NEAR-INFRARED (NIR) TRANSPARENT NEUTRAL BLACK SOLID SOLUTION PIGMENT

Abstract

The present invention relates to a solid solution comprising (a) at least one compound according to formula (I), and (b) at least one compound according to formula (II), or at least one compound according to formula (III), or a mixture of at least one compound according to formula (II) and at least one compound according to formula (III), wherein R.sub.1 and R.sub.2 may, independently of one another, stand for (CH.sub.2).sub.nX, wherein X stands for hydrogen, methyl, a C.sub.1-C.sub.5 alkoxyl, hydroxy, phenyl, C.sub.1-C.sub.5 alkylphenyl, C.sub.1-C.sub.5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C.sub.1-C.sub.5 alkylpyridyl, C.sub.1-C.sub.5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n stands for 0, 1, 2, 3, 4 or 5; R.sub.3 and R.sub.4 may, independently of one another, stand for phenylene, C.sub.1-C.sub.5 alkylphenylene, C.sub.1-C.sub.5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C.sub.1-C.sub.5 alkylpyridinediyl, C.sub.1-C.sub.5 alkoxy-pyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R.sub.3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R.sub.3; wherein the 2 nitrogen atoms bound to R.sub.4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R.sub.4; X.sub.1 to X.sub.8 may, independently from one another, stand for hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, hydroxy, phenyl or halide. The present invention further relates to a process for producing the solid solution. Furthermore, the present invention relates to a solid solution obtainable or obtained according to said process and to the use of the inventive solid solution, in particular as a NIR transparent black colorant in a NIR non-absorbing component.

##STR00001##

Claims

1. A solid solution comprising (a) a compound according to formula (I) ##STR00013## and (b) a compound according to formula (II), or a compound according to formula (III), or a mixture of a compound according to formula (II) and a compound according to formula (III) ##STR00014## wherein R.sub.1 and R.sub.2 are independently of one another (CH.sub.2).sub.nX, wherein X is hydrogen, methyl, a C.sub.1-C.sub.5 alkoxyl, hydroxy, phenyl, C.sub.1-C.sub.5 alkylphenyl, C.sub.1-C.sub.5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C.sub.1-C.sub.5 alkylpyridyl, C.sub.1-C.sub.5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R.sub.3 and R.sub.4 are independently of one another phenylene, C.sub.1-C.sub.5 alkylphenylene, C.sub.1-C.sub.5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C.sub.1-C.sub.5 alkylpyridinediyl, C.sub.1-C.sub.5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R.sub.3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R.sub.3; wherein the 2 nitrogen atoms bound to R.sub.4 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R.sub.4; X.sub.1 to X.sub.8 are independently from one another hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, hydroxy, phenyl or halide.

2. The solid solution of claim 1, wherein X is methoxyphenyl or phenyl and n is 1 or 2; R.sub.3 and R.sub.4 are independently of one another phenylene, methyl-phenylene, methoxyphenylene, chloro-phenylene, dichloro-phenylene or naphthalenediyl; and X.sub.1 to X.sub.8 are hydrogen.

3. The solid solution of claim 1, wherein R.sub.1 and R.sub.2 are independently from one another CH.sub.2C.sub.6H.sub.4OCH.sub.3 or CH.sub.2CH.sub.2C.sub.6H.sub.5; R.sub.3 and R.sub.4 are independently of one another phenylene, 4-chloro-phenylene, naphthalenediyl or 4,5-dichloro-phenylene; and X.sub.1 to X.sub.8 are hydrogen.

4. The solid solution of claim 1, wherein X is 4-methoxyphenyl and n is 1; R.sub.3 and R.sub.4 are phenylene; and X.sub.1 to X.sub.8 are hydrogen; and/or X is 4-methoxyphenyl and n is 1; R.sub.3 and R.sub.4 are naphthalenediyl; and X.sub.1 to X.sub.8 are hydrogen; and/or X is 4-methoxyphenyl and n is 1; R.sub.3 and R.sub.4 are 4-chloro-phenylene; and X.sub.1 to X.sub.8 are hydrogen; and/or X is 4-methoxyphenyl and n is 1; R.sub.3 and R.sub.4 are 4,5-dichloro-phenylene; and X.sub.1 to X.sub.8 are hydrogen; and/or X is phenyl and n is 2; R.sub.3 and R.sub.4 are phenylene; and X.sub.1 to X.sub.8 are hydrogen; and/or X is phenyl and n is 2; R.sub.3 and R.sub.4 are naphthalenediyl; and X.sub.1 to X.sub.8 are hydrogen; and/or X is phenyl and n is 2; R.sub.3 and R.sub.4 are 4-chloro-phenylene; and X.sub.1 to X.sub.8 are hydrogen.

