DE102008023114A1 - Mixture useful for mass-coloring of plastics and for coloring of synthetic fibers comprises red dyes and orange dyes - Google Patents

Abstract

A mixture comprises at least one red dye; and at least one orange dye. A mixture comprises at least one red dye of formulae (I), (II) or (III); and at least one orange dye of formulae (IV)-(VI), isoindolo[2,1-a]perimidin-12-one, (VIII) and (IX). B 1-O-B 2-O- or -CH 2-B 3-CH 2-; R 11-8C alkyl or 3-8C cycloalkyl (both optionally substituted) or H; B 2phenyl, biphenyl, naphthyl, 1,4-phenylene-X-1,4-phenylene (substituted both the 2nd positions of phenyl rings by R 2), 1,4-phenylene-C(CF 3) 2-1,4-phenylene, 1,4-phenylene-C(CH 3) 2-phenyl-C(CH 3) 2-1,4-phenylene, 1,4-phenylene-C(=O)-1,4-phenylene, 1,4-phenylene-C(CH 2) 4-1,4-phenylene, 1,4-phenylene-C(CH 2) 5-1,4-phenylene, 1,4-phenylene-C(CH 2) 6-1,4-phenylene, -phenyl-O-Y 1-O-phenyl-, 1,4-cyclohexyl-X-1,4-cyclohexyl, cyclohexyl-O-Y 1-O-cyclohexyl, -(CH 2) n-O-Y 1-O-(CH 2) m-, -(CH 2) n-phenyl-(CH 2) l-, phenyl-C(=O)-O-(CH 2) q-O-C(=O)-phenyl, -(CH 2) n-C(=O)-O-(CH 2) q-O-C(=O)-(CH 2) m-, -(CH 2) n-cyclohexyl-(CH 2) l-, -(CH 2) p-, -(CH 2) q-[O-(CH 2) q] sor -CH 2-CH(CH 3)-[O-CH 2-CH(CH 3)] t-; B 3cyclohexyl, phenyl, naphthyl, phenyl-O-Y 1-O-phenyl or (CH 2) p-; R 2H, methyl, ethyl, methoxy or F; X : -(CH 2) p, -C(CH 3) 2-, cyclopentane-1,1-diyl, cyclohexane-1,1-diyl, cycloheptane-1,1-diyl, O, S, SO 2or CO; Y 1-(CH 2) p, -(CH 2) q-[O-(CH 2) q] s-, -CH 2-CH(CH 3)-[O-CH 2-CH(CH 3)] t-, phenyl, -C(=O)-phenyl-C(=O)-, -C(=O)-(CH 2) t-C(=O)-, -C(=O)-NH-phenyl-NH-C(=O)- or -C(=O)-NH-(CH 2) q-NH-C(=O)-; l : 0-8; m, n, p and r : 1-8; q : 2-8; s and t : 1-4; R 20and R 22cyano or optionally substituted 1-8C alkoxycarbonyl; R 21H or optionally substituted 1-3C alkyl; R 231-8C alkyl or 1-8C alkoxycarbonyl (both optionally substituted) or H; R 241-8C alkylsulfonyl, or 1-8C alkoxycarbonyl (both optionally substituted) or cyano; R 251-8C alkyl, 3-7C cycloalkyl, or 6-10C aryl (all optionally substituted); R 26H or R 25;or NR 25R 26pyrrolidino, piperidino or morpholino; R 27H, 1-8C alkyl, 1-8C alkoxy, 3-7C cycloalkyl or 6-10C aryl (all optionally substituted), fluoro, or cyano; R 281-8C alkyl (optionally substituted) or H; R 101-8C alkyl, 1-8C alkoxy, 1-8C alkylsulfonyl, or 1-8C alkoxycarbonyl (all optionally substituted), nitro, H, cyano or fluoro; R 111-8C alkyl, 1-8C alkoxy, or 1-8C alkoxycarbonyl (all optionally substituted), H, nitro, cyano or fluoro; R 121-8C alkyl, or 3-8C cycloalkyl (both optionally substituted) or H; R 13R 23; R 14R 24; X 1O or S; X 2N or C-CN; R 15and R 161-8C alkyl, 3-8C cycloalkyl or 6-10C aryl (all optionally substituted);or NR 15R 16pyrrolidino, piperidino or morpholino; R 17H or optionally substituted 1-8C alkyl; R 186-10C aryl (optionally substituted); R 23' : R 23; R 24' : R 24; R 25' : R 25; R 26' : R 26;or NR 25'R 26' : pyrrolidino, piperidino or morpholino; R 43and R 44H, 1-4C alkyl, or 1-4C alkoxycarbonyl (all optionally substituted), nitro, or cyano;and R 45H, methyl, fluoro or chloro. Independent claims are included for the following: (1) new substituted bisanthraquinone compounds of formula (IA); (2) preparation of (IA); (3) a masterbatch comprising the mixture (15-80 wt.%) or compound (IA) (15-90 wt.%), and a carrier; and (4) mass-coloring of plastics involving incorporating the mixture or (IA) into the melted mass of plastic or adding to the starting components for producing the plastic prior to the polymerization. B 1a-O-B 2a-O or -CH 2-B 3-CH 2-; B 2anaphthyl, 1,4-phenylene-X-1,4-phenylene (substituted at both the 2nd positions of phenyl rings by R 2a), 1,4-phenylene-C(CF 3) 2-1,4-phenylene, 1,4-phenylene-C(CH 3) 2-phenyl-C(CH 3) 2-1,4-phenylene, 1,4-phenylene-C(=O)-1,4-phenylene, 1,4-phenylene-C(CH 2) 4-1,4-phenylene, 1,4-phenylene-C(CH 2) 5-1,4-phenylene, 1,4-phenylene-C(CH 2) 6-1,4-phenylene, -phenyl-O-Y 1-O-phenyl-, 1,4-cyclohexyl-X-1,4-cyclohexyl, cyclohexyl-O-Y 1-O-cyclohexyl, -(CH 2) n-O-Y 1-O-(CH 2) m-, -(CH 2) n-phenyl-(CH 2) l-, phenyl-C(=O)-O-(CH 2) q-O-C(=O)-phenyl, -(CH 2) n-C(=O)-O-(CH 2) q-O-C(=O)-(CH 2) m-, -(CH 2) n-cyclohexyl-(CH 2) l-, -(CH 2) p-, -(CH 2) q-[O-(CH 2) q] sor -CH 2-CH(CH 3)-[O-CH 2-CH(CH 3)] t-;and R 2amethyl, ethyl, methoxy or F. [Image] [Image] [Image] [Image].

Description

The The invention relates to mixtures containing specific red dyes and special orange dyes, masterbatches based thereon and their use for mass dyeing of plastics that are dyed plastics in itself as well as new special red dyes and processes too their production.

sowie eine weiteren Gelb- und Grünfarbstoff enthält. Diese Farbmischung hat einen sehr verbreiteten Braunton etabliert. Der coloristischen Vorgabe dieses Brauntons auf der einen Seite stehen gestiegene anwendungstechnische Anforderungen sowie die Notwendigkeit nach chlorfreien Ersatzstoffen auf der anderen Seite entgegen. Neben hoher Lichtechtheit, Thermostabilität und Farbstärke sowie guter Löslichkeit im Kunststoff werden auch Sublimations- und Migrierechtheiten verlangt.In recent years, the demand for brown-colored plastic bottles, especially PET bottles, has risen sharply. So far, a brown dye mixture was used for coloring, the red dye as the C. I Solvent Red 135, the perinone of the formula

and another yellow and green dye. This color mixture has established a very common shade of brown. The coloristic specification of this brown clay on the one hand is opposed by increased application requirements and the need for chlorine-free substitutes on the other. In addition to high light fastness, thermal stability and color strength and good solubility in the plastic and sublimation and migration fastness is required.

task The present invention was therefore a coloristic replacement for the Red component of the brown mixture to find the same time exceeds required performance characteristics.

insbesondere der Formel (Ia)

worin
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht,
B für eine Brücke der Formeln -O-B¹-O- oder -CH₂-B²-CH₂- steht,
B¹ für eine Brücke der Formel

B² für eine Brücke der Formel

steht,
R² für Wasserstoff, Methyl, Ethyl, Methoxy oder Fluor steht,
X für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 8 steht,
m, n, p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen,
und
R²⁰ und R²² unabhängig voneinander für Cyano oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl stehen,
R²¹ für Wasserstoff oder gegebenenfalls substituiertes C₁-C₃-Alkyl steht,
R²³ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
R²⁴ für Cyano, gegebenenfalls substituiertes C₁-C₈-Alkylsulfonyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
R²⁵ für gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl, gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
R²⁶ für Wasserstoff oder unabhängig von R²⁵ die Bedeutung von R²⁵ hat oder
NR²⁵R²⁶ für Pyrrolidino, Piperidino oder Morpholino steht,
R²⁷ für einen oder mehrere Reste mit der Bedeutung Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, Halogen, Cyano, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
R²⁸ für Wasserstoff oder gegebenenfalls substituiertes C₁-C₈-Alkyl steht,
und wenigstens einen Orangefarbstoff der Formel
(L), (LI), (LII), (LIII), (LIV) oder (LV)

worin
R¹⁰ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, gegebenenfalls substituiertes C₁-C₈-Alkylsulfonyl, gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl, Nitro, Cyano oder Fluor steht,
R¹¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl, Nitro, Cyano oder Fluor steht,
R¹² für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht,
R¹³ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
R¹⁴ für Cyano, gegebenenfalls substituiertes C₁-C₈-Alkylsulfonyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
X¹ für O oder S steht,
X² für N oder C-CN steht,
R¹⁵ und R¹⁶ unabhängig voneinander für gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₃-C₈-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl stehen oder
NR¹⁵R¹⁶ für Pyrrolidino, Piperidino oder Morpholino steht,
R¹⁷ für Wasserstoff oder C₁-C₈-Alkyl steht,
R¹⁸ für gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
R^23' für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
R^24' für Cyano, gegebenenfalls substituiertes C₁-C₈-Alkylsulfonyl oder gegebenenfalls substituiertes C₁-C₈-Alkoxycarbonyl steht,
R^25' für gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl, gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
R^26' für Wasserstoff oder unabhängig von R^25' die Bedeutung von R^25' hat oder
NR^25'R^26' für Pyrrolidino, Piperidino oder Morpholino steht,
R⁴³ und R⁴⁴ unabhängig voneinander für Wasserstoff, gegebenenfalls substituiertes C₁-C₄-Alkyl, insbesondere durch ein oder mehrere Fluor substituiertes C₁-C₄-Alkyl, Nitro, Cyano, C₁-C₄-Alkoxycarbonyl stehen und
R⁴⁵ für Wasserstoff, Methyl, Cyano, Fluor oder Chlor steht.A mixture has now been found containing at least one red dye of the formula (I), (C) or (CI)

in particular of the formula (Ia)

wherein
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl,
B represents a bridge of the formulas -OB ¹ -O- or -CH ₂ -B ² -CH ₂ -,
B ¹ for a bridge of the formula

