Electroluminescent device including diketopyrrolopyrroles

[0001] In the present invention, (a) an anode (anode), (b) a hole transport layer, (c) a light emitting layer, (d) an electron transport layer in some cases, and (e) a cathode (cathode) in this order. In addition, a luminescent substance is contained, and the luminescent substance is represented by the formula I or the formula III [0002] [Chemical Formula 11].<img file="JP3854792B2_D0001.tif" />[0003] (in the formula, R₁And R₂Are independent of each other, C₁~ C₂₅Alkyl, C₁~ C₃Alkyl or Ar₃Allyl or -CR which may be replaced 1 to 3 times with₃R₄-(CH₂)_m-Ar₃Represents R₃And R₄Are independent of each other, hydrogen or C₁~ C₄Represents alkyl or C₁~ C₃Represents a phenyl that may be substituted 1 to 3 times with alkyl, Ar₃Is C₁~ C₈Alkyl, C₁~ C₈Alkoxy, halogen or phenyl (C₁~ C₈Alkyl or C₁~ C₈Represents phenyl or 1- or 2-naphthyl which may be substituted 1 to 3 times with alkoxy (may be substituted 1 to 3 times), and m represents 0, 1, 2, 3 or 4 and represents. Ar₁And Ar₂Are independent of each other and are aryl groups, preferably [0004] [Chemical formula 12].<img file="JP3854792B2_D0002.tif" />[0005] Or C₁~ C₄Alkyl, C₁~ C₄Eurolysyl, which may be substituted 1 to 4 times with alkoxy or phenyl, [0006] [Chemical Formula 13]<img file="JP3854792B2_D0003.tif" />[0007] or [0008] [Chemical 14]<img file="JP3854792B2_D0004.tif" />[0009] and R₅, R₆And R₇Independent of each other, hydrogen, cyano, halogen, C₁~ C₆Alkyl, -NR₈R₉, -OR₁₀, -S (O)_nR₈, -Se (O)_nR₈Or C₁~ C₈Alkyl or C₁~ C₈Represents a phenyl that may be substituted 1 to 3 times with alkoxy, R₈And R₉Are independent of each other, hydrogen, phenyl, C₁~ C₂₅Alkyl, C₅~ C₁₂Cycloalkyl, -CR₃R₄-(CH₂)_m-Ph or R₁₀(R₁₀Is C₆~ C₂₄Represents an aryl) or a saturated or unsaturated heterocyclic group containing 5 to 7 ring atoms, the ring of which is 1 to 3 hetero selected from the group consisting of carbon atoms and nitrogen, oxygen and sulfur. Consisting of atoms, Ph, the aryl and heterocyclic groups are C₁~ C₈Alkyl, C₁~ C₈May be substituted 1-3 times with alkoxy or halogen, or R₈And R₉Is -C (O) R₁₁Represents R₁₁Is C₁~ C₂₅Alkyl, C₅~ C₁₂Cycloalkyl, R₁₀, -OR₁₂Or -NR₁₃R₁₄Can be R₁₂, R₁₃And R₁₄Is C₁~ C₂₅Alkyl, C₅~ C₁₂Cycloalkyl, C₆~ C₂₄Represents a saturated or unsaturated heterocyclic group containing aryl or 5-7 ring atoms, the ring consisting of a carbon atom and 1-3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur. , Where the aryl and heterocyclic groups are C₁~ C₈Alkyl or C₁~ C₈May be substituted 1-3 times with alkoxy, or -NR₈R₉Is R₈And R₉Together with tetramethylene, pentamethylene, -CH₂-CH₂-O-CH₂-CH₂-Or-CH₂-CH₂-NR₅-CH₂-CH₂-, preferably -CH₂-CH₂-O-CH₂-CH₂Represents a five- or six-membered heterocyclic group representing-, n represents 0, 1, 2 or 3, Z represents a single bond, C₁~ C₄Alkyl, C₁~ C₄May be substituted 1-3 times with alkoxy or phenyl C₂~ C₆Represents a diradical selected from the group consisting of alkylene, phenylene or naphthylene), which is a diketopyrrolopyrrole (DPP), an electroluminescent device.

[0010] Thin film type electroluminescent devices usually consist essentially of a pair of electrodes and at least one charge transport layer between them. Usually, there are two charge transport layers, a hole transport layer (adjacent to the anode) and an electron transport layer (adjacent to the cathode). Any one of these contains an inorganic or organic fluorescent material as the luminescent material, depending on its properties as a hole-transporting material or an electron-transporting material. In addition, it is common to use the luminescent material as a further layer between the hole transport layer and the electron transport layer.

[0011] Currently, an organic electroluminescence (EL) device containing an organic fluorescent substance is generally manufactured by the vacuum vapor deposition method described in, for example, Appl. Phys. Lett., 51, 913 (1987). Is. In general, there are two types of vacuum deposition methods-one-component and two-component (or "host-guest" or "dual") methods (eg, J. Appl. Phys., 65, 3610) depending on the structure of the luminescent material. 1989))-is applied.

[0012] In order to emit red, green or blue light in a one-component system, the luminescent substance itself must emit strong fluorescence of red, green or blue. Furthermore, the vacuum deposition method must be able to form a homogeneous vapor deposition film, which film has proper (carrier) mobility for holes and / or electrons, ie. Must be endowed with the properties of the semiconductor.

[0013] Many substances that emit light in the green or blue region are known.

JP-B22,749,407 (Pioneer Electron &amp; Nippon Kayaku) contains N, N'-bis (2,5-di-tert-butylphenyl) -3,4,9,10-perylene as a luminescent substance. Carboximide is described. However, its brightness is not enough for industrial use 27cd / m²There is only.

JP-A2,296,891 (Ricoh) contains a positive electrode, a negative electrode, and one organic compound layer or a plurality of organic compound layers held between the positive electrode and the negative electrode, but is a hole transporting substance. We are claiming a patent for an electroluminescence element that does not contain. At least one layer of the organic compound layer is a layer containing a pyrrolopyrrole compound represented by the following formula II.

[0016] [Chemical 15]<img file="JP3854792B2_D0005.tif" />[0017] In the formula, Y₁And Y₂Represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group independently of each other, and Y₃And Y₄Represents a hydrogen atom or a substituted or unsubstituted alkyl or aryl group independently of each other, and X represents an oxygen atom or a sulfur atom. The four compounds, namely X, represent oxygen in all cases, and (a) Y₃= Y₄= Methyl and Y₁= Y₂= p-Trill compound, (b) Y₃= Y₄= Methyl and Y₁= Y₂= Compound that is hydrogen, (c) Y₃= Y₄= Hydrogen, Y₁= Y₂= P-trill compound and (d) Y₃= Y₄= Y₁= Hydrogen, Y₂Only compounds that are = p-chlorophenyl are explicitly listed. However, according to JP-A25,532,633 (see below), a follow-up study by the same inventor revealed that luminescence was only seen when DPP Compound II was used with other compounds. This observation shows that even if DPP II is used alone, ie Tris (8-hydroxyquinolinato) aluminum ("Alq".₃This is supported by Comparative Example 2 of JP-A25,320,663, which shows that no luminescence is observed without the addition of ").

[0018] JP-A25,320,663 (Sumitomo) has a light emitting layer containing 0.005 to 15 parts by mass of a luminescent substance of a DDP compound between a pair of electrodes, and at least one of the electrodes is transparent or translucent. We are claiming a patent for an organic EL element. The main claim is Alq₃Although the use of is not described, from the specification and examples, especially Comparative Example 2, Alq₃Is clearly an essential feature of the EL device according to the claim.

JP-A29003448 (Toyo Ink) has a light emitting layer containing a DDP compound as an electron transporting substance or an organic compound thin film layer containing a light emitting layer and an electron injection layer between a pair of electrodes, and the electron injection layer. Claims an organic EL device containing a DPP compound as an electron transporting substance. In addition, another EL device is claimed that further includes a hole injection layer. The drawback of the EL element according to the claim is, as usual, Alq.₃And phenanthrene diamine must always be used as a hole injecting material.

[0020] Japanese Patent No. 499,011 claims an organic EL device containing a DPP compound. However, only systems without an electron transport layer have been proven. Furthermore, only highly crystalline organic pigments should be used as luminescent materials. However, one of the requirements for luminescent materials is their morphological stability. Crystalline materials tend to change morphologically in the vapor deposition film. This is a drawback in guaranteeing device durability.

[0021] Normally, a host-guest type luminescent material utilizes sensitized fluorescence generated by Felster type excitation energy transfer from a host to a guest. Therefore, in addition to the above conditions, it is important for this type of substance to satisfy the condition that the fluorescence spectrum of the host in the solid state overlaps with the absorption spectrum of the guest in the solution state.

[0022] Regarding green emission, Alq₃As a host and a quinacridone derivative as a guest, an EL luminous efficiency as high as> 10 lm / W is achieved. Such a system is put into practical use in a monochrome display device.

Regarding blue luminescence, Appl. Phys. Lett., 67, 3853 (1995) reported a high EL emission of 1.5 lm / W by using a distyryl derivative as a host and an amino-substituted distyryl derivative as a guest. It reports that efficiency can be achieved. Similar to the above, the guest material does not have to have high carrier mobility and therefore does not have to be a semiconductor.

[0024] Many of the known orange, red or yellow fluorescent dyes for use as dye lasers have high fluorescent quantum yields in solution. However, those Stokes shifts are generally small. That is, most of the yellow, orange or red fluorescent dyes absorb yellow, orange or red light in the solution state and emit yellow, orange or red fluorescence. Therefore, yellow, orange or red fluorescent dyes are considered guests, and the host material is a solution of yellow, orange or red fluorescence specified by the conditions required to achieve sensitized fluorescence by Ferster-type excitation energy transfer. It should be a substance that emits in the state.

[0025] Furthermore, in addition to the conditions similar to the conditions required for the one-component luminescent material, compatibility with the guest must be considered. In conclusion, in order to achieve yellow, orange or red organic electroluminescence in a two-component system, the host material must be a yellow, orange or red solid fluorescent material. However, at this stage, no satisfactory yellow, orange or red luminescent substance is known for the same reason as in the case of the one-component system.

[0026] Japanese Patent No. 648770 describes a solid fluorescence-soluble latent pigment. However, since the latent pigment changes to an insoluble non-fluorescent DPP pigment when heated, it cannot be used in the above-mentioned vacuum deposition method.

[0027] Therefore, an object of the present invention is to provide an electroluminescent element that emits yellow, orange, or red light. In this device, an organic luminescent substance that satisfies the following conditions should be used.

[0028] For strong photoluminescence hole and / or electron carrier mobile vacuum deposition in the solid state in the case of monocomponent and / or binary hosts and in the solution state in the case of binary guests. Required properties (eg, ability to sublimate or evaporate) Ability to form homogeneous films Properties that exhibit "pure" color Ability to match electron potential with electrodes and / or adjacent substances Solid hosts and molecules when a dual system is desired Guest compatibility High durability (thermal, electrical, etc.) and morphological stability [0029] Therefore, the electroluminescent element has been found. In addition, its manufacturing method and new luminescent substances have been found.

