Title: Thermally stable, anthraquinone colorants containing copolymerizable vinyl groups
Abstract: Disclosed are thermally-stable, anthraquinone colorant compounds (dyes) which contain one or more vinyl groups which render the compounds copolymerizable with reactive vinyl monomers to produce colored, polymeric compositions such as acrylate and methacrylate polymeric materials. The compounds possess good fastness (stability) to ultraviolet (UV) light, good solubility in vinyl monomers, good color strength and excellent thermal stability. Also disclosed are (1) coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the dye compounds described above, and (iii) a photoinitiator and (2) polymeric materials, i.e., polymers derived from one or more acrylic acid esters, one or more methacrylic acid esters, one or more other polymerizable vinyl compounds or mixtures of any two or more thereof, having copolymerized therein one or more of the anthraquinone colorant compounds.
Patent Number: 6,870,062 Issued on 03/22/2005 to Cyr, et al.
| Inventors:
|
Cyr; Michael John (Kingsport, TN);
Weaver; Max Allen (Kingsport, TN);
Rhodes; Gerry Foust (Piney Flats, TN);
Pearson; Jason Clay (Kingsport, TN);
Cook; Phillip Michael (Kingsport, TN);
De Wit; Jos Simon (Kingsport, TN);
Johnson; Larry Keith (Kingsport, TN)
|
| Assignee:
|
Eastman Chemical Company (Kingsport, TN)
|
| Appl. No.:
|
719883 |
| Filed:
|
November 21, 2003 |
| Current U.S. Class: |
552/234; 8/675 |
| Intern'l Class: |
C09B 001//00; C09B 001//34 |
| Field of Search: |
552/234
8/675
|
References Cited [Referenced By]
U.S. Patent Documents
| 3288778 | Nov., 1966 | Blout et al. | 534/682.
|
| 3364186 | Jan., 1968 | Wilhelm et al.
| |
| 3689501 | Sep., 1972 | Weaver et al.
| |
| 4115056 | Sep., 1978 | Koller et al.
| |
| 4267306 | May., 1981 | Davis et al.
| |
| 4359570 | Nov., 1982 | Davis et al.
| |
| 4403092 | Sep., 1983 | Davis et al.
| |
| 4804719 | Feb., 1989 | Weaver et al.
| |
| 4943617 | Jul., 1990 | Etzbach et al.
| |
| 4999418 | Mar., 1991 | Krutak et al. | 528/272.
|
| 5032670 | Jul., 1991 | Parham et al. | 528/220.
|
| 5055602 | Oct., 1991 | Melpolder.
| |
| 5109097 | Apr., 1992 | Klun et al.
| |
| 5194463 | Mar., 1993 | Krutak et al.
| |
| 5362812 | Nov., 1994 | Holmes et al.
| |
| 5367039 | Nov., 1994 | Yabuuchi et al.
| |
| 5372864 | Dec., 1994 | Weaver et al.
| |
| 5578419 | Nov., 1996 | Itoh et al.
| |
| 5900445 | May., 1999 | Chandler et al.
| |
| 5955564 | Sep., 1999 | Weaver et al.
| |
| 5962557 | Oct., 1999 | Weaver et al.
| |
| 6197223 | Mar., 2001 | Weaver et al.
| |
| 6331204 | Dec., 2001 | Carr et al.
| |
| Foreign Patent Documents |
| 0322808 | Jul., 1989 | EP.
| |
| 1046751 | Oct., 1966 | GB.
| |
| WO 96/01283 | Jan., 1996 | WO.
| |
| WO 97/48744 | Dec., 1997 | WO.
| |
Other References
Asquith et al, "Self-Coloured Polymers Based on Anthraquinone Residues",
Journal of the Society of Dyes and Colourists (J.S.D.C.), Apr., 1977, pp.
114-125.
John Wiley & Sons, Encyclopedia of Polymer Science and Eng., Second Ed.,
vol. 11, pp. 558-571.
John Wiley & Sons, Chemistry & Technology of UV & EB Formulation for
Coatings, Inks, and Paints, vol. II: Prepolymers and Reactive Diluents, G.
Webster, London, 1997, pp. 35-250.
|
Primary Examiner: Badio; Barbara P.
Attorney, Agent or Firm: Blake; Michael J., Graves, Jr.; Bernard J.
Parent Case Text
CROSS REFERENCE TO RELATED APPLICATION
This application is a divisional of U.S. application Ser. No. 09/911,789
filed Jul. 24, 2001, now U.S. Pat. No. 6,689,828, which is a
continuation-in-part of U.S. application Ser. No. 09/633,548 filed Aug. 7,
2000, now abandoned.
Claims
We claim:
1. Anthraquinone dye compounds having formula X. or formula XIV.:
##STR37##
wherein:
R is hydrogen or 1-3 groups selected from C.sub.1 -C.sub.6 -alkyl, C.sub.1
-C.sub.6 -alkoxy and halogen;
R.sub.5 is C.sub.1 -C.sub.6 -alkyl, substituted C.sub.1 -C.sub.6 alkyl,
C.sub.3 -C.sub.8 -cycloalkyl, aryl, heteroaryl, --L.sub.1 --Z--Q,
##STR38##
X is a covalent bond or a divalent linking group selected from --O--,
--S--, --SO.sub.2 --, and --CON(Y)-- wherein Y is hydrogen, C.sub.1
-C.sub.6 -alkyl, substituted C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.8
-cycloalkyl, C.sub.3 -C.sub.8 -alkenyl, aryl or --L--Z--Q;
L is a divalent linking group selected from C.sub.1 -C.sub.8 -alkylene,
C.sub.1 -C.sub.6 -alkylene-arylene, arylene, C.sub.1 -C.sub.6
-alkylene-arylene-C.sub.1 -C.sub.6 -alkylene, C.sub.3 -C.sub.8
-cycloalkylene, C.sub.1 -C.sub.6 -alkylene-C.sub.3 -C.sub.8
-cycloalkylene-C.sub.1 -C.sub.6 -alkylene, C.sub.1 -C.sub.6
-alkylene-Z.sub.1 -arylene-Z.sub.1 --C.sub.1 -C.sub.6 -alkylene or C.sub.2
-C.sub.6 -alkylene-[--Z.sub.1 --C.sub.2 -C.sub.6 -alkylene-].sub.n --
wherein Z.sub.1 is --O--, --S-- or --SO.sub.2 -- and n is 1-3;
L.sub.1 is a divalent linking group selected from C.sub.2 -C.sub.6
-alkylene, C.sub.1 -C.sub.6 -alkylene-C.sub.3 -C.sub.8
-cycloalkylene-C.sub.1 -C.sub.6 -alkylene, C.sub.1 -C.sub.6
-alkylene-arylene, C.sub.3 -C.sub.8 -cycloalkylene, and C.sub.2 -C.sub.6
-alkylene-[--Z.sub.1 --C.sub.2 -C.sub.6 -alkylene-].sub.n -, wherein
Z.sub.1 is --O--, --S-- or --SO.sub.2 -- and n is 1-3;
Z is a divalent group selected from --O--, --S--, --NH--, --N(C.sub.1
-C.sub.6 -alkyl)-, --N(C.sub.3 -C.sub.8 alkenyl)-, --N(C.sub.3 -C.sub.8
cycloalkyl)-, --N(aryl)-, --N(SO.sub.2 C.sub.1 -C.sub.6 -alkyl) or
--N(SO.sub.2 aryl)-, provided that when Q is a photopolymerizable
optionally substituted maleimide radical, Z represents a covalent bond;
Q is an ethylenically-unsaturated, photosensitive polymerizable group; and
is 0 or 1.
