RUSS, Werner (Bad Weilbachstraße 9, Flörsheim-Wicke, 65926, DE)
HARFMANN, Carsten (Friedrichstraße 42, Frankfurt am Main, 65956, DE)
BARBIERU, Roxana (Lynnsville, Pasir Panjang Road 221Unit 331C, Singapore 8, 11746, SG)
RUSS, Werner (Bad Weilbachstraße 9, Flörsheim-Wicke, 65926, DE)
HARFMANN, Carsten (Friedrichstraße 42, Frankfurt am Main, 65956, DE)
| What is claimed is:- 1. A dye of formula (I) (I) where X, Y, Z and T each independently represent a group of formula (1 ) or (2) -R .FT (1 ) (2) where R1 to R3 each have identical or different meanings within a molecule of formula (I) and each independently represent a group Ar; heteroaryl; cyclo- (C3-C8)-alkyl; heterocycloalkyl; (C1-C35)-alkyl; (C2-C35)-alkyl interrupted by one or more (Ci-C35)-alkyl substituted by one or more of the substituents G1 to G4; (C2-C35)-alkyl interrupted by one or more heteroatoms and substituted by one or more of the substituents G1 to G4; or a group of formula (3) and R1 may also represent hydrogen; where R4 represents hydrogen, (C1-C35)-alkyl, singly or multiply oxygen- interrupted (C1-C35)-alkyl, aryl, aryl-(C1-C35)-alkyl, (C1-C35)-alkyl-aryl, aryloxy, (Ci-C35)-alkoxy, monohydroxy-(Ci-C35)-alkyl or polyhydroxy-(Ci- C35)-alkyl; and has identical or different meanings within a molecule of formula (I); v represents a number from 1 to 35; t represents a rational number from 0.1 to 200 and has identical or different meanings within a molecule of formula (I); and R5 and R6 each independently represent hydrogen, (C1-C35)-alkyl, singly or multiply oxygen-interrupted (Ci-C35)-alkyl, aryl, aryloxy, (Ci-C35)-alkoxy, monohydroxy-(C1-C35)-alkyl or polyhydroxy-(C1-C35)-alkyl; where R5 and R6 each have identical or different meanings within a molecule of formula (I); and where when R5 and R6 have different meanings within a molecule of formula (I) these different meanings are randomly distributed or regions of respectively identical meanings follow each other; U represents hydrogen, hydroxyl, amino, mono-(Ci-C35)-alkylamino, N1N- di-(Ci-C35)-alkylamino, (Ci-C35)-alkyl, aryl, aryloxy, (Ci-C35)-alkoxy, monohydroxy-(C1-C35)-alkyl, polyhydroxy-(C1-C35)-alkyl or (C1-C35)-alkyl- aryloxy; G1 represents trifluoromethyl; cyclo-(C3-C8)-alkyl; aryl; halogen; cyano; nitro; hydroxyl; (Ci-C35)-alkoxy; (Ci-C35)-alkoxycarbonyl; aryloxy; (C2-C35)- acyl; arylcarbonyl, (C2-C35)-acyloxy; arylcarbonyloxy; (C2-C35)-acylamino; (Ci-C35)-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-monocyclo-(C3-C8)-alkyl-carbamoyl; N-mono-(Ci-C35)-alkyl- carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C35)-alkyl- carbamoyl; N-monoaryl-carbamoyl; N,N-diaryl-carbamoyl; N-monocyclo- (C3-C8)-alkyl-N-monoarylcarbamoyl; N-mono-(Ci-C35)-alkyl-N- monoarylcarbamoyl; (C1-C35)-alkoxycarbonyl; aryloxycarbonyl; amino; monocyclo-(C3-C8)-alkyl-amino; mono-(Ci-C35)-alkyl-amino; di(cyclo)-(C3- C8)-alkyl-amino; monoaryl-amino; diarylamino; monocyclo-(C3-C8)- alkylmonoarylamino; mono-(Ci-C35)-alkylmonoaryl-amino; aminothiocarbonylamino; aminocarbonylamino; sulfamoyl; N-monocyclo- (C3-C8)-alkyl-sulfamoyl; N-mono-(Ci-C35)-alkyl-sulfannoyl; N,N-dicyclo-(C3- C8)-alkyl-sulfannoyl; N,N-di-(Ci-C35)-alkyl-sulfannoyl; N-monoaryl-sulfamoyl; N,N-diaryl-sulfamoyl; N-monocyclo-(C3-C8)-alkyl-N-nnonoarylsulfannoyl; N- mono-(Ci-C35)-alkyl-N-nnonoarylsulfannoyl; aminosulfonylamino; (C1-C35)- alkylthio; arylthio; (C1-C35)-alkylsulfonyl or arylsulfonyl; G2 represents (C2-C35)-alkoxy; (C2-C35)-alkoxycarbonyl; (C2-C35)-acyl; (C2- C35)-acyloxy; (C2-C35)-acylamino; (C2-C35)-alkylsulfonylamino; N-mono-(C2- C35)-alkyl-carbamoyl; N,N-di-(C2-C35)-alkyl-carbamoyl; N-mono-(C2-C35)- alkyl-N-monoarylcarbamoyl; (C2-C35)-alkoxycarbonyl; mono-(C2-C35)-alkyl- amino; mono-(C2-C35)-alkylmonoaryl-amino; N-mono-(C2-C35)-alkyl- sulfamoyl; N,N-di-(C2-C35)-alkyl-sulfamoyl; N-mono-(C2-C35)-alkyl-N- monoarylsulfamoyl; (C2-C35)-alkylthio or (C2-C35)-alkylsulfonyl wherein the alkyl radical is interrupted by one or more hetero atoms; G3 represents cyclo-(C3-C8)-alkyl; (C1-C35)-alkoxy; (C1-C35)-alkoxycarbonyl; (C2-C35)-acyl; (C2-C35)-acyloxy; (C2-C35)-acylamino; (C1-C35)- alkylsulfonylamino; N-monocyclo-(C3-C8)-alkyl-carbamoyl; N-mono-(Ci- C35)-alkyl-carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C35)- alkyl-carbamoyl; N-monocyclo-(C3-C8)-alkyl-N-monoarylcarbamoyl; N- mono-(Ci-C35)-alkyl-N-monoarylcarbamoyl; (Ci-C35)-alkoxycarbonyl; monocyclo-(C3-C8)-alkyl-amino; mono-(Ci-C35)-alkyl-amino; di(cyclo)-(C3- C8)-alkyl-amino; monocyclo-(C3-C8)-alkylmonoarylamino; mono-(Ci-C35)- alkylmonoaryl-amino; N-monocyclo-(C3-C8)-alkyl-sulfamoyl; N-mono- (Ci-C35)-alkyl-sulfamoyl; N,N-dicyclo-(C3-C8)-alkyl-sulfamoyl; N,N-di-(Ci- C35)-alkyl-sulfamoyl; N-monocyclo-(C3-C8)-alkyl-N-monoarylsulfamoyl; N- mono-(Ci-C35)-alkyl-N-monoarylsulfamoyl; (Ci-C35)-alkylthio or (C1-C35)- alkylsulfonyl wherein the alkyl radical is substituted by a substituent G1; G4 represents G2 wherein the alkyl radical is substituted by a substituent G1; Ar represents a group of formula (5) or (6) where R7 to R13 each independently have one of the meanings G11 or G12 or represent a group of formula (7) or (8) where G11 represents hydrogen, (C1-C35)-alkyl; trifluoromethyl; cyclo-(C3-C8)-alkyl; aryl; heteroaryl; heterocycloalkyl; halogen; cyano; nitro; hydroxyl; (C1-C35)- alkoxy; aryloxy; (C2-C35)-acyl; cyclo-(C3-C8)-alkylcarbonyl, arylcarbonyl, (C2-C35)-acyloxy; arylcarbonyloxy; (C2-C35)-acylamino; (C1-C35)- alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N- monocyclo-(C3-C8)-alkyl-carbamoyl; N-mono-(Ci-C35)-alkyl-carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C35)-alkyl-carbamoyl; N- monoaryl-carbamoyl; N,N-diaryl-carbamoyl; N-monocyclo-(C3-C8)-alkyl-N- monoarylcarbamoyl; N-mono-(Ci-C35)-alkyl-N-monoarylcarbamoyl; (d- C35)-alkoxycarbonyl; aryloxycarbonyl; amino; monocyclo-(C3-C8)-alkyl- amino; mono-(Ci-C35)-alkyl-amino; di(cyclo)-(C3-C8)-alkyl-amino; di-(Ci- C35)-alkyl-amino; monoaryl-amino; diaryl-amino; monocyclo-(C3-C8)- alkylmonoarylamino; mono-(Ci-C35)-alkylmonoaryl-amino; aminothiocarbonylamino; aminocarbonylamino; sulfamoyl; N-monocyclo- (C3-C8)-alkyl-sulfamoyl; N-mono-(Ci-C35)-alkyl-sulfamoyl; N,N-dicyclo-(C3- C8)-alkyl-sulfamoyl; N,N-di-(Ci-C35)-alkyl-sulfamoyl; N-monoaryl-sulfamoyl; N,N-diaryl-sulfamoyl; N-monocyclo-(C3-C8)-alkyl-N-monoarylsulfamoyl; N- mono-(Ci-C35)-alkyl-N-monoarylsulfamoyl; aminosulfonylamino; (C1-C35)- alkylthio; arylthio; (C1-C35)-alkylsulfonyl