U.S. patent application number 12/019875 was filed with the patent office on 2008-05-22 for colorant compositions.
This patent application is currently assigned to XEROX CORPORATION. Invention is credited to Jeffrey H. Banning, Clifford R. King, Donald R. Titterington.
Application Number | 20080119644 12/019875 |
Document ID | / |
Family ID | 32681904 |
Filed Date | 2008-05-22 |
United States Patent
Application |
20080119644 |
Kind Code |
A1 |
Banning; Jeffrey H. ; et
al. |
May 22, 2008 |
COLORANT COMPOSITIONS
Abstract
Disclosed is a colorant composition of the formula ##STR1##
wherein R is an alkyl group, an aryl group, an arylalkyl group, or
an alkylaryl group, and wherein R can be joined to the phenyl
moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said colorant has no more than one
--OH, --SH, or primary or secondary amino group per molecule.
Inventors: |
Banning; Jeffrey H.;
(Hillsboro, OR) ; Titterington; Donald R.;
(Newberg, OR) ; King; Clifford R.;
(Hendersonville, NC) |
Correspondence
Address: |
PATENT DOCUMENTATION CENTER
XEROX CORPORATION
100 CLINTON AVE., SOUTH, XEROX SQUARE, 20TH FLOOR
ROCHESTER
NY
14644
US
|
Assignee: |
XEROX CORPORATION
45 Glover Avenue, P.O. Box 4505
Norwalk
CT
06856-4505
|
Family ID: |
32681904 |
Appl. No.: |
12/019875 |
Filed: |
January 25, 2008 |
Related U.S. Patent Documents
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Application
Number |
Filing Date |
Patent Number |
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11204612 |
Aug 16, 2005 |
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12019875 |
Jan 25, 2008 |
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10854580 |
May 25, 2004 |
6969759 |
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12019875 |
Jan 25, 2008 |
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10422742 |
Apr 24, 2003 |
6764541 |
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12019875 |
Jan 25, 2008 |
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Current U.S.
Class: |
534/788 ;
534/844 |
Current CPC
Class: |
C09B 29/0003 20130101;
C09D 11/36 20130101; C09B 29/0813 20130101; C09B 29/0088 20130101;
C09D 11/34 20130101 |
Class at
Publication: |
534/788 ;
534/844 |
International
Class: |
C09B 29/045 20060101
C09B029/045; C09B 29/00 20060101 C09B029/00 |
Claims
1. A compound of the formula ##STR56##
2. A compound which is the reaction product of a colorant
composition of the formula ##STR57## wherein R is an alkyl group,
an aryl group, an arylalkyl group, or an alkylaryl group, and
wherein R can be joined to the phenyl moiety to form a ring, R' is
an aromatic- or heteroaromatic-containing group, each R.sub.a,
independently of the others, is a halogen atom, an alkyl group, an
alkoxy group, a nitrile group, a nitro group, an amide group, or a
sulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an
integer representing the number of carbon atoms in each repeat
alkylene oxide unit, and x is an integer representing the number of
repeat alkylene oxide units, wherein said colorant has no more than
one --OH, --SH, or primary or secondary amino group per molecule,
and a monoisocyanate.
3. A compound according to claim 2 wherein the monoisocyanate is
octadecylisocyanate; hexadecylisocyanate; octylisocyanate; butyl
isocyanate; t-butylisocyanate; cyclohexyl isocyanate; adamantyl
isocyanate; ethylisocyanatoacetate; ethoxycarbonylisocyanate;
phenylisocyanate; alphamethylbenzyl isocyanate; 2-phenylcyclopropyl
isocyanate; benzylisocyanate; 2-ethylphenylisocyanate;
benzoylisocyanate; meta-tolylisocyanate; para-tolylisocyanate;
2-nitrophenylisocyanate; 3-nitrophenylisocyanate;
4-nitrophenylisocyanate; 2-ethoxyphenyl isocyanate; 3-methoxyphenyl
isocyanate; 4-methoxyphenylisocyanate; ethyl 4-isocyanatobenzoate;
2,6-dimethylphenylisocyante; 1-naphthylisocyanate;
(naphthyl)ethylisocyante; or mixtures thereof.
4. A compound which is the reaction product of a colorant
composition of the formula ##STR58## wherein R is an alkyl group,
an aryl group, an arylalkyl group, or an alkylaryl group, and
wherein R can be joined to the phenyl moiety to form a ring, R' is
an aromatic- or heteroaromatic-containing group, each R.sub.a,
independently of the others, is a halogen atom, an alkyl group, an
alkoxy group, a nitrile group, a nitro group, an amide group, or a
sulfonamide group, w is an integer of 0, 1, 2, 3, or 4, n is an
integer representing the number of carbon atoms in each repeat
alkylene oxide unit, and x is an integer representing the number of
repeat alkylene oxide units, wherein said colorant has no more than
one --OH, --SH, or primary or secondary amino group per molecule,
and a monoanhydride.
5. A compound according to claim 4 wherein the anhydride is a
cyclic anhydride.
6. A compound according to claim 4 wherein the anhydride is an
alkylsuccinic anhydride, an alkenylsuccinic anhydride, or a mixture
thereof.
7. A compound according to claim 4 wherein the anhydride is maleic
anhydride, 2,3-diphenylmaleic anhydride, trimellitic anhydride,
2-phenylglutaric anhydride, homophthalic anhydride, isatoic
anhydride, n-methylisatoic anhydride, 5-chloroisatoic anhydride,
phthalic anhydride, 4-methylphthalic anhydride,
3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,
4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,
tetrachlorophthalic anhydride, tetrabromophthalic anhydride,
3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,
3-nitrophthalic anhydride, 4-nitrophthalic anhydride, diphenic
anhydride, 1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic
anhydride, 4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic
anhydride, 3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic
anhydride, 4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride
dipotassium salt, cis-1,2,3,6-tetrahydrophthalic anhydride,
cis-5-norbornene-endo-2,3dicarboxylic anhydride,
endo-bicyco[2,2,2]oct-5-ene-2,3dicarboxylic anhydride, cantharidin,
methyl-5-norbornene-2,3-dicarboxylic anhydride,
exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,
s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,
citraconic anhydride, 2,3-dimethylmaleic anhydride,
1-cyclopentene-1,2-dicarboxylic anhydride,
3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,
dichloromaleic anhydride,
1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,
cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric
anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric
anhydride, 3-ethyl-3-methylglutaric anhydride,
3,3tetramethyleneglutaric anhydride, hexafluoroglutaric anhydride,
3,5-diacetyltetrahydropyran-2,4,6-trione, diglycolic anhydride,
succinic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic
anhydride, isobuteneylsuccinic anhydride, 2-octen-1-ylsuccinic
anhydride, octadecenylsuccinic anhydride,
3-oxabicyclo[3,1,0]hexane-2,4-dione,
cis-1,2-cyclohexanedicarboxylic anhydride,
trans-1,2-cyclohexanedicarboxylic anhydride,
hexahydro-4-methylphthalic anhydride, itaconic anhydride,
2-dodecen-1-ylsuccinic anhydride, or mixtures thereof.
Description
[0001] This application is a divisional of U.S. application Ser.
No. 11/204,612, filed Aug. 16, 2005, U.S. Publication 20050272902,
which is a divisional of U.S. application Ser. No. 10/854,580,
filed May 25, 2004, now U.S. Pat. No. 6,969,759, which is a
divisional of U.S. application Ser. No. 10/422,742, filed Apr. 24,
2003, now U.S. Pat. No. 6,764,541, the disclosures of each of which
are totally incorporated herein by reference.
CROSS-REFERENCES TO COPENDING APPLICATIONS
[0002] Copending application U.S. Ser. No. 10/422,755, filed Apr.
24, 2003, now U.S. Pat. No. 7,034,185, entitled "Colorant Precursor
Compositions," with the named inventors Jeffery H. Banning, Donald
R. Titterington, and Clifford R. King, the disclosure of which is
totally incorporated herein by reference, discloses colorant
precursor compounds of the formula ##STR2## wherein R is an alkyl
group, an aryl group, an arylalkyl group, or an alkylaryl group,
and wherein R can be joined to the phenyl moiety to form a ring,
each R', independently of the others, is a halogen atom, an alkyl
group, an alkoxy group, a nitrile group, a nitro group, an amide
group, or a sulfonamide group, z is an integer of 0, 1, 2, 3, or 4,
n is an integer representing the number of carbon atoms in each
repeat alkylene oxide unit, and x is an integer representing the
number of repeat alkylene oxide units, wherein said colorant
precursor has no more than one --OH, --SH, or primary or secondary
amino group per molecule.
[0003] Copending application U.S. Ser. No. 10/422,897, filed Apr.
24, 2003, now U.S. Pat. No. 6,790,267, entitled "Colorant
Compositions," with the named inventors Jeffery H. Banning, Donald
R. Titterington, and Clifford R. King, the disclosure of which is
totally incorporated herein by reference, discloses colorant
compounds of the formula ##STR3## wherein R is an alkyl group, an
aryl group, an arylalkyl group, or an alkylaryl group, and wherein
R can be joined to the phenyl moiety to form a ring, each R',
independently of the others, is a halogen atom, an alkyl group, an
alkoxy group, a nitrile group, a nitro group, an amide group, or a
sulfonamide group, z is an integer of 0, 1, 2, 3, or 4, n is an
integer representing the number of carbon atoms in each repeat
alkylene oxide unit, x is an integer representing the number of
repeat alkylene oxide units, and A and B each, independently of the
other, are hydrogen atoms, halogen atoms, tertiary amino groups,
imine groups, ammonium groups, cyano groups, pyridine groups,
pyridinium groups, ether groups, ester groups, amide groups,
sulfate groups, sulfonate groups, sulfide groups, sulfoxide groups,
phosphine groups, phosphonium groups, phosphate groups, nitrile
groups, mercapto groups, nitro groups, sulfone groups, acyl groups,
azo groups, cyanato groups, alkyl groups, alkoxy groups, aryl
groups, aryloxy groups, arylalkyl groups, arylalkyloxy groups,
alkylaryl groups, or alkylaryloxy groups, wherein said colorant has
no more than one --OH, --SH, or primary or secondary amino group
per molecule.
[0004] Copending application U.S. Ser. No. 10/422,895, filed Apr.
24, 2003, U.S. Publication 20040214918, entitled "Colorant
Compositions," with the named inventors Jeffery H. Banning, Donald
R. Titterington, and Clifford R. King, the disclosure of which is
totally incorporated herein by reference, discloses colorant
compounds of the formula ##STR4## wherein R, R.sub.1, R.sub.2,
R.sub.3, and R.sub.4 each, independently of the others, is an alkyl
group, an aryl group, an arylalkyl group, or an alkylaryl group,
and wherein R, R.sub.1, R.sub.2, R.sub.3, and R.sub.4 each can be
joined to a phenyl moiety to form a ring, each R'.sub.a, R'.sub.b,
and R'.sub.c, independently of the others, is a halogen atom, an
alkyl group, an alkoxy group, a nitrile group, a nitro group, an
amide group, or a sulfonamide group, z1, z2, and z3 each,
independently of the others, is an integer of 0, 1, 2, 3, or 4, n
is an integer representing the number of carbon atoms in each
repeat alkylene oxide unit, x is an integer representing the number
of repeat alkylene oxide units, D is an anion, and g is the charge
on the anion, wherein said colorant has no more than one --OH,
--SH, or primary or secondary amino group per molecule.
BACKGROUND OF THE INVENTION
[0005] The present invention is directed to specific colorant
compounds and to ink compositions containing these colorant
compounds. More specifically, the present invention is directed to
specific reactive azo colorant compounds and to ink compositions
containing these colorant compounds. One embodiment of the present
invention is directed to a colorant composition of the formula
##STR5## wherein R is an alkyl group, an aryl group, an arylalkyl
group, or an alkylaryl group, and wherein R can be joined to the
phenyl moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said colorant has no more than one
--OH, --SH, or primary or secondary amino group per molecule.
Another embodiment of the present invention is directed to a
compound comprising two or more moieties of the formula ##STR6##
wherein R is an alkyl group, an aryl group, an arylalkyl group, or
an alkylaryl group, and wherein R can be joined to the phenyl
moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said moieties each contain no --OH
groups, --SH groups, or primary or secondary amino groups, said
moieties being linked by a central atom or group of atoms or bonded
to a polymer. Yet another embodiment of the present invention is
directed to a phase change ink comprising a phase change ink
carrier and a colorant compound comprising one or more moieties of
the formula ##STR7## wherein R is an alkyl group, an aryl group, an
arylalkyl group, or an alkylaryl group, and wherein R can be joined
to the phenyl moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein, when the colorant compound contains
exactly one of the moieties, the moiety contains no more than one
--OH, --SH, or primary or secondary amino group per molecule, and
when the colorant compound contains more than one of the moieties,
said moieties each contain no --OH groups, --SH groups, or primary
or secondary amino groups.