2. Anthraquinone compounds according to claim 1 wherein the
ethylenically-unsaturated, photosensitive copolymerizable groups
represented by Q are selected from the following organic radicals:
##STR39##
##STR40##
wherein:
R.sub.11 is hydrogen or C.sub.1 -C.sub.6 -alkyl;
R.sub.12 is hydrogen; C.sub.1 -C.sub.6 -alkyl; phenyl or phenyl substituted
with one or more groups selected from C.sub.1 -C.sub.6 -alkyl, C.sub.1
-C.sub.6 -alkoxy, --N(C.sub.1 -C.sub.6 -alkyl), nitro, cyano, C.sub.1
-C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.6 -alkanoyloxy and halogen; 1- or
2-naphthyl which may be substituted with C.sub.1 -C.sub.6 -alkyl or
C.sub.1 -C.sub.6 -alkoxy; 2- or 3-thienyl which may be substituted with
C.sub.1 -C.sub.6 -alkyl or halogen; 2- or 3-furyl which may be substituted
with C.sub.1 -C.sub.6 -alkyl;
R.sub.13 and R.sub.14 are hydrogen, C.sub.1 -C.sub.6 -alkyl, substituted
C.sub.1 -C.sub.6 -alkyl, aryl or may be combined to represent a
--[--CH.sub.2 --].sub.3-5 -radical;
R.sub.15 is hydrogen, C.sub.1 -C.sub.6 -alkyl, substituted C.sub.1 -C.sub.6
-alkyl, C.sub.3 -C.sub.8 -alkenyl, C.sub.3 -C.sub.8 -cycloalkyl or aryl
and;
R.sub.16 is hydrogen, C.sub.1 -C.sub.6 -alkyl- or aryl.
3. Anthraquinone compounds according to claim 2 having the formula:
##STR41##
wherein Z is --O--.
4. Anthraquinone compounds according to claim 2 having the formula:
##STR42##
wherein Z is --O--.
5. Anthraquinone compounds according to claim 2 wherein Q is organic
radical Ia.
6. Anthraquinone compounds according to claim 2 wherein Q is organic
radical Ia wherein R.sub.11 is hydrogen or methyl and R.sub.12 is
hydrogen.
7. Anthraquinone compounds according to claim 2 wherein Q is organic
radical VIIa.
8. Anthraquinone compounds according to claim 2 wherein Q is organic
radical VIIa wherein R.sub.11 is hydrogen.
9. Anthraquinone compounds according to claim 2 wherein Q is organic
radical VIIIa.
10. Anthraquinone compounds according to claim 2 wherein Q is organic
radical VIIIa wherein R.sub.11 is hydrogen or methyl and R.sub.13 and
R.sub.14 are methyl.
11. A coating composition comprising (i) one or more polymerizable vinyl
compounds, (ii) one or more of the dye compounds of claim 1, and (iii) a
photoinitiator.
12. A coating composition comprising (i) one or more polymerizable vinyl
compounds, (ii) one or more of the dye compounds of claim 2 present in a
concentration of about 0.05 to 15 weight percent based on the weight of
component (i), and (iii) a photoinitiator present in a concentration of
about 1 to 15 weight percent based on the weight of the polymerizable
vinyl compound(s) present in the coating composition.
13. A coating composition according to claim 12 wherein the polymerizable
vinyl compounds comprise a solution of a polymeric, polymerizable vinyl
compound selected from acrylated and methacrylated polyesters, acrylated
and methacrylated polyethers, acrylated and methacrylated epoxy polymers,
acrylated or methacrylated urethanes, and mixtures thereof, in a diluent
selected from monomeric acrylate and methacrylate esters.
14. A polymeric coating composition comprising a polymer of one or more
acrylic acid esters, one or more methacrylic acid esters or other
copolymerizable vinyl compounds, having copolymerized therein one or more
of the dye compounds defined in claim 1.
15. A polymeric coating composition comprising a coating of an acrylic
polymer of one or more acrylic acid esters, one or more methacrylic acid
esters or a mixture thereof having copolymerized therein one or more of
the dye compounds defined in claim 2.
16. A polymeric coating composition comprising a coating of an unsaturated
polyester containing one or more maleate/fumarate residues; one or more
monomers which contain one or more vinyl ether groups, one or more vinyl
ester groups, or a combination thereof, and, optionally, one or more
acrylic or methacrylic acid esters; or a mixture thereof having
copolymerized therein one or more of the dye compounds defined in claim 2.
17. A polymeric coating according to claim 16 containing from about 0.05 to
15.0 weight percent of the residue of one or more of the dye compounds
based on the weight of the coating.
Description
FIELD OF THE INVENTION
This invention pertains to certain thermally-stable, anthraquinone colorant
compounds (dyes) which contain one or more vinyl groups which render the
compounds copolymerizable with reactive vinyl monomers to produce colored,
polymeric compositions such as acrylate and methacrylate polymeric
materials. The compounds possess good fastness (stability) to ultraviolet
(UV) light, good solubility in vinyl monomers, good color strength and
excellent thermal stability. The present invention includes acrylic
polymeric materials, i.e., polymers derived from acrylic acid esters,
methacrylic acid esters and/or other copolymerizable vinyl compounds,
having copolymerized therein one or more of the dye compounds of the
present invention.
BACKGROUND AND PRIOR ART
It is known (J.S.D.C., April 1977, pp 114-125) to produce colored polymeric
materials by combining a reactive polymer such terepolymers having epoxy
groups or polyacryloyl chloride with anthraquinone dyes containing
nucleophilic reactive groups such as amino or hydroxy groups; to graft
acryloylaminoanthraquinone dyes to the backbone of vinyl or divinyl
polymers; and to polymerize anthraquinone dyes containing certain olefinic
groups to produce polymeric dyes/pigments. U.S. Pat. No. 4,115,056
describes the preparation of blue, substituted 1,4-diaminoanthraquinone
dyes containing one acryloyloxy group and and the use of the dyes in
coloring various fibers, especially polyamide fibers. U.S. Pat. No.
4,943,617 discloses liquid crystalline copolymers containing certain blue,
substituted 1,5-diamino-4,8-dihydroxyanthraquinone dyes containing an
olefinic group copolymerized therein to provide liquid crystal copolymers
having high dichromism. U.S. Pat. No. 5,055,602 describes the preparation
of certain substituted 1,4-diaminoanthraquinone dyes containing
polymerizable acryloyl and methacryloyl groups and their use in coloring
polyacrylate contact lens materials by copolymerizing.
U.S. Pat. No. 5,362,812 discloses the conversion of a variety of dye
classes, including anthraquinones, into polymeric dyes by (a) polymerizing
2-alkenylazlactones and reacting the polymer with dyes containing
nucleophilic groups and by (b) reacting a nucleophilic dye with an
alkenylazlactone and then polymerizing the free radically polymerizable
dyes thus produced. The polymeric dyes are reported to be useful for
photoresist systems and for colorproofing. U.S. Pat. No. 5,367,039
discloses a process for preparing colored vinyl polymers suitable for
inks, paints, toners and the like by emulsion polymerization of a vinyl
monomer with reactive anthraquinone dyes prepared by functionalizing
certain anthraquinone dyes with methacryloyl groups.
The preparation of a variety of dyes, including some anthraquinones, which
contain photopolymerizable groups and their use for color filters suitable
for use in liquid crystal television sets, color copying machines,
photosensitive resist resin compositions, and the like are described in
U.S. Pat. No. 5,578,419.
