WO2010060849A2 - Dyes for polymer coloration, their preparation and their use - Google Patents

Dyes for polymer coloration, their preparation and their use Download PDF

Info

Publication number
WO2010060849A2
WO2010060849A2 PCT/EP2009/065430 EP2009065430W WO2010060849A2 WO 2010060849 A2 WO2010060849 A2 WO 2010060849A2 EP 2009065430 W EP2009065430 W EP 2009065430W WO 2010060849 A2 WO2010060849 A2 WO 2010060849A2
Authority
WO
WIPO (PCT)
Prior art keywords
alkyl
amino
mono
formula
carbamoyl
Prior art date
Application number
PCT/EP2009/065430
Other languages
French (fr)
Other versions
WO2010060849A3 (en
Inventor
Roxana Barbieru
Werner Russ
Carsten Harfmann
Original Assignee
Dystar Colours Deutschland Gmbh
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Dystar Colours Deutschland Gmbh filed Critical Dystar Colours Deutschland Gmbh
Priority to BRPI0921179A priority Critical patent/BRPI0921179A2/en
Priority to EP09759930A priority patent/EP2370522A2/en
Priority to JP2011536859A priority patent/JP2012509950A/en
Priority to CN2009801466171A priority patent/CN102224203A/en
Publication of WO2010060849A2 publication Critical patent/WO2010060849A2/en
Publication of WO2010060849A3 publication Critical patent/WO2010060849A3/en

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C09—DYES; PAINTS; POLISHES; NATURAL RESINS; ADHESIVES; COMPOSITIONS NOT OTHERWISE PROVIDED FOR; APPLICATIONS OF MATERIALS NOT OTHERWISE PROVIDED FOR
    • C09B—ORGANIC DYES OR CLOSELY-RELATED COMPOUNDS FOR PRODUCING DYES, e.g. PIGMENTS; MORDANTS; LAKES
    • C09B1/00—Dyes with anthracene nucleus not condensed with any other ring
    • C09B1/005—Di-anthraquinonyl and derivative compounds
    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
    • C08K5/00—Use of organic ingredients
    • C08K5/0008—Organic ingredients according to more than one of the "one dot" groups of C08K5/01 - C08K5/59
    • C08K5/0041—Optical brightening agents, organic pigments

Definitions

  • 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.
  • 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.
  • 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.
  • 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.
  • 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)
  • 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);
  • 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)-alky
  • 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-
  • 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-
  • G 4 represents G 2 wherein the alkyl radical is substituted by a substituent 1 .
  • Ar represents a group of formula (5) or (6)
  • 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)
  • 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
  • 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-
  • aryl represents a group of formula (9) or (10)
  • R 17 to R 23 each independently represent hydrogen; (Ci-Ci 2 )-alkyl; cyclo-
  • 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.
  • decyl such as n-decyl
  • dodecyl such as n-dodecyl
  • hexadecyl such as n-he
  • 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.
  • 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)
  • R 1 may also represent hydrogen
  • R i4' represents hydrogen or (C 1 -C 35 )-alkyl
  • w 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;
  • Ar represents a group of formula (5a) or (6a)
  • 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;
  • R 10 to R 13 each independently represent hydrogen, (C 1 -C 18 )-alkyl or a group of formula (7a) or (8a)
  • 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)
  • 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-C ⁇ J-alkyl.
  • R 1 represents hydrogen or (Ci-C 4 )-alkyl
  • 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
  • dyes of formula (Ia) are the dyes of formulae (Ia1 ) to (Ia28)
  • 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)
  • 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;
  • aryl represents a group of formula (9a) or (10a)
  • 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.
  • 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.
  • 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)
  • 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;
  • aryl represents a group of formula (9a) or (10a)
  • 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.
  • 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.
  • the dyes of formula (I) are obtainable by condensing the compound of formula (II)
  • 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-
  • 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.
  • 2,4,6-trichloro-1 ,3,5-triazine is commercially available, for example under the name cyanuric chloride.
  • 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.
  • the dyes of formula (I) according to the present invention form statistical mixtures.
  • 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.
  • auxiliaries for example surface modifiers and dispersants
  • Preparations comprising dyes of formula (I) may further comprise auxiliaries for modifying viscosity/flowability.
  • 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.
  • 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.
  • Example 1 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).
  • 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
  • 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.
  • 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.
  • 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).
  • 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.