5. The solid solution of claim 1, exhibiting a non-color depending black value M.sub.Y in the range of from 200 to 350, and a color depending black value M.sub.C in the range of from 200 to 350, M.sub.Y and M.sub.C being determined according to DIN EN 18314-3.

6. The solid solution of claim 1, wherein in the solid solution, the weight ratio of the compound of formula (I) relative to the compound according to formula (II) or to the compound according to formula (III) or to the mixture of a compound according to formula (II) and a compound according to formula (III), weight((I)):weight((II)(III)), is in the range of from 60:40 to 99:1.

7. The solid solution of claim 1, wherein from 80 to 100 weight-% of the solid solution consist of (a) the compound according to formula (I) and (b) the compound according to formula (II), or the compound according to formula (III), or the mixture of the compound according to formula (II) and the compound according to formula (III).

8. A process for producing a solid solution, comprising (i) providing a mixture comprising (a) a compound according to formula (I) ##STR00015## and (b) a compound according to formula (II), or a compound according to formula (III), or a mixture of a compound according to formula (II) and a compound according to formula (III) ##STR00016## wherein R.sub.1 and R.sub.2 are independently of one another (CH.sub.2).sub.nX, wherein X is hydrogen, methyl, a C.sub.1-C.sub.5 alkoxyl, hydroxy, phenyl, C.sub.1-C.sub.5 alkylphenyl, C.sub.1-C.sub.5 alkoxyphenyl, hydroxyphenyl, halogenated phenyl, pyridyl, C.sub.1-C.sub.5 alkylpyridyl, C.sub.1-C.sub.5 alkoxypyridyl, halogenated pyridyl, pyridylvinyl or naphthyl; wherein n is 0, 1, 2, 3, 4 or 5; R.sub.3 and R.sub.4 are independently of one another phenylene, C.sub.1-C.sub.5 alkylphenylene, C.sub.1-C.sub.5 alkoxyphenylene, hydroxyphenylene, halogenated phenylene, pyridinediyl, C.sub.1-C.sub.5 alkylpyridinediyl, C.sub.1-C.sub.5 alkoxypyridinediyl, halogenated pyridinediyl, anthraquinonediyl or naphthalenediyl, wherein the 2 nitrogen atoms bound to R.sub.3 according to formula (II) and (III) form a 5-membered or a 6-membered heterocycle with 2 atoms of an aromatic ring of R.sub.3; wherein the 2 nitrogen atoms bound to R.sub.4 according to formula (II) and (III) form a 5-membered heterocycle with 2 atoms of an aromatic ring of R.sub.4; X.sub.1 to X.sub.8 are independently from one another hydrogen, C.sub.1-C.sub.5 alkyl, C.sub.1-C.sub.5 alkoxy, hydroxy, phenyl or halide; (ii) subjecting the mixture provided according to (i) to mechanical treatment; (iii) adding water to the mixture obtained from (ii); (iv) subjecting the mixture obtained from (iii) to solid-liquid separation; (v) washing the solids obtained from (iv) with a suitable washing agent; and (vi) drying the solids obtained from (v), obtaining the solid solution.

9. The process of claim 8, wherein the mechanical treatment comprises one or more kneading and milling, wherein kneading comprises coextrusion, salt kneading, single-shaft kneading and double-shaft kneading and wherein milling comprises wet milling, ball milling, bead milling, vibration milling, planetary milling and attritor milling.

10. The process of claim 9, wherein the mechanical treatment is kneading, wherein said kneading is carried out at a temperature of the mixture in the range of from 40 to 120 C.

11. The process of claim 9, wherein the mechanical treatment further comprises, either directly before and/or during kneading, adding one or more of a synergist comprising sulfonic and carboxylic acid derivatives of perylene, indanthrone, phthalocyanine and diketopyrrolopyrrole.