or arylsulfonyl; G12 represents (C2-C35)-alkyl; (C2-C35)-alkoxy; (C2-C35)-acyl; (C2-C35)- acyloxy; (C2-C35)-acylamino; (C2-C35)-alkylsulfonylamino; N-mono-(C2-C35)- alkyl-carbamoyl; N,N-di-(C2-C35)-alkyl-carbamoyl; N-mono-(C2-C35)-alkyl-N- monoarylcarbamoyl; (C2-C35)-alkoxycarbonyl; mono-(C2-C35)-alkyl-annino; di-(C2-C35)-alkyl-annino; mono-(C2-C35)-alkylnnonoaryl-annino; N-mono-(C2- C35)-alkyl-sulfannoyl; N,N-di-(C2-C35)-alkyl-sulfamoyl; N-mono-(C2-C35)- alkyl-N-monoarylsulfannoyl; (C2-C35)-alkylthio or (C2-C35)-alkylsulfonyl where the alkyl radical is interrupted by one or more hetero atoms; R ,14 to R ,16 each independently represent cyclo-(C5-C6)-alkyl; heterocycloalkyl; heteroaryl; aryl, (C1-C35)-alkyl; (C2-C35)-alkyl interrupted by one or more hetero atoms; (Ci-C35)-alkyl substituted by one or more of the substituents G13, or (C2-C35)-alkyl interrupted by one or more hetero atoms and substituted by one or more of the substituents G13, and R14 and R15 may each also represent hydrogen; G13 represents trifluoromethyl; cyclo-(C3-C8)-alkyl; aryl; heteroaryl; heterocycloalkyl; halogen; cyano; nitro; hydroxyl; (Ci-C35)-alkoxy; aryloxy; (C2-C35)-acyl; arylcarbonyl, (C2-C35)- acyloxy; arylcarbonyloxy; (C2-C35)-acylamino; amino; monocyclo-(C3-C8)- alkyl-amino; mono-(Ci-C35)-alkyl-amino; di(cyclo)-(C3-C8)-alkyl-amino; di- (Ci-C35)-alkyl-amino; monoarylamino; diarylamino; monocyclo-(C3-C8)- alkylmonoarylamino; mono-(Ci-C35)-alkylmonoarylamino; (Ci-C35)-alkylthio; arylthio; (C1-C35)-alkylsulfonyl or arylsulfonyl; and aryl represents a group of formula (9) or (10) where R17 to R23 each independently represent hydrogen; (Ci-Ci2)-alkyl; cyclo- (C3-Cs)-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (Ci-Cβ)- alkoxy; (C2-C6)-acyl; (C2-C6)-acylamino; (Ci-C6)-alkylsulfonylamino; carbamoyl; N-mono-(Ci-C6)- alkyl-carbamoyl; N,N-di-(C1-C6)-alkyl-carbamoyl; amino; N-mono-(C1-C6)- alkyl-amino; di-N,N-(Ci-C6)-alkyl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C1-C6)-alkyl-sulfamoyl; di-N,N-(C1-C6)-alkyl-sulfamoyl; aminosulfonylamino; (Ci-CβJ-alkylthio or (Ci-C6)-alkylsulfonyl. 2. The dye as claimed in claim 1 , conforming to formula (Ia) a) where R1 and R2 each have identical or different meanings within a molecule of formula (Ia) and each independently represent Ar; cyclo-(C5-C6)-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C1-C18)-alkyl; (C2-Cis)-alkyl interrupted by one or more hetero atoms; (C1-C18)-alkyl substituted by one or more substituents G14; (C2-Ci8)- alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G14; or a group of formula (3a) and R1 may also represent hydrogen; wherein R D4' represents hydrogen or (C1-C35)-alkyl; w represents 1 , 2 or 3; s represents a rational number from 0.1 to 100 and has identical or different meanings within a molecule of formula (I); R5 and R6 each independently represent hydrogen or (C1-C35)-alkyl; where R5 and R6 within a molecule of formula (I) each have identical or different meanings; and where when R5 and R6 have different meanings within a molecule of formula (I) these different meanings are randomly distributed or regions of respectively identical meanings follow each other; U' represents hydrogen, (Ci-C35)-alkyl, aryl, aryloxy, (Ci-C35)-alkoxy or (d- C35)-alkyl-aryloxy; G14 represents thfluoromethyl; cyclo-(C5-C6)-alkyl; aryl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; hydroxyl; (C1-C18)-alkoxy; (C1-C18)-alkoxycarbonyl; aryloxy; (C2-Ci8)-acyl, (C2-C18)- acyloxy or arylcarbonyl; Ar represents a group of formula (5a) or (6a) where R to R 59' each independently represent hydrogen; (C2-C18)-alkyl; trifluoromethyl; cyclo-(C5-C6)-alkyl; aryl; halogen; cyano; nitro; hydroxyl; (C1-C18)-alkoxy; aryloxy; (C2-Cis)-acyl; arylcarbonyl, (C2-Ci8)-acylamino; (C1-C18)-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C1-C18)-alkyl-carbamoyl; amino; mono-(C1-C18)-alkyl- amino; di-(C1-C18)-alkyl-amino; monoaryl-amino; mono-(C1-C18)- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C1-C18)- alkyl-sulfamoyl; aminosulfonylamino; (C1-C18)-alkylthio; arylthio; (C1-C18)- alkylsulfonyl or arylsulfonyl; and R10 to R13 each independently represent hydrogen, (C2-C18)-alkyl or a group of formula (7a) or (8a) where R >14' to R >16' each independently represent (C5-C6)-cycloalkyl; heterocycloalkyl having 5 or 6 ring members; heteroaryl having 5 or 6 ring members; aryl; (C1-C18)-alkyl; (C2-Cis)-alkyl interrupted by one or more hetero atoms; (C1-C18)-alkyl substituted by one or more substituents G15; or (C2-Cis)-alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G15; and R14 and R15 may each also represent hydrogen; G15 represents trifluoromethyl; cyclo-(C5-C6)-alkyl; aryl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; halogen; cyano; nitro; hydroxyl; (C1-C18)-alkoxy; aryloxy; (C2-C18)-acyl; arylcarbonyl, di-(C1-C18)-alkyl-amino; monoaryl-amino; diaryl-amino; mono- (C1-C18)- alkylmonoaryl-amino; (C2-C18)-alkylthio; arylthio; (C1-C18)-alkylsulfonyl or arylsulfonyl; and aryl represents a group of formula (9a) or (10a) where R17 to R19 each independently represent hydrogen; (C2-C12)-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C1-C6)-alkoxy; (C2-C6)- acyl; amino; (C2-C6)-acyl-amino, mono-(C1-C6)-alkyl-amino; sulfamoyl; carbamoyl or (C1-C6)-alkylthio; and R20 to R23 each independently represent hydrogen or (C1-C6)-alkyl. 