Compositions: coating or plastic – Coating or plastic compositions – Marking
Reexamination Certificate
2000-01-19
2002-04-09
Klemanski, Helene (Department: 1755)
Compositions: coating or plastic
Coating or plastic compositions
Marking
C106S031780, C540S145000
Reexamination Certificate
active
06368396
ABSTRACT:
TECHNICAL FIELD
The present invention relates to an improved method for making porphines, and in particular 5,10,15,20-tetraphenyl-21H,23H-porphine-o,o
1
,o
11
,o
111
-tetrasulfonic acid, tetrasodium salt (designated o-TPPS4). The present invention is also directed to a method of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4) from o-TPPS4. The improved process allows the production of o-CuTPPS4 at lower cost and higher yields compared to conventional methods of making o-CuTPPS4. The present invention further relates to the use of o-CuTPPS4 as a colorant stabilizer for a variety of colorants, especially magenta colorants. The o-CuTPPS4, according to the present invention, provides a more stable and more “blue” colorant stabilizer compared to known colorant stabilizers, such as Cu-meso-tetra-(p-phenylcarboxylic acid)-porphine. The new porphine compounds may be used alone as a magenta dye or may be used in combination with one or more colorants to provide light stability to colorants. The present invention further relates to inks containing the new porphine compounds.
BACKGROUND OF THE INVENTION
U.S. patent application Ser. No. 08/757,222 filed Nov. 27, 1996, now U.S. Pat. No. 5,782,963; U.S. patent application Ser. No. 08/788,863 filed Jan. 23, 1997, now U.S. Pat. No. 6,099,628; U.S. patent application Ser. No. 08/843,410 filed Apr. 15, 1997, now U.S. Pat. No. 5,855,655; U.S. patent application Ser. No. 08/903,911 filed Jul. 31, 1997, now U.S. Pat. No. 5,891,229; and U.S. Provisional patent applications Ser. Nos. 60/055,785 filed Aug. 15, 1997, and 60/062,643 filed Oct. 22, 1997; all of which are assigned to Kimberly Clark Worldwide, Inc., disclose the use of a variety of porphines as colorant stabilizers. Porphines disclosed in the above-referenced applications include, but are not limited to, porphines having the following general structure:
wherein R is any proton-donating moiety and M is iron, cobalt or copper. Desirably, R is SO
3
H,
COOH, or R
1
COOH wherein R
1
is an alkyl group of from 1 to 6 carbons. R may also be in its corresponding salt form, such as
SO
3
Na for SO
3
H or
An attempt to make o-CuTPPS4 is disclosed in Treibs et al.,
Leibigs Ann. Chem.,
718, 183, 1998 (hereafter, “Treibs”). Treibs tried to prepare o-TPPS4 from 2-formylbenzenesulfonic acid, pyrrole, and propionoic acid. However, Treibs could not isolate the resulting product. Treibs reported a yield by GLC analysis of less than about 10%.
Although porphines provide excellent light stability to colorants, some porphines are relatively unstable and/or tend to “yellow” colorant compositions containing magenta dyes. A more desirable porphine molecule would be one that has less tendency to “yellow” a colorant composition, and moreover, to make the colorant composition more “blue.”
Also, while the above-described porphines provide excellent colorant stability to one or more colorants associated with the porphines, they do not provide an orange/red color to a composition containing the porphines.
Accordingly, there exists a need in the art for a convenient, low cost, high yield method of making o-TPPS4, o-CuTPPS4, and compositions containing o-CuTPPS4. Further, there exists a need for improved porphines, which are capable of providing superior colorant stability while being more stable and without the tendency to “yellow” colorant compositions containing magenta dyes. Finally, there exists a need in the art for a new family of compounds that may be used alone as an orange/red colorant or may be used as a colorant stabilizer for one or more colorants associated with the new compounds.