B ² for a bridge of the formula

stands,
R ^{2 is} hydrogen, methyl, ethyl, methoxy or fluorine,
X for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 8,
m, n, p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently of one another represent an integer from 1 to 4,
and
R ²⁰ and R ^{22 are} independently cyano or optionally substituted C ₁ -C ₈ alkoxycarbonyl ste hen,
R ^{21 is} hydrogen or optionally substituted C ₁ -C ₃ -alkyl,
R ^{23 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
R ^{24 is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
R ^{25 is} optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl, optionally substituted C ₆ -C ₁₀ -aryl,
R ^{26 is} hydrogen or independently of R ^{25 has} the meaning of R ²⁵ or
NR ²⁵ R ^{26 represents} pyrrolidino, piperidino or morpholino,
R ^{27 is} one or more radicals which are hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, halogen, cyano, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ aryl,
R ^{28 is} hydrogen or optionally substituted C ₁ -C ₈ -alkyl,
and at least one orange dye of the formula
(L), (LI), (LII), (LIII), (LIV) or (LV)

wherein
R ^{10 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, optionally substituted C ₁ -C ₈ -alkylsulfonyl, optionally substituted C ₁ -C ₈ -alkoxycarbonyl, nitro, cyano or fluorine stands,
R ^{11 represents} hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, optionally substituted C ₁ -C ₈ -alkoxycarbonyl, nitro, cyano or fluorine,
R ^{12 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl,
R ^{13 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
R ^{14 is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
X ^{1 is} O or S,
X ^{2 is} N or C-CN,
R ¹⁵ and R ¹⁶ independently of one another represent optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₈ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl or
NR ¹⁵ R ^{16 represents} pyrrolidino, piperidino or morpholino,
R ^{17 is} hydrogen or C ₁ -C ₈ -alkyl,
R ^{18 is} optionally substituted C ₆ -C ₁₀ -aryl,
R ^{23 'is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
R ^{24 'is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl,
R ^{25 'is} optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl, optionally substituted C ₆ -C ₁₀ -aryl,
R ^{26 'is} hydrogen or independently of R ^{25' has} the meaning of R ^{25 '} or
NR ^{25 '} R ^{26' represents} pyrrolidino, piperidino or morpholino,
R ⁴³ and R ⁴⁴ independently of one another represent hydrogen, optionally substituted C ₁ -C ₄ -alkyl, in particular C ₁ -C ₄ -alkyl substituted by one or more fluorine, nitro, cyano, C ₁ -C ₄ -alkoxycarbonyl and
R ^{45 is} hydrogen, methyl, cyano, fluorine or chlorine.

insbesondere der Formel Ia.The compound of the formula I preferably corresponds to the formulas (Ia) to (Ic)

in particular of the formula Ia.

in the Traps of naphthalene structure grab the indefinite bonds preferably in the positions 1,5-, 1,8-, 2,6- or 2,7-. in the Traps of benzene and cyclohexane structures attack the indefinite Bindings in the positions 1,2-, 1,3- or 1,4-.

C ₁ -C ₈ -alkyl is here and below used to mean straight-chain or branched C ₁ -C ₈ -alkyl, eg. As methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl or 2-ethylhexyl understood.

Substituted C ₁ -C ₈ -alkyl is understood as meaning straight-chain or branched C ₁ -C ₈ -alkyl, as described above, which is represented by at least one of fluorine, cyano, hydroxyl, C ₁ -C ₄ -alkoxy, acetoxy, propoxy , Butoxy, C ₁ -C ₄ alkoxycarbonyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, e.g. For example, trifluoromethyl, perfluorobutyl, 2-chloroethyl, cyanomethyl, 2-cyanoethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-acetoxyethyl, 2-methoxycarbonylethyl, cyclohexylmethyl, benzyl, phenethyl or phenylpropyl.

Here and in the following, for example, butyl is always n-butyl, 2-butyl, iso-butyl or tert-butyl, if not expressly meant other is said.

C ₃ -C ₈ -cycloalkyl is understood here and below to mean cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. By substituted C ₃ -C ₈ -cycloalkyl is meant, for example, methylcyclohexyl.

Preferably, R ^{1 is} hydrogen. Also preferably R ^{1 is} methyl.

steht,
R² für Methyl, Ethyl, Methoxy oder Fluor steht,
X für eine Brücke der Formeln

steht,
Y für eine Brücke der Formeln

steht,
l für eine ganze Zahl von 0 bis 8 steht,
m, n, p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen.Preferred compounds of the formula I are those in which
B ¹ for a bridge of the formula

stands,
R ^{2 is} methyl, ethyl, methoxy or fluorine,
X for a bridge of formulas

stands,
Y for a bridge of formulas

stands,
l is an integer from 0 to 8,
m, n, p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently represent an integer from 1 to 4.

worin
R² für Methyl steht,
X für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 4 steht,
m, n und p unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen,
q und r unabhängig voneinander für eine ganze Zahl von 2 bis 6 steht,
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 2 stehen und
die unbestimmten Ringpositionen 1,2-, 1,3- oder 1,4- bedeuten.Particularly preferred bridges of the formula B ¹ are those

wherein
R ^{2 is} methyl,
X for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 4,
m, n and p independently of one another represent an integer from 1 to 4,
q and r are independently an integer from 2 to 6,
s and t are independently an integer from 1 to 2 and
the indefinite ring positions 1,2-, 1,3- or 1,4- mean.

worin
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 1 bis 2 steht,
m, n und p unabhängig voneinander für eine ganze Zahl von 1 bis 2 stehen,
q für eine ganze Zahl von 2 bis 4 steht,
s und t unabhängig voneinander für 1 stehen und
die unbestimmten Ringpositionen 1,4- bedeuten.Very particularly preferred bridges B ¹ are:

wherein
Y for a bridge of the formula

stands,
l is an integer from 1 to 2,
m, n and p independently of one another represent an integer from 1 to 2,
q is an integer from 2 to 4,
s and t are independently 1 and
the indefinite ring positions mean 1,4-.

worin
Y für eine Brücke der Formeln

steht,
p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen.Preferred bridges B ² are:

wherein
Y for a bridge of formulas

stands,
p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently represent an integer from 1 to 4.

worin
Y für eine Brücke der Formel

steht,
p für eine ganze Zahl von 1 bis 6 steht und
r für eine ganze Zahl von 2 bis 6 steht
und die unbestimmten Ringpositionen bei Benzol- oder Cyclohexanringen 1,2-, 1,3- oder 1,4- und beim Napththalinring 2,6- oder 2,7- bedeuten.Particularly preferred bridges B ² are

wherein
Y for a bridge of the formula

stands,
p is an integer from 1 to 6 and
r is an integer from 2 to 6
and the indefinite ring positions in benzene or cyclohexane rings 1,2-, 1,3- or 1,4- and the naphthalene ring 2,6- or 2,7- mean.

worin
p für eine ganze Zahl von 1 bis 4 steht
und die unbestimmten Ringpositionen 1,4- bedeuten.Very particularly preferred B ² bridges are:

wherein
p is an integer from 1 to 4
and the indefinite ring positions are 1,4-.

Preferred red dyes of the formula (C) are those in which
R ^{20 is} cyano, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano or methoxycarbonyl, very particularly preferably methoxycarbonyl,
R ²² for cyano,
R ^{21 is} hydrogen or methyl, particularly preferably methyl,
R ^{23 is} methyl, trifluoromethyl or methoxycarbonyl, particularly preferably methyl,
R ^{24 is} cyano, methanesulfonyl, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano,
R ^{25 is} methyl, ethyl, propyl, butyl, methoxyethyl, methoxypropyl, cyanoethyl, benzyl, cyclohexyl, phenyl or tolyl, particularly preferably ethyl, propyl, butyl, methoxyethyl, methoxypropyl, benzyl, cyclohexyl or phenyl, very particularly preferably propyl, Butyl or methoxypropyl,
R ^{26 is} hydrogen or, independently of R ^25, the meaning of R ²⁵ , or
NR ²⁵ R ²⁶ for pyrrolidino, piperidino or morpholino,

Preferred red dyes of the formula (CI) are those in which
R ^{27 is} hydrogen, methyl, ethyl, propyl, butyl, benzyl, cyano, cyclohexyl, phenyl or tolyl, particularly preferably p-methyl, ethyl, propyl, butyl, cyclohexyl or phenyl, very particularly preferably p-butyl or Cyclohexyl, and
R ^{28 is} hydrogen.

The Dyes of the formula (I) and at least one orange dye of the Formula (L) to (LV) are preferably in the ratio of 1:99 to 99: 1, preferably from 20:80 to 97: 3, more preferably from 40:60 to 95: 5, all the way more preferably mixed 50:50 to 90:10.

The Red dyes of the formula (C) and at least one orange dye of the formulas (L) to (LV) are preferably in the ratio of 1:99 to 99: 1, preferably 20:80 to 97: 3, more preferably 30:70 to 95: 5, especially preferably mixed from 40:60 to 90:10. Very particularly preferred is a mixture of the dyes of formulas (C) and (L) in the ratio 40:60 until 60:40.

The Dyes of the formula (CI) and at least one orange dye of the Formula (L) to (LV) are preferably in the ratio of 1:99 to 99: 1, preferably from 20:80 to 97: 3, more preferably from 40:60 to 95: 5, all the way more preferably mixed 50:50 to 90:10.

The Mixture can be done, for example, by mixing the dyes in solid form, for example as a powder, granules or pastes. In the case of moist pastes, for example, it is then possible to dry become. It can also be done by mixing suspensions the dyes, for example, then spray-dried or spray-granulated become. Finally, the mixture can be made at the same time Preparation of masterbatches or in the dyeing of polymeric materials.

suitable Color locations for red according to the invention Mixtures are according to the Lab values L of 35-60, a of 65-85 and b from 20-75, prefers L from 40-50, a from 65-75 and b from 40-75.

For the orange dyes (L) to (LV) are preferred
R ^{10 represents} hydrogen, methyl, ethyl, methoxy, methanesulfonyl, methoxycarbonyl, ethoxycarbonyl, nitro, cyano or fluorine, particularly preferably hydrogen, methanesulfonyl or methoxycarbonyl, very particularly preferably methoxycarbonyl,
R ^{11 represents} hydrogen, methyl, methoxy, methoxycarbonyl, nitro, cyano or fluorine, particularly preferably hydrogen,
R ^{12 is} methyl, ethyl, propyl, butyl, 2-methoxyethyl, 2-cyanoethyl, benzyl or cyclohexyl, particularly preferably methyl, ethyl, propyl, butyl or benzyl, very particularly preferably methyl or ethyl,
R ^{13 is} methyl or methoxycarbonyl, particularly preferably methyl,
R ^{14 is} cyano, methanesulfonyl, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano,
X ^{1 is} O or S, particularly preferably S,
X ^{2 is} N or C-CN,
R ¹⁵ and R ¹⁶ independently of one another are methyl, ethyl, propyl, butyl, cyanoethyl, benzyl, cyclopentyl, cyclohexyl, phenyl or tolyl, particularly preferably methyl, ethyl, cyanoethyl, benzyl, cyclohexyl or phenyl, very particularly preferably methyl or ethyl , or
NR ¹⁵ R ¹⁶ for pyrrolidino, piperidino or morpholino,
R ^{17 is} hydrogen or methyl, particularly preferably hydrogen,
R ^{18 is} phenyl, tolyl, dimethylphenyl, trimethylphenyl, particularly preferably tolyl or dimethylphenyl,
R ^{23 'is} methyl, trifluoromethyl or methoxycarbonyl,
R ^{24 'is} cyano, methylsulfonyl, trifluoromethylsulfonyl, methoxy- or ethoxycarbonyl,
R ^{25 'is} methyl, ethyl, propyl, butyl, chloroethyl, methoxyethyl, methoxypropyl, dimethylaminopropyl, phenyl, tolyl, methoxyphenyl, fluorophenyl, chlorophenyl or cyanophenyl,
R ^{26 'is} hydrogen or
NR ^{25 '} R ^26' for pyrrolidino, piperidino or morpholino,
R ⁴³ and R ⁴⁴ independently of one another represent trifluoromethyl, nitro, cyano, methoxy or ethoxycarbonyl, it being possible for one or both to additionally represent hydrogen,
R ⁴⁵ for hydrogen.