3. The dye as claimed in claim 1 , conforming to formula (Ib) where R3 has identical or different meanings within a molecule of formula (Ib) and represents Ar; cyclo-(C5-C6)-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C1-C18)-alkyl; (C2-Ci8)-alkyl interrupted by one or more hetero atoms; (C1-C18)-alkyl substituted by one or more substituents G14; or (C2-Ci8)-alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G14; where G14 is as defined in claim 2; Ar represents a group of formula (5a) or (6a) where R to R 9' each independently represent hydrogen; (C1-C18)-alkyl; trifluoromethyl; cyclo-(C5-C6)-alkyl; aryl; halogen; cyano; nitro; hydroxyl; (C1-C18)-alkoxy; aryloxy; (C2-Ci8)-acyl; arylcarbonyl, (C2-Ci8)-acylamino; (C1-C18)-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C1-C18)-alkyl-carbamoyl; amino; mono-(C1-C18)-alkyl- amino; di-(C1-C18)-alkyl-amino; monoaryl-amino; mono-(C1-C18)- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C1-C18)- alkyl-sulfamoyl; aminosulfonylamino; (C1-C18)-alkylthio; arylthio; (C1-C18)- alkylsulfonyl or arylsulfonyl; and R10 to R13 each independently represent hydrogen, (C1-C18)-alkyl; aryl represents a group of formula (9a) or (10a) where R > 17' to R > 19' each independently represent hydrogen; (Ci-Ci2)-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C1-C6)-alkoxy; (C2-C6)- acyl; amino; (C2-C6)-acyl-amino, mono-(Ci-C6)-alkyl-amino; sulfamoyl; carbamoyl or (C1-C6)-alkylthio; and R20 to R23 each independently represent hydrogen or (Ci-CβJ-alkyl. 4. The dye as claimed in claim 1 , conforming to formula (Ic) where R1", R2 and R3 each have identical or different meanings within a molecule of formula (Ic) and each independently represent Ar; cyclo-(C5-C6)-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C1-C18)-alkyl; (C2-Ci8)-alkyl interrupted by one or more hetero atoms; (C2-C18)-alkyl substituted by one or more substituents G14; (C2-C18)- alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G14; and R1 may also represent hydrogen; where G14 is as defined in claim 2; Ar represents a group of formula (5a) or (6a) where R7 to R9 each independently represent hydrogen; (C1-C18)-alkyl; trifluoromethyl; cyclo-(C5-C6)-alkyl; aryl; halogen; cyano; nitro; hydroxyl; (C1-C18)-alkoxy; aryloxy; (C2-Ci8)-acyl; arylcarbonyl, (C2-Ci8)-acylamino; (C1-C18)-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C1-C18)-alkyl-carbamoyl; amino; mono-(C1-C18)-alkyl- amino; di-(C1-C18)-alkyl-amino; monoaryl-amino; mono-(C1-C18)- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C1-C18)- alkyl-sulfamoyl; aminosulfonylamino; (C1-C18)-alkylthio; arylthio; (C2-C18)- alkylsulfonyl or arylsulfonyl; and R10 to R13 each independently represent hydrogen, (C1-C18)-alkyl; aryl represents a group of formula (9a) or (10a) where R17 to R19 each independently represent hydrogen; (Ci-Ci2)-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (Ci-C6)-alkoxy; (C2-C6) - acyl; amino; (C2-C6)-acyl-amino, mono-(C1-C6)-alkyl-amino; sulfamoyl; carbamoyl or (C1-C6)-alkylthio; and R20 to R23 each independently represent hydrogen or (C1-C6)-alkyl. 5. A process for preparing a dye of formula (I) as claimed in claim 1 , which comprises condensing the compound of formula (II) with a compound of formula (III) or (IV) or with a mixture of the compounds of formulae (lll) and (IV) where R1 to R3 are each as defined in claim 1. 6. The use of a dye of formula (I) as claimed in one or more of claims 1 to 4 for coloring a polymer. 7. A masterbatch, comprising a compound of formula (I) as claimed in one or more of claims 1 to 4 and a carrier material. |
Polymers can be colored with dyes in various ways. One way is mass coloration of polymers whereby for example a pigment or a dye is mixed with the polymer and the polymer is melted to transport the dye into the polymer matrix. Other processes involve the polymer being colored, or to be more precise dyed, by the dyes diffusing into the polymer from a solution or dispersion, examples being the dyeing of polymeric fibers composed of polyester, polyacrylonitrile, polyurethane, cellulose or polyamide for example with, for example, disperse dyes, cationic dyes, acid dyes, metallized dyes or reactive dyes. The use of reactive dyes results in a covalent bond being performed between the dye and the substrate, conferring particularly high fastnesses on the dyeings/colorations. Another way to color a polymer is to add the dye to the polymer's monomers or oligomers, before the polymer is formed or as it is being formed. Dyes capable of forming covalent bonds with the polymer scaffold may likewise result in colorations of high fastness being obtained. For this, the dyes used, or to be more precise their chromophores, have to be sufficiently stable under the conditions of the polymerization. Commercially available pigments when used in mass coloration of polymers do give colored polymers of predominantly high fastnesses, but the colorations are dull, i.e., lack transparency. Commercially available dyes for polymers are usually disperse dyes or solvent dyes and produce, when used for the coloration of polymers, colored polymers in which the dye often only has low bleed fastnesses. In addition, many of the known dyes have poor lightfastnesses or low thermal stabilities in polyolefins.
Dyes having good bleed fastnesses, good lightfastnesses, good thermal stabilities as well as high saturation and transparency in polyolefins without adversely affecting the properties of the polyolefins used are not known in large numbers. EP 0 423 068 A1 , EP 0648 817 A1 and JP 2003-43680 describe dianthraquinonyl dyes which meet the above-recited requirements to some extent. However, the dyes mentioned give only a limited palette of hues and also only a limited degree of saturation when high bleed fastness is desired. There is therefore a need for dyes which have the recited properties and thus are useful for the coloration of polyolefins.