Abstract

The present invention relates to a compound of formula (I) where X, Y, S and T are each as defined in claim 1, to its preparation and to its use.

Description

Dyes for polymer coloration, their preparation and their use
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)
Figure imgf000003_0001
where X, Y, Z and T each independently represent a group of formula (1 ) or (2)
Figure imgf000003_0002
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)
Figure imgf000004_0001
and R1 may also represent hydrogen; where
R 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- monoarylcarbannoyl; (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-(C1-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-(C1-C35)-alkyl-sulfamoyl; N-monoaryl-sulfamoyl; N,N-diaryl-sulfamoyl; N-monocyclo-(C3-C8)-alkyl-N-nnonoarylsulfannoyl; N- mono-(Ci-C35)-alkyl-N-monoarylsulfamoyl; 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 1 .
G ';
Ar represents a group of formula (5) or (6)
Figure imgf000006_0001
where
R7 to R13 each independently have one of the meanings G11 or G12 or represent a group of formula (7) or (8)
Figure imgf000006_0002
where
G11 represents hydrogen, (C1-C35)-alkyl; thfluoromethyl; 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)- a I kyl -carbamoyl; N,N-di-(C2-C35)-alkyl-carbamoyl; N-mono-(C2-C35)-alkyl-N- monoarylcarbamoyl; (C2-C35)-alkoxycarbonyl; mono-(C2-C35)-alkyl-amino; di-(C2-C35)-alkyl-annino; mono-(C2-C35)-alkylmonoaryl-amino; N-mono-(C2- C35)-alkyl-sulfamoyl; N,N-di-(C2-C35)-alkyl-sulfannoyl; N-mono-(C2-C35)- alkyl-N-monoarylsulfamoyl; (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; (C1-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 thfluoromethyl; cyclo-(C3-C8)-alkyl; aryl; heteroaryl; heterocycloalkyl; halogen; cyano; nitro; hydroxyl; (C1-C35)-alkoxy; aryloxy; (C2-C35)-acyl; arylcarbonyl, (C2-C35)-acyloxy; arylcarbonyloxy; (C2-C35)- acylamino; amino; monocyclo-(C3-C8)-alkyl-amino; mono-(C1-C35)-alkyl- amino; di(cyclo)-(C3-C8)-alkyl-amino; di-(C1-C35)-alkyl-amino; monoarylamino; diarylamino; monocyclo-(C3-C8)-alkylmonoarylamino; mono-(C1-C35)-alkylmonoarylamino; (C1-C35)-alkylthio; arylthio; (C1-C35)- alkylsulfonyl or arylsulfonyl; and
aryl represents a group of formula (9) or (10)
Figure imgf000007_0001
where
R17 to R23 each independently represent hydrogen; (Ci-Ci2)-alkyl; cyclo-
(C3-C8)-alkyl; thfluoromethyl; halogen; cyano; nitro; hydroxyl; (CrC6)- alkoxy; (C2-C6)-acyl;
(C2-C6)-acylamino; (C1-C6)-alkylsulfonylamino; carbamoyl; N-mono-(C1-C6)- 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; (C1-C6)-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 -NR24, where R24 represents (C1-C6)-alkyl, monohydroxy- (C1-C6)-alkyl, polyhydroxy-(C1-C6)-alkyl, (Cr C4)-alkyloxy-(C1-C6)-alkyl, phenoxy-(C1-C6)-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)
Figure imgf000009_0001
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-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; or a group of formula (3a)
Figure imgf000009_0002
and R1 may also represent hydrogen; wherein
R i4' 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 (Cr 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-Ci8)- acyloxy or arylcarbonyl;
Ar represents a group of formula (5a) or (6a)
Figure imgf000010_0001
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; (C2-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 or a group of formula (7a) or (8a)
Figure imgf000010_0002
where R14' to R16 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-Ci8)-alkyl interrupted by one or more hetero atoms; (C1-C18)-alkyl substituted by one or more substituents G15; or (C2-Ci8)-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 thfluoromethyl; 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-Ci8)-acyl; arylcarbonyl, di-(C2-C18)-alkyl-amino; monoaryl-amino; diaryl-amino; mono-(C1-C18)- alkylmonoaryl-amino; (C1-C18)-alkylthio; arylthio; (C1-C18)-alkylsulfonyl or arylsulfonyl; and
