CA2034060C - Method of preparing a solution of sulfonated aryl azo/diaryl guanidine-complexed dye - Google Patents
Method of preparing a solution of sulfonated aryl azo/diaryl guanidine-complexed dyeInfo
- Publication number
- CA2034060C CA2034060C CA002034060A CA2034060A CA2034060C CA 2034060 C CA2034060 C CA 2034060C CA 002034060 A CA002034060 A CA 002034060A CA 2034060 A CA2034060 A CA 2034060A CA 2034060 C CA2034060 C CA 2034060C
- Authority
- CA
- Canada
- Prior art keywords
- guanidine
- organic solvent
- diaryl
- dye
- phase
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Classifications
-
- C—CHEMISTRY; METALLURGY
- C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
- C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
- C09B69/00—Dyes not provided for by a single group of this subclass
- C09B69/02—Dyestuff salts, e.g. salts of acid dyes with basic dyes
- C09B69/04—Dyestuff salts, e.g. salts of acid dyes with basic dyes of anionic dyes with nitrogen containing compounds
Abstract
A liquid dyestuff, useful as a major component of a ballpoint ink is prepared. A dye base, having both a sulfonic acid group and an azo group bonded to the same aromatic ring system, is provided in the aqueous phase of a two-phase system in which the organic phase is about 30 percent or more benzyl alcohol. In this two-phase system, the dye base is complexed with a diaryl guanidine, and the resulting dye concentrates in the organic solvent phase.
Description
! ~ 20~060 MET~OD OF PREPARING A SO~UTION OF
SULFONATED ARYL AZO/DIARYL GUANIDINE-COMPLEXED DYE
The present invention is directed to a method of preparing a non-aqueous liquid dye formulated for ink applications in which a sulfonated aryl azo moiety is complexed to an aryl guanidine moiety, and particularly, to a method of preparing such a dyestuff without the complexed dye being initially produced in powdered form.
.
BACKGROUND OF THE INVENTION
The dyes of the present invention have both a sulfonic acid group and an azo group directly bonded to the same aromatic ring system and diaryl guanidine complexed to the sulfate. In many widely used dyes of this type, there are two such aromatic ring systems to which an azo and aryl guanidine-complexed sulfonic acid group are directly bonded. Dyes of this type are especially useful in inks, such as those used in ballpoint pens.
Dyes of this type are generally prepared by synthesizing compounds containing one or more aromatic ring systems directly to sulfonic acid and azo groups in an aqueous medium and then complexing this compound with a diaryl guanidine within the aqueous medium. The complexed dye precipitates from the aqueous medium as a fine powder which is collected, pressed and dried as a filter cake. In preparing inks from such dyes, the dyes are dissolved in an organic solvent system.
It has been found to be inconvenient and expensive to prepare solid complexed dyes and then to dissolve them in organic solvents. Handling powder is difficult and results in potentially hazardous human exposure.
Powdered dyes are difficult to solubilize in organic ~'~
~ ?,~`~
SULFONATED ARYL AZO/DIARYL GUANIDINE-COMPLEXED DYE
The present invention is directed to a method of preparing a non-aqueous liquid dye formulated for ink applications in which a sulfonated aryl azo moiety is complexed to an aryl guanidine moiety, and particularly, to a method of preparing such a dyestuff without the complexed dye being initially produced in powdered form.
.
BACKGROUND OF THE INVENTION
The dyes of the present invention have both a sulfonic acid group and an azo group directly bonded to the same aromatic ring system and diaryl guanidine complexed to the sulfate. In many widely used dyes of this type, there are two such aromatic ring systems to which an azo and aryl guanidine-complexed sulfonic acid group are directly bonded. Dyes of this type are especially useful in inks, such as those used in ballpoint pens.
Dyes of this type are generally prepared by synthesizing compounds containing one or more aromatic ring systems directly to sulfonic acid and azo groups in an aqueous medium and then complexing this compound with a diaryl guanidine within the aqueous medium. The complexed dye precipitates from the aqueous medium as a fine powder which is collected, pressed and dried as a filter cake. In preparing inks from such dyes, the dyes are dissolved in an organic solvent system.