[0006] 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 recording
substrate, either directly or via an intermediate heated transfer
belt or drum, they quickly solidify to form a predetermined pattern
of solidified ink drops. Phase change inks have also been used in
other printing technologies, such as gravure printing, as disclosed
in, for example, U.S. Pat. No. 5,496,879 and German Patent
Publications DE 4205636AL and DE 4205713AL, the disclosures of each
of which are totally incorporated herein by reference.
[0007] Phase change inks for color printing typically comprise a
phase change ink carrier composition which is combined with a phase
change ink compatible colorant. In a specific embodiment, a series
of colored phase change inks can be formed by combining ink carrier
compositions with compatible subtractive primary colorants. The
subtractive primary colored phase change inks can comprise four
component dyes, namely, cyan, magenta, yellow and black, although
the inks are not limited to these four colors. These subtractive
primary colored inks can be formed by using a single dye or a
mixture of dyes. For example, magenta can be obtained by using a
mixture of Solvent Red Dyes or a composite black can be obtained by
mixing several dyes. U.S. Pat. No. 4,889,560, U.S. Pat. No.
4,889,761, and U.S. Pat. No. 5,372,852, the disclosures of each of
which are totally incorporated herein by reference, teach that the
subtractive primary colorants employed can comprise dyes from the
classes of Color Index (C.I.) Solvent Dyes, Disperse Dyes, modified
Acid and Direct Dyes, and Basic Dyes. The colorants can also
include pigments, as disclosed in, for example, U.S. Pat. No.
5,221,335, the disclosure of which is totally incorporated herein
by reference. U.S. Pat. No. 5,621,022, the disclosure of which is
totally incorporated herein by reference, discloses the use of a
specific class of polymeric dyes in phase change ink
compositions.
[0008] Phase change inks have also been used for applications such
as postal marking, industrial marking, and labelling.
[0009] Phase change inks are desirable for ink jet printers because
they remain in a solid phase at room temperature during shipping,
long term storage, and the like. In addition, the problems
associated with nozzle clogging as a result of ink evaporation with
liquid ink jet inks are largely eliminated, thereby improving the
reliability of the ink jet printing. Further, in phase change ink
jet printers wherein the ink droplets are applied directly onto the
final recording substrate (for example, paper, transparency
material, and the like), the droplets solidify immediately upon
contact with the substrate, so that migration of ink along the
printing medium is prevented and dot quality is improved.
[0010] Compositions suitable for use as phase change ink carrier
compositions are known. Some representative examples of references
disclosing such materials include U.S. Pat. No. 3,653,932, U.S.
Pat. No. 4,390,369, U.S. Pat. No. 4,484,948, U.S. Pat. No.
4,684,956, U.S. Pat. No. 4,851,045, U.S. Pat. No. 4,889,560, U.S.
Pat. No. 5,006,170, U.S. Pat. No. 5,151,120, U.S. Pat. No.
5,372,852, U.S. Pat. No. 5,496,879, European Patent Publication
0187352, European Patent Publication 0206286, German Patent
Publication DE 4205636AL, German Patent Publication DE 4205713AL,
and PCT Patent Application WO 94/04619, the disclosures of each of
which are totally incorporated herein by reference. Suitable
carrier 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, for example), and many synthetic resins,
oligomers, polymers, and copolymers.
[0011] U.S. Pat. No. 5,864,002 (Stephens et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
method of providing for manufacturing a colored polymer resin
having the steps of: (a) blending a disazo colorant into a mixture
of monomers, the colorant having a poly(oxyalkylene) substituent
comprising from 2 to 200 alkylene oxide residues, bonded to each
end of the disazo chromophore, the poly(oxyalkylene) substituent
having a nucleophilic terminal group which is capable of reacting
with at least a portion of the monomers; (b) providing conditions
under which the monomers and disazo colorant polymerize to form a
colored polymer resin.
[0012] U.S. Pat. No. 5,591,833 (Hines et al.), the disclosure of
which is totally incorporated herein by reference, discloses
colorants and compositions useful as a fugitive or permanent
colorant for a variety of substrates, or as intermediates for their
manufacture, and having one or more improved properties of enhanced
aqueous washability, compatibility with and non-extractibility from
thermoplastic resins, or reactivity with resins having reactive
functionality, said composition having the formula C(Z).sub.1-8
wherein C is the residue of a reactant having from 1 to 8
nucleophilic site residues to which the Z moieties are attached;
said Z moieties containing at least about 60 weight percent of
poly(oxyalkylene) which comprises (a) at least one glycidol residue
segment of 2 to 6 glycidol residues attached to a nucleophilic site
of C, wherein said poly(oxyalkylene) contains a total of from 2 to
20 glycidol residues, (b) and wherein said poly(oxyalkylene)
further contains the residues of one or more other epoxide
reactants of ethylene oxide (EO), propylene oxide (PO), or butylene
oxide (BO), or mixtures thereof, wherein said poly(oxyalkylene)
contains a total of from about 10 to about 600 of said EO, PO, or
BO residues, or mixtures thereof, at least about 75 mole percent of
which are EO residues, (c) and with the provisions that the ratio
of the total of --O--PO-- and --O--BO-- linkages of all glycidol
residues to the total of all functional oxy linkages of said
glycidol residues is less than one, and the molar ratio of EO
residues to glycidol residues is from 4 to 75.
[0013] U.S. Pat. No. 5,290,921 (Moody et al.), the disclosure of
which is totally incorporated herein by reference, discloses
primary hydroxyl enhanced colorants having markedly improved
reactivities in e.g., polyurethane foams for imparting permanent
coloring thereto, the colorants having the formula C-(Z).sup.1-4
wherein C is an azo, methine, or azamethine chromogen and Z is a
poly(oxyalkylene) moiety comprising (1) at least two (A) units
independently selected from those of the formulae
--CH.sub.2CH(O-T)CH.sub.2O-- or --CH.sub.2CH(O-T)CH.sub.2O-T and
(2) from none to about 200 (B) units of the formula (--RO--)
wherein R is straight or branched chain hydrocarbon of 2 to 4
carbons, T is a moiety of the formula
--CH.sub.2CH(R.sub.1)--O--(RO).sub.0-40--CH.sub.2CH.sub.2OH wherein
R.sub.1 is selected from unsubstituted or substituted alkyl, aryl,
alkenyloxyalkyl, alkoxyalkyl, or aryloxyalkyl, and wherein the A
units comprise at least 0.5 percent of the total A+B units.
[0014] U.S. Pat. No. 5,108,460 (Hines et al.), the disclosure of
which is totally incorporated herein by reference, discloses azo
chromophores having polyoxyalkylene substituents that are linked
together by a covalent bond or by an intervening connecting group
to form dimers or trimers. The polyoxyalkylene substituents are
straight or branched chain polymers primarily of ethylene oxide
which make the dimer and trimer colorants useful as fugitive
tints.
[0015] U.S. Pat. No. 5,082,938 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses
enhanced branched chain hydroxyl compounds of formula Y-(Z).sub.1-6
wherein Y is the residue of a nucleophile devoid of conjugated
divalent linking moieties, and each Z is a poly(oxyalkylene) moiety
having a molecular weight of from about 200 to 10,000 and
containing at least one glycidol residue, wherein at least one of
the primary oxy sites of said glycidol residue is linked preferably
directly to a first epoxide residue of three or more carbons, and
wherein said first epoxide residue is linked through a secondary
oxy site preferably directly to a second epoxide reside having a
primary terminal hydroxyl.
[0016] U.S. Pat. No. 5,043,013 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
washable aqueous ink composition having a viscosity of from about
1.0 to about 6.0 centipoise and containing from about 10 to about
50 percent by weight of one or more polymeric colorants of the
formula {R.sub.1[(RO).sub.a--Y].sub.b}.sub.c wherein X is a polar
group such as sulfonic acids, sulfonic acid salts, sulfonamides,
sulfonates or the like; R is alkylene; Y is H, alkanoyl, carbamoyl,
or the like; R.sub.1 is nitrogen, oxygen, sulfur, or a
sulfur-containing divalent linking group; a is an integer of from
six to about forty; b and c are each independently selected from
one or two; d is an integer of from one to four; the product of (a)
(b) (c) is an integer of from 6 to about 40; and CHROM is a
chromophore such as nitro, nitroso, monoazo, disazo and trisazo,
diarylmethane, triarylmethane, xanthane, acridine, methine,
thiazole, indamine, azine, oxazine, or anthraquinone, wherein the
(RO).sub.a moiety is bonded to a carbocyclic aromatic ring of the
(CHROM) through R.sub.1.
[0017] U.S. Pat. No. 4,751,254 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
process for coloring polyurethane resins during the production of
same with reactive colorants derived from
polyalkoxytrifluoroaniline intermediates. These colorants impart
increased brightness in shade for both aromatic and heteroaromatic
derivatives and increased resistance to stannous octanoate catalyst
over conventional polymeric colorants derived for heteroaromatic
compounds. These colorants have the structure ##STR8## wherein
R.sub.1 is selected from H, a lower alkyl group containing from 1
to about 10 carbon atoms, CH.sub.2Cl, CH.sub.2OH, phenyl, or
##STR9## where R.sub.6 is H or a lower alkyl group containing from
1 to about 9 carbon atoms; R.sub.2 is selected from OH, NH.sub.2,
or SH; R.sub.3 is selected from a lower alkyl group containing from
1 to about 9 carbon atoms, cyanoalkyl, acetoxyalkyl, or ##STR10##
where R.sub.1 and R.sub.2 are as given above; R.sub.4 is H,
CF.sub.3, a lower alkyl group containing from 1 to about 9 carbon
atoms, Cl, or Br and n is 0 or an integer from 1 to about 125.
R.sub.5 is an aromatic or heteroaromatic containing group, said
colorants being resistant to stannous octanoate, being
characterized as having improved brightness and which have
functionality through reactive substituents thereof.
[0018] U.S. Pat. No. 4,658,064 (Moore et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
compound of the formula ##STR11## wherein R.sub.1 is selected from
alkyl, halide, or alkoxy; R.sub.2 is selected from H or alkyl; Y is
a number of from 2 to about 200; and Z is selected from H or
##STR12## where W is alkyl.
[0019] U.S. Pat. No. 4,594,454 (Moore et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
compound of the formula ##STR13## wherein R.sub.1 is selected from
alkyl, halide, or alkoxy; R.sub.2 is selected from H or alkyl; Y is
a number of from 2 to about 200; and Z is selected from H or
##STR14## where W is alkyl.
[0020] U.S. Pat. No. 4,400,320 (Keller et al.), the disclosure of
which is totally incorporated herein by reference, discloses
fugitive tints which are characterized by the formula ##STR15##
where R is selected from meta-toluidene, meta-amino phenol,
aniline, or dimethoxy aniline, A is selected from N, O, S, or
CO.sub.2; the alkylene group of the alkyleneoxy constituent
contains from 2 to about 4 carbon atoms; n is an integer of from 2
to about 300; m is 1 when A is O, S, or CO.sub.2, and 2 when A is
N; x is an integer of from 1 to about 5; and the product of n times
m times x (nmx) is from 2 to about 400. Also disclosed is a process
for preparing alkyleneoxy fugitive tints.
[0021] U.S. Pat. No. 4,284,729 (Cross et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
process for coloring thermosetting resins, made by polyaddition
reaction of a nucleophile with an electrophile, with a polymeric
liquid reactive coloring agent suitable for incorporation in the
resin with the formation of covalent bonds, said coloring agent
having the formula R-(polymeric constituent-X).sub.n wherein R is
an organic dyestuff radical; the polymeric constituent is selected
from polyalkylene oxides and copolymers of polyalkylene oxides in
which the alkylene moiety of the polymeric constituent contains 2
or more carbon atoms and such polymeric constituent has a molecular
weight of from about 44 to about 1500; and n is an integer of from
1 to about 6; and X is selected from --OH, --NH.sub.2, and --SH,
said coloring agent being added in an amount sufficient to provide
coloration of said thermosetting resin.