aryl represents a group of formula (9a) or (10a)
Figure imgf000011_0001
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.
In particularly preferred dyes of formula (Ia)
R1 represents hydrogen or (Ci-C4)-alkyl; and
R2 represents (Ci-Ci2)-alkyl; (Ci-C4)-alkyl substituted by (Ci-C4)-alkoxy, cyclohexyl or hydroxyl; cyclohexyl; phenyl; phenyl substituted by fluorine; a group of formula (7a) where R14 and R15 each represent (Ci-C4)-alkyl or a group of formula (8a) where R16 represents (Ci-C4)-alkyl; or a group of formula (3a) where
R4 represents hydrogen or methyl;
R5 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)
Figure imgf000012_0001
Figure imgf000013_0001
Figure imgf000014_0001
Figure imgf000015_0001
(Ia13) (Ia14)
Figure imgf000016_0001
Figure imgf000017_0001
Figure imgf000018_0001
Figure imgf000019_0001
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; (C2-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 above;
Ar represents a group of formula (5a) or (6a)
Figure imgf000020_0001
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)
Figure imgf000020_0002
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 R 20' i t.o R23' each independently represent hydrogen or (C1-C6)-alkyl.
In particularly preferred dyes of formula (Ib) R3 represents (Ci-Ci2)-alkyl; (C1-C12)-alkyl interrupted by two oxygen atoms; (C1-C4)-alkyl substituted by trifluoromethyl, cyano, chlorine, one or two hydroxyl groups, phenyl, phenoxy or (Ci-C8)-alkoxycarbonyl; cyclopentyl; cyclohexyl; phenyl; fluorophenyl or naphthyl.
Figure imgf000021_0001
Figure imgf000022_0001
Figure imgf000023_0001
Figure imgf000024_0001
Figure imgf000025_0001
Further particularly preferred dyes of formula (I) according to the present invention conform to formula (Ic)
Figure imgf000026_0001
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-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; and R1 may also represent hydrogen; where G14 is as defined above;
Ar represents a group of formula (5a) or (6a)
Figure imgf000026_0002
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-C18)-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)
Figure imgf000027_0001
where
R17 to R19 each independently represent hydrogen; (C1-C12)-alkyl; trifluoromethyl; halogen; cyano; nitro; hydroxyl; (C1-C6)-alkoxy; (C2-C6)- acyl; amino; (C2-C6)-acyl-amino, mono-(Ci-C6)-alkylamino; sulfamoyl; carbamoyl or (C1-C6)-alkylthio; and R20 to R23 each independently represent hydrogen or (C1-C6)-alkyl.
In particularly preferred dyes of formula (Ic)
R ,1 " represents hydrogen;
R2 represents (C1-C10)-alkyl; and R3 " rreepprreesseennttss (C1-C12)--alkkyl;; (C1-C 4-)alkyl substituted by trifluoromethyl, hydroxyl or (Ci-C4)-alkoxycarbonyl; phenyl; fluorophenyl or naphthyl.
Figure imgf000027_0002
(Ic2)
Figure imgf000028_0001
(Ic4)
Figure imgf000028_0002
(Ic6)
Figure imgf000029_0001
The dyes of formula (I) are obtainable by condensing the compound of formula (II)
Figure imgf000029_0002
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 R1 to R3 are each as defined above.
This condensation reaction is particularly carried out at a temperature of 50-2000C, more preferably 50-1800C, 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)
Figure imgf000031_0001
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 1000C 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 (4200C 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 (4200C
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 (4200C 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 (4200C
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 (4200C 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 (4200C 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.

