printing process, but at a lower pressure than was possible with
prior art inks.
[0051] Many other patents describe other materials for use in phase
change ink jet inks. Some representative examples include U.S. Pat.
Nos. 3,653,932; 4,390,369; 4,484,948; 4,684,956; 4,851,045;
5,006,170; 5,151,120; EP Application Nos. 0187352 and 0206286; and
PCT Patent Application WO 94/04619. These other materials can
include paraffins, microcrystalline waxes, polyethylene waxes,
ester waxes, amide waxes, fatty acids, fatty alcohols, fatty amides
and other waxy materials, sulfonamide materials, resinous materials
made from different natural sources (tall oil rosins and rosin
esters are an example) and many synthetic resins, oligomers,
polymers, co-polymers, and ionomers. It will be obvious to those
skilled in the art that the isocyanate-derived materials of this
invention could be used in inks made from many different
combinations of these materials.
[0052] The aforementioned U.S. Pat. No. 5,496,879 and German patent
publications DE 4205636AL and DE 4205713AL, assigned to Siegwerk
Farbenfabrik Keller, Dr. Rung and Co., describe materials used for
phase change or hot melt gravure printing. It will be obvious to
those skilled in the art that the isocyanate-derived materials of
this current invention would be compatible with those materials and
could also be used in that application or other similar printing
methods that employ hot melt ink technology.
[0053] It also will be obvious to those skilled in the art that
other ink colors besides the subtractive primary colors are
desirable for applications, such as postal marking or industrial
marking and labeling using phase change printing, and that this
invention is applicable to these needs. Infrared (IR) or
ultraviolet (UV) absorbing dyes can also be incorporated into the
inks of this invention for use in applications such as "invisible"
coding or marking of products.
[0054] The inks of the present invention can be equally well
employed in apparatus for direct or indirect (offset) printing
applications. When employed in direct printing applications a
suitable method of printing or producing a layer of a phase change
colored ink directly on the surface of a substrate can
comprise:
[0055] (1) forming a phase change ink composition in the solid
phase, comprising an admixture of (a) a phase change carrier
composition containing at least one isocyanate-derived resin or wax
and (b) a phase change compatible colorant.
[0056] (2) transferring the solid phase, phase change colored ink
composition to a phase change ink application means or print
head;
[0057] (3) raising the operating temperature of the application
means or print head to a level whereby a liquid phase, phase change
colored ink composition is formed;
[0058] (4) providing a substrate in proximity to the application
means;
[0059] (5) applying a predetermined pattern of the liquid phase,
phase change colored ink composition to at least one surface of the
substrate; and
[0060] (6) lowering the temperature of the applied ink composition
to form a solid phase, phase change ink pattern on the
substrate.
[0061] An appropriate direct printing process is described in
greater detail in U.S. Pat. No. 5,195,430.
[0062] When employed in indirect or offset printing applications a
suitable method of printing or producing a layer of a phase change
colored ink indirectly on the surface of a substrate by
transferring from an intermediate transfer surface can
comprise:
[0063] (1) forming a phase change ink composition in the solid
phase, comprising an admixture of (a) a phase change carrier
composition containing at least one isocyanate-derived resin or wax
and (b) a phase change compatible colorant.
[0064] (2) transferring the solid phase, phase change colored ink
composition to a phase change ink application means or a print
head;
[0065] (3) raising the operating temperature of the application
means or print head to a level whereby a liquid phase, phase change
colored ink composition is formed;
[0066] (4) providing an intermediate transfer surface in proximity
to the application means;
[0067] (5) applying a predetermined pattern of the liquid phase,
phase change colored ink composition to the intermediate transfer
surface;
[0068] (6) lowering the temperature of the applied ink composition
to form a solid phase, phase change ink pattern on the intermediate
transfer surface at a second, intermediate temperature;
[0069] (7) transferring said phase change ink composition from the
intermediate transfer surface to a final substrate; and
[0070] (8) fixing the phase change ink composition to the substrate
to form a printed substrate, the phase change ink composition
having (a) a compressive yield strength which will allow it to be
malleable to spread and deform without an increase in stress when
compressive forces are applied thereto at the second operating
temperature, and sufficient internal cohesive strength to avoid
shear banding and weak behavior when said phase change ink
composition is transferred and fixed to said substrate, and (b) a
ductility on the substrate after fixing.
[0071] An appropriate offset or indirect printing process is
described in greater detail in U.S. Pat. No. 5,389,958.
[0072] The present invention is further described in detail by
means of the following Examples and Comparisons. All parts and
percentages are by weight and all temperatures are degrees Celsius
unless explicitly stated otherwise. It is to be noted that while
the following examples may recite only one colorant, it is to be
understood that each individual example is only illustrative and
any of the primary colorants (cyan, yellow, magenta and black) used
in subtractive color printing could be employed in each
instance.
EXAMPLE 1
[0073] The Reaction Product of Hydroabietyl Alcohol and Isophorone
Diisocyanate
[0074] About 391.9 grams (1.351 moles) of Abitol E hydroabietyl
alcohol.sup.1 was added to a 1000 ml four-neck resin kettle
equipped with a Trubore stirrer, an N.sub.2 atmosphere inlet, 200
ml addition funnel, and a thermocouple-temperature controller. The
kettle was heated to about 100.degree. C. with stirring under an
N.sub.2 atmosphere and about 150.0 grams (0.676 moles) of
isophorone diisocyanate.sup.2 was added to the addition funnel.