[0030] The typical structure of the latest organic electroluminescence device is as follows.

(I) Electron / hole transport layer / electron transport layer / cathode (Compound I is a hole transport compound or light emitting layer and electron transport layer used to form a light emitting layer and a hole transport layer. Used as an electron-transporting compound that can be used to form) [0032] (ii) Electron / hole-transporting layer / light-emitting layer / electron-transporting layer / cathode (Compound I is a hole or electron in this structure. Forming a light emitting layer, whether or not it exhibits transportability) [0033] The light emitting layer can consist of two or more fluorescent materials of formula I for energy donors and / or energy acceptors.

[0034] The device can be manufactured by several methods. Generally, vacuum deposition is widely used in manufacturing. Preferably, the organic layer is laminated in the above order on a commercially available indium tin oxide (ITO) glass substrate maintained at room temperature, which acts as an anode in the structure. The film thickness is preferably in the range of 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, such as Mg / Ag alloy and Li-Al binary system, is laminated on the organic layer. The vacuum during deposition is preferably 0.1333 Pa (1 x 10).^-3Less than Torr), more preferably 1.333 × 10^-3Pa (1 × 10^-5Less than Torr), more preferably 1.333 × 10^-4Pa (1 × 10^-6Less than Torr).

[0035] As the anode, ordinary anode materials having a high work function, such as metals such as gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead and manganese. Metal alloys such as tungsten, eg magnesium / copper, magnesium / silver, magnesium / aluminum, aluminum / indium, semiconductors such as Si, Ge, GaAs, metal oxides such as indium tin oxide (ITO), ZnO etc. , Metal compounds such as CuI, and conductive polymers such as polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene, etc., preferably ITO, most preferably ITO on glass as a substrate. Among these electrode materials, metals, metal alloys, metal oxides and metal compounds can be formed on the electrodes by, for example, a sputtering method. When a metal or metal alloy is used as the material for the electrode, the electrode can also be formed by vacuum deposition. Furthermore, when a metal or metal alloy is used as the electrode forming material, the electrodes can also be formed by chemical plating (eg, Handbook of Electrochemistry, pp 383-387, Mazuren, 1985). When a conductive polymer is used, the electrode can be manufactured by molding it into a film by an anodizing polymerization method and applying a conductive coating film to a pre-applied substrate. The thickness of the electrode formed on the substrate is not limited to a specific numerical value, but when the substrate is used as a light emitting surface, the thickness of the electrode is preferably in the range of 1 nm to 100 nm, in order to guarantee transparency. It is preferably in the range of 5 to 50 nm.

[0036] In a preferred embodiment, ITO is used on the substrate with an ITO film thickness in the range of 10 nm (100 Å) to 1 μ (10000 Å), preferably 20 nm (200 Å) to 500 nm (5000 Å). Generally, the area resistance of ITO film is 100Ω / cm.²Range not exceeding, preferably 50Ω / cm²It is selected within the range that does not exceed.

[0037] Such anodes are commercially available from Japanese manufacturers such as Geomatech, Sanyo Vacuum, Nippon Sheet Glass.

[0038] A conductive or insulating material can be used as the substrate. When using a conductive substrate, a light emitting layer or hole transport layer is formed directly on it, and when using an insulating substrate, an electrode is first formed on it, and then a light emitting layer or positive The hole transport layers are superimposed.

[0039] The substrate may be transparent, translucent, or opaque. However, when the substrate is used as a display surface, the substrate must be transparent or translucent.

[0040] The transparent insulating substrate may be an inorganic compound, such as an organic polymer compound such as glass, quartz, such as polyethylene, polypropylene, polymethylmethacrylate, polyacrylonitrile, polyester, polycarbonate, polyvinyl chloride, polyvinyl alcohol, polyacetic acid. For example, vinyl. Each of these substrates can be formed into a transparent conductive substrate by providing electrodes by any of the above methods.

[0041] Examples of translucent insulating substrates include inorganic compounds such as alumina and organic polymer compounds such as YSZ (yttria-stabilized zirconia), such as polyethylene, polypropylene, polystyrene and epoxy resins. Each of these substrates can be formed into a translucent conductive substrate by providing electrodes by any of the above methods.

Examples of opaque conductive substrates include various electroplated metals, metal alloys, such as metals such as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold and platinum. For example, there are semiconductors such as bronze and stainless steel, and conductive polymers such as Si, Ge and GaAs, such as polyaniline, polythiophene, polypyrrole, polyacetylene and polyparaphenylene.

[0043] A substrate can be obtained by forming any of the above substrate materials into a desired size. The substrate preferably has a smooth surface. However, even if it has a rough surface, there is no problem in practical use as long as it is flat enough to have a curvature of 20 μm or more. There are no restrictions on the thickness of the substrate as long as sufficient mechanical strength is guaranteed. As the cathode, ordinary cathode materials with low work function, such as alkali metals, alkaline earth metals, Group 13 elements, silver and copper and their alloys or mixtures, 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 European Publication No. 499,011 such as conductive polymers. , For example, polypyrrole, polythiophene, polyaniline, polyacetylene, etc., preferably Mg / Ag alloys or Li-Al mixtures can be used.

[0044] In a preferred embodiment, a magnesium-silver alloy or a mixture of magnesium and silver or a lithium aluminum alloy or a mixture of lithium and aluminum is prepared from 10 nm (100 Å) to 1 μm (10000 Å), preferably 20 nm (200 Å) to 500 nm ( It can be used with a film thickness in the range of 5000 Å).

[0045] Such a cathode can be deposited on the electron transport layer by the above-mentioned known vacuum deposition technique.

[0046] In a preferred embodiment of the present invention, a light emitting layer can be used between the hole transport layer and the electron transport layer. It is usually made by forming a thin film of the DPP compound of formula I on the hole transport layer.

[0047] Examples of the method for forming the thin film include a vacuum deposition method, a spin coating method, a casting method, and a Langmuir-Brojet (LB) method. Of these methods, the vacuum deposition method, the spin coating method and the casting method are particularly preferable from the viewpoint of ease of processing and cost.

[0048] When a thin film is formed by a vacuum deposition method using DPP compound I, the conditions for performing vacuum deposition usually largely depend on the properties, shape, and crystalline state of the compound. However, the optimum conditions are, for example, a heating tank temperature of 100 to 400 ° C, a substrate temperature of -100 to 350 ° C, and 1.33 × 10.⁴Pa (1 × 10²Torr) ~ 1.33 × 10^-4Pa (1 × 10^-6It can be selected from the pressure range of Torr) and the deposition rate of 1 pm to 6 nm / sec.

[0049] In an organic EL device, the thickness of the light emitting layer is one of the factors that determine the light emitting property. For example, if the light emitting layer is not thick enough, a short circuit easily occurs between the two electrodes sandwiching the light emitting layer, and as a result, EL light emission cannot be obtained. On the other hand, if the light emitting layer is too thick, a large potential drop occurs inside the light emitting layer due to its high electrical resistance, resulting in an increase in the threshold voltage for EL light emission. Therefore, it is necessary to limit the thickness of the organic light emitting layer to the range of 5 nm to 5 μm. Preferred thickness is in the range of 10 nm to 500 nm.

When the light emitting layer is formed using the spin coating method and the casting method, DPP I is added to a suitable organic solvent at a concentration of 0.0001 to 90% by mass, for example, benzene, toluene, xylene, tetrahydrofuran, methyl tetrahydrofuran, The coating can be carried out using a solution prepared by dissolving in N, N-dimethylformamide, dichloromethane, dimethyl sulfoxide and the like. At this time, the higher the concentration of DPP I, the thicker the obtained film, and the lower the concentration, the thinner the obtained film. However, above 90% by weight, the solution is usually so sticky that it can no longer form a smooth, homogeneous film. On the other hand, as a general rule, if the concentration is less than 0.0001% by mass, the efficiency of forming the film becomes too low and the economy is lost. Therefore, the preferred concentration of DPP I is in the range of 0.01-80% by weight.

[0051] When using the spin coating or casting method, it is possible to further improve the homogeneity and mechanical strength of the resulting layer by adding a polymer binder to the solution for forming the light emitting layer. In principle, any polymer binder may be used as long as it is soluble in the solvent in which DPP I dissolves. Examples of such polymer binders are polycarbonate, polyvinyl alcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinyl acetate, epoxy resin and the like. The solution for forming the light emitting layer may have any concentration of DDP I, polymer binder and solvent. However, if the solid content of the polymer binder and DDP I exceeds 99% by weight, the fluidity of the solution is usually too low to form a homogeneous light emitting layer. On the other hand, if the content of DPP I is substantially lower than the content of the polymer binder, the electrical resistance of the layer will generally be very high and will not emit light unless a high voltage is applied to it. Furthermore, in this case, DPP in the layer Due to the low concentration of I, its luminous efficiency is relatively low. Therefore, the preferred composition ratio of the polymer binder to DPP I is selected in the range of 10: 1 to 1:50 mass ratio, and the solid content composed of both components in the solution is preferably 0.01 to 80 mass. It is in the range of%, more preferably in the range of about 0.1 to 60% by mass.

[0052] When the light emitting layer is formed by the spin coating method or the casting method, the thickness of the layer can be selected in the same manner as when the light emitting layer is formed by the vacuum vapor deposition method. That is, the layer thickness is preferably selected in the range of 5 nm to 5 μm, more preferably in the range of 10 nm to 500 nm.

[0053] As the hole transport layer, known organic hole transport compounds such as polyvinylcarbazole [0054] [Chemical Formula 16]<img file="JP3854792B2_D0006.tif" />[0055], TPD compounds disclosed in J. Amer. Chem. Soc. 90 (1968) 3925 [0056] [Chemistry 17]<img file="JP3854792B2_D0007.tif" />[0057] (During the formula, Q₁And Q₂Represents a hydrogen atom or a methyl group, respectively) [0058], J. Appl. Phys. 65 (9) (1989) 3610.<img file="JP3854792B2_D0008.tif" />[0060], Stilbene-based compounds [0061] [Chemical 19]<img file="JP3854792B2_D0009.tif" />[0062] (in the formula, T and T₁Represents an organic group), a hydrazone-based compound [0063] [Chemical 20]<img file="JP3854792B2_D0010.tif" />[0064] and so on.

[0065] The compound used as a hole transporting substance is not limited to the above compounds. Any compound that has the property of transporting holes, such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, Stillbenyl anthracene derivatives, fluorenone derivatives, hydrazone derivatives, stillben derivatives, aniline derivative copolymers, conductive oligomers, especially thiophene oligomers, porphyrin compounds, aromatic tertiary amine compounds, stillbenylamine compounds, etc. as hole transport substances. Can be used. 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'-diaminodiphenyl ether, 4,4'-bis (diphenylamino) quaterphenyl, N, N, N- Tri (p-tolyl) amine, 4- (di-p-tolylamino) -4'-[4- (di-p-tolylamino) styryl] stillben, 4-N, N-diphenylamino- (2-diphenylvinyl) Benzene, 3-methoxy-4'-N, N-diphenylaminostilben, N-phenylcarbazole and the like.

