KR20040086312A - Fluorescent compositions comprising diketopyrrolopyrroles - Google Patents

Abstract

The present invention relates to diketopyrroles, in which the absorption spectrum of the guest chromophore overlaps the fluorescence emission spectrum of the host chromophore and the host chromophore exhibits a photoluminescence emission peak at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm. A fluorescent composition comprising a guest chromophore and a host chromophore, which is pyrrole and a diketopyrrolopyrrole having a guest chromophore at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm, and an ink, colorant, It relates to pigment particles for coating, impact-printing materials, color filters, cosmetics, polymeric ink particles, toners, dye lasers and their use for the production of electroluminescent devices. The light emitting device comprising the composition according to the present invention has high electrical energy utilization efficiency and high luminance.

Description

Fluorescent compositions comprising diketopyrrolopyrroles

In the present invention, an absorption spectrum of a guest chromophore overlaps with a fluorescence emission spectrum of a host chromophore, and the host chromophore is 500 to 720 nm, preferably 500 to 600 nm, and most preferably 520 to 580 nm. A diketopyrrolopyrrole exhibiting a photoluminescent emission peak and comprising a guest chromophore and a host chromophore, the diketopyrrolopyrrole exhibiting an absorption peak at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm. Fluorescent compositions, and their use for the production of inks, colorants, pigment particles for coating, impact-printing materials, color filters, cosmetics, polymeric ink particles, toners, dye lasers and electroluminescent devices. The light emitting device comprising the composition according to the present invention has high electrical energy utilization efficiency and high luminance.

At present, the vacuum evaporation process [Appl. Phys. Lett., 51, 913 (1987)] it is common to manufacture organic electroluminescent ("EL") devices containing organic fluorescent materials. In general, two types of such vacuum evaporation processes, one-component processes and two-component (or "host-guest type" or "binary system") processes, Applies according to structure. See J. Appl. Phys., 65, 3610 (1989).

In order to emit light of a red, green or blue color in a one-component system, the luminescent material itself must emit a strong fluorescence of a red, green or blue color. In addition, the vacuum evaporation process must provide a deposited film of uniform quality, and the film thus formed must be endowed with adequate ("carrier") mobility for positive holes and / or electrons, i. do.

Many materials that emit light in the green or blue region are known.

Japanese Patent Publication No. 2,749,407 [see: Pioneer Electron Corp.]. & Nippon Kayaku Co. Ltd.] discloses N, N'-bis (2,5-di-tert-butylphenyl) -3,4,9,10-perylenedicarboximide as a light emitting material. However, its brightness is low at 27 cd / m ² , which is insufficient for normal use.

Riko's Japanese Patent Laid-Open No. 2,296,891 claims a positive electrode, a negative electrode, and an electroluminescent device comprising a single organic compound layer or a plurality of organic compound layers contained between a positive electrode and a negative electrode, but claim a hole transport material. It wasn't. At least one of the organic compound layers is a layer containing a pyrrolopyrrole compound of formula II ″.

In formula (II) above,

Y ₁ and Y ₂ are independently substituted or unsubstituted alkyl, cycloalkyl or aryl groups,

Y ₃ and Y ₄ are independently a hydrogen atom or a substituted or unsubstituted alkyl or aryl group,

X represents an oxygen or sulfur atom.

Only four compounds are explicitly mentioned, where X is oxygen in all cases, (a) Y ₃ and Y ₄ are methyl and Y ₁ and Y ₂ are p-tolyl, and (b) Y ₃ and Y ₄ is methyl, Y ₁ and Y ₂ are hydrogen, (c) Y ₃ and Y ₄ are hydrogen, Y ₁ and Y ₂ are p-tolyl, and (d) Y ₃ , Y ₄ and Y ₁ are hydrogen Y ₂ is p-chlorophenyl. However, according to Japanese Patent Laid-Open No. 5,320,633 (see below), subsequent studies by the same inventors show that the emission of light is only observed when DPP-Compound II "is used with other compounds. Supported by Comparative Example 2 of Patent Publication No. 5,320,633, which discloses that DPP-Compound II "is used alone, i.e. without the addition of tris (8-hydroxyquinolinate) aluminum (" Alq ₃ "). No emission was observed.

Sumitomo JP 5,320,633 claims an organic EL device having a light emitting layer comprising 0.005 to 15 parts by weight of a positive luminescent material between a pair of electrodes, wherein at least one electrode is transparent or translucent. Although the main claim is not mention the use of Alq _3, being an essential feature in the description and Examples, especially Comparative Example 2. The EL device or the device is charged from the Alq ₃ the art will be apparent.

Japanese Unexamined Patent Publication No. 9,003,448 of Toyo Ink includes a light emitting layer containing a DPP compound as an electron transporting material or an electron injection layer containing a DPP compound as an electron transporting material and a light emitting layer between a pair of electrodes. An organic EL device having a compound thin film layer is claimed. In addition, another EL element is further claimed that further includes a hole injection layer. A disadvantage of the claimed EL device is that Alq ₃ and phenanthrene diamine must always be used (as a hole injection material) according to this embodiment.

EP-A-499,011 describes an electroluminescent device comprising a DPP compound. In particular, Example 1 describes DPP derivatives of Formula III '.

WO 98/33862 describes the use of a DPP compound of formula IV 'as guest molecule in an electroluminescent device.

EP 1 087 005 relates to fluorescent diketopyrrolopyrroles of the formula I '("DPP").

In Formula I 'above,

R _{1 '} and R _2' are, independently from each other, C ₁ -C ₂₅ alkyl; Allyl which may be substituted one to three times with C ₁ -C ₃ alkyl or Ar _{3 ′} ; Or —CR _{3 ′} R _{4 ′} — (CH ₂ ) _{m ′} —Ar _{3 ′} wherein R _{3 ′} and R _{4 ′} are independently of each other hydrogen; C ₁ -C ₄ alkyl; or C ₁ -C ₃ alkyl Phenyl which may be substituted one to three times, Ar _{3 ′} may be substituted one to three times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen or phenyl and C ₁ -C ₈ alkyl or C ₁ Phenyl, 1-naphthyl or 2-naphthyl, which may be substituted one to three times with -C ₈ alkoxy, m 'is 0, 1, 2, 3 or 4, and C ₁ -C ₂₅ alkyl or -CR _{3 '} R _4' -(CH ₂ ) _m -Ar _{3 '} , preferably C ₁ -C ₂₅ alkyl, is a functional group capable of increasing solubility in water such as tertiary amino groups, -S0 ₃ ^- or PO ₄ ^2- May be substituted with a group),

Ar ₁ and Ar ₂ are independently of each other Wherein R ₆ ′ and R ₇ ′ independently of one another are hydrogen, C ₁ -C ₆ alkyl, —NR ₈ 'R ₉ ', -OR ₁₀ ', -S (O) _n R ₈ ' or -Se (O ) _n R ₈ 'or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, but not at the same time), and R _{8 ′} and R _{9 ′} are independently of each other Hydrogen, C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl, —CR _{3 ′} R _{4 ′} — (CH ₂ ) _{m ′} —Ph, and R _{10 ′} is C ₆ -C ₂₄ aryl, or nitrogen, oxygen And 1 to 3 heteroatoms selected from the group consisting of sulfur and 5 to 7 ring atoms consisting of carbon atoms, saturated or unsaturated heterocyclic lycals, wherein Ph, aryl and heterocyclic radicals are C ₁ -C ₈ alkyl May be substituted one to three times with C ₁ -C ₈ alkoxy or halogen, or R _{8 ′} and R _{9 ′} are —C (O) R _{10 ′} , R _{11 ′} is C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ -cycloalkyl, R _{10 '} , -OR _12' or -NR _{13 '} R _14' , wherein R _{12 '} , R _13' and R _{14 ′} is C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₂₄ aryl, or 5 to 7 heteroatoms and carbon atoms selected from the group consisting of nitrogen, oxygen and sulfur Aryl and heterocyclic radicals may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or —NR _{8 ′.} R _{9 '} is R _8' and R _{9 '} is tetramethylene, pentamethylene, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -or -CH ₂ -CH ₂ -NR ₅ -CH ₂ -CH _2- , Preferably -CH ₂ -CH ₂ -O-CH ₂ -CH _2- , is a 5 or 6 membered heterocyclic radical, and n 'is 0, 1, 2 or 3.

DPP compounds can be used in the manufacture of inks, colorants, coating pigment particles, impact-printing materials, colored filters or cosmetics, or in the manufacture of polymeric ink particles, toners, pigment lasers and electroluminescent devices.