About 0.50 grams of dibutyltindilaurate.sup.3 catalyst was added to
the Abitol E, followed by dropwise addition of the isophorone
diisocyanate over 3 hours. The temperature was gradually increased
to about 155.degree. C. during this 3 hour period. After an
additional 2 hours at about 155.degree. C., a Fourier Transform
Infrared Spectroscopy (FT-IR) of the product was run to insure all
of the isocyanate (NCO) was consumed. The absence (disappearance)
of a peak at about 2285 cm.sup.-1 (NCO) and the appearance (or
increase in magnitude) of peaks at about 1740-1680 cm.sup.-1 and
about 1540-1530 cm.sup.-1 corresponding to urethane frequencies
were used to confirm this. The final di-urethane resin product was
poured into aluminum molds and allowed to cool and harden. This
final product was a clear solid resin at room temperature
characterized by the following physical properties: viscosity of
about 4,072.9 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of from about
72.0.degree. C. to about 76.0.degree. C. as measured by an
electrothermal capillary melting point apparatus, and a T.sub.g of
about 48.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter at a scan rate of
20.degree. C./minute. 1 Abitol E--Hydroabietyl alcohol available
from Hercules Inc. of Wilmington, Del. 2 Desmodur I--Isophorone
Diisocyanate available from Bayer Corp. of Pittsburg, Pa. 3
Dibutyltindilaurate available from Aldrich Chemicals of Milwaukee,
Wis.
EXAMPLE 2
[0075] The Reaction Product of 1.5 Parts Hydroabietyl Alcohol, 0.5
Parts Octadecyl Amine, and Isophorone Diisocyanate
[0076] About 240.2 grams (0.676 moles) of hydroabietyl
alcohol.sup.1 was added to a 1000 ml four-neck resin kettle
equipped with a Trubore stirrer, an N.sub.2 atmosphere inlet, 200
ml addition funnel, and a thermocouple-temperature controller.
About 100.0 grams (0.45 moles) of isophorone diisocyanate.sup.2 was
added to the addition funnel. Agitation of the hydroabietyl alcohol
first was begun and then all of the isophorone diisocyanate was
added over approximately 5 minutes. About 0.22 grams of
dibutyltindilaurate.sup.3 catalyst was added and the reaction
mixture heated to about 125.degree. C. under an N.sub.2 atmosphere.
After 4 hours at 125.degree. C., about 59.95 grams (0.225 moles) of
octadecyl amine.sup.4 was added and the temperature raised to about
150.degree. C. and held for approximately 2 hours. An FT-IR of the
reaction product was run to insure all of the NCO functionality was
consumed. The absence (disappearance) of a peak at about 2285
cm.sup.-1 (NCO) and the appearance (or increase in magnitude) of
peaks at about 1705-1635 cm.sup.-1 and about 1515-1555 cm.sup.-1
corresponding to urea frequencies and about 1740-1680 cm.sup.-1 and
about 1540-1530 cm.sup.-1 corresponding to urethane frequencies
were used to confirm this. The final mixed urethane/urea resin
product was poured into aluminum molds and allowed to cool and
harden. This final product was a clear solid resin at room
temperature characterized by the following physical properties:
viscosity of about 314.8 cPs as measured by a Ferranti-Shirley
cone-plate viscometer at about 140.degree. C., a melting point of
from about 67.9.degree. C. to about 87.0.degree. C. as measured by
an electrothermal capillary melting point apparatus, and a T.sub.g
of about 23.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter at a scan rate of
200.degree. C./minute. 1 Abitol E--Hydroabietyl alcohol available
from Hercules Inc. of Wilmington, Del. 2 Desmodur I--Isophorone
diisocyanate available from Bayer Corp. of Pittsburg, Pa. 3
Dibutyltindilaurate available from Aldrich Chemicals of Milwaukee,
Wis. 4 Octadecyl amine (technical grade) available from ACROS
Organics of New Jersey.
EXAMPLE 3
[0077] The Reaction Product of 1.25 Parts Hydroabietyl Alcohol,
0.75 Parts Octadecyl Amine and Isophorone Diisocyanate
[0078] About 150.1 grams (0.422 moles) of hydroabietyl
alcohol.sup.1 and about 75.0 grams (0.338 moles) of isophorone
diisocyanate.sup.2 were added to a 500 ml three-neck resin kettle
equipped with a Trubore stirrer, an N.sub.2 atmosphere inlet, and a
thermocouple-temperature controller. Agitation was begun and then
about 0.22 grams of dibutyltindilaurate.sup.3 catalyst was added
and the reaction mixture heated to about 130.degree. C. under an
N.sub.2 atmosphere. After 4 hours at about 130.degree. C., about
67.45 grams (0.253 moles) of octadecyl amine.sup.4 was added and
the temperature raised to about 150.degree. C. and held for
approximately 2 hours. An FT-IR of the reaction product was run to
insure all of the NCO functionality consumed. The absence
(disappearance) of a peak at about 2285 cm.sup.-1 (NCO) and the
appearance (or increase in magnitude) of peaks at about 1705-1635
cm.sup.-1 and about 1515-1555 cm.sup.-1 corresponding to urea
frequencies and about 1740-1680 cm.sup.-1 and about 1540-1530
cm.sup.-1 corresponding to urethane frequencies were used to
confirm this. The final mixed urethane/urea resin product was then
poured into aluminum molds and allowed to cool and harden. This
final product was a clear solid resin at room temperature
characterized by the following physical properties: viscosity of
about 275.0 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of from about
68.4.degree. C. to about 89.0.degree. C. as measured by an
electrothermal capillary melting point apparatus, and a T.sub.g of
about 17.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter at a scan rate of
20.degree. C./minute. 1 Abitol E--Hydroabietyl alcohol available
from Hercules Inc. of Wilmington, Del. 2 Desmodur I--Isophorone
diisocyanate available from Bayer Corp. of Pittsburg, Pa. 3
Dibutyltindilaurate available from Aldrich Chemicals of Milwaukee,
Wis. 4 Octadecyl amine (technical grade) available from ACROS
Organics of New Jersey.