[0066] Furthermore, the 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, three triphenylamine units disclosed in US Pat. No. 5,061,569 are "stars". Compounds bonded to nitrogen atoms in a "burst" structure, such as 4,4', 4'-tris [N- (3-methylphenyl) -N-phenyl] disclosed in European Publication No. 508,562. Amino] Triphenylamine.

[0067] The hole transport layer can be formed by producing an organic film containing at least one hole transport substance on the anode. The hole transport layer can be formed by a vacuum deposition method, a spin coating method, a casting method, an LB method, or the like. Of these methods, the vacuum deposition method, spin coating method and casting method are particularly preferable from the viewpoint of simplicity and cost.

[0068] 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 hole transport layer containing two or more hole transport substances, a co-deposition method can be used with the desired compound.

[0069] When the hole transport layer is formed by the spin coating method or the casting method, the layer can be formed under the conditions described with respect to the formation of the light emitting layer (see above).

[0070] A smoother, more homogeneous solution by using a solution containing a binder and at least one hole transporter, as in the case of forming a light emitting layer using a solution containing a polymer binder. A hole transport layer can be formed. Coatings using such solutions can be performed in the same manner as when forming a light emitting layer using a polymer binder. Any polymer binder may be used as long as it is soluble in a solvent in which at least one hole transporter is soluble. Examples of suitable polymer binders and suitable and preferred concentrations are those mentioned above when describing the formation of the light emitting layer.

The thickness of the hole transport layer is preferably selected in the range of 0.5 to 1000 nm, preferably in the range of 1 to 100 nm, and more preferably in the range of 2 to 50 nm.

[0072] The electron transport material in the electron transport layer preferably has high electron injection efficiency from the cathode and high electron transfer. The following substances can be mentioned as examples of electron transporting substances. Tris (8-hydroxyquinolinato) -aluminum (III) and its derivatives, bis (10-hydroxybenzo [h] quinolinolato) berylium (II) and its derivatives, oxadiazole derivatives such as 2- (4-biphenyl)- 5- (4-tert-butylphenyl) -1,3,4-oxadiazole and its dimer system, 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, triazole derivatives, phenanthroline derivatives or perylene tetracarboxylic acid derivatives such as Appl. Phys. Lett. 48 (2) (1986) 183 What is disclosed in.

[0073] The electron transport layer can be formed by producing an organic film containing at least one electron transport substance on the hole transport layer or the light emitting layer. The electron transport layer can be formed by a vacuum deposition method, a spin coating method, a casting method, an LB method, or the like.

[0074] By using a solution containing a binder and at least one electron-transporting substance, as in the case of forming a light emitting layer or a hole transporting layer by using a solution containing a polymer binder. A smoother and more homogeneous electron transport layer can be formed.

[0075] The thickness of the electron transport layer is preferably selected in the range of 0.5 to 1000 nm, preferably in the range of 1 to 100 nm, and more preferably in the range of 2 to 50 nm.

[0076] The yellow to red fluorescent compound used has a fluorescence maximum value preferably in the range of 500 to 780 nm, more preferably in the range of 520 to 750 nm, and more preferably in the range of 540 to 700 nm. Means to have. Furthermore, the compound of the present invention preferably exhibits an absorption maximum value in the range of 450 to 580 nm.

Luminescent compound I typically exhibits a fluorescence quantum yield (FQY) of 1> FQY 0.3 (measured in aerated toluene or DMF). Furthermore, in general, Compound I of the present invention exhibits a molar absorption coefficient in the range of 5000 to 100,000.

[0078] A preferred embodiment is R₁= R₂And Ar₁= Ar₂DDP compound I, particularly preferably in addition to the above, R₃= R₄DDP compound I with = H, m = 0 and n = 0, most preferably (a) R₁= R₂= C₁~ C₈Alkyl and Ar₁= Ar₂= Phenyl or stilbene, R₇= At 4 positions -NR₈R₉And R₅= R₆= Hydrogen, R₈= R₉= C₁~ C₈DDP compounds that are alkyl or phenyl, or (b) R₁= R₂= C₁~ C₈Alkyl,-(CH₂)_m-Ph and Ar₁= Ar₂= Phenyl or stilbene, R₅= R₆= Hydrogen, R₇=-SR₇, -OR₁₀, -N (R)₈)₂Or unsubstituted phenyl or phenyl substituted at the para position, R₈= C₁~ C₈Alkyl, phenyl or unsubstituted or substituted heterocyclic group or C₅~ C₁₂DDP compound which is cycloalkyl, or (c) R₁= R₂=-CH₂-Ph, phenyl is phenyl, naphthyl or C₁~ C₄It may be substituted up to 2 times with alkyl, Ar₁= Ar₂= Phenyl or 1 or 2-naphthyl, R₅= R₆= Hydrogen, R₇But Ar₁= Ar₂If = 1 or 2-naphthyl, then hydrogen or -OMe, and in all other cases, C₁~ C₈With respect to DDP compounds which are alkyl or phenyl.

[0079] Particularly preferred DPP compound I is the following compound.

[0080] [Chemical 21]<img file="JP3854792B2_D0011.tif" />[0081] [Chemical 22]<img file="JP3854792B2_D0012.tif" />[0082] C₁~ C₂₅Alkyl is usually linear or branched, and if possible, methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-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, Dodecyl, Tetradecyl , Pentadecyl, hexadecyl, heptadecyl, octadecyl, eikosyl, heneikosyl, docosyl, tetracosyl or pentacosyl, preferably C₁~ C₈Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, more preferably C₁~ C₄Alkyl, such as methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl. C₁~ C₆Alkyl stands for methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, tert-butyl, n-pentyl, 3-pentyl, 2,2-dimethyl-propyl, n-hexyl and C.₁~ C₃Alkyl represents methyl, ethyl, n-propyl or isopropyl.

[0083] C₁~ C₈Alkoxy is usually methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy, n-pentoxy, 2-pentoxy, 3-pentoxy, 2,2-dimethylpropoxy, n- Hexoxy, n-heptoxy, n-octoxy, 1,1,3,3-tetramethylbutoxy and 2-ethylhexoxy, preferably C₁~ C₄Alkoxy, such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, sec-butoxy, isobutoxy, tert-butoxy.

[0084] C₆~ C₂₄Aryl is usually phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, 2 or 9-fluorenyl or anthrasenyl, preferably C.₆~ C₁₂Aryl, such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl.

[0085] C₇~ C₂₄Aralkyl is usually benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl. , Ω-Phenyl-Octadecyl, ω-Phenyl-Eicosyl or ω-Phenyl-Docosyl, preferably C₇~ C₁₈Aralkyl, for example benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenyl-butyl, ω, ω-dimethyl-ω-phenyl-butyl, ω-phenyl-dodecyl or ω-Phenyl-octadecyl, especially preferably C₇~ C₁₂Aralkyl, such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenyl-butyl or ω, ω-dimethyl-ω-phenyl-butyl.

[0086] C₅~ C₁₂Cycloalkyl is usually cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl, preferably cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl.

[0087] A heteroaryl having 5 to 7 ring atoms (here, a heteroatom capable of nitrogen, oxygen or sulfur) usually has 5 to 18 atoms having at least 6 conjugated π electrons. Unsaturated heterocyclic groups such as thienyl, benzo [b] thienyl, dibenzo [b, d] thienyl, thianthrenyl, frill, furfuryl, 2H-pyranyl, benzofuranyl, isobenzofuranyl, dibenzofuranyl, phenoxythienyl, pyrrolyl. , Imidazolyl, pyrazolyl, pyridyl, bipyridyl, triazinyl, pyrimidinyl, pyrazinyl, pyridadinyl, indolidinyl, isoindrill, indrill, indazolyl, prynyl, quinolidinyl, quinolyl, isoquinolyl, phthalazinyl, naphthylidineyl, quinoxalinyl, quinazolinyl Triazolyl, benzoxazolyl, phenanthridinyl, acridinyl, perimidinyl, phenanthrolinyl, phenazinyl, isothiazolyl, phenothiazine, isoxazolyl, flazanyl or phenoxadinyl, preferably the monocyclic or bicyclic heterocyclic type. Is the basis.

[0088] The DPP compound I of the present invention can be synthesized by a method well known in the art, for example, as described in European Patent Publication No. 133,156, for example, in the same manner as in Example 15.

A preferred embodiment of the present invention is a method for producing the compound I or III of the present invention, wherein in the first step, the formula Va or Vb [0090] [Chemical Formula 23].<img file="JP3854792B2_D0013.tif" />[0091] The DPP derivative of [0091] is treated with a base, and in the second step, the reaction mixture obtained in the first step is treated with an ordinary alkylating agent, and the base is used in the first step. Is a hydride, alkali metal alkoxide or carbonate, and the alkylating agent is sulfonate, tosylate, mesylate, carbonate, sulfate or formula (R).₁)_1or2X (X is SO₃-, (P-Me-Phenyl) SO₂-, (2,4,6-trimethyl-phenyl) SO₂-, -CO₃-,-SO₄-Or a halogen compound of halogen, such as chloro, bromo, fluorine or iodine, preferably chloro, bromo or iodine, particularly preferably bromo or iodine) or (R).₁)_1or2X and (R₂)_1or2Regarding the method of being a mixture with X.

As the hydride, alkali metal hydrides such as sodium hydride, lithium hydride or potassium hydride can usually be used, and the alkali metal alkoxide is generally alkali metal C.₁~ C₄Alkoxides such as sodium or potassium tert-butoxide and sodium tert-amylate can be used, and as the carbonate, sodium carbonate or potassium can be usually used, preferably sodium hydride can be used.

[0093] Generally, the first step of a preferred method of producing compound I or III starting from compound Va or Vb is carried out at a temperature of -25 to 100 ° C, preferably 0 to 25 ° C.

[0094] Preferably, the reaction is carried out in a solvent, preferably a bipolar aprotic solvent such as carboxamides, lactams, urea derivatives, sulfants and nitrobenzenes such as dimethylformamide (DMF), dimethylacetamide (DMA), N-. It is carried out in the presence of methylpyrrolidone (NMP), N, N'-dimethylethyleneurea and N, N'-dimethylpropyleneurea.

[0095] When a solvent is used, the mass ratio of the solvent to the DPP compound is selected from the range of 100: 1 to 5: 1, preferably the range of 25: 1 to 10: 1.

[0096] In addition, the first step is preferably carried out in the presence of a phase transfer catalyst, such as tetraalkylammonium halide, such as tetraethylammonium bromide.

[0097] Usually, the molar ratio of the base to the DPP compound Va or Vb is selected in the range of 10: 1 to 2: 1, preferably in the range of 4: 1 to 2: 1.

