STABILIZATION OF C.I. PIGMENT YELLOW 139

Abstract

An alkali-resistant pigment composition is provided comprising (a) a C.I. Pigment Yellow 139 and (b) an adduct containing a compound of formula (II) or a tautomeric form thereof, wherein X is O, S or NR.sup.1; Y is O, S or NR.sup.1; the group -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3-, —CR.sup.4R.sup.5—CR.sup.6R.sup.7-, —CY—CR.sup.8R.sup.9-, —CX—NR.sup.10-, —CR.sup.11═N—, —CR.sup.12R.sup.13-NR.sup.14- and R.sup.1 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.7cycloalkyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14are independently of each other hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, or C.sub.6-C.sub.10aryl, or R.sup.2 and R.sup.3 form a benzoannellated ring; and/or a melamine- or pyrimidine-based compound, which is optionally substituted. The pigment composition may be used as colorant in various applications, especially in coloring high molecular weight organic material, for example, coating compositions, paints, printing inks, liquid inks, plastics, films or fibers.

##STR00001##

Claims

1. A pigment composition, comprising: (a) a pigment of formula (I): ##STR00018##  and (b) an adduct selected from the group consisting of (b1) an adduct comprising: a compound of formula (II): ##STR00019##  or a tautomeric form thereof, wherein X is O, S or NR.sup.1; Y is O, S or NR.sup.1; -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3—, —CR.sup.4R.sup.5—CR.sup.6R.sup.7—, —CY—CR.sup.8R.sup.9—, —CR.sup.12R.sup.13—NR.sup.14— and ##STR00020## R.sup.1 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.7cycloalkyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl or C.sub.6-C.sub.10aryl, or R.sup.2 and R.sup.3 form a benzoannellated ring;  said alkyl, cycloalkyl or alkenyl is unsubstituted or substituted with halogen or OH;  said aryl or benzoannellated ring is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; and a compound of formula (III) ##STR00021##  or a tautomeric form thereof, wherein Z is N or CR.sup.18, R.sup.18 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen, C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.10aryl, C.sub.7-C.sub.10aralkyl or a group of formula (IV): ##STR00022## said alkyl or alkenyl is unsubstituted or substituted with halogen or OH; and said aryl is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; or (b2) an adduct comprising: a compound of formula (II): ##STR00023##  or a tautomeric form thereof, wherein X is O, S or NR.sup.1; Y is O, S or NR.sup.1; -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3—, —CR.sup.4R.sup.5—CR.sup.6R.sup.7—, —CY—CR.sup.8R.sup.9—, —CX—NR.sup.10, —CR.sup.11═N—, —CR.sup.12R.sup.13—NR.sup.14— and ##STR00024## R.sup.1 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.7cycloalkyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10 aralkyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.13 and R.sup.14 are independently of each other hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, or C.sub.6-C.sub.10aryl, or R.sup.2 and R.sup.3 form a benzoannellated ring; said alkyl, cycloalkyl or alkenyl is unsubstituted or substituted with halogen or OH; said aryl or benzoannellated ring is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; and (b3) an adduct comprising: a compound of formula (III): ##STR00025##  or a tautomeric form thereof, wherein Z is N or CR.sup.18; R.sup.18 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen, C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.10aryl, C.sub.7-C.sub.10aralkyl or a group of formula (IV): ##STR00026## said alkyl or alkenyl is unsubstituted or substituted with halogen or OH; and said aryl is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl.

2. The pigment composition according to claim 1, comprising the adduct (b1) which comprises: the compound of formula (II) or a tautomeric form thereof, wherein X and Y are O; -A-B— is —CY—CR.sup.8R.sup.9— or —CX—NR.sup.10—; R.sup.8, R.sup.9 and R.sup.10 are hydrogen; and the compound of formula (III) or a tautomeric form thereof, wherein Z is N; and R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen or C.sub.1-C.sub.4alkyl.

3. The pigment composition according to claim 1, comprising the adduct (b1) which comprises: the compound of formula (II) or a tautomeric form thereof, wherein X and Y are O; -A-B— is —CY—CR.sup.8R.sup.9— or —CX—NR.sup.10—; R.sup.8, R.sup.9 and R.sup.10 are hydrogen; and the compound of formula (III) or a tautomeric form thereof, wherein Z is CR.sup.18; R.sup.18 is hydrogen, C.sub.1-C.sub.4alkyl, phenyl or C.sub.7-C.sub.10aralkyl; and R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen or C.sub.1-C.sub.4alkyl.