EXAMPLE 4
[0079] The Reaction Product of 1 Part Hydroabietyl Alcohol, 1 Part
Octadecyl Amine and Isophorone Diisocyanate
[0080] About 120.1 grams (0.338 moles) of hydroabietyl
alcohol.sup.1 and about 75.0 grams (0.338 moles) of isophorone
diisocyanate.sup.2 was added to a 500 ml three-neck resin kettle
equipped with a Trubore stirrer, an N2 atmosphere inlet, and a
thermocouple-temperature controller. Agitation was begun and then
about 0.22 grams of dibutyltindilaurate.sup.3 catalyst was added
and the reaction mixture heated to about 90.degree. C. under an
N.sub.2 atmosphere. After 1 hour at about 90.degree. C. the
temperature was increased to about 110.degree. C. and held for 2
hours. About 89.93 grams (0.338 moles) of octadecyl amine.sup.4 was
added and the temperature raised to about 130.degree. C. and held
for approximately 2 hours. An FT-IR of the reaction product was run
to insure all of the NCO functionality was consumed. The absence
(disappearance) of a peak at about 2285 cm.sup.-1 (NCO) and the
appearance (or increase in magnitude) of peaks at about 1705-1635
cm.sup.-1 and about 1515-1555 cm.sup.-1 corresponding to urea
frequencies and about 1740-1680 cm.sup.-1 and about 1540-1530
cm.sup.-1 corresponding to urethane frequencies were used to
confirm this. The final mixed urethane/urea resin product was
poured into aluminum molds and allowed to cool and harden. This
final product was a clear solid resin at room temperature
characterized by the following physical properties: viscosity of
about 15.7 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of from about
73.2.degree. C. to about 110.degree. C. as measured by an
electrothermal capillary melting point apparatus, and a T.sub.g of
about 16.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter at a scan rate of
20.degree. C./minute. 1 Abitol E--Hydroabietyl alcohol available
from Hercules Inc. of Wilmington, Del. 2 Desmodur I-Isophorone
diisocyanate available from Bayer Corp. of Pittsburg, Pa. 3
Dibutyltindilaurate available from Aldrich Chemicals of Milwaukee,
Wis. 4 Octadecyl amine (technical grade) available from ACROS
Organics of New Jersey.
EXAMPLE 5
[0081] The Reaction Product of Octylphenol Ethoxylate and
Isophorone Diisocyanate
[0082] About 450.4 grams (1.802 moles) of Triton X15 octylphenol
ethoxylate.sup.1 and about 200.0 grams (0.901 moles) of isophorone
diisocyanate.sup.2 was added to a 1000 ml three-neck resin kettle
equipped with a Trubore stirrer, an N.sub.2 atmosphere inlet, and a
thermocouple-temperature controller. The mixture was agitated for
10 minutes and then about 0.33 grams of dibutyltindilaurate.sup.3
catalyst was added and the reaction mixture heated to about
150.degree. C. under an N.sub.2 atmosphere. After 5.5 hours at
about 150.degree. C. an FT-IR of the product was run to insure all
of the NCO was consumed. The absence (disappearance) of a peak at
about 2285 cm.sup.-1 (NCO) and the appearance (or increase in
magnitude) of peaks at about 1740-1680 cm.sup.-1 and about
1540-1530 cm.sup.-1 corresponding to urethane frequencies were used
to confirm this. The final di-urethane resin product was poured
into aluminum molds and allowed to cool and harden. This final
product was a clear solid resin at room temperature characterized
by the following physical properties: viscosity of about 124.7 cPs
as measured by a Ferranti-Shirley cone-plate viscometer at about
140.degree. C., a melting point of from about 51.3.degree. C. to
about 81.9.degree. C. as measured by an electrothermal capillary
melting point apparatus, and a T.sub.g of about 36.degree. C. as
measured by differential scanning calorimetry using a DuPont 2100
calorimeter at a scan rate of 20.degree. C./minute. 1 Triton X15
octylphenol ethoxylate is available from Union Carbide Chemicals
and Plastics Company Inc. of Danbury, Conn. Note: IGEPAL CA-210
octylphenol ethoxylate, available from Rhone-Poulenc Co., Cranbury,
N.J., can be directly substituted for Triton X15 in this reaction.
2 VESTANAT IPDI--Isophorone diisocyanate available from Huls
America, Inc. of Piscataway, N.J. 3 Dibutyltindilaurate available
from Aldrich Chemicals of Milwaukee, Wis.
EXAMPLE 6
[0083] The Reaction Product of Octadecyl Alcohol, Octadecyl Amine
and Isophorone Diisocyanate
[0084] About 243.2 grams (0.901 moles) of octadecyl alcohol.sup.1
and about 200.0 grams (0.901 moles) of isophorone
diisocyanate.sup.2 were added to a 1000 ml three-neck resin kettle
equipped with a Trubore stirrer, an N.sub.2 atmosphere inlet, and a
thermocouple-temperature controller. Agitation was begun and then
about 0.33 grams of dibutyltindilaurate.sup.3 catalyst was added
and the reaction mixture heated to about 90.degree. C. under an
N.sub.2 atmosphere. After 4 hours the temperature was raised to
about 120.degree. C. and about 239.8 grams (0.901 moles) of
octadecyl amine.sup.4 was added over 15 minutes. The temperature
was raised to about 150.degree. C. and held for approximately 4
hours. An FT-IR of the product was run to insure all of the NCO
functionality was consumed. The absence (disappearance) of a peak
at about 2285 cm.sup.-1 (NCO) and the appearance (or increase in
magnitude) of peaks at about 1705-1635 cm.sup.-1 and about
1515-1555 cm.sup.-1 corresponding to urea frequencies and about
1740-1680 cm.sup.-1 and about 1540-1530 cm.sup.-1 corresponding to
urethane frequencies were used to confirm this. The final mixed
urethane/urea resin product was poured into aluminum molds and
allowed to cool and harden. This final product was a clear solid
resin at room temperature characterized by the following physical
properties: viscosity of about 39.9 cPs as measured by a
Ferranti-Shirley cone-plate viscometer at about 140.degree. C., a
melting point of from about 63.2.degree. C. to about 92.0.degree.