[0098] The molar ratio of the DPP compound Va or Vb to the phase transfer catalyst is preferably selected in the range of 100: 1 to 5: 1, preferably in the range of 25: 1 to 10: 1.

[0099] In general, the reaction time depends, among other things, on the reactivity of the selected reactants and the selected temperature. As an example, if room temperature is selected as the reaction temperature, the reaction time is in principle in the range of 0.5 to 24 hours.

[0100] Preferably, the halogen compound R₁-X (or the mixture) is added to the reaction mixture obtained in the first step in the same solvent used in the first step. The reaction temperature of the second step is usually selected in the range of 0 to 160 ° C, preferably 25 to 110 ° C, depending in particular on the desired reaction pressure and solvent used. The reaction temperature is generally selected in the range of 0.5 to 120 hours, preferably 12 to 60 hours.

[0101] As a general rule, R₁The molar ratio of -X to the DPP compound Va or Vb is selected in the range of 10: 1 to 2: 1, preferably in the range of 4: 1 to 2: 1.

[0102] When using a solvent, the amount of solvent is usually the halogen compound R.₁Select in the range of 100: 1 to 5: 1, preferably in the range of 25: 1 to 10: 1, based on the amount of -X. Further, preferably, if a solvent is used in the first step, the same solvent as in the first step is used. If no solvent is used in the first step, the same solvent as described above can be used.

The resulting reaction mixture is precipitated by applying a method well known in the art, eg, in the presence of a suitable solvent, eg water, and if necessary in a suitable solvent, eg ethanol. It can be processed by recrystallizing with. Another method is, for example, the method of adding alcohol to quench the excess base and then filtering.

Compound Va is described, for example, in US Pat. No. 4,579,949, wherein the appropriate nitrile is reacted with the corresponding dialkyl succinate or diaryl succinate according to the methods described therein. For example NC-Ar₁Can also be produced by reacting with sodium tert-amyl alcohol and then adding diisopropyl succinate. This method is Ar₁And / or Ar₂Represents a biphenyl group (ie, R₅And / or R₆Is preferred in the case of phenyl or 4-position substituted phenyl) or in the case of the compounds described below (DPP VIa).

[0105] Compound Vb can be produced, for example, by the following route .

[0106] [Chemical 24]<img file="JP3854792B2_D0014.tif" />[0107] Naturally, R₁Instead of using Hal, R₁-Hal and R₂A mixture with -Hal can also be used to reach the general formula Vb. Usually R₁Hal or R₁-Hal and R₂The mixture with -Hal is used in molar quantities in the range 0.4 to 0.6: 1 with respect to the starting DPP derivative. Therefore, in general, the molar amount of Hal-Z-Hal / intermediate is selected in the range of 0.4 to 0.6: 1.

Compounds I and III are also expressed in formula VIa or VIb [0109].<img file="JP3854792B2_D0015.tif" />[0110] In the formula, Hal represents a halogen, eg, fluoro, chloro, bromo or iodine, preferably chloro or bromo) as a nucleophile, eg, a secondary amine HNR.₈R₉, Thiol HSR₈Or HS (O)_nR₈, Alcohol HOR₁₀, Diselenide R₈(O)_nSe-Se (O)_nR₈And preferably 1.2: 1 ~ 0.8: 1 or R₂Is R₁If it has the same meaning as, the molar ratio of DPP VIa or VIb in the range of 1: 2.5 to 1: 1 to the nucleophile is usually 0.1 to 15 per mole of anhydrous bipolar aprotic solvent and nucleophile. Obtained in the same manner as described in European Patent Publication No. 353,184, comprising reacting in the presence of a molar amount of anhydrous base, usually at a temperature of 100-220 ° C and generally at a pressure of 100-300 kPa. Can be done.

Examples of suitable anhydrous bipolar aprotic solvents are carboxamides, lactams, urea derivatives, sulfones and nitrobenzenes such as DMF, DMA, NMP, N, N'-dimethylethyleneurea and N, N'. -Dimethylpropylene urea.

Suitable anhydrous bases are, for example, anhydrous organic bases, such as quinoline or preferably excess secondary amines used for amination, said carbonates, such as sodium or potassium carbonate and alkali metal hydrides, such as hydrides. It is sodium. Diserenide R₇(O)_nSe-Se (O)_nR₇When using, an alkali metal hydride, preferably sodium hydride, must be used as the base.

[0113] Corresponding 1 and 2-naphthyl derivatives can be produced in the same manner.

DPP compounds VIa and VIb are known or react dialkyl succinate or diaryl succinate with a nitrile, eg, p-chlorobenzo dimethyl succinate according to Example 6 of US Pat. No. 4,579,949. The corresponding DPP compound VIa in which H represents chloro can be obtained by preparation according to the method described in US Pat. No. 4,579,949, including reaction with nitrile.

Compound R₁-X is commercially available and can also be manufactured by methods well known in the art.

A further embodiment of the invention is a method of producing compound I or III of the invention, wherein in (a) first step, a DPP derivative of formula VIa or VIb is used as a nucleophile, eg, a secondary amine. HNR₈R₉, Thiol HSR₈Or HS (O)_nR₈, Alcohol HOR₁₀, Diselenide R₈(O)_nSe-Se (O)_nR₈And preferably 1.2: 1 ~ 0.8: 1 or R₂Is R₁If it has the same meaning as, the molar ratio of DPP VIa or VIb in the range of 1: 2.5 to 1: 1 to the nucleophile is usually 0.1 to 15 per mole of anhydrous bipolar aproton solvent and nucleophile. Treatment in the presence of a molar amount of anhydrous base, usually at a temperature of 100-220 ° C and generally a pressure of 100-300 kPa, and in some cases isolation of the resulting compound V, and (b) then In the second step, after treating the obtained compound Va or Vb with a base, the reaction mixture obtained in the first step of (b) is treated with an ordinary alkylating agent, which comprises the treatment of (b). In the first step, the base is a hydride, alkali metal alkoxide or carbonate and the alkylating agent is a sulfonate, tosylate, mesylate, carbonate, sulfate or formula (R).₁)_1or2X (X is SO₃-, (P-Me Phenyl) SO₂-, (2,4,6-trimethylphenyl) SO₂-, -CO₃-,-SO₄-Or a halogen compound (representing halogen) or (R)₁)_1or2X and (R₂)_1or2Regarding the method of being a mixture with X. (R₁)_1or2R in X₁The number of units (1 or 2) depends on the nature of the selected group X, i.e. X is a divalent anion, eg-CO.₃-,-SO₄-Only when representing etc., 2 Rs₁It is clear that the unit exists.

[0117] Water-soluble compound I or III, i.e., a functional group capable of increasing water solubility, such as a tertiary amino group, SO.₃^-Or PO₄^2-The compound I or III of the present invention substituted with is can be produced using a method well known in the art. The following routes are representative examples, and thus the present invention is not limited to these examples.

[0118] [Chemical 26]<img file="JP3854792B2_D0016.tif" />[0119] In the equation, r usually represents an integer of 2 to 25. Instead of a linear alkyl group, a branched chain alkyl or aralkyl group, such as Br- (CH)₂)_r1-Aryl- (CH₂)_r2-Br (r)₁And r₂Is usually an integer in the range 0-10).

[0120] [Chemical 27]<img file="JP3854792B2_D0017.tif" />[0121] Therefore, the corresponding compound III can be obtained by such a route.

Another embodiment of the present invention is a high molecular weight organic material (usually 10) by incorporating the fluorescent DPP compound I or III of the present invention by a method known in the art.³~10⁷It relates to a method of coloring (having a molecular weight in the range of g / mol).

[0123] As the high molecular weight organic substance, for example, biopolymers and plastic materials (including fibers) can be used below.

The present invention preferably relates to the use of the DPP I or III of the present invention to produce:

[0125] Flexo printing, screen printing, packaging printing, security ink printing, indentation printing or offset printing, pre-press stage and printing, office, household or graphics, such as paper products, such as ball pens, felt chips. , Fiber chips, cards, wood, stains, metals, ink pads or inks for impact printing methods (using impact pressure ink ribbon), paints, industrial or commercial, textile decoration and industrial markings, roller coatings Colorants for powder coatings or automotive finishes, high solids (low solvent) water content or colorants for metallic or water-based paints, colored plastics for coatings, fibers, platters or mold carriers, digital Non-impact printing materials for printing, thermal brazing transfer printing, inkjet printing or thermal transfer printing, especially color for visible light in the 400-700 nm range, liquid crystal display (LCD) or charge coupling element (CCD) Filters, cosmetics, or polymer ink particles, toners, dry copy toners, liquid copy toners or electrophotographic toners.

[0126] Fluorescent DPP of the present invention Representative examples of suitable high molecular weight organic substances that can be colored with I or III are vinyl polymers such as polystyrene, poly-α-methylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p. -Hydroxyphenylstyrene, polymethylmethacrylate and polyacrylamide and corresponding methacrylic acid compounds, polymethylmaleate, polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinylfluoride, polyvinylidene chloride, vinylidene fluoride, vinylacetate. , Polymethyl Vinyl Ether and Polybutyl Vinyl Ether; Polymers Derived from Maleimido and / or Maleic Acid Anhydrous, eg Copolymers of Maleic Acid Anhydrous and Styrene; Polyvinylpyrrolidone; ABS; ASA; Polyamide; Polyether sulfone; Polyphenylene oxide; Polyurethane; Polyurea; Polycarbonate; Polyarylene; Polyarylene sulfide; Polyepoxide; Polypropylene, eg polyethylene and polypropylene; Polyalkandien; Biopolymers and derivatives thereof, such as cellulose, cellulose ethers and esters, For example ethyl cellulose, nitro cellulose, cellulose acetate and cellulose butyrate, starch, chitin, chitosan, gelatin, zein; natural resins; synthetic resins such as alkyd resins, acrylic resins, phenolic resins, epoxy resins, aminoformaldehyde resins such as urea / formaldehyde resins. And melamine / cellulose resins, vulverized rubbers; casein; silicones and silicone resins; rubbers, chlorinated rubbers; and polymers used, for example, as binders in paint systems, such as C.₁~ C₆Aldehydes such as formaldehyde and acetaldehyde and, optionally, one or two Cs₁~ C₉Dinuclear or mononuclear, preferably mononuclear phenol substituted with an alkyl group, one or two halogen atoms or one phenyl ring, such as o-, m- or p-cresol, xylene, p-tert -Novolak derived from butylphenol, o-, m- or p-nonylphenol, p-chlorophenol or p-phenylphenol or compounds with two or more phenolic groups such as resorcinol, bis (4-hydroxyphenyl) methane Alternatively, 2,2-bis (4-hydroxyphenyl) propane and a suitable mixture of the above substances.