Claims

What is claimed is:-
1. A dye of formula (I)
Figure imgf000037_0001
(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)
Figure imgf000037_0002
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)
Figure imgf000040_0001
where
R7 to R13 each independently have one of the meanings G11 or G12 or represent a group of formula (7) or (8)
Figure imgf000040_0002
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)
Figure imgf000041_0001
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)
Figure imgf000042_0001
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)
Figure imgf000042_0002
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)
Figure imgf000043_0001
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)
Figure imgf000044_0001
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)
Figure imgf000044_0002
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)
Figure imgf000045_0001
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)
Figure imgf000045_0002
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)
Figure imgf000046_0001
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)
Figure imgf000046_0002
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)
Figure imgf000047_0001
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)
Figure imgf000047_0002
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)
Figure imgf000048_0001
with a compound of formula (III) or (IV) or with a mixture of the compounds of formulae (lll) and (IV)
Figure imgf000048_0002
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.
PCT/EP2009/065430 2008-11-26 2009-11-19 Dyes for polymer coloration, their preparation and their use WO2010060849A2 (en)

Priority Applications (4)

Application Number Priority Date Filing Date Title
BRPI0921179A BRPI0921179A2 (en) 2008-11-26 2009-11-19 dyes for polymer coloring, their preparation and use
EP09759930A EP2370522A2 (en) 2008-11-26 2009-11-19 Dyes for polymer coloration, their preparation and their use
JP2011536859A JP2012509950A (en) 2008-11-26 2009-11-19 Dyes for polymer coloring, methods for their preparation and their use
CN2009801466171A CN102224203A (en) 2008-11-26 2009-11-19 Dyes for polymer coloration, their preparation and their use

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
DE200810059110 DE102008059110A1 (en) 2008-11-26 2008-11-26 Dyes for polymer dyeing, process for their preparation and their use
DE102008059110.6 2008-11-26

Publications (2)

Publication Number Publication Date
WO2010060849A2 true WO2010060849A2 (en) 2010-06-03
WO2010060849A3 WO2010060849A3 (en) 2010-07-29

Family

ID=42114676

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/EP2009/065430 WO2010060849A2 (en) 2008-11-26 2009-11-19 Dyes for polymer coloration, their preparation and their use

Country Status (6)

Country Link
EP (1) EP2370522A2 (en)
JP (1) JP2012509950A (en)
CN (1) CN102224203A (en)
BR (1) BRPI0921179A2 (en)
DE (1) DE102008059110A1 (en)
WO (1) WO2010060849A2 (en)

Families Citing this family (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP5952228B2 (en) * 2013-07-01 2016-07-13 大日精化工業株式会社 Pigment colorant

Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2173812A (en) * 1983-10-18 1986-10-22 Toyo Ink Mfg Co Triazine dyes and pigments for use as pigment dispersants
US20070202272A1 (en) * 2005-07-01 2007-08-30 Toyo Ink Co., Ltd. Red colored film, red colored composition, color filter and liquid crystal display device

Family Cites Families (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
DE59007845D1 (en) 1989-10-10 1995-01-12 Ciba Geigy Ag New dianthraquinonyl compounds.
DE59408909D1 (en) 1993-10-13 1999-12-16 Ciba Sc Holding Ag New fluorescent dyes
JP3149707B2 (en) 1994-10-28 2001-03-26 東洋インキ製造株式会社 Pigment dispersion method and aqueous pigment dispersion
JPH09137075A (en) * 1995-11-14 1997-05-27 Nippon Kayaku Co Ltd Pigment dispersant and pigment composition using the same
JP3837772B2 (en) * 1996-04-08 2006-10-25 東洋インキ製造株式会社 Method for producing pigment composition, pigment composition and colorant composition
US6605126B1 (en) 2000-06-02 2003-08-12 Milliken & Co. Low-viscosity polymeric colorants exhibiting high color strength characteristics
JP4089180B2 (en) 2001-07-30 2008-05-28 東洋インキ製造株式会社 Coloring composition for color filter and color filter
JP4576890B2 (en) * 2004-06-04 2010-11-10 東洋インキ製造株式会社 Red coloring composition for color filter and color filter
JP5315608B2 (en) * 2005-12-21 2013-10-16 東洋インキＳｃホールディングス株式会社 Pigment dispersion and colored resin composition
JP4802746B2 (en) * 2006-02-08 2011-10-26 凸版印刷株式会社 Photosensitive coloring composition and color filter