C. as measured by an electrothermal capillary melting point
apparatus, and a T.sub.g of about -29.degree. C. as measured by
differential scanning calorimetry using a DuPont 2100 calorimeter
at a scan rate of 20.degree. C./minute. 1 Octadecyl alcohol
available from Aldrich Chemicals of Milwaukee, Wis. 2 Desmodur
I--Isophorone diisocyanate available from Bayer Corp. of Pittsburg,
Pa. 3 Dibutyltindilaurate available from Aldrich Chemicals of
Milwaukee, Wis. 4 Octadecyl amine (technical grade) available from
ACROS Organics of New Jersey.
EXAMPLE 7
[0085] The Reaction Product of Octadecyl Alcohol and Isophorone
Diisocyanate
[0086] About 103.14 grams (0.382 moles, 0.382 equiv.) of octadecyl
alcohol.sup.1 was added to a 500 ml four-neck resin kettle equipped
with a Trubore stirrer, an N.sub.2 atmosphere inlet, a 200 ml
addition funnel, and a thermocouple-temperature controller. The
kettle was heated to about 80.degree. C. with stirring under an
N.sub.2 atmosphere and about 42.4 grams (0.191 moles, 0.382 equiv.)
of isophorone diisocyanate.sup.2 was added to the addition funnel.
Isophorone diisocyanate was then added dropwise over 1 hour at
about 80.degree. C. The temperature was increased to about
120.degree. C. and held for 3 hours. An FT-IR of the product was
run to insure all of the NCO functionality was consumed. The
absence (disappearance) of a peak at 2285 cm.sup.-1 (NCO) and the
appearance (or increase in magnitude) of peaks at 1740-1680
cm.sup.-1 and 1540-1530 cm.sup.-1 corresponding to urethane
frequencies were used to confirm this. The final di-urethane resin
product was poured into aluminum molds and allowed to cool and
harden. This final product was a clear solid resin at room
temperature characterized by the following physical properties:
viscosity of about 10.8 cPs as measured by a Ferranti-Shirley
cone-plate viscometer at about 140.degree. C., and a melting point
of about 51.2.degree. C. as measured by an electrothermal capillary
melting point apparatus. An attempt was made to measure the T.sub.g
using differential scanning calorimetry with a DuPont 2100
calorimeter at a scan rate of 20.degree. C./minute, but the T.sub.g
was determined not to be measurable. .sup.1 Octadecyl alcohol
available from Aldrich Chemicals of Milwaukee, Wis. .sup.2 Desmodur
I--Isophorone diisocyanate available from Bayer Corp. of Pittsburg,
Pa.
EXAMPLE 8
[0087] The Reaction Product of Octadecyl Amine and Isophorone
Diisocyanate
[0088] About 359.7 grams (1.351 moles) of octadecyl amine.sup.1 was
added to a 1000 ml four-neck resin kettle equipped with a Trubore
stirrer, an N.sub.2 atmosphere inlet, addition funnel (200 ml), and
thermocouple-temperature controller. The kettle was heated to about
70.degree. C. with stirring under an N.sub.2 atmosphere and about
150 grams (0.676 moles) of isophorone diisocyanate.sup.2 was added
to the addition funnel. Isophorone diisocyanate was then added
dropwise to the octadecyl amine over 2 hours with the temperature
gradually increased to about 165.degree. C. as the viscosity
increased. The contents were held at about 165.degree. C. for 1
hour and an FT-IR of the product was run to insure all of the NCO
functionality was consumed. The absence (disappearance) of a peak
at about 2285 cm.sup.-1 (NCO) and the appearance (or increase in
magnitude) of peaks at about 1705-1635 cm.sup.-1 and about
1515-1555 cm.sup.-1 corresponding to urea frequencies were used to
confirm this. The final di-urea resin product was poured into
aluminum molds and allowed to cool and harden. This final product
was a clear solid resin at room temperature characterized by the
following physical properties: viscosity of about 988.0 cPs as
measured by a Ferranti-Shirley cone-plate viscometer at about
140.degree. C., a melting point of from about 84.4.degree. C. to
about 93.9.degree. C. as measured by an electrothermal capillary
melting point apparatus, and a T.sub.g of about -14.degree. C. as
measured by differential scanning calorimetry using a DuPont 2100
calorimeter at a scan rate of 20.degree. C./minute. 1 Octadecyl
amine (technical grade) available from ACROS Organics of New
Jersey. 2 Desmodur I--Isophorone diisocyanate available from Bayer
Corp. of Pittsburg, Pa.