It has now been found that dianthraquinonyl dyes which are substituted by two triazine rings constitute useful dyes for the coloration of polyolefins and other substrates. They have high stability under application conditions, are readily soluble in the polymer, or miscible with suitable organic solvents, and afford highly transparent colorations having very good fastnesses.
The present invention thus provides dyes of formula (I)
where X, Y, Z and T each independently represent a group of formula (1 ) or (2)
where
R 1 to R 3 each have identical or different meanings within a molecule of formula (I) and each independently represent a group Ar; heteroaryl; cyclo- (C 3 -C 8 )-alkyl; heterocycloalkyl; (C 1 -C 35 )-alkyl; (C 2 -C 35 )-alkyl interrupted by one or more (Ci-C3 5 )-alkyl substituted by one or more of the substituents G 1 to G 4 ; (C 2 -C 3 5)-alkyl interrupted by one or more heteroatoms and substituted by one or more of the substituents G 1 to G 4 ; or a group of formula (3) and R 1 may also represent hydrogen; where
R represents hydrogen, (C 1 -C 35 )-alkyl, singly or multiply oxygen- interrupted (C 1 -C 35 )-alkyl, aryl, aryl-(C 1 -C 35 )-alkyl, (C 1 -C 35 )-alkyl-aryl, aryloxy, (Ci-C3 5 )-alkoxy, monohydroxy-(Ci-C3 5 )-alkyl or polyhydroxy-(Ci- C3 5 )-alkyl; and has identical or different meanings within a molecule of formula (I);
v represents a number from 1 to 35;
t represents a rational number from 0.1 to 200 and has identical or different meanings within a molecule of formula (I); and
R 5 and R 6 each independently represent hydrogen, (C 1 -C 35 )-alkyl, singly or multiply oxygen-interrupted (Ci-C3 5 )-alkyl, aryl, aryloxy, (Ci-C3 5 )-alkoxy, monohydroxy-(C 1 -C 35 )-alkyl or polyhydroxy-(C 1 -C 35 )-alkyl; where R 5 and R 6 each have identical or different meanings within a molecule of formula (I); and where when R 5 and R 6 have different meanings within a molecule of formula (I) these different meanings are randomly distributed or regions of respectively identical meanings follow each other;
U represents hydrogen, hydroxyl, amino, mono-(Ci-C3 5 )-alkylamino, N 1 N- di-(Ci-C 3 5)-alkylamino, (Ci-C 3 5)-alkyl, aryl, aryloxy, (Ci-C 3 5)-alkoxy, monohydroxy-(C 1 -C 35 )-alkyl, polyhydroxy-(C 1 -C 35 )-alkyl or (C 1 -C 35 )-alkyl- aryloxy;
G 1 represents trifluoromethyl; cyclo-(C 3 -C 8 )-alkyl; aryl; halogen; cyano; nitro; hydroxyl; (Ci-C3 5 )-alkoxy; (Ci-C3 5 )-alkoxycarbonyl; aryloxy; (C2-C35)- acyl; arylcarbonyl, (C 2 -C 3 5)-acyloxy; arylcarbonyloxy; (C 2 -C 3 5)-acylamino; (Ci-C3 5 )-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-monocyclo-(C3-C 8 )-alkyl-carbamoyl; N-mono-(Ci-C 3 5)-alkyl- carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C3 5 )-alkyl- carbamoyl; N-monoaryl-carbamoyl; N,N-diaryl-carbamoyl; N-monocyclo- (C3-C8)-alkyl-N-monoarylcarbamoyl; N-mono-(Ci-C35)-alkyl-N- monoarylcarbannoyl; (C 1 -C 35 )-alkoxycarbonyl; aryloxycarbonyl; amino; monocyclo-(C3-C8)-alkyl-amino; mono-(Ci-C3 5 )-alkyl-amino; di(cyclo)-(C3- C 8 )-alkyl-amino; monoaryl-amino; diarylamino; monocyclo-(C3-C8)- alkylmonoarylamino; mono-(C 1 -C 35 )-alkylmonoaryl-amino; aminothiocarbonylamino; aminocarbonylamino; sulfamoyl; N-monocyclo- (C3-C8)-alkyl-sulfamoyl; N-mono-(Ci-C3 5 )-alkyl-sulfamoyl; N,N-dicyclo-(C3- C 8 )-alkyl-sulfamoyl; N,N-di-(C 1 -C 35 )-alkyl-sulfamoyl; N-monoaryl-sulfamoyl; N,N-diaryl-sulfamoyl; N-monocyclo-(C3-C8)-alkyl-N-nnonoarylsulfannoyl; N- mono-(Ci-C 3 5)-alkyl-N-monoarylsulfamoyl; aminosulfonylamino; (C1-C35)- alkylthio; arylthio; (C 1 -C 35 )-alkylsulfonyl or arylsulfonyl;
G 2 represents (C2-C3 5 )-alkoxy; (C2-C3 5 )-alkoxycarbonyl; (C2-C3 5 )-acyl; (C2- C 3 5)-acyloxy; (C 2 -C 3 5)-acylamino; (C 2 -C 3 5)-alkylsulfonylamino; N-mono-(C 2 - C3 5 )-alkyl-carbamoyl; N,N-di-(C2-C3 5 )-alkyl-carbamoyl; N-mono-(C2-C3 5 )- alkyl-N-monoarylcarbamoyl; (C 2 -C 35 )-alkoxycarbonyl; mono-(C 2 -C 35 )-alkyl- amino; mono-(C2-C3 5 )-alkylmonoaryl-amino; N-mono-(C2-C3 5 )-alkyl- sulfamoyl; N,N-di-(C 2 -C 3 5)-alkyl-sulfamoyl; N-mono-(C 2 -C 3 5)-alkyl-N- monoarylsulfamoyl; (C2-C3 5 )-alkylthio or (C2-C3 5 )-alkylsulfonyl wherein the alkyl radical is interrupted by one or more hetero atoms;
G 3 represents cyclo-(C 3 -C 8 )-alkyl; (C 1 -C 35 )-alkoxy; (C 1 -C 35 )-alkoxycarbonyl; (C 2 -C 3 5)-acyl; (C 2 -C 3 5)-acyloxy; (C 2 -C 3 5)-acylamino; (C1-C35)- alkylsulfonylamino; N-monocyclo-(C3-C8)-alkyl-carbamoyl; N-mono-(Ci- C3 5 )-alkyl-carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C3 5 )- alkyl-carbamoyl; N-monocyclo-(C3-C8)-alkyl-N-monoarylcarbamoyl; N- mono-(Ci-C3 5 )-alkyl-N-monoarylcarbamoyl; (Ci-C3 5 )-alkoxycarbonyl; monocyclo-(C3-C 8 )-alkyl-amino; mono-(Ci-C 3 5)-alkyl-amino; di(cyclo)-(C 3 - C 8 )-alkyl-amino; monocyclo-(C3-C8)-alkylmonoarylamino; mono-(Ci-C3 5 )- alkylmonoaryl-amino; N-monocyclo-(C3-C8)-alkyl-sulfamoyl; N-mono- (Ci-C 3 5)-alkyl-sulfamoyl; N,N-dicyclo-(C 3 -C 8 )-alkyl-sulfamoyl; N,N-di-(Ci- C 3 5)-alkyl-sulfamoyl; N-monocyclo-(C3-C 8 )-alkyl-N-monoarylsulfamoyl; N- mono-(Ci-C3 5 )-alkyl-N-monoarylsulfamoyl; (Ci-C3 5 )-alkylthio or (C1-C35)- alkylsulfonyl wherein the alkyl radical is substituted by a substituent G 1 ;
G 4 represents G 2 wherein the alkyl radical is substituted by a substituent 1 .