BRIEF SUMMARY OF THE INVENTION
One embodiment of the present invention concerns anthraquinone dye or
colorant compounds represented by general Formulae I-XXI set forth below.
The dyes having Formulae I-VII are blue-cyan colorants, the dyes having
Formulae VIII-XVIII are red-magenta colorants, and the dyes having
Formulae XIX-XXI are yellow colorants.
##STR1##
##STR2##
##STR3##
##STR4##
##STR5##
##STR6##
wherein
R is selected from hydrogen or 1-3 groups selected from C.sub.1 -C.sub.6
-alkyl, C.sub.1 -C.sub.6 -alkoxy and halogen;
R.sub.1 is selected from C.sub.1 -C.sub.6 -alkyl, substituted C.sub.1
-C.sub.6 -alkyl, C.sub.3 -C.sub.8 -alkenyl, C.sub.3 -C.sub.8 -cycloalkyl,
aryl and --L.sub.1 --Z--Q; R.sub.2.dbd. selected from hydrogen, C.sub.1
-C.sub.6 -alkyl, substituted C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.8
-cycloalkyl and aryl;
R.sub.3 and R.sub.4 are independently selected from C.sub.1 -C.sub.6 -alkyl
and bromine;
R.sub.5 is selected from C.sub.1 -C.sub.6 -alkyl, substituted C.sub.1
-C.sub.6 alkyl, C.sub.3 -C.sub.8 -cycloalkyl, aryl, heteroaryl, --L.sub.1
--Z--Q,
##STR7##
R.sub.6 is selected from
##STR8##
##STR9##
R.sub.7 is selected from hydrogen, substituted or unsubstituted C.sub.1
-C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, halogen, hydroxy, substituted
or unsubstituted C.sub.1 -C.sub.6 -alkylthio, sulfamoyl and substituted
sulfamoyl;
R.sub.8 is selected from hydrogen and C.sub.1 -C.sub.6 -alkyl;
R.sub.9 is selected from the groups represented by R.sub.1 and --L--Z--Q;
R.sub.10 is selected from hydrogen and halogen;
X is a covalent bond or a divalent linking group selected from --O--,
--S--, --SO.sub.2 --, --CO.sub.2 --, --CON(Y)-- and --SO.sub.2 N(Y)--,
wherein Y is selected from hydrogen, C.sub.1 -C.sub.6 -alkyl, substituted
C.sub.1 -C.sub.6 -alkyl, C.sub.3 C.sub.8 -cycloalkyl, C.sub.3 -C.sub.8
-alkenyl, aryl and --L--Z--Q;
X.sub.1 is selected from --O--, --S--, --SO.sub.2 -- and --SO.sub.2 N(Y)--;
X.sub.2 is selected from --CO.sub.2 -- and --SO.sub.2 N(Y.sub.1), wherein
Y.sub.1 is a group selected from hydrogen, C.sub.1 -C.sub.6 -alkyl,
substituted C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.8 -alkenyl, C.sub.3
-C.sub.8 -cycloalkyl, aryl heteroaryl and --CH.sub.2 -p-C.sub.6 H.sub.4
--C(R).sub.8.dbd.CH.sub.2 ;
X.sub.3 is selected from --CO.sub.2 --, --SO.sub.2 N(Y)--;
X.sub.4 is selected from --CO.sub.2 --, --O-- and --SO.sub.2 N(Y.sub.1)--;
L is a divalent linking group selected from C.sub.1 -C.sub.8 -alkylene,
C.sub.1 -C.sub.6 -alkylene-arylene, arylene, C.sub.1 -C.sub.6
-alkylene-arylene-C.sub.1 -C.sub.6 -alkylene, C.sub.3 -C.sub.8
-cycloalkylene, C.sub.1 -C.sub.6 -alkylene-C.sub.3 -C.sub.8
-cycloalkylene-C.sub.1 -C.sub.6 -alkylene, C.sub.1 -C.sub.6
-alkylene-Z.sub.1 -arylene -Z.sub.1 --C.sub.1 -C.sub.6 -alkylene and
C.sub.2 -C.sub.6 -alkylene-[--Z.sub.1 --C.sub.2 -C.sub.6 -alkylene-].sub.n
-- wherein Z.sub.1 is selected from --O--, --S-- and --SO.sub.2 and n is
1-3;
L.sub.1 is a divalent linking group selected from C.sub.2 -C.sub.6
-alkylene, C.sub.1 -C.sub.6 -alkylene-C.sub.3 -C.sub.8
-cycloalkylene-C.sub.1 -C.sub.6 -alkylene, C.sub.1 -C.sub.6
-alkylene-arylene, C.sub.3 -C.sub.8 -cycloalkylene, and C.sub.2 -C.sub.6
-alkylene-[--Z.sub.1 --C.sub.2 -C.sub.6 -alkylene-].sub.n --;
L.sub.2 is selected from C.sub.2 -C.sub.6 -alkylene, C.sub.1 -C.sub.6
-alkylene-arylene-C.sub.1 -C.sub.6 alkylene and C.sub.1 -C.sub.6
-alkylene-C.sub.3 -C.sub.8 -cycloalkylene-C.sub.1 -C.sub.6 -alkylene;
Z is a divalent group selected from --O--, --S--, --NH--, --N(C.sub.1
-C.sub.6 -alkyl)-, --N(C.sub.3 -C.sub.8 alkenyl)-, --N(C.sub.3 -C.sub.8
cycloalkyl)-, --N(aryl)-, --N(SO.sub.2 C.sub.1 -C.sub.6 -alkyl) and
--N(SO.sub.2 aryl)-, provided that when Q is a photopolymerizable
optionally substituted maleimide radical, Z represents a covalent bond; Q
is an ethylenically-unsaturated, photosensitive polymerizable group; and
m and m.sub.1 each is O or 1.
The ethylenically-unsaturated, photosensitive copolymerizable groups
represented by Q are selected from the following organic radicals:
##STR10##
##STR11##
wherein:
R.sub.11 is selected from hydrogen and C.sub.1 -C.sub.6 -alkyl;
R.sub.12 is selected from hydrogen; C.sub.1 -C.sub.6 -alkyl; phenyl and
phenyl substituted with one or more groups selected from C.sub.1 -C.sub.6
-alkyl, C.sub.1 -C.sub.6 -alkoxy, --N(C.sub.1 -C.sub.6 -alkyl), nitro,
cyano, C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.6 -alkanoyloxy and
halogen; 1- and 2-naphthyl which may be substituted with C.sub.1 -C.sub.6
-alkyl or C.sub.1 -C.sub.6 -alkoxy; 2- and 3-thienyl which may be
substituted with C.sub.1 -C.sub.6 -alkyl or halogen; 2- or 3-furyl which
may be substituted with C.sub.1 -C.sub.6 -alkyl;
R.sub.13 and R.sub.14 are selected from hydrogen, C.sub.1 -C.sub.6 -alkyl,
substituted C.sub.1 -C.sub.6 -alkyl, aryl or may be combined to represent
a --[--CH.sub.2 --].sub.3-5 -- radical;
R.sub.15 is selected from hydrogen, C.sub.1 -C.sub.6 -alkyl, substituted
C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.8 -alkenyl, C.sub.3 -C.sub.8
-cycloalkyl and aryl;
R.sub.16 is selected from hydrogen, C.sub.1 -C.sub.6 -alkyl and aryl.