4. The pigment composition according to claim 1, comprising the adduct (b1) which comprises: the compound of formula (II) or a tautomeric form thereof, wherein X and Y are O; -A-B— is —CY—CR.sup.8R.sup.9— or —CX—NR.sup.10—; R.sup.8, R.sup.9 and R.sup.10 are hydrogen; and the compound of formula (III) or a tautomeric form thereof, wherein Z is N; and R.sup.15, R.sup.16 and R.sup.17 are hydrogen.

5. The pigment composition according to claim 1, comprising the adduct (b3) which comprises: the compound of formula (III) or a tautomeric form thereof; and a compound of formula (V):
HOOC—R.sup.19—COOH  (V), wherein R.sup.19 is a direct bond, C.sub.1-C.sub.8alkylene, C.sub.2-C.sub.8alkenylene, C.sub.3-C.sub.7cycloalkylene or C.sub.6-C.sub.10arylene; said alkylene, cycloalkylene or alkenylene is unsubstituted or substituted with halogen or OH, and said alkylene may further be interrupted by O, S, NR.sup.20, phenyl, naphthyl or cyclohexylene, said arylene is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; and R.sup.20 is hydrogen or C.sub.1-C.sub.4alkyl.

6. The pigment composition according to claim 1, wherein the mole ratio of compound of formula (II) to compound of formula (III), or the mole ratio of compound of formula (III) to compound of formula (V) is of from 0.4:0.6 to 0.7:0.3.

7. The pigment composition according to claim 1, comprising the adduct (b2) which comprises the compound of formula (II) or a tautomeric form thereof, wherein X and Y are O, -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3—, —CY—CR.sup.8R.sup.9— and —CX—NR.sup.10—; R.sup.2, R.sup.3 and R.sup.10 are hydrogen; and R.sup.8 and R.sup.9 are independently of each other hydrogen, halogen or C.sub.1-C.sub.4alkyl.

8. The pigment composition according to claim 1, wherein the weight ratio of component (a) to component (b) is of from 0.85:0:15 to 0.5:0.5.

9. The pigment composition according to claim 1, consisting essentially of component (a) and component (b).

10. A process for preparing a pigment composition of claim 1, the process comprising treating the pigment (a) of formula (I) with the adduct (b) to obtain the pigment composition.

11. The process according to claim 10, wherein the pigment (a) of formula (I) is treated with the adduct (b) by salt kneading, wet milling or dispersing, wherein optionally the adduct is prepared in situ during the treating step.