G ';
Ar represents a group of formula (5) or (6)
where
R 7 to R 13 each independently have one of the meanings G 11 or G 12 or represent a group of formula (7) or (8)
where
G 11 represents hydrogen, (C 1 -C 35 )-alkyl; thfluoromethyl; cyclo-(C 3 -C 8 )-alkyl; aryl; heteroaryl; heterocycloalkyl; halogen; cyano; nitro; hydroxyl; (C1-C35)- alkoxy; aryloxy; (C 2 -C 35 )-acyl; cyclo-(C 3 -C 8 )-alkylcarbonyl, arylcarbonyl, (C 2 -C 3 5)-acyloxy; arylcarbonyloxy; (C 2 -C 3 5)-acylamino; (C1-C35)- alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N- monocyclo-(C 3 -C 8 )-alkyl-carbamoyl; N-mono-(Ci-C 3 5)-alkyl-carbamoyl; N,N-dicyclo-(C3-C8)-alkyl-carbamoyl; N,N-di-(Ci-C3 5 )-alkyl-carbamoyl; N- monoaryl-carbamoyl; N,N-diaryl-carbamoyl; N-monocyclo-(C3-C8)-alkyl-N- monoarylcarbamoyl; N-mono-(Ci-C3 5 )-alkyl-N-monoarylcarbamoyl; (d- C 35 )-alkoxycarbonyl; aryloxycarbonyl; amino; monocyclo-(C 3 -C 8 )-alkyl- amino; mono-(Ci-C3 5 )-alkyl-amino; di(cyclo)-(C3-C8)-alkyl-amino; di-(Ci- C 3 5)-alkyl-amino; monoaryl-amino; diaryl-amino; monocyclo-(C 3 -C 8 )- alkylmonoarylamino; mono-(Ci-C3 5 )-alkylmonoaryl-amino; aminothiocarbonylamino; aminocarbonylamino; sulfamoyl; N-monocyclo- (C3-C8)-alkyl-sulfamoyl; N-mono-(Ci-C3 5 )-alkyl-sulfamoyl; N,N-dicyclo-(C3- C 8 )-alkyl-sulfamoyl; N,N-di-(Ci-C 3 5)-alkyl-sulfamoyl; N-monoaryl-sulfamoyl; N,N-diaryl-sulfamoyl; N-monocyclo-(C 3 -C 8 )-alkyl-N-monoarylsulfamoyl; N- mono-(Ci-C 3 5)-alkyl-N-monoarylsulfamoyl; aminosulfonylamino; (C1-C35)- alkylthio; arylthio; (C 1 -C 35 )-alkylsulfonyl or arylsulfonyl; G 12 represents (C 2 -C 3 5)-alkyl; (C 2 -C 3 5)-alkoxy; (C 2 -C 35 )-acyl; (C 2 -C 35 )- acyloxy; (C 2 -C 35 )-acylamino; (C 2 -C 35 )-alkylsulfonylamino; N-mono-(C 2 -C 35 )- a I kyl -carbamoyl; N,N-di-(C 2 -C 3 5)-alkyl-carbamoyl; N-mono-(C 2 -C 35 )-alkyl-N- monoarylcarbamoyl; (C 2 -C 35 )-alkoxycarbonyl; mono-(C 2 -C 3 5)-alkyl-amino; di-(C 2 -C 35 )-alkyl-annino; mono-(C 2 -C 3 5)-alkylmonoaryl-amino; N-mono-(C 2 - C 35 )-alkyl-sulfamoyl; N,N-di-(C 2 -C 35 )-alkyl-sulfannoyl; N-mono-(C 2 -C 35 )- alkyl-N-monoarylsulfamoyl; (C 2 -C 35 )-alkylthio or
(C 2 -C 35 )-alkylsulfonyl where the alkyl radical is interrupted by one or more hetero atoms;
R 14 to R 16 each independently represent cyclo-(C 5 -C 6 )-alkyl; heterocycloalkyl; heteroaryl; aryl, (C 1 -C 35 )-alkyl; (C 2 -C 35 )-alkyl interrupted by one or more hetero atoms; (C 1 -C 35 )-alkyl substituted by one or more of the substituents G 13 ; or (C 2 -C 35 )-alkyl interrupted by one or more hetero atoms and substituted by one or more of the substituents G 13 , and R 14 and R 15 may each also represent hydrogen;
G 13 represents thfluoromethyl; cyclo-(C 3 -C 8 )-alkyl; aryl; heteroaryl; heterocycloalkyl; halogen; cyano; nitro; hydroxyl; (C 1 -C 35 )-alkoxy; aryloxy; (C 2 -C 35 )-acyl; arylcarbonyl, (C 2 -C 35 )-acyloxy; arylcarbonyloxy; (C 2 -C 35 )- acylamino; amino; monocyclo-(C 3 -C 8 )-alkyl-amino; mono-(C 1 -C 35 )-alkyl- amino; di(cyclo)-(C 3 -C8)-alkyl-amino; di-(C 1 -C 35 )-alkyl-amino; monoarylamino; diarylamino; monocyclo-(C 3 -C8)-alkylmonoarylamino; mono-(C 1 -C 35 )-alkylmonoarylamino; (C 1 -C 35 )-alkylthio; arylthio; (C 1 -C 35 )- alkylsulfonyl or arylsulfonyl; and
aryl represents a group of formula (9) or (10)
where
R 17 to R 23 each independently represent hydrogen; (Ci-Ci 2 )-alkyl; cyclo-
(C 3 -C 8 )-alkyl; thfluoromethyl; halogen; cyano; nitro; hydroxyl; (CrC 6 )- alkoxy; (C 2 -C 6 )-acyl;
(C 2 -C 6 )-acylamino; (C 1 -C 6 )-alkylsulfonylamino; carbamoyl; N-mono-(C 1 -C 6 )- a I kyl -carbamoyl; N,N-di-(Ci-C6)-alkyl-carbamoyl; amino; N-mono-(Ci-C6)- alkyl-amino; di-N,N-(Ci-C6)-alkyl-amino; aminocarbonylamino; sulfamoyl; N-mono-(Ci-C6)-alkyl-sulfamoyl; di-N,N-(Ci-C6)-alkyl-sulfamoyl; aminosulfonylamino; (C 1 -C 6 )-alkylthio or (Ci-C6)-alkylsulfonyl.
In the abovementioned definitions, alkyl groups may be straight chain or branched and be for example methyl, ethyl, n-propyl, isopropyl, n-butyl or isobutyl, but also hexyl, such as n-hexyl, heptyl, such as n-heptyl, octyl, such as n-octyl and isooctyl, nonyl, such as n-nonyl, decyl, such as n-decyl, dodecyl, such as n-dodecyl, hexadecyl, such as n-hexadecyl, or octadecyl, such as n-octadecyl. The same holds mutatis mutandis for alkoxy and alkylthio groups.