EXAMPLE 9
[0089] The Reaction Product of Octadecyl Amine and
Octadecylisocyanate
[0090] About 250.0 grams (0.877 moles) of octadecylisocyanate.sup.1
and about 233.3 grams (0.877 moles) of octadecylamine.sup.2 were
added to a 1000 ml three-neck resin kettle equipped with a Trubore
stirrer, an N.sub.2 atmosphere inlet, and thermocouple-temperature
controller. The kettle was heated to about 130.degree. C. with
stirring under an N.sub.2 atmosphere and held for 6 hours. An FT-IR
of the product was run to insure all of the NCO functionality was
consumed. The absence (disappearance) of a peak at about 2285
cm.sup.-1 (NCO) and the appearance (or increase in magnitude) of
peaks at about 1705-1635 cm.sup.-1 and about 1515-1555 cm.sup.-1
corresponding to urea frequencies were used to confirm this. The
final mono-urea wax product was poured into aluminum molds and
allowed to cool and harden. This final product was a white waxy
solid at room temperature characterized by the following physical
properties: viscosity of about 13.2 cPs as measured by a
Ferranti-Shirley cone-plate viscometer at about 140.degree. C., and
a melting point of from about 113.4.degree. C. to about
113.6.degree. C. as measured by an electrothermal capillary melting
point apparatus. .sup.1 Mondur O--Octadecylisocyanate available
from Bayer Corp. of Pittsburg, Pa. .sup.2 Octadecyl amine
(technical grade) available from ACROS Organics of New Jersey.
EXAMPLE 10
[0091] The Reaction Product of Octadecyl Alcohol and
Octadecylisocyanate
[0092] About 250.0 grams (0.877 moles) of octadecylisocyanate.sup.1
and about 236.7 grams (0.867 moles) of octadecyl alcohol.sup.2 was
added to a 1000 ml three-neck resin kettle equipped with a Trubore
stirrer, an N.sub.2 atmosphere inlet, and a
thermocouple-temperature controller. The kettle was heated to about
120.degree. C. with stirring under an N.sub.2 atmosphere and about
0.5 grams of dibutyltindilaurate.sup.3 catalyst was added. The
reaction mixture was heated at about 120.degree. C. for
approximately 4 hours, then increased to about 140.degree. C. and
held for 2 hours. An FT-IR of the product was run to insure all of
the NCO functionality was consumed. The absence (disappearance) of
a peak at about 2285 cm.sup.-1 (NCO) and the appearance (or
increase in magnitude) of peaks at about 1740-1680 cm.sup.-1 and
about 1540-1530 cm.sup.-1 corresponding to urethane frequencies
were used to confirm this. The final mono-urethane wax product was
poured into aluminum molds and allowed to cool and harden. This
final product was a white waxy solid at room temperature
characterized by the following physical properties: viscosity of
about 3.7 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., and a melting point of from
about 84.5.degree. C. to about 87.7.degree. C. as measured by an
electrothermal capillary melting point apparatus. .sup.1 Mondur
O--Octadecylisocyanate available from Bayer Corp. of Pittsburg, Pa.
.sup.2 Alfol 18 Alcohol (octadecyl alcohol) available from Vista
Chemical Company of Houston, Tex. .sup.3 Dibutyltindilaurate
available from Aldrich Chemicals of Milwaukee, Wis.
EXAMPLE 11
[0093] Cyan Ink Made From Mono-Amide Wax, Urethane Resin and
Tackifier Resin
[0094] About 62.5 grams of the di-urethane resin reaction product
from Example 5, about 62.5 grams of a rosin ester tackifier resin
available commercially as Arakawa KE-100.sup.1, about 125 grams of
stearyl stearamide available commercially as Witco S-180.sup.2 and
about 0.4 grams of Uniroyal Naugard 445 antioxidant.sup.3 were
combined in a stainless steel beaker. The materials were melted
together at a temperature of about 140.degree. C. in an oven, then
blended by stirring in a temperature controlled mantle at about
115.degree. C. for about 1/2 hour. To this mixture was added about
5 grams of Solvent Blue 44. After stirring for about 1/2 hour, the
cyan ink was filtered through a heated Mott apparatus (available
from Mott Metallurgical) using #3 Whatman filter paper and a
pressure of 15 psi. The filtered phase change ink was poured into
molds and allowed to solidify to form ink sticks. This final ink
product was characterized by the following physical properties:
viscosity of about 12.4 cPs as measured by a Ferranti-Shirley
cone-plate viscometer at about 140.degree. C., a melting point of
about 90.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter, and a T.sub.g of about
42.degree. C. as measured by Dynamic Mechanical Analysis using a
Rheometrics Solids Analyzer (RSAII). The spectral strength of the
ink was determined using a spectrophotographic procedure based on
the measurement of the colorant in solution by dissolving the solid
ink in butanol and measuring the absorbance using a Perkin Elmer
Lambda 2S UV/VIS spectrophotometer. The spectral strength of the
ink was measured as about 2705 milliliters.multidot.Absorbance
Units per gram at .lambda.max. .sup.1 KE-100--Glycerol ester of
hydrogenated abietic (rosin) acid available from Arakawa Chemical
Industries, Ltd. of Osaka, Japan. .sup.2 Kemamide S-180--Stearyl
stearamide available from Witco Chemical Company of Memphis, Tenn.
.sup.3 Naugard 445--antioxidant available from Uniroyal Chemical
Company of Oxford, Conn.
EXAMPLE 12
[0095] Cyan Ink Made From Amide Wax, Mixed Urethane/Urea Resin and
Tackifier Resin
[0096] In a stainless steel beaker were combined about 62.5 grams
of the reaction product mixture of urethane/urea resin material
from Example 6, about 65 grams of a rosin ester tackifier resin
available commercially as Arakawa KE-100.sup.1, about 120 grams of
Witco S-180.sup.2 stearyl stearamide and 0.4 grams of Uniroyal
Naugard 445 antioxidant.sup.3. The materials were melted together
at a temperature of about 140.degree. C. in an oven, then blended
by stirring in a temperature controlled mantle at about 115.degree.