12. A pigment composition obtainable by the process of claim 10.

13. A process for enhancing alkali stability of a pigment of formula (I): ##STR00027## the process comprising adding an adduct to the pigment of formula (I), said adduct being selected from the group consisting of (b1) an adduct comprising: a compound of formula (II): ##STR00028##  or a tautomeric form thereof, wherein X is O, S or NW; Y is O, S or NW; -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3—, —CR.sup.4R.sup.5—CR.sup.6R.sup.7—, —CY—CR.sup.8R.sup.9—, —CX—NR.sup.10—, —CR.sup.11═N—, —CR.sup.12R.sup.13—NR.sup.14— and ##STR00029## R is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.7cycloalkyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl or C.sub.6-C.sub.10aryl, or R.sup.2 and R.sup.3 form a benzoannellated ring;  said alkyl, cycloalkyl or alkenyl is unsubstituted or substituted with halogen or OH;  said aryl or benzoannellated ring is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; and a compound of formula (III) ##STR00030##  or a tautomeric form thereof, wherein Z is N or CR.sup.18, R.sup.18 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10 aralkyl; R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen, C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.10aryl, C.sub.7-C.sub.10aralkyl or a group of formula (IV): ##STR00031## said alkyl or alkenyl is unsubstituted or substituted with halogen or OH; and said aryl is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; or (b2) an adduct comprising: a compound of formula (II): ##STR00032##  or a tautomeric form thereof, wherein X is O, S or NR.sup.1; Y is O, S or NR.sup.1; -A-B— is selected from the group consisting of —CR.sup.2═CR.sup.3—, —CR.sup.4R.sup.5—CR.sup.6R.sup.7—, —CY—CR.sup.8R.sup.9—, —CR.sup.11—N—, —CR.sup.12R.sup.13—NR.sup.14— and ##STR00033## R.sup.1 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.3-C.sub.7cycloalkyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.2, R.sup.3, R.sup.4, R.sup.5, R.sup.6, R.sup.7, R.sup.8, R.sup.9, R.sup.10, R.sup.11, R.sup.12, R.sup.13 and R.sup.14 are independently of each other hydrogen, halogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, or C.sub.6-C.sub.10aryl, or R.sup.2 and R.sup.3 form a benzoannellated ring; said alkyl, cycloalkyl or alkenyl is unsubstituted or substituted with halogen or OH, said aryl or benzoannellated ring is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl; and (b3) an adduct comprising: a compound of formula (III): ##STR00034##  or a tautomeric form thereof, wherein Z is N or CR.sup.18; R.sup.18 is hydrogen, C.sub.1-C.sub.8alkyl, C.sub.2-C.sub.8alkenyl, C.sub.6-C.sub.10aryl or C.sub.7-C.sub.10aralkyl; R.sup.15, R.sup.16 and R.sup.17 are independently of each other hydrogen, C.sub.1-C.sub.8alkyl, C.sub.6-C.sub.10aryl, C.sub.7-C.sub.10aralkyl or a group of formula (IV): ##STR00035## said alkyl or alkenyl is unsubstituted or substituted with halogen or OH; and said aryl is unsubstituted or substituted with halogen, OH or C.sub.1-C.sub.4alkyl.

14. A process for coloring a composition, the process comprising adding the pigment composition of claim 1 to a composition selected from the group consisting of a coating composition, a paint, a printing ink, a liquid ink, plastics, a film and a fiber.

15. A colored composition, comprising: the pigment composition of claim 1 as a colorant; and a composition selected from the group consisting of a coating composition, a paint, a printing ink, a liquid ink, plastics, a film and a fiber.

16. A process for coloring a composition, the process comprising adding the pigment composition of claim 9 to a composition selected from the group consisting of a coating composition, a paint, a printing ink, a liquid ink, plastics, a film and a fiber.

Description

EXAMPLES

[0157] The pigment compositions produced below are evaluated for their alkali stability and colorimetric data in an alkyd melamine paint.

[0158] The alkali stability is determined in the paint in white reduction as follows: 1 drop of 2N NaOH solution are deposed on the paint surface and covered with a watch-glass. The changes in color are observed after 2, 4 and 24 hours. The drops are eliminated therefor with a tissue and rinsed with water.

[0159] Evaluation takes place by the following criteria (by visual assessment):

+ good/excellent (no visible change)
0/+ between 0 and +
fair (slightly brownish, but acceptable)
0/− between 0 and −
− bad (failed)

[0160] To determine the CIELAB values of hue h [°], chroma C* and lightness L*, the coating films obtained (in masstone) are measured using a Minolta Spectrophotometer CM-3610d. Evaluation takes place on the data obtained at a measurement angle of 45°. The color strength is also determined in white reduction.

Example 1

[0161] a) 60 g of melamine (2,4,6-triamino-1,3,5-triazine) are dissolved at 45° C. in 600 ml of water (solution A). 60 g of barbituric acid (pyrimidine-2,4,6-trione) are dissolved at 45° C. in 1000 ml of water (solution B). Solution A is slowly added to solution B under stirring. The precipitate of the formed 1:1 adduct of melamine and barbituric acid is isolated by filtration and dried at 60° C. in a vacuum oven.

[0162] b) 85 g of Pigment Yellow 139 (crude of Paliotol Yellow K 1841) and 68.7 g of the precipitate of step a) are blended with 340 g of sodium chloride (milled grade) and 142 g of diacetone alcohol and kneaded in a 1 l Z-blade kneader (Meili) for 3 hours at 40° C. The resulting paste is then dispersed in 3 l of water, the product is isolated by filtration, washed salt-free with water and dried in a vacuum oven overnight at 80° C.