It has been found to be inconvenient and expensive to prepare solid complexed dyes and then to dissolve them in organic solvents. Handling powder is difficult and results in potentially hazardous human exposure.
Powdered dyes are difficult to solubilize in organic ~'~
~ ?,~`~
- 2 - 20340~0 solvents and invariably result in high insoluble levels.
Alæo, it is difficult to produce dye solutions with high solids content by dissolving powdered complex dyes.
It is a general object of the present invention to produce liquid dyestuffs of the type in which a sulfonated aryl azo moiety is complexed with a diaryl guanidine without first producing a dye powder.
SUMMA~Y OF THE INVENTION
An aqueous solution of a dye base compound having at least one aromatic ring system to which both an azo group and a sulfate group are directly bonded is prepared, either by synthesizing the dye base in the aqueous medium or dissolving a dye base in an aqueous medium. The aqueous solution is contacted with an organic solvent phase comprising at least about 30 wt.
percent benzyl alcohol and additional water-immiscible organic solvent so as to maintain a two phase system.
The dye base is complexed with a diaryl guanidine in this two phase system; whereupon, the complexed dye concentrates in the solvent phase.
DETAI~ED DESCRIPTION OF CERTAIN PREFERRED EMBODIMENTS
The dye base according to the present invention contains at least one aromatic ring system to which both a sulfate group and either an azo group (-N=N=) or an N-N grouping of another aromatic ring system are generally attached. Thus the dye base of the present invention contains at least one moiety of the general formulae:
(I) (II) S03~-Ar-N=N- or S03~-Ar- ~ where N ~ N ~
represents a second aromatic ring system, such as:
o~
_~ ~C-H
Il I
N ---C-If the moiety is of formula (I), the -N=N- group is typically bonded directly to a further aromatic ring system. The Ar of formulae (I) and (II) may be a single, double or fused aromatic ring system, it being required only that the azo or aromatic N-N grouping and sulfonic acid group be bonded directly to the ring system, not necessarily on the same ring of the ring system. The Ar group generally is a carbon ring system, but may be a heterocyclic ring system. Typically, the dye base will contain two or more moieties of the formulae (I) and/or (II).
The diaryl guanidine has the general formula:
NH
Ar'-NH-C-NH-Ar' where the (Ar')'s are the same or dif~erent aromatic ring systems, of single or multiple, carbon or heterocyclic aromatic ring systems. Generally, Ar' is a single carbon ring system (benzene ring), substituted or unsubstituted. Commercially available diaryl guanidines include di-phenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and mixed diaryl-guanidine (MDAG). The double-bonded nitrogen of the diaryl guanidine acts as a proton receptor to form a cation, whereby these compounds are strongly alkaline in aqueous solution. The cation of the diaryl guanidine complexes with the sulfonic acid groups of the dye base.
Generally, sufficient diaryl guanidine is complexed with the dye base to complex all available sulfate groups.
Several of the useful dye bases are prepared by _ 4 _ 203~060 diazotization of a compound having at least one amine group and one sulfonic acid group directly bonded to an aromatic ring and then coupling two such diazotized compounds through an aromatic coupling component. The dye base which is then produced is then complexed to the diaryl guanidine. The synthesis of one such dye, "~uxol" Brown K is as follows:
F~, ~, o ~ 8 _ a ~ _ C
c o p: ;FZ
~: o ~;+ ' o~
C ~ ~
-~ X L
C
,~.
_ 5 _ 203~ 0 60 The following table give~ the amine/sulfate compound that i~ diazotized, the coupling component, and the diaryl guanidine of a number of "Luxol"~ dyes.
"Luxol" Table Couplinq Complexinq "Luxol"~3~ Dye Diazo ComPonent Aqent HQ3 ~ 2 ( ~ O.H DOTG
OH ~
Blue ARn ~ ~Q3H MDAG
HO~S`-' - SO H ~ NH-~
Brown G ~ ~ ~ CH3 EIO ~ MDAG
~ - HO S
OrangeH ~ N=N ~ N2 ~ ~H~ ~ MDAG
Orange GS ~ 2 HO~ ~ ~OII DOTG
Red B HO3S ~ N=N< ~ NH , ~ OH MDAG
- 6 - 203406~
In addition, Yellow TN is produced by complexing tartrazine with DOTG.