A preferred mixture according to the invention contains a red dye of the formula (I) and at least one orange dye of formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular of the formula (L).

A likewise preferred mixture according to the invention contains a Red dye of the formula (C) and at least one orange dye of formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular of the formula (L).

A likewise preferred mixture according to the invention contains a Red dye of the formula (CI) and at least one orange dye of formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular of the formula (L).

Particularly preferred is a mixture according to the invention containing a red dye of the formula (C), wherein
R ^{20 is} cyano, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano or methoxycarbonyl, very particularly preferably methoxycarbonyl,
R ²² for cyano,
R ^{21 is} hydrogen or methyl, particularly preferably methyl,
R ^{23 is} methyl or methoxycarbonyl, particularly preferably methyl,
R ^{24 is} cyano, methanesulfonyl, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano,
R ^{25 is} methyl, ethyl, propyl, butyl, methoxyethyl, methoxypropyl, cyanoethyl, benzyl, cyclohexyl, phenyl or tolyl, particularly preferably ethyl, propyl, butyl, methoxyethyl, methoxypropyl, benzyl, cyclohexyl or phenyl, very particularly preferably propyl, Butyl or methoxypropyl,
R ^{26 is} hydrogen or, independently of R ^25, the meaning of R ²⁵ , or
NR ²⁵ R ²⁶ for pyrrolidino, piperidino or morpholino,
stands, especially if
R ^{20 is} COOCH ₃ , R ²¹ and R ^{23 are} CH ₃ , R ²² and R ^{24 are} CN, R ^{25 is} -CH ₂ CH ₂ CH ₂ OCH ₃ and R ^{26 is} H.
and an orange dye of the formula (L), in particular wherein
R ^{10 is} COOCH ₃ and R ^{11 is} H.

vorzugsweise im Verhältnis 50:50,

vorzugsweise im Verhältnis 45:55,

vorzugsweise im Verhältnis 83:17,

vorzugsweise im Verhältnis 83:17,

vorzugsweise im Verhältnis 50,8:48,2,

vorzugsweise im Verhältnis 48:52,

vorzugsweise im Verhältnis 50:50.Examples of such mixtures are:

preferably in the ratio 50:50,

preferably in the ratio 45:55,

preferably in the ratio 83:17,

preferably in the ratio 83:17,

preferably in the ratio 50.8: 48.2,

preferably in the ratio 48:52,

preferably in the ratio 50:50.

The mixtures according to the invention can, if they only use red and orange dyes as coloring components contain, to the mass-coloring of plastics with other dyes, especially those be used to obtain a brown color, the other Dyes can but also be included in the mix already.

• a) wenigstens einen Gelbfarbstoff, vorzugsweise einen mit mit einem λ_max-Wert von 420 bis 460 nm und wenigstens einen Grünfarbstoff, vorzugsweise mit einem maximalen Wert von 610 bis 700 nm oder
• b) wenigstens einen Gelbfarbstoff, vorzugsweise einen mit mit einem λ_max-Wert von 420 bis 460 nm und wenigstens einen Blaufarbstoff, vorzugsweise einer mit einem λ_max-Wert von 570 bis 640 nm.

The mixtures according to the invention therefore preferably contain

• a) at least one yellow dye, preferably one having a λ _max value of 420 to 460 nm and at least one green dye, preferably having a maximum value of 610 to 700 nm or
• b) at least one yellow dye, preferably one having a λ _max value of 420 to 460 nm and at least one blue dye, preferably one having a λ _max value of 570 to 640 nm.

worin
R²⁹ für einen oder mehrere Reste mit der Bedeutung Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, Fluor, Cyano, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
R³⁰ für Wasserstoff, Methyl, Ethyl oder Methoxy steht,
R³¹ für Cyano, C₁-C₈-Alkoxycarbonyl oder C₁-C₈-Alkansulfonyl steht,
R³² für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₇-Cycloalkyl steht,
R³³ für Wasserstoff substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl steht,
B³ für eine Brücke der Formel

steht.Particularly preferred yellow dyes are, for example, those of the formulas

wherein
R ^{29 is} one or more radicals which are hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, fluorine, cyano, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ aryl,
R ^{30 is} hydrogen, methyl, ethyl or methoxy,
R ^{31 is} cyano, C ₁ -C ₈ -alkoxycarbonyl or C ₁ -C ₈ -alkanesulfonyl,
R ^{32 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₇ -cycloalkyl,
R ^{33 represents} hydrogen-substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl,
B ³ for a bridge of the formula

stands.

Preferably stand
R ^{29 represents} hydrogen, methyl, ethyl, propyl, butyl, benzyl, cyano, cyclohexyl, phenyl or tolyl, particularly preferably p-substituted methyl, ethyl, propyl, butyl, cyclohexyl or phenyl, very particularly preferably p-butyl or cyclohexyl,
R ^{30 is} hydrogen or methyl,
R ^{31 is} cyano, methoxycarbonyl, ethoxycarboyl or methanesulfonyl, particularly preferably cyano or methoxycarbonyl, very particularly preferably cyano,
R ^{32 represents} methyl, ethyl, propyl or cyclohexyl, particularly preferably methyl or ethyl,
R ^{33 represents} methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, methoxy, ethoxy, cyclopentyl, cyclohexyl, phenyl or tolyl, particularly preferably p-substituted butyl, pentyl, hexyl, heptyl, octyl, cyclohexyl or phenyl , most preferably p-substituted n-butyl, tert-butyl, 1,1,3,3-tetramethylbutyl, 2-ethylhexyl, cyclohexyl or phenyl,
and
B ³ for a bridge of the formula

worin
R³⁴ und R³⁵ unabhängig voneinander für Wasserstoff, Hydroxy oder C₁-C₄-Alkoxy stehen,
R³⁶ und R³⁷ unabhängig voneinander für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₁-C₈-Alkoxy, Fluor, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl stehen.Particularly preferred green dyes are, for example, those of the formula (CCLI)

wherein
R ³⁴ and R ³⁵ independently of one another represent hydrogen, hydroxyl or C ₁ -C ₄ -alkoxy,
R ³⁶ and R ³⁷ independently of one another represent hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, fluorine, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ - Aryl stand.

Preferably stand
R ³⁴ and R ^{35 are} hydrogen or hydroxy, more preferably hydrogen, and are the same
R ³⁶ and R ³⁷ are each independently hydrogen, methyl, ethyl, propyl, butyl, methoxy, bromo, cyclohexyl or phenyl, more preferably p-methyl, ethyl, butyl, most preferably both equally for p-methyl or tert .-butyl.

worin
R³⁸ und R³⁹ unabhängig voneinander für gegebenenfalls substituiertes C₁-C₈-Alkyl, gegebenenfalls substituiertes C₃-C₇-Cycloalkyl oder gegebenenfalls substituiertes C₆-C₁₀-Aryl stehen.Particularly preferred blue dyes are those of the formula (CCCI)

wherein
R ³⁸ and R ³⁹ independently of one another represent optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl.

R⁴⁰ Methyl, Ethyl oder Propyl,
R⁴¹ für Wasserstoff, Methyl, Ethyl, Propyl, Butyl oder Cyclohexyl,
R⁴² Wasserstoff, Methyl, Ethyl oder Propyl.Preferably stand
R ³⁸ and R ³⁹ independently of one another are methyl, ethyl, propyl, butyl, pentyl, hexyl, cyclopentyl, cyclohexyl or a phenyl radical of the formula

R ^{40 is} methyl, ethyl or propyl,
R ^{41 is} hydrogen, methyl, ethyl, propyl, butyl or cyclohexyl,
R ^{42 is} hydrogen, methyl, ethyl or propyl.

und sind gleich,
R⁴⁰ Methyl oder Ethyl,
R⁴¹ für Wasserstoff, Methyl oder Ethyl,
R⁴² Methyl oder Ethyl.Particularly preferred stand
R ³⁸ and R ^{39 are} methyl, ethyl, propyl, butyl, cyclohexyl or a phenyl radical of the formula

and are the same,
R ^{40 is} methyl or ethyl,
R ^{41 is} hydrogen, methyl or ethyl,
R ^{42 is} methyl or ethyl.

The mixtures according to the invention, containing at least one red dye of the formula (I) and at least An orange dye of the formula (L) to (LV) is further preferably with a yellow and a green or blue dye in proportion from [(I) + (L) to (LV)]: yellow: [green or blue] from 30-70: 20-50: 1-30, preferably 45-65: 25-40: 15-25 mixed.

The mixtures according to the invention, containing at least one red dye of the formula (C) and at least an orange dye of the formula (L) to (LV) are indicated by a yellow and a green one or blue dye in proportion from [(C) or (CI) + (L) to (LV)]: yellow: [green or blue] from 15-40: 20-70: 20-50, preferably 20-35: 25-65: 25-40 mixed.

The mixtures according to the invention, containing at least one red dye of the formula (CI) and at least An orange dye of the formula (L) to (LV) is further preferably with a yellow and a green or blue dye in proportion from [(I) + (L) to (LV)]: yellow: [green or blue] from 30-70: 20-50: 1-30, preferably 45-65: 25-40: 15-25 mixed.

suitable Color locations for For example, such brown blends are in the Lab system for L of 30-80, a of 10-30 and b from 40-80, preferably L from 50-75, a from 10-25 and b of 42-70.

vorzugsweise im Verhältnis 16,3:15,8:40,9:27,0,

vorzugsweise im Verhältnis 16,0:15,5:41,8:26,7,

im Verhältnis 9,0:8,7:66,7:15,6,

vorzugsweise im Verhältnis 33,8:20,1:27,1:18,0,

vorzugsweise im Verhältnis 32,1:19,4:29,1:19,4,

vorzugsweise im Verhältnis 38,1:17,3:26,8:17,8,

vorzugsweise im Verhältnis 9,0:8,5:67,0:15,5.Examples are:

preferably in the ratio 16.3: 15.8: 40.9: 27.0,

preferably in the ratio 16.0: 15.5: 41.8: 26.7,

in the ratio 9.0: 8.7: 66.7: 15.6,

preferably in the ratio 33.8: 20.1: 27.1: 18.0,

preferably in the ratio 32.1: 19.4: 29.1: 19.4,

preferably in the ratio 38.1: 17.3: 26.8: 17.8,

preferably in the ratio 9.0: 8.5: 67.0: 15.5.

to Avoid dosing problems and achieve a homogeneous Distribution of the mixture according to the invention in plastics, many plastic processors prefer a concentrate the respective additive, in this case the dye mixture in the base polymers or other carriers.

These Concentrates are called masterbatches in this application.

The Invention therefore also relates to masterbatches containing 15-70% by weight, preferably 40 to 70% by weight of the mixture according to the invention and a carrier.

Preferably the amount of the carrier as the remainder to 95 wt.%, Preferably to 98% by weight, in particular to 99% by weight of the masterbatch.

When Carrier are preferably the base polymers to be dyed Plastic itself. Such masterbatches are usually solid. Particularly preferred base polymers are thermoplastics, for example Vinyl polymers, polyesters, polyamides and polyolefins, in particular Polyethylene and polypropylene, or polycarbonates.

suitable Vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, Polymethacrylate, polyvinyl chloride u. a.

Farther suitable are polyesters such as polyethylene terephthalates, Polycarbonates and cellulose esters.