[0022] U.S. Pat. No. 4,132,840 (Hugl et al.), the disclosure of
which is totally incorporated herein by reference, discloses
polyurethane plastics that are dyed with dyestuffs of the formula
##STR16## wherein R.sub.1, denotes hydrogen, halogen, optionally
substituted C.sub.1-C.sub.4 alkyl, optionally substituted
C.sub.1-C.sub.4 alkoxy, and optionally substituted C.sub.1-C.sub.4
alkylcarbonylamino and R.sub.2 denotes hydrogen, optionally
substituted C.sub.1-C.sub.4 alkyl, and optionally substituted
C.sub.1-C.sub.4 alkoxy, while A and B denote optionally branched
alkylene chains which can be identical or different and preferably
have 2 to 6 carbon atoms, with formation of covalent bonds, in that
the dyestuffs are added before or during the polyaddition reaction
to the reaction mixture of polyol and polyisocyanate or to one of
the components.
[0023] U.S. Pat. No. 3,994,835 (Wolf et al.), the disclosure of
which is totally incorporated herein by reference, discloses
dispersions of dyestuffs which contain at least one free amino or
hydroxyl group capable of reacting with isocyanates under the
conditions of polyaddition and liquids in which the dyes are
soluble to an extent less than 2 percent which are suitable for the
production of colored polyurethane foams. The dye dispersions can
be added before or during the polyaddition reaction.
[0024] U.S. Pat. No. 5,270,363 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
colorant for natural or synthetic resinous or polymeric materials,
having the formula A-[SO.sub.2--N(R.sub.2)--Y].sub.1-4 wherein
R.sub.2 is selected for example from hydrogen, methyl, cyclohexyl,
phenyl or Y; A is a nonionic metallophthalocyanine chromophore
which can be substituted for example with halogen, alkyl, alkoxy,
alkylthio, or aryloxy; Y is a poly(oxyalkylene) moiety containing
at least three monomeric units or mixtures thereof of the formula
(--RO--) wherein each R is straight or branched alkylene of 1 to 4
carbons or mixtures thereof, up to about 20 mole percent of said
monomeric units may be connected by one or more linking groups such
as alkyleneoxy, --NH--, or --NHCONH--, and wherein Y can be
terminated by hydrogen, or by at branch substituents, containing 1
to 3 groups or moieties selected from alkyl, cycloalkyl, acyl, or
aryl; wherein any of the above recited hydrocarbon groups, moieties
or substituents may themselves be substituted with up to four
substituents selected, for example, from alkyl, halogen, mercapto,
alkoxycarbonyl, hydroxy, alkoxy, or the like; and wherein each
aliphatic hydrocarbon portion or moiety of the groups, moieties or
substituents recited above contains from 1 to 20 carbons.
[0025] U.S. Pat. No. 4,912,203 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses
thiophene based colorants useful for coloring thermoset resins such
as polyurethanes being of the formula ##STR17## wherein R.sub.1,
R.sub.2, and R.sub.3 are selected from halogen, carboxylic acid,
alkanoyl, aryloyl, carbocyclic forming polymethylene chains, alkyl,
aryl, cyano, thioalkyl, dithioalkyl, thioaryl, dithioaryl,
thiocyano, carboxyalkyl, carboxyaryl, amidoalkyl, amidodialkyl,
amidoaryl, amidodiaryl, oxyalkyl, thioamidoalkyl, thioamidodialkyl,
or hydrogen when an adjacent group is isobutyryl; R.sub.4, R.sub.5,
and R.sub.7 are selected from hydrogen alkyl, oxyalkyl,
sulfonamidoalkyl, sulfonamidoaryl, amidoalkyl, amidodialkyl,
amidoaryl, amidodiaryl, halogen, thioalkyl, and thioaryl; and
R.sub.8 and R.sub.9 are selected from polyalkylene oxide,
copolymers of polyalkylene oxides, and hydroxyalkylenes.
[0026] U.S. Pat. No. 4,846,846 (Rekers et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
process for coloring polyurethane resins made by a polyaddition
reaction of a polyol and an isocyanate which comprises adding to
the reaction mixture before or during the polyaddition reaction a
reactive coloring agent suitable for incorporation in the resin
with the formation of covalent bonds, said coloring agent having
the formula ##STR18## in which R.sub.1 and R.sub.2 are
independently selected from an alkyl group having from 1 to about
12 carbon atoms, X is --CH.sub.2--, a and a' are integers from 1 to
about 6, and Y and Y' are independently selected from polymeric
units of hydroxy alkylenes or alkylene oxide monomers selected from
ethylene oxide, propylene oxide, butylene oxide, cyclohexene oxide,
or glycidol, b and b' are independently either 0 or 1, and Z and Z'
are reactive groups independently selected from --OH, --NH.sub.2,
or --SH.
[0027] U.S. Pat. No. 4,507,407 (Kluger et al.), the disclosure of
which is totally incorporated herein by reference, discloses a
process of coloring polyurethane resins during the production of
same with reactive colorants having the formula ##STR19## wherein
R.sub.1, R.sub.2, R.sub.3 are selected from halogen, carboxylic
acid, alkanoyl, aryloyl, alkyl, aryl, cyano, sulfonylalkyl,
sulfonylaryl, thioalkyl, thioaryl, sulfinylalkyl, sulfinylaryl,
dithioalkyl, dithioaryl, thiocyano, amidoalkyl, amidodialkyl,
oxyalkyl, oxyaryl, hydrogen, sulfonamidoalkyl, sulfonamidoaryl,
sulfonamidodialkyl, sulfonamidodiaryl, carbocyclic forming
polymethylene chains, sulfenamidoalkyl, sulfenamidodialkyl,
sulfenamidoaryl, sulfenamidodiaryl, sulfinamidoalkyl,
sulfinamidodialkyl, sulfinamidoaryl, sulfinamidodiaryl; and A is an
organic dyestuff coupler that is resistant to stannous octanoate
and flame retardant compounds and which has functionality through
reactive substituents thereof.
[0028] U.S. Pat. No. 5,919,839 (Titterington et al.), the
disclosure of which is totally incorporated herein by reference,
discloses colored waxes made by reacting selected nucleophiles,
including alcohol containing colorants, with an isocyanate. A phase
change ink is made by blending the colored wax with a clear ink
carrier composition. The clear ink carrier composition can be a
fatty amide-based material and/or a combination of
isocyanate-derived resins in which 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 colored wax materials are
useful as ingredients with phase change ink carrier compositions to
make phase change ink jet inks.
[0029] U.S. Pat. No. 5,456,725 (Bruhnke), the disclosure of which
is totally incorporated herein by reference, discloses a process
for temporarily coloring a polyamide substrate whereby a
poly(oxyalkylene) substituted methine colorant is applied to the
substrate followed by heating the substrate with superheated steam
at a temperature of 250.degree. F. or greater, which effectively
decolorizes the methine colorant.
[0030] PCT Patent Application WO 97/13816, the disclosure of which
is totally incorporated herein by reference, discloses a colored
material suitable for use in a hot melt ink comprising a oligomeric
hot melt ink jet vehicle formed of molecules having a backbone and
at least one pendant side-chain. A dyestuff is reacted onto the
backbone. The material is preferably obtainable as the reaction
product of an aliphatic or aromatic mono- or di-isocyanate and a
hydroxyl group functional dye component, and optionally one or more
other suitable material. Such suitable materials include mono- and
dihydric alcohols, primary and secondary monoamines, functional
amides, hydroxyl functional amines and hydroxyl containing
components having a terminal unsaturated bond.
[0031] "Polymeric Colorants," J. Miley, IUPAC Pure and Applied
Chemistry, Vol. 68, No. 7, p. 1423 (1996), the disclosure of which
is totally incorporated herein by reference, discloses specific
examples of polymeric colorants and how they meet functional
requirements.
[0032] While known compositions are suitable for their intended
purposes, a need remains for improved reactive azo colorants. In
addition, a need remains for reactive azo colorants that are easily
purified. Further, a need remains for reactive azo colorants that
exhibit reduced toxicity. Additionally, a need remains for reactive
azo colorants that are liquid at room temperature. There is also a
need for reactive azo colorants that can be tailored for
compatibility with various hydrophobic or hydrophilic applications.
In addition, there is a need for reactive azo colorants that, when
reacted with or reacted to form oligomers or polymers such as
polyurethanes, polyanhydrides, or the like, resist migration and/or
settling. Further, there is a need for reactive azo colorants that,
when reacted with other materials, do not result in the formation
of products of undesirably high molecular weight. Additionally,
there is a need for reactive azo colorants that, when reacted with
other materials, do not result in the formation of products with
undesirable crosslinking. A need also remains for reactive azo
colorants that, when reacted with other materials, form products
suitable for use in phase change ink compositions. In addition, a
need remains for reactive azo colorants that, when reacted with
other materials, form products that, when incorporated into phase
change ink compositions, exhibit reduced precipitation of the
colorant from the ink. Further, a need remains for reactive azo
colorants that, when reacted with other materials, form products
that, when incorporated into phase change ink compositions, exhibit
reduced clogging of printer heads and resulting printer
failure.
SUMMARY OF THE INVENTION
[0033] The present invention is directed to a colorant composition
of the formula ##STR20## wherein R is an alkyl group, an aryl
group, an arylalkyl group, or an alkylaryl group, and wherein R can
be joined to the phenyl moiety to form a ring, R' is an aromatic-
or heteroaromatic-containing group, each R.sub.a, independently of
the others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said colorant has no more than one
--OH, --SH, or primary or secondary amino group per molecule.
Another embodiment of the present invention is directed to a
compound comprising two or more moieties of the formula ##STR21##
wherein R is an alkyl group, an aryl group, an arylalkyl group, or
an alkylaryl group, and wherein R can be joined to the phenyl
moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said moieties each contain no --OH
groups, --SH groups, or primary or secondary amino groups, said
moieties being linked by a central atom or group of atoms or bonded
to a polymer. Yet another embodiment of the present invention is
directed to a phase change ink comprising a phase change ink
carrier and a colorant compound comprising one or more moieties of
the formula ##STR22## wherein R is an alkyl group, an aryl group,
an arylalkyl group, or an alkylaryl group, and wherein R can be
joined to the phenyl moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein, when the colorant compound contains
exactly one of the moieties, the moiety contains no more than one
--OH, --SH, or primary or secondary amino group per molecule, and
when the colorant compound contains more than one of the moieties,
said moieties each contain no --OH groups, --SH groups, or primary
or secondary amino groups.