In accordance with the invention, the complexing step is performed in a two phase system, including an aqueous phase and an organic solvent phase, which organic solvent phase comprises at least 30~ benzyl alcohol; balance a compatible water-immiscible solvent.
The dye ba8es are generally soluble in water. The diaryl guanidines are typically sparsely soluble in water, but more soluble in the solvent phase. The complexed dyes are generally much more soluble in the solvent phase than in the water phase. By complexing the dye base with the diaryl guanidine in a two phase system, precipitation of the dye is avoided Instead the dye concentrates as a solution in the solvent phase in sufficiently high weight percentages to be used directly as the colorant of a ballpoint pen ink or as a major component of such ink.
Benzyl alcohol is selected as the major constituent of the solvent phase, primarily due to its viscosity, which is very appropriate ~or ballpoint pen inks.
senzyl alcohol is utilized at about 30 wt. percent of the solvent phase, up to 100 percent. Cosolvents, particularly water-immiscible alcohols, glycols and ethers, may be used to increase the solubility of the complexed dye, to adjust the viscosity or to impart drying properties to the ink. Suitable cosolvents of benzyl alcohol include, but are not limited to ethylene glycol phenyl ether, dipropylene glycol, propylene glycol, and mixtures thereof.
In addition to the advantage of not having to deal with powders and the attendant problems with resolubilizing powdered dyes, an important advantage of the method of the present invention is the simplicity of by which solutions of 40-60 wt. percent solids is obtained. Inks for ballpoint pens are typically in this - 7 - 2 03 ~0 ~
solids range, whereby the solvent phase containing the dye is suitable, without modification, for use as a colorant in ballpoint pen inks. Any downward adjustment in solids content may be made by addition of additional benzyl alcohol/cosolvent mixture.
Another advantage of the process of the present invention is that a much smaller aqueous phase is required. As noted above, the diaryl guanidines are sparsely soluble in water, and prior art processes have required a great deal of water. Because the present invention requires contacting separate solvent and aqueous phases, with the guanidine base being substantially more soluble in the solvent phase, the total amount of aqueous phase is substantially reduced.
In accordance with a further aspect of the invention, the method of complexing in a two-phase system as described above may be used to produce another important "Luxol"~ dye, Blue MBSN, which is a complex of MDAG and sulfonated copper phthalocyanine. Also, complexes of sulfonated copper phthalocyanine with other diaryl guanidines, such as DPG and DOTG may be per~ormed by this method. Sulfonated copper phthalocyanine is not technically a sulfonated aryl azo compound, but has related structures and complexes with diaryl guanidines in a similar manner. Sulfonated copper phthalocyanine has the formula:
- 8 - 2031~
N =~ S03H
~1 ~
C~--~N~,"~
S03H ; ~ N ~_ - 9 - 203406~
The above formula shows three sulfonic acid groups;
however, the number of such groups may vary from molecule to molecule. An average number of sulfonic acid groups of between about 2.5 and about 2.8 per molecule are considered optimal. The diaryl guanidine is provided in a molar ratio relative to said sulfonated copper phthalocyanine of at least about 1:1, but preferably is provided in an amount sufficient to complex all of the sulfonic acid groups.
The invention will now be described in greater detail by way of specific example.
EXAMPLE
To a 12 liter 4-neck round bottom flask was charged 1350 gm Water and 265 gm Amino G Acid K+ Salt (80~) and 61 gm 50~ caustic soda. This was stirred to a clear solution. 1.68 mole HC1 (36~) was then added.
The solution was cooled to 8-10C with ice. The compound was diazotized with 47 gm sodium nitrite (100~) basis. The reaction proceeded until the compound fully diazotized with negative sulphone reagent test and positive congo red.
Now added to the flask was: 38 gm Resorcinol flake, with stirring to dissolve. Then over a 90 minute period, 171.4 gm sodium carbonate dissolved in 250 cc water was added. At the end of addition, there is a negative Beta Naphthol solution coupling test and a solution pH of 6.5-7.5.