EP 1 087 006 discloses (a) an anode, (b) a hole transport layer, (c) a light emitting layer, (d) any electron transport layer and (e) a cathode and a diketopyrrolopyrrole of formula (I ') And an electroluminescent device sequentially comprising a luminescent material.

Further fluorescent DPP compounds and their use in electroluminescent devices are described in EP 01 810 636.

Surprisingly, it has been found that when a specific combination of DPP compounds is used as the light emitting material, a light emitting device having high electrical energy utilization efficiency and high brightness can be obtained.

Accordingly, the present invention provides that the absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore and the host chromophore exhibits a photoluminescence emission peak at 500 to 720 nm, preferably 500 to 600 nm and most preferably 520 to 580 nm. It relates to a composition comprising a guest chromophore and a host chromophore, which is diketopyrrolopyrrole and diketopyrrolopyrrole with a guest chromophore exhibiting an absorption peak at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm.

In a preferred embodiment, the present invention provides a composition comprising diketopyrrolopyrrole of formula (I) and DPP of formula (II), an electroluminescent device comprising the abovementioned composition, and the use of the composition for coloring high molecular weight organic materials, ie It relates to the use of the composition for the preparation of inks, colorants, pigment particles for coating, impact-printing materials, color filters, cosmetics, polymeric ink particles, toners, color lasers and electroluminescent devices.

In Formula I and Formula II above,

R ¹ , R ² , R ³ and R ⁴ are independently of each other C ₁ -C ₂₅ alkyl, which may be substituted by fluorine, chlorine or bromine, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl which may be condensed one or two times with phenyl which may be substituted one to three times with halogen, nitro or cyano, or with silyl, A ⁵ or -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ wherein R ¹¹ and R ¹² are independently of each other hydrogen, fluorine, chlorine, bromine or cyano, or C ₁ -C ₄ alkyl which may be substituted by fluorine, chlorine or bromine, or C ₁ -C Phenyl which may be substituted 1-3 times with ₃ alkyl, and A ⁵ is phenyl, 1-naph, which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen, nitro or cyano Yl or 2-naphthyl, phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or —NR ¹³ R ¹⁴ wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₂₅ Alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₂₄ aryl), in particular phenyl which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen or cyano, 1 -Naphthyl or 2-naphthyl, or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, m is 0, 1, 2, 3 or 4;

A ¹ and A ² are independently of each other [Wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkoxy, -OCR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , cyano, halogen , -OR ¹⁰ or -S (O) _p R ¹³ or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, R ¹⁰ is C ₆ -C ₂₄ aryl, or Saturated or unsaturated heterocyclic radical containing 5 to 7 ring atoms consisting of 1 to 3 heteroatoms and carbon atoms selected from the group consisting of nitrogen, oxygen and sulfur, R ¹³ is C ₁ -C ₂₅ alkyl, C _5- C ₁₂ cycloalkyl or —CR ¹¹ R ¹² — (CH ₂ ) _m —Ph, R ¹⁵ is C ₆ -C ₂₄ aryl, p is 0, 1, 2 or 3, n is 0, 1, 2, 3 or 4],

A ³ and A ⁴ are independent of each other [Wherein R ⁸ and R ⁹ independently of one another are hydrogen, C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl, -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ or C ₆ -C ₂₄ aryl , In particular A ^1, or a saturated or unsaturated heterocyclic radical comprising 5 to 7 ring atoms consisting of 1 to 3 heteroatoms and carbon atoms selected from the group consisting of nitrogen, oxygen and sulfur, R ¹⁶ and R ¹⁷ are mutually Independently hydrogen and C ₆ -C ₂₄ aryl, especially phenyl.

The present invention provides a red or orange fluorescent composition having high thermal stability and good solubility in materials such as polymers, hydrocarbon fuels, lubricants, and the like, and in plastics, especially polyamides and paints, without degradation and loss of light fastness. It provides the ability to be used under high electroluminescence (EL) emission intensity.

R ¹ , R ² , R ³ and R ⁴ independently of _one another are C ₁ -C ₂₅ alkyl, preferably C ₁ -C ₈ alkyl, in particular n-butyl, tertiary butyl, neopentyl or C ₅ -C ₁₂ cycles C ₅ -C ₁₂ cycloalkyl, in particular C ₁ -C ₈ alkyl, which may be alkyl or may be condensed one or two times with phenyl which may be substituted one to three times with C ₁ -C ₄ alkyl, halogen and cyano; Or cyclohexyl, in particular 2,6-diisopropylcyclohexyl, which may be substituted one to three times with C ₁ -C ₈ alkoxy, , Silyl, in particular trimethylsilyl, A ⁵ or -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , wherein R ¹¹ and R ¹² are independently of each other hydrogen or C ₁ -C ₄ alkyl, or C ₁ -C Phenyl which may be substituted 1-3 times with ₃ alkyl, and A ⁵ is phenyl, 1-naph, which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen, nitro or cyano Yl or 2-naphthyl, phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or wherein -NR ¹³ R ¹⁴ , wherein R ¹³ and R ¹⁴ are C _1- C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₂₄ aryl), in particular phenyl which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen or cyano, Phenyl, in particular 3,5-dimethylphenyl, 3,5-di-3, which may be 1-naphthyl or 2-naphthyl, or may be substituted 1-3 times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy Tertiary butylphenyl, 3-methylphenyl and 2,6-diisopropylphenyl, m is 0, 1, 2, 3 or Is 4, in particular 0 or 1].

Preferably, R ¹ and R ² are each independently of the other C ₁ -C ₈ alkyl, Or -CR ¹¹ R ¹² -A ⁵ , wherein R ¹¹ is hydrogen, R ¹² is hydrogen, in particular methyl or phenyl, A ⁵ is (Wherein R ⁵ , R ⁶ and R ⁷ are independently of each other hydrogen, C ₁ -C ₄ alkyl or halogen, in particular Br), a group Wherein R ⁵ , R ⁶ and R ⁷ are hydrogen; R ⁶ is C ₁ -C ₄ alkyl, phenyl or Br, R ⁵ and R ⁷ are hydrogen; R ⁵ is C ₁ -C ₄ alkyl, R ⁶ and R ⁷ are hydrogen; R ⁶ is hydrogen and R ⁵ and R ⁷ are most preferably C ₁ -C ₄ alkyl.

Preferably, R ³ and R ⁴ independently of _one another are C ₁ -C ₈ alkyl or —CR ¹¹ R ¹² -A ⁵ , wherein R ¹¹ is hydrogen, R ¹² is methyl or phenyl, in particular hydrogen, A ⁵ Is Wherein R ⁵ , R ⁶ and R ⁷ are independently of each other hydrogen, C ₁ -C ₄ alkyl or CN) or a group Wherein R ⁵ , R ⁶ and R ⁷ are hydrogen; R ⁶ is CN or C ₁ -C ₄ alkyl, R ⁵ and R ⁷ are hydrogen, R ⁵ and R ⁶ are CN, and R ⁷ is hydrogen Or R ⁵ is C ₁ -C ₄ alkyl and R ⁶ and R ⁷ are hydrogen; R ⁶ is hydrogen and R ⁵ and R ⁷ are C ₁ -C ₄ alkyl. .

The weight ratio of DPP compound of formula I to DPP compound of formula II is generally 50:50 to 99.99: 0.01, preferably 90:10 to 99.99: 0.01, more preferably 95: 5 to 99.9: 0.1, most preferably Is 98: 2 to 99.9: 0.1.

DPP compounds of formula (I) and formula (II) are distinguished by substituents A ¹ and A ² and A ³ and A ⁴ , respectively.

A ¹ and A ² are independently of each other Wherein R ⁵ , R ⁶ , R ⁷ , n and R ¹⁵ have the meanings mentioned above.

When phenyl or naphthyl substituent is substituted by a vinyl group, A ¹ and A ² are independently of each other [Where n is an integer from 1 to 4, in particular 1 or 2, R ⁵ and R ⁶ are independently of each other hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, R ¹⁵ is C ₆ -C ₂₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably C ₆ -C ₁₂ aryl, for example phenyl, 1-naphthyl, 2-naphthyl or 4-biphenyl, which may be unsubstituted or substituted by C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy. , Chemical formula Groups of are preferred.

A ¹ and A ² are independently of each other R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, -OCR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , cyano, chloro Or —OR ¹⁰ wherein R ¹⁰ is C ₆ -C ₂₄ aryl (eg, phenyl, 1-naphthyl or 2-naphthyl), R ¹¹ and R ¹² are hydrogen or C ₁ -C ₄ alkyl, m is 0 or 1 and A ⁵ is phenyl, 1-naphthyl or 2-naphthyl] or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, Chemical formula

(Wherein R ⁵ is C ₁ -C ₈ alkyl).