DETAILED DESCRIPTION
[0034] The present invention is directed to a colorant of the
formula ##STR23## wherein R is an alkyl group (including linear,
branched, saturated, unsaturated, cyclic, and unsubstituted alkyl
groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the alkyl group), in one embodiment with at least 1 carbon atom,
and in another embodiment with at least about 2 carbon atoms, and
in one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
an aryl group (including unsubstituted and substituted aryl groups,
and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the aryl group), in one embodiment with at least about 5 carbon
atoms, and in another embodiment with at least about 6 carbon
atoms, and in one embodiment with no more than about 50 carbon
atoms, and in another embodiment with no more than about 48 carbon
atoms, although the number of carbon atoms can be outside of these
ranges, an arylalkyl group (including unsubstituted and substituted
arylalkyl groups, and wherein hetero atoms, such as oxygen,
nitrogen, sulfur, silicon, phosphorus, and the like either may or
may not be present in either or both of the alkyl portion and the
aryl portion of the arylalkyl group), in one embodiment with at
least about 6 carbon atoms, and in another embodiment with at least
about 7 carbon atoms, and in one embodiment with no more than about
50 carbon atoms, and in another embodiment with no more than about
48 carbon atoms, although the number of carbon atoms can be outside
of these ranges, or an alkylaryl group (including unsubstituted and
substituted alkylaryl groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in either or both of the alkyl portion
and the aryl portion of the alkylaryl group), in one embodiment
with at least about 6 carbon atoms, and in another embodiment with
at least about 7 carbon atoms, and in one embodiment with no more
than about 50 carbon atoms, and in another embodiment with no more
than about 48 carbon atoms, although the number of carbon atoms can
be outside of these ranges, wherein the substituents on the
substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be
(but are not limited to) halogen atoms, tertiary amino groups,
imine groups, ammonium groups, cyano groups, pyridine groups,
pyridinium groups, ether groups, ester groups, amide groups,
sulfate groups, sulfonate groups, sulfide groups, sulfoxide groups,
phosphine groups, phosphonium groups, phosphate groups, nitrile
groups, mercapto groups, nitro groups, sulfone groups, acyl groups,
azo groups, cyanato groups, and the like, as well as mixtures
thereof, and wherein two or more substituents can be joined
together to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit (the alkylene oxide units can each have different
numbers of carbon atoms; for example, the polyalkylene oxide chain
can comprise a mixture of repeat ethylene oxide, propylene oxide,
and/or butylene oxide units), and in one embodiment is at least
about 2, and in one embodiment is no more than about 18, and in
another embodiment is no more than about 4, although the value of n
can be outside of these ranges, and x is an integer representing
the number of repeat alkylene oxide units, and in one embodiment is
at least about 2, and in another embodiment is at least about 5,
and in one embodiment is no more than about 100, and in another
embodiment is no more than about 20, although the value of x can be
outside of these ranges, wherein said colorant has no more than one
--OH, --SH, or --NHR.sub.b group (i.e., primary or secondary amino
group) per molecule, wherein R.sub.b is a hydrogen atom, an alkyl
group (including linear, branched, saturated, unsaturated, cyclic,
and unsubstituted alkyl groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in the alkyl group), in one embodiment
with at least 1 carbon atom, and in another embodiment with at
least about 2 carbon atoms, and in one embodiment with no more than
about 50 carbon atoms, and in another embodiment with no more than
about 48 carbon atoms, although the number of carbon atoms can be
outside of these ranges, an aryl group (including unsubstituted and
substituted aryl groups, and wherein hetero atoms, such as oxygen,
nitrogen, sulfur, silicon, phosphorus, and the like either may or
may not be present in the aryl group), in one embodiment with at
least 5 carbon atoms, and in another embodiment with at least about
6 carbon atoms, and in one embodiment with no more than about 50
carbon atoms, and in another embodiment with no more than about 48
carbon atoms, although the number of carbon atoms can be outside of
these ranges, an arylalkyl group (including unsubstituted and
substituted arylalkyl groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in either or both of the alkyl portion
and the aryl portion of the arylalkyl group), in one embodiment
with at least about 6 carbon atoms, and in another embodiment with
at least about 7 carbon atoms, and in one embodiment with no more
than about 50 carbon atoms, and in another embodiment with no more
than about 48 carbon atoms, although the number of carbon atoms can
be outside of these ranges, such as benzyl or the like, or an
alkylaryl group (including unsubstituted and substituted alkylaryl
groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in either or both of the alkyl portion and the aryl portion of the
alkylaryl group), in one embodiment with at least about 6 carbon
atoms, and in another embodiment with at least about 7 carbon
atoms, and in one embodiment with no more than about 50 carbon
atoms, and in another embodiment with no more than about 48 carbon
atoms, although the number of carbon atoms can be outside of these
ranges, such as tolyl or the like, and wherein the substituents on
the substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be
(but are not limited to) those indicated hereinabove for the R
group.
[0035] If desired, various substituents (shown as R.sub.a groups on
the structure) can be present on the central phenyl moiety of the
structure to affect the color of the colorant. From 1 to 4 of such
substituents can be present, which can be the same as each other or
different from each other. Examples of such substituents include
(but are not limited to) halogen atoms, such as fluorine, chlorine,
bromine, and iodine, alkyl groups, in one embodiment with at least
1 carbon atom, and in one embodiment with no more than about 25
carbon atoms, such as methyl, ethyl, and the like, alkoxy groups,
in one embodiment with at least 1 carbon atom, and in one
embodiment with no more than about 25 carbon atoms, such as methoxy
groups, ethoxy groups, and the like, nitrile groups, nitro groups,
amide groups, such as an acetamido group or the like, including
(but not limited to) those of the general formula ##STR24## wherein
R.sub.m is a hydrogen atom, an alkyl group (including linear,
branched, saturated, unsaturated, cyclic, and unsubstituted alkyl
groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the alkyl group), in one embodiment with at least 1 carbon atom,
and in another embodiment with at least about 2 carbon atoms, and
in one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
an aryl group (including unsubstituted and substituted aryl groups,
and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the aryl group), in one embodiment with at least 5 carbon atoms,
and in another embodiment with at least about 6 carbon atoms, and
in one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
an arylalkyl group (including unsubstituted and substituted
arylalkyl groups, and wherein hetero atoms, such as oxygen,
nitrogen, sulfur, silicon, phosphorus, and the like either may or
may not be present in either or both of the alkyl portion and the
aryl portion of the arylalkyl group), in one embodiment with at
least about 6 carbon atoms, and in another embodiment with at least
about 7 carbon atoms, and in one embodiment with no more than about
50 carbon atoms, and in another embodiment with no more than about
48 carbon atoms, although the number of carbon atoms can be outside
of these ranges, such as benzyl or the like, or an alkylaryl group
(including unsubstituted and substituted alkylaryl groups, and
wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,
phosphorus, and the like either may or may not be present in either
or both of the alkyl portion and the aryl portion of the alkylaryl
group), in one embodiment with at least about 6 carbon atoms, and
in another embodiment with at least about 7 carbon atoms, and in
one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyl or the like, and wherein the substituents on the
substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be
(but are not limited to) those indicated hereinabove for the R
group, such as an acetamido group or the like, sulfonamide groups,
including (but not limited to) those of the formula ##STR25##
wherein R.sub.p is a hydrogen atom, an alkyl group (including
linear, branched, saturated, unsaturated, cyclic, and unsubstituted
alkyl groups, and wherein hetero atoms, such as oxygen, nitrogen,
sulfur, silicon, phosphorus, and the like either may or may not be
present in the alkyl group), in one embodiment with at least 1
carbon atom, and in another embodiment with at least about 2 carbon
atoms, and in one embodiment with no more than about 50 carbon
atoms, and in another embodiment with no more than about 48 carbon
atoms, although the number of carbon atoms can be outside of these
ranges, an aryl group (including unsubstituted and substituted aryl
groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the aryl group), in one embodiment with at least 5 carbon atoms,
and in another embodiment with at least about 6 carbon atoms, and
in one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
an arylalkyl group (including unsubstituted and substituted
arylalkyl groups, and wherein hetero atoms, such as oxygen,
nitrogen, sulfur, silicon, phosphorus, and the like either may or
may not be present in either or both of the alkyl portion and the
aryl portion of the arylalkyl group), in one embodiment with at
least about 6 carbon atoms, and in another embodiment with at least
about 7 carbon atoms, and in one embodiment with no more than about
50 carbon atoms, and in another embodiment with no more than about
48 carbon atoms, although the number of carbon atoms can be outside
of these ranges, such as benzyl or the like, or an alkylaryl group
(including unsubstituted and substituted alkylaryl groups, and
wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,
phosphorus, and the like either may or may not be present in either
or both of the alkyl portion and the aryl portion of the alkylaryl
group), in one embodiment with at least about 6 carbon atoms, and
in another embodiment with at least about 7 carbon atoms, and in
one embodiment with no more than about 50 carbon atoms, and in
another embodiment with no more than about 48 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyl or the like, and wherein the substituents on the
substituted alkyl, aryl, arylalkyl, and alkylaryl groups can be
(but are not limited to) those indicated hereinabove for the R
group, or the like.
[0036] It should be noted that the R group can also be joined to
the central phenyl moiety to form a ring; for example, compounds of
the formulae ##STR26## are within the scope of the above
formula.
[0037] The colorants of the present invention can be prepared by,
for example, reacting an N-alkyl aniline with suitable reactants to
form a material of the formula ##STR27## wherein R, R.sub.a, w, n,
and x are as defined hereinabove. More specifically, the
corresponding N-alkyl aniline can be reacted with an epoxide
compound containing the desired number of carbon atoms in the
presence of a Lewis acid or a base. More specifically, if one
wants, for example, a compound wherein n is 3 (i.e., a
polypropylene oxide substituted compound), one can react the
aniline with an epoxide compound of the formula ##STR28## If one
wants a compound wherein n is 2 (i.e., a polyethylene oxide
substituted compound), one can react the aniline with an epoxide
compound of the formula ##STR29## The molar ratio of epoxide
compound to N-alkyl aniline is such that the desired number of
repeat alkylene oxide units per N-alkyl aniline molecule is
obtained; for example, if it is desired to have a molecule with an
average of about 10 repeat alkylene oxide units (i.e., x=10), the
molar ratio of epoxide compound to N-alkyl aniline is about
10:1.
[0038] The reaction can take place in the presence of a catalyst
which is either a base, such as potassium hydroxide or the like, or
a Lewis acid, such as BF.sub.3 etherate or the like. The catalyst
is present in any desired or effective amount, in one embodiment at
least about 0.01 mole of catalyst per every one mole of aniline, in
another embodiment at least about 0.05 mole of catalyst per every
one mole of aniline, and in yet another embodiment at least about
0.1 mole of catalyst per every one mole of aniline, and in one
embodiment no more than about 0.3 mole of catalyst per every one
mole of aniline, in another embodiment no more than about 0.2 mole
of catalyst per every one mole of aniline, and in yet another
embodiment no more than about 0.1 mole of catalyst per every one
mole of aniline, although the relative amounts can be outside of
these ranges.
[0039] Further information regarding these kinds of reactions is
disclosed in, for example, Preparation I of U.S. Pat. No.
4,091,034, Example 1 of U.S. Pat. No. 4,167,510, Example I of U.S.
Pat. No. 4,400,320, and Example 1A of U.S. Pat. No. 5,290,921, the
disclosures of each of which are totally incorporated herein by
reference.
[0040] Materials of the formula ##STR30## are also commercially
available. For example, a material of this formula wherein n is 2
and x is 10 is available from, for example, Henkel Corporation,
Mauldin, S.C. From the same company is also available as SO-7864 a
similar material wherein both ethylene oxide and propylene oxide
groups are randomly distributed through the polyalkylene oxide
chain in an average molar ratio of about 3.5 moles of ethylene
oxide groups to 6.5 moles of propylene oxide groups.
[0041] The azo colorants of the present invention are of the
general formula ##STR31## wherein R, n, and x are as defined
hereinabove, and R' is an aromatic- or heteroaromatic-containing
group. R' can be any aromatic-containing or
heteroaromatic-containing group suitable for azo colorants. R' can
be an aryl group (including unsubstituted and substituted aryl
groups, and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in the aryl group), in one embodiment with at least about 2 carbon
atoms, and in another embodiment with at least about 4 carbon
atoms, and in one embodiment with no more than about 60 carbon
atoms, and in another embodiment with no more than about 50 carbon
atoms, although the number of carbon atoms can be outside of these
ranges, an arylalkyl group (including unsubstituted and substituted
arylalkyl groups, and wherein hetero atoms, such as oxygen,
nitrogen, sulfur, silicon, phosphorus, and the like either may or
may not be present in either or both of the alkyl portion and the
aryl portion of the arylalkyl group), in one embodiment with at
least about 3 carbon atoms, in another embodiment with at least
about 5 carbon atoms, and in yet another embodiment with at least
about 7 carbon atoms, and in one embodiment with no more than about
60 carbon atoms, in another embodiment with no more than about 50
carbon atoms, and in yet another embodiment with no more than about
18 carbon atoms, although the number of carbon atoms can be outside
of these ranges, such as benzyl or the like, or an alkylaryl group
(including unsubstituted and substituted alkylaryl groups, and
wherein hetero atoms, such as oxygen, nitrogen, sulfur, silicon,
phosphorus, and the like either may or may not be present in either
or both of the alkyl portion and the aryl portion of the alkylaryl
group), in one embodiment with at least about 3 carbon atoms, in
another embodiment with at least about 5 carbon atoms, and in yet
another embodiment with at least about 7 carbon atoms, and in one
embodiment with no more than about 60 carbon atoms, in another
embodiment with no more than about 50 carbon atoms, and in yet
another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
such as tolyl or the like, and wherein the substituents on the
substituted aryl, arylalkyl, and alkylaryl groups can be (but are
not limited to) those indicated hereinabove as suitable for the R
group.
[0042] Examples of R' groups include (but are not limited to)
thiophene derivatives, benzothiazole derivatives, benzoisothiazole
derivatives, thiadiazole derivatives, benzene derivatives,
imidazole derivatives, and the like.