200 gm each of Benzyl alcohol and "Dowanol EPH" are now added to the flask. At temperature of 15-20C a solution of the following is added:
5000 gm water 105 gm Formic Acid 550 gm Di-o-Tolyl Guanidine Trademark for ethylene glycol phenyl ether.
20~1060 The reaction is followed by a spot test to see when conversion is completed. The dye was now in liquid phase at the bottom of the flask. The organic layer was now decanted and washed with water to conductivity levels of 2000 micro ohms or below. Water was removed from the dye by vacuum stripping. The final dye was standardized to 50~ of solid standard by spectrophotometric absorbance measurement.
While the invention has been described with reference to the certain preferred embodiments, modifications obvious to one with ordinary skill in the art may now be made without departing from the scope of the present invention.
Various features of the invention are set forth in the following claims.
Alæo, it is difficult to produce dye solutions with high solids content by dissolving powdered complex dyes.
It is a general object of the present invention to produce liquid dyestuffs of the type in which a sulfonated aryl azo moiety is complexed with a diaryl guanidine without first producing a dye powder.
SUMMA~Y OF THE INVENTION
An aqueous solution of a dye base compound having at least one aromatic ring system to which both an azo group and a sulfate group are directly bonded is prepared, either by synthesizing the dye base in the aqueous medium or dissolving a dye base in an aqueous medium. The aqueous solution is contacted with an organic solvent phase comprising at least about 30 wt.
percent benzyl alcohol and additional water-immiscible organic solvent so as to maintain a two phase system.
The dye base is complexed with a diaryl guanidine in this two phase system; whereupon, the complexed dye concentrates in the solvent phase.
DETAI~ED DESCRIPTION OF CERTAIN PREFERRED EMBODIMENTS
The dye base according to the present invention contains at least one aromatic ring system to which both a sulfate group and either an azo group (-N=N=) or an N-N grouping of another aromatic ring system are generally attached. Thus the dye base of the present invention contains at least one moiety of the general formulae:
(I) (II) S03~-Ar-N=N- or S03~-Ar- ~ where N ~ N ~
represents a second aromatic ring system, such as:
o~
_~ ~C-H
Il I
N ---C-If the moiety is of formula (I), the -N=N- group is typically bonded directly to a further aromatic ring system. The Ar of formulae (I) and (II) may be a single, double or fused aromatic ring system, it being required only that the azo or aromatic N-N grouping and sulfonic acid group be bonded directly to the ring system, not necessarily on the same ring of the ring system. The Ar group generally is a carbon ring system, but may be a heterocyclic ring system. Typically, the dye base will contain two or more moieties of the formulae (I) and/or (II).
The diaryl guanidine has the general formula:
NH
Ar'-NH-C-NH-Ar' where the (Ar')'s are the same or dif~erent aromatic ring systems, of single or multiple, carbon or heterocyclic aromatic ring systems. Generally, Ar' is a single carbon ring system (benzene ring), substituted or unsubstituted. Commercially available diaryl guanidines include di-phenylguanidine (DPG), di-ortho-tolylguanidine (DOTG), and mixed diaryl-guanidine (MDAG). The double-bonded nitrogen of the diaryl guanidine acts as a proton receptor to form a cation, whereby these compounds are strongly alkaline in aqueous solution. The cation of the diaryl guanidine complexes with the sulfonic acid groups of the dye base.
Generally, sufficient diaryl guanidine is complexed with the dye base to complex all available sulfate groups.
Several of the useful dye bases are prepared by _ 4 _ 203~060 diazotization of a compound having at least one amine group and one sulfonic acid group directly bonded to an aromatic ring and then coupling two such diazotized compounds through an aromatic coupling component. The dye base which is then produced is then complexed to the diaryl guanidine. The synthesis of one such dye, "~uxol" Brown K is as follows:
F~, ~, o ~ 8 _ a ~ _ C
c o p: ;FZ
~: o ~;+ ' o~
C ~ ~
-~ X L
C
,~.
_ 5 _ 203~ 0 60 The following table give~ the amine/sulfate compound that i~ diazotized, the coupling component, and the diaryl guanidine of a number of "Luxol"~ dyes.