The term "C.sub.1 -C.sub.6 -alkyl" is used herein to denote a straight or
branched chain, saturated, aliphatic hydrocarbon radical containing one to
six carbon atoms. The term "substituted C.sub.1 -C.sub.6 -alkyl" is used
to denote a C.sub.1 -C.sub.6 -alkyl group substituted with one or more
groups, preferably one to three groups, selected from the group consisting
of hydroxy, halogen, cyano, aryl, aryloxy, arylthio, C.sub.1 -C.sub.6
alkylthio, C.sub.3 -C.sub.8 -cycloalkyl, C.sub.1 -C.sub.6 -alkanoyloxy and
--[--O--R.sub.17 --)--R.sub.18, wherein R.sub.17 is selected from the
group consisting of C.sub.1 -C.sub.6 alkylene, C.sub.1 -C.sub.6
-alkylene-arylene, cyclohexylene, arylene, C.sub.1 -C.sub.6
-alkylene-cyclohexylene and C.sub.1 -C.sub.6
-alkylene-cyclohexylene-C.sub.1 -C.sub.6 -alkylene;
R.sub.18 is selected from the group consisting of hydrogen, hydroxy,
carboxy, C.sub.1 -C.sub.6 -alkanoyloxy, C.sub.2 -C.sub.6 -alkoxycarbonyl,
aryl and C.sub.3 -C.sub.8 -cycloalkyl; and p is 1, 2, or 3.
A second embodiment of the present invention pertains to a coating
composition comprising (i) one or more polymerizable vinyl compounds, (ii)
one or more of the dye compounds described above, and (iii) a
photoinitiator. A third embodiment of the present invention pertains to a
polymeric composition, typically a coating, comprising a polymer of one or
more acrylic acid esters, one or more methacrylic acid esters and/or other
polymerizable vinyl compounds, having copolymerized therein one or more of
the dye compounds described above.
DETAILED DESCRIPTION
The terms "C.sub.1 -C.sub.6 -alkylene" and "C.sub.1 -C.sub.8 -alkylene" are
used to denote straight or branched chain, divalent, aliphatic hydrocarbon
radicals containing one to six and one to eight carbons, respectively, and
these radicals substituted with one to three groups selected from C.sub.1
-C.sub.6 -alkoxy, C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.6
-alkanoyloxy, hydroxy, aryl and halogen. Similarly, the term "C.sub.2
-C.sub.6 -alkylene" is used to denote a straight or branched chain,
divalent, hydrocarbon radical which may be unsubstituted or substituted as
described in this paragraph for the C.sub.1 -C.sub.6 -alkylene and C.sub.1
-C.sub.8 -alkylene radicals.
The terms "C.sub.1 -C.sub.6 -alkoxy", "C.sub.1 -C.sub.6 -alkoxycarbonyl",
"C.sub.1 -C.sub.6 -alkanoyloxy" and "C.sub.1 -C.sub.6 -alkanoylamino" are
used to denote radicals corresponding to the structures --OR.sub.19,
--CO.sub.2 R.sub.19, --OCOR.sub.19 and NHCOR.sub.19, respectively, wherein
R.sub.19 is C.sub.1 -C.sub.6 -alkyl or substituted C.sub.1 -C.sub.6
-alkyl. The term "C.sub.3 -C.sub.8 -alkenyl" is used to denote an
aliphatic hydrocarbon radical containing at least one double bond. The
term "C.sub.3 -C.sub.8 -cycloalkyl" is used to denote a saturated,
carbocyclic hydrocarbon radical having three to eight carbon which may be
unsubstituted or substituted with one to three C.sub.1 -C.sub.6 -alkyl
group(s). The term "C.sub.3 -C.sub.8 -cycloalkylene" is used to denote a
carbocyclic, divalent hydrocarbon radical which contains three to eight
carbon atoms, preferably five or six carbons.
The term "aryl" as used herein denotes phenyl and phenyl substituted with
one to three substituents selected from C.sub.1 -C.sub.6 -alkyl,
substituted C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 alkoxy, halogen,
carboxy, cyano, C.sub.1 -C.sub.6 -alkanoyloxy, C.sub.1 -C.sub.6
-alkylthio, C.sub.1 -C.sub.6 alkylsulfonyl, trifluoromethyl, hydroxy,
C.sub.1 -C.sub.6 -alkoxycarbonyl, C.sub.1 -C.sub.6 alkanoylamino and
--O--R.sub.20, S--R.sub.20, --SO.sub.2 --R.sub.20, --NHSO.sub.2 R.sub.20
and --NHCO.sub.2 R.sub.20, wherein R.sub.20 is phenyl or phenyl
substituted with one to three groups selected from C.sub.1 -C.sub.6
-alkyl, C.sub.1 -C.sub.6 -alkoxy and halogen. The term "arylene" as used
herein denotes includes 1,2-, 1,3- and 1,4-phenylene and such divalent
radicals substituted with one to three groups selected from C.sub.1
-C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy and halogen. The term
"heteroaryl" as used herein denotes a 5- or 6-membered aromatic ring
containing one to three hetero atom selected from oxygen, sulfur and
nitrogen. Examples of such heteroaryl groups are thienyl, furyl, pyrrolyl,
imidazolyl, pyrazolyl, thiazolyl, isothiazolyl, oxazolyl, isoxazolyl,
triazolyl, thiadiazolyl, oxadiazolyl, tetrazolyl, pyridyl, pyrimidyl,
benzoxazolyl, benothiazolyl, benzimidazolyl, indolyl and the like. The
heteroaryl radicals may be substituted with one to three groups selected
from C.sub.1 -C.sub.6 -alkyl, C.sub.1 -C.sub.6 -alkoxy, substituted
C.sub.1 -C.sub.6 -alkyl, halogen, C.sub.1 -C.sub.6 -alkylthio, aryl,
arylthio, aryloxy, C.sub.1 -C.sub.6 -alkoxycarbonyl and C.sub.1 -C.sub.6
-alkanoylamino.
The term "halogen" is used to include fluorine, chlorine, bromine, and
iodine. The terms "sulfamoyl and substituted sulfamoyl" denote radicals
having the structure --SO.sub.2 N(R.sub.21)R.sub.22, wherein R.sub.21, and
R.sub.22 are independently selected from hydrogen, C.sub.1 -C.sub.6
-alkyl, substituted C.sub.1 -C.sub.6 -alkyl, C.sub.3 -C.sub.8 -alkenyl,
C.sub.3 -C.sub.8 -cycloalkyl, aryl and heteroaryl.
The preferred dye compounds of Formulae I, II, III, IV, V, VI, VIII, IX, X,
XII, XIII, XIV, XVI, XVII, XIX, and XX are those where Z is --O--. These
dyes are prepared by reacting the corresponding dihydroxy dye [Dye
(OH).sub.2 ] with a reagent to introduce the reactive vinyl functionality.
For example, the dyes wherein Q corresponds to structure Ia, VIa, XIa,
respectively, are prepared by reacting the dihydroxy dyes with the
corresponding acid chlorides and/or anhydrides as follows:
##STR12##
The dyes wherein Z is --O-- and Q corresponds to structures IIa, IIIa, and
VIIIa are prepared by reacting the dihydroxy dyes with the corresponding
isocyanates:
##STR13##
The dyes were Z is --O-- and where Q corresponds to structure IVa are
prepared by reacting the dihydroxy dyes with 2-alkenylazlactones as
generally described in Encyclopedia of Polymer Science and Eng., Second
Ed., Vol. 11, John Wiley & Sons, pp. 558-571:
##STR14##
The dyes wherein Z is --O-- and Q corresponds to structure Va are generally
prepared by reacting the dihydroxy dyes with maleic anhydride to give the
mono maleate esters:
##STR15##
The remaining acid groups may be esterified by the usual type
esterification reactions such as heating in alcohols in the presence of
acid catalysts and reacting the alkali metal salts of the acids with
alkylating agents such as alkyl halides, alkyl sulfates and alkyl
sulfonates, such as methyl 4-toluene sulfonate, to prepare the methyl
ester. Fumaric acid and its derivatives also may be used to prepare the
dyes where Q is radical Va. Itaconic anhydride (methylenesuccinic
anhydride) may be used to react with the dihydroxy dyes to prepare the
functionalized dyes wherein Z is --O-- and Q corresponds to structure XIIa
(R.sub.15.dbd.H). These acidic compounds may be esterified as described
above for preparing the dyes where Q corresponds to structure Va.