In addition, R ¹ and R ² is C ₁ -C ₂₅ alkyl, especially C ₁ -C ₂₅ alkyl, the group -CR ¹¹ R on which all or some of the hydrogen atoms can be replaced by a fluorine atom ¹² -A ⁵ (wherein, R ¹¹ is hydrogen or C ₁ -C ₁₄ alkyl, especially methyl, R ¹² is CF ₃ or F, A ⁵ is phenyl) or a group —CR ¹¹ R ¹² -A ⁵ , wherein R ¹¹ is hydrogen, R ¹² is C ₁ -C ₄ alkyl, especially methyl, and A ⁵ is a group (Wherein R ⁶ is fluorine, chlorine, bromine, preferably cyano or nitro), the DPP compound of formula (I) is preferred.

The term “fluorine-substituted C ₁ -C ₂₅ alkyl” is a straight or branched C ₁ -C ₂₅ alkyl group in which all or part of the hydrogen atoms are replaced by fluorine atoms. Examples of such groups are -CH ₂ F, -CHF ₂ , -F ₃ , FH ₂ CCH _2- , FH ₂ CCHF-, F ₂ HCCH _2- , F ₂ HCCHF-, F ₃ CCH _2- , F ₂ HCCF ₂ -, F ₃ CCHF-, F ₃ CCF _2- , CF ₃ CF ₂ CF _2- , CF ₃ CF ₂ CF ₂ CF ₂ -or F ₃ C (CF ₂ ) ₃ CF _2- .

Particularly preferred DPP compounds of formula I are the following compounds:

Formula I

A ³ and A ⁴ are independent of each other Wherein R ⁵ , R ⁶ , R ⁸ , R ⁹ , R ¹⁶ and R ¹⁷ are as mentioned above.

A ³ and A ⁴ are independently of each other R ⁵ and R ⁶ are preferably hydrogen, R ⁸ is preferably C ₁ -C ₆ alkyl or phenyl, and R ¹⁶ and R ¹⁷ are preferably hydrogen or phenyl.

A ³ and A ⁴ are independently of each other R ⁵ and R ⁶ are preferably hydrogen, and R ⁸ is preferably C ₁ -C ₆ alkyl or phenyl.

In particular, A ³ and A ⁴ are independently of each other [Wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, -OCR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , cyano, chloro Or —OR ¹⁰ where R ¹⁰ is C ₆ -C ₂₄ aryl, eg phenyl, 1-naphthyl or 2-naphthyl, R ¹¹ and R ¹² are hydrogen or C ₁ -C ₄ alkyl, m is 0 or 1, A ⁵ is phenyl, 1-naphthyl or 2-naphthyl, or is phenyl which may be substituted 1-3 times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy), R ⁸ and R ⁹ independently of one another are hydrogen, C ₁ -C ₈ alkyl, C ₅ -C ₁₂ cycloalkyl, in particular cyclohexyl, -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , C ₆ -C ₂₄ Aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-fluorenyl or anthracenyl, preferably C _6- C ₁₂ aryl, e.g., unsubstituted or optionally substituted phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, or especially a ^1, a nitrogen, Between bovine and saturated containing from 5 to 7 ring atoms consisting of selected from one to three heteroatoms and carbon atoms from the group consisting of sulfur, or an unsaturated heterocyclic radical is.

In particular, the chemical formula Wherein R ⁸ and R ⁹ are independently of each other Wherein R ²¹ , R ²² and R ²³ are independently of each other hydrogen, C ₁ -C ₈ alkyl, hydroxyl group, mercapto group, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen , Halo-C ₁ -C ₈ alkyl, cyano group, aldehyde group, ketone group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group or siloxanyl group). Preferably, R ²¹ , R ²² and R ²³ are independently of each other hydrogen, C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy or C ₁ -C ₈ alkylthio. Particularly preferred DPP compounds of formula II are the following compounds:

Particularly preferred compositions of the invention include compounds A-2 and B-1, A-2 and B-3, A-2 and B-7, A-11 and B-1 or A-11 and B-7 .

DPP compounds of the present invention of Formula I or Formula II are described, for example, in U.S. Patent No. 4,579,949, EP 353,184, EP 133,156, EP 1,087,005 and EP 20 As described in Publication 1,087,006, it can be synthesized according to or similar to methods well known in the art.

The term "halogen" means fluorine, chlorine, bromine and iodine.

C ₁ -C ₂₅ alkyl is usually optionally linear or branched methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl, decyl, undecyl, dodec Yarn, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, eicosyl, henecosyl, docosyl, tetracosyl or pentacosyl, preferably C ₁ -C ₈ alkyl, for example methyl, ethyl , n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, more preferably C ₁ -C ₄ alkyl, for example usually methyl, ethyl, n-propyl, isopropyl, n- Butyl, secondary butyl, isobutyl or tertiary butyl; C ₁ -C ₃ alkyl is methyl, ethyl, n-propyl or isopropyl; C ₁ -C ₆ alkyl is methyl, ethyl, n-propyl, isopropyl, n-butyl, secondary butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, 2,2-dimethyl Propyl or n-hexyl.

"Aldehyde group, ketone group, ester group, carbamoyl group and amino group" includes groups substituted with unsubstituted or substituted aliphatic hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, heterocyclic groups, and the like. . The term "silyl group" refers to a group of silicon compounds such as trimethylsilyl. The term "siloxanyl group" refers to a group of silicon compounds bonded through an intermediate of an ether bond, such as trimethylsiloxanyl and the like.

Examples of C ₁ -C ₈ alkoxy are methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tertiary butoxy, n-pentoxy, 2-phene Methoxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C ₁ -C ₄ alkoxy, for example, usually methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, secondary butoxy, isobutoxy, tert-butoxy. The term "alkylthio group" means the same group as the alkoxy group, with the oxygen atom of the ether bond being replaced by a sulfur atom.

The term "aryl group" usually refers to C ₆ -C ₂₄ aryl, for example phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, terphenyl, pyrenyl, 2- or 9-flu Orenyl or anthracenyl, preferably C ₆ -C ₁₂ aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, which may be unsubstituted or substituted.

The term “cycloalkyl group” is usually C ₅ -C ₁₂ cycloalkyl, eg, unsubstituted or substituted cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cyclodecyl, cyclo Dodecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl or cyclooctyl. The term "cycloalkenyl group" refers to an unsaturated alicyclic hydrocarbon group containing one or more double bonds, such as unsubstituted or substituted cyclopentyl, cyclopentadienyl, cyclohexanyl, and the like. Cycloalkyl groups, in particular cyclohexyl groups, may be condensed 1-2 times with phenyl which may be substituted 1-3 times with C ₁ -C ₄ alkyl, halogen and cyano. Examples of such condensed cyclohexyl groups are , Especially Wherein R ²¹ , R ²² , R ²³ , R ²⁴ , R ²⁵ and R ²⁶ are independently of each other C ₁ -C ₄ alkyl, halogen and cyano, in particular hydrogen. The term "heterocyclic radical" is a ring consisting of 5 to 7 ring atoms (where nitrogen, oxygen or sulfur is a possible hetero atom) and is usually unsaturated heterocylic consisting of 5 to 18 atoms having 6 or more conjugated π-electrons Click radicals such as thiethyl, benzo [b] thiethyl, dibenzo [b, d] thiethyl, thianthrenyl, furyl, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, Dibenzofuranyl, phenoxycyenyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, thiazinyl, pyrimidinyl, pyrazinyl, pyridazinyl, indolinyl, isoindoleyl, indole Reel, indazolyl, furinyl, quinolinyl, chinolyl, isocinonolyl, phthalazinyl, naphthyridinyl, chinoxalinyl, cinazolinyl, chinolinyl, putridinyl, carbanolyl, carbolinyl, Benzotriazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, penazi Nil, isothiazolyl, phenothiazinyl, isoxazolyl, furazanyl or phenoxazinyl, preferably the mono- or bicyclic heterocyclic radicals mentioned above.

Substituents mentioned above include C ₁ -C ₈ alkyl, hydroxyl group, mercapto group, C ₁ -C ₈ alkoxy, C ₁ -C ₈ alkylthio, halogen, halo-C ₁ -C ₈ alkyl, cyano group, It may be substituted by an aldehyde group, ketone group, carboxyl group, ester group, carbamoyl group, amino group, nitro group, silyl group or siloxanyl group.

The invention further relates to an electroluminescent device having a composition according to the invention between an anode and a cathode and emitting light by the action of electrical energy.