"Luxol" Table Couplinq Complexinq "Luxol"~3~ Dye Diazo ComPonent Aqent HQ3 ~ 2 ( ~ O.H DOTG
OH ~
Blue ARn ~ ~Q3H MDAG
HO~S`-' - SO H ~ NH-~
Brown G ~ ~ ~ CH3 EIO ~ MDAG
~ - HO S
OrangeH ~ N=N ~ N2 ~ ~H~ ~ MDAG
Orange GS ~ 2 HO~ ~ ~OII DOTG
Red B HO3S ~ N=N< ~ NH , ~ OH MDAG
- 6 - 203406~
In addition, Yellow TN is produced by complexing tartrazine with DOTG.
In accordance with the invention, the complexing step is performed in a two phase system, including an aqueous phase and an organic solvent phase, which organic solvent phase comprises at least 30~ benzyl alcohol; balance a compatible water-immiscible solvent.
The dye ba8es are generally soluble in water. The diaryl guanidines are typically sparsely soluble in water, but more soluble in the solvent phase. The complexed dyes are generally much more soluble in the solvent phase than in the water phase. By complexing the dye base with the diaryl guanidine in a two phase system, precipitation of the dye is avoided Instead the dye concentrates as a solution in the solvent phase in sufficiently high weight percentages to be used directly as the colorant of a ballpoint pen ink or as a major component of such ink.
Benzyl alcohol is selected as the major constituent of the solvent phase, primarily due to its viscosity, which is very appropriate ~or ballpoint pen inks.
senzyl alcohol is utilized at about 30 wt. percent of the solvent phase, up to 100 percent. Cosolvents, particularly water-immiscible alcohols, glycols and ethers, may be used to increase the solubility of the complexed dye, to adjust the viscosity or to impart drying properties to the ink. Suitable cosolvents of benzyl alcohol include, but are not limited to ethylene glycol phenyl ether, dipropylene glycol, propylene glycol, and mixtures thereof.
In addition to the advantage of not having to deal with powders and the attendant problems with resolubilizing powdered dyes, an important advantage of the method of the present invention is the simplicity of by which solutions of 40-60 wt. percent solids is obtained. Inks for ballpoint pens are typically in this - 7 - 2 03 ~0 ~
solids range, whereby the solvent phase containing the dye is suitable, without modification, for use as a colorant in ballpoint pen inks. Any downward adjustment in solids content may be made by addition of additional benzyl alcohol/cosolvent mixture.
Another advantage of the process of the present invention is that a much smaller aqueous phase is required. As noted above, the diaryl guanidines are sparsely soluble in water, and prior art processes have required a great deal of water. Because the present invention requires contacting separate solvent and aqueous phases, with the guanidine base being substantially more soluble in the solvent phase, the total amount of aqueous phase is substantially reduced.
In accordance with a further aspect of the invention, the method of complexing in a two-phase system as described above may be used to produce another important "Luxol"~ dye, Blue MBSN, which is a complex of MDAG and sulfonated copper phthalocyanine. Also, complexes of sulfonated copper phthalocyanine with other diaryl guanidines, such as DPG and DOTG may be per~ormed by this method. Sulfonated copper phthalocyanine is not technically a sulfonated aryl azo compound, but has related structures and complexes with diaryl guanidines in a similar manner. Sulfonated copper phthalocyanine has the formula:
- 8 - 2031~
N =~ S03H
~1 ~
C~--~N~,"~
S03H ; ~ N ~_ - 9 - 203406~
The above formula shows three sulfonic acid groups;
however, the number of such groups may vary from molecule to molecule. An average number of sulfonic acid groups of between about 2.5 and about 2.8 per molecule are considered optimal. The diaryl guanidine is provided in a molar ratio relative to said sulfonated copper phthalocyanine of at least about 1:1, but preferably is provided in an amount sufficient to complex all of the sulfonic acid groups.
The invention will now be described in greater detail by way of specific example.