Prefers are polystyrene, styrene copolymers, polyethylene terephthalates, Polycarbonates, polymethacrylates and polyamides. Especially preferred are polystyrene, polyethylene terephthalates, polycarbonates and polymethacrylates to call. Especially suitable are polyethylene terephthalates.

Preferably For example, to prepare such masterbatches, a base polymer is used or a mixture of several base polymers with the dye mixture according to the invention heated melted, mixed and transferred into a pourable form, for example in granular form, z. B. as solidified droplets, balls, Hollow balls, scales and the like.

Should the dye mixtures only after the polymerization of the plastics are used, they are, for example, with the plastic granules dry mixed or ground and this mixture z. B. on mixing rollers or plasticized and homogenized in screws. You can do that Add blends but also to the molten mass and through stir distribute homogeneously. The thus pre-dyed material is then z. As by spinning into bristles, threads, etc. or by extrusion or further processed by injection molding into molded parts.

When Carriers are also preferred as dispersion carriers. The usage such carrier leads preferably to liquid, pumpable masterbatches.

The The invention further relates to the use of the mixture according to the invention to the mass-coloring of Plastics.

Under bulk dyeing In this case, in particular processes are understood in which the Dye mixture incorporated into the molten plastic mass be, for. B. with the aid of an extruder extruder, or where the dye already the starting components for the preparation of Kuststoffs, z. As monomers before the polymerization is added.

Especially preferred plastics are thermoplastics, for example vinyl polymers, Polyesters, polyamides and polyolefins, in particular polyethylene and polypropylene, or polycarbonates.

suitable Vinyl polymers are polystyrene, styrene-acrylonitrile copolymers, styrene-butadiene copolymers, styrene-butadiene-acrylonitrile terpolymers, Polymethacrylate, polyvinyl chloride u. a.

Farther suitable are polyesters such as polyethylene terephthalates, Polycarbonates and cellulose esters.

Prefers are polystyrene, styrene copolymers, polyethylene terephthalates, Polycarbonates, polymethacrylates and polyamides. Especially preferred are polystyrene, polyethylene terephthalates, polycarbonates and polymethacrylates.

The mentioned high molecular weight compounds can individually or in mixtures, as plastic masses or melts available. Particularly preferred is polyethylene terephthalate (PET).

The mixtures according to the invention are used, for example, in finely divided form, which dispersants can be used, but need not. she can However, for example, in masterbatches, such as granulated Shape, z. B. as solidified droplets, Spheres, hollow spheres, scales and the like brought to application become.

There the dye mixtures against polymerization catalysts, in particular Peroxides are resistant, it is also possible to add them to the monomeric starting materials for the plastics and then to polymerize in the presence of polymerization catalysts. For this, the dye mixtures are preferably in the monomers Components solved or intimately mixed with them.

The dye mixtures according to the invention are preferably used in amounts of from 0.0001 to 1 % By weight, in particular from 0.01 to 0.5% by weight, based on the plastic or the synthetic fibers.

at Use of masterbatches is done the amount so that preferably also these dye mixture proportions, based on the plastic, result.

By Addition of insoluble in the polymers Pigments such. As titanium dioxide, corresponding valuable muted dyes to be obtained.

Titanium dioxide may be in an amount of 0.01 to 10% by weight, preferably 0.1 to 5 wt.% Based on the amount of polymer used.

you receives transparent or muted bluish red colorations with good heat resistance as well as good light, weather, sublimation and migration fastness. at Co-use of yellow and green, or blue dyes one brown dyeings with the same fastnesses.

The The invention therefore also relates to a process for mass coloration of Plastics, characterized in that the mixture according to claim 1, preferably in the form of its masterbatch in the molten Plastic compound incorporates or already the starting components added for the preparation of the plastic before the polymerization.

The The invention further relates to plastics containing the color mixture according to the invention. Such plastics are in particular hollow bodies such as bottles, in particular Beverage bottles.

you receives transparent or muted red or brown dyeings with good heat resistance as well as good light, weather, sublimation and migration fastness.

In particular, the sublimation and migration fastnesses of the dyes of the formula (I) according to the invention are significantly improved compared with, for example, the dye of the formula (CI) with R ²⁷ = R ²⁸ = H (= CI Solvent Red 60).

The red according to the invention and brown mixtures also show good fastness properties, in particular good sublimation and Migration fastness. These mixtures are also distinguished high solubility in plastics, especially in masterbatches. Compared with brown mixtures based on C.I. Solvent Red 135 is the solubility significantly increased in masterbatches, because of the relatively high molecular weight of the bridged dyes of the invention of the formula (I) is unexpected.

worin
-B- für -O-B¹-O- oder -CH₂-B²-CH₂- steht,
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht,
B¹ für eine Brücke der Formel

steht,
B² für eine Brücke der Formel

steht,
R² für Methyl, Ethyl, Methoxy oder Fluor steht,
X für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 8 steht,
m, n, p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen.The invention further relates to compounds of the formula I.

wherein
-B- is -OB ¹ -O- or -CH ₂ -B ² -CH ₂ -,
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl,
B ¹ for a bridge of the formula

stands,
B ² for a bridge of the formula

stands,
R ^{2 is} methyl, ethyl, methoxy or fluorine,
X for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 8,
m, n, p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently represent an integer from 1 to 4.

insbesondere Formel (Ia).The compound of the formula (I) preferably corresponds to the formulas (Ia) to (Ic)

in particular formula (Ia).

in the Traps of naphthalene structure grab the indefinite bonds preferably in the positions 1,5-, 1,8-, 2,6- or 2,7-. in the Traps of benzene and cyclohexane structures attack the indefinite Bindings in the positions 1,2-, 1,3- or 1,4-.

C ₁ -C ₈ -alkyl is here and below used to mean straight-chain or branched C ₁ -C ₈ -alkyl, eg. As methyl, ethyl, n-propyl, 2-propyl, n-butyl, 2-butyl, iso-butyl, tert-butyl, pentyl, hexyl, heptyl, octyl, 2-ethylhexyl understood.

Substituted C ₁ -C ₈ -alkyl is understood as meaning straight-chain or branched C ₁ -C ₈ -alkyl, as described above, which is represented by at least one of fluorine, cyano, hydroxy, C ₁ - to C ₄ -alkoxy, acetoxy , Propoxy, butoxy, C ₁ -C ₄ alkoxycarbonyl, cyclopentyl, cyclohexyl, phenyl, naphthyl, e.g. For example, trifluoromethyl, perfluorobutyl, cyanomethyl, 2-cyanoethyl, 2-methoxyethyl, 2-ethoxyethyl, 2-acetoxyethyl, 2-methoxycarbonylethyl, cyclohexylmethyl, benzyl, phenethyl or phenylpropyl.

Here and in the following, for example, butyl is always n-butyl, 2-butyl, iso-butyl or tert-butyl, if not expressly meant Other is said.

C ₃ -C ₈ -cycloalkyl is understood here and below to mean cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. By substituted C ₃ -C ₈ -cycloalkyl is meant, for example, methylcyclohexyl.

Preferably, R ^{1 is} hydrogen. Also preferably R ^{1 is} methyl.

worin
R² für Methyl steht,
X für eine Brücke der Formeln

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 4 steht,
m, n und p unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen,
q und r unabhängig voneinander für eine ganze Zahl von 2 bis 6 steht,
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 2 stehen und
die unbestimmten Ringpositionen 1,2-, 1,3- oder 1,4- bedeuten.Preferred bridges B ¹ are:

wherein
R ^{2 is} methyl,
X for a bridge of formulas

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 4,
m, n and p independently of one another represent an integer from 1 to 4,
q and r are independently an integer from 2 to 6,
s and t are independently an integer from 1 to 2 and
the indefinite ring positions 1,2-, 1,3- or 1,4- mean.

worin
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 1 bis 2 steht,
m, n und p unabhängig voneinander für eine ganze Zahl von 1 bis 2 stehen,
q für eine ganze Zahl von 2 bis 4 steht,
s und t unabhängig voneinander für 1 stehen und
die unbestimmten Ringpositionen 1,4- bedeuten.Particularly preferred bridges B ¹ are:

wherein
Y for a bridge of the formula

stands,
l is an integer from 1 to 2,
m, n and p independently of one another represent an integer from 1 to 2,
q is an integer from 2 to 4,
s and t are independently 1 and
the indefinite ring positions mean 1,4-.

worin
Y für eine Brücke der Formeln

steht,
p für eine ganze Zahl von 1 bis 6 steht und
r für eine ganze Zahl von 2 bis 6 steht.Preferred bridges B ² are:

wherein
Y for a bridge of formulas

stands,
p is an integer from 1 to 6 and
r is an integer from 2 to 6.

worin
p für eine ganze Zahl von 1 bis 4 steht.Particularly preferred B ² bridges are:

wherein
p is an integer from 1 to 4.

worin
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht und
R für Chlor, Brom oder Phenoxy steht,
mit einem bifunktionellen Alkohol der Formel (III) umsetzt HO-B¹-OH (III),worin
B¹ für eine Brücke der Formel

steht,
R² für Methyl, Ethyl, Methoxy oder Fluor steht,
X für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 8 steht,
m, n, p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen.Another object of the invention is a process for the preparation of the dyes of the formula (I) according to the invention,
wherein
B stands for a bridge -OB ¹ -O-,
characterized in that an anthraquinone compound of the formula (II)

wherein
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and
R is chlorine, bromine or phenoxy,
with a bifunctional alcohol of the formula (III) HO-B ¹ -OH (III), wherein
B ¹ for a bridge of the formula

stands,
R ^{2 is} methyl, ethyl, methoxy or fluorine,
X for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 8,
m, n, p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently represent an integer from 1 to 4.

steht,
worin
Y für eine bifunktionelle Gruppe der Formel

steht,
m, n und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen und n und m gleich sind und
q für eine ganze Zahl von 2 bis 8 steht,
dadurch gekennzeichnet, dass man eine Anthrachinonverbindung der Formel (IV)

worin
R¹ für Wasserstoff substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht und
n für eine ganze Zahl von 1 bis 8 steht,
mit einem bifunktionellen Säurechlorid oder Ester der Formeln (V)

oder (VI) A-CO-(CH₂)_r-CO-A (VI)oder einem bifunktionellen Isocyanat der Formeln (VII)

oder (VIII) O=C=N-(CH₂)_q-N=C=O (VIII) worin
A für Cl oder Methoxy steht,
r für eine ganze Zahl von 1 bis 8 steht und
q für eine ganze Zahl von 2 bis 8 steht,
umsetzt.Another object of the invention is a process for the preparation of the dyes of the formula (I) according to the invention,
wherein
B stands for a bridge -OB ¹ -O- and
B ¹ for a bridge of the formula

stands,
wherein
Y is a bifunctional group of the formula

stands,
m, n and r are independently an integer from 1 to 8 and n and m are the same and
q is an integer from 2 to 8,
characterized in that an anthraquinone compound of the formula (IV)

wherein
R ^{1 is} hydrogen-substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and
n is an integer from 1 to 8,
with a bifunctional acid chloride or ester of the formulas (V)

or (VI) A-CO- (CH ₂ ) _r -CO-A (VI) or a difunctional isocyanate of the formula (VII)

or (VIII) O = C = N- (CH ₂ ) _q -N = C = O (VIII) wherein
A is Cl or methoxy,
r stands for an integer from 1 to 8 and
q is an integer from 2 to 8,
implements.

steht,
R² für Methyl, Ethyl, Methoxy oder Fluor steht,
X für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
l für eine ganze Zahl von 0 bis 8 steht,
m, n, p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen,
dadurch gekennzeichnet, dass man eine Anthrachinonverbindung der Formel (II)

worin
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht und
R für Chlor, Brom oder Phenoxy steht,
mit einer Anthrachinonverbindung der Formel (IX)

worin
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht
umsetzt.Another object of the invention is a process for the preparation of the dyes of the formula (I) according to the invention,
wherein B stands for a bridge -OB ¹ -O- and
B ¹ for a bridge of the formula

stands,
R ^{2 is} methyl, ethyl, methoxy or fluorine,
X for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
l is an integer from 0 to 8,
m, n, p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently of one another represent an integer from 1 to 4,
characterized in that an anthraquinone compound of the formula (II)

wherein
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and
R is chlorine, bromine or phenoxy,
with an anthraquinone compound of the formula (IX)

wherein
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl
implements.

at Formulas (II), (IV) and (IX) are analogous to formula (I) Isomers meant, for. B.