[0043] Specific examples of classes of R' groups include (but are
not limited to) (a) those of the formula ##STR32## wherein A, G,
and J each, independently of the others, is a carbon atom or a
hetero atom, such as nitrogen, oxygen, sulfur, phosphorus, silicon,
or the like, and R.sub.1, R.sub.2, and R.sub.3 each, independently
of the other, is a hydrogen atom, a halogen atom, such as fluorine,
chlorine, bromine, or iodine, a cyano group, an alkyl group
(including linear, branched, saturated, unsaturated, cyclic, and
unsubstituted alkyl groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in the alkyl group), in one embodiment
with at least 1 carbon atom, and in one embodiment with no more
than about 50 carbon atoms, and in another embodiment with no more
than about 18 carbon atoms, although the number of carbon atoms can
be outside of these ranges, an aryl group (including unsubstituted
and substituted aryl groups, and wherein hetero atoms, such as
oxygen, nitrogen, sulfur, silicon, phosphorus, and the like either
may or may not be present in the aryl group), in one embodiment
with at least about 5 carbon atoms, and in another embodiment with
at least about 6 carbon atoms, and in one embodiment with no more
than about 50 carbon atoms, and in another embodiment with no more
than about 18 carbon atoms, although the number of carbon atoms can
be outside of these ranges, an arylalkyl group (including
unsubstituted and substituted arylalkyl groups, and wherein hetero
atoms, such as oxygen, nitrogen, sulfur, silicon, phosphorus, and
the like either may or may not be present in either or both of the
alkyl portion and the aryl portion of the arylalkyl group), in one
embodiment with at least about 5 carbon atoms, in another
embodiment with at least about 6 carbon atoms, and in yet another
embodiment with at least about 7 carbon atoms, and in one
embodiment with no more than about 50 carbon atoms, and in another
embodiment with no more than about 18 carbon atoms, although the
number of carbon atoms can be outside of these ranges, an alkylaryl
group (including unsubstituted and substituted alkylaryl groups,
and wherein hetero atoms, such as oxygen, nitrogen, sulfur,
silicon, phosphorus, and the like either may or may not be present
in either or both of the alkyl portion and the aryl portion of the
alkylaryl group), in one embodiment with at least about 5 carbon
atoms, in another embodiment with at least about 6 carbon atoms,
and in yet another embodiment with at least about 7 carbon atoms,
and in one embodiment with no more than about 50 carbon atoms, and
in another embodiment with no more than about 18 carbon atoms,
although the number of carbon atoms can be outside of these ranges,
alkoxy, aryloxy, arylalkyloxy, and alkylaryloxy groups, all of
which either may or may not be substituted, wherein the alkyl,
aryl, arylalkyl, and alkylaryl portions thereof are as defined
hereinabove, sulfonamidoalkyl, sulfonamidoaryl,
sulfonamidoarylalkyl, sulfonamidoalkylaryl, sulfonamidodialkyl,
sulfonamidodiaryl, sulfonamidodiarylalkyl, and
sulfonamidodialkylaryl groups, as well as combinations thereof, all
of which either may or may not be substituted, wherein the alkyl,
aryl, arylalkyl, and alkylaryl portions thereof are as defined
hereinabove, amidoalkyl, amidoaryl, amidoarylalkyl, amidoalkylaryl,
amidodialkyl, amidodiaryl, amidodiarylalkyl, amidodialkylaryl, and
amidodiarylalkyl groups, as well as combinations thereof, all of
which either may or may not be substituted, wherein the alkyl,
aryl, arylalkyl, and alkylaryl portions thereof are as defined
hereinabove, thioalkyl, thioaryl, thioarylalkyl, and thioalkylaryl
groups, all of which either may or may not be substituted, wherein
the alkyl, aryl, arylalkyl, and alkylaryl portions thereof are as
defined hereinabove, ester groups of the formula ##STR33## wherein
R'' can be substituted or unsubstituted alkyl, aryl, arylalkyl, and
alkylaryl as defined hereinabove, ketone groups of the formula
##STR34## wherein R''' can be substituted or unsubstituted alkyl,
aryl, arylalkyl, and alkylaryl as defined hereinabove, sulfone
groups of the formula --SO.sub.2R'''' wherein R'''' can be
substituted or unsubstituted alkyl, aryl, arylalkyl, and alkylaryl
as defined hereinabove, and the like, wherein the substituents on
any of the substituted forms of these groups can be (but are not
limited to) those indicated hereinabove for the R group; (b) those
of the formula ##STR35## wherein A and G are as defined hereinabove
and wherein R.sub.4, R.sub.5, R.sub.6, R.sub.7, R.sub.8, and
R.sub.9 are defined as R.sub.1, R.sub.2, and R.sub.3 hereinabove;
or (c) those of the formula ##STR36## wherein R.sub.10, R.sub.11,
R.sub.12, R.sub.13, and R.sub.14 are defined as R.sub.1, R.sub.2,
and R.sub.3 hereinabove; and the like. It is to be understood that
the A, G, and J groups have valencies appropriate to the selected
atom, and that the number of "R" groups attached thereto can vary
depending on the valency of the atom. For example, in groups of
formula (b), when G is a carbon or silicon atom, two R groups can
be attached thereto; when G is a nitrogen or phosphorus atom and
the molecule is nonionic, one R group can be attached thereto; when
G is a nitrogen or phosphorus atom and the molecule is cationic,
two R groups can be attached thereto accompanied by a suitable
anion; when G is an oxygen or sulfur atom and the molecule is
nonionic, no R groups are attached thereto; and the like.
[0044] The material of the formula ##STR37## can be used as an
intermediate material and reacted with a suitable diazonium
compound to form an azo colorant. Suitable diazonium compounds have
a diazonium salt group that can react with the intermediate
material to form azo colorants as follows: ##STR38## One specific
example of a suitable reaction is as follows: ##STR39## More
specifically, a diazonium salt corresponding to the appropriate R'
group is first prepared by dissolving or dispersing the
corresponding primary amine R'--NH.sub.2 in a cold mineral acid,
typically at ice bath temperatures, with examples of suitable
mineral acids including (but not being limited to) hydrochloric,
hydrobromic, sulfuric, phosphoric, and the like, as well as
mixtures thereof. If desired, a defoaming agent such as
2-ethylhexanol can also be present in the reaction mixture. The
primary amine in acid is then reacted with an azotizing agent, such
as sodium nitrite (NaNO.sub.2), nitrosyl sulfuric acid
(HO.sub.3SONO), or the like, as well as mixtures thereof, to form
the diazonium salt R'--N.ident.N.sup.+. Thereafter, the reaction
mixture can be neutralized to remove any excess NO.sup.+ by
addition of a NO.sup.+ scavenger, such as sulfamic acid, urea, or
the like, as well as mixtures thereof. The diazonium salt is then
added to a solution containing the material of the formula
##STR40## in a solvent, such as water, other polar solvents, or the
like, as well as mixtures thereof, typically at ice bath
temperatures, to form the azo colorant.
[0045] Colorants of the present invention can be reacted with
various atoms, groups of atoms, monomers, oligomers, or polymers to
form various colored monomers, oligomers, or polymers having
covalently bonded thereto a colorant according to the present
invention. Another embodiment of the present invention is directed
to a compound comprising two or more moieties of the formula
##STR41## wherein R is an alkyl group, an aryl group, an arylalkyl
group, or an alkylaryl group, and wherein R can be joined to the
phenyl moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said moieties each contain no --OH
groups, --SH groups, or primary or secondary amino groups, said
moieties being linked by a central atom or group of atoms or bonded
to a polymer.
[0046] Examples of colored groups of atoms, monomers, oligomers, or
polymers which can be prepared with the colorants of the present
invention include urethane isocyanate-derived monomers, oligomers,
or polymers, urea isocyanate-derived monomers, oligomers, or
polymers, urethane/urea isocyanate-derived monomers, oligomers, or
polymers, anhydride monomers, oligomers, or polymers, such as
styrene-maleic anhydride monomers, oligomers, or polymers,
ester/polyester monomers, oligomers, or polymers,
carbonate/polycarbonate monomers, oligomers, or polymers, and the
like. Colored urethane isocyanate-derived monomers, oligomers, or
polymers, urea isocyanate-derived monomers, oligomers, or polymers,
and urethane/urea isocyanate-derived monomers, oligomers, or
polymers having covalently bonded thereto a colorant according to
the present invention are generally the reaction product of a
colorant according to the present invention and an isocyanate.
Colored urethane isocyanate-derived monomers, oligomers, or
polymers, urea isocyanate-derived monomers, oligomers, or polymers,
and urethane/urea isocyanate-derived monomers, oligomers, or
polymers having covalently bonded thereto a colorant according to
the present invention can be prepared by, for example, processes
such as those disclosed in U.S. Pat. No. 5,919,839; U.S. Pat. No.
3,994,835; U.S. Pat. No. 4,132,840; U.S. Pat. No. 4,751,254; U.S.
Pat. No. 5,290,921; U.S. Pat. No. 5,270,363; U.S. Pat. No.
4,912,203; U.S. Pat. No. 4,846,846; U.S. Pat. No. 4,507,407; U.S.
Pat. No. 4,284,729; U.S. Pat. No. 5,864,002; PCT Patent Application
WO97/13816; 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. IM isophorone diisocyanate
technical product information sheet; the disclosures of each of
which are totally incorporated herein by reference. Further
information on isocyanate-derived resins is disclosed in, for
example, U.S. Pat. No. 5,782,966; U.S. Pat. No. 5,750,604; U.S.
Pat. No. 5,827,918; U.S. Pat. No. 5,830,942; U.S. Pat. No.
5,994,453; U.S. Pat. No. 6,180,692; U.S. Pat. No. 6,018,005; U.S.
Pat. No. 6,028,138; U.S. Pat. No. 6,048,925; U.S. Pat. No.
6,057,399; and U.S. Pat. No. 5,783,658; the disclosures of each of
which are totally incorporated herein by reference.
[0047] For example, a monoisocyanate reacts with an alcohol to form
a urethane as follows: ##STR42## Diisocyanates react similarly; for
example, isophorone diisocyanate reacts with two moles of alcohol
to form a diurethane as follows: ##STR43## Monomeric, oligomeric,
and polymeric materials can be prepared when HO--R.sub.b is a
colorant according to the present invention.
[0048] Examples of suitable isocyanates include monoisocyanates,
diisocyanates, triisocyanates, copolymers of a diisocyanate,
copolymers of a triisocyanate, polyisocyanates (having more than
three isocyanate functional groups), and the like, as well as
mixtures thereof. Examples of monoisocyanates include
octadecylisocyanate; hexadecylisocyanate; 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, as well as mixtures
thereof. Examples of diisocyanates include isophorone diisocyanate
(IPDI); toluene diisocyanate (TDI);
diphenylmethane-4,4'-diisocyanate (MDI); hydrogenated
diphenylmethane-4,4'-diisocyanate (H12MDI); tetramethyl 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-diisocyanatododecane; 1,5-diisocyanato-2-methylpentane;
1,4-diisocyanatobutane; dimer diisocyanate and cyclohexylene
diisocyanate and its isomers; uretidione dimers of HDI; and the
like, as well as mixtures thereof. 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, as well as mixtures
thereof. Examples of higher isocyanate functionalities include
copolymers of TDI/HDI, and the like, and MDI oligomers, as well as
mixtures thereof.
[0049] Any suitable reaction condition for making urethane
compounds by condensing alcohols with isocyanates can be used to
prepare polymeric colorants according to the present invention.
Typically (although not necessarily), the reaction is carried out
at elevated temperatures (for example, from about 60 to about
160.degree. C.) in the presence of an optional urethane reaction
catalyst, such as dibutyl tindilaurate, bismuth tris-neodecanoate,
cobalt benzoate, lithium acetate, stannous octoate, triethylamine,
or the like. In a specific embodiment, the reaction conditions are
conducted in an inert atmosphere, such as argon or nitrogen gas or
other suitable gases, to prevent oxidizing or yellowing of the
reaction products and to prevent undesirable side reactions. The
reaction can employ an inert solvent, such as toluene or the like,
or can be performed neat (i.e., without a solvent). 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-substituted or amine-substituted antioxidant typically
remaining. The reactants can be added together in any order and/or
added to the reaction as physical mixtures. See, for example, 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. IM isophorone diisocyanate technical product
information sheet, the disclosures of each of which are totally
incorporated herein by reference, which provide further explanation
of this chemistry.
[0050] Colored anhydride resins having covalently bonded thereto a
colorant according to the present invention are generally the
reaction product of a monomeric colorant according to the present
invention and an anhydride. Colored anhydride resins having
covalently bonded thereto a colorant according to the present
invention can be prepared as disclosed in, for example, U.S. Pat.