EXAMPLE
To a 12 liter 4-neck round bottom flask was charged 1350 gm Water and 265 gm Amino G Acid K+ Salt (80~) and 61 gm 50~ caustic soda. This was stirred to a clear solution. 1.68 mole HC1 (36~) was then added.
The solution was cooled to 8-10C with ice. The compound was diazotized with 47 gm sodium nitrite (100~) basis. The reaction proceeded until the compound fully diazotized with negative sulphone reagent test and positive congo red.
Now added to the flask was: 38 gm Resorcinol flake, with stirring to dissolve. Then over a 90 minute period, 171.4 gm sodium carbonate dissolved in 250 cc water was added. At the end of addition, there is a negative Beta Naphthol solution coupling test and a solution pH of 6.5-7.5.
200 gm each of Benzyl alcohol and "Dowanol EPH" are now added to the flask. At temperature of 15-20C a solution of the following is added:
5000 gm water 105 gm Formic Acid 550 gm Di-o-Tolyl Guanidine Trademark for ethylene glycol phenyl ether.
20~1060 The reaction is followed by a spot test to see when conversion is completed. The dye was now in liquid phase at the bottom of the flask. The organic layer was now decanted and washed with water to conductivity levels of 2000 micro ohms or below. Water was removed from the dye by vacuum stripping. The final dye was standardized to 50~ of solid standard by spectrophotometric absorbance measurement.
While the invention has been described with reference to the certain preferred embodiments, modifications obvious to one with ordinary skill in the art may now be made without departing from the scope of the present invention.
Various features of the invention are set forth in the following claims.
Claims (9)
1. A method of preparing a liquid dyestuff in organic solvent, the method comprising, preparing an aqueous solution of a dye base having at least one moiety of the general formulae selected from:
(I) (II) SO3- -Ar-N=N- or represents a second aromatic ring system, and the AR of formulae (I) or (II) may be a single, double or multiple aromatic ring system, provided that the azo or aromatic N-N grouping and the sulfonic acid group be bonded directly to the ring system, adding an organic solvent phase comprising between about 30 and about 100 wt. percent benzyl alcohol, balance a water-immiscible organic solvent, complexing said dye base with a diaryl guanidine in said two phase system, whereby the dye which is produced is contained in said organic solvent phase, and separating said organic solvent phase.
(I) (II) SO3- -Ar-N=N- or represents a second aromatic ring system, and the AR of formulae (I) or (II) may be a single, double or multiple aromatic ring system, provided that the azo or aromatic N-N grouping and the sulfonic acid group be bonded directly to the ring system, adding an organic solvent phase comprising between about 30 and about 100 wt. percent benzyl alcohol, balance a water-immiscible organic solvent, complexing said dye base with a diaryl guanidine in said two phase system, whereby the dye which is produced is contained in said organic solvent phase, and separating said organic solvent phase.
2. The method according to Claim 1 wherein said dye base has at least two moieties of formulae (I) and/or (II).
3. The method according to claim 1 wherein the diaryl guanidine is added in an amount sufficient to complex substantially all of the sulphonic acid groups of said dye base.
4. A method according to claim 1 wherein said diaryl guanidine is selected from the group selected from di-phenyl guanidine, di-ortho-tolylguanidine, and mixed diaryl-guanidine.
5. A method according to claim 1 wherein said water-immiscible solvent is selected from the group consisting of ethylene glycol phenylether, dipropylene glycol, propylene glycol and mixtures thereof.
6. A method of preparing a liquid dyestuff in organic solvent, the method comprising:
preparing an aqueous solution of sulfonated copper phthalocyanine, adding an organic solvent phase comprising between about 30 and about 100 wt. percent benzyl alcohol, balance a water-immiscible organic solvent, complexing said sulfonated copper phthalocyanine with a diaryl guanidine in said two-phase system, whereby the dye which is produced is contained in said organic solvent phase, and separating said organic solvent phase.
preparing an aqueous solution of sulfonated copper phthalocyanine, adding an organic solvent phase comprising between about 30 and about 100 wt. percent benzyl alcohol, balance a water-immiscible organic solvent, complexing said sulfonated copper phthalocyanine with a diaryl guanidine in said two-phase system, whereby the dye which is produced is contained in said organic solvent phase, and separating said organic solvent phase.