C. for about 1/2 hour. To this mixture was added about 5 grams of
Solvent Blue 44. After stirring for about 1/2 hour, the cyan ink
was filtered through a heated Mott apparatus (available from Mott
Metallurgical) using #3 Whatman filter paper and a pressure of
about 15 psi. The filtered phase change ink was poured into molds
and allowed to solidify to form ink sticks. This final ink product
was characterized by the following physical properties: viscosity
of about 12.9 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
88.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 41.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 2698 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 KE-100--Glycerol ester of hydrogenated
abietic (rosin) acid available from Arakawa Chemical Industries,
Ltd. of Osaka, Japan. .sup.2 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.3
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 13
[0097] Cyan Ink Made From Amide Wax, Urethane Resin and Tackifier
Resin
[0098] In a stainless steel beaker were combined about 57.5 grams
of the di-urethane resin reaction product from Example 1, about
57.5 grams of a rosin ester tackifier resin available commercially
as Arakawa KE-100.sup.1, about 135 grams of Witco S-180 stearyl
stearamide.sup.2 and about 0.5 grams of Uniroyal Naugard 445
antioxidant.sup.3. The materials were melted together at a
temperature of about 140.degree. C. in an oven, then blended by
stirring in a temperature controlled mantle at about 115.degree. C.
for about 1/2 hour. To this mixture was added about 5 grams of
Solvent Blue 44. After stirring for about 1/2 hour, the cyan ink
was filtered through a heated Mott apparatus (available from Mott
Metallurgical) using #3 Whatman filter paper and a pressure of
about 15 psi. The filtered phase change ink was poured into molds
and allowed to solidify to form ink sticks. This final ink product
was characterized by the following physical properties: viscosity
of about 13.2 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
90.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 49.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 2721 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 KE-100--Glycerol ester of hydrogenated
abietic (rosin) acid available from Arakawa Chemical Industries,
Ltd. of Osaka, Japan. .sup.2 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.3
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 14
[0099] Cyan Ink Made from Amide Wax, Urethane Resin and Urea
Resin
[0100] About 56.25 grams of the di-urethane resin reaction product
from Example 5, about 56.25 grams of the di-urea resin reaction
product from Example 8, about 137.5 grams of Witco S-180 stearyl
stearamide.sup.1 and about 0.5 grams of Uniroyal Naugard 445
antioxidant.sup.2 were combined in a stainless steel beaker. The
materials were melted together at a temperature of about
140.degree. C. in an oven, then blended by stirring in a
temperature controlled mantle at about 115.degree. C. for about 1/2
hour. To this mixture was added about 5 grams of Solvent Blue 44.
After stirring for about {fraction (1/2)} hr., the cyan ink was
filtered through a heated Mott apparatus (available from Mott
Metallurgical) using #3 Whatman filter paper and a pressure of
about 15 psi. The filtered phase change ink was poured into molds
and allowed to solidify to form ink sticks. This final ink product
was characterized by the following physical properties: viscosity
of about 14.1 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
90.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 30.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 2690 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.2
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 15
[0101] Cyan Ink Made From Amide Wax, Urethane Resin and Mixed
Urethane/Urea Resin
[0102] About 70 grams of the reaction product urethane material
from Example 5, about 70 grams of the reaction product
urethane/urea mixture material from Example 6, about 110 grams of
Witco S-180 stearyl stearamide.sup.1 and about 0.5 grams of
Uniroyal Naugard 445 antioxidant.sup.2 were combined in a stainless
steel beaker. The materials were melted together at a temperature
of about 140.degree. C. in an oven, then blended by stirring in a
temperature controlled mantle at about 115.degree. C. for about 1/2
hour. To this mixture was added about 5 grams of Solvent Blue 44.
After stirring for about 1/2 hour, the cyan ink was filtered
through a heated Mott apparatus (available from Mott Metallurgical)
using #3 Whatman filter paper and a pressure of about 15 psi. The
filtered phase change ink was poured into molds and allowed to
solidify to form ink sticks. This final ink product was
characterized by the following physical properties: viscosity of
about 12.9 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
88.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 24.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 2714 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.2
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 16
[0103] Yellow Ink Made from Urethane Wax, Urethane Resin, Tackifier
Resin and Polymeric Dye
[0104] In a stainless steel beaker were combined about 77.8 grams
of the reaction product urethane material from Example 5, about
77.7 grams of a rosin ester tackifier resin available commercially
as Arakawa KE-100.sup.1, about 132.5 grams of the reaction product
mono-urethane wax material from Example 10 (stearyl stearurethane)
and about 0.5 grams of Uniroyal Naugard 445 antioxidant. The
materials were melted together at a temperature of about
140.degree. C. in an oven, then blended by stirring in a
temperature controlled mantle at about 115.degree. C. for about 1/2
hour. To this mixture was added about 11.6 grams of Milliken
Chemical Y869 polymeric colorant. After stirring for about
{fraction (1/2)} hour, the yellow ink was filtered through a heated
Mott apparatus (available from Mott Metallurgical) using #3 Whatman
filter paper and a pressure of about 15 psi. The filtered phase
change ink was poured into molds and allowed to solidify to form
ink sticks. This final ink product was characterized by the
following physical properties: viscosity of about 11.8 cPs as
measured by a Ferranti-Shirley cone-plate viscometer at about
140.degree. C. and a melting point of about 80.degree. C. as
measured by differential scanning calorimetry using a DuPont 2100
calorimeter. The T.sub.g of the final ink product was not measured.
The spectral strength of the ink was determined using a
spectrophotographic procedure based on the measurement of the
colorant in solution by dissolving the solid ink in butanol and
measuring the absorbance using a Perkin Elmer Lambda 2S UV/VIS
spectrophotometer. The spectral strength of the ink was measured as
about 726 milliliters.multidot.Absorbance Units per gram at
.lambda.max. .sup.1 KE-100--Glycerol ester of hydrogenated abietic
(rosin) acid available from Arakawa Chemical Industries, Ltd. of
Osaka, Japan.