The Implementation takes place, for example, in the molar ratio (II) / (III) or (IV) / (V) or (IV) / (VI) or (IV) / (VII) or (IV) / (VIII) of 2/1 or im molar ratio (II) / (IX) of 1/1. However, it may also be advantageous to one of to use both components in excess relative to this ratio.

The Reaction is advantageously carried out in a solvent. Examples are dipolar aprotic solvents such as N-methyl or -ethylpyrrolidone, dimethylformamide and aromatic solvent such as toluene, xylene, chlorobenzene, 1,2-dichlorobenzene, methyl benzoate and heterocycles such as pyridine, quinoline.

The Reaction takes place advantageously in the presence of a base. suitable For example, bases are hydroxides, carbonates, amines, e.g. B. alkali hydroxides such as sodium or potassium hydroxide, alkali metal carbonates such as sodium or Potassium carbonate, amines such as pyridine, quinoline, triethylamine.

Phase transfer catalysts like quaternary Ammonium salts or crown ethers also be added. Examples are tetrabutylammonium bromide, Trimethylbenzylammonium hydroxide, tricaprylmethylammonium chloride, 18-crown-6.

The Implementation takes place, for example, at temperatures in the range 80 up to 220 ° C, preferably in the range 80 to 180 ° C, particularly preferably in Range 100 to 160 ° C.

Especially preference is given in the reaction of the compounds of the formula (II) with those of formula (III) anhydrous sodium or potassium carbonate as the base and N-methyl or -ethylpyrrolidone as the solvent or anhydrous sodium or potassium carbonate as the base, 1,2-dichlorobenzene as a solvent and 18-crown-6 or tetrabutylammonium bromide or tricaprylmethylammonium chloride as a phase transfer catalyst.

To completed implementation can for example, the reaction products by the addition of alcohols such as methanol or ethanol or water or mixtures thereof precipitated and isolated by filtration and optionally further purified become.

entspricht,
worin
R¹ für Wasserstoff, gegebenenfalls substituiertes C₁-C₈-Alkyl oder gegebenenfalls substituiertes C₃-C₈-Cycloalkyl steht,
mit einem bifunktionellen Aldehyd der Formel (XI) OCH-B²-CHO (XI), worin
B² für eine Brücke der Formel

steht,
Y für eine Brücke der Formel

steht,
p und r unabhängig voneinander für eine ganze Zahl von 1 bis 8 stehen,
q für eine ganze Zahl von 2 bis 8 steht und
s und t unabhängig voneinander für eine ganze Zahl von 1 bis 4 stehen,
umsetzt.Another object of the invention is a process for the preparation of the dyes of the formula (I) according to the invention,
wherein
B represents a bridge -CH ₂ -B ² -CH ₂ -,
characterized in that a dihydroanthraquinone compound which is in a tautomeric form of the formula (X)

corresponds,
wherein
R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl,
with a bifunctional aldehyde of the formula (XI) OCH-B ² -CHO (XI), wherein
B ² for a bridge of the formula

stands,
Y for a bridge of the formula

stands,
p and r independently of one another represent an integer from 1 to 8,
q stands for an integer from 2 to 8 and
s and t independently of one another represent an integer from 1 to 4,
implements.

The Implementation takes place, for example, in the molar ratio (X) / (XI) of 2/1. It however, it may also be advantageous to relatively one of the two components to this relationship in excess use.

The reaction is advantageously carried out in a solvent. Examples of these are C ₁ -C ₁₀ -alcohols such as methanol, ethanol, propanol, 2-propanol, butanol, pentanol, hexanol, benzyl alcohol, dipolar aprotic solvents such as N-methyl- or -ethylpyrrolidone, dimethylformamide and aromatic solvents such as toluene, xylene, Chlorobenzene, 1,2-dichlorobenzene, methyl benzoate and heterocycles such as pyridine, quinoline.

The Reaction takes place advantageously in the presence of acids and / or bases. suitable acids are, for example, hydrochloric acid, benzenesulfonic, toluene sulfonic acid, Acetic acid, Methane sulfonic acid. Suitable bases are, for example, amines such as piperidine, morpholine, Piperazine, pyridine, quinoline, triethylamine. Also advantageous is the combination of acids and bases, for example acetic acid and piperidine.

The Implementation takes place, for example, at temperatures in the range 40 up to 180 ° C, preferably in the range 70 to 120 ° C.

To completed implementation can For example, the reaction products, optionally by addition of alcohols such as methanol or ethanol or of water or mixtures of which precipitated and isolated by filtration and optionally further purified become.

One Another object of the invention are masterbatches containing 15 to 70 wt.%, Preferably 40 to 70 wt.% Of the dye of the invention the formula I and a carrier.

The The invention further relates to the use of the compounds according to the invention of the formula I to the mass coloring of plastics.

The The invention further relates to the use of the compound according to the invention of the formula I or the mixtures according to the invention for dyeing Synthetic fibers, preferably in dispersed form.

Examples

example 1

• UV/VIS (NMP): = λ_max = 523, 561 nm, ε = 24880 l mol^–1 cm^–1 (bei 523 nm).

2.70 g of cyclohexylidene-bisphenol were under nitrogen atmosphere in 20 ml of N-methylpyrrolidone with 4 ml of 50 percent strength. Potash solution stirred at 100 ° C for 3 h. Subsequently, 6.40 g of 1-amino-2-bromo-4-hydroxyanthraquinone were added. 2 h was stirred at 120 ° C, cooled to 80 ° C, diluted with 15 ml of methanol and filtered with suction after cooling to room temperature. After washing with 10 ml of methanol and 100 ml of hot water was dried at 80 ° C in vacuo. This gave 3.90 g (52% of theory) of a red powder of the formula

• UV / VIS (NMP): = λ _max = 523, 561 nm, ε = 24880 l mol ^-1 cm ^-1 (at 523 nm).

Example 2

• UV/VIS (NMP): λ_max = 523, 560 nm, ε = 20850 l mol^–1 cm^–1 (bei 523 nm).

Analogously to Example 1, but using 3.5 g of 4,4- (1,3-phenylenediisopropylidene) bisphenol gave 4.80 g (57.6% of theory) of a red powder of the formula

• UV / VIS (NMP): λ _max = 523, 560 nm, ε = 20850 l mol ^-1 cm ^-1 (at 523 nm).

Example 3

• UV/VIS (NMP): λ_max = 522, 558 nm, ε = 23970 l mol^–1 cm^–1 (bei 522 nm).

2.30 g of 2,2-bis (4-hydroxy-3-methylphenyl) propane were in a nitrogen atmosphere in 15 ml of N-methylpyrrolidone with 4 ml of 50 percent strength. Potash solution stirred at 100 ° C for 3 h. Subsequently, 5.71 g of 1-amino-2-bromo-4-hydroxyanthraquinone were added. Stirred at 120 ° C for 7 h, cooled to 80 ° C, diluted with 15 ml of methanol and filtered with suction after cooling to room temperature. After washing with 10 ml of methanol and 100 ml of hot water was dried at 80 ° C in vacuo. 1.07 g (16% of theory) of a red powder of the formula were obtained

• UV / VIS (NMP): λ _max = 522, 558 nm, ε = 23970 l mol ^-1 cm ^-1 (at 522 nm).

Example 4

• UV/VIS (NMP): λ_max = 518, 555 nm, ε = 24420 l mol^–1 cm^–1 (bei 518 nm).

Under a nitrogen atmosphere, 2.50 g of 1,4-bis (2-hydroxyethoxy) benzene, 1.42 g of potassium hydroxide and 8.36 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone in 20 ml of N-ethylpyrrolidone registered and 11 Stirred at 130 ° C h. After cooling to 80 ° C was diluted with 60 ml of methanol and filtered with suction after cooling to room temperature. After washing with 10 ml of methanol and 100 ml of hot water was dried at 80 ° C in vacuo. This gave 6.80 g (80% of theory) of a red powder of the formula

• UV / VIS (NMP): λ _max = 518, 555 nm, ε = 24420 1 mol ^-1 cm ^-1 (at 518 nm).

Example 5

• UV/VIS (NMP): λ_max = 525, 560 nm, ε = 26710 l mol^–1 cm^–1 (bei 525 nm).

Under a nitrogen atmosphere, 2.50 g of 2,7-dihydroxynaphthalene, 3.31 g of anhydrous sodium carbonate, 0.83 g of 18-crown-6 and 9.93 g of 1-amino-2-bromo-4-hydroxyanthraquinone in 25 ml of 1, Added 2-dichlorobenzene and stirred at 165 ° C for 4 h. After cooling to 80 ° C was diluted with 60 ml of methanol, stirred for 1 h at 60 ° C and filtered with suction after cooling to room temperature. After washing with 10 ml of methanol and 100 ml of hot water was dried at 80 ° C in vacuo. This gave 7.51 g (76% of theory) of a red powder of the formula

• UV / VIS (NMP): λ _max = 525, 560 nm, ε = 26710 1 mol ^-1 cm ^-1 (at 525 nm).

Example 6

erhalten.

• UV/VIS (NMP): λ_max = 525, 561 nm, ε = 23870 l mol^–1 cm^–1 (bei 525 nm).

Analogously to Example 5, using 2.50 g of 2,6-dihydroxynaphthalene, 8.00 g (80.8% of theory) of a red powder of the formula

receive.

• UV / VIS (NMP): λ _max = 525, 561 nm, ε = 23870 1 mol ^-1 cm ^-1 (at 525 nm).

Example 7

• UV/VIS (NMP): λ_max = 518, 556 nm, ε = 14740 l mol^–1 cm^–1 (bei 518 nm).

Under a nitrogen atmosphere, 2.50 g of 1,4-butanediol and 5.88 g of sodium carbonate in 35 ml of N-ethylpyrrolidone were stirred at 150 ° C. for 3 hours. Then 18.4 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone were added and it was stirred at 160 ° C for 24 h. After cooling to 80 ° C was diluted with 60 ml of methanol, stirred for 1 h at 60 ° C and filtered with suction after cooling to room temperature. After washing with 10 ml of methanol and 100 ml of hot water was dried at 80 ° C in vacuo. This gave 8.53 g of a red powder. This was boiled for purification twice in 100 ml of toluene for 2 h, filtered off with suction while hot and washed with 250 ml of hot toluene and then 100 ml of hot methanol. Finally, it was washed with 100 ml of hot water and dried at 80 ° C in a vacuum. This gave 5.42 g (35% of theory) of a red powder of the formula

• UV / VIS (NMP): λ _max = 518, 556 nm, ε = 14740 l mol ^-1 cm ^-1 (at 518 nm).

