Naphthol as-pigments
10752779 ยท 2020-08-25
Assignee
Inventors
Cpc classification
G03F7/105
PHYSICS
C08K5/0041
CHEMISTRY; METALLURGY
International classification
G03F7/00
PHYSICS
Abstract
Naphthol AS-pigments of formula (I), wherein R1 represents methyl or C3-C8-alkyl; R2 represents hydrogen or C1-C4-alkyl; Y represents C1-C4-alkyl or C1-C4-alkoxy; and Z represents hydrogen, phenyl, naphthyl, or substituted phenyl or substituted naphthyl, wherein the number of substituents can be 1, 2, 3 or 4 and are selected from the group consisting of halogen, nitro, cyano, C1-C4-alkoxycarbonyl, carbamoyl, C1-C4-alkylcarbamoyl, di(C1-C4)-alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfannoyl, C1-C4-alkylsulfamoyl, di(C1-C4)-alkylsulfamoyl, C1-C4-acylamino, C1-C4-alkyl and C1-C4-alkoxy.
Claims
1. A pigmented electrophotographic toner or developer comprising a high molecular weight organic material of natural or synthetic origin comprising a pigment of the formula (I) ##STR00049## wherein R.sup.1 is methyl or C.sub.3-C.sub.8-alkyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy; and Z is hydrogen, naphthyl, or substituted phenyl or substituted naphthyl, where the substituents are 1, 2, 3 or 4 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkoxycarbonyl, carbamoyl, C.sub.1-C.sub.4-alkylcarbamoyl, di(C.sub.1-C.sub.4)-alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C.sub.1-C.sub.4-alkylsulfamoyl, di(C.sub.1-C.sub.4)-alkylsulfamoyl, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
2. The pigmented electrophotographic toner or developer of claim 1, wherein R.sup.1 is methyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy; and Z is substituted phenyl, where the substituents are 1, 2 or 3 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
3. The pigmented electrophotographic toner or developer of claim 1, wherein R.sup.2 is hydrogen.
4. The pigmented electrophotographic toner or developer of claim 1, wherein Z is nitro-, cyano- or C.sub.1-C.sub.4-alkyl-substituted phenyl.
5. The pigmented electrophotographic toner or developer of claim 1, wherein Z is phenyl substituted by one, two or three radicals selected from the group consisting of methyl, ethyl and nitro.
6. The pigmented electrophotographic toner or developer of claim 1, wherein R.sup.1 is methyl; R.sup.2 is hydrogen; Y is C.sub.1-C.sub.2-alkoxy; and Z is methylphenyl or nitrophenyl.
7. An inkjet ink comprising a high molecular weight organic material of natural or synthetic origin comprising a pigment of the formula (I) ##STR00050## wherein R.sup.1 is methyl or C.sub.3-C.sub.8-alkyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy; and Z is hydrogen, naphthyl, or substituted phenyl or substituted naphthyl, where the substituents are 1, 2, 3 or 4 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkoxycarbonyl, carbamoyl, C.sub.1-C.sub.4-alkylcarbamoyl, di(C.sub.1-C.sub.4)-alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C.sub.1-C.sub.4-alkylsulfamoyl, di(C.sub.1-C.sub.4)-alkylsulfamoyl, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
8. The inkjet ink of claim 7, wherein R.sup.1 is methyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy; and Z is substituted phenyl, where the substituents are 1, 2 or 3 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
9. The inkjet ink of claim 7, wherein R.sup.2 is hydrogen.
10. The inkjet ink of claim 7, wherein Z is nitro-, cyano- or C.sub.1-C.sub.4-alkyl-substituted phenyl.
11. The inkjet ink of claim 7, wherein Z is phenyl substituted by one, two or three radicals selected from the group consisting of methyl, ethyl and nitro.
12. The inkjet ink of claim 7, wherein R.sup.1 is methyl; R.sup.2 is hydrogen; Y is C.sub.1-C.sub.2-alkoxy; and Z is methylphenyl or nitrophenyl.