When alkyl groups are interrupted by one or more hetero atoms, hetero atoms are oxygen, sulfur and also the group -NR 24 , where R 24 represents (C 1 -C 6 )-alkyl, monohydroxy- (C 1 -C 6 )-alkyl, polyhydroxy-(C 1 -C 6 )-alkyl, (Cr C 4 )-alkyloxy-(C 1 -C 6 )-alkyl, phenoxy-(C 1 -C 6 )-alkyl or phenyl. Cycloalkyl groups are in particular cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl. Heterocycloalkyl has in particular 3 to 8 ring members and preferably represents pyrrolidine, piperidine, morpholine or piperazine.
Heteroaryl has in particular 5 or 6 ring members and is preferably pyridine, pyrimidine, pyridazine, pyrazine, pyrrole, imidazole, pyrazole, 1 ,2,4- thiadiazole, 1 ,2,4-triazole, tetrazole, thiophene, thiazole, isothiazole, 1 ,3,4- thiadiazole, furan, oxazole or isoxazole. Halogen is in particular fluorine, chlorine or bromine.
Preferred dyes of formula (I) according to the present invention have a symmetrical substitution pattern wherein X, Y, Z and T are identical or wherein X and Z and Y and T are each identical pairs.
Particularly preferred dyes of formula (I) according to the present invention conform to formula (Ia) where
R 1 and R 2 each have identical or different meanings within a molecule of formula (Ia) and each independently represent Ar; cyclo-(C 5 -C 6 )-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C 1 -C 18 )-alkyl; (C 2 -Ci 8 )-alkyl interrupted by one or more hetero atoms; (C 2 -C 18 )-alkyl substituted by one or more substituents G 14 ; (C2-C18)- alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G 14 ; or a group of formula (3a)
and R 1 may also represent hydrogen; wherein
R i4' represents hydrogen or (C 1 -C 35 )-alkyl;
w represents 1 , 2 or 3;
s represents a rational number from 0.1 to 100 and has identical or different meanings within a molecule of formula (I);
R 5 and R 6 each independently represent hydrogen or (C 1 -C 35 )-alkyl; where R 5 and R 6 within a molecule of formula (I) each have identical or different meanings; and where when R 5 and R 6 have different meanings within a molecule of formula (I) these different meanings are randomly distributed or regions of respectively identical meanings follow each other;
U' represents hydrogen, (Ci-C3 5 )-alkyl, aryl, aryloxy, (Ci-C3 5 )-alkoxy or (Cr C 3 5)-alkyl-aryloxy;
G 14 represents thfluoromethyl; cyclo-(C 5 -C 6 )-alkyl; aryl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; hydroxyl;
(C 1 -C 18 )-alkoxy; (C 1 -C 18 )-alkoxycarbonyl; aryloxy; (C 2 -Ci 8 )-acyl, (C 2 -Ci 8 )- acyloxy or arylcarbonyl;
Ar represents a group of formula (5a) or (6a)
where
R 7 to R 9 each independently represent hydrogen; (C 1 -C 18 )-alkyl; trifluoromethyl; cyclo-(C 5 -C 6 )-alkyl; aryl; halogen; cyano; nitro; hydroxyl;
(C 1 -C 18 )-alkoxy; aryloxy; (C 2 -Ci 8 )-acyl; arylcarbonyl, (C 2 -Ci 8 )-acylamino; (C 2 -C 18 )-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C 1 -C 18 )-alkyl-carbamoyl; amino; mono-(C 1 -C 18 )-alkyl- amino; di-(C 1 -C 18 )-alkyl-amino; monoaryl-amino; mono-(C 1 -C 18 )- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C 1 -C 18 )- alkyl-sulfamoyl; aminosulfonylamino; (C 1 -C 18 )-alkylthio; arylthio; (C 1 -C 18 )- alkylsulfonyl or arylsulfonyl; and
R 10 to R 13 each independently represent hydrogen, (C 1 -C 18 )-alkyl or a group of formula (7a) or (8a)
where R 14 ' to R 16 each independently represent (C 5 -C 6 )-cycloalkyl; heterocycloalkyl having 5 or 6 ring members; heteroaryl having 5 or 6 ring members; aryl; (C 1 -C 18 )-alkyl; (C 2 -Ci 8 )-alkyl interrupted by one or more hetero atoms; (C 1 -C 18 )-alkyl substituted by one or more substituents G 15 ; or (C 2 -Ci 8 )-alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G 15 ; and R 14 and R 15 may each also represent hydrogen;
G 15 represents thfluoromethyl; cyclo-(C 5 -C 6 )-alkyl; aryl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; halogen; cyano; nitro; hydroxyl; (C 1 -C 18 )-alkoxy; aryloxy; (C 2 -Ci 8 )-acyl; arylcarbonyl, di-(C 2 -C 18 )-alkyl-amino; monoaryl-amino; diaryl-amino; mono-(C 1 -C 18 )- alkylmonoaryl-amino; (C 1 -C 18 )-alkylthio; arylthio; (C 1 -C 18 )-alkylsulfonyl or arylsulfonyl; and
aryl represents a group of formula (9a) or (10a)
where
R > 17' to R > 19' each independently represent hydrogen; (Ci-Ci 2 )-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C 1 -C 6 )-alkoxy; (C 2 -C 6 )- acyl; amino; (C 2 -C6)-acyl-amino, mono-(Ci-C6)-alkyl-amino; sulfamoyl; carbamoyl or (C 1 -C 6 )-alkylthio; and R 20 to R 23 each independently represent hydrogen or (Ci-CβJ-alkyl.
In particularly preferred dyes of formula (Ia)
R 1 represents hydrogen or (Ci-C 4 )-alkyl; and
R 2 represents (Ci-Ci 2 )-alkyl; (Ci-C 4 )-alkyl substituted by (Ci-C 4 )-alkoxy, cyclohexyl or hydroxyl; cyclohexyl; phenyl; phenyl substituted by fluorine; a group of formula (7a) where R 14 and R 15 each represent (Ci-C 4 )-alkyl or a group of formula (8a) where R 16 represents (Ci-C 4 )-alkyl; or a group of formula (3a) where
R 4 represents hydrogen or methyl;
R 5 represents hydrogen or methyl;
U' represents (Ci-Cio)-alkoxy; v represents 2; and t represents a number from 8 to 12.