Example 8

• a) 2.24 g of potassium hydroxide were dissolved in 62 g of ethylene glycol. 9.9 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone were added and it was stirred for 6 h at 120 ° C under a nitrogen atmosphere. After cooling to room temperature was filtered off, washed with 20 ml of ethylene glycol and 100 ml of water and dried at 80 ° C in a vacuum. 7.7 g (86% of theory) of a red powder of the formula were obtained
  
• b) 2.0 g of the product from a) were initially charged under nitrogen in 25 ml of pyridine. 0.68 g of terephthalic acid dichloride was added and stirred at reflux for 7 hours. After cooling to room temperature was filtered off, washed with 10 ml of methanol and 100 ml of hot water and dried at 80 ° C in a vacuum. 1.85 g (76% of theory) of a red powder of the formula were obtained
  
  UV / VIS (NMP): λ _max = 518, 555 nm.

Example 9

• UV/VIS (NMP): λ_max = 519, 555 nm, ε = 21960 l mol^–1 cm^–1 (bei 519 nm).

2.53 g of 1,4-cyclohexanedimethanol 3.71 g of anhydrous sodium carbonate were stirred in 30 ml of N-ethylpyrrolidone under nitrogen atmosphere at 120 ° C. for 3 hours. 11.49 g of 1-amino-2-phenoxy-4-hydroxyanthraquinone were added and then stirred at 160 ° C for 15 h. After cooling to 100 ° C was diluted with 60 ml of methanol and cooled to room temperature. It was filtered off, washed with 10 ml of methanol and 100 ml of hot water and dried at 80 ° C in a vacuum. The crude product was boiled in 100 ml of toluene with stirring for 3 h, filtered off with suction while hot, washed with 10 ml of hot toluene and 30 ml of methanol and dried at 80 ° C. in vacuo. This gave 2.71 g (25% of theory) of a red powder of the formula

• UV / VIS (NMP): λ _max = 519, 555 nm, ε = 21960 1 mol ^-1 cm ^-1 (at 519 nm).

Example 10

erhalten.

• UV/VIS (NMP): = 521, 552 nm, ε = 13450 l mol^–1 cm^–1 (bei 521 nm).

Analogously to Example 1, 2.73 g of 2,2-bis (4-hydroxyphenyl) propane and 6.69 g of 1-amino-2-bromo-4-methoxyanthraquinone were admixed with 4.73 g (64.3%). d. Th.) of the red dye of the formula

receive.

• UV / VIS (NMP): = 521, 552 nm, ε = 13450 l mol ^-1 cm ^-1 (at 521 nm).

Example 11

erhalten.Analogously to Example 1 using 2,2-bis (4-hydroxyphenyl) propane and 1-amino-3-bromo-4-hydroxyanthraquinone, the dye of the formula

receive.

Example 12

• UV/VIS (NMP): λ_max = 538, 574 nm.

6.70 g of terephthaldehyde, 24.1 g of 1-amino-4-hydroxy-dihydroanthraquinone, 2.55 g of piperidine and 1.80 g of glacial acetic acid were stirred under nitrogen atmosphere in 150 ml of N-methylpyrrolidone with stirring at 150 ° C for 8 h. After cooling to room temperature, the violet suspension was filtered off, washed with 40 ml of N-methylpyrrolidone, 100 ml of methanol and 300 ml of hot water. After drying at 80 ° C. in vacuo, 15.8 g (54% of theory) of a violet powder of the formula were obtained

• UV / VIS (NMP): λ _max = 538, 574 nm.

Dyeing

• a) 100 g of polystyrene granules and 0.02 g of the Dye of Example 4 are in the drum mixer during 15 min intensively mixed. The dry-dyed granules are at 240 ° C on a screw injection processed. You get transparent bluish red plates of very good lightfastness and migrant authenticity.

Instead of of polystyrene polymer can also copolymers with butadiene and acrylonitrile can be used.

• b) 0,025 g des Farbstoffs aus Beispiel 4 werden mit 100 g Polyethylenterephthalat einer transparenten Type vermischt und in einem Zweiwellenextruder bei 280°C homogenisiert. Man erhält eine transparente blaustichig rote Färbung mit guter Lichtechtheit und Migrierechtheit. Nach anschließender Granulierung kann der eingefärbte Kunststoff nach den üblichen Methoden der thermoplastischen Verformung verarbeitet werden.

If, in addition, 0.5 g of titanium dioxide is added, the result is strong, covered colorings.

• b) 0.025 g of the dye from Example 4 are mixed with 100 g of polyethylene terephthalate of a transparent type and homogenized in a twin-screw extruder at 280 ° C. This gives a transparent bluish red coloration with good light fastness and migration fastness. After subsequent granulation of the colored plastic can be processed by the usual methods of thermoplastic deformation.

• c) 100 g eines handelsüblichen Polycarbonats werden in Form von Granulat mit 0,03 g des Farbstoffs aus Beispiel 4 trocken vermischt. Das so bestäubte Granulat in einem Zweiwellenextruder bei 290°C homogenisiert. Man erhält eine transparente blaustichig rote Färbung mit guter Lichtechtheit und Migrierechtheit. Das gefärbte Polycarbonat wird als Strang aus dem Extruder ausgetragen und zu Granulat verarbeitet. Das Granulat kann nach den üblichen Methoden der Konfektionierung thermoplastischer Massen verarbeitet werden.

If you work with the addition of 1% titanium dioxide, you get a muted color.

• c) 100 g of a commercial polycarbonate are dry blended in the form of granules with 0.03 g of the dye of Example 4. The granules so dusted in a twin-screw extruder at 290 ° C homogenized. This gives a transparent bluish red coloration with good light fastness and migration fastness. The dyed polycarbonate is discharged as a strand from the extruder and processed into granules. The granules can be processed by the usual methods of manufacturing thermoplastic materials.

• d) Analog wird verfahren unter Benutzung eines Stryrol-Acrylnitri-Copolymerisats, jedoch wird bei 190°C homogenisiert.
• e) In 98,9 g Styrol werden 0,05 g tert.-Dodecylmercaptan sowie 0,05 g des Farbstoffs aus Beispiel 4 gelöst. Diese Lösung dispergiert man in einer Lösung aus 200 g entsalztem Wasser, 0,3 g teilverseiftem Polyvinylacetat (z. B. Mowiol^® 50/88) und 0,05 g Dodecylbenzolsulfonat. Nach Zugabe von 0,1 g Dibenzoylperoxid gelöst in 1 g Styrol wird die Dispersion unter kräftigem Rühren auf 80°C erhitzt und die Polymerisation gestartet. Bei Anwendung folgender Polymerisationsbedingungen: 4 h bei 80°C, 2 h bei 90°C, 3 h bei 110°C, 2 h bei 130°C, erhält man das Polymerisat in einer Ausbeute von 98% der Theorie. Das Polymerisat fällt in Form von Perlen an, die je nach Rührbedingungen einen Durchmesser von 0,1 bis 1,5 mm (D₅₀-Wert) aufweisen. Das Polymerisat wird durch Filtration vom Serum getrennt und bei 110°C auf eine Restfeuchte von 0,5% getrocknet. Nach dem Aufschmelzen (Heißwalze) weren 0,5% Zinkstearat ind 0,2% Ionol zugemischt und das Polymerisat granuliert.

If you work with the addition of 1% titanium dioxide, you get a muted color.

• d) The procedure is analogous using a styrene-acrylonitrile copolymer, but homogenized at 190 ° C.
• e) In 98.9 g of styrene, 0.05 g of tert-dodecyl mercaptan and 0.05 g of the dye of Example 4 are dissolved. This solution was dispersed in deionized water a solution of 200 g, 0.3 g of partially hydrolyzed polyvinyl acetate (z. B. Mowiol ^® 50/88) and 0.05 g dodecylbenzenesulfonate. After addition of 0.1 g of dibenzoyl peroxide dissolved in 1 g of styrene, the dispersion is heated with vigorous stirring to 80 ° C and the polymerization started. When using the following polymerization conditions: 4 h at 80 ° C, 2 h at 90 ° C, 3 h at 110 ° C, 2 h at 130 ° C, the polymer is obtained in a yield of 98% of theory. The polymer is obtained in the form of beads which, depending on the stirring conditions, have a diameter of 0.1 to 1.5 mm (D ₅₀ value). The polymer is separated by filtration from the serum and dried at 110 ° C to a residual moisture content of 0.5%. After melting (hot roller), 0.5% zinc stearate and 0.2% ionol are mixed in and the polymer is granulated.

The bluish red colored Polymerizate can according to the usual Methods of thermoplastic deformation, z. B. injection molding, be processed to bluish red transparent moldings.

In analogous manner, the dyes of Examples 1-3 and 5-11 and use the dyes and mixtures of the following table. You get red or brown colors with good fastnesses.

mixing examples

• (1) = Formel (Ia) mit R¹ = H und
  
• (2) = Formel (Ia) mit R¹ = H und
  
• (3) = Beispiel 4 = Formel (Ia) mit R¹ = H und
  
• (4) = Formel (L) mit R¹⁰ = COOCH₃ und R¹¹ = H
• (5) = Formel (C) mit R²⁰ = COOCH₃, R²¹ = R²³ = CH₃, R²² = R²⁴ = CN, R²⁵ = -CH₂CH₂CH₂OCH₃, R²⁶ = H.
• (6) = Formel (LIII)
• 
• 
• (9) = Formel (CI) mit R²⁷ = R²⁸ = H
• (10) = Formel (CCI)
• (11) = Formel (CCII) mit R²⁹ = H
• (12) = Formel (CCIII) mit R³⁰ = CH₃, R³¹ = CN, R³² = Ethyl, R³³ = p-ständiges Cyclohexyl
• (13) = Formel (CCLI) mit R³⁴ = R³⁵ = H, R³⁶ = R³⁷ = p-ständiges CH₃
• 
• (15) = Beispiel 1 = Formel (Ia) mit R¹ = H und
  

The following dyes were used:

• (1) = formula (Ia) with R ¹ = H and
  
• (2) = formula (Ia) with R ¹ = H and
  
• (3) = Example 4 = Formula (Ia) with R ¹ = H and
  
• (4) = Formula (L) with R ¹⁰ = COOCH ₃ and R ¹¹ = H
• (5) = formula (C) where R ²⁰ = COOCH ₃ , R ²¹ = R ²³ = CH ₃ , R ²² = R ²⁴ = CN, R ²⁵ = -CH ₂ CH ₂ CH ₂ OCH ₃ , R ²⁶ = H.
• (6) = formula (LIII)
• 
• 
• (9) = formula (CI) with R ²⁷ = R ²⁸ = H
• (10) = formula (CCI)
• (11) = formula (CCII) with R ²⁹ = H
• (12) = formula (CCIII) where R ³⁰ = CH _3, R ³¹ = CN, R ³² = ethyl, R ³³ = p-permanent cyclohexyl
• (13) = formula (CCLI) with R ³⁴ = R ³⁵ = H, R ³⁶ = R ³⁷ = p-position CH ₃
• 
• (15) = Example 1 = Formula (Ia) with R ¹ = H and
  