The general structure of recent organic electroluminescent devices is as follows:

(i) anode / hole transporting layer / electron transporting layer / cathode, wherein the composition can be used as a positive hole transporting composition used to form a light emitting and hole transporting layer, or can be used to form a light emitting and electron transporting layer Used as an electron transport composition),

(ii) anode / hole transporting layer / light emitting layer / electron transporting layer / cathode, wherein the composition forms a light emitting layer regardless of whether it exhibits positive holes or electron transporting properties in the structure;

(iii) anode / hole injection layer / hole transport layer / light emitting layer / electron transport layer / cathode,

(iv) anode / hole transport layer / light emitting layer / positive hole suppression layer / electron transport layer / cathode and

(v) anode / hole injection layer / hole transport layer / light emitting layer / positive hole suppression layer / electron transport layer / cathode.

Thin film electroluminescent devices typically consist essentially of one electrode pair and one or more charge transport layers therebetween. Usually, there are two charge transport layers, a hole transport layer (almost anode) and an electron transport layer (almost cathode). One of these includes inorganic or organic fluorescent materials as luminescent materials-depending on their properties as hole transport materials or electron transport materials. It is also common for a luminescent material to be used as an additional layer between the hole transport layer and the electron transport layer. In the above-mentioned device structure, the hole injection layer may be configured between the anode and the hole transport layer and / or the positive hole suppression layer is configured between the light emitting layer and the electron transport layer to maximize the number of holes and electrons in the light emitting layer, and charge recombination The efficiency is increased and the light emission is intense.

The device can be manufactured in various ways. Usually, vacuum evaporation is used for its preparation. Preferably, the organic layer is sequentially deposited on a commercially available indium-tin-oxide ("ITO") glass substrate maintained at room temperature, which acts as an anode in the above structure. The film thickness is preferably 1 to 10,000 nm, more preferably 1 to 5,000 nm, more preferably 1 to 1,000 nm, and more preferably 1 to 500 nm. A cathode metal of about 200 nm (eg Mg / Ag alloy or binary Li-Al system) is deposited on top of the organic layer. The vacuum rate during deposition is preferably 0.1333 Pa (1 × 10 ^-3 Torr) or less, more preferably 1.333 × 10 ^-3 Pa (1 × 10 ^-5 Torr) or less, more preferably 1.333 × 10 ^-4 Pa (1 × 10 ^-6 Torr) or less.

As the anode, a metal (e.g., gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten, etc.) or a metal alloy (e.g. magnesium / Copper, magnesium / silver, magnesium / aluminum, aluminum / indium, etc.), semiconductors (e.g., Si, Ge, GaAs, etc.), metal oxides (e.g., indium-tin-oxide ("ITO"), ZnO, etc.), metal compounds (E.g., CuI, etc.), and further electrically conductive polymers (e.g., polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene, etc.), preferably high working capability such as ITO, most preferably glassy ITO Ordinary positive electrode materials can be used.

Among these electrode materials, metals, metal alloys, metal oxides and metal compounds can be converted into electrodes by, for example, sputtering. In the case of using a metal or a metal alloy as the material for the electrode, the electrode may be formed by vacuum deposition. In the case of using a metal or a metal alloy as the material for forming the electrode, the electrode may be further formed by a chemical plating method (Handbook of Electrochemistry, pp 383-387, Mazuren, 1985). In the case of using an electrically conductive polymer, the electrode can be prepared by forming in one film by an anodizing polymerization method onto a substrate previously provided with an electrically conductive coating. The thickness of the electrode formed on the substrate is not limited to a particular value, but when the substrate is used as a light emitting plane, the electrode thickness is preferably in the range of 1 to 100 nm, more preferably 5 to 50 nm so as to ensure transparency. Mine

In a preferred embodiment, ITO is used on a substrate having an ITO film thickness in the range of 10 nm (100 mm 3) to 1 μm (10,000 mm 3), preferably 20 nm (200 mm 3) to 500 nm (5,000 mm 3). In general, the sheet resistance of the ITO film is selected in the range of 100? / Cm ² or less, preferably 50? / Cm ² or less.

Such an anode is manufactured by a Japanese manufacturer [Geomatech Co. Ltd. , Sanyo Vacuum Co. Ltd., Nippon Sheet Glass Co. Ltd.].

As the substrate, an electrically conductive or electrically insulating material can be used. In the case of using the electrically conductive material, the light emitting layer or the positive hole transporting layer is formed directly, while in the case of using the electrically insulating material, the electrode is formed first and then the light emitting layer or the positive hole transporting layer is overlapped.

The substrate may be transparent, translucent or opaque. However, when the substrate is used as the pointing plane, the substrate may be transparent or translucent.

Transparent electrically insulating materials include, for example, inorganic compounds (e.g. glass, quartz, etc.), organic polymeric compounds (e.g. polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyesters, polycarbonates, Polyvinyl chloride, polyvinyl alcohol, polyvinylacetate, etc.). Each of these substrates can be converted to a transparent electrically conductive substrate by providing it to the electrode according to one of the methods mentioned above.

Examples of translucent electrically insulating substrates are inorganic compounds such as alumina, YSZ (yttrium stabilized zirconia) and the like, organic polymeric compounds such as polyethylene, polypropylene, polystyrene, epoxy resins and the like. Each of these substrates can be converted to a translucent electrically conductive substrate by providing it to the electrode according to one of the methods mentioned above.

Examples of opaque electrically conductive substrates include metals (e.g. aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum, etc.), various electroplating metals, metal alloys (e.g. bronze, Stainless steel, etc.), semiconductors (eg, Si, Ge, GaAs, etc.), electrically conductive polymers (eg, polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene, etc.).

The substrate can be made by forming one of the substrate materials described above to the desired size. It is preferable that the substrate has a smooth surface. Even when the substrate has a rough surface, no problem arises in practical use as long as the curvature partitions the nonuniformity of 20 mu m or more. As for the substrate thickness, there is no limitation as long as sufficient mechanical strength is ensured.

As the negative electrode, not only alkali metals, alkaline earth metals, group 13 elements, silver and copper, but also alloys or mixtures thereof, such as sodium, lithium, potassium, sodium-potassium alloys, magnesium, magnesium-silver alloys, magnesium-copper alloys , Magnesium-aluminum alloys, magnesium-indium alloys, aluminum, aluminum-aluminum oxide alloys, aluminum-lithium alloys, indium, calcium and materials exemplified in EP 499,011, for example electrically conductive polymers (e.g. Ordinary negative electrode materials having low working function can be used, such as polypyrrole, polythiophene, polyaniline, polyacetylene, etc.), preferably Ag / Ag alloy or Li-Al composition.

In a preferred embodiment, the magnesium-silver alloy or magnesium-silver mixture, or the lithium-aluminum alloy or lithium-aluminum mixture is 10 nm (100 kV) to 1 μm (10,000 kPa), preferably 20 nm (200 kPa) to 500 nm (5000 kPa). Can be used as the film thickness.

Such a cathode may be deposited over the previous electron transport layer by the known vacuum deposition technique mentioned above.

In a preferred embodiment of the present invention, the light emitting layer can be used between the hole transport layer and the electron transport layer. Usually, the light emitting layer is produced by forming a thin film on the hole transport layer.

As a method of forming a thin film, a vacuum vapor deposition method, a spin coating method, the casting method, the Langmuir-Blodgett ("LB") method, etc. are mentioned, for example. Among these methods, vacuum deposition, spin coating and casting are particularly preferred because of their ease of operation and cost.

In the case of forming a thin film using the composition by the vacuum deposition method, the conditions under which the vacuum deposition is performed usually depend greatly on the property, form and crystal state of the compound. However, the optimum conditions are usually as follows: temperature of the heat boat: 100-400 ° C .; Substrate temperature: -100 to 350 ° C; Pressure: 1.33 × 10 ⁴ Pa (1 × 10 ² Torr) to 1.33 × 10 ⁻⁴ Pa (1 × 10 ⁻⁶ Torr); And deposition rate: 1 pm to 6 nm / sec.

In the organic EL device, the thickness of the light emitting layer is one of the factors for determining the light emission characteristics. For example, when the light emitting layer is sufficiently thick, a short circuit can easily occur between two electrodes sandwiching the light emitting layer, and EL emission is not obtained for this. On the other hand, when the light emitting layer is excessively thick, a large potential drop occurs inside the light emitting layer due to the high electrical resistance, thereby increasing the threshold voltage for EL emission. Therefore, the thickness of the organic light emitting layer is limited to the range of 5nm to 5㎛, preferably 10 to 500nm.