SUMMARY OF THE INVENTION
The present invention addresses the needs described above by providing a new family of porphine compounds having the following general formula:
where M is iron, cobalt or copper; R represents
and R
1
represents an alkyl group having from 1 to 6 carbon atoms, an aryl group, or a substituted aryl group. The porphine compounds may be used as a magenta colorant and/or as a colorant stabilizer for other colorants. The new porphine compounds, when used as a colorant stabilizer, do not “yellow” magenta dyes. Consequently, unstable dyes, such as Acid Red 52, do not need to be used to make a magenta composition. The result is a more “blue” magenta color and a higher porphine to dye ratio, which creates superior light stability.
The present invention also addresses the needs described above by providing processes of making o-TPPS4 at a lower cost and higher yields. The present invention also relates to processes of making Cu-meso-tetra-(2-sulfanatophenyl)-porphine (designated o-CuTPPS4), and the use of o-CuTPPS4 as a colorant stabilizer for a variety of colorants, especially magenta colorants. o-CuTPPS4 has excellent stability and provides superior stability to a variety of colorants.
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with one or more of the new porphine compounds. The present invention also relates to a process of making the new porphine compounds and the use of the porphine compounds in ink compositions.
These and other features and advantages of the present invention will become apparent after a review of the following detailed description of the disclosed embodiments and the appended claims.
DETAILED DESCRIPTION OF THE INVENTION
The present invention is directed to a new family of porphine compounds having the following general formula:
where M is iron, cobalt or copper; R represents
and where R
1
represents an alkyl group having from 1 to 6 carbon atoms, an aryl group, or a substituted aryl group. The new compounds may be used alone as a orange/red colorant or may be used as a colorant stabilizer.
In one embodiment of the present invention, the new porphine compound has one of the following structures:
The present invention also relates to colorant compositions having improved stability, wherein the colorant is associated with one or more colorant stabilizers comprising the above-described porphine compounds. Desirably, one or more of the new porphine compounds are admixed with a colorant solution. The colorant stabilizer may be one or more of the new porphine compounds alone or in combination with at least one metal or metal salt. Suitable metals and metal salts are disclosed in U.S. Pat. No. 5,891,229, assigned to Kimberly Clark Worldwide, Inc., the entirety of which is incorporated herein by reference. Optionally, the new porphine compounds may be associated with a molecular includant, chelating agent, or other material to improve solubility and/or interaction of the porphine compound and the colorant. Suitable molecular includants, chelating agents, and other composition materials are also disclosed in U.S. Pat. No. 5,891,229, assigned to Kimberly Clark Worldwide, Inc., the entirety of which is incorporated herein by reference.
The new porphine compounds may be associated with a variety of dyes or colorants. A suitable dye or colorant, for example, may be an organic dye. Organic dye classes include, by way of illustration only, triarylmethyl dyes, such as Malachite Green Carbinol base {4-(dimethylamino)-_-[4-(dimethylamino)phenyl]-_-phenyl-benzene-methanol}, Malachite Green Carbinol hydrochloride {N-4-[[4-(dimethylamino)phenyl]phenyl-methylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)phenyl]phenylmethylium chloride}, and Malachite Green oxalate {N-4-[[4-(dimethylamino)-phenyl]-phenylmethylene]-2,5-cyclohexyldien-1-ylidene]-N-methyl-methanaminium chloride or bis[p-(dimethylamino)-phenyl]phenylmethylium oxalate}; monoazo dyes, such as Cyanine Black, Chrysoidine [Basic Orange 2; 4-(phenylazo)-1,3-benzenediamine monohydrochloride], Victoria Pure Blue BO, Victoria Pure Blue B, basic fuschin and &bgr;-Naphthol Orange; thiazine dyes, such as Methylene Green, zinc chloride double salt [3,7-bis(dimethylamino)-6-nitrophenot
MacDonald John Gavin
Nohr Ronald Sinclair
Kilpatrick & Stockton LLP
Kimberly--Clark Worldwide, Inc.
Klemanski Helene
LandOfFree
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