Colorant compounds containing copolymerizable vinyl groups

Details Colorant compounds containing copolymerizable vinyl groups Colorant compounds containing copolymerizable vinyl groups

2001-08-02

2004-04-27

Aulakh, Charanjit S. (Department: 1625)

Organic compounds -- part of the class 532-570 series

Organic compounds

Polycyclo ring system containing anthracene configured ring...

C430S281100, C430S007000, C552S221000, C552S234000, C552S261000, C552S268000

Reexamination Certificate

active

06727372

ABSTRACT:

FIELD OF THE INVENTION
This invention pertains to certain novel colorant compounds which contain one or more ethylenically-unsaturated (vinyl), photopolymerizable radicals which may be copolymerized (or cured) with ethylenically-unsaturated monomers to produce colored compositions such as colored acrylic polymers, e.g., polymers produced from acrylate and methacrylate esters, colored polystyrenes, and similar colored polymeric materials derived from other ethylenically-unsaturated monomers. The present invention also pertains to processes for preparing certain of the photopolymerizable colorant compounds.
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
The first embodiment of the present invention concerns colorant compounds having Formulas I and II:
wherein
A, is a mono-, di-, tri- or tetravalent chromophore;
X is —R
1
—O—Q or the phtopolymerizable group —CH
2
—C
6
H
4
-p-C(R
2
)═CH
2
;
Y is —R
1
—O—Q, —CH
2
—C
6
H
4
-p-C(R
2
)═CH
2
or Q;
R is selected from hydrogen, C
1
-C
6
alkyl, aryl and C
3
-C
8
cycloalkyl;
R
1
is selected from C
2
-C
8
alkylene, —(—CH
2
CH
2
O—)
m
—CH
2
CH
2
— and 1,4-cyclohexylenedimethylene;
R
2
is selected from hydrogen and C
1
-C
6
alkyl;
n is 1 to 4;
m is 1-3;
Q is a photopolymerizable group selected from an organic radical having the formulae:
—COC(R
3
)═CH—R
1
  Ia
—CONHCOC(R
3
)═CH—R
4
  IIa
—CONH—C
1
-C
6
-alkylene OCOC(R
3
)═CH—R
4
  IIIa
 wherein
R
3
is selected from hydrogen or C
1
-C
6
alkyl;
R
4
is selected from hydrogen; C
1
-C
6
alkyl; phenyl; phenyl substituted with one or more groups selected from C
1
-C
6
alkyl, C
1
-C
6
alkoxy, —N(C
1
-C
6
alkyl)
2
, nitro, cyano, C
2
-C
6
alkoxycarbonyl, C
2
-C
6
alkanoyloxy and halogen; 1- and 2-naphthyl; 1- and 2-naphthyl substituted with C
1
-C
6
alkyl or C
1
-C
6
alkoxy; 2- and 3-thienyl; 2- and 3-thienyl substituted with C
1
-C
6
alkyl or halogen; 2- and 3-furyl; and 2- and 3-furyl substituted with C
1
-C
6
alkyl;
R
5
and R
6
are independently selected from hydrogen, C
1
-C
6
alkyl, substituted C
1
-C
6
alkyl; aryl; or R
5
and R
6
may be combined to represent a —(—CH
2
—)
3-5
— radical;
R
7
is selected from hydrogen or a group selected from C
1
-C
6
alkyl, substituted C
1
-C
6
alkyl, C
3
-C
8
alkenyl, C
3
-C
8
cycloalkyl and aryl; and
R
8
is selected from hydrogen, C
1
-C
6
alkyl and aryl. The colorant compounds have good color strength, good solubility in the reactive monomers and good light-fastness. Certain of the colorant compounds exhibit outstanding thermal stability.
A second embodiment of the present invention concerns a process for preparing photopolymerizable colorants having Formula I, wherein X is a p-vinylbenzyl radical having the formula —CH
2
—C
6
H
4
-p-C(R
2
)═CH
2
which comprises reacting colored acidic compounds having the structure:
 A&Parenopenst;CO
2
—H)
n
with the compounds having the structure ClCH
2
—C
6
H
4
-p-C(R
2
)═CH
2
in the presence of base, wherein A, R
2
and n are as defined previously.
A third embodiment of the present invention concerns a process for preparing photopolymerization colorants having Formula II, wherein Y is a p-vinylbenzyl radical having the formula —CH
2
—C
6
H
4
-p-C(R
2
)═CH
2
which comprises reacting colored acidic compounds having the structure
with 4-chloromethylstyrene compounds having the structure ClCH
2
—C
6
H
4
-p-C(R
2
)═CH
2
in the presence of a base, wherein A, R, R
2
and n are defined above.
A fourth embodiment of the invention concerns a process for preparing colored photopolymerizable compounds having Formula I and Formula II, respectively, wherein X and Y are —CH
2
CH
2
—O—Q or —CH
2
CH(CH
3
)—O—Q, which comprises the steps of
(a) reacting a colored acidic compounds having the structures:
 respectively, with at least about n molecular equivalents of ethylene or propylene carbonate for each molecular equivalent of acidic compounds to produce the 2-hydroxyalkyl derivatives of said acidic compounds followed by:
(b) reaction of said colored hydroxyalkyl derivatives with about n molecular equivalents of one or more acylating agents having the structures
 ClCOC(R
3
)═CH—R
4
or O[COC(R
3
)═CH—R
4
]
2
,  Ib
O═C═N—COC(R
3
)═CH—R
4
,  IIb
O═C═N—C
1
-C
6
alkylene OCOC(R
3
)═CH—R
4
,  IIIb
wherein A, n, Q, R, R
3
, R
4
, R
5
, R
6
, R
8
are defined previously.
A fifth embodiment of the present invention concerns a process for preparing compounds of Structure II wherein Y is a photopolymerizable group Q which comprises reacting colored acidic compounds having the structure:
with at least about n molecular equivalents of one or more acylating agents Ib through IXb described above wherein A, R, n and Q are defined above.
A sixth embodiment of the present invention pertains to a coating composition comprising (i) one or more polymerizable vinyl compounds, (ii) one or more of the colorant compounds having Formulas I and II described above, and (iii) a photoinitiator. A seventh 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 colorant compounds having Formulas I and II described above.
DETAILED DESCRIPTION
In formulas I and II, A represents a mono-, di-, tri- or tetravalent residue of a chromophore, i.e., a colored compound, including residues which in combination with —CO
2
X produces a chromophore. Examples of the chromophoric residues which A may represent include anthraquinone, anthrapyridone (3H-dibenz-[f,ij]-isoquinoline-2,7-dione, anthrapyrimidine (7H-dibenz-[f,ij

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