No. 6,110,264 and U.S. Pat. No. 6,322,624, the disclosures of each
of which are totally incorporated herein by reference. Examples of
suitable anhydrides include cyclic anhydrides, such as
alkylsuccinic anhydrides, alkenylsuccinic anhydrides, and the like,
as well as mixtures thereof. Specific examples include (but are not
limited to) maleic anhydride, 2,3-diphenylmaleic anhydride,
trimellitic anhydride, 2-phenylglutaric anhydride, homophthalic
anhydride, isatoic anhydride, n-methylisatoic anhydride,
5-chloroisatoic anhydride, phthalic anhydride,
3,3',4,4'-benzophenone tetracarboxylic dianhydride,
4-methylphthalic anhydride,
4,4'-(hexafluoroisopropylidine)-diphthalic anhydride,
3,6-difluorophthalic anhydride, 3,6-dichlorophthalic anhydride,
4,5-dichlorophthalic anhydride, tetrafluorophthalic anhydride,
tetrachlorophthalic anhydride, tetrabromophthalic anhydride,
3-hydroxyphthalic anhydride, 1,2,4-benzenetricarboxylic anhydride,
3-nitrophthalic anhydride, 4-nitrophthalic anhydride,
1,2,4,5-benzenetetracarboxylic dianhydride, diphenic anhydride,
1,8-naphthalic anhydride, 4-chloro-1,8-naphthalic anhydride,
4-bromo-1,8-naphthalic anhydride, 4-amino-1,8-naphthalic anhydride,
3-nitro-1,8-naphthalic anhydride, 4-nitro-1,8-naphthalic anhydride,
4-amino-3,6,disulfo-1,6-disulfo-1,8-napthalic anhydride dipotassium
salt, 1,4,5,8-naphthalenetetracarboxylic dianhydride,
3,4,9,10-perylenetetracarboxylic dianhydride,
cis-1,2,3,6-tetrahydrophthalic anhydride,
cis-5-norbornene-endo-2,3dicarboxylic anhydride,
endo-bicyco[2,2,2]oct-5-ene-2,3dicarboxylic anhydride, cantharidin,
methyl-5-norbornene-2,3-dicarboxylic anhydride,
exo-3,6,epoxy-1,2,3,6-tetrahydrophthalic anhydride,
s-acetylmercaptosuccinic anhydride, diacetyl tartaric anhydride,
bicyclo[2,2,2]octo-7-ene-2,3,5,6-tetracarboxylic dianhydride,
citraconic anhydride, 2,3-dimethylmaleic anhydride,
1-cyclopentene-1,2-dicarboxylic anhydride,
3,4,5,6-tetrahydrophthalic anhydride, bromomaleic anhydride,
dichloromaleic anhydride,
1,4,6,7,7-hexachloro-5-norbornene-2,3-dicarboxylic anhydride,
cis-aconitic anhydride, glutaric anhydride, 3-methylglutaric
anhydride, 2,2-dimethylglutaric anhydride, 3,3-dimethylglutaric
anhydride, 3-ethyl-3-methylglutaric anhydride,
3,3tetramethyleneglutaric anhydride, hexafluoroglutaric anhydride,
3,5-diacetyltetrahydropyran-2,4,6-trione,
ethylenediaminetetraacetic dianhydride,
diethylenetriaminepentaacetic dianhydride, diglycolic anhydride,
succinic anhydride, methylsuccinic anhydride, 2,2-dimethylsuccinic
anhydride, isobuteneylsuccinic anhydride, 2-octen-1-ylsuccinic
anhydride, octadecenylsuccinic anhydride,
3-oxabicyclo[3,1,0]hexane-2,4-dione,
cis-1,2-cyclohexanedicarboxylic anhydride,
trans-1,2-cyclohexanedicarboxylic anhydride,
hexahydro-4-methylphthalic anhydride, itaconic anhydride,
2-dodecen-1-ylsuccinic anhydride, and the like, as well as mixtures
thereof. For example, colored styrene-maleic anhydride resins
having covalently bonded thereto a colorant according to the
present invention are generally the reaction product of a monomeric
colorant according to the present invention and styrene-maleic
anhydride. Copolymers of anhydrides with styrene, butadiene,
methoxyvinylether, ethylene, alpha-olefins, mixtures thereof, and
the like, are all suitable examples of polymeric materials with
which the monomeric colorants of the present invention can be
reacted to form colored polymeric materials. Specific examples of
suitable copolymers include (but are not limited to) poly(methyl
vinyl ether-maleic acid), poly(acrylic acid-co-maleic acid),
poly(vinyl chloride-co-vinyl-acetate-co-maleic acid),
poly(ethylene-maleic anhydride), poly(maleic
anhydride-1-octadecene), poly(styrene-co-maleic anhydride),
poly(methyl vinyl ether-maleic anhydride), poly(ethylene-co-ethyl
acrylate-co-maleic anhydride), poly(ethylene-co-vinyl
acetate)-graft-maleic anhydride, polyethylene-graft-maleic
anhydride, polypropylene-graft-maleic anhydride, and the like, as
well as mixtures thereof.
[0051] The monomeric colorant compounds of the present invention,
i.e., those containing only one moiety of the formula ##STR44##
have no more than one --OH, --SH, or --NHR.sub.b group per
molecule, wherein R.sub.b is a hydrogen atom, an alkyl group, an
aryl group, an arylalkyl group, or an alkylaryl group. By this it
is meant that, for example, if the molecule has one --OH group, it
has no --SH groups, no --NHR.sub.b groups, and no additional --OH
groups. Because the colorant compounds of the present invention
have one and only one of these groups, in some embodiments of the
invention various advantages can be achieved. For example, when
these colorants are reacted with other materials to form colored
resins, there is no formation of products of undesirably high
molecular weight and no undesired crosslinking. Some advantages are
particularly desirable for phase change ink applications. For
example, when these colorants are reacted with other materials to
form colored resins and when these colored resins are incorporated
into a phase change ink, precipitation of the colorant from the ink
is reduced; more specifically, when multifunctional colorants,
rather that the chain terminating colorants of the present
invention, are employed in reactions of di- or tri-isocyanates and
monohydric alcoholic species, some higher molecular weight species
are produced which can be insoluble in the ink base, often
resulting or being manifested as a precipitate in the prepared
material and/or the final ink. In addition, when these colorants
are reacted with other materials to form colored resins and when
these colored resins are incorporated into a phase change ink,
clogging of printheads and the printer failure accompanying such
clogging can be reduced.
[0052] The present invention is also directed to phase change inks.
Another embodiment of the present invention is directed to a phase
change ink comprising a phase change ink carrier and a colorant
compound comprising one or more moieties of the formula ##STR45##
wherein R is an alkyl group, an aryl group, an arylalkyl group, or
an alkylaryl group, and wherein R can be joined to the phenyl
moiety to form a ring, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein, when the colorant compound contains
exactly one of the moieties, the moiety contains no more than one
--OH, --SH, or primary or secondary amino group per molecule, and
when the colorant compound contains more than one of the moieties,
said moieties each contain no --OH groups, --SH groups, or primary
or secondary amino groups.
[0053] In the direct printing mode, the phase change carrier
composition in one embodiment contains one or more materials that
enable the phase change ink (1) to be applied in a thin film of
uniform thickness on the final recording substrate (such as paper,
transparency material, and the like) when cooled to ambient
temperature after printing directly to the recording 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.
[0054] In an offset printing transfer or indirect printing mode,
the phase change carrier composition in one embodiment exhibits not
only the characteristics desirable for direct printing mode inks,
but also certain fluidic and mechanical properties desirable for
use in such a system, as described in, for example, U.S. Pat. No.
5,389,958 the disclosure of which is totally incorporated herein by
reference.
[0055] When the phase change ink of the present invention comprises
a colored oligomer or polymer to which colorant molecules of the
present invention are covalently bonded, this colored oligomer or
polymer can function as the sole ink carrier. In addition, such a
colored oligomer or polymer can be present in combination with
another phase change ink carrier composition. Further, when the
phase change ink of the present invention comprises a colorant of
the present invention having only one moiety of the formula
##STR46## the colorant is generally present in combination with a
phase change ink carrier composition. Any desired or effective
carrier composition can be used. Examples of suitable ink carrier
materials include fatty amides, such as monoamides, tetraamides,
mixtures thereof, and the like. Specific examples of suitable fatty
amide ink carrier materials include stearyl stearamide, a dimer
acid based tetra-amide that is the reaction product of dimer acid,
ethylene diamine, and stearic acid, a dimer acid based tetra-amide
that is the reaction product of dimer acid, ethylene diamine, and a
carboxylic acid having at least about 36 carbon atoms, and the
like, as well as mixtures thereof. When the fatty amide ink carrier
is a dimer acid based tetra-amide that is the reaction product of
dimer acid, ethylene diamine, and a carboxylic acid having at least
about 36 carbon atoms, the carboxylic acid is of the general
formula ##STR47## wherein R is an alkyl group, including linear,
branched, saturated, unsaturated, and cyclic alkyl groups, said
alkyl group in one embodiment having at least about 36 carbon
atoms, in another embodiment having at least about 40 carbon atoms,
said alkyl group in one embodiment having no more than about 200
carbon atoms, in another embodiment having no more than about 150
carbon atoms, and in yet another embodiment having no more than
about 100 carbon atoms, although the number of carbon atoms can be
outside of these ranges. Carboxylic acids of this formula are
commercially available from, for example, Baker Petrolite, Tulsa,
Okla., and can also be prepared as described in Example 1 of U.S.
Pat. No. 6,174,937, the disclosure of which is totally incorporated
herein by reference. Further information on fatty amide carrier
materials is disclosed in, for example, U.S. Pat. No. 4,889,560,
U.S. Pat. No. 4,889,761, U.S. Pat. No. 5,194,638, U.S. Pat. No.
4,830,671, U.S. Pat. No. 6,174,937, U.S. Pat. No. 5,372,852, U.S.
Pat. No. 5,597,856, U.S. Pat. No. 6,174,937, and British Patent GB
2 238 792, the disclosures of each of which are totally
incorporated herein by reference.
[0056] Also suitable as phase change ink carrier materials are
isocyanate-derived resins and waxes, such as urethane
isocyanate-derived materials, urea isocyanate-derived materials,
urethane/urea isocyanate-derived materials, mixtures thereof, and
the like. Further information on isocyanate-derived carrier
materials is disclosed in, for example, U.S. Pat. No. 5,750,604,
U.S. Pat. No. 5,780,528, U.S. Pat. No. 5,782,966, U.S. Pat. No.
5,783,658, U.S. Pat. No. 5,827,918, U.S. Pat. No. 5,830,942, U.S.
Pat. No. 5,919,839, U.S. Pat. No. 6,255,432, U.S. Pat. No.
6,309,453, British Patent GB 2 294 939, British Patent GB 2 305
928, British Patent GB 2 305 670, British Patent GB 2 290 793, PCT
Publication WO 94/14902, PCT Publication WO 97/12003, PCT
Publication WO 97/13816, PCT Publication WO 96/14364, PCT
Publication WO 97/33943, and PCT Publication WO 95/04760, the
disclosures of each of which are totally incorporated herein by
reference.
[0057] Mixtures of fatty amide materials and isocyanate-derived
materials can also be employed as the ink carrier composition for
inks of the present invention.
[0058] Additional suitable phase change ink carrier materials for
the present invention 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
(such as, for example, tall oil rosins and rosin esters), and many
synthetic resins, oligomers, polymers and copolymers, such as
ethylene/vinyl acetate copolymers, ethylene/acrylic acid
copolymers, ethylene/vinyl acetate/acrylic acid copolymers,
copolymers of acrylic acid with polyamides, and the like, ionomers,
and the like, as well as mixtures thereof. One or more of these
materials can also be employed in a mixture with a fatty amide
material and/or an isocyanate-derived material.