When the light emitting layer is formed using spin coating and casting methods, the coating is appropriate organic such as benzene, toluene, xylene, tetrahydrofuran, methyltetrahydrofuran, N, N-dimethylformamide, dichloromethane, dimethyl sulfoxide and the like. It is carried out using a solution prepared by dissolving the composition at a concentration of 0.0001 to 90% by weight in a solvent. If the concentration exceeds 90% by weight, the solution is usually viscous and does not form a flat and homogeneous film. On the other hand, when the concentration is less than 0.0001% by weight, the film formation efficiency is so low that it is not economical. Therefore, the preferred concentration of the composition is 0.1 to 80% by weight.

When using the spin coating method or the casting method mentioned above, a polymer binder can be added to the solution forming the light emitting layer to further improve the homogeneity and mechanical strength of the resulting layer. In principle, any polymeric binder can be used as long as the composition is dissolved in the solvent in which it is dissolved. Examples of such polymer binders are polycarbonates, polyvinyl alcohols, polymethacrylates, polymethylmethacrylates, polyesters, polyvinylacetates, epoxy resins and the like. However, when the solid content composed of the polymer binder and the composition exceeds 99% by weight, the fluidity of the solution is usually too low to form a light emitting layer having excellent homogeneity. On the other hand, when the content of the composition is substantially lower than the content of the polymer binder, the electrical resistance of this layer is so high that it does not emit light unless a high voltage is applied. Thus, the preferred ratio of polymer binder to composition is selected within the range of 10: 1 to 1: 50% by weight and the solids content of the two components is preferably 0.01 to 80% by weight, more preferably 0.1 to 60% by weight. It is in the range of.

Organic hole transport compounds known as the hole transport layer, for example polyvinyl carbazole , J. Amer. Chem. Soc. 90 (1968) 3925]. (Wherein Q ₁ and Q ₂ each represent a hydrogen atom or a methyl group), see J. Appl. Phys. 65 (9) (1989) 3610. ; Stilbene compound Where T and T ₁ are organic radicals; Hydrazone Compound (Where Rx, Ry and Rz are organic radicals) and the like can be used.

The compound used as the positive hole transport material is not limited to the compound mentioned above. Any compound having a positive hole-carrying property may be a positive hole-carrying material such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylene diamine Derivatives, arylamine derivatives, amino substituted calcon derivatives, oxazole derivatives, stilbenylanthracene derivatives, fluorenone derivatives, hydrozone derivatives, stilbene derivatives, copolymers of aniline derivatives, electrically conductive oligomers, in particular thiophene oligomers, porphyrin compounds , Aromatic tertiary amine compounds, stilbenyl amine compounds and the like. In particular, aromatic tertiary amine compounds such as N, N, N ', N'-tetraphenyl-4,4'-diaminobiphenyl, N, N'-diphenyl-N, N'-bis ( 3-methylphenyl) -4,4'-diaminobiphenyl (TPD), 2,2'-bis (di-p-tolylaminophenyl) propane, 1,1'-bis (4-di-tolylaminophenyl) 4-phenylcyclohexane, bis (4-dimethylamino-2-methylphenyl) phenylmethane, bis (4-di-p-tolylaminophenyl) phenylmethane, N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl, N, N, N ', N'-tetraphenyl-4,4'-diaminodiphenylether, 4,4'-bis (di Phenylamino) quaterphenyl, N, N, N-tri (p-tolyl) amine, 4- (di-p-tolylamino) -4 '-[4- (di-p-tolylamino) styryl] stilbene , 4-N, N-diphenylamino- (2-diphenylvinyl) benzene, 3-methoxy-4'-N, N-diphenylaminostilbene, N-phenylcarbazole and the like are used.

In addition, 4,4'-bis [N- (1-taphthyl) -N-phenylamino] biphenyl described in US Pat. No. 5,061,569, wherein three triphenylamine units are bonded to a nitrogen atom, and Europe The compounds described in WO 508,562 can be used, for example 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine.

The positive hole transport layer can be formed by making an organic layer containing one or more positive hole transport materials at the anode. The positive hole transport layer can be formed by vacuum deposition, spin coating, casting, LB, or the like. Among these methods, vacuum deposition, spin coating and casting are particularly preferred in view of ease and cost.

When using the vacuum deposition method, the deposition conditions can be selected in the same manner as described for the formation of the light emitting layer (see above). If it is desired to form a positive hole transport layer comprising one or more positive hole transport materials, co-deposition may be used with the compound of interest.

When forming the positive hole transport layer by spin coating or casting, the layer can be formed under the conditions mentioned for the formation of the light emitting layer (see above).

In the case of forming the light emitting layer, a smoother and more homogeneous positive hole transport layer can be formed using a solution comprising a binder and one or more positive hole transport materials. The coating using this solution can be carried out in the same manner as mentioned for the light emitting layer. Any polymeric binder can be used as long as one or more positive hole transport materials are dissolved in the dissolved solvent. Examples of suitable polymeric binders and suitable and preferred concentrations are defined above when referring to the formation of the emissive layer.

The thickness of the positive hole transport layer is preferably selected within the range of 0.5 to 1,000 nm, preferably 1 to 100 nm, more preferably 2 to 50 nm.

As the hole injection material, known organic hole transport compounds such as metal-free phthalocyanine (H ₂ Pc), copper phthalocyanine (Cu-Pc), and those described, for example, in Japanese Patent Publication No. 64-7635 Derivatives of may be used. In addition, some aromatic amines defined as the above hole transport materials, which have lower ionization potential than the hole transport layer, can be used.

The hole injection layer can be formed by making an organic film containing one or more hole injection materials between the anode layer and the hole transport layer. The hole injection layer may be formed by vacuum deposition, spin coating, casting, LB, or the like. The thickness of the layer is preferably 5 nm to 5 mu m, more preferably 10 to 100 nm.

The electron transporting material should have high electron injection efficiency (from the cathode) and high electron mobility. For electron transport materials the following materials are described in Appl. Phys. Lett. 48 (2) (1986) 183] tris (8-hydroxyquinolinato) -aluminum (III) and derivatives thereof, bis (10-hydroxybenzo [h] quinolinolato) be Nelium (II) and derivatives thereof, oxadiazole derivatives such as 2- (4-biphenyl) -5- (4-tert-butylphenyl) -1,3,4-oxadiazole and dimers thereof Systems such as 1,3-bis (4-tert-butylphenyl-1,3,4) oxadiazolyl) biphenylene and 1,3-bis (4-tert-butylphenyl-1,3, 4-oxadiazolyl) phenylene, dioxazole derivatives, triazole derivatives, coumarin derivatives, imidazopyridine derivatives, phenanthroline derivatives or perylene tetracarboxylic acid derivatives.

The electron transport layer can be formed by manufacturing an organic film containing one or more electron transport materials in the hole transport layer or the light emitting layer. The electron transport layer can be formed by vacuum deposition, spin coating, casting LB, or the like.

The positive hole suppressing material for the positive hole suppressing layer has a higher electron injection efficiency / transportation efficiency from the electron transporting layer to the light emitting layer, and also has a higher ionization potential than the light emitting layer, thereby suppressing a drop in the luminous efficiency by suppressing the flow of the positive holes from the light emitting layer. .

As positive hole suppressing substances, known substances can be used, for example Balq, TAZ and phenanthroline derivatives, for example vatcouproin (BCP):

The positive hole transport layer can be formed by making an organic film containing one or more positive hole suppression materials between the electron transport layer and the light emitting layer. The positive hole transport layer may be formed by vacuum deposition, spin coating, casting, LB, or the like. The layer thickness is preferably selected within the range of 5 nm to 2 μm, more preferably 10 to 100 nm.

As the case of forming a pore layer or a positive hole transport layer, a smoother and more homogeneous electron transport layer can be formed using a solution containing a binder and one or more electron transport materials.

The thickness of the electron transporting layer is preferably selected in the range of 0.5 to 1,000 nm, preferably 1 to 100 nm, more preferably 2 to 50 nm.

The maximum fluorescence emission range of the luminescent composition is from 500 to 780 nm, preferably from 520 to 750 nm, more preferably from 540 to 700 nm. In addition, the compounds of the present invention preferably have an absorption maximum range of 450 to 580 nm.

Luminescent compositions typically have a fluorescence quantum yield ("FQY") in the range 1> FQY> 0.3 (measured by aeration toluene or DMF). Also, the compositions of the present invention generally have a molar absorption coefficient ranging from 5,000 to 100,000.