Dyeing examples of the mixtures CIE color values transmission measurement PET transparent 2 mm Illum angle L * a * b * (7) (comparative) D65 10 ° 54.1 68.9 48.9 (8) (comparative) D65 10 ° 52.8 66.5 70.5 (14) (comparative) D65 10 ° 37.2 70.9 56.8 (5) (comparative) D65 10 ° 38.4 74.4 29.6 Amber 1 a (comparison) D65 10 ° 61.1 14.9 59.3 Amber 1 b D65 10 ° 63.0 13.6 59.0 Amber 1 c D65 10 ° 62.3 13.9 58.6 Amber 1 d D65 10 ° 61.9 14.3 59.3 Amber 2 a (comparison) D65 10 ° 59.7 10.8 46.0 Amber 2 b D65 10 ° 60.9 10.1 45.3 Amber 2 c D65 10 ° 61.6 10.7 45.4 Amber 2 d D65 10 ° 58.7 11.7 46.0 Amber 3 a (comparison) D65 10 ° 77.3 3.2 43.6 Amber 3 b D65 10 ° 77.0 2.8 45.5 Amber 3 c (comparative) D65 10 ° 62.8 13.7 58.5 Amber 3 d D65 10 ° 62.4 14.0 59.4 Amber 3 e (comparison) D65 10 ° 35.5 28.3 55.4 Amber 3 f D65 10 ° 35.7 29.4 55.1 Amber 4 a (comparison) D65 10 ° 74.6 3.7 33.6 Amber 4 b D65 10 ° 74.9 3.5 33.6 Amber 4 c (comparative) D65 10 ° 60.8 10.1 45.3 Amber 4 e (comparison) D65 10 ° 30.0 21.2 44.7 Amber 4 f D65 10 ° 30.6 22.8 44.7 (5) (comparative) D65 10 ° 43.8 80.3 3.4 (1) D65 10 ° 52.1 80.4 -13.6 (2) D65 10 ° 50.2 81.0 -12.1 (3) D65 10 ° 55.7 77.2 -4.9 Red 1 a D65 10 ° 42.5 73.2 72.5 Red 1 b D65 10 ° 50.4 71.2 54.5 Red 1 c D65 10 ° 62.2 56.8 32.7 (7) (comparative) D65 10 ° 54.0 69.0 48.9 Red 2 a D65 10 ° 48.2 72.1 51.3 Red 2 b D65 10 ° 46.6 72.4 51.1 Red 2 c D65 10 ° 51.9 69.8 59.9 Red 2 d D65 10 ° 47.5 71.3 59.1 Red 2 e D65 10 ° 46.1 71.7 57.9 Red 2 f D65 10 ° 51.1 69.6 66.0 Amber 5 a (comparison) D65 10 ° 61.7 14.5 59.2 Amber 5 b D65 10 ° 61.0 13.1 50.9 Amber 5 c D65 10 ° 60.8 13.2 48.8 Amber 5 d D65 10 ° 62.6 13.3 55.2 Amber 5 e D65 10 ° 57.0 24.9 70.3 Amber 5 f D65 10 ° 56.8 24.2 66.7 Amber 5 g D65 10 ° 59.0 23.3 73.1 Dye / 100 g PET [g] PET transparent 2 mm (7) comparison (8) Comparison (14) Comparison (5) Total dye (7) (comparative) 0.05000 0.050000 (8) (comparative) 0.05000 0.050000 (14) (comparative) 0.05000 0.050000 (5) (comparative) 0.05000 0.050000 Dye / 100 g PET [g] PET transparent 2 mm (7) comparison (5) + (4) 50.8 / 49.2 (13) (10) (11) (12) Total dye Amber 1 a 0.01210 0.00315 0.00475 0.020000 (Comparison) Amber 1 b 0.00370 0.00314 0.00492 0.011760 Amber 1 c 0.00350 0.00310 0.01320 0.019800 Amber 1 d 0.00370 0.00310 0.00470 0.011500 0.000000 Amber 2 a 0.01230 0.00460 0.00310 0.020000 (Comparison) Amber 2 b 0.00370 0.00400 0.00290 0.010601 Amber 2 c 0.00340 0.00360 0.00830 0.015300 Amber 2 d 0.00370 0.00410 0.00300 0.010800 Amber 3 a 0.00605 0.00157 0.00238 0.010000 (Comparison) Amber 3 b 0.00019 0.00016 0.00025 0.000588 Amber 3 c 0.01210 0.00315 0.00475 0.020000 (Comparison) Amber 3 d 0.00370 0.00314 0.00492 0.011760 Amber 3 e 0.03024 0.00787 0.01189 0.050000 (Comparison) Amber 3 f 0.00925 0.00785 0.01230 0.029400 Amber 4 a 0.00615 0.00229 0.00156 0.010000 (Comparison) Amber 4 b 0.00185 0.00200 0.00145 0.005300 Amber 4 c 0.01229 0.00459 0.00312 0.020000 (Comparison) Amber 4 d 0.00370 0.00400 0.00290 0.010600 Amber 4 e 0.03070 0.01150 0.00780 0.050000 (Comparison) Amber 4 f 0.00925 0.01000 0.00725 0.026500 Dye / 100 g PET [g] PET transparent 2 mm (7) comparison (5) (1) (2) (3) (4) Total dye 0.02500 0.025000 (5) (comparative) (1) 0.02500 0.025000 (2) 0.02500 0.025000 (3) 0.02500 0.025000 Red 1 a 0.02540 0.02460 0.050000 Red 1 b 0.02700 0.00550 0.032500 Red 1 c 0.01350 0.00280 0.016300 0.05000 0.050000 (7) (comparative) Red 2 a 0.03000 0.01800 0.048000 Red 2 b 0.03000 0.01800 0.048000 Red 2 c 0.03000 0.01800 0.048000 Red 2 d 0.03000 0.00600 0.036000 Red 2 e 0.03000 0.00600 0.036000 Red 2 f 0.03000 0.00600 0.036000 Dye / 100 g PET [g] PET transparent 2 mm (7) comparison (1) (2) (3) (13) (4) (6) (10) Total dye Amber 5 a 0.01210 0.00315 0.00475 0.020000 (Comparison) Amber 5 b 0.00570 0.00320 0.00340 0.00480 0.017100 Amber 5 c 0.00530 0.00320 0.00310 0.00480 0.016400 Amber 5 d 0.00600 0.00320 0.00360 0.00480 0.017600 Amber 5 e 0.00530 0.00320 0.00320 0.00480 0.016500 Amber 5 f 0.00500 0.00320 0.00300 0.00480 0.016000 Amber 5 g 0.00550 0.00320 0.00330 0.00480 0.016800

Solutions of the mixtures

• E11 = Extinktion von 1 g dieser Lösung in 100 ml N-Methylpyrrolidon gemessen in einer 1-cm-Küvette

The maximum solubility of the dyes was determined in methyl benzoate. To these saturated solutions was finally added the indicated amount of the orange dye (4) (= formula (L) with R ¹⁰ = COOCH ₃ and R ¹¹ = H). This dye was also completely dissolved. Maximum solubility of the dyes in methyl benzoate and spectral data dye Solubility g / 100 ml absorption maximum E11 (7) 0,107 496 nm 0.17 (5) 0.37 536 nm 3.2 (15) 0.57 523, 558 nm 1.8 (1) 0.55 523, 558 nm 1.75 (2) 0.05 524, 560 nm 0.06 (4) 1.64 471 nm 19

• E11 = Absorbance of 1 g of this solution in 100 ml of N-methylpyrrolidone measured in a 1 cm cuvette

• E11 = Extinktion von 1 g dieser Lösung in 100 ml N-Methylpyrrolidon gemessen in einer 1-cm-Küvette
• (sh) = Schulter

Solutions of red mixtures in methyl benzoate and spectral data Dye 1 Amount q / 100 ml Dye 2 Amount g / 100 ml absorption maximum E11 (7) 0,107 - 496 nm 0.17 (5) 0.37 (4) 0.346 490 nm 5 (15) 0.57 (4) 0.6 477, 557 (sh) nm 7.45 (15) 0.57 (4) 0,383 481, 517 (sh), 558 nm 5 (15) 0.57 (4) 0.15 489, 519, 559 nm 2.6 (1) 0.55 (4) 0.583 475, 556 (sh) nm 6.65 (1) 0.55 (4) 0.138 489, 519, 558 nm 2.8 (2) 0.05 (4) 0.07 473, 557 (sh) nm 0.7 (2) 0.05 (4) 0,035 492, 521, 560 nm 0.66

• E11 = Absorbance of 1 g of this solution in 100 ml of N-methylpyrrolidone measured in a 1 cm cuvette
• (sh) = shoulder

maximal erzielbare Farbstärke (= Extinktion) die Lösungen der erfindungsgemäßen Rotfarbstoffe und Rotmischungen bis über 80 mal farbstärker sind.The spectral data of the solutions were investigated. It can be seen that, relative to that with a saturated solution of the reference dye (7)

maximum achievable color strength (= extinction), the solutions of the red dyes and red mixtures according to the invention are more than 80 times stronger in color.

extrusion tests

• a) mit dem Vergleichs-Farbstoff (7)
• b) mit einer 50/50 Mischung aus dem roten Farbstoff (5) und dem orangen Farbstoff (4).

The extrusion trials were carried out with PET as plastic and

• a) with the comparative dye (7)
• b) with a 50/50 mixture of the red dye (5) and the orange dye (4).

For the experiments an extruder from Leistritz ZSE 18 HP was used.

The Speed was constant at 600 rpm and the jacket temperature of the Cylinder at 245 ° C held.

The Dosing of the PET / dye mixture was carried out via a metering unit of Type Grabender DS28 with single screw at a speed of 25 Upm The PET type Voridian 9921 W was used.

As can be seen from the following table, the mass pressure increases when using dye (7) already significantly from 12 to 16 bar, if one increases the concentration of the dye from 20 to 30%. In contrast, the mass pressure when using a dye mixture of equal parts of dye (5) and (4) and a total dye content of 30% at 4 bar is significantly lower and surprisingly does not increase further at a total dye concentration to 45%. It is therefore possible a much higher loading of the batch. Pressure (bar) dye content Mixture of dye (5) and (4) 1: 1 Dye (7) 20 7 12 30 4 16 40 4 - 45 4 -

Claims (25)

Mixtures containing at least one red dye of the formula (I), (C) or (CI)

in which R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl, B is a bridge of the formulas -OB ¹ -O- or -CH ₂ -B ² -CH ₂ - R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl, B ^{1 is} a bridge of the formula

B ^{2 is} a bridge of the formula

R ^{2 is} hydrogen, methyl, ethyl, methoxy or fluoro, X is a bridge of the formula