Particularly preferred high molecular weight organic substances for producing paints, printing inks or inks are, for example, cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate, natural resins or synthetic resins. (Polymerized or condensed resins), such as aminoplasts, especially urea / formaldehyde and melamine / formaldehyde resins, alkyd resins, phenol plastics, polycarbonates, polyolefins, polystyrenes, polyvinyl chlorides, polyamides, polyurethanes, polyesters, ABS, ASA, polyphenylene oxides, Sulfurized rubber, casein, polystyrene and silicone resins and possible mixtures of them.

It is also possible to use dissolved forms of high molecular weight organic substances such as heated linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine / formaldehyde and urea / formaldehyde resins and acrylic resins as film-forming agents. ..

[0129] The high molecular weight organic substance can be obtained alone or in a mixed state, for example, in the form of granules, plastic materials, melts, and particularly when producing spinning liquids, paints, paints, inks or printing inks. Can also be obtained in the form of a solution.

[0130] In a particularly preferred embodiment of the invention, the fluorescent DPP I or III of the invention is an internal coloration of polyvinyl chloride, polyamide and especially polyolefins such as polyethylene and polypropylene and powder coatings, inks, printing inks, color filters and Used in the manufacture of paints, including coating colors.

[0131] Typical examples of preferred binders for paints are acrylic resin-based two-component lacquers that can be crosslinked with alkyd / melamine resin paints, acrylic / melamine resin paints, cellulose acetate / butyrate cellulose paints and polyisocyanates. Is.

[0132] According to the observations carried out to date, the fluorescent DPP I or III of the present invention can be added in any desired amount to the material to be colored, depending on the requirements for end use. In the case of high molecular weight organic material, for example, the fluorescent DPP I or III produced according to the present invention is in the range of 0.01 to 40% by mass, preferably 0.01 to 5 based on the total mass of the high molecular weight organic material to be colored. It can be used in amounts in the range of mass%.

[0133] Therefore, another embodiment of the present invention is (a) 0.01 to 50% by mass, preferably 0.01 to 5% by mass, particularly preferably 0.01, based on the total mass of the colored high molecular weight organic material. 99.99 to 50% by mass, preferably 99.99 to 95% by mass, particularly preferably 99.99 to 50% by mass, based on the total mass of the fluorescent DPP I or III of the present invention of ~ 2% by mass and (b) the colored high molecular weight organic substance. 99.99-98% by weight of high molecular weight organic material and (c) optionally an effective amount, eg 0-50% by weight based on the total mass of (a) and (b), such as leology With respect to compositions comprising improvers, dispersants, fillers, paint aids, desiccants, plasticizers, UV stabilizers and / or additional pigments or corresponding precursors.

[0134] In order to produce non-brittle molded articles or reduce their brittleness, so-called plasticizers can be added to the high molecular weight organic material prior to molding. The plasticizer can be, for example, an ester of phosphoric acid, phthalic acid and sebacic acid. The plasticizer may be added before, during, or after the high molecular weight organic material is colored with the fluorescent DPP I or III of the present invention.

To obtain different shades, the fluorescent DPP I or III of the present invention was advantageously mixed with the desired amount of filler, clear and opaque white, colored and / or black pigments and customary gloss pigments. You may use it in the state.

[0136] In order to produce paints, paints, color filters, inks and printing inks, the corresponding high molecular weight organic substances such as binders, synthetic resin dispersions and the like are usually used with the fluorescent DPP I or III of the present invention. Is dispersed or dissolved in a common solvent or solvent mixture, if desired, with conventional additives such as dispersants, fillers, paint aids, desiccants, plasticizers and / or additional pigments or pigment precursors. This can be achieved by dispersing or dissolving the individual components one by one or several components together and then combining all the components, or by adding all at once.

[0137] Therefore, a further embodiment of the present invention is a method of using the fluorescent DPP I or III of the present invention to produce a dispersion and a corresponding dispersion and a paint system or paint containing the fluorescent DPP I or III of the present invention. , Color filters, inks and printing inks.

Particularly preferred embodiments are applications of DPP I or III of the invention and DPP I or III of the invention for producing fluorescent tracers for detecting leaks in, for example, fluids such as lubricants, cooling systems and the like. With respect to fluorescent tracers or lubricants, including. Usually, such lubricant compositions, for example for refrigerants, are naphthalene oils, paraffin oils, alkylated benzene oils, polyalkyl silicate oils, polyglycols, esters, polyether polyols, polyvinyl ethers, polycarbonates, fluorine. Includes oils selected from the group consisting of chemicalized silicones, perfluoroethers, aromatic compounds with fluoroalkyloxy or fluoroalkylthio substituents. The amount of DPP I or III of the present invention in the lubricant is generally selected in an amount of 100-1000 ppm. If Compound I of the present invention is water-soluble, it may be used in water as a tracer.

[0139] Specific embodiments of the present invention relate to inkjet inks containing the fluorescent compositions of the present invention.

The desired ink can contain up to 30% by weight of the fluorescent composition, but generally in most thermal inkjet printing applications, it is in the range of 0.1-10% by weight, preferably 0.1-% of the total ink composition. It is in the range of 8% by mass.

In addition, inks typically contain polymer dispersants such as random, block, branched or grafted polymers or copolymers. Most preferred are polymer dispersants produced by group transfer polymerization. The reason is that they generally do not contain the relatively high molecular weight seeds that tend to clog the pen nozzles.

[0142] In AB or BAB block copolymers, the A segment is usually a hydrophobic homopolymer or copolymer that acts to bind to the fluorescent compositions of the invention, and the B block is generally a hydrophilic homopolymer or copolymer or a salt thereof. And preferably acts to disperse the pigment in the selected aqueous medium. Such polymer dispersants and their synthesis are known from US Pat. No. 5,085,698.

ABC triblock is also useful as a dispersant. In the ABC triblock, the A block is usually a water-compatible polymer, the B block is a polymer capable of binding to the fluorescent composition, and the C block is compatible with organic solvents. Preferably, the A and C blocks are the terminal blocks. The ABC triblock and its synthesis are disclosed, for example, in European Patent Publication No. 556,649. Suitable graft polymers are disclosed in US Pat. No. 5,231,131.

Representative compounds useful for this purpose are, for example, polyvinyl alcohol polymers, cellulosic compounds and ethylene oxide modified polymers and dispersant compounds containing ionizing groups such as acrylic acid, maleic acid or sulfonic acid. including.

The polymer dispersant is generally present in an amount in the range of 0.1-30% by weight, preferably 0.1-8% by weight of the total ink composition.

Surfactants may be used as the dispersant in addition to or instead of the preferred polymer dispersants. It can be an anionic, non-ionic or amphoteric surfactant. A detailed list of non-polymers and some polymer dispersants is disclosed in the Dispersants section of Manufacturing Confection Publishing (1990) p.110-129, McCutcheon's Functional Materials North American Edition.

Inks typically contain an aqueous medium, such as water or a mixture of water and at least one water-soluble organic solvent. Water-soluble organic solvents are well known, and representative examples thereof are disclosed, for example, in US Pat. No. 5,085,698. The choice of a suitable mixture of water and a water-soluble organic solvent usually depends on the requirements of the particular application, such as the desired surface tension and viscosity, the drying time of the ink and the medium substrate on which the ink is printed.

Particularly preferred are mixtures of water-soluble solvents having at least two hydroxyl groups, such as diethylene glycol and water, especially deionized water.

[0149] When a mixture of water and a water-soluble organic solvent is used as an aqueous medium, water usually comprises 30-95% by weight, preferably 60-95% by weight, based on the total mass of the aqueous medium. There will be.

[0150] The amount of the aqueous medium is generally in the range of 70-99.8% by mass, preferably 84-99.8% by mass, based on the total mass of the ink.

[0151] The ink may contain other components well known to those of skill in the art, such as surfactants for varying surface tension and maximizing penetration. However, care should be taken to ensure compatibility between the surfactant and other ink components, as the surfactant may destabilize the dispersion. In general, in a water-based ink, the surfactant can be present in an amount in the range of 0.01 to 5% by mass, preferably in the range of 0.2 to 3% by mass, based on the total mass of the ink.

[0152] Biocides may be used in the ink composition to suppress the growth of microorganisms. Sequestrants such as EDTA may be included to eliminate the adverse effects of heavy metal impurities. Other known additives, such as viscosity regulators, may be added.

Further embodiments relate to the use of the fluorescent compound I of the present invention in phase change inkjet inks. The production of such inks is well known in the art and is described in detail, for example, in European Patent Publication No. 816,410.

[0154] For coloring high molecular weight organic matter, the DPP I or III of the present invention, in the form of a master batch, in the form of a master batch, is usually used with a high molecular weight organic material using a roll mill, a mixing device or a kneading device. Mix. Generally, the colored material is then subjected to conventional treatments such as rolling, compression molding, extrusion, coating, casting or injection molding to the desired final form. In order to produce non-rigid moldings or reduce their brittleness, it is often desirable to incorporate so-called plasticizers into high molecular weight organics prior to molding. Examples of compounds that can be used as such plasticizers are esters of phosphoric acid, phthalic acid or sebacic acid. The plasticizer can be added before or after incorporating the DPP I or III of the invention into the polymer. It is also possible to add fillers or other coloring components such as white, color or black pigments to high molecular weight organics in desired amounts in addition to the DPPs I or III of the invention to achieve different hues. is there.

When coloring lacquer, paints and printing inks, generally high molecular weight organics and DPPs I or III of the invention alone or with additives such as fillers, other pigments, desiccants or plasticizers. , Dissolve or disperse in a common organic solvent or solvent mixture. In this case, it is possible to adopt a method in which individual components are dispersed or dissolved separately, or two or more kinds are dispersed or dissolved together, and then all the components are combined.

[0156] The present invention further relates to an ink containing an effective amount of coloring of the DPP I or III pigment dispersion of the present invention.

Methods of producing inks, especially for inkjet printing, are generally known and are described, for example, in US Pat. No. 5,106,412.

[0158] The ink can be produced, for example, by mixing a pigment dispersion containing the DPP I or III of the present invention with a polymer dispersant.

Mixing of the pigment dispersion with the polymer dispersant is preferably carried out according to a known mixing method, such as stirring or mechanical mixing. Preferably, it is recommended to use a centralized mixer, such as the ULTRATURAX® agitator from Kunkel &amp; Jahn, Staufen (Germany).

[0160] When mixing DPP I or III with the polymer dispersant, it is preferable to use a water-dilutable organic solvent.

[0161] The mass ratio of the pigment dispersion liquid to the ink is generally selected in the range of 0.001 to 75% by mass, preferably 0.01 to 50% by mass, based on the total mass of the ink.

Examples of suitable polymer dispersants are those obtained by addition polymerization of carboxyl-containing polyacrylic acid resins such as polymer methacrylic acid or crotonic acid, in particular acrylic acid or acrylic acid with other acrylic monomers such as acrylates. Is.