[0059] In one specific embodiment, the phase change ink carrier
comprises the ink carrier comprises (a) a polyethylene wax, present
in the ink in an amount in one embodiment of at least about 25
percent by weight of the ink, in another embodiment of at least
about 30 percent by weight of the ink, and in yet another
embodiment of at least about 37 percent by weight of the ink, and
in one embodiment of no more than about 60 percent by weight of the
ink, in another embodiment of no more than about 53 percent by
weight of the ink, and in yet another embodiment of no more than
about 48 percent by weight of the ink, although the amount can be
outside of these ranges; (b) a stearyl stearamide wax, present in
the ink in an amount in one embodiment of at least about 8 percent
by weight of the ink, in another embodiment of at least about 10
percent by weight of the ink, and in yet another embodiment of at
least about 12 percent by weight of the ink, and in one embodiment
of no more than about 32 percent by weight of the ink, in another
embodiment of no more than about 28 percent by weight of the ink,
and in yet another embodiment of no more than about 25 percent by
weight of the ink, although the amount can be outside of these
ranges; (c) a dimer acid based tetra-amide that is the reaction
product of dimer acid, ethylene diamine, and a carboxylic acid
derivative of a long chain alcohol having greater than thirty six
carbon atoms, present in the ink in an amount in one embodiment of
at least about 10 percent by weight of the ink, in another
embodiment of at least about 13 percent by weight of the ink, and
in yet another embodiment of at least about 16 percent by weight of
the ink, and in one embodiment of no more than about 32 percent by
weight of the ink, in another embodiment of no more than about 27
percent by weight of the ink, and in yet another embodiment of no
more than about 22 percent by weight of the ink, although the
amount can be outside of these ranges; (d) a urethane resin derived
from the reaction of two equivalents of hydroabietyl alcohol and
one equivalent of isophorone diisocyanate, present in the ink in an
amount in one embodiment of at least about 6 percent by weight of
the ink, in another embodiment of at least about 8 percent by
weight of the ink, and in yet another embodiment of at least about
10 percent by weight of the ink, and in one embodiment of no more
than about 16 percent by weight of the ink, in another embodiment
of no more than about 14 percent by weight of the ink, and in yet
another embodiment of no more than about 12 percent by weight of
the ink, although the amount can be outside of these ranges; (e) a
urethane resin that is the adduct of three equivalents of stearyl
isocyanate and a glycerol-based alcohol, present in the ink in an
amount in one embodiment of at least about 2 percent by weight of
the ink, in another embodiment of at least about 3 percent by
weight of the ink, and in yet another embodiment of at least about
4.5 percent by weight of the ink, and in one embodiment of no more
than about 13 percent by weight of the ink, in another embodiment
of no more than about 10 percent by weight of the ink, and in yet
another embodiment of no more than about 7.5 percent by weight of
the ink, although the amount can be outside of these ranges; and
(f) an antioxidant, present in the ink in an amount in one
embodiment of at least about 0.01 percent by weight of the ink, in
another embodiment of at least about 0.05 percent by weight of the
ink, and in yet another embodiment of at least about 0.1 percent by
weight of the ink, and in one embodiment of no more than about 1
percent by weight of the ink, in another embodiment of no more than
about 0.5 percent by weight of the ink, and in yet another
embodiment of no more than about 0.3 percent by weight of the ink,
although the amount can be outside of these ranges.
[0060] The ink carrier is present in the phase change ink of the
present invention in any desired or effective amount, in one
embodiment of at least about 0.1 percent by weight of the ink, in
another embodiment of at least about 50 percent by weight of the
ink, and in yet another embodiment of at least about 90 percent by
weight of the ink, and in one embodiment of no more than about 99
percent by weight of the ink, in another embodiment of no more than
about 98 percent by weight of the ink, and in yet another
embodiment of no more than about 95 percent by weight of the ink,
although the amount can be outside of these ranges.
[0061] The phase change inks of the present invention contain a
colorant compound comprising one or more moieties of the formula
##STR48## wherein R is an alkyl group, an aryl group, an arylalkyl
group, or an alkylaryl group, R' is an aromatic- or
heteroaromatic-containing group, each R.sub.a, independently of the
others, is a halogen atom, an alkyl group, an alkoxy group, a
nitrile group, a nitro group, an amide group, or a sulfonamide
group, w is an integer of 0, 1, 2, 3, or 4, n is an integer
representing the number of carbon atoms in each repeat alkylene
oxide unit, and x is an integer representing the number of repeat
alkylene oxide units, wherein said moieties each contain no --OH
groups, --SH groups, or primary or secondary amino groups, said
moieties being linked by a central atom or group of atoms or bonded
to a polymer. This colorant is present in the ink in any desired or
effective amount to obtain the desired color or hue, in one
embodiment of at least about 1 percent by weight of the ink, in
another embodiment of at least about 2 percent by weight of the
ink, and in yet another embodiment of at least about 3 percent by
weight of the ink, and in one embodiment of no more than about 20
percent by weight of the ink, in another embodiment of no more than
about 13 percent by weight of the ink, and in yet another
embodiment of no more than about 6 percent by weight of the ink,
although the amount can be outside of these ranges. The colorant
according to the present invention can either be the sole colorant
in the ink or can be present in combination with other colorants,
such as dyes, pigments, mixtures thereof, and the like.
[0062] The inks of the present invention can also 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 NAUGUARD.RTM. 524, NAUGUARD.RTM. 76, and NAUGUARD.RTM. 512,
commercially available from Uniroyal Chemical Company, Oxford,
Conn., IRGANOX.RTM. 1010, commercially available from Ciba Geigy,
and the like. When present, the optional antioxidant is present in
the ink in any desired or effective amount, in one embodiment of at
least about 0.01 percent by weight of the ink, in another
embodiment of at least about 0.1 percent by weight of the ink, and
in yet another embodiment of at least about 1 percent by weight of
the ink, and in one embodiment of no more than about 20 percent by
weight of the ink, in another embodiment of no more than about 5
percent by weight of the ink, and in yet another embodiment of no
more than about 3 percent by weight of the ink, although the amount
can be outside of these ranges.
[0063] The inks of the present invention can also optionally
contain a viscosity modifier. Examples of suitable viscosity
modifiers include aliphatic ketones, such as stearone, and the
like. When present, the optional viscosity modifier is present in
the ink in any desired or effective amount, in one embodiment of at
least about 0.1 percent by weight of the ink, in another embodiment
of at least about 1 percent by weight of the ink, and in yet
another embodiment of at least about 10 percent by weight of the
ink, and in one embodiment of no more than about 99 percent by
weight of the ink, in another embodiment of no more than about 30
percent by weight of the ink, and in yet another embodiment of no
more than about 15 percent by weight of the ink, although the
amount can be outside of these ranges.
[0064] Other optional additives to the inks include clarifiers,
such as UNION CAMP.RTM. X37-523-235 (commercially available from
Union Camp), in an amount in one embodiment of at least about 0.01
percent by weight of the ink, in another embodiment of at least
about 0.1 percent by weight of the ink, and in yet another
embodiment of at least about 5 percent by weight of the ink, and in
one embodiment of no more than about 98 percent by weight of the
ink, in another embodiment of no more than about 50 percent by
weight of the ink, and in yet another embodiment of no more than
about 10 percent by weight of the ink, although the amount can be
outside of these ranges, tackifiers, such as FORAL.RTM. 85, a
glycerol ester of hydrogenated abietic (rosin) acid (commercially
available from Hercules), FORAL.RTM. 105, a pentaerythritol ester
of hydroabietic (rosin) acid (commercially available from
Hercules), CELLOLYN.RTM. 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 NEVTAC.RTM. 2300, NEVTAC.RTM.
100, and NEVTAC.RTM. 80 (commercially available from Neville
Chemical Company), WINGTACK.RTM. 86, a modified synthetic
polyterpene resin (commercially available from Goodyear), and the
like, in an amount in one embodiment of at least about 0.1 percent
by weight of the ink, in another embodiment of at least about 5
percent by weight of the ink, and in yet another embodiment of at
least about 10 percent by weight of the ink, and in one embodiment
of no more than about 98 percent by weight of the ink, in another
embodiment of no more than about 75 percent by weight of the ink,
and in yet another embodiment of no more than about 50 percent by
weight of the ink, although the amount can be outside of these
range, adhesives, such as VERSAMID.RTM. 757, 759, or 744
(commercially available from Henkel), in an amount in one
embodiment of at least about 0.1 percent by weight of the ink, in
another embodiment of at least about 1 percent by weight of the
ink, and in yet another embodiment of at least about 5 percent by
weight of the ink, and in one embodiment of no more than about 98
percent by weight of the ink, in another embodiment of no more than
about 50 percent by weight of the ink, and in yet another
embodiment of no more than about 10 percent by weight of the ink,
although the amount can be outside of these ranges, plasticizers,
such as UNIPLEX.RTM. 250 (commercially available from Uniplex), the
phthalate ester plasticizers commercially available from Monsanto
under the trade name SANTICIZER.RTM., such as dioctyl phthalate,
diundecyl phthalate, alkylbenzyl phthalate (SANTICIZER.RTM. 278),
triphenyl phosphate (commercially available from Monsanto),
KP-140.RTM., a tributoxyethyl phosphate (commercially available
from FMC Corporation), MORFLEX.RTM. 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 in one embodiment of at least
about 0.1 percent by weight of the ink, in another embodiment of at
least about 1 percent by weight of the ink, and in yet another
embodiment of at least about 2 percent by weight of the ink, and in
one embodiment of no more than about 50 percent by weight of the
ink, in another embodiment of no more than about 30 percent by
weight of the ink, and in yet another embodiment of no more than
about 10 percent by weight of the ink, although the amount can be
outside of these ranges, and the like.
[0065] The ink compositions of the present invention in one
embodiment have melting points of no lower than about 50.degree.
C., in another embodiment of no lower than about 70.degree. C., and
in yet another embodiment of no lower than about 80.degree. C., and
have melting points in one embodiment of no higher than about
160.degree. C., in another embodiment of no higher than about
140.degree. C., and in yet another embodiment of no higher than
about 100.degree. C., although the melting point can be outside of
these ranges.
[0066] The ink compositions of the present invention generally have
melt viscosities at the jetting temperature (in one embodiment no
lower than about 75.degree. C., in another embodiment no lower than
about 100.degree. C., and in yet another embodiment no lower than
about 120.degree. C., and in one embodiment no higher than about
180.degree. C., and in another embodiment no higher than about
150.degree. C., although the jetting temperature can be outside of
these ranges) in one embodiment of no more than about 30
centipoise, in another embodiment of no more than about 20
centipoise, and in yet another embodiment of no more than about 15
centipoise, and in one embodiment of no less than about 2
centipoise, in another embodiment of no less than about 5
centipoise, and in yet another embodiment of no less than about 7
centipoise, although the melt viscosity can be outside of these
ranges.
[0067] 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, to a
temperature in one embodiment of at least about 100.degree. C., and
in one embodiment of no more than about 140.degree. C., although
the temperature can be outside of these ranges, and stirring until
a homogeneous ink composition is obtained, followed by cooling the
ink to ambient temperature (typically from about 20 to about
25.degree. C.). The inks of the present invention are solid at
ambient temperature.
[0068] The inks of the present invention can be employed in
apparatus for direct printing ink jet processes and in indirect
(offset) printing ink jet applications. Another embodiment of the
present invention is directed to a process which comprises
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
substrate. A direct printing process is also disclosed in, for
example, U.S. Pat. No. 5,195,430, the disclosure of which is
totally incorporated herein by reference. Yet another embodiment of
the present invention is directed to a process which comprises
incorporating an ink of the present invention into an ink jet
printing apparatus, melting the ink, causing droplets of the melted
ink to be ejected in an imagewise pattern onto an intermediate
transfer member, and transferring the ink in the imagewise pattern
from the intermediate transfer member to a final recording
substrate. In a specific embodiment thereof, the intermediate
transfer member is heated to a temperature above that of the final
recording sheet and below that of the melted ink in the printing
apparatus. An offset or indirect printing process is also disclosed
in, for example, U.S. Pat. No. 5,389,958, the disclosure of which
is totally incorporated herein by reference. In one specific
embodiment, the printing apparatus employs a piezoelectric printing
process wherein droplets of the ink are caused to be ejected in
imagewise pattern by oscillations of piezoelectric vibrating
elements. Inks of the present invention can also be employed in
other hot melt printing processes, such as hot melt acoustic ink
jet printing, hot melt thermal ink jet printing, hot melt
continuous stream or deflection ink jet printing, and the like.
Phase change inks of the present invention can also be used in
printing processes other than hot melt ink jet printing
processes.
[0069] Any suitable substrate or recording sheet can be employed,
including plain papers such as XEROX.RTM. 4024 papers, XEROX.RTM.
Image Series papers, Courtland 4024 DP paper, ruled notebook paper,
bond paper, silica coated papers such as Sharp Company silica
coated paper, JuJo paper, Hammermill Laserprint Paper, and the
like, transparency materials, fabrics, textile products, plastics,
polymeric films, inorganic substrates such as metals and wood, and
the like.
[0070] 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.
EXAMPLE I
Phase Separation of N-Ethyl Aniline Ethoxylate
[0071] To a 100 milliliter beaker equipped with a magnetic stirrer
was added about 50 milliliters of POE(10) N-ethyl aniline, of the
formula ##STR49## (obtained from Henkel Corp, Mauldin, S.C.) and
about 65 milliliters of deionized water. The mixture was placed on
a magnetic stirring hot plate and stirring and heating were
initiated. When the temperature reached 90.degree. C., the beaker
was removed from heat and stirring and was allowed to cool slowly.
After several minutes, separation of layers began to occur, and
after about 2 hours, the temperature had returned to room
temperature and the separation was complete. A separation of the
two layers was visually observed, and separation of the layers was
performed with a separatory funnel.