Examples of dyes of formula (Ia) are the dyes of formulae (Ia1 ) to (Ia28)
(Ia13) (Ia14)
where
R 3 has identical or different meanings within a molecule of formula (Ib) and represents Ar; cyclo-(C 5 -C 6 )-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C 1 -C 18 )-alkyl; (C 2 -Ci 8 )-alkyl interrupted by one or more hetero atoms; (C 2 -C 18 )-alkyl substituted by one or more substituents G 14 ; or (C 2 -Ci 8 )-alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G 14 ; where G 14 is as defined above;
Ar represents a group of formula (5a) or (6a)
where
R to R 9' each independently represent hydrogen; (C 1 -C 18 )-alkyl; trifluoromethyl; cyclo-(C 5 -C 6 )-alkyl; aryl; halogen; cyano; nitro; hydroxyl;
(C 1 -C 18 )-alkoxy; aryloxy; (C2-Ci 8 )-acyl; arylcarbonyl, (C2-Ci8)-acylamino;
(C 1 -C 18 )-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C 1 -C 18 )-alkyl-carbamoyl; amino; mono-(C 1 -C 18 )-alkyl- amino; di-(C 1 -C 18 )-alkyl-amino; monoaryl-amino; mono-(C 1 -C 18 )- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C 1 -C 18 )- alkyl-sulfamoyl; aminosulfonylamino; (C 1 -C 18 )-alkylthio; arylthio; (C 1 -C 18 )- alkylsulfonyl or arylsulfonyl; and R 10 to R 13 each independently represent hydrogen, (C 1 -C 18 )-alkyl;
aryl represents a group of formula (9a) or (10a)
where
R > 17 ' to R > 19 ' each independently represent hydrogen; (Ci-Ci 2 )-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C 1 -C 6 )-alkoxy; (C 2 -C 6 )- acyl; amino; (C2-C6)-acyl-amino, mono-(Ci-C6)-alkyl-amino; sulfamoyl; carbamoyl or (C 1 -C 6 )-alkylthio; and R 20 ' i t.o R 23 ' each independently represent hydrogen or (C 1 -C 6 )-alkyl.
In particularly preferred dyes of formula (Ib) R 3 represents (Ci-Ci2)-alkyl; (C 1 -C 12 )-alkyl interrupted by two oxygen atoms; (C 1 -C 4 )-alkyl substituted by trifluoromethyl, cyano, chlorine, one or two hydroxyl groups, phenyl, phenoxy or (Ci-C 8 )-alkoxycarbonyl; cyclopentyl; cyclohexyl; phenyl; fluorophenyl or naphthyl.
Further particularly preferred dyes of formula (I) according to the present invention conform to formula (Ic)
where
R 1" , R 2 and R 3 each have identical or different meanings within a molecule of formula (Ic) and each independently represent Ar; cyclo-(C 5 -C 6 )-alkyl; heteroaryl having 5 or 6 ring members; heterocycloalkyl having 5 or 6 ring members; (C 1 -C 18 )-alkyl; (C2-Cis)-alkyl interrupted by one or more hetero atoms; (C 1 -C 18 )-alkyl substituted by one or more substituents G 14 ; (C 2 -Ci 8 )- alkyl interrupted by one or more hetero atoms and substituted by one or more substituents G 14 ; and R 1 may also represent hydrogen; where G 14 is as defined above;
Ar represents a group of formula (5a) or (6a)
where R to R 9' each independently represent hydrogen; (C 1 -C 18 )-alkyl; trifluoromethyl; cyclo-(C 5 -C 6 )-alkyl; aryl; halogen; cyano; nitro; hydroxyl;
(C 1 -C 18 )-alkoxy; aryloxy; (C 2 -C 18 )-acyl; arylcarbonyl, (C2-Ci8)-acylamino;
(C 1 -C 18 )-alkylsulfonylamino; arylsulfonylamino; arylcarbonylamino; carbamoyl; N-mono-(C 1 -C 18 )-alkyl-carbamoyl; amino; mono-(C 1 -C 18 )-alkyl- amino; di-(C 1 -C 18 )-alkyl-amino; monoaryl-amino; mono-(C 1 -C 18 )- alkylmonoaryl-amino; aminocarbonylamino; sulfamoyl; N-mono-(C 1 -C 18 )- alkyl-sulfamoyl; aminosulfonylamino; (C 1 -C 18 )-alkylthio; arylthio; (C 1 -C 18 )- alkylsulfonyl or arylsulfonyl; and R 10 to R 13 each independently represent hydrogen, (C 1 -C 18 )-alkyl;
aryl represents a group of formula (9a) or (10a)
where
R 17 to R 19 each independently represent hydrogen; (C 1 -C 12 )-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C 1 -C 6 )-alkoxy; (C 2 -C 6 )- acyl; amino; (C2-C6)-acyl-amino, mono-(Ci-C6)-alkylamino; sulfamoyl; carbamoyl or (C 1 -C 6 )-alkylthio; and R 20 to R 23 each independently represent hydrogen or (C 1 -C 6 )-alkyl.
In particularly preferred dyes of formula (Ic)
R ,1 " represents hydrogen;
R 2 represents (C 1 -C 10 )-alkyl; and R 3 " rreepprreesseennttss (C 1 -C 12 )--alkkyl;; (C 1 -C 4 -)alkyl substituted by trifluoromethyl, hydroxyl or (Ci-C 4 )-alkoxycarbonyl; phenyl; fluorophenyl or naphthyl.
(Ic2)
(Ic4) (Ic6)
The dyes of formula (I) are obtainable by condensing the compound of formula (II)
with a compound of formula (III) or (IV) or with a mixture of the compounds offormulae(lll)and (IV) N 3
R (III) S (IV)
where R 1 to R 3 are each as defined above.
This condensation reaction is particularly carried out at a temperature of 50-200 0 C, more preferably 50-180 0 C, in the absence or presence of a base such as pyridine, piperidine, sodium acetate, potassium carbonate or aluminum chloride and preferably in the absence of moisture. The reaction medium used is preferably an inert solvent or a mixture of inert solvents. Useful solvents include chlorinated solvents such as chlorobenzene or 1 ,2- dichlorobenzene, alcohols such as for example n-pentanol, 1 -methoxy-2- propanol, 2-ethylhexanol, 2-methyl-1 -butanol, isoamyl alcohol, benzyl alcohol, cyclohexanol, glycols and derivatives thereof such as for example ethylene glycol diethyl ether, ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monobutyl ether, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol monomethyl ether, ethylene glycol, diethylene glycol monoethyl ether, dipropylene glycol, ethers such as for example dibutyl ether, diisobutyl ether, diisoamyl ether, di-n-amyl ether, or further polar or apolar inert solvents such as for example ethylbenzene, anisole, N,N-dimethylformamide, N,N-dimethylacetamide, sulfolane, N- methyl pyrrol idone, toluene, 1 ,2-xylene, 1 ,3-xylene, 1 ,4-xylene or mixtures thereof. Such reactions are known for example from DE 3514077 and EP 0 710 706 A2.
In the case of asymmetrically substituted dyes of formula (I), the condensation reactions can be carried out in succession with or without intervening isolation of the intermediates formed.
The compound of formula (II) is obtainable by reacting a compound of formula (V) with 2,4,6-trichloro-1 ,3,5-triazine. This condensation reaction is preferably carried out as indicated above for the reaction of the compound of formula (II).
The compound of formula (V) is obtainable as Colour Index dye C.I. Pigment Red 177 and commercially. Similarly, 2,4,6-trichloro-1 ,3,5-triazine is commercially available, for example under the name cyanuric chloride.
Similarly, the compounds of formulae (III) and (IV) are commercially available or are obtainable by following known methods. Useful compounds of formula (III) include particularly the products sold under the brand name of Jeffamine ® by Huntsman, The Woodlands, TX, USA. Examples are Jeffamine M-600, Jeffamine M-2005, Jeffamine M- 2070, Jeffamine M-1000, Jeffamine D-230, Jeffamine D-400, Jeffamine D- 2000, Jeffamine D-4000, Jeffamine HK-511 , Jeffamine ED-600, Jeffamine ED-900, Jeffamine ED-2003, Jeffamine ED-2001 , Jeffamine EDR-148, Jeffamine EDR-176, Jeffamine T-403, Jeffamine M-3000, Jeffamine T- 5000, Jeffamine XTJ-435 and Jeffamine XTJ-436. When these compounds are used, the dyes of formula (I) according to the present invention form statistical mixtures.