13. A pigmented color filter comprising a high molecular weight organic material of natural or synthetic origin comprising a pigment of the formula (I) ##STR00051## wherein R.sup.1 is methyl or C.sub.3-C.sub.8-alkyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.4-alkyl or C.sub.1-C.sub.4-alkoxy; and Z is hydrogen, naphthyl, or substituted phenyl or substituted naphthyl, where the substituents are 1, 2, 3 or 4 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkoxycarbonyl, carbamoyl, C.sub.1-C.sub.4-alkylcarbamoyl, di(C.sub.1-C.sub.4)-alkylcarbamoyl, phenylcarbamoyl, sulfamoyl, phenylsulfamoyl, C.sub.1-C.sub.4-alkylsulfamoyl, di(C.sub.1-C.sub.4)-alkylsulfamoyl, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
14. The pigmented color filter of claim 13, wherein R.sup.1 is methyl; R.sup.2 is hydrogen or C.sub.1-C.sub.4-alkyl; Y is C.sub.1-C.sub.2-alkyl or C.sub.1-C.sub.2-alkoxy; and Z is substituted phenyl, where the substituents are 1, 2 or 3 in number and are selected from the group consisting of halogen, nitro, cyano, C.sub.1-C.sub.4-alkyl and C.sub.1-C.sub.4-alkoxy.
15. The pigmented color filter of claim 13, wherein R.sup.2 is hydrogen.
16. The pigmented color filter of claim 13, wherein Z is nitro-, cyano- or C.sub.1-C.sub.4-alkyl-substituted phenyl.
17. The pigmented color filter of claim 13, wherein Z is phenyl substituted by one, two or three radicals selected from the group consisting of methyl, ethyl and nitro.
18. The pigmented color filter of claim 13, wherein R.sup.1 is methyl; R.sup.2 is hydrogen; Y is C.sub.1-C.sub.2-alkoxy; and Z is methylphenyl or nitrophenyl.
Description
EXAMPLE 1
(1) a1) Preparation of the Diazonium Salt Solution:
(2) 2200 g of demineralized water are initially charged, 180 g of N-methyl-3-amino-4-methoxybenzamide are scattered in and the mixture is stirred homogeneously at room temperature. After 15 minutes, the mixture is cooled to 2 C. by adding 800 g of ice and by additional external cooling, and then 290 g of hydrochloric acid (31%) are added. The precipitated hydrochloride is diazotized by adding 179 g of sodium nitrite solution (40%) at 5 to 10 C. over the course of 15 to 20 minutes. The diazonium salt solution is stirred in an excess of nitrite for 1.5 h, then a clarifying aid is added and then the mixture is filtered and any nitrite excess is eliminated by addition of amidosulfonic acid.
(3) a2) Preparation of a Solution of the Coupling Component:
(4) 2720 g of water are initially charged and heated to 80 C. While stirring, 308 g of N-(3-nitrophenyl)-3-hydroxynaphthalene-2-carboxamide are introduced and dissolved under alkaline conditions at 90 to 95 C. by adding sodium hydroxide solution (33%). Subsequently, the mixture is cooled down to below 80 C. by adding ice and the warm solution is optionally filtered with the aid of a clarifying aid.
(5) a3) Azo Coupling:
(6) The clarified diazonium salt solution from a1) is initially charged, adjusted to pH 4.3-4.5 by adding about 38 g of sodium acetate (in the form of a 4 N solution) and cooled to 10 C. by adding ice. Thereafter, the warm coupler solution from a2) is metered in over the course of 1 to 1.5 h while stirring, while keeping the pH at 4.8-5 by simultaneous addition of a total of about 190 g of hydrochloric acid (31%). Subsequently, the mixture is stirred for about 2.5-3 h or until the disappearance of the diazo component at RT to 30 C. and pH 5 to 6. After the coupling reaction has ended, the mixture is heated to above 50 C. for another 1 h, then filtered and washed with water.
(7) After drying and grinding, 499 g of a dark red bluish powder of the pigment of the formula (1) are obtained.