Example 2

[0163] a) 60 g of melamine (2,4,6-triamino-1,3,5-triazine) are dissolved at 45° C. in 1000 ml of water (solution a). 60 g of cyanuric acid (1,3,5-triazinetriol) are dissolved at 45° C. in 2000 ml of water (solution B). Solution A is slowly added to solution B under stirring. The precipitate of the 1:1 adduct of melamine and cyanuric acid is isolated by filtration and dried at 60° C. in a vacuum oven.

[0164] b) 85 g Pigment Yellow 139 (crude of Paliotol Yellow K 1841) and 68.7 g of the precipitate of step a) are blended with 340 g of sodium chloride and 150 g (125 g from the beginning and 25 g are added during the kneading) of diacetone alcohol and kneaded in a 1 l Z-blade kneader for 3 hours at 40° C. The resulting paste is then dispersed in 3 l of water, the product is isolated by filtration, washed salt-free with water and dried in a vacuum oven overnight at 80° C.

Example 3a-3d

[0165] 50 g of Pigment Yellow 139 (crude of Paliotol Yellow K 1841) and 50 g of a 1:1 adduct of melamine and barbituric acid (prepared according to Example 1a) are dispersed in 450 g of water with a teeth-stirrer for 1 hour at 1000 rpm. A 400 ml glass WAB Willy A. Bachofen DynoMill KDL—equipped with two PU disks, 3000 rpm, filled with 250 ml of Yttrium stabilized Zirkonia pearls (ø 1.2-1.4 mm) is fed—through a peristaltic pump at a speed of 600 ml per min—with 400 ml of water followed by the pigment suspension. The suspension is milled for 3 hours at about 40° C. (Example 3d). Samples are taken after 30 min (Example 3a), 1 hour (Example 3b) and 2 hours (Example 3c). At the end, the product (as well as the intermediate samples) are isolated by filtration, washed with water and dried at 80° C. in a vacuum oven.

Example 4a-4d

[0166] The procedure of Example 3 is repeated with the exception that an adduct of melamine and cyanuric acid (prepared according to Example 2a) is used instead of an adduct of melamine and barbituric acid, and the weight ratio of Pigment Yellow 139 to adduct is of 55:45.

Example 5a

[0167] 50 g of C.I. Pigment Yellow 139 (crude of Paliotol Yellow K 1841) and 50 g of a 1:1 adduct of melamine and barbituric acid (prepared according to Example 1a) are dispersed in 250 g of water in a dissolver (Dispermat) with beads (ø 1.2 to 1.4 mm) for 6 hours at 1000 rpm. The product is isolated by filtration, washed with water and dried at 80° C. in a vacuum oven.

Comparative Example 5b

[0168] The procedure of Example 5a is repeated with the exception that the suspension is dispersed without beads (milling media) for 6 hours at 1000 rpm. The product is isolated by filtration, washed with water and dried at 80° C. in a vacuum oven.

Example 6

[0169] 107.6 g of C.I. Pigment Yellow 139 (crude of Paliotol Yellow K 1841) and 46.1 g of barbituric acid are blended with 340 g of sodium chloride and 133 g of diacetone alcohol in a 1 l Z-blade kneader and kneaded for 3 hours at 40° C. The resulting paste is then dispersed in 3 l of water, the product is isolated by filtration, washed salt-free with water and dried in a vacuum oven overnight at 80° C.

Application Example A: Alkyd Melamine (AM) Paint (Full Shade)

[0170] The components are carefully blended during 20 min by 1450 rpm to prepare the alkyd resin A:

150 g of Alkydal F310 (60 wt.-% in SN100) (short oil alkyd resin; Bayer)
47.5 g of xylene (mixture of isomers)
5.0 g of butanol
5.0 g of 1-methoxy-2-propanol
2.5 g of Baysilone MA (1 wt.-% in xylene) (silicone oil; Bayer)

[0171] In order to prepare the alkyd melamine paint B

34.27 g of alkyd resin A;
4 g of a pigment composition (Examples 1 to 6);
12 g of DisperByk-161 (dispersant; high molecular weight block copolymer with pigment affinic groups; BYK); and
10.53 g of Maprenal MF650 (cross-linking agent based on a melamine resin; UCB);
are dispersed in a shaker (Skandex) for 1 hour with glass beads (ø 2 mm).