After synthesis, the dyes of formula (I) can be isolated by filtration, extraction or evaporation and, if necessary, drying. However, they can also be used without further workup.
The dyes of formula (I) according to the present invention can be used directly for polymer coloration, or they are subjected to a finishing (conditioning) operation to convert them into a salable dye preparation. Finishing can be effected proceeding from a single dye of formula (I) or from a mixture of two or more dyes of formula (I) or mixtures of one or more of the dyes of formula (I) and dyes of other dye classes, for example pigments or solvent dyes, if appropriate with the assistance of auxiliaries, for example surface modifiers and dispersants, by dispersing, suspending or dissolving in a liquid or solid carrier material and also if appropriate standardizing to a desired color strength and a desired hue and if appropriate drying the preparation thus obtained.
Preparations comprising dyes of formula (I) may further comprise auxiliaries for modifying viscosity/flowability.
Useful auxiliaries of this kind are described for example in US 6,605,126.
Preferred examples are ethylene glycols, propylene glycols, polyether polyols, polyester polyols, lactones and carbonic esters.
The present invention accordingly also provides dye preparations comprising one or more dyes of formula (I) and also one or more auxiliaries for modifying viscosity/flowability.
These dye preparations preferably contain one or more dyes of formula (I) in amounts of 5% to 100% by weight and one or more auxiliaries for modifying viscosity/flowability in amounts of 0% to 95% by weight, all based on the dye preparation.
The present invention further provides for the use of the dyes of formula (I) for coloring a polymer.
A possible procedure here is for the dyes of formula (I) to be admixed to the polymer.
In addition, dyes of formula (I) according to the present invention can also be used in the form of masterbatches. Masterbatches are dye concentrates consisting of carrier materials and colorants, the colorants being present in higher concentration than in the final use and the carrier materials being constituted such that they have compatibility with the materials to be colored. The carrier materials used can be polymers, for example polyolefins, polyurethane, polyvinyl chloride, polyesters, polyamides, polycarbonates or polystyrene. Preferred polymers are polyolefins, for example polyethylene or polypropylene and copolymers with polyolefins. Useful carrier materials further include paraffin oils and polyglycols. The dye masterbatches are characterized in particular in that they contain one or more dyes of formula (I) according to the present invention in amounts of 5% to 60% by weight and one or more carrier materials in amounts of 40% to 95% by weight.
The dyes of formula (I) have advantages in bleed/migration fastness in polyolefin mass coloration in particular, compared with commercially available solvent dyes. These advantages are particularly noticeable in the coloration of polypropylene, polypropylene copolymers and polypropylene blends. To achieve good bleed fastnesses for the colored polymer, it is preferable to use compounds of formula (I) that have sufficiently high molar mass.
The examples hereinbelow serve to elucidate the invention without restricting the invention to these examples. Parts and percentages are by weight, unless otherwise stated. Parts by weight relate to parts by volume as the kilogram relates to the liter.
Example 1 a) A mixture of 20.0 parts of 1 ,4-dioxane, 13.5 parts of the compound of formula (V) and 55.0 parts of cyanuhc chloride (from Fluka) is stirred at 100 0 C for 10 hours, cooled down and filtered off, and the isolated precipitate is purified with 2-propanol and dried to leave the compound of formula (II).
b) A mixture of 10.0 parts of the compound of formula (II), 15.0 parts of 2- ethylhexylamine (from Merck) and 75.0 parts of 1 ,4-dioxane is stirred under reflux at the boiling temperature of the mixture for 7 hours, cooled down and admixed with methanol, and the isolated precipitate is washed neutral with water and dried to leave the compound of formula (Ia3).
c) 0.9 g of the dye obtained as per b) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell). This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leisthtz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C 1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN14469-4, a high color stability to heat as per EN12877-2 and high light fastness as per EN ISO 105-B01.
Example 2 a) A mixture of 8.0 parts of compound of formula (II), 8.3 parts of 3- methoxypropylamine (from Aldrich) and 70.0 parts of 1 ,4-dioxane is stirred under reflux at the boiling temperature of the mixture for 8 hours, cooled down and admixed with water, and the isolated precipitate is purified with methanol and dried to leave the compound of formula (Ia1 ).
b) 0.8 g of the dye obtained as per a) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell).
This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leisthtz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C
1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN 14469-4, a very good color stability to heat as per EN12877-2 and very good light fastness as per
EN ISO 105-B01.
Example 3 a) A mixture of 10.0 parts of compound of formula (II), 25.0 parts of dodecanethiol (from Aldrich), 7.8 parts of anhydrous potassium carbonate and 75.0 parts of 1 ,4-dioxane is stirred under reflux at the boiling temperature of the mixture for 10 hours, cooled down and admixed with methanol. The precipitate formed is filtered off, stirred with water until neutral and subsequently purified with methanol and dried to leave the compound of formula (Ib14).
b) 1.0 g of the dye obtained as per a) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell).
This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leistritz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C 1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN14469-4, a high color stability to heat as per EN 12877-2 and high light fastness as per EN ISO 105-B01.
Example 4 a) A mixture of 7.5 parts of compound of formula (II), 6.8 parts of hexanethiol (from Aldrich), 7.7 parts of anhydrous potassium carbonate and 75.0 parts of sulfolane is stirred at 125-140°C for 10 hours, cooled down and admixed with methanol. The precipitate formed is filtered off, stirred with water until neutral and subsequently purified with methanol and dried to leave the compound of formula (IbI O).
b) 1.0 g of the dye obtained as per a) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell). This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leistritz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C
1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN14469-4, a high color stability to heat as per EN 12877-2 and high light fastness as per EN ISO 105-B01.
Example 5 a) A mixture of 10.0 parts of compound of formula (II), 22.7 parts of dodecylamine (Aldrich) and 75.0 parts of 1 ,4-dioxane is stirred under reflux at the boiling temperature of the mixture for 2 hours, cooled down and admixed with methanol. The isolated precipitate is stirred with water until neutral and subsequently purified with methanol and dried to leave the compound of formula (Ia27).
b) 1.0 g of the dye obtained as per a) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell). This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leistritz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C 1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN14469-4, a high color stability to heat as per EN 12877-2 and high light fastness as per EN ISO 105-B01.
Example 6 a) A mixture of 7.5 parts of compound of formula (II), 9.6 parts of butylamine (from Aldrich) and 100 parts of 1 ,4-dioxane is stirred at 100°C under superatmospheric pressure (1.3 bar) for 7 hours, cooled down and admixed with methanol. The resulting precipitate is stirred with water until neutral and subsequently purified with methanol and dried to leave the compound of formula (Ia2).
b) 1.0 g of the dye obtained as per a) is comminuted in a mortar and added to altogether 2 kg of polypropylene pellet (Moplen RP340R from Basell). This mixture is mulled on a roller mill until homogeneous and then extruded in a twin-screw extruder (ZSE 18HP-D40 from Leisthtz) and pelletized. The pellet obtained can be processed in an injection-molding machine (420 0 C 1000-100 from Arburg) to form transparent yellow sample plaques. The dye has high bleed fastness as per prEN14469-4, a high color stability to heat as per EN 12877-2 and high light fastness as per EN ISO 105-B01.
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