Anthraquinone dyes containing aliphatic hydroxy groups useful for reacting
as described above to produce dyes containing reactive Q groups are
disclosed in U.S. Pat. Nos. 4,267,306, 4,359,570, 4,403,092, 4,804,719,
4,999,418, 5,032,670, 5,194,463, 5,372,864, 5,955,564 and 5,962,557.
Anthraquinone dyes containing 1(H)-1,2,4-triazol-3ylthio groups which are
useful in preparing dyes of Formulae III, IX, XIII and XX are disclosed in
U.S. Pat. Nos. 3,689,501, 4,267,306, 5,962,557 and 6,197,223.
Anthraquinone dyes containing carboxy groups and which are useful in the
practice of the invention are disclosed in U.S. Pat. Nos. 4,359,570,
4,403,092, 4,999,418, 5,372,864, 5,955,564, 5,962,557 and U.S. Pat. No.
6,197,223. Hydroxy alkyl groups may be introduced into these compounds by
alkylation of the acids with hydroxyalkyl halides or alkylene carbonates
to give the hydroxyalkyl derivatives useful for reacting further as shown
herein to introduce reactive Q groups.
To prepare the dyes wherein Z is --S--, --NH--, --N(C.sub.1 -C.sub.6
alkyl)-, --N(C.sub.3 -C.sub.8 alkenyl)-, --N(C.sub.3 -C.sub.8
cycloalkyl)-, --N(aryl)-, --N(SO.sub.2 C.sub.1-C.sub.6 alkyl)- and
--N(SO.sub.2 aryl)-, the corresponding anthraquinone dyes containing two
of the following nucleophilic ZH groups, respectively, are reacted with
the reagents mentioned above for preparing the dyes where Z.dbd.--O--:
--SH, --NH(C.sub.1 -C.sub.6 alkyl), --NH(C.sub.3 -C.sub.8 alkenyl),
--NH(C.sub.3 -C.sub.8 cycloalkyl), --NH(aryl)-, NH(SO2 C.sub.1 -C.sub.6
alkyl) and --NH(SO.sub.2 aryl). All of the dyes mentioned above containing
two ZH groups may be reacted with vinylsulfonyl halides to prepare dyes
where Q.dbd.--SO.sub.2 C(R.sub.11).dbd.CH.sub.2 (Structure IXa). When Q
corresponds to Structure IXa, the preferred Z group is --NH--. Dyes
wherein Q corresponds to structure Xa and XIIIa and Z is a covalent bond
are prepared by reacting dyes containing two primary amine groups with,
for example, maleic anhydride and itaconic anhydride, respectively.
The functionalized dyes of Formulae VII, XI, XV, XVIII and XXI wherein
X.sub.2 and X.sub.4 are --CO.sub.2 -- are prepared by alkylating the
intermediate dye containing two carboxy groups with an alkylating agent
having the structure ClCH.sub.2 -p-C.sub.6 H.sub.4
--C(R.sub.8).dbd.CH.sub.2, with 4-vinylbenzyl chloride (R.sub.8.dbd.H)
being particularly preferred. The reaction is easily accomplished in the
presence of alkali metal carbonates and trialkyl amines as bases. The
functionalized dyes corresponding to Formulae III, IX, XIII and XX wherein
m is O are prepared by reacting the intermediate dyes containing two
1(H)-1,2,4-triazol-3ylthio groups with an alkylating agent having the
structure ClCH.sub.2 -p-C.sub.6 H.sub.4 --C(R.sub.8).dbd.CH.sub.2, with
4-vinylbenzyl chloride (R.sub.8.dbd.H) being preferred, in the presence of
a base such as alkali metal carbonates or trialkylamines.
A group of preferred anthraquinone compounds comprise compounds having
structures XVI and XIX wherein X.sub.3 is --CO.sub.2 --, L is propylene,
1,4-cyclo-hexylenedimethylene or 2,2-dimethyltrimethylene, R is hydrogen,
Z is --O--, and Q is an organic radical having the structure
--COC(R.sub.11).dbd.CH.sub.2 wherein R.sub.11 is hydrogen, methyl or
ethyl, or Q is an organic radical having structure VIIIa wherein R.sub.11,
R.sub.13 and R.sub.14 each is methyl.
The yellow, red-magenta, blue-cyan dyes of this invention are particularly
useful for making combination shades as subtractive colors. They have
particular value for copolymerizing into acrylic polymeric materials by
free radical polymerization, having one or more advantages over the prior
art dyes such as thermal stability, solubility in the acrylate or
methacrylate ester comonomer(s) to be used, fastness to UV light, color
strength, ease of manufacture and the like. The dyes of this invention are
particularly useful for providing acrylic polymer color coatings for glass
optical fibers where good thermal stability of dyes is required.
COLORANT EXAMPLES
The copolymerizable dye compounds provided by the present invention and the
preparation thereof are further illustrated by the following examples.
Example 1
A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S. Pat. No.
4,359,570, Example 1) (5.13 g, 0.01 mol), potassium carbonate (2.84 g,
0.02 mol) and N,N-dimethylformamide (DMF, 100 mL) was stirred and heated
to about 100.degree. C. To the stirred mixture, was added 4-vinylbenzyl
chloride (Aldrich, 3.76 g, 0.022 m). Thin-layer chromatography (TLC) using
a 50/50 mixture of tetrahydrofuran(THF)/cyclohexane after heating the
reaction mixture at about 105.degree. C. for 30 min. showed only one spot
with no starting material or mono-reacted product being observed. The
reaction mixture was heated for an additional 20 minutes and the yellow
dye precipitated by the addition of a mixture of methanol and water. The
solid dye was collected by filtration, washed with water and then with a
little methanol. The yield of air-dried product was 6.85 g (92% of the
theoretical yield). Field desorption mass spectrometry (FDMS) supported
the following structure:
##STR16##
An absorption maximum at 447 nm was observed in the UV-visible absorption
spectrum in DMF.
Example 2
A mixture of 1,5-bis-(2-carboxyanilino) anthraquinone (U.S. Pat. No.
4,359,570, Example 2) (4.78 g, 0.01 mol), potassium carbonate (2.76 g,
0.02 mol) and DMF (100 mL) was stirred and heated to about 90.degree. C.
and 4-vinylbenzyl chloride (Aldrich, 3.76 g, 0.022 mol) was added and
heating and stirring continued at about 100.degree. C. for 60 min. TLC
(50/50 THF/cyclohexane) showed complete reaction. Methanol (120 mL) was
added gradually with stirring to precipitate the red product, which was
collected by filtration, washed with water and then dried in air
(yield-6.18 g, 87% of the theoretical yield). FDMS supports the following
structure:
##STR17##
Example 3
A mixture of 1,5-bis-(isobutylamino)-4,8-bis-(2-carboxyphenylthio)
anthraquinone (U.S. Pat. No. 6,197,223, Example 2) (6.54 g, 0.01 mol),
potassium carbonate (2.76 g, 0.02 m) and DMF (150 mL) was stirred and
heated to about 100.degree. C. To the stirred reaction mixture was added
4-vinylbenzyl chloride (3.76 g, 0.02 mol). The reaction mixture was heated
at 95-100.degree. C. for about 60 minutes The reaction mixture was cooled
and the gummy product was drowned out by the addition of methanol/water.