Another aspect of the invention is the incorporation of a composition of the invention by methods known in the art (comprising a plastics material having a molecular weight range of typically 10 ³ to 10 ⁷ g / mol and comprising biopolymers and fibers) ) A method of coloring a high molecular weight organic material.

The composition of the present invention, as described for the DPP compound of formula (I ') described in EP 1 087 005,

For printing inks, flexographic printing, screen printing, packaging printing, security ink printing, engraved printing or offset printing, prepress steps and textile printing in the printing process, for office, home or graphic use, eg for paper products For example, ballpoint pens, felt tips, fabric tips, cards, wood, (wood) coloring, metals, inks for ink pads or inks for impact printing processes (with impact press ink ribbons) Manufacturing,

Colorants for coloring materials, for industrial or commercial use, for textile decoration and industrial marking, for roller coating or powder coating or for automotive finishes, for high temperature solids (cold solvents), for water containing or metal coating materials or for aqueous paints. Manufacturing,

Production of pigment plastics for coatings, fibers, platters or mold carriers,

For the production of impact-free printing materials for digital printing, for thermal wax transport printing processes, for ink jet printing processes or for thermal transport printing processes,

In particular, the manufacture of color filters for visible light, liquid crystal display (LCD) or charge coupled device (CCD) in the range of 400 to 700 nm,

Manufacture of cosmetics or

Polymer ink particles, toners, dye lasers, anhydrous copy toners, liquid copy toners or electrophotographic toners and electroluminescent devices.

Another preferred embodiment relates to the use of the compositions of the present invention for color changing media. The three main techniques for realizing full color organic electroluminescent devices are:

(i) the use of three primary colors produced by electroluminescence, blue, green and red,

(ii) conversion of electroluminescent blue or white to photoluminescent green and red via electroluminescent blue and green and red fluorescence absorbing color change media (CCM),

(iii) conversion of white luminescence emission through blue color filter to blue, green and red.

The compounds of the present invention are useful for EL materials for category (i) above and, further, technique (ii) mentioned above. This is because the combination of the compounds of the present invention can exhibit not only electroluminescence but also strong photoluminescence.

Technique (ii) is known, for example, from US Pat. No. 5,126,214, wherein a maximum wavelength of about 470-480 nm is coumarin, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylamino Styryl) -4H-pyran, pyridine, rhodamine 6G, phenoxazone or other dyes are used to convert EL blue to green and red.

Illustrative examples of suitable high molecular weight organic materials that can be colored with the compositions of the present invention are described in EP 1 087 005.

In particular, particularly preferred high molecular weight organic materials for the production of paint systems, printing inks or inks are, for example, cellulose ethers and esters such as ethylcellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetics Resins (polymerization or condensation resins), for example aminoplasts, in particular urea / formaldehyde and melamine / formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrenes, polyvinyl chlorides, polyamides, poly Urethane, polyester, ABS, ASA, polyphenylene oxide, vulcanized rubber, casein, silicone and silicone resins as well as others and possible mixtures thereof.

It is also possible to use high molecular weight organic materials in dissolved form as film forming agents such as boiling cottonseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine / formaldehyde and urea / formaldehyde resins as well as acrylic resins.

Such high molecular weight organic materials can be obtained alone or in mixtures, for example in the form of granules, plastic materials, melts or in the form of solutions, in particular for the production of spin solutions, paint systems, coating materials, inks or printing inks. Can be.

In a particularly preferred embodiment of the invention, the compositions of the invention are suitable for the bulk coloring of polyvinyl chlorides, polyamides and especially polyolefins such as polyethylene and polypropylene, as well as powder coatings, inks, printing inks, colors Used for the manufacture of paint systems, including filters and coating collars.

Illustrative examples of binders for preferred paint systems are two pack system lacquers based on alkyd / melamine resin paints, acrylic / melamine resin paints, cellulose acetate / cellulose butyrate paints and acrylic resins crosslinkable with polyisocyanates.

According to the observations made to date, the compositions of the present invention can be added in any desired amount to the material to be colored according to the end use requirements.

Thus, another aspect of the present invention

(a) 0.01 to 50% by weight, preferably 0.01 to 5% by weight, particularly preferably 0.01 to 2% by weight, based on the total weight of the colored high molecular weight organic material,

(b) 99.99 to 50% by weight, preferably 99.99 to 95% by weight, particularly preferably 99.99 to 98% by weight, based on the total weight of the colored high molecular weight organic material and

(c) Any conventional additives such as rheology enhancers, dispersants, fillers, paint aids, desiccants, plasticizers, UV-stabilizers and / or further pigments or corresponding precursors in effective amounts, for example, ( It relates to a composition comprising a) and (b) and in an amount of 0 to 50% by weight, based on the total weight.

In order to obtain different shades, the fluorescent DPP compounds of the formula (I) of the present invention can advantageously be used in admixture with fillers, transparent and opaque white, colored and / or black pigments as well as conventional luster pigments in the desired amounts.

To produce paint systems, coating materials, color filters, inks and printing inks, the corresponding high molecular weight organic materials such as binders, synthetic resin dispersions and the like are usually dissolved or, if desired, conventional compositions. It is dissolved in a conventional solvent or solvent mixture together with additives such as dispersants, fillers, paint aids, desiccants, plasticizers and / or further pigments or pigment precursors. This can be achieved by dispersing or dissolving each component alone, or with several components, and then including all components together or adding all together at the same time.

Thus, a further aspect of the invention relates to a method of using the composition of the invention for the production of a dispersion and a corresponding ink for printing, comprising the corresponding dispersion, paint system, coating material, color filter, ink and composition of the invention. .

Particularly preferred embodiments relate to the use of the compositions of the invention for the detection of leaks in fluids such as fluorescent tracers, for example lubricants, cooling systems, etc., as well as for the manufacture of fluorescent tracers or lubricants comprising the compositions of the invention.

The composition of the present invention is mixed, optionally in masterbatch form, with a high molecular weight organic material, a mixing device or a polishing device using a roll mill for coloring the high molecular weight organic material. In general, the pigment material may subsequently be led to the desired final form by conventional methods, such as calendering, compression molding, extrusion, development, casting or injection molding.

In order to color lacquers, coating materials and printing inks, the high molecular weight organic materials and the compositions of the present invention are generally used alone or in combination with additives such as fillers, other pigments, desiccants or plasticizers in a conventional organic solvent or solvent mixture. Dissolve or disperse at In this case, a process may be adopted in which each component is dispersed or dissolved individually or two or more components are dispersed or dissolved together and then all components are mixed.

The invention further relates to an ink comprising a pigmentally effective amount of a pigment dispersion of a composition of the invention.

The weight ratio of pigment dispersion to ink is generally selected in the range of 0.001 to 75% by weight, preferably 0.01 to 50% by weight, based on the total weight of the ink.

Methods and uses of color filters or color pigmented high molecular weight organic materials are well known in the art and are described in Displays 14/2, 1151 (1993), EP 784 085 or UK Patent Publications. 2,310,072.

The color filter may be coated using, for example, an ink, in particular a printing ink, which may comprise a pigment dispersion comprising the composition of the invention or chemically, thermally disperse a pigment dispersion comprising the composition of the invention. It can be prepared by mixing with a high-molecular weight organic material (so-called resistance), or photodegradable structure. Subsequent manufacturing methods are carried out similarly to, for example, EP 654 711 by applying to a substrate, for example a liquid crystal display (LCD) and subsequently light structuring and developing. can do.

Particularly preferred for the production of color filters are pigment dispersions comprising the composition of the invention with a non-aqueous solvent or dispersion medium for the polymer.

The present invention further provides a non-impact-printing material comprising the composition of the invention in the form of colorants, colored plastics, polymeric ink particles, or preferably dispersions, or high molecular weight organic colored in a compositionally effective amount of the composition of the invention. It is about matter.

The chromatographically effective amount of the pigment dispersion according to the invention comprising the composition of the invention is generally 0.0001 to 99.99% by weight, preferably 0.001 to 50% by weight, particularly preferred, based on the total weight of the colored material. Preferably 0.01 to 50% by weight. The composition of the present invention may be applied to colored polyamides because the composition does not decompose during incorporation into the polyamide. In addition, the compositions have exceptionally good light fastness and particularly excellent thermal stability in plastics.

The organic EL device of the present invention has considerable industrial value, which can be adopted for flat panel elements, flat panel light emitting devices, light sources for copiers or printers, light sources for liquid crystal display or counters, display signs and signal lights for wall-mounted television sets. Because there is. The composition of the present invention can be used in the fields of organic EL devices, electrophotographic photoreceivers, photoelectric converters, solar cells, image sensors and the like.

