Naphthol AS—pigment-mixtures
10787572 · 2020-09-29
Assignee
Inventors
Cpc classification
C08K2201/014
CHEMISTRY; METALLURGY
G03F7/0045
PHYSICS
G03F7/0007
PHYSICS
International classification
Abstract
The invention relates to azo pigment mixtures which contain at least one azo pigment of formula (IIIa) and at least one azo pigment of formula (IIIb) ##STR00001##
where X.sup.1, Y, Z.sup.1 and V in formula (IIIa) and formula (IIIb) are independent of each other and are defined as described, and the azo pigments of formula (IIIa) and formula (IIIb) are different.
Claims
1. An azo pigment mixture, comprising at least one azo pigment of the formula (IIIa) and at least one azo pigment of the formula (IIIb) ##STR00071## wherein, independently of one another, X.sup.1 is carbamoyl, C.sub.1-C.sub.2-alkylcarbannoyl or di(C.sub.1-C.sub.2)-alkylcarbamoyl; Y is methyl, methoxy, ethyl or ethoxy; Z.sup.1 is phenyl or as phenyl substituted by one, two or three radicals from the group consisting of methyl, ethyl, methoxy, ethoxy and chlorine; Z.sup.2 is nitrophenyl or cyanophenyl, and the azo pigments of formula (IIIa) and formula (IIIb) are different.
2. The azo pigment mixture as claimed in claim 1, comprising 1% to 99% by weight of a component of the formula (IIIa) and 99% to 1% by weight of a component of the formula (IIIb), based on the total weight of the pigment mixture.
3. The azo pigment mixture as claimed in claim 1, comprising one or more additional colorants of the formula (IV) in proportions of up to 10% by weight, based on the total weight of the azo pigment mixture, ##STR00072## wherein X.sup.1 is carbamoyl, C.sub.1-C.sub.4-alkylcarbannoyl, di(C.sub.1-C.sub.4)-alkylcarbamoyl, sulfamoyl, phenylsulfamoyl, C.sub.1-C.sub.4-alkylsulfannoyl or di(C.sub.1-C.sub.4)-alkylsulfamoyl; X.sup.2 is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, halogen or nitro; Y is hydrogen, C.sub.1-C.sub.4-alkyl, C.sub.1-C.sub.4-alkoxy, halogen or C.sub.1-C.sub.4-alkoxycarbonyl; and M is hydrogen, an alkali metal, an alkaline earth metal or ammonium.
4. The azo pigment mixture as claimed in claim 1, comprising one or more additional colorants for shading from the group consisting of quinacridone pigments, naphthol AS pigments and combinations thereof, wherein the naphthol AS pigments are different than the azo pigments of the formula (IIIa) and (IIIb).
5. The azo pigment mixture as claimed in claim 1, comprising at least the azo pigments of formulae (IIIa) and (IIIb), wherein X.sup.1 is carbamoyl, methylcarbamoyl or ethylcarbamoyl; Y is methoxy or ethoxy; Z.sup.1 is nnethylphenyl, ethylphenyl, methoxyphenyl or ethoxyphenyl; and Z.sup.2 is nitrophenyl or cyanophenyl.
6. The azo pigment mixture as claimed in claim 5, comprising at least the azo pigments of formulae (IIIa) and (IIIb), wherein X.sup.1 is carbamoyl or methylcarbamoyl; Y is methoxy; Z.sup.1 is methylphenyl; and Z.sup.2 is nitrophenyl.
7. The azo pigment mixture as claimed in claim 6, comprising at least the azo pigments of formulae (IIIa) and (IIIb), wherein Z.sup.1 is o-methylphenyl; and Z.sup.2 is m-nitrophenyl.
Description
SYNTHESIS EXAMPLE 1a
(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 (1.0 mol) 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 Mixture:
(4) 2000 g of water are initially charged and 186 g (0.67 mol) of N-(2-methylphenyl)-3-hydroxynaphthalene-2-carboxamide and 103 g (0.33 mol) of N-(3-nitrophenyl)-3-hydroxynaphthalene-2-carboxamide are introduced while stirring, and the mixture is heated to 95 C. and 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 cooled to from 80 C. to 60 C. and kept at this temperature. The warm solution can optionally still be filtered with addition of a clarifying aid.
(5) a3) Azo Coupling:
(6) The clarified diazonium salt solution from a1) is initially charged, adjusted to pH 4.3 to 4.5 by adding about 38 g of sodium acetate (in the form of a 4 N solution), and cooled to 10 C. Thereafter, the 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 to 5 by simultaneous addition of a total of about 190 g of hydrochloric acid (31%).