[0163] Depending on the field of use, or when using DPP I or III, if desired, a small proportion of water-miscible organic solvent of 0.01-30% by weight is added and mixed depending on the total mass of the ink. Alternatively, water and / or a base can be added and mixed to obtain a pH in the range of 7 to 11. Similarly, depending on the field of use, it may be advantageous to add, for example, preservatives, defoamers, surfactants, light stabilizers and pH regulators to the inks of the present invention.

Examples of suitable pH regulators are inorganic salts such as lithium hydroxide or lithium carbonate, quaternary ammonium hydroxide or ammonium carbonate. Examples of preservatives and antifoaming agents are, for example, sodium dehydroacetate, 2,2-dimethyl-6-acetoxydioxane or ammonium thioglycolate. It is also possible to adjust the viscosity or surface tension and use, for example, known agents described in US Pat. No. 5,085,698.

[0165] An example of a water-miscible organic solvent is aliphatic C.₁~ C₄Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tert-butanol, ketones such as acetone methyl ethyl ketone, methyl isobutyl ketone or diacetone alcohols and polyols, Cellosolve® and carbitols, For example, ethylene glycol, diethylene glycol, triethylene glycol, glycerol, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, Diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl or monoethyl ether and N-methyl-2-pyrrolidone, 2-pyrrolidone, N, N'-dimethylformamide or N, N'-dimethylacetamide.

[0166] If desired, the ink produced as described above can be further processed. The treatment of the ink can be carried out by a separation technique, for example by sieving or centrifuging the coarse particles from the resulting dispersion, by the usual method for treating the dispersion. It is advantageous to perform centrifugation in two stages with different strengths, for example, in the first step at 2000-4000 rpm for 10 minutes to 1 hour, and then in the second step at 6000-10000 rpm for 10 minutes to 1 hour. I understood.

After centrifugation or sieving, the dispersion can usually be used as is, for example, as an ink for inkjet printing.

The present invention further comprises a transparent substrate by using Red Compound I and known blue and green compounds, and layers of red, blue and green adhered thereto in a desired order. It relates to a method of manufacturing a color filter. Layers of different colors preferably show a pattern that does not overlap at least 5% of their respective surfaces, and very preferably does not overlap at all.

The manufacture and use of color filters or colored high molecular weight organics is well known in the art, for example, Displays 14 / 2, 1151 (1993), European Publication No. 784085 or UK Publication No. 2,310,072. It is described in.

[0170] The color filter can also be coated using, for example, an ink that can contain a pigment dispersion containing the DPP I or III of the present invention, particularly a printing ink, or, for example, a pigment containing DPP I or III. It can also be produced by mixing the dispersion with a high molecular weight organic substance (so-called resist) capable of chemically, thermally or photodegradably structuring. Subsequent production can be carried out, for example, in the same manner as in European Patent Publication No. 654711, by subjecting the substrate to a substrate, for example, an LCD, optical composition, and development.

Particularly preferred for the production of color filters are pigment dispersions containing DPP I or III, which have a non-aqueous solvent or dispersion medium for the polymer.

[0172] The present invention further relates to a pigment dispersion containing DPP I or III or a toner containing a high molecular weight organic substance colored with an amount of DPP I or III having a coloring effect.

[0173] In a particular embodiment of the method of the invention, a master batch of toner, paint, ink or colored plastic is processed in a roll mill, mixer or kneading device to produce the toner, paint, ink or colored plastic. To do.

[0174] The present invention further comprises a colorant, a colored plastic, a polymer containing a high molecular weight organic substance colored with the present invention DPP I or III, preferably in the form of a dispersion, or an amount of DPP I or III having a coloring effect. Regarding ink particles or non-impact printing materials.

[0175] The coloring effective amount of the pigment dispersion of the present invention containing the DPP I or III of the present invention is generally 0.0001 to 99.99% by mass, preferably 0.001 based on the total mass of the substance colored thereby. It refers to ~ 50% by mass, particularly preferably 0.01 ~ 50% by mass.

[0176] Furthermore, the compound I of the present invention can also be used for printing and dyeing paper.

Another preferred embodiment relates to the use of the compounds of the invention for tarnishing media. There are three main technologies for realizing a full-color organic electroluminescence device.

(I) A technique for using the three primary colors blue, red and green by electroluminescence. (ii) A technique for converting electroluminescence blue into photoluminescence green and red by a color-changing medium that absorbs the above-mentioned electroluminescence blue and emits green and red fluorescence. (iii) A technique for converting white electroluminescence emission into blue, green and red using a conventional color filter.

[0179] The compound of the present invention is useful for EL substances in the above category (i). In addition, the compounds of the present invention are also useful in the above technique (ii). The reason is that the compounds of the present invention can exhibit strong photoluminescence and electroluminescence.

Technology (ii) uses, for example, coumarin, 4- (dicyanomethylene) -2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, pyridine, rhodamine 6G, phenoxazone and other dyes. It is known from US Pat. No. 5,126,214, which describes a method for converting EL blue having a maximum wavelength of about 480 nm into green, yellow-green, orange, and red.

[0181] Unlike the known red fluorescent dye (thioindigo), the DPP I or III of the present invention can be applied to a color polyamide. The reason is that it does not decompose even if it is incorporated into polyamide. Furthermore, it exhibits exceptionally good light-hardening wax resistance and excellent thermal stability, especially in plastics.

[Example] The solid state absorption spectrum was measured with a Perkin-Elmer Lambda 9 UV / VIS spectrometer, and the solid state fluorescence spectrum was measured with a Perkin-Elmer MPF66 using a 5 cm Ulbricht sphere. The measurement was carried out using a soft PVC containing 0.02% by mass of the compound of the present invention.

Example 11-Methyl-2-pyrrolidone (2 liters) in 1,4-diketo-3,6-bis- (4'-tert-butylphenyl) pyrrole [3,4-c] pyrrole (140 g, 0.33) Sodium hydride (60% dispersion in mineral oil, 47 g, 1.175 mol) was added to the mol) slurry under nitrogen little by little over 30 minutes without external cooling. After 2 hours, the reaction mixture was cooled in an ice water bath for 30 minutes and benzyl bromide (216 g, 1.263 mol) was added dropwise (over 30 minutes). The reaction mixture was then slowly warmed to room temperature (by keeping the reaction flask in a cooling bath and melting the ice in the tank) and stirring at this temperature for 10 hours. Next, acetic acid (50 ml), water (50 ml) and acetone (1.5 liters) were added in that order. After stirring for 1 hour, the red solid is filtered off, washed with acetone (500 ml), water (4 liters), ethanol (1 liter), hexane (1 liter) and acetone (500 ml), and reduced to 50 ° C under reduced air atmosphere. It was dried for 24 hours. Yield: Bright red solid 1,4-diketo-2,5-dibenzyl-3,6-bis- (4'-tert-butylphenyl) pyrrole [3,4-c] pyrrole 104g (53%) [0184 Example 21,4-Diketo-3,6-bis- (4'-Chlorophenyl) Pyrrole [3,4-c] Repeat Example 1 except that pyrrole was used, 1,4-Diketo-2,5 -Dibenzyl-3,6-di- (4'-chloro-phenyl) pyrrole [3,4-c] pyrrole was obtained. Yield 58% [0185] Example 3 Sodium hydride (60% by mass in mineral oil, 3.84 g, in DMF (200 ml) in di- (4-chlorophenyl) diselenide (16.76 g, 0.044 mol) at room temperature under a nitrogen atmosphere, 0.088 mol) was added little by little. The reaction mixture is then heated in an oil bath at 70 ° C. for 1 hour to 1,4-diketo-2,5-dibenzyl-3,6-di-(4'-chloro-phenyl) pyrrole [3,4-c]. Pyrrole (obtained in Example 2) (21.5g, 0. 040 mol) was added and the reaction mixture was heated at 140 ° C. for 5 hours. After cooling to room temperature, water (500 ml) was added and the reaction mixture was heated at 100 ° C. for 30 minutes. The resulting solid was filtered off, washed with water, then washed with ethanol and finally dried under reduced pressure at 50 ° C. for 24 hours. Yield: Dark red solid 1,4-diketo-2,5-dibenzyl-3,6-di-(4-(4-chlorophenylserenyl) phenyl) pyrolo [3,4-c] pyrrole 96% (32.44 g, 0.038 mol) Melting point 248 ~ 250 ° C [0186] Example 4 Example 1 was repeated except that n-butyl iodide was used as an alkylating agent. Yield 33% [0187] Example 51,4-Diketo-3,6-bis- (4'-methylphenyl) Pyrrole [3,4-c] Example 4 was repeated except that pyrrole was used. Yield 54% [0188] Example 61,4-Diketo-3,6-bis- (4'-biphenyl) Pyrrole [3,4-c] Example 5 was repeated except that pyrrole was used. Yield 58% [0189] Example 7 Example 6 was repeated except that 2-naphthylmethyl bromide was used as an alkylating agent. Yield 51% [0190] Example 81,4-Diketo-3,6-bis- (4- (4-morpholinyl) phenyl) Pyrrole [3,4-c] Pyrrole (Example 4 of European Patent Publication No. 353,184) Example 1 was repeated except that (obtained according to) was used. Yield 64% [0191] Example 91,4-Diketo-3,6-bis-(4- (4-morpholinyl) phenyl) Pyrrole [3,4-c] Repeat Example 7 except that pyrrole was used. It was. Yield 19% [0192] Example 10 (a) Triphenylamine (98.32 g, 0.393 mol) was suspended in DMF (280 ml). Phosphoryl oxychloride (66.24 g, 0.432 mol) was added dropwise to it over 30 minutes without external cooling. After stirring for another 1 hour, the reaction is heated at 80 ° C (tank temperature). Heated for 5 hours. After cooling to room temperature, the reaction was slowly poured into ice-cold water (8 liters) with vigorous stirring. After 30 minutes, aqueous sodium hydroxide solution (5N, 250 ml) was added to the reaction and stirring was continued for 1 hour. The resulting precipitate was filtered off, washed with water (2 liters), then washed with methanol (2 liters) and dried to give 4-diphenylaminobenzaldehyde a beige solid (90.47 g, 0.331 mol, 84). %) Obtained as. It was used in the next step without further purification.

(B) 48.7 g of 4-diphenylaminobenzaldehyde (0.178 mol) obtained above was suspended in formic acid (400 ml). Hydroxylamine sulfate (16.08 g, 0.098 mol) was added, and then sodium formate (14.15 g, 0.214 mol) was added. The reaction was heated under reflux for 3 hours. The solvent was then removed under vacuum. The residue was suspended in toluene (800 ml). The residual solid was filtered and discarded. The solvent was evaporated and the residue was dissolved in a minimum amount of dichloromethane. The solution was filtered through a pad of silica gel using dichloromethane as a solvent. The solvent was then evaporated under vacuum. The solid thus obtained was placed in toluene (350 ml) and heated to reflux in the presence of charcoal. After filtering while hot, the solvent was removed from the filtrate to give 4-diphenyl-aminobenzonitrile (42.01 g, 0.155 mol, 87%) as a beige solid. This was carried over to the next step without further purification.

