Novel Pyridone Dyes
20170015829 ยท 2017-01-19
Assignee
Inventors
Cpc classification
C09B29/3626
CHEMISTRY; METALLURGY
International classification
Abstract
The invention relates to compounds of the formula (I):
##STR00001## in which R.sup.0 is C.sub.1-C.sub.6-alkyl or CF.sub.3; R.sup.1 is sulfo, carboxyl, C.sub.1-C.sub.4-alkylenesulfo, C.sub.1-C.sub.4-alkylenecarboxy, CONH.sub.2, CONH(C.sub.1-C.sub.4-alkyl) or CN, R.sup.2 is C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, hydroxy-C.sub.1-C.sub.18-alkyl, or (C.sub.1-C.sub.6-alkylene-O).sub.mR where R is defined as H, C.sub.1-C.sub.16-alkyl or hydroxy-C.sub.1-C.sub.16-alkyl and m is a number from 1 to 20, R.sup.3 is H, sulfo, carboxyl, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, R.sup.4 is H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, R.sup.5 is OH, OM, C.sub.1-C.sub.6-alkyl, unsubstituted C.sub.6-C.sub.10-aryl or C.sub.1-C.sub.6-alkyl-, halogen-(e.g. F, Cl, Br), carboxyl- or sulfo-substituted where the compounds of the formula (I) contain at least one anionic radical from the group of sulfo and carboxyl having the countercation M.sup.+, where M.sup.+ is an alkali metal cation or an organic cation.
The compounds of the formula (I) are especially suitable for use in color filters.
Claims
1. A compound of the formula (I): ##STR00055## wherein R.sup.0 is C.sub.1-C.sub.6-alkyl or CF.sub.3; R.sup.1 is sulfo, carboxyl, C.sub.1-C.sub.4-alkylenesulfo, C.sub.1-C.sub.4-alkylenecarboxy, CONH.sub.2, CONH(C.sub.1-C.sub.4-alkyl) or CN, R.sup.2 is C.sub.1-C.sub.18-alkyl, C.sub.2-C.sub.18-alkenyl, hydroxy-C.sub.1-C.sub.18-alkyl, or (C.sub.1-C.sub.6-alkylene-O).sub.mR where R is H, C.sub.1-C.sub.16-alkyl or hydroxy-C.sub.1-C.sub.16-alkyl and m is a number from 1 to 20, R.sup.3 is H, sulfo, carboxyl, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, R.sup.4 is H, C.sub.1-C.sub.6-alkyl or C.sub.1-C.sub.6-alkoxy, R.sup.5 is OH, OM, C.sub.1-C.sub.6-alkyl, unsubstituted C.sub.6-C.sub.10-aryl or C.sub.1-C.sub.6-alkyl-, halogen-, carboxyl- or sulfo-substituted where the compound of the formula (I) contains at least one anionic radical from the selected from the group consisting of sulfo and carboxyl having the countercation M.sup.+, wherein M.sup.+ is an alkali metal cation or an organic cation.
2. A compound as claimed in claim 1, wherein the compound of the formula (I) contains at least one sulfo group having the countercation M.sup.+.
3. A compound as claimed in claim 1, wherein the countercation M.sup.+ is an organic cation selected from the group consisting of the imidazolium cations, alkylguanidinium cations, phosphonium cations, primary, secondary, tertiary or quaternary ammonium cations, benzotriazolyl cations and pyridinium cations.
4. A compound as claimed in claim 1, wherein R.sup.0 is C.sub.1-C.sub.2-alkyl.
5. A compound as claimed in claim 1, wherein R.sup.1 is (C.sub.1-C.sub.2-alkylene)sulfo, CONH(C.sub.1-C.sub.2-alkyl) or CONH.sub.2.
6. A compound as claimed in claim 1, wherein R.sup.2 is C.sub.1-C.sub.8-alkyl, hydroxy-C.sub.1-C.sub.8-alkyl or (C.sub.1-C.sub.4-alkylene-O).sub.mR, wherein R is H or C.sub.1-C.sub.10-alkyl, and m is a number from 1 to 15.
7. A compound as claimed in claim 1, wherein R.sup.3 is H, a sulfo group, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy.
8. A compound as claimed in claim 1, wherein R.sup.4 is H, C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy.
9. A compound as claimed in claim 1, wherein R.sup.5 is OH, O.sup.M.sup.+, C.sub.1-C.sub.2-alkyl-, halogen- or sulfo-substituted phenyl or unsubstituted phenyl, where wherein M.sup.+ is an alkali metal cation, a quaternary ammonium cation or a phosphonium cation.