(7) Subsequently, the mixture is stirred for about 2.5 to 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 about 50 C. for another 1 h, then filtered and washed with water. After drying and grinding, 480 g of the inventive bluish dark red pigment mixture containing the following pigments of the formulae (1) and (2) in a mass ratio of 65:35 are obtained:
(8) ##STR00009##
SYNTHESIS EXAMPLE 1b
(9) The preparation of the diazonium salt solution is accomplished analogously to example 1a, a1).
(10) The preparation of the solution of the coupling component mixture is accomplished analogously to example 1a, a2).
(11) a3) Azo Coupling:
(12) 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. and then, with good stirring, the solution of the coupling components from a2) is added dropwise, in the course of which they precipitate out and give rise to a suspension. The temperature is kept at 10 to 15 C. by addition of ice and, on completion of coupler addition, the pH is adjusted to 5. The diazo solution from a1) is added dropwise to the coupler suspension over the course of 1.5 h and pH is kept at 5 to 5.5 with sodium hydroxide solution. After the diazo addition has ended, the mixture is stirred at RT to 30 C. and pH 5.5 to 6.5 until the diazo component has disappeared. After the coupling reaction has ended, the mixture is heated to about 50 C. for another 1 h, then filtered and washed with water. After drying and grinding, 480 g of an inventive dark red pigment mixture containing the pigments of the formulae (1) and (2) in a mass ratio of 65:35 are obtained.
(13) The pigment mixtures listed in table 1 below were prepared analogously to example 1a or 1 b:
(14) TABLE-US-00001 TABLE 1 Ex- Mixing ample Pigment of formula (1a) Pigment of formula (1b) ratio 2 (1) (2) 50:50 3 (1) (2) 30:70 4
(15) The inventive pigment mixtures of examples 2 to 35 show the desired bluish-red magenta hue and simultaneously high brilliance.
EXAMPLE 36
(16) 65 g of a dry pigment of the formula (3)
(17) ##STR00067##
and 35 g of a dry pigment of the formula (6)
(18) ##STR00068##
are mixed and ground homogeneously in a mill. This gives 100 g of an inventive bluish-dark red pigment mixture.
(19) The examples comprising the individual compounds from table 1 that are cited in table 2 below were prepared analogously to example 36:
(20) TABLE-US-00002 TABLE 2 Pigment of Pigment of Mixing Example formula (Ia) formula (Ib) ratio 37 (3) (2) 65:35 38 (5) (4) 65:35 39 (37) (16) 50:50 40 (40) (20) 58:42 41 (42) (6) 60:40 42 (49) (14) 67:33
EXAMPLE 43
(21) 70 g of a pigment of the formula (13) and 30 g of a pigment of the formula (2), each in the form of a moist presscake, are introduced into 1000 g of water and homogenized by stirring at RT to 95 C. for a further 1 hour. After filtration, drying and grinding, 100 g of an inventive bluish-dark red pigment mixture are obtained.
(22) The examples comprising the individual compounds from table 1 that are cited in table 3 below were prepared analogously to example 43:
(23) TABLE-US-00003 TABLE 3 Pigment of Pigment of Example formula (Ia) formula (Ib) Mixing ratio 44 (1) (2) 65:35 45 (1) (6) 57:43 46 (5) (2) 60:40 47 (11) (14) 70:30 48 (23) (38) 60:40 49 (41) (8) 55:45 50 (48) (24) 70:30
EXAMPLE 51
(24) To a reaction mixture obtained according to example 1a or 1b, containing 480 g of a mixture of the pigments of the formulae (1) and (2) in a mass ratio of 65:35, are added 72 g of C.I. Pigment Red 269 of the formula
(25) ##STR00069##
and the mixture is homogenized by stirring at RT to 95 C. for a further 1 hour. After subsequent filtration, drying and grinding, 552 g of an inventive bluish-dark red pigment mixture are obtained.
EXAMPLE 52
(26) To a reaction mixture obtained according to example 1a or 1b, containing 480 g of a mixture of the pigments of the formulae (1) and (2) in a mass ratio of 65:35, are added 96 g of C.I. Pigment Red 122 having the formula
(27) ##STR00070##
and the mixture is homogenized by stirring at RT to 95 C. for a further 1 hour. After subsequent filtration, drying and grinding, 576 g of an inventive bluish-dark red pigment mixture are obtained.