EXAMPLE 17
[0105] Black Ink Made From Urethane Wax, Urethane Resin and Urea
Resin
[0106] In a stainless steel beaker were combined about 79.3 grams
of the reaction product urethane material from Example 5, about
79.3 grams of the reaction product urea resin material from Example
8, about 135 grams of the reaction product mono-urethane wax
material from Example 10 (stearyl stearurethane) and about 0.5
grams of Uniroyal Naugard 445 antioxidant.sup.1. The materials were
melted together at a temperature of about 140.degree. C. in an
oven, then blended by stirring in a temperature controlled mantle
at about 115.degree. C. for about 1/2 hour. To this mixture was
added about 5.8 grams of Solvent Black 45. After stirring for about
1/2 hour, the black ink was filtered through a heated Mott
apparatus (available from Mott Metallurgical) using #3 Whatman
filter paper and a pressure of about 15 psi. The filtered phase
change ink was poured into molds and allowed to solidify to form
ink sticks. This final ink product was characterized by the
following physical properties: viscosity of about 15.2 cPs as
measured by a Ferranti-Shirley cone-plate viscometer at about
140.degree. C., a melting point of about 81.degree. C. as measured
by differential scanning calorimetry using a DuPont 2100
calorimeter, and a T.sup.g of about 25.degree. C. as measured by
Dynamic Mechanical Analysis using a Rheometrics Solids Analyzer
(RSAII). The spectral strength of the ink was determined using a
spectrophotographic procedure based on the measurement of the
colorant in solution by dissolving the solid ink in butanol and
measuring the absorbance using a Perkin Elmer Lambda 2S UV/VIS
spectrophotometer. The spectral strength of the ink was measured as
about 583 milliliters.multidot.Absorbance Units per gram at
.lambda.max. .sup.1 Naugard 445--antioxidant available from
Uniroyal Chemical Company of Oxford, Conn.
EXAMPLE 18
[0107] Cyan Ink Made from Amide Wax, Mixed Urethane/Urea Resin and
Cyan Colored Urethane Resin
[0108] In a stainless steel beaker were combined about 250 grams of
the cyan colored resin from Example 2 of co-pending U.S. patent
application Ser. No. 08/672,617 and assigned to the assignee of the
present invention, about 250 grams of the reaction product
urethane/urea mixture material from Example 2, about 540 grams of
Witco S-180 stearyl stearamide.sup.1 and about 2.0 grams of
Uniroyal Naugard 445 antioxidant.sup.2. The materials were melted
together at a temperature of 140.degree. C. in an oven, then
blended by stirring in a temperature controlled mantle at about
115.degree. C. for about 1/2 hour. To this mixture was added about
5 grams of Solvent Blue 44. After stirring for about 1/2 hour, the
cyan ink was filtered through a heated Mott apparatus (available
from Mott Metallurgical) using #3 Whatman filter paper and a
pressure of about 15 psi. The filtered phase change ink was poured
into molds and allowed to solidify to form ink sticks. This final
ink product was characterized by the following physical properties:
viscosity of about 13.0 cPs as measured by a Ferranti-Shirley
cone-plate viscometer at about 140.degree. C., a melting point of
about 89.degree. C. as measured by differential scanning
calorimetry using a DuPont 2100 calorimeter, and a T.sub.g of about
27.5.degree. C. as measured by Dynamic Mechanical Analysis using a
Rheometrics Solids Analyzer (RSAII). The spectral strength of the
ink was determined using a spectrophotographic procedure based on
the measurement of the colorant in solution by dissolving the solid
ink in butanol and measuring the absorbance using a Perkin Elmer
Lambda 2S UV/VIS spectrophotometer. The spectral strength of the
ink was measured as about 1069 milliliters.multidot.Absorbance
Units per gram at .lambda.max. .sup.1 Kemamide S-180--Stearyl
stearamide available from Witco Chemical Company of Memphis, Tenn.
.sup.2 Naugard 445--antioxidant available from Uniroyal Chemical
Company of Oxford, Conn.
EXAMPLE 19
[0109] Yellow Ink Made from Amide Wax, Mixed Urethane/Urea Resin
and Yellow Colored Urethane Resin
[0110] In a stainless steel beaker were combined about 98.6 grams
of the colored resin from Example 1 of co-pending U.S. patent
application Ser. No. 08/672,617 and assigned to the assignee of the
present invention, about 80.7 grams of the material from Example 2,
about 179 grams of Witco S-180 stearyl stearamide.sup.1 and about
0.7 grams of Uniroyal Naugard 445 antioxidant.sup.2. The materials
were melted together at a temperature of about 140.degree. C. in an
oven, then blended by stirring in a temperature controlled mantle
at about 115.degree. C. for about 1/2 hour. The yellow ink was then
filtered through a heated Mott apparatus (available from Mott
Metallurgical) using #3 Whatman filter paper and a pressure of
about 15 psi. The filtered phase change ink was poured into molds
and allowed to solidify to form ink sticks. This final ink product
was characterized by the following physical properties: viscosity
of about 13.6 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
90.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 20.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 1497 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.2
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 20
[0111] Black Ink Made from Amide Wax, Mixed Urethane/Urea Resin and
Black Colored Urethane Resin
[0112] In a stainless steel beaker were combined about 301 grams of
the colored resin from Example 3 of co-pending U.S. patent
application Ser. No. 08/672,617 and assigned to the assignee of the
present invention, about 374 grams of the reaction product
urethane/urea mixture material from Example 2, about 802 grams of
Witco S-180 stearyl stearamide.sup.1 and about 3.0 grams of
Uniroyal Naugard 445 antioxidant.sup.2. The materials were melted
together at a temperature of about 140.degree. C. in an oven, then
blended by stirring in a temperature controlled mantle at about
115.degree. C. for about 1/2 hour. The black ink was then filtered
through a heated Mott apparatus (available from Mott Metallurgical)
using #3 Whatman filter paper and a pressure of about 15 psi. The
filtered phase change ink was poured into molds and allowed to
solidify to form ink sticks. This final ink product was
characterized by the following physical properties: viscosity of
about 13.3 cPs as measured by a Ferranti-Shirley cone-plate
viscometer at about 140.degree. C., a melting point of about
89.degree. C. as measured by differential scanning calorimetry
using a DuPont 2100 calorimeter, and a T.sub.g of about 16.degree.