Y stands for a bridge of the formula

l is an integer from 0 to 8, m, n, p and r independently of one another are an integer from 1 to 8, q is an integer from 2 to 8 and s and t independently of one another are integers from 1 to 4, R ²⁰ and R ²² independently of one another are cyano or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{21 is} hydrogen or optionally substituted C ₁ -C ₃ -alkyl, R ^{23 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{24 is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{25 is} optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl, optionally substituted C ₆ -C ₁₀ -aryl, R ^{26 is} hydrogen or independently of R ^{25 has} the meaning of R ²⁵ or NR ²⁵ R ²⁶ for pyrrolidino, piperidino o the morpholino, R ^{27 is} one or more radicals which are hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, fluorine, cyano, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl, R ^{28 is} hydrogen or optionally substituted C ₁ -C ₈ -alkyl, and at least one orange dye of the formula (L), (LI), (LII), (LIII), ( LIV) or (LV)

wherein R ^{10 is} hydrogen, optionally substituted C ₁ -C ₈ alkyl, optionally substituted C ₁ -C ₈ alkoxy, optionally substituted C ₁ -C ₈ alkylsulfonyl, optionally substituted C ₁ -C ₈ alkoxycarbonyl, nitro, cyano or Fluorine, R ^{11 is} hydrogen, optionally substituted C ₁ -C ₈ alkyl, optionally substituted C ₁ -C ₈ alkoxy, ge optionally substituted C ₁ -C ₈ alkoxycarbonyl, nitro, cyano or fluorine, R ^{12 is} hydrogen, optionally substituted C ₁ - ₈ alkyl or optionally substituted C ₃ -C ₈ cycloalkyl, R ^{13 is} hydrogen, optionally substituted C C ₁ -C ₈ -alkyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{14 is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, X ^{1 is} O or S. X ^{2 is} N or C-CN, R ¹⁵ and R ¹⁶ independently of one another are optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₈ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl or NR ¹⁵ R ^{16 is} pyrrolidino, piperidino or morpholino, R ^{17 is} hydrogen or C ₁ -C ₈ -alkyl, R ^{18 is} optionally substituted C ₆ -C ₁₀ -aryl, R ^{23 'is} hydrogen, optionally substituted C C ₁ -C ₈ alkyl or ge optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{24 'is} cyano, optionally substituted C ₁ -C ₈ -alkylsulfonyl or optionally substituted C ₁ -C ₈ -alkoxycarbonyl, R ^{25' is} optionally substituted C ₁ -C ₈ - Alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl, optionally substituted C ₆ -C ₁₀ -aryl, R ^{26 'is} hydrogen or independently of R ^{25' has} the meaning of R ^{25 '} or NR ^25' R ^{26 '} for pyrrolidino , Piperidino or morpholino, R ⁴³ and R ^{44 are} independently hydrogen, optionally substituted C ₁ -C ₄ alkyl, in particular by one or more fluorine-substituted C ₁ -C ₄ alkyl, nitro, cyano, C ₁ -C ₄ Alkoxycarbonyl and R ^{45 is} hydrogen, methyl, fluorine or chlorine. Mixture according to claim 1 comprising a red dye of the formula (I) and at least one Orange dye of the formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular the formula (L). Mixture according to claim 1 comprising a red dye of the formula (C) and at least one Orange dye of the formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular the formula (L). Mixtures according to claim 1 containing a red dye of the formula (CI) and at least an orange dye of the formula (L), (LI), (LII), (LIII), (LIV) or (LV), in particular of the formula (L). Mixture according to claim 1, comprising a red dye of the formula I in which R ^{1 is} hydrogen or methyl, B ^{1 is} a bridge of the formula

R ^{2 is} methyl or chlorine, X is a bridge of the formula

Y stands for a bridge of the formula

where l is an integer from 0 to 4, m, n and p are independently an integer from 1 to 4, q and r are independently an integer from 2 to 6, s and t are independently are an integer from 1 to 2 and the indefinite ring positions are 1,2-, 1,3- or 1,4-. A mixture according to claim 1 containing a red dye of formula (I) wherein R ^{1 is} hydrogen or methyl, B ^{2 is} a bridge of formula

Y stands for a bridge of the formula

p is an integer from 1 to 6 and r is an integer from 2 to 6 and the indefinite ring positions in benzene or cyclohexane rings 1,2-, 1,3- or 1,4- and the naphthalene ring 2 , 6- and 2,7- mean. Mixture according to Claim 1, containing a red dye of the formula (C) in which R ^{20 is} cyano, methoxycarbonyl or ethoxycarbonyl, particularly preferably cyano or methoxycarbonyl, very particularly preferably methoxycarbonyl, R ^{22 is} cyano, R ^{21 is} hydrogen or methyl preferably methyl, R ^{23 is} methyl or methoxycarbonyl, more preferably methyl, R ^{24 is} cyano, methanesulfonyl, methoxycarbonyl or ethoxycarbonyl, more preferably cyano, R ^{25 is} methyl, ethyl, propyl, butyl, methoxyethyl, methoxypropyl, cyanoethyl, benzyl , Cyclohexyl, phenyl or tolyl, particularly preferably ethyl, propyl, butyl, methoxyethyl, methoxypropyl, benzyl, cyclohexyl or phenyl, very particularly preferably propyl, butyl or methoxypropyl, R ^{26 is} hydrogen or, independently of R ^25, the meaning of R ²⁵ , or NR ²⁵ R ^{26 is} pyrrolidino, piperidino or morpholino, especially when R ^{20 is} COOCH ₃ , R ²¹ and R ^{23 is} CH ₃ , R ²² and R ^{24 is} CN, R ^{25 is} -CH ₂ CH ₂ CH ₂ OCH ₃ and R ^{26 is} H and an orange dye of the formula (L), in particular wherein R ^{10 is} COOCH ₃ and R ^{11 is} H. Mixture according to claim 1, further comprising at least a) a yellow dye, preferably with a λ _max of 420 to 460 nm and at least one green dye, preferably with a λ _max of 610 to 700 nm or b) a yellow dye, preferably with one λ _max of 420 to 460 nm and at least one blue dye, preferably one of 570 to 640 nm. Mixtures according to Claim 1, characterized in that they additionally contain a) at least one yellow dye of the formula (CCI), (CCII), (CCIII), (CCIV) or (CCV)

wherein R ^{29 is} one or more radicals which are hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, fluorine, cyano, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C C ₆ -C ₁₀ -aryl, R ^{30 is} hydrogen, methyl, ethyl or methoxy, R ^{31 is} cyano, C ₁ -C ₈ -alkoxycarbonyl or C ₁ -C ₈ -alkanesulfonyl, R ^{32 is} hydrogen, optionally substituted C C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₇ -cycloalkyl, R ^{33 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₁ -C ₈ -alkoxy, optionally substituted C ₃ -C ₇ Cycloalkyl or optionally substituted C ₆ -C ₁₀ aryl, and B ^{3 is} a bridge of the formula

and at least one green dye of the formula (CCLI) contains

wherein R ³⁴ and R ³⁵ are independently hydrogen, hydroxy or C ₁ -C ₄ alkoxy, R ³⁶ and R ³⁷ are independently hydrogen, optionally substituted C ₁ - C ₈ alkyl, optionally substituted C ₁ -C ₈ - Alkoxy, fluorine, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl, or b) at least one yellow dye of the formula (CCI), (CCII), (CCIII), (CCIV) or ( CCV) and at least one blue dye of the formula (CCCI)

wherein R ³⁸ and R ³⁹ independently of one another represent optionally substituted C ₁ -C ₈ -alkyl, optionally substituted C ₃ -C ₇ -cycloalkyl or optionally substituted C ₆ -C ₁₀ -aryl. Masterbatch containing 15-80, in particular 15-70% by weight a mixture according to claim 1 and a carrier. Use of a mixture according to claim 1 for mass-dyeing Plastics. Process for the mass coloration of plastics, thereby in that the mixture according to claim 1, preferably in the form of their masterbatch incorporated into the molten plastic mass or already the starting components for the production of the plastic added before the polymerization. Plastics containing a mixture according to claim 1. Compounds of the formula I

in particular of the formula (Ia)

wherein -B- is -OB ¹ -O- or -CH ₂ -B ² -CH ₂ -, R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl, B ¹ for a bridge of the formula

B ^{2 is} a bridge of the formula

R ^{2 is} methyl, ethyl, methoxy or fluoro, X is a bridge of the formula

Y stands for a bridge of the formula

l is an integer from 0 to 8, m, n, p and r independently of one another are an integer from 1 to 8, q is an integer from 2 to 8 and s and t independently of one another integer from 1 to 4 stand. Compounds according to claim 14, characterized in that R ^{1 represents} hydrogen or methyl, B ^{1 represents} a bridge of formula

R ^{2 is} methyl, X is a bridge of the formula

Y stands for a bridge of the formula

where l is an integer from 0 to 4, m, n and p are independently an integer from 1 to 4, q and r are independently an integer from 2 to 6, s and t are independently are an integer from 1 to 2 and the indefinite ring positions are 1,2-, 1,3- or 1,4-. Compounds according to claim 14, characterized in that R ^{1 is} hydrogen or methyl, B ^{2 is} a bridge of formula

Y stands for a bridge of the formula

p is an integer from 1 to 6 and r is an integer from 2 to 6 and the indefinite ring positions in the benzene or cyclohexane ring 1,2-, 1,3- or 1,4- and the naphthalene ring 2 Mean 6 or 2,7. Process for the preparation of the dyes of the compound of the formula (I) in which B is a -OB ¹ -O- radical, according to Claim 14, characterized in that an anthraquinone compound of the formula (II)

in which R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and R is chlorine, bromine or phenoxy, with a bifunctional alcohol of the formula (III) HO-B ¹ -OH (III), wherein B ^{1 is} a bridge of formula

R ^{2 is} methyl, ethyl, methoxy or fluoro, X is a bridge of the formula

Y stands for a bridge of the formula

l is an integer from 0 to 8, m, n, p and r independently of one another are an integer from 1 to 8, q is an integer from 2 to 8 and s and t independently of one another integers from 1 to 4 are converted. A process for the preparation of compounds of formula (I) according to claim 14, wherein B is a bridge -OB ¹ -O- and B ^{1 is} a bridge of the formula

where Y is a bifunctional group of the formula

m, n and r independently of one another are an integer from 1 to 8 and n and m are identical and q is an integer from 2 to 8, characterized in that an anthraquinone compound of the formula (IV)

in which R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and n is an integer from 1 to 8, with a bifunctional acid chloride or ester of the formulas (V)

or (VI) A-CO- (CH ₂ ) _r -CO-A (VI) or a difunctional isocyanate of the formula (VII)

or (VIII) O = C = N- (CH ₂ ) _q -N = C = O (VIII) wherein A is Cl or methoxy, r is an integer from 1 to 8 and q is an integer from 2 to 8 reacted. A process for the preparation of the dyes of the formula (I) according to claim 14, wherein B is a bridge -OB ¹ -O-, and B ^{1 is} a bridge of the formula

R ^{2 is} methyl, ethyl, methoxy or fluoro, X is a bridge of the formula

Y stands for a bridge of the formula

l is an integer from 0 to 8, m, n, p and r independently of one another are an integer from 1 to 8, q is an integer from 2 to 8 and s and t independently of one another are integers from 1 to 4, characterized in that an anthraquinone compound of the formula (II)

in which R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ -alkyl or optionally substituted C ₃ -C ₈ -cycloalkyl and R is chlorine, bromine or phenoxy, with an anthraquinone compound of the formula (IX)

wherein R ^{1 is} hydrogen, optionally substituted C ₁ -C ₈ alkyl or optionally substituted C ₃ -C ₈ cycloalkyl. A process for the preparation of the dyes of the formula (I) according to claim 14, in which B is a bridge -CH ₂ -B ² -CH ₂ -, which comprises reacting a dihydroanthraquinone compound which is in a tautomeric form of the formula (X)

in which R ^{1 is} hydrogen, optionally substituted C ₁ - to C ₈ -alkyl or optionally substituted C ₃ - to C ₈ -cycloalkyl, with a bifunctional aldehyde of the formula (XI) OCH-B ² -CHO (XI), wherein B ^{2 is} a bridge of the formulas

Y stands for a bridge of formulas

each of p and r independently represents an integer of 1 to 8, q represents an integer of 2 to 8, and s and t independently represent an integer of 1 to 4. Masterbatch containing 15-90% by weight, in particular 15-70% by weight a compound of the formula I according to claim 14 and a carrier. Use of compounds according to claim 14 for mass-dyeing plastics Process for the mass coloration of plastics, thereby in that a compound according to claim 14, preferably incorporated into the molten plastic mass in the form of their masterbatch or already the starting components for the production of the plastic added before the polymerization. Plastics containing a compound according to claim 14th Use of the mixtures according to claim 1 or the compounds according to claim 14 for dyeing of synthetic fibers, preferably in dispersed form.