Patent Citations (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
GB2173812A (en) * 1983-10-18 1986-10-22 Toyo Ink Mfg Co Triazine dyes and pigments for use as pigment dispersants
US20070202272A1 (en) * 2005-07-01 2007-08-30 Toyo Ink Co., Ltd. Red colored film, red colored composition, color filter and liquid crystal display device

Non-Patent Citations (6)

* Cited by examiner, † Cited by third party
Title
DATABASE WPI Week 199731 Thomson Scientific, London, GB; AN 1997-337197 XP002581151 -& JP 9 137075 A (NIPPON KAYAKU KK) 27 May 1997 (1997-05-27) *
DATABASE WPI Week 199801 Thomson Scientific, London, GB; AN 1998-004306 XP002581147 -& JP 9 272812 A (TOYO INK MFG CO LTD) 21 October 1997 (1997-10-21) *
DATABASE WPI Week 200413 Thomson Scientific, London, GB; AN 2004-125379 XP002581184 -& JP 2003 043680 A (TOYO INK MFG CO LTD) 13 February 2003 (2003-02-13) cited in the application *
DATABASE WPI Week 200603 Thomson Scientific, London, GB; AN 2006-025329 XP002581150 -& JP 2005 345884 A (TOYO INK MFG CO LTD) 15 December 2005 (2005-12-15) *
DATABASE WPI Week 200763 Thomson Scientific, London, GB; AN 2007-669733 XP002581149 -& JP 2007 191699 A (TOYO INK MFG CO LTD) 2 August 2007 (2007-08-02) *
DATABASE WPI Week 200824 Thomson Scientific, London, GB; AN 2008-D23496 XP002581148 -& JP 2007 212654 A (TOPPAN PRINTING CO LTD) 23 August 2007 (2007-08-23) *

Also Published As

Publication number Publication date
DE102008059110A1 (en) 2010-05-27
WO2010060849A3 (en) 2010-07-29
JP2012509950A (en) 2012-04-26
CN102224203A (en) 2011-10-19
EP2370522A2 (en) 2011-10-05
BRPI0921179A2 (en) 2018-10-16

Similar Documents

Publication Publication Date Title
ES2494290T3 (en) Quinacridone pigment compositions comprising asymmetrically substituted components
CN1481424B (en) Rheology Improvers and pigment compositions having improved rheology
US20090069467A1 (en) Pigment formulations
EP2379647B1 (en) Dyes for polymer coloration, their preparation and their use
WO2010060849A2 (en) Dyes for polymer coloration, their preparation and their use
EP2084233B1 (en) Heat-stable encapsulated pigments
US20120174324A1 (en) Dyes for polymer coloration, their preparation and their use
WO2010063606A2 (en) Dyes for polymer coloration, their preparation and their use
US6890977B2 (en) Warp-free pigment compositions comprising diaryldiketopyrrolo[3,4-c]pyrroles
US11377787B2 (en) Basic dye mixtures for aramid fibres
EP2334738B1 (en) N-alkoxylated 2,3-anthraquinonedicarboximides for polymer coloration, preparation and use
US20120272462A1 (en) Dyes for polymer coloration, their preparation and their use
WO2009040318A2 (en) Dyes for polymer coloration, their preparation and their use
US5527922A (en) Pyrrolo[3,4-c]pyrroles containing cyanimino groups
US5571899A (en) Salts of metal-free anionic substituted-2-hydroxy-1-phenylazonaphthalene dyes having cations containing sterically hindered amine groups

Legal Events

Date Code Title Description
WWE Wipo information: entry into national phase

Ref document number: 200980146617.1

Country of ref document: CN

121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 09759930

Country of ref document: EP

Kind code of ref document: A2

WWE Wipo information: entry into national phase

Ref document number: 2009759930

Country of ref document: EP

WWE Wipo information: entry into national phase

Ref document number: 2011536859

Country of ref document: JP

NENP Non-entry into the national phase in:

Ref country code: DE

ENP Entry into the national phase in:

Ref document number: PI0921179

Country of ref document: BR

Kind code of ref document: A2

Effective date: 20110524