EXAMPLE 53
(28) 50 g of a dry pigment of the formula (1), 30 g of a dry pigment of the formula (6) and 20 g of C.I. Pigment Red 122 are mixed in a mill and ground homogeneously. This gives 100 g of an inventive bluish-dark red pigment mixture.
Use Examples
(29) The chroma and the hue angle were determined in an alkyd resin (0.5% strength).
(30) In the resin system and test system mentioned, the chroma C of the pigment mixtures 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).
(31) a) Production of the 0.5% Alkyd Resin:
(32) In a plastic cup, 0.45 g of a pigment mixture 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.
(33) 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-Soligen 173 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.
(34) b) Paint Test for Coloristic Properties:
(35) 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, for example with a DatacolorSpectraflashSF600PLUS CT spectrophotometer, according to DIN 5033-7, ISO 7724-2.
(36) The test results of pigment mixtures of the invention are reported in table 4 below.
(37) TABLE-US-00004 TABLE 4 Use Pigment of Pigment of Hue example formula (Ia) formula (Ib) Mixing ratio Chroma C angle h 1 (1) (2) 65:35 67.4 4.0 2 (1) (2) 50:50 66.8 1.1 3 (1) (2) 30:70 64.4 357.2 4 (1) (2) 10:90 58.9 353.3 5 (1) (12) 65:35 58.2 1.8
Use Examples for Color Filters
Use Example COF-1
(38) 15.0 g of the inventive pigment mixture according to example 1 are mixed by stirring in a paint shaker cup with 52.1 g of methoxypropyl acetate (PGMEA), 5.0 g of n-butanol and 16.0 g of Disperbyk 2001 (BYK-Chemie, polymeric dispersing aid solution) and 11.9 g of Ripoxy SPC-2000 (Showa Highpolymers Japan, 38% polymeric binder solution). After addition of 250 g of zirconia beads (0.3 mm), dispersion is effected in a Lau (Dispermat) dispersing unit for seven hours. The resultant millbase is separated from the beads by filtration. 20.0 g of the resultant millbase are mixed with 30.0 g of a 10% by weight solution of Ripoxy SPC-2000 in PGMEA by agitating without beads for 10 minutes. Subsequently, the dispersion is filtered.
(39) The resultant binder-containing pigment dispersion is applied with the aid of a spin-coater (POLOS Wafer Spinner) to glass plates (SCHOTT, laser-cut, 1010 cm) in a layer thickness that enables setting of the color coordinates x specified in table 5 as reference values with use of a light source C.
(40) The layer thickness in each case is about 1 to 2 micrometers.
(41) The glass plates are left to flash off and then dried at 80 C. for 10 minutes in an air circulation drying cabinet (from Binder). The values for the color coordinates (x, y, Y, and CIELAB, Datacolor 650 spectrophotometer, illuminant C, 2 observer), transmission curves (ditto) and contrast values (Tsubosaka CT-1 contrast tester) of the glass plates were measured.
(42) The contrast ratios ascertained and the x values measured for the glass plates of each sample are used to determine a line of best fit by calculation. This line describes the dependence of the contrast value on the color coordinate x. With the aid of the equation of the line, the contrast ratio at a defined x value is calculated and compared with the contrast ratio of the comparative sample at this x value.
Use Examples COF-2COF-5
(43) The procedure is as in use example COF-1, except that, rather than the pigment composition according to example 1, the inventive mixtures as specified in claim 5 are used.
Comparative Example: COF-V1
(44) The millbase and color dispersion are produced analogously to the case of use example COF-1. However, what is used is not a pigment mixture of the invention, but rather a conventional magenta-colored quinacridone pigment for use in color filters (Hostaperm Red EG-COF, C.I. Pigment Red 209; Clariant Produkte Deutschland GmbH).
(45) TABLE-US-00005 TABLE 5 Relative contrast Use Pigment of Pigment of Mixing ratio CR example formula (Ia) formula (Ib) ratio (at fixed x = 0.500) COF-1 (1) (2) 65:35 135% COF-2 (1) (2) 50:50 123% COF-3 (1) (2) 30:70 117% COF-4 (1) (2) 10:90 122% COF-5 (1) (12) 65:35 113% COF-C1 Hostaperm Red EG-COF 100% (C.I. Pigment Red 209)
(46) The relative contrast ratio CR relates to the color of the comparative example COF-C1 (100%) at a linear-extrapolated x value of x=0.500.
(47) The value x relates to the color coordinates in the CIE-Yxy standard color space.
(48) Result: The inventive examples each exhibit colors with good contrast value and high color intensity.