[0172] The alkyd melamine paints are applied as full shade on a Leneta black/white contrast carton (wet application of a thickness of 100 μm). After a flash time of 30 min the paints are dried at 120° C. for 30 min.

Application Example B: White Reduction

[0173] A white paint containing 74 g of alkyd resin A, 0.5 g of Aerosil 200 (Evonik) and 25 g of TiO.sub.2 (Kronos 2310) is used. 4.76 g of the alkyd melamine paint B made in Application Example A are blended with 15.24 g of the white paint.

[0174] The paints as white reduction are applied on a Leneta black/white contrast carton (wet application of a thickness of 100 μm), after a flash time of 30 min the paints are dried at 120° C. for 30 min.

Comparative Example 1

[0175] Paliotol K 1841 applied with the corresponding amount of the pigment composition.

Comparative Example 2 (Physically Mixed Blend of Pigment Yellow 139 and Adduct)

[0176] 85 g of Pigment Yellow 139 (crude pigment) and 50 g of a 1:1 adduct of melamine and barbituric acid (prepared according to Example 1a) are dispersed in 450 g of water with a teeth-stirrer for 30 min at 1000 rpm to form a homogenous suspension. The product is isolated by filtration, washed with water and dried at 80° C. in a vacuum oven.

[0177] The results of alkali stability tests of the Examples are shown in Table 1. The coloristic data are listed in Table 2.

TABLE-US-00001 TABLE 1 White reduction; Application Example B Pigment Alkali stability after composition 0 hours 2 hours 4 hours 24 hours Ex. 1b + + + + Ex. 2b + + + + Ex. 3a + 0/+ 0/+ 0/+ Ex. 3b + 0/+ 0/+ 0/+ Ex. 3c + + + + Ex. 3d + + + + Ex. 4a + 0/+ 0/+ 0/+ Ex. 4b + 0/+ 0/+ 0/+ Ex. 4c + + + + Ex. 4d + + + + Ex. 5a + + + + Comp. Ex. 5b + 0/− 0/− 0/− Ex. 6 + + + + Comp. Ex. 1 + − − − Comp. Ex. 2 + − − −

TABLE-US-00002 TABLE 2 (White reduction; Application Example B) Pigment Content of pigment (a) Color Intrinsic color composition (wt. %) strength strength** Comp. Ex. 1 100  100* 100 Comp. Ex. 2 55  55 100 Ex. 1b 55 119 216 Ex. 6 70 108 154 *Color strength of Comp. Ex. 1a as a reference (= 100) **Color strength re-calculated for 100 wt % pigment

Application Example D: Heat Stability in Polypropylene in Full Shade (0.1 wt.-%)

[0178] 1 g of a pigment prepared according to Example 2b is blended with 1000 g of polypropylene HF420 FB (Borealis) on a Turbula (Fuchs) during 20 min. The blend is extruded in a Twin Screw 25 mm extruder (Collin, Ebersberg) at 200° C. (temperature profile: cold, 150° C., 195° C., 200° C., 200° C., 200° C., 200° C.). The spaghettis are granulated in a granulator (Sheer, Stuttgart) and then injected in the injection molding Boy 30A (Dr. Boy GmbH, Neustadt) following the scheme:

2 min at 200° C., 5 min at 220° C., 5 min at 240° C., 5 min at 260° C., 5 min at 280° C., 5 min at 300° C.; mold 40° C.

[0179] The results of the heat stability test of Example 2b are shown in Table 3.

TABLE-US-00003 TABLE 3 (full shade; Application Example D) Pigment ΔE ΔE ΔE ΔE ΔE ΔE comp. 200° C. 220° C. 240° C. 260° C. 280° C. 300° C. Ex. 1b 0 1.8 4.1 7.2 15.7 19.3 Ex. 2b 0 1.5 2.8 6.6 6.7 11.7 Comp. Ex. 1 0 3.4 8.2 19.1 31.9 25.3

[0180] The pigment composition of Example 1 b shows a significantly improved thermal stability up to about 260° C., the pigment composition of Example 2b shows a significantly improved thermal stability up to about 280° C. in polypropylene.