The following examples illustrate various aspects of the invention, but the scope of the invention is not so limited. In this example, unless stated otherwise, "parts" means "parts by weight" and "percent" means "percent by weight".

Example

Example 1

2.03 g (6.4 mmol) of 1,4-diketo-3,6-bis (4-methylphenyl) pyrrolopyrrole is slurried in 1-methyl-2-pyrrolidone for 2 hours at room temperature. 1.31 g (11.53 mmol) of potassium tert-butoxide is added to the slurry under nitrogen. After stirring for 2 hours, 20.5 g (11.1 mmol) of 1-bromoethylbenzene is added to the reaction mixture and further shaken for 2 hours. The mixture is then poured into 50 ml of water, the precipitate is collected by filtration, purified by column chromatography (silica gel, dichloromethane as eluent) and washed with methanol. After drying, 780 mg of a fluorescent orange solid was obtained (melting point: 262 ° C., yield: 24%).

Example 2

Example 1 is repeated but 1,4-diketo-3,6-bis (1-naphthyl) -pyrrolo (3,4-c) -pyrrole is used as starting material. Orange solid (melting point: 263 ° C., yield: 32%).

Example 3

2,5-dibenzyl-1,4-diketo-3,6- (4-bromophenyl) pyrrolo (3,4, -c) pyrrole (1.0 mmol), tolylamine 2.5 mmol, palladium (II 5 mg of acetate, 1 mg of tertiary butylphosphine and 50 ml of anhydrous xylene are placed in a three neck flask and stirred at 120 ° C. for 13 hours under nitrogen. After completion of the reaction, xylene is removed under reduced pressure and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.4 g of the desired product is obtained as a red solid (melting point: 395 ° C.).

Example 4

Example 3 was repeated but 2,5-dibutyl-1,4-diketo-3,6- (4-bromophenyl) pyrrolo (3,4-c) pyrrole was used as starting material and bis ( 2-naphthyl) amine is used as reactant to give a red solid (melting point: 222-224 ° C., yield: 46%).

Example 5

Example 3 is repeated, but 2-naphthylphenylamine is used instead of ditolylamine to give a red solid (melting point: 361 ° C., yield: 53%).

Example 6

A glass substrate (product made by Asahi Glass Co., an electron beam evaporation method) on which an ITO transparent electrically conductive film is deposited to a thickness of about 210 nm or less is cut to an size of 30 × 40 nm and etched. The substrate thus obtained is ultrasonically cleaned with acetone for 15 minutes, ultrasonically cleaned with Semikoklin 56 for 15 minutes and then with ultrapure water. Subsequently, the substrate is ultrasonically cleaned with isopropyl alcohol for 15 minutes, immersed in hot methanol for 15 minutes and then dried. Immediately before forming the substrate into one device, the substrate thus produced is subjected to UV-ozone treatment for 1 hour, placed in a vacuum deposition apparatus, and the apparatus is brought to an internal pressure of 1 × 10 ^-5 Pa or less. Evaporate. Subsequently, N, N'-diphenyl-N, N '-(3-methylphenyl) -1,1'-diphenyl-4,4'-diamine (TPD) was positively tested to a thickness of 50 nm or less according to the resistance heating method. Deposition as a hole transport material to form a positive hole transport layer. Subsequently, the DPP compounds obtained in Example 1 (A-1) and Example 6 (B-4) were adjusted to a deposition rate (A-1: B-4 = 99: about 1) to a thickness of 50 nm or less. Is simultaneously deposited as a light emitting layer to form a uniform light emitting layer. Subsequently, an Alq ₃ layer is deposited to form an electron transport layer having a thickness of 50 nm. On top of this layer, an Mg-Ag alloy (10: 1) was deposited to form a cathode having a thickness of 150 nm, thereby producing a device of 5 x 5 mm ² size. The peak emission wavelength and emission intensity of the light emitting device thus produced are shown in Table 1.

(Example 104 of European Patent Publication No. 1 087 006)

Example 7, Example 8, Example 9 and Example 10

Example 6 is repeated but the release material of Example 6 is replaced with the release material as described in Table 1.

Example device Emitter EL characteristics Compound of Formula I [99 wt%] Compound of Formula I [about 1% by weight] Peak (nm) Intensity (cd / m ² ) Example 6 A-1 B-4 590 10980 Example 7 A-1 B-1 608 9026 Example 8 A-2 B-1 610 9216 Example 9 A-2 B-2 594 6773 Example 10 A-2 B-3 600 12260 Reference Example 1 A-3 (100%) - 566 5260 Reference Example 2 A-1 (100%) - 534 2600

Example 11

Example 2 is repeated but 3- (1-broloethyl) -1-tertiary butylbenzene is used in place of 1-bromoethylbenzene. Orange solid (melting point: 307 ° C., yield: 18%).

Example 12

Example 2 is repeated but 3- (1-bromoethyl) toluene is used in place of 1-bromoethylbenzene. Orange solid (melting point: 243 ° C., yield: 14%).

Example 13

Example 2 is repeated, but 2- (1-bromoethyl) naphthalene is used in place of 1-bromoethylbenzene. Orange solid (melting point: 325 to 329 ° C., yield: 10%).

Example 14

Example 2 is repeated, but 1- (1-bromoethyl) naphthalene is used in place of 1-bromoethylbenzene. Orange solid (melting point: 266 ° C., yield: 17%).

Example 15

Example 2 is repeated but 4-bromo-1- (1-bromoethyl) benzene is used instead of 1-bromoethylbenzene. Orange solid (melting point: 223 to 225 ° C., yield: 32%).

Example 16

Example 2 is repeated but 4-phenyl-1- (1-bromoethyl) benzene is used instead of 1-bromoethylbenzene. Orange solid (melting point: 293 ° C., yield: 16%).

Example 17

Example 2 is repeated but isopropyl iodide is used in place of 1-bromoethylbenzene. Orange solid (melting point: 294-295 ° C., yield: 3%).

Example 18

Example 2 is repeated but 1-bromo-1,2,3,4-tetrahydronaphthalene is used in place of 1-bromoethylbenzene. Orange solid (melting point: 360 ° C., yield: 3%).

Example 19

Example 2 is repeated but bromo d-phenyl methane is used instead of 1-bromoethylbenzene. Orange solid (melting point: 258 to 266 ° C., yield: 11%).

Example 20

Example 1 is repeated but 1,4-diketo-3,6-bis (1-phenanthrenyl) -pyrrolo- (3,4-c) pyrrole is used as starting material. Orange solid (melting point: 326 ° C., yield: 4%).

Example 21

Example 3 was repeated, with 2,5-bis- (4-cyanobenzyl) -1,4-diketo-3,6- (4-bromophenyl) pyrrolo (3,4-c) pyrrole and 1,1'-bis (diphenylphosphino) ferrocene is used as starting material and Pd ligand, respectively. Red violet solid (melting point: 376 ° C., yield: 45%).

Example 22

Example 16 was repeated but 2,5-bis- (4,5-d-cyanobenzyl) -1,4-diketo-3,6- (4-bromophenyl) pyrrolo (3,4- c) pyrrole is used as starting material. Red violet solid (melting point: 353 to 356 ° C., yield: 17%).

Example 23

Example 4 is repeated, but benzyl bromide is used in place of iodobutane. Reddish violet solid (melting point: 359-361 ° C., yield: 12%).

Examples 24-26

Example 6 is repeated but the release material of Example 6 is replaced with the release material as described in Table 2.

Example device Emitter EL characteristics Compound of Formula I (% by weight) Compound of formula II (% by weight) Peak (nm) Intensity (cd / m ² ) Example 24 A-2 (97.3) B-7 (2.7) 624 2717 Example 25 A-11 (97.5) B-1 (2.5) 610 3996 Example 26 A-11 (97.3) B-7 (2.7) 614 5094

Example 27

Example 2 is repeated but 2- (1-bromoethyl) toluene is used in place of 1-bromoethylbenzene. Yellow solid (melting point: 276 to 278 ° C, yield: 9%).

Reference Example 1

Example 8 is repeated, but the following compound (A-3: Example 81 of EP 1 087 006) is used as the luminescent material. The maximum luminescence is 5260 Cd / m ² .

Reference Example 2

Example 6 is repeated, but A-1 (Example 93 of EP 1 087 006) is used as the luminescent material. The maximum luminance is 2600 Cd / m ² .

As is evident from this example, the compositions of the present invention comprising DPP of formula (I) and DPP of formula (II) are characterized by high electrical energy utilization efficiency and much higher luminescence than the respective DPP compounds of formula (I) and formula (II). A light emitting device is provided.