(C) A piece of sodium (24.5 g, 1.064 mol) was added to tert-amyl alcohol (400 ml). Next, anhydrous FeCl₃20 mg was added. The reaction mixture was slowly heated until a gentle reflux was obtained. After 2 hours, all sodium was reacting. 134.54 g (0.501 mol) of 4-diphenylaminobenzonitrile obtained above was added little by little over 15 minutes. Next, di-tert-butyl succinate (79.5 g, 0.346 mol) in tert-amyl alcohol (300 ml) was added over 1.75 hours. After heating in reflux for an additional hour, the reaction mixture was cooled to room temperature and stirred overnight. The reaction mixture was then slowly added to the mixture of water (1200 ml) and methanol (600 ml) and stirred for 3 hours. The solid thus obtained was then filtered, washed first with water and then with ethanol, and then dried overnight at 50 ° C. 70.96 g (0.114 mol, 46%) of 1,4-diketo-3,6-bis- (4-diphenylaminophenyl) -pyrrolo [3,4-c] pyrrole was obtained as a purple powder.

【0195】¹H-NMR (300 MHz, d⁶-DMSO): 6.91 (d, 4 H, J = 9 Hz); 7.15-7.22 (m, 12 H); 7.38-7.43 (m, 8 H); 8.32 (d, 4 H, J = 9 Hz); 11.02 (broad s, 2 H). [0196] (d) The 1,4-diketo-3,6-bis- (4-diphenylaminophenyl) pyrrole [3,4-c] pyrrole obtained above was used. Except for that, Example 1 was repeated. Yield 56% [0197] Example 111,4-Diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 1.02 g (2.3 mmol), 1-methyl-2 -Slurryed in 15 ml of pyrrolidinone at room temperature for 2 hours. 0.35 g of sodium hydride (60-72% dispersion in mineral oil) was added to the slurry under nitrogen. After stirring for 2 hours, 1.62 g (6.6 mmol) of 2-phenylbenzyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.327 g (18%) of a red solid was obtained.

Example 12 Example 11 was repeated except that 4-tert-butylbenzyl bromide was used as the alkylating agent. Red solid (yield 63%) [0199] Example 131,4-diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.09 g (4.75 mmol), 1 -Slurryed in 30 ml of methyl-2-pyrrolidinone at room temperature for 2 hours. 1.29 g (11.52 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.05 g (11.1 mmol) of 3-methylbenzyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 1.89 g (61%) of a red solid was obtained.

Example 11 was repeated except that Example 141,4-diketo-3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Red Solid (Yield 18%) Example 15 Example 14 was repeated except that 4-tert-butylbenzyl bromide was used as the alkylating agent. Red Solid (Yield 13%) Example 16 Example 14 was repeated except that 2-methylbenzyl bromide was used as the alkylating agent. Red Solid (27% Yield) Example 17 Example 14 was repeated except that 3-methylbenzyl bromide was used as the alkylating agent. Red solid (yield 9.3%) Example 18 Example 13 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Red Solid (24% Yield) Example 19 Example 14 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Red Solid (54% Yield) Example 20 Example 13 was repeated except that 4-methylbenzyl bromide was used as the alkylating agent. Red Solid (62% Yield) Example 21 Example 14 was repeated except that 4-methylbenzyl bromide was used as the alkylating agent. Red Solid (Yield 57%) Example 22 Potassium tert-butoxide 24.6 g, 2-naphthonitrile 30 g and tert-amyl alcohol 200 ml were heated to 100 ° C. under a nitrogen atmosphere. Immediately after reaching this temperature, a solution of 23 g of di-n-butyl succinate and 70 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 16 hours, cooled to 65 ° C., neutralized with 20 ml glacial acetic acid and boiled for a short time in reflux. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was isolated again by filtration, and finally washed with methanol and water until the wash was colorless and dried at 100 ° C in an atmosphere under reduced pressure. , 1,4-Jiketo-3,

Example 18 was then repeated, except that 1,4-diketo-3,6-bis- (2-naphthyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Red Solid (36% Yield) Example 23 Example 22 was repeated except that benzyl bromide was used as the alkylating agent. Orange Solid (30% Yield) Example 24 Example 22 was repeated except that 2-methylbenzyl bromide was used as the alkylating agent. Orange Solid (30% Yield) Example 25 Example 22 was repeated except that 2-phenylbenzyl bromide was used as the alkylating agent. Red Solid (Yield 8%) Example 26 Example 13 was repeated except that 4-phenylbenzyl bromide was used as the alkylating agent. Red solid (yield 50%) [0214] Example 271,4-diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.0 g (4.54 mmol), 1 -Slurryed in 30 ml of methyl-2-pyrrolidinone at room temperature for 2 hours. 1.3 g (11.61 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.07 g (11.2 mmol) of 2-methylbenzyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.866 g (29%) of a red solid was obtained.

Example 28 Example 27 was repeated except that 3-phenylbenzyl bromide was used as an alkylating agent. Red solid (38% yield) [0216] Example 29 3-methylbenzyl bromide and 1,4-diketo-3,6-bis- (2-naphthyl) -pyrrolo- (3,4-c) -pyrrole Example 22 was repeated except that it was used as an alkylating agent and a starting material, respectively. Red Solid (30% Yield) Example 30 Example 29 was then repeated, except that 4-methylbenzyl bromide was used as an alkylating agent. Red Solid (36% Yield) Example 31 Example 29 was repeated except that 4-phenylbenzyl bromide was used as the alkylating agent. Orange solid (yield 30%) [0219] Example 321,4-Diketo-3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Except, Example 31 was repeated. Red solid (30% yield) [0220] Example 27 was repeated except that Example 331-bromoethylbenzene was used as the alkylating agent. Yellow solid (yield 11.4%) [0221] Example 341,4-Diketo-3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Except, Example 33 was repeated. Yellow solid (yield 35%) [0222] Example 35 Potassium tert-butoxide 9.2 g, 6-methoxy-2-naphthonitrile 15 g and tert-amyl alcohol 80 ml were heated to 100 ° C. under a nitrogen atmosphere. Immediately after reaching this temperature, di-n-butyl succinate 9. A solution of 4 g and 20 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 12 hours, cooled to 65 ° C., neutralized with 20 ml glacial acetic acid and boiled for a short time in a recirculated state. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was isolated again by filtration, and finally washed with methanol and water until the wash was colorless and dried at 100 ° C in an atmosphere under reduced pressure. , 1,4-Diketo-3,6-bis- (2- (6-methoxynaphthyl))-pyrrolo- (3,4-c) -pyrrole 4.2 g (23% of logical value based on dibutyl succinate) ) Was obtained. Example 29 was repeated except that 1,4-diketo-3,6-bis- (6-methoxy-2-naphthyl) -pyrrolo- (3,4-c) -pyrrole was used as the starting material. Yellow Solid (21% Yield) Example 36 Example 35 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Yellow solid (yield 38%) [0224] Example 371,4-diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.2 g (5.0 mmol), 1 -Slurryed in 20 ml of methyl-2-pyrrolidinone at room temperature for 2 hours. 1.4 g (13.0 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.78 g (12 mmol) of (2-iodoethyl) benzene was added to the reaction mixture. The mixture was heated to 80 ° C and stirred for an additional 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.16 g (5%) of a red solid was obtained. Example 29 was repeated except that 6-bis- (6-methoxy-2-naphthyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Yellow Solid (21% Yield) Example 36 Example 35 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Yellow solid (yield 38%) [0224] Example 371,4-diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.2 g (5.0 mmol), 1 -Slurryed in 20 ml of methyl-2-pyrrolidinone at room temperature for 2 hours. 1.4 g (13.0 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.78 g (12 mmol) of (2-iodoethyl) benzene was added to the reaction mixture. The mixture was heated to 80 ° C and stirred for an additional 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.16 g (5%) of a red solid was obtained. Example 29 was repeated except that 6-bis- (6-methoxy-2-naphthyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. Yellow Solid (21% Yield) Example 36 Example 35 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Yellow solid (yield 38%) [0224] Example 371,4-diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.2 g (5.0 mmol), 1 -Slurryed in 20 ml of methyl-2-pyrrolidinone at room temperature for 2 hours. 1.4 g (13.0 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.78 g (12 mmol) of (2-iodoethyl) benzene was added to the reaction mixture. The mixture was heated to 80 ° C and stirred for an additional 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.16 g (5%) of a red solid was obtained. 78 g (12 mmol) was added to the reaction mixture. The mixture was heated to 80 ° C and stirred for an additional 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.16 g (5%) of a red solid was obtained. 78 g (12 mmol) was added to the reaction mixture. The mixture was heated to 80 ° C and stirred for an additional 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.16 g (5%) of a red solid was obtained.

Example 381,4-Diketo-3,6-bis- (2-naphthyl) -pyrrolo- (3,4-c) -pyrrole was repeated except for the use of pyrrole as a starting material (yield). Rate 29%).

Example 39 Example 32 was repeated except that 3-methoxybenzyl bromide was used as an alkylating agent. Yellow solid (38% yield) Example 40 Example 27 was repeated except that 3-methoxybenzyl bromide was used as an alkylating agent. Yellow Solid (49% Yield) Example 41 Example 32 was repeated except that 3-phenylbenzyl bromide was used as the alkylating agent. Yellow solid (33% yield) Example 42 Example 29 was repeated except that 3-phenylbenzyl bromide was used as the alkylating agent. Orange Solid (Yield 35%) Example 43 Example 27 was repeated except that 3-chlorobenzyl bromide was used as the alkylating agent. Yellow solid (52% yield) Example 44 Example 27 was repeated except that 3,4-dichlorobenzyl bromide was used as the alkylating agent. Yellow solid (36% yield) Example 45 Example 29 was repeated except that 3-methoxybenzyl bromide was used as the alkylating agent. Orange solid (30% yield) [0233] Example 46 Potassium tert-butoxide 50.4 g (0.45 mol), 3-tornitrile 50 g and tert-amyl alcohol 300 ml were heated to 100 ° C. under a nitrogen atmosphere. Immediately after reaching this temperature, a solution of 50.6 g (0.22 mol) of di-n-butyl succinate and 50 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 19 hours, cooled to 65 ° C., neutralized with 40 ml glacial acetic acid and boiled for a short time in a recirculated state. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was isolated again by filtration, and finally washed with methanol and water until the wash was colorless and dried at 100 ° C in an atmosphere under reduced pressure. , 1,4-Diketo-3,6-bis- (3-Methylphenyl) -pyrrolo- (3,4-c) -pyrrole 28.8 g (42% of the logical value based on dibutyl succinate) was obtained. .. 1,4-Diketop-3, Example 29 was repeated except that 6-bis- (3-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as the starting material. Yellow Solid (Yield 34%) Example 47 Example 46 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Yellow solid (yield 42%) [0235] Example 48 Potassium tert-butoxide 53 g (0.47 mol), 3-methoxybenzonitrile 50 g (0.38 ml) and tert-amyl alcohol 250 ml were heated to 100 ° C. under a nitrogen atmosphere. .. Immediately after reaching this temperature, a solution of 50.6 g (0.22 mol) of di-n-butyl succinate and 50 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 20 hours, cooled to 65 ° C., neutralized with 35 ml glacial acetic acid and boiled for a short time in reflux. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 500 ml of water, the pigment was isolated again by filtration, and finally washed with methanol and water until the wash was colorless and dried at 100 ° C in an atmosphere under reduced pressure. , 1,4-Diketo-3,6-bis- (3-methoxyphenyl) -pyrrolo- (3,4-c) -pyrrole 42.3 g (65% of the logical value based on dibutyl succinate) was obtained. .. Example 29 was repeated except that 1,4-diketo-3,6-bis- (3-methoxyphenyl) -pyrrolo- (3,4-c) -pyrrole was used as the starting material. Yellow Solid (45% Yield) Example 49 Example 48 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Yellow solid (38% yield) Example 50 Example 32 was repeated except that 3,5-di-tert-butylbenzoyl bromide was used as the alkylating agent. Yellow solid (yield 27%) [0238] Example 511,4-Diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.2 g (5. 0 mmol) was slurried in 20 ml of 1-methyl-2-pyrrolidinone at room temperature for 2 hours. 1.46 g (13.0 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.53 g (13 mmol) of neopentyl iodide was added to the reaction mixture. The mixture was heated to 120 ° C. and stirred for an additional 12 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.13 g (4%) of an orange solid was obtained.