(8) ##STR00004##
EXAMPLE 2
(9) a1) the Preparation of the Diazonium Salt Solution is Effected as Described in Example 1, a1).
(10) a2) Preparation of a Solution of the Coupling Component:
(11) 2000 g of water are initially charged and 277 g of N-(2-methylphenyl)-3-hydroxynaphthalene-2-carboxamide are introduced with stirring, the mixture is heated to 95 C. and the solids are dissolved under alkaline conditions by adding 330 g of sodium hydroxide solution (33%) at 90 to 95 C. within a few minutes. Subsequently, the mixture is rapidly cooled to below 80 to 60 C. by adding ice and kept at this temperature. The warm solution can optionally still be filtered with addition of a clarifying aid.
(12) a3) Azo Coupling:
(13) 3000 g of water/ice are initially charged, 280 g of acetic acid and 110 g of sodium acetate (in the form of a 4 N solution) are added and the pH is adjusted to 4. The temperature is adjusted to 10 C. by adding ice and then, with good stirring, the coupler solution from a2) is added dropwise, in the course of which the coupler precipitates out and gives rise to a suspension. The temperature is kept at 10 to 15 C. by adding further ice and, on completion of coupler addition, the pH is adjusted to 5. The diazonium salt solution from a1) is added dropwise to the coupler suspension over the course of 1.5 h and the pH is kept at 5 to 5.5 with sodium hydroxide solution. After the diazonium salt addition has ended, the mixture is stirred at room temperature to 30 C. and pH 5.5 to 6 until the diazo component has disappeared. After the coupling reaction has ended, the mixture is heated to above 50 C. for another 1 h, then filtered and washed with water. After drying and grinding, 468 g of a dark red powder of the pigment of the formula (2) are obtained.
(14) ##STR00005##
(15) Further naphthol AS pigments of the invention were produced analogously to example 1 or 2 and are listed in table 1 below.
(16) In addition, the chroma and the hue angle were determined in an alkyd resin (0.5% strength).
(17) In the resin system and test system mentioned, the chroma C of the pigments of the invention is preferably between 58 and 74 (74>C>58) and more preferably between 60 and 70 (70>C>60). In the case of a bluish magenta pigment, the hue h is preferably between 345 and 360 or between 0 and 15 and more preferably between 350 and 360 or between 0 and 10 (CIELAB coordinates).
(18) a) Production of the 0.5% Alkyd Resin:
(19) In a plastic cup, 0.45 g of a pigment of the invention and 29.55 g of 31.8% grinding varnish (45.38% Vialkyd AS 673 h/70% WS, 2.58% Octa-Soligen 10% Ca, 2.82% STA soya lecithin concentrate and 49.22% 145/200 petroleum spirit) are weighed out and dispersed at 660 rpm with an agitating machine with addition of 85 g of glass beads having a diameter of 3 mm for 15 min.
(20) Into this varnish are gradually weighed, in 5 portions of increasing size, a total of 60 g of siccatived letdown mixture, 54% strength (77.14% Vialkyd AS 673 h/70% WS, 0.9% Bykanol-N, 19.16% 145/200 petroleum spirit and 2.8% Octa-Soligen173 desiccant), and immediately mixed thoroughly each time. On completion of addition, the mixture is mixed homogeneously with the agitating machine for another 3 minutes and then the glass beads are sieved off.
(21) b) Paint Test for Coloristic Properties:
(22) The paint thus obtained is applied by means of a manual coater to a film applicator and applied in a wet film thickness of 100 m to a test card (Chromo board, white, cast-coated on one side, 300 g/m.sup.2, size 100230 mm). The paint card is dried first at room temperature for 15 min and then in a drying cabinet at 60 C. for 60 min. The values for chroma (C) and hue (h) are measured by means of a D65 standard illuminant lamp at an observation angle of 10 with a DatacolorSpectraflashSF600PLUS CT spectrophotometer, according to DIN 5033-7, ISO 7724-2.
(23) The test results in the paint are reported in table 1 below.
(24) TABLE-US-00001 TABLE 1 Example Pigment of formula (I) Chroma C Hue angle h 1