Example 28 (Membrane Preparation of Color Changing Media)

8 mg of A-2, 2 mg of B-7 and 1 g of PMMA (Wako Pure Chemical Industries, Ltd.) are placed in one bottle and the mixture is dissolved in 5 g of toluene. The solution is dropped onto the slide organic substrate and coated on glass using a spin coater at a rotation rate of 500 rpm for 30 seconds. The membrane obtained is dried over 80 ° C. and a CCM membrane is obtained. The film is evaluated using a fluorescence spectrophotometer F-4500 (Hitachi, Ltd.). When the film is irradiated with blue light at 470 nm, the film emits red light and the peak is located at 597 nm. Thus, it has been found that a composition comprising a host and a guest is applied to a CCM that effectively converts blue light into red light.

Claims (12)

The absorption spectrum of the guest chromophore overlaps with the fluorescence emission spectrum of the host chromophore, and the host chromophore is diketopyrrolopyrrole exhibiting a photoluminescence emission peak at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm. A composition comprising a guest chromophore and a host chromophore, wherein the chromophore is diketopyrrolopyrrole exhibiting an absorption peak at 500 to 720 nm, preferably 500 to 600 nm, most preferably 520 to 580 nm. The composition of claim 1, wherein the host chromophore is diketopyrrolopyrrole of formula I (“DPP”) and the guest chromophore is DPP of formula II. Formula I Formula II In Formula I and Formula II above, R ¹ , R ² , R ³ and R ⁴ are independently of each other C ₁ -C ₂₅ alkyl, which may be substituted by fluorine, chlorine or bromine, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl which may be condensed one or two times with phenyl which may be substituted one to three times with halogen, nitro or cyano, or with silyl, A ⁵ or -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ wherein R ¹¹ and R ¹² are independently of each other hydrogen, fluorine, chlorine, bromine or cyano, or C ₁ -C ₄ alkyl which may be substituted by fluorine, chlorine or bromine, or C ₁ -C Phenyl which may be substituted 1-3 times with ₃ alkyl, and A ⁵ is phenyl, 1-naph, which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen, nitro or cyano Yl or 2-naphthyl, phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or —NR ¹³ R ¹⁴ wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₂₅ Alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₂₄ aryl), especially phenyl which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen or cyano, 1- Naphthyl or 2-naphthyl, or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, m is 0, 1, 2, 3 or 4; A ¹ and A ² are independently of each other [Wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkoxy, -OCR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , cyano, halogen , -OR ¹⁰ or -S (O) _p R ¹³ , wherein R ¹⁰ is C ₆ -C ₂₄ aryl or 5 to 7 hetero carbons and 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur A saturated or unsaturated heterocyclic radical containing a ring atom, R ¹³ is C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl or -CR ¹¹ R ^12- (CH ₂ ) _m -Ph, p is 0 , 1, 2 or 3, R ¹¹ , R ¹² and m are as defined above), or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, R ¹⁵ Is C ₆ -C ₂₄ aryl, n is 0, 1, 2, 3 or 4], A ³ and A ⁴ are independent of each other [Wherein R ⁸ and R ⁹ independently of one another are hydrogen, C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl, -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ or C ₆ -C ₂₄ aryl , In particular A ^1, or a saturated or unsaturated heterocyclic radical comprising 5 to 7 ring atoms consisting of 1 to 3 heteroatoms and carbon atoms selected from the group consisting of nitrogen, oxygen and sulfur, R ¹⁶ and R ¹⁷ are mutually Independently hydrogen or C ₆ -C ₂₄ aryl. The compound of claim 2, wherein A ¹ and A ² are independently of each other. Wherein R ⁵ is C ₁ -C ₈ alkyl. The compound according to claim 2 or 3, wherein A ³ and A ⁴ are independently of each other. [Wherein R ⁸ and R ⁹ are independently of each other Wherein R ⁵ , R ⁶ and R ⁷ are independently of each other hydrogen, C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy. The compound according to claim ² , wherein R ¹ , R ² , R ³ and R ⁴ are independently of each other C ₁ -C ₈ alkyl, or C ₁ -C ₈ alkyl and / or C ₁ -C. ₈ alkoxy or by one to three optionally substituted C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₈ alkyl and / or C ₁ -C ₈ alkoxy one to three times, which may be substituted phenyl, 1-naphthyl Or 2-naphthyl, or -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , wherein R ¹¹ and R ¹² are hydrogen and A ⁵ is C ₁ -C ₈ alkyl and / or C ₁ -C ₈ Phenyl, 1-naphthyl or 2-naphthyl, m is 0 or 1, which may be substituted 1-3 times with alkoxy. 6. The composition of claim 2, 3 or 5, wherein the compound of formula I is selected from compounds A-1 to A-29. 7. Formula I TABLE Ia TABLE Ib TABLE Ic The composition of any one of claims 2, 4 and 5, wherein the compound of formula II is selected from compounds B-1 to B-9. An electroluminescent device comprising the composition according to any one of claims 1 to 7. The electroluminescent device according to claim 8, comprising sequentially (a) an anode, (b) a hole transport layer, (c) a light emitting layer, (d) any electron transport layer, and (e) a cathode. (a) 0.01 to 50% by weight of the composition according to any one of claims 1 to 7, based on the total weight of the colored high molecular weight organic material and (b) 99.99 to 50% by weight of the high molecular weight organic material, based on the total weight of the colored high molecular weight organic material. Use of a composition according to any one of claims 1 to 6 for coloring high molecular weight organic materials and in a color change medium. Diketopyrrolopyrrole of formula (I) or formula (II). Formula I Formula II In Formula I and Formula II above, R ¹ , R ² , R ³ and R ⁴ are independently of each other C ₁ -C ₂₅ alkyl, which may be substituted by fluorine, chlorine or bromine, C ₅ -C ₁₂ cycloalkyl, C ₁ -C ₄ alkyl, C ₅ -C ₁₂ cycloalkyl which may be condensed one or two times with phenyl which may be substituted one to three times with halogen, nitro or cyano, or with silyl, A ⁵ or -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ wherein R ¹¹ and R ¹² are independently of each other hydrogen, fluorine, chlorine, bromine or cyano, or C ₁ -C ₄ alkyl which may be substituted by fluorine, chlorine or bromine, or C ₁ -C Phenyl which may be substituted 1-3 times with ₃ alkyl, and A ⁵ is phenyl, 1-naph, which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen, nitro or cyano Yl or 2-naphthyl, phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, or —NR ¹³ R ¹⁴ wherein R ¹³ and R ¹⁴ are hydrogen, C ₁ -C ₂₅ Alkyl, C ₅ -C ₁₂ cycloalkyl or C ₆ -C ₂₄ aryl), in particular phenyl which may be substituted 1-3 times with C ₁ -C ₈ alkyl, C ₁ -C ₈ alkoxy, halogen or cyano, 1 -Naphthyl or 2-naphthyl, or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, m is 0, 1, 2, 3 or 4; A ¹ and A ² are independently of each other [Wherein R ⁵ , R ⁶ and R ⁷ are each independently hydrogen, C ₁ -C ₂₅ alkyl, C ₁ -C ₂₅ alkoxy, -OCR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ , cyano, halogen , -OR ¹⁰ or -S (O) _p R ¹³ , wherein R ¹⁰ is C ₆ -C ₂₄ aryl or 5 to 7 hetero carbons and 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur A saturated or unsaturated heterocyclic radical containing a ring atom, R ¹³ is C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl or -CR ¹¹ R ^12- (CH ₂ ) _m -Ph, p is 0 , 1, 2 or 3, R ¹¹ , R ¹² and m are as defined above), or phenyl which may be substituted one to three times with C ₁ -C ₈ alkyl or C ₁ -C ₈ alkoxy, R ¹⁵ Is C ₆ -C ₂₄ aryl, n is 0, 1, 2, 3 or 4], A ³ and A ⁴ are independent of each other [Wherein R ⁸ and R ⁹ independently of one another are hydrogen, C ₁ -C ₂₅ alkyl, C ₅ -C ₁₂ cycloalkyl, -CR ¹¹ R ^12- (CH ₂ ) _m -A ⁵ or C ₆ -C ₂₄ aryl , In particular A ^1, or a saturated or unsaturated heterocyclic radical comprising 5 to 7 ring atoms consisting of 1 to 3 heteroatoms and carbon atoms selected from the group consisting of nitrogen, oxygen and sulfur, R ¹⁶ and R ¹⁷ are mutually Independently hydrogen or C ₆ -C ₂₄ aryl.