Example 521,4-diketo-3,6-bis- (4-dimethylaminophenyl) -pyrrolo- (3,4-c) -pyrrole 1.87 g (5.0 mmol), 1-methyl-2-pyrrolidinone. Slurryed in 60 ml at room temperature for 2 hours. 1.68 g (15.0 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 2.78 g (15 mmol) of 1-bromoethylbenzene was added to the reaction mixture. The mixture was then heated to 80 ° C and stirred for an additional 2 hours. After cooling to room temperature, the mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.2 g (10%) of a red solid was obtained.

Example 53 Example 52 was repeated except that 3,5-di-tert-butylbenzyl bromide was used as an alkylating agent. Red Solid (33% Yield) Example 54 Example 52 was repeated except that 3-bromobenzyl bromide was used as the alkylating agent. Red solid (yield 23%) [0242] Example 551,4-Diketo-3,6-bis- (6-methoxy-2-naphthyl) -pyrrolo- (3,4-c) -pyrrole is used as a starting material Example 53 was repeated except for the above. Red solid (21% yield) [0243] Except for the use of Example 561,4-diketo-3,6-bis- (4-chlorophenyl) -pyrrolo- (3,4-c) -pyrrole as a starting material. Example 53 was repeated. Yellow solid (25% yield) [0244] Except for the use of Example 571,4-diketo-3,6-bis- (2-naphthyl) -pyrrolo- (3,4-c) -pyrrole as a starting material. Example 53 was repeated. Red Solid (Yield 23%) [0245] Example 581,4-Diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole and 1-bromo-n-propylbenzene Example 53 was repeated, except that was used as a starting material and an alkylating agent, respectively. Red solid (yield 5%) [0246] Example 59 Potassium tert-butoxide 6.7 g (60 mmol), 4-cyano-trans-stilbene 10.7 g (52 mmol) and 100 ml of tert-amyl alcohol at 100 ° C in a nitrogen atmosphere. It was heated. Immediately after reaching this temperature, di-n-butyl succinate 5. A solution of 98 g (26 mmol) and 50 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 16 hours, cooled to 65 ° C., neutralized with 20 ml glacial acetic acid and boiled for a short time at reflux temperature. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 100 ml of methanol, the pigment was isolated by filtration, and finally washed with methanol and water until the wash was colorless and dried at 100 ° C in an atmosphere under reduced pressure. Obtained 2.5 g of 1,4-diketo-3,6-bis- (4-trans-stilben) -pyrrolo- (3,4-c) -pyrrole (20% of the logical value based on dibutyl succinate). .. Example 53 was repeated except that 1,4-diketo-3,6-bis- (4-trans-stilbene) -pyrrolo- (3,4-c) -pyrrole was used as the starting material. Red Solid (20% Yield) Example 60 Example 59 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. Red solid (yield 33%) [0248] Example 611-Methyl-2-pyrrolidone (2 liters) in 1,4-diketo-3,6-bis- (4'-biphenyl) pyrrole [3,4-c] Sodium hydride (60% dispersion in mineral oil, 47 g, 1.175 mol) in a slurry of pyrrole (140 g, 0.318 mol, obtained according to Example 19 of US Pat. No. 4,579,949) for 30 minutes under nitrogen. It was added little by little without external cooling. After 2 hours, the reaction mixture was cooled in an ice water bath for 30 minutes and benzyl bromide (216 g, 1.263 mol) was added dropwise (over 30 minutes). The reaction mixture was then slowly warmed to room temperature (by keeping the reaction flask in a cooling bath and melting the ice in the tank) and stirring at this temperature for 60 hours. Next, acetic acid (50 ml), water (50 ml) and acetone (1. 5 liters) were added in order. After stirring for 1 hour, the red solid is filtered off, washed with acetone (500 ml), water (4 liters), ethanol (1 liter), hexane (1 liter) and acetone (500 ml), and 50 ° under reduced pressure atmosphere. Allowed to dry in C for 24 hours. Yield: Bright red solid 1,4-diketo-2,5-dibenzyl-3,6-bis- (4'-biphenyl) pyrolo [3,4-c] pyrrol 129.50g (66%) Element analysis: C83 .05% (calculated value 85.14%), H5.36% (calculated value 5.20%), N4.15% (calculated value 4.51%), maximum absorption (solid state) 497 nm, maximum fluorescence (solid state) 557 nm, toluene (calculated value) Absorption (maximum value) 492 nm, fluorescence (maximum value) 557 nm in toluene (ventilation), molar absorption coefficient (in toluene) 27579, quantum yield (in toluene) 0.50 [0249] Example 621,4-Diketo-3 Example 61 was repeated except that 6,6-bis- (4-methylphenyl) pyrolo [3,4-c] pyrrol was used as a starting material. Red solid (yield 42%) [0250] Example 631,4-Diketo-3,6-bis- (4-cis-stilbene) -pyrrolo- (3,4-c) Pyrrole was used as a starting material. Except, Example 53 was repeated. Red Solid (36% Yield) Example 64 Example 36 was repeated except that 3-phenylbenzyl bromide was used as the alkylating agent. Red Solid (25% Yield) Example 65 Example 46 was repeated except that 1-phenylethyl bromide was used as the alkylating agent. Red Solid (Yield 11%) Example 66 Example 61 was repeated except that 3,5-di-tert-butylbenzyl bromide was used as the alkylating agent. Red solid (yield 11%) [0254] Example 67 Bromide 3, Example 48 was repeated except that 5-di-tert-butylbenzyl was used as the alkylating agent. Red solid (yield 42%) [0255] Example 68 In a paint shaker, the compound of the present invention (0.12 g each) was added to the engineering plastics (400 g each) in the form of chips listed below, and the mixture was shaken for 90 seconds. Then, the obtained chip containing the adhered compound of the present invention was molded using a BA400Battenfeld injection molding machine at the temperature specified in Table 1.

[0256] [Table 1]<img file="JP3854792B2_D0018.tif" />HIPS: Impact Resistant Polystyrene (Fina Oil and Chemical 825P1, Melt Flow (g / 10 min) 8 (See ASTM TEST 200 / 5.0D-1238)) ABS: Acrylic-butadiene-styrene copolymer (Diamond Polymer) Natural ABS3501-002, Meltflow (g / 10 min) 7.5 (See ASTM Method D-1238)) Nylon 6, 12: Polyamide (Du Pont Engineering Polymers ZYTEL® 158L, Internal Viscosity 1.15) PMMA : Polymethylmethacrylate (Atohaas PLEXIGLAS (registered trademark) V825, melt flow (g / 10 minutes) 3.7 (see ASTM method D-1238)) [0258] Obtained from an injection molding machine after uniform color distribution. Collected 5 chips (from the same series).

The color chip was then attached to the CI135A Atlas xenon weathering tester with its thickest portion (0.31 cm) exposed. Table 2 lists the parameters of the weathering tester.

The color chips were then exposed to weathering testers for 100, 250, 500, 750 and 1000 hours. The color chips were evaluated each time the fading interval was reached. Weatherability and wax resistance were subjectively evaluated using a grayscale rating of 1-5. Rating 5 indicates no fading or color change. If the color chip appeared dark, a darkening rating d was applied to the grayscale rating. If the color chip lost most of its color, a fading rating f was applied to the grayscale rating.

[0261] [Table 2]<img file="JP3854792B2_D0019.tif" />Automatic voltage: Controls irradiance (equivalent to the irradiance seen on sunny summer days in southern Florida) 1) Temperature is measured by a sensor attached to the sample holder and heated by room air and xenon light. The temperature readings resulting from were obtained. 2) The difference between the air temperature (measured by the so-called dry-bulb sensor) and the wet-bulb temperature (measured by the wet-bulb sensor). The wet bulb is covered with a moistened core. Due to the cooling effect of evaporation, the wet-bulb reading is usually lower than the dry-bulb reading (except when the relative humidity is 100%).

[0263] [Table 3]<img file="JP3854792B2_D0020.tif" />[Grayscale evaluates the difference in color after exposure from 1 to 5. 5 means no change in color).

For comparison, the commercially available thioingigo Vat Red 41 (Clariant's Hostasol® Red 5B) was degraded in nylon. That is, no color was found in the manufactured nylon chips.

[0266] [Table 4]<img file="JP3854792B2_D0021.tif" />[0267] [Table 5]<img file="JP3854792B2_D0022.tif" />[0268] [Table 6]<img file="JP3854792B2_D0023.tif" />Example 69 ITO glass substrate (Geomatech, ITO film thickness 200 nm, area resistance 10 Ω / cm²) Above, the following formula [0270] [Chemical 28]<img file="JP3854792B2_D0024.tif" />The TPD compound of [0271] was used as a hole transporting substance by vacuum deposition at 6.665 × 10.^-4Pa (5.0 × 10^-6A hole transport layer was formed by vapor deposition up to a film thickness of 50 nm at a reduced pressure of Torr) and a vapor deposition rate of 0.05 nm / s. Next, on the hole transport layer thus produced, the compound of Example 1 was used as a luminescent substance at 6.665 × 10.^-4Pa (5.0 × 10^-6A light emitting layer was formed by vapor deposition up to a film thickness of 50 nm under the deposition conditions of Torr) and 0.05 nm / s. Next, on the light emitting layer, lithium was first co-deposited with the above compound at a rate of 0.015 nm / sec to form a layer having a thickness of 1 nm, and then aluminum was vapor-deposited on the light emitting layer to a film thickness of 200 nm