C. as measured by Dynamic Mechanical Analysis using a Rheometrics
Solids Analyzer (RSAII). The spectral strength of the ink was
determined using a spectrophotographic procedure based on the
measurement of the colorant in solution by dissolving the solid ink
in butanol and measuring the absorbance using a Perkin Elmer Lambda
2S UV/VIS spectrophotometer. The spectral strength of the ink was
measured as about 869 milliliters.multidot.Absorbance Units per
gram at .lambda.max. .sup.1 Kemamide S-180--Stearyl stearamide
available from Witco Chemical Company of Memphis, Tenn. .sup.2
Naugard 445--antioxidant available from Uniroyal Chemical Company
of Oxford, Conn.
EXAMPLE 21
[0113] Yield Stress Versus Temperature Curve for the Ink from
Example 20 Compared to a Prior Art Phase Change Ink
[0114] These results illustrated in FIG. 1 show that the test ink
from Example 20 requires less pressure to fuse the test ink at
elevated temperatures than the prior art ink and is therefore
better adapted for offset printing applications, although it is
also suitable for direct printing. FIG. 1 is a graphical
representation of the compression yield data for the ink of Example
20 plotted versus a prior art phase change ink found in Example 2
of U.S. Pat. No. 5,372,852. The tests were done on a MTS SYNTECH
2/D mechanical tester using cylindrical sample blocks of about 19
millimeters by 19 millimeters in size.
Print Testing
[0115] The inks in examples 11-20 were tested in a Tektronix
Phaser.RTM. 340 printer, which uses an offset transfer printing
system. All of the above inks were found to completely transfer and
to give images of good color, print quality and durability either
as primary colors or when used in combination with each other or
the commercially available Phaser.RTM. 340 printer inks.
[0116] The inks in Examples 18-20 were tested in a Tektronix
Phaser.RTM. 300 printer, which uses a direct printing system. All
of the above inks were found to give images of good color, print
quality and durability either as primary colors or when used in
combination with each other or the commercially available
Phaser.RTM. 300 printer inks.
Physical Properties of Selected Waxes, Resins, and Inks
[0117] Tables 1 and 2 are used to illustrate the differences in
physical properties that can be achieved by the proper selection of
functionality in analogous test molecules.
1TABLE 1 Analogous Waxes MELTING POINT VISCOSITY @ 140.degree. C.
Stearyl Stearurethane 84.degree. C. 3.7 cPs (EXAMPLE 10) Stearyl
Stearamide 92.degree. C. 5.9 cPs (Witco S-180) Stearyl Stearurea
113.degree. C. 13.2 cPs (EXAMPLE 9)
[0118]
2TABLE 2 Analogous Stearyl/LPDI Products MELTING POINT VISCOSITY @
140.degree. C. Stearyl/IPDI Urethane 48.degree. C. 11 cPs (EXAMPLE
7) Mixed Stearyl/IPDI 82.degree. C. 40 cPs Urea/Urethane (EXAMPLE
6) Stearyl/IPDI Urea 107.degree. C. 988 cPs (EXAMPLE 8)
[0119] Table 3 illustrates the difference in physical properties of
resins that can be obtained by mixing both functionality and
molecular shape and size.
3TABLE 3 Mixtures of Abietic Alcohol and Stearyl Amine, Reacted
with IPDI Alcohol/Amine Ratio T.sub.g's/Melting Point/Viscosity
100% Alcohol 48.degree. C./ 72-76.degree. C./4079 cPs @ 140.degree.
C. (EXAMPLE 1) 75% Alcohol/25% Amine 23.degree. C./68-87.degree.
C./315 cPs @ 140.degree. C. (EXAMPLE 2) 62.5% Alcohol/37.5% Amine
17.degree. C./68-89.degree. C./275 cPs @ 140.degree. C. (EXAMPLE 3)
50% Alcohol/50% Amine 16.degree. C./73-110.degree. C./15.7 cPs @
140.degree. C. (EXAMPLE 4)
[0120] While the invention has been described above with reference
to specific embodiments thereof, it is apparent that many changes,
modifications and variations can be made without departing from the
inventive concept disclosed herein. For example, it should be noted
where a urethane reaction product is obtained, a single alcohol
precursor or multiple alcohol precursors may be used with an
appropriate isocyanate as long as the required stoichiometric ratio
is maintained. Similarly, where a urea is the reaction product, a
single amine precursor or multiple amine precursors may employed as
long as the required stoichiometric ratio is maintained. Where a
urethane/urea reaction product is obtained, single or multiple
alcohol and amine precursors may be employed within the appropriate
stoichiometric ratios. Accordingly, it is intended to embrace all
such changes, modifications and variations that fall within the
spirit and broad scope of the appended claims. All patent
applications, patents and other publications cited herein are
incorporated by reference in their entirety.
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