Colorant Preparation
[0072] To a 500 milliliter 3-necked kettle equipped with a
thermometer, Trubore stirrer, and constant pressure addition funnel
was added about 115 grams of 85 percent H.sub.3PO.sub.4 (obtained
from Olin Corp., Norwalk, Conn.) in water, about 31 grams of 95
percent H.sub.2SO.sub.4 (obtained from Olin Corp., Norwalk, Conn.)
in water, and 2 drops of 2-ethylhexanol (obtained from Aldrich
Chemical Co., Milwaukee, Wis.). Stirring was then initiated and the
kettle was placed in a salt/ice bath to cool the mixture to about
0.degree. C. Once 0.degree. C. was reached, 10.2 grams of
2-amino-4-methylbenzothiazole (obtained from Aldrich Chemical Co.)
was added with stirring and the temperature was maintained at
0.degree. C. To the constant pressure addition funnel was then
added about 21.7 grams of nitrosyl sulfuric acid (obtained from
Aldrich Chemical Co.) in a dropwise fashion, maintaining the
temperature at about 0.degree. C., over a period of about 1.5
hours. The reaction mixture was subsequently maintained at
0.degree. C. with stirring for an additional 1.5 hours to ensure
complete diazotization. Thereafter, about 0.7 gram of sulfamic acid
(obtained from Aldrich Chemical Co.) was added with stirring to
neutralize any excess NO.sup.+. The diazo mixture was then slowly
added over about 0.75 hour to a 1 liter beaker equipped with a stir
magnet in a 5.degree. C. ice bath, the beaker containing about 36.0
grams of the POE(10) N-ethyl aniline purified as indicated above,
150 milliliters of deionized water, and about 2.0 grams of urea
(obtained from Aldrich Chemical Co.). The diazo colorant was
allowed to stir cool for about 2 hours, followed by stirring at
room temperature overnight. The diazo colorant was then neutralized
to a pH of about 7 with a 50 percent aqueous solution of sodium
hydroxide (solid material obtained from Aldrich Chemical Co.),
keeping the temperature below about 60.degree. C. Following
neutralization, the colorant was poured into a 1 liter separatory
funnel and allowed to phase separate. The bottom salt/water layer
was discarded and the liquid colored product layer was dissolved in
methylene chloride (obtained from Aldrich Chemical Co.) and run
through a small "plug" of silica gel (70-230 mesh, for column
chromatography, obtained from Aldrich Chemical Co.) to remove any
polar impurities. The methylene chloride layer was then collected
and the methylene chloride removed via rotary evaporation, yielding
a viscous red liquid. The resulting colorant is expected to have an
absorption maxima consistent with the following structure:
##STR50##
EXAMPLE II
[0073] To a 500 milliliter 3-necked kettle equipped with a
thermometer, Trubore stirrer, and constant pressure addition funnel
was added about 27.0 grams of deionized water, about 20 grams of 95
percent H.sub.2SO.sub.4 (obtained from Olin Corp., Norwalk, Conn.)
in water, and 2 drops of 2-ethylhexanol (obtained from Aldrich
Chemical Co., Milwaukee, Wis.). Stirring was then initiated and the
kettle was placed in a salt/ice bath to cool the mixture to about
0.degree. C. Once 0.degree. C. was reached, 10.3 grams of
2-chloro-4-(methylsulfone) aniline (CAMSU, obtained from Clariant
Corp., Charlotte, N.C.) was added with stirring and the temperature
was maintained at 0.degree. C. To the constant pressure addition
funnel was then added about 21.0 grams of nitrosyl sulfuric acid
(obtained from Aldrich Chemical Co.) in a dropwise fashion,
maintaining the temperature at about 0.degree. C., over a period of
about 1.5 hours. The reaction mixture was subsequently maintained
at 0.degree. C. with stirring for an additional 1.5 hours to ensure
complete diazotization. Thereafter, about 1.0 gram of sulfamic acid
(obtained from Aldrich Chemical Co.) was added with stirring to
neutralize any excess NO.sup.+. The diazo mixture was then slowly
added over about 0.75 hour to a 1 liter beaker equipped with a stir
magnet in a 5.degree. C. ice bath, the beaker containing about 29.1
grams of the POE(10) N-ethyl aniline purified as indicated in
Example I, 150 milliliters of deionized water, and about 2.0 grams
of urea (obtained from Aldrich Chemical Co.). The diazo colorant
was allowed to stir cool for about 2 hours, followed by stirring at
room temperature overnight. The diazo colorant was then neutralized
to a pH of about 7 with a 50 percent aqueous solution of sodium
hydroxide (solid material obtained from Aldrich Chemical Co.),
keeping the temperature below about 60.degree. C. Following
neutralization, the colorant was poured into a 1 liter separatory
funnel and allowed to phase separate. The bottom salt/water layer
was discarded and the liquid colored product layer was dissolved in
methylene chloride (obtained from Aldrich Chemical Co.) and run
through a small "plug" of silica gel (70-230 mesh, for column
chromatography, obtained from Aldrich Chemical Co.) to remove any
polar impurities. The methylene chloride layer was then collected
and the methylene chloride removed via rotary evaporation, yielding
a viscous orange liquid. The resulting colorant was consistent with
the following formula: ##STR51##
EXAMPLE III
[0074] The process of Example I is repeated except that a random
POE (3.5) POP (6.5) N-ethyl aniline, of the formula ##STR52##
wherein 3.5 represents the average number of repeat polyoxyethylene
units per molecule and 6.5 represents the average number of repeat
polyoxypropylene units per molecule, and wherein the
polyoxyethylene and polyoxypropylene units are randomly mixed
within the polyoxyalkylene chain (available as SO-7864 from Henkel
Corp., Mauldin, S.C.) is substituted for the POE(10) N-ethyl
aniline. It is believed that a colorant consistent with the formula
##STR53## will be obtained.
EXAMPLE IV
[0075] The process of Example II is repeated except that a random
POE (3.5) POP (6.5) N-ethyl aniline, of the formula ##STR54##
wherein 3.5 represents the average number of repeat polyoxyethylene
units per molecule and 6.5 represents the average number of repeat
polyoxypropylene units per molecule, and wherein the
polyoxyethylene and polyoxypropylene units are randomly mixed
within the polyoxyalkylene chain (available as SO-7864 from Henkel
Corp., Mauldin, S.C.) is substituted for the POE(10) N-ethyl
aniline. It is believed that a colorant of the formula ##STR55##
will be obtained.
EXAMPLE V
Reaction Product of Benzophenonetetracarboxylic Dianhydride,
Octophenol Ethoxylate, and Red Azo Monohydroxyl Polyoxyalkylene
Colorant
[0076] To a 1,000 milliliter three-neck resin kettle equipped with
a Trubore stirrer, N.sub.2 inlet, and thermocouple-temperature
controller is added 150.0 grams (0.93 equivalents) of
benzophenonetetracarboxylic dianhydride (available from Aldrich
Chemical Co., Milwaukee, Wis.) and 211.6 grams (0.83 equivalents)
of IGEPAL.RTM. CA-210 (octylphenol ethoxylate, available from
Rhone-Poulenc Co., Cranbury, N.J. Note: TRITON.RTM. X15 octylphenol
ethoxylate, available from Union Carbide Chemicals and Plastics
Company Inc., Danbury, Conn., can be directly substituted for
IGEPAL.RTM. CA-210 in this reaction). The reaction mixture is
heated to 150.degree. C. with stirring under nitrogen. After 1.0
hours at 150.degree. C., the temperature is increased to
170.degree. C. and held at that temperature for 3.5 hours. A red
azo monohydroxyl polyoxyalkylene colorant (74.3 grams; 0.098
equivalents) corresponding to the colorant prepared in Example I is
then added and allowed to react for 3 hours. The final red colored
resin product is then poured into aluminum molds and allowed to
cool and harden.
EXAMPLE VI
[0077] The colored resin prepared in Example V (20.5 grams) is
combined with 58.7 grams of stearyl stearamide wax (KEMAMIDE.RTM.
S-180, available from Crompton Corporation, Greenwich, Conn.), 20.5
grams of glycerol ester of hydrogenated abietic [rosin] acid
(KE-100, available from Arakawa Chemical Industries, Ltd.), and 0.2
gram of NAUGUARD.RTM. 445 antioxidant (available from Uniroyal
Chemical Co., Middlebury, Conn.). The ingredients are heated to
115.degree. C. until molten, mixed, filtered through a disc filter,
poured into sticks, and used to generate prints in a XEROX.RTM.
PHASER 860 printer.
EXAMPLE VII
Reaction Product of Octylphenol Ethoxylate, Isophorone
Diisocyanate, and Red Azo Monohydroxyl Polyoxyalkylene Colorant
[0078] 525.0 grams (4.73 equivalents) of isophorone diisocyanate
(DESMODUR I; isophorone diisocyanate, available from Bayer Corp.,
Pittsburgh, Pa.) and 1.5 grams of dibutyltindilaurate catalyst
(available from Aldrich Chemical Co., Milwaukee, Wis.), followed by
1,150 grams (4.52 equivalents) of octylphenol ethoxylate (IGEPAL
CA-210, octylphenol ethoxylate, available from Rhone-Poulenc Co.,
Cranbury, N.J.), are added to a 3,000 milliliter three-neck resin
kettle equipped with a Trubore stirrer, N.sub.2 atmosphere inlet,
and a thermocouple-temperature controller. The reaction mixture is
heated to about 135.degree. C. with stirring under nitrogen. After
2.0 hours at about 135.degree. C., 156 grams (0.210 equivalents) of
a red azo monohydroxyl polyoxyalkylene colorant prepared as
described in Example I is added and the reaction mixture is heated
for approximately 2 hours. An additional 110.0 grams (0.433
equivalents) of octylphenol ethoxylate are added and the reaction
mixture is heated at about 150.degree. C. for approximately 2
hours. An FT-IR of the product is obtained to ensure that all of
the isocyanate (NCO) functionality has been 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 are used to confirm that the isocyanate has been
consumed. The diurethane reaction product is then poured into
aluminum molds and allowed to cool and harden.
EXAMPLE VIII
[0079] In a stainless steel beaker are combined 500 grams of
stearyl stearamide wax (KEMAMIDE.RTM. S-180, available from
Crompton Corporation, Greenwich, Conn.), 125 grams of UNIREZ 2970
tetra-amide resin (available from Union Camp, Wayne, N.J.), 208
grams of the colored resin prepared as described in Example VII,
and 1.6 grams of NAUGUARD.RTM. 445 antioxidant (available from
Uniroyal Chemical Co., Middlebury, Conn.). The materials are 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 0.5 hour. After stirring, the resulting
ink is 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 is then poured into
molds, allowed to solidify to form ink sticks, and used to generate
prints in a XEROX.RTM. PHASER 860 printer.
EXAMPLE IX
Reaction Product of Styrene-Maleic Anhydride Polymer with Neodol
1-3 and Red Azo Monohydroxyl Polyoxyalkylene Colorant
[0080] To a 500 milliliter three-neck resin kettle equipped with a
TEFLON.RTM. coated magnet, oil bath, and condenser was added 14.0
grams (0.068 equivalents) of styrene-maleic anhydride polymer (SMA
1000, available from Atochem Inc., Malvern, Pa.), 15.9 grams (0.052
equivalents) of an alcohol of the formula
C.sub.11H.sub.22--O--(CH.sub.2CH.sub.2O).sub.nH wherein n has an
average value of 3 (NEODOL 1-3, available from Shell Chemical
Company, Houston, Tex.), 12.7 grams (0.017 equivalents) of the red
azo monohydroxyl polyoxyalkylene colorant prepared in Example I,
about 250 grams of acetonitrile (available from Aldrich Chemical
Co., Milwaukee, Wis.), and 2 drops of 1-methylimidazole catalyst
(available from Aldrich Chemical Co.). The reaction mixture was
heated with stirring to reflux and held at that state for 2 days.
After 2 days, the acetonitrile was removed by distillation. The red
viscous colored product still in the flask was then placed in a
vacuum oven to remove any residue of acetonitrile. The final red
viscous material had a T.sub.g of -38.degree. C.
EXAMPLE X
[0081] To a 100 milliliter beaker equipped with magnetic stir was
added about 8 grams of the red material prepared as described in
Example IX and 35 milliliters of concentrated ammonia solution.
Stirring was continued until all the solid material dissolved.
About 2 milliliters of this aqueous solution was placed on the
platen of a K-proofer and prints were made. The prints were allowed
to dry and tested for washfastness. No bleeding of color was
observed.
[0082] 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.
[0083] The recited order of processing elements or sequences, or
the use of numbers, letters, or other designations therefor, is not
intended to limit a claimed process to any order except as
specified in the claim itself.
* * * * *