10. A compound as claimed in claim 1, wherein R.sup.0 is methyl, R.sup.1 is CH.sub.2-sulfo or CONH.sub.2, R.sup.2 is ethyl or (C.sub.2-C.sub.3-alkylene-O).sub.mR, wherein R is defined as H or methyl and m is a number from 1 to 12, R.sup.3 is H or methyl, R.sup.4 is H, R.sup.5 is OH, O.sup.M.sup.+, methyl, tolyl or phenyl, wherein the compounds of the formula (I) contain 1 or 2 sulfo groups and the counter-cation M.sup.+ is an alkali metal cation, an organic ammonium cation or an organic phosphonium cation.
11. A process for preparing the compound as claimed in claim 1, comprising the steps of diazotizing amines of the formula (A) and azo coupling with one equivalent of the pyridone coupling component of the formula (P) ##STR00056## wherein R.sup.0 to R.sup.5 are each as defined in claim 1 and Ex is a leaving group, and, optionally, subsequent cation exchange with introduction of the cation M.sup.+.
12. A solution comprising 0.01% to 45% by weight of one or more compounds of the formula (I) as claimed in claim 1, dissolved in an organic solvent.
13. A binder-containing colorant solution comprising 0.01% to 40% by weight of one or more compounds of the formula (I) as claimed in claim 1, dissolved in at least one organic solvent, at least one polymeric binder and, optionally, further auxiliaries.
14. A colored high molecular weight organic material of natural or synthetic origin comprising one or more compounds of the formula (I) as claimed in claim 1.
15. A colored color filter, a colored liquid crystal display, a colored OLED display or a colored bulk polymer comprising a colored high molecular weight organic material of natural or synthetic origin.
Description
EXAMPLES
Preparation of the Acid Azo Dye (I a)
[0078] ##STR00011##
[0079] A suspension consisting of 17.1 g of 4-aminophenyl methyl sulfone (0.10 mol) in 100 mL of water and 22 mL of conc. hydrochloric acid (37% by weight) is diazotized at 0-5 C. with 17.3 g of sodium nitrite solution (40% by weight; 0.1 mol of NaNO.sub.3). The resultant diazonium salt is added in portions at 0 to 5 C. to a suspension consisting of 24.6 g (0.1 mol) of the compound of the following formula
##STR00012##
in 9 mL of 30% sodium hydroxide solution and 50 mL of water. By adding 15% by weight sodium carbonate solution, the pH is kept at 7 to 9. The volume of the dye suspension is made up to about 700 mL with water, then the mixture is heated to 90 C. for 30 min. After cooling, the solids are filtered off with suction, washed with water and dried under reduced pressure. This gives 40.2 g of a yellow dye powder of the formula (I a).
Preparation of the Hexaalkylguanidinium Chloride (C2a)
[0080] ##STR00013##
[0081] To a solution of 15.5 mL (0.13 mol) of tetramethylurea in 60 mL of toluene are added dropwise, at 60-65 C., 13 mL (0.13 mol) of phosphoryl chloride. After stirring for two hours, the mixture is cooled and, at 0-5 C., a mixture of 18 mL of triethylamine and 40 mL (0.14 mol) of bis(2-ethylhexyl)amine in 30 mL of toluene is added dropwise. Subsequently, the temperature is allowed to rise to about 20 C., and stirring is continued overnight. Then the pale yellow mixture is admixed with 54 mL of NaOH (30% by weight) while cooling. The mixture is stirred together with 150 mL of NaCl solution. The toluene phase is separated off and dried with magnesium sulfate, and the solvent is removed under reduced pressure. This gives 47 g of a pale beige, waxy solid.
Preparation of the Hexaalkylguanidinium Dye Salt (I b)
[0082] ##STR00014##
[0083] 27.5 g (66 mmol) of the hexaalkylguanidinium chloride (C2a) are dissolved at 90 C. in 500 mL of water while stirring (solution A).
[0084] 29.2 g (64 mmol) of the yellow acid azo dye of the formula (I a) are introduced into 500 mL of water and, after the addition of five drops of 15% by weight sodium carbonate solution, heated to 60 to 65 C. This suspension is added in portions at about 90 C. to solution A. After one hour of reaction time at this temperature, an emulsion is obtained, which is cooled, and then the water phase is decanted off. The oily organic phase is taken up with 350 mL of methoxypropyl acetate, dried with magnesium sulfate and stored at 4 C. for one night. After the precipitated solid has been filtered off, the solvent is removed under reduced pressure and the resultant residue is dried to constant weight.