12. The process of claim 9, wherein the mechanical treatment comprises milling, wherein said milling is carried out at a temperature of the mixture in the range of from 40 to 120 C.

13. The process of claim 12, wherein the process further comprises, directly after milling, adding a suitable acid or solvent to the milled mixture under stirring at a temperature of the mixture in the range of from 40 to 200 C.

14. A solid solution obtained by a process according to claim 8.

15. An article comprising-a solid solution according to claim 1, wherein the article is selected from the group consisting of a coating composition, a light detection and ranging (LiDAR) device, a near-infrared (NIR) non-absorbing component, a photovoltaic component, a heat management component, a thermal insulation component, a coloring paint, a printing ink, a recyclable plastic article, a biodegradable mulch, a toner, a charge-generating material, a color filter, a LC display and a security print component.

16. A method to increase the signal to noise ratio in nearinfrared (NIR) radiation detection in a coating or object, comprising replacing the nearinfrared (NIR) absorbing black pigments in the coating or object with a solid solution of claim 1.

17. A multilayer coating comprising: a primer coating comprising a solid solution according to claim 1 and a white pigment or a reflective pigment having a reflectance of >50% in the range of 700 to 2500 nm, in a weight ratio of from 1:99 to 99:1; a basecoat comprising a black color, metallic or interference pigment; and optionally a clear topcoat.

18. A solid solution according to claim 1, comprised in one or more of a thermoplastic, elastomeric, crosslinked or inherently crosslinked polymer, in an amount from 0.01 weight % to 70 weight-% based on the total weight of the polymer.

19. The solid solution of claim 5, exhibiting a non-color depending black value M.sub.Y in the range of from 220 to 330, and a color depending black value M.sub.C in the range of from 220 to 330, M.sub.Y and M.sub.C being determined according to DIN EN 18314-3.

20. The solid solution of claim 19, exhibiting a non-color depending black value M.sub.Y in the range of from 230 to 300 and a color depending black value M.sub.C in the range of from 242 to 280, M.sub.Y and M.sub.C being determined according to DIN EN 18314-3.

Description

BRIEF DESCRIPTION OF THE FIGURES

[0226] FIG. 1 shows a XRD spectrum of Example 1.1

[0227] FIG. 2 shows a XRD spectrum of Example 1.2

[0228] FIG. 3 shows a XRD spectrum of Example 1.5

[0229] FIG. 4 shows a XRD spectrum of Example 1.6

[0230] FIG. 5 shows a XRD spectrum of Example 1.7

[0231] FIG. 6 shows a XRD spectrum of Comparative Example 1

[0232] FIG. 7 shows a XRD spectrum of Comparative Example 2

[0233] FIG. 8 shows a XRD spectrum of Comparative Example 3

[0234] FIG. 9 shows a XRD spectrum of Comparative Example 4

[0235] FIG. 10 shows a XRD spectrum of Comparative Example 5

[0236] FIG. 11 shows a Pigment masstone basecoat (2.5% pigment of Example 1) prepared according to Sample Preparation 6

[0237] FIG. 12 shows a 10:90 weight-% Pigment (Example 1):Titanium Dioxide White Reduction prepared according to Sample Preparation 8

[0238] FIG. 13a shows all angles of a CIELAB panel of a 50:50 weight-% Pigment (Example 1):Aluminium Reduction prepared according to Sample Preparation 9

[0239] FIG. 13b shows zoom in all angles of a CIELAB panel of a 50:50 weight-% Pigment:Aluminium Reduction prepared according to Sample Preparation 9

[0240] FIG. 14 shows Vis-NIR reflectance

[0241] FIG. 15 shows a XRD spectrum of Example 1.11

[0242] FIG. 16 shows a XRD spectrum of Example 1.12

LIST OF CITED PRIOR ART

[0243] WO2018/081613 [0244] U.S. Pat. No. 7,083,675 [0245] EP0636666B1 [0246] WO91/02034A1 [0247] EP2316886A1 EP504922A1 [0248] US2012018687A1 [0249] CN110591445A [0250] Justus Liebigs Annalen der Chemie, 1984, 483 [0251] U.S. Pat. No. 4,450,273 [0252] US 2010/0184983A1