The liquid was decanted off and the product triturated with methanol. The
resulting dark blue solid was collected by filtration, washed with
methanol and dried in air (yield-6.95 g, 78% of the theoretical yield).
FDMS supported the following structure:
##STR18##
Absorption maxima at 600 nm and 645 nm were observed in the UV-visible
absorption spectra in DMF.
Example 4
A mixture of
1,5-bis-(2-carboxyphenylthio)-4,8-bis-(4-tolylthio)-anthra-quinone (U.S.
Pat. No. 6,197,223) (7.56 g, 0.01 mol), potassium carbonate (K.sub.2
CO.sub.3) and DMF (300 mL) was stirred and heated to about 100.degree. C.
and then 4-vinylbenzyl chloride (3.84 g, 0.025 mol) was added. The
reaction mixture was heated and stirred at about 100.degree. C. for 60
minutes. TLC (50/50 THF/cyclohexanol) showed complete reaction. After
cooling, the sticky product was obtained by drowning the reaction mixture
with methanol/water. The red product solidified upon standing in contact
with methanol and was collected by filtration and dried in air (yield-7.67
g, 78% of the theoretical yield). FDMS supported the following structure:
##STR19##
An absorption maximum was observed at 520 nm in the UV-visible absorption
in DMF.
Example 5
A mixture of 1,5-bis-[(1H)-1,2,4-triazol-3ylthio)] anthraquinone (U.S. Pat.
No. 3,689,501) (4.06 g, 0.01 mol), potassium carbonate (2.76 g, 0.02 mol)
and DMF (100 mL) was stirred and heated to about 100.degree. C. and
4-vinylbenzyl chloride (3.76 g, 0.022 mol) was added. TLC (50/50
THF/cyclohexane) still showed some mono-substituted product after heating
the reaction mixture for 2 hrs. Additional quantities of 4-vinylbenzyl
chloride (4.14 g) and potassium chloride (1.38 g) were added and heating
continued for another hour to complete the reaction. A gummy yellow solid
was produced by drowning the cooled reaction mixture with water. The
product was washed by decantation with water and then dissolved in DMF.
The DMF solution was drowned gradually into cold water with good stirring
and the yellow solid was collected by filtration and dried in air (3.46 g,
54% of the theoretical yield). FDMS supported the following structure:
##STR20##
An absorption maximum at 420 nm was observed in the UV-visible absorption
spectrum in DMF.
Example 6
A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino) anthraquinone
(U.S. Pat. No. 4,999,418, Example 1) (4.10 g, 0.01 mol), DMF (25 mL) and
3-isopropenyl-.varies.,.varies.-dimethylbenzyl isocyanate (Aldrich; 5 mL,
0.025 mol) was heated and stirred at about 75.degree. C. for 48 hrs. TLC
(50/50-THF/cyclohexane) showed all of the starting material to be reacted
and a mixture of the desired product plus the mono-reaction product. After
addition of an additional quantity (1 mL) of
3-isopropenyl-.varies.,.varies.-dimethylbenzyl isocyanate, the reaction
mixture was heated and stirred at about 90.degree. C. for 12 hrs.
Triethylamine (0.5 mL) was added and the reaction mixture was stirred at
about 100.degree. C. for another 24 hrs. The cooled reaction mixture was
drowned into water (200 mL) to produce a sticky solid which hardened upon
standing. The water was decanted off and the solid redissolved in DMF (200
mL) by heating on a steambath. Water (50 mL) was added gradually to the
hot DMF with stirring. After allowing to stand overnight a red solid had
formed. Additional water (150 mL) was added and the product was collected
by filtration, washed with water and dried in air. Essentially a
quantitative yield of the following product was obtained:
##STR21##
which was soluble in methanol, methylene chloride and somewhat soluble in
hexane.
Example 7a
A mixture of 1,5-bis-(2-carboxyphenylthio) anthraquinone (U.S. Pat. No.
4,359,570, Example 1) (30.6 g, 0.06 mol), ethylene carbonate (88.0 g, 1.0
mol), ethylene glycol (50 mL) and pulverized potassium iodide (5.2 g) was
heated and stirred at about 125.degree. C. for about 2.0 hours and then
allowed to cool. The reaction mixture was drowned into cold water (150 mL)
with stirring. The yellow solid was collected by filtration, washed with
warm water and dried in air (yield-35.2 g, 97.8% of the theoretical
yield). FDMS supported the following structure:
##STR22##
Example 7b
A mixture of the product of Example 7a (6.0 g, 0.01 mol), DMF (25 mL) and
3-isopropenyl-.varies.,.varies.-dimethylbenzyl isocyanate (6 mL, 0.03 mol)
was heated and stirred, under nitrogen at about 95-100.degree. C. for
about 48 hours. Triethylamine (0.5 mL) was added and heating continued for
an additional 48 hours. Water (60 mL) was added portionwise to the hot
reaction mixture with stirring. After allowing to cool to room
temperature, the yellow product was collected to filtration, washed with
water and dried in air. Essentially a quantitative yield of the following
product was obtained:
##STR23##
Example 8
A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino) anthraquinone
(U.S. Pat. No. 4,999,418, Example 1) (1.0 g, 2.44 mmol) and toluene (50
mL) was prepared and then most of the toluene was evaporated under reduced
pressure to remove any water present. DMF (50 mL), hydroquinone (50 mg),
4-(dimethyl-amino)pyridine (DMAP; 59.6 mg), triethylamine (1.0 mL) and
methacrylic anhydride (1.33 g, 7.32 mmol) were added and the reaction
mixture was stirred at room temperature for about 20 hours. TLC (50/50
hexane/ethyl acetate) indicated complete reaction. The reaction mixture
was poured into water (300 mL) and the red product was collected by
filtration, washed with water and dried in vacuo (yield-1.30 g, 98% of the
theoretical yield). FDMS supported the following structure:
##STR24##
The functionalized red dye had an absorption maximum at 526 nm in DMF
solution in the UV-visible absorption spectrum.
Example 9
The dye of Example 7a above (2.0 g, 3.33 mmol) and toluene (20 mL) were
mixed and stirred while most of the toluene was removed under reduced
pressure. DMF (50 mL), DMAP (82 mg), triethylamine (1.4 mL), hydroquinone
(50 mg) and methacrylic anhydride (1.53 g, 9.99 mmol) were added and the
reaction mixture stirred at room temperature for 15 hours. The yellow
functionalized dye which was precipitated by drowning into water (200 mL)
and allowing to stand for several days was collected by filtration, washed
with water and 1:1 methanol: water and dried in vacuo. The yield was 2.23
g (91% of the theoretical yield). FDMS supported the following structure:
##STR25##
An absorption maximum at 444 nm was observed in the UV-visible absorption
spectrum in DMF.
Example 10a
A mixture of 1,5-bis-(carboxyanilino) anthraquinone (U.S. Pat. No.