[0085] The dyes in table 1 were obtained by an analogous procedure.
[0086] For the dye anion of example I I, rather than 4-aminophenyl methyl sulfone, an equivalent amount of 4-aminophenyl p-tolyl sulfone is used. For the dye anions of examples I m to I p, rather than 4-aminophenyl methyl sulfone, an equivalent amount of 4-aminophenylsulfonic acid is used.
TABLE-US-00001 TABLE 1 (dye salts prepared) No.: Countercation M.sup.+ Dye anion I a Na.sup.+
[0087] Each of these are yellow substances having breakdown points >200 C.
[0088] Further dye anions were prepared proceeding from the following nitrilopyridones:
##STR00046##
[0089] They are obtainable from methyl cyanoacetate, methyl acetoacetate and the corresponding aminemethoxypropylamine or Jeffamine M600. The nitrile group can be removed by heating with dilute sulfuric acid. The resultant 3,5-unsubstituted pyridones are reacted with formaldehyde and sodium bisulfite by a known procedure (analogously to DE 2162858), giving the following pyridone coupling agents:
##STR00047##
[0090] R=methyl.
[0091] These were used to obtain the dyes I q and I s. The reaction of the Na dye salts mentioned with the respective quaternary ammonium compounds analogously to the preparation of I b gave the dye salts I r and I t therefrom.
TABLE-US-00002 No.: Countercation M.sup.+ Dye anion I q Na.sup.+
Color Filter Application Test:
Use Example A1
[0092] ##STR00054##
[0093] 1.00 g of compound (I b) is added to 22.9 g of 1-methoxy-2-propyl acetate. 0.33 g of n-butanol, 0.65 g of Disperbyk 2001 (BYK-Chemie GmbH, modified acrylate block copolymer, solution in methoxypropyl acetate/butyl glybol/methoxypropanol 2/2/1) and 10.8 g of Ripoxy SPC 2000 (Showa Highpolymer Co., Ltd., acrylate polymer, solution in methoxypropyl acetate) are added, and the mixture is stirred at room temperature for 2 h. The resultant mixture is filtered.
[0094] The resultant binder-containing colorant solution is applied with the aid of a spin-coater (POLOS Wafer Spinner) to glass plates (SCHOTT, laser-cut, 1010 cm), in a layer thickness which enables setting, in the case of use of a C light source, of the color coordinates y specified in Table 2 as reference values.
[0095] The layer thickness in each case is about 1 to 2 micrometers.
[0096] The glass plates are left to flash off and then dried at 80 C. in an air circulation drying cabinet (from Binder) for 10 min. The so-called prebake values of the color coordinates (x, y, Y, and CIELAB, Spectrophotometer Datacolor 650, illuminant C, 2 observer), transmission curves (ditto) and contrast values (Tsubosaka CT-1 Contrast Tester; blank 5000) of the glass plates were analyzed. The glass plates are subsequently subjected to a heat treatment in an air circulation drying cabinet at 230 C. for 1 h and analyzed again, from which the postbake values are obtained.
Use Examples A2-A10
[0097] The solutions are produced analogously to the case of use example A1. However, rather than compound I b, the compounds specified in table 2 are used.
[0098] Table 2 shows the results of the inventive examples in postbake. The x, y and Y values denote the measured color coordinates in the CIE-Yxy standard color space, where Y is a measure of the brightness.
TABLE-US-00003 TABLE 2 (reference to y values). Use y Y Contrast example Compound (Ref.) = x = value value A1 I b 0.460 0.3896 87.3 3451 A2 I c 0.460 0.3938 83.9 2811 A3 I d 0.420 0.3686 86.0 3918 A4 I f 0.420 0.3669 88.1 3507 A5 I g 0.460 0.3927 83.8 2999 A6 1 j 0.420 0.3643 88.9 3881 A7 1 l 0.460 0.3864 88.9 3974 A8 1 n 0.420 0.3693 86.2 3703 A9 1 o 0.420 0.3696 87.4 3867
[0099] The coated glass plates (color filters) of the compositions of the invention each have transparent, greenish yellow hues. The dyeings each have high contrast values and brightness values Y. They likewise have steep transmission curves.