7. The method according to claim 1 wherein the diaryl guanidine is added in an amount sufficient to complex substantially all of the groups of said sulfonated copper phthalocyanine.
8. A method according to claim 6 wherein said diaryl guanidine is selected from the group selected from di-phenyl guanidine, di-ortho-tolylguanidine, and mixed diaryl-guanidine.
9. A method according to claim 6 wherein said water-immiscible solvent is selected from the group consisting of ethylene glycol phenylether, dipropylene glycol, propylene glycol and mixtures thereof.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| US07/474,427 | 1990-02-02 | ||
| US07/474,427 US5049189A (en) | 1990-02-02 | 1990-02-02 | Method of preparing a solution of sulfonated aryl azo/diaryl guanidine-complexed dye |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2034060A1 CA2034060A1 (en) | 1991-08-03 |
| CA2034060C true CA2034060C (en) | 1995-06-06 |
Family
ID=23883488
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002034060A Expired - Fee Related CA2034060C (en) | 1990-02-02 | 1991-01-11 | Method of preparing a solution of sulfonated aryl azo/diaryl guanidine-complexed dye |
Country Status (4)
| Country | Link |
|---|---|
| US (1) | US5049189A (en) |
| EP (1) | EP0440368A3 (en) |
| JP (1) | JPH0816201B2 (en) |
| CA (1) | CA2034060C (en) |
Families Citing this family (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5131776A (en) * | 1990-07-13 | 1992-07-21 | Binney & Smith Inc. | Aqueous permanent coloring composition for a marker |
| US5334435A (en) * | 1992-11-20 | 1994-08-02 | Eastman Kodak Company | Ink-jet recording liquids |
| US5378269A (en) * | 1993-12-29 | 1995-01-03 | Scitex Digital Printing, Inc. | Recording liquids for ink-jet recording |
| JP4883299B2 (en) * | 2004-10-14 | 2012-02-22 | 日産化学工業株式会社 | Resist composition containing organic solvent-soluble dye and color filter using the same |
Family Cites Families (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| FR612382A (en) * | 1926-03-08 | 1926-10-22 | Du Pont | Water-insoluble color and dye enhancements |
| DE469179C (en) * | 1926-03-18 | 1928-12-04 | Du Pont | Process for the preparation of dye compounds soluble in organic solvents |
| DE955082C (en) * | 1954-07-27 | 1956-12-27 | Hoechst Ag | Process for the preparation of disazo dye salts |
| US2990405A (en) * | 1959-05-26 | 1961-06-27 | American Cyanamid Co | Spirit soluble black dyes |
| FR2044181A5 (en) * | 1969-05-12 | 1971-02-19 | Pechiney Saint Gobain | |
| FR2123154B1 (en) * | 1971-01-26 | 1973-11-30 | Ugine Kuhlmann | |
| GB1418204A (en) * | 1973-05-05 | 1975-12-17 | Ciba Geigy Ag | Dyeing process |
| DE2848447C3 (en) * | 1977-11-10 | 1981-12-17 | CIBA-GEIGY AG, 4002 Basel | Dyeing process |
| EP0021619A1 (en) * | 1979-06-12 | 1981-01-07 | Imperial Chemical Industries Plc | A method of making concentrated aqueous solutions of dyes and these solutions |
-
1990
- 1990-02-02 US US07/474,427 patent/US5049189A/en not_active Expired - Lifetime
-
1991
- 1991-01-11 CA CA002034060A patent/CA2034060C/en not_active Expired - Fee Related
- 1991-01-24 EP EP19910300527 patent/EP0440368A3/en not_active Withdrawn
- 1991-02-01 JP JP3011775A patent/JPH0816201B2/en not_active Expired - Lifetime
Also Published As
| Publication number | Publication date |
|---|---|
| CA2034060A1 (en) | 1991-08-03 |
| JPH0816201B2 (en) | 1996-02-21 |
| JPH06248192A (en) | 1994-09-06 |
| EP0440368A3 (en) | 1992-10-14 |
| EP0440368A2 (en) | 1991-08-07 |
| US5049189A (en) | 1991-09-17 |
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