4,359,570, Example 2) (59.75 g, 0.125 mol), ethylene carbonate (165 g,
1.875 mol), ethylene glycol (550 mL) and pulverized potassium iodide (11.3
g) was heated at 120-125.degree. C. for 6.5 hours -and the mixture allowed
to cool. Methanol (400 mL) was added to the stirred reaction mixture. The
red solid was collected by filtration, washed with water and dried in air
(yield-69.5 g, 98.2% of the theoretical yield). FDMS supported the
following structure:
##STR26##
Example 10b
A portion (2.0 g, 3.53 mmol) of the dye of Example 10a above was mixed with
toluene (10 mL) and most of the toluene removed under vacuum. DMF (50 mL),
DMAP (86 mg), triethylamine (1.5 mL), hydroquinone (20 mg) and methacrylic
anhydride (1.63 g, 10.6 mmol) were added and the resulting solution was
stirred for 15 hours at room temperature. The reaction mixture was drowned
into water (200) and allowed to stand at room temperature for several
days. The functionalized red dye was collected by filtration, washed with
water and dried in vacuo (yield-2.10 g. 85% of the theoretical yield).
FDMS supported the following structure:
##STR27##
An absorption maximum at 525 nm was observed in DMF solution in the
UV-visible absorption spectrum.
Example 11
A mixture of
1,5-bis-(2,2-dimethly-3-hydroxypropylamino)-4,8-bis-(tolylthio)anthraquino
ne (U.S. Pat. No. 5,955,564) (2.0 g, 3.06 mmol) and toluene (10 mL) was
stirred and most of the toluene removed under vacuum. DMF (50 mL),
triethylamine (1.3 mL), DMAP (75 mg), hydroquinone (20 mg) and methacrylic
anhydride (1.41 g, 9.18 mmol) were added and the reaction mixture was
stirred at room temperature for 15 hours. After drowning into water (200
mL) and allowing the mixture to stand for several days the functionalized
blue dye was collected by filtration, washed with water and dried in
vacuo. Essentially a quantitative yield was obtained. FDMS supported the
following structure:
##STR28##
An absorption maximum at 650 nm was observed in DMF solution in the
UV-visible light absorption spectrum.
Example 12
A mixture of
1,5-bis-[5-(N-ethyl-N-(2-hydroxyethyl)sulfamoyl)-2-methoxyanilino]anthraqu
inone (U.S. Pat. No. 5,372,864, Example 21) (2.0 g, 2.66 mmol) and toluene
(10 mL) was stirred and most of the toluene was removed under reduced
pressure. DMF (50 mL), DMAP (65 mg), triethylamine (1.1 mL), hydroquinone
(20 mg) and methacrylic anhydride (1.22 g, 7.98 mmol) were added and the
reaction mixture was stirred overnight at room temperature for about 15
hours. The functionalized blue dye was precipitated by drowning into water
(200 mL) and allowing the mixture to stand for several days at room
temperature and was collected by filtration washed with water and dried in
vacuo. Essentially a quantitative yield was obtained. FDMS supported the
following structure:
##STR29##
An absorption maximum at 527 nm in DMF solution was observed in the
UV-visible absorption spectrum.
Example 13
A portion (2.0 g, 3.53 mmol) of the dye from Example 10a above was mixed
with toluene and stirred while most of the toluene was removed under
reduced pressure. DMF (50 mL), DMAP (86 mg), triethylamine (1.5 mL),
hydroquinone (20 mg) and crotonic anhydride (1.63 g, 10.6 mmol) were added
and the reaction mixture was stirred for 24 hours. The functionalized red
dye was isolated by drowning into water (200 mL), allowing the mixture to
stand for a little while and then collecting by filtration. After washing
with water the dye was dried in vacuo (yield-2.11 g, 85% of the
theoretical yield). FDMS supported the following structure:
##STR30##
An absorption maximum at 522 nm in DMF solution was observed in the
UV-visible light absorption spectrum.
Example 14
A mixture of
1,5-bis-(2,2-dimethyl-3-hydroxypropylamino)-4,8-bis-(4-tolylthio)
anthraquinone (U.S. Pat. No. 5,955,564) (2.0 g, 3.06 mmol) and toluene (10
mL) was stirred and most of the toluene removed under reduced pressure.
DMF (50 mL), DMAP (75 mg), triethylamine (1.3 mL), hydroquinone (20 mg)
and crotonic anhydride (1.41 g, 9.18 mmol) were added. The reaction
mixture was stirred at room temperature for 24 hours and then drowned into
water (200 mL). After allowing the mixture to stand for awhile, the
functionalized blue dye was collected by filtration, washed with water and
dried in vacuo. The yield was essentially quantitative. FDMS supported the
following structure:
##STR31##
An absorption maximum at 650 nm was observed in DMF in the UV-visible
absorption spectrum.
Example 15
A mixture of 1,5-bis-[5-(N-ethyl-N-(2-hydroxyethyl)
sulfamoyl-2-methoxyanilino]-anthraquinone (U.S. Pat. No. 5,372,864,
Example 21) (2.0 g, 2.66 mmol) and toluene (10 mL) were stirred and most
of the toluene removed under reduced pressure. DMF (50 mL), DMAP (65 mg),
triethylamine (1.1 mL), hydroquinone (20 mg) and crotonic anhydride (1.23
g, 7.98 mmol) were added. After being stirred at room temperature for 24
hours the reaction mixture was drowned into water (200 mL) and the mixture
allowed to stand for awhile. The functionalized red dye was collected by
filtration, washed with water and dried in vacuo. The yield was 1.96 g of
product (83% of the theoretical yield). FDMS supported the following
structure:
##STR32##
An absorption maximum at 529 nm was observed in the UV-visible light
absorption spectrum.
Example 16
A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino) anthraquinone
(U.S. Pat. No. 4,999,418, Example 1) (2.0 g, 4.88 mmol) and toluene (10
mL) was stirred and most of the toluene was removed under reduced
pressure. DMF (50 mL), DMAP (120 mg), triethyl amine (2.0 mL) and crotonic
anhydride (2.25 g, 14.6 mmol) were added. The reaction mixture was stirred
at room temperature for 24 hours and then drowned into water (200 mL) and
the mixture allowed to stand awhile. The functionalized red dye was
collected by filtration, washed with water and dried in vacuo. The yield
was 2.24 g (98% of the theoretical yield). FDMS supported the following
structure:
##STR33##
An absorption maximum at 527 nm was observed in the UV-visible light
spectrum in DMF as the solvent.
Example 17
A mixture of a portion (2.0 g, 3.33 mmol) of the dye of Example 7a above
and toluene (10 mL) was stirred and most of the toluene removed under
vacuum. DMF (50 mL), DMAP (86 mg) triethylamine (1.4 mL), hydroquinone (20
mg) and crotonic anhydride (7.54 g, 9.99 mmol) were added. The reaction
mixture was stirred at room temperature for 24 hours and drowned into
water (200 mL) with stirring. The mixture was allowed to stand awhile and
the functionalized yellow dye was collected by filtration, washed with
water and dried in vacuo (yield 2.01 g, 82% of the theoretical yield).
FDMS supported the following structure:
##STR34##
An absorption maximum at 446 nm was observed in DMF in the UV-visible light
absorption spectrum.
Example 18
A mixture of 1,5-bis-(2,2-dimethyl-3-hydroxypropylamino) anthraquinone
(U.S. Pat. No. 4,999,418, Example 1) (1.0 g, 2.44 mmol) and toluene (50
mL) was stirred and most of the toluene removed under reduced pressure.
DMF (50 mL), DMAP (60 mg), triethylamine (1.0 mL), hydroquinone (50 mg)
and cinnamoyl chloride (Aldrich; 1.22 g, 7.35 mmol) were added. The
reaction mixture was stirred at about 50.degree. C. temperature for about
12 hours and then drowned into water (100 mL). The functionalized red dye
was collected by filtration, washed with water and dried in vacuo
(yield-1.61 g, 99% of the theoretical yield). FDMS supports the following
structure:
##STR35##
An absorption maximum at 527 nm was observed in DMF in the UV-visible
absorption spectrum.
The functionalized dyes or colorants which contain vinyl or substituted
vinyl groups are polymerizable or copolymerizable, preferably by free
radical mechanisms, said free radicals being generated by exposure to UV
light by methods known in the art of preparing UV-cured resins.
Polymerization can be facilitated by the addition of photoinitiators. The
colored polymeric materials normally are prepared by dissolving the
functionalized colorants containing copolymerizable groups in a
polymerizable vinyl monomer with or without another solvent and then
combining with an oligomeric or polymeric material which contains one or
more vinyl or substituted vinyl groups.
The second embodiment of the present invention is a coating composition
comprising (i) one or more polymerizable vinyl compounds, i.e., vinyl
compounds which are copolymerizable with the dye compounds described
herein, (ii) one or more of the dye compounds described above, and (iii)
at least one photoinitiator. The polymerizable vinyl compounds useful in
the present invention contain at least one unsaturated group capable of
undergoing polymerization upon exposure to UV radiation in the presence of
a photoinitiator, i.e., the coating compositions are radiation-curable.
Examples of such polymerizable vinyl compounds include acrylic acid,
methacrylic acid and their anhydrides; crotonic acid; itaconic acid and
its anhydride; cyanoacrylic acid and its esters; esters of acrylic and
methacrylic acids such as allyl, methyl, ethyl, n-propyl, isopropyl,
butyl, tetrahydrofurfuryl, cyclohexyl, isobornyl, n-hexyl, n-octyl,
isooctyl, 2-ethylhexyl, lauryl, stearyl, and benzyl acrylate and
methacrylate; and diacrylate and dimethacrylate esters of ethylene and
propylene glycols, 1,3-butylene glycol, 1,4-butanediol, diethylene and
dipropylene glycols, triethylene and tripropylene glycols, 1,6-hexanediol,
neopentyl glycol, polyethylene glycol, and polypropylene glycol,
ethoxylated bisphenol A, ethoxylated and propoxylated neopentyl glycol;
triacrylate and trimethacrylate esters of
tris-(2-hydroxyethyl)isocyanurate, trimethylolpropane, ethoxylated and
propoxylated trimethylolpropane, pentaerythritol, glycerol, ethoxylated
and propoxylated glycerol; tetraacrylate and tetramethacrylate esters of
pentaerythritol and ethoxylated and propoxylated pentaerythritol;
acrylonitrile; vinyl acetate; vinyl toluene; styrene; N-vinyl
pyrrolidinone; alpha-methylstyrene; maleate/fumarate esters;
maleic/fumaric acid; crotonate esters, and crotonic acid.
The polymerizable vinyl compounds useful in the present invention include
polymers which contain unsaturated groups capable of undergoing
polymerization upon exposure to UV radiation in the presence of a
photoinitiator. The preparation and application of these polymerizable
vinyl compounds are well known to those skilled in the art as described,
for example, in Chemistry and Technology of UV and EB Formulation for
Coatings, Inks, and Paints, Volume II: Prepolymers and Reactive Diluents,
G. Webster, editor, John Wiley and Sons, London, 1997. Examples of such
polymeric, polymerizable vinyl compounds include acrylated and
methacrylated polyesters, acrylated and methacrylated polyethers,
acrylated and methacrylated epoxy polymers, acrylated or methacrylated
urethanes, acrylated or methacrylated polyacrylates (polymethacrylates),
and unsaturated polyesters. The acrylated or methacrylated polymers and
oligomers typically are combined with monomers which contain one or more
acrylate or methacrylate groups, e.g., monomeric acrylate and methacrylate
esters, and serve as reactive diluents. The unsaturated polyesters, which
are prepared by standard polycondensation techniques known in the art, are
most often combined with either styrene or other monomers, which contain
one or more acrylate or methacrylate groups and serve as reactive
diluents. A second embodiment for the utilization of unsaturated
polyesters that is known to the art involves the combination of the
unsaturated polyester with monomers that contain two or more vinyl ether
groups or two or more vinyl ester groups (WO 96/01283, WO 97/48744, and EP
0 322 808).
The coating compositions of the present invention optionally may contain
one or more added organic solvents if desired to facilitate application
and coating of the compositions onto the surface of substrates. Typical
examples of suitable solvents include, but are not limited to ketones,
alcohols, esters, chlorinated hydrocarbons, glycol ethers, glycol esters,
and mixtures thereof. Specific examples include, but are not limited to
acetone, 2-butanone, 2-pentanone, ethyl acetate, propyl acetate, isopropyl
acetate, butyl acetate, isobutyl acetate, ethylene glycol diacetate, ethyl
3-ethoxypropionate, methyl alcohol, ethyl alcohol, propyl alcohol,
isopropyl alcohol, butyl alcohol, ethylene glycol, propylene glycol,
ethylene glycol monomethyl ether, ethylene glycol monoethyl ether,
ethylene glycol monopropyl ether, ethylene glycol monobutyl glycol,
diethylene glycol monomethyl ether, diethylene glycol monoethyl ether,
diethylene glycol monobutyl ether, propylene glycol monomethyl ether,
diethylene glycol monobutyl ether acetate, diethylene glycol monoethyl
ether acetate, ethylene glycol monobutyl ether acetate, propylene glycol
monomethyl ether acetate, methylene chloride, chloroform, and mixtures
thereof. The amount of added or extraneous solvent which may be present in
our novel coating compositions may be in the range of about 1 to 70 weight
percent, more typically about 1 to 25 weight percent, based on the total
weight of the coating composition.
Certain polymerizable vinyl monomers may serve as both reactant and
solvent. These contain at least one unsaturated group capable of
undergoing polymerization upon exposure to UV radiation in the presence of
a photoinitiator. Specific examples include, but are not limited to:
methacrylic acid, acrylic acid, ethyl acrylate and methacrylate, methyl
acrylate and methacrylate, hydroxyethyl acrylate and methacrylate,
diethylene glycol diacrylate, trimethylolpropane triacrylate, 1,6
hexanediol di(meth)acrylate, neopentyl glycol diacrylate and methacrylate,
vinyl ethers, divinyl ethers such as diethyleneglycol divinyl ether,
1,6-hexanediol divinyl ether, cyclohexanedimethanol divinyl ether,
1,4-butanediol divinyl ether, triethyleneglycol divinyl ether,
trimethylolpropane divinyl ether, and neopentyl glycol divinyl ether,
vinyl esters, divinyl esters such as divinyl adipate, divinyl succinate,
divinyl glutarate, divinyl 1,4-cyclohexanedicarboxylate, divinyl
1,3-cyclohexanedicarboxylate, divinyl isophthalate, and divinyl
terephthalate, N-vinyl pyrrolidone, and mixtures thereof.
In addition, the compositions of the present invention may be dispersed in
water rather than dissolved in a solvent to facilitate application and
coating of the substrate surface. In the water-dispersed compositions of
the present invention a co-solvent is optionally used. Typical examples of
suitable cosolvents include but are not limited to acetone, 2-butanone,
methanol, ethanol, isopropyl alcohol, ethylene glycol monomethyl ether,
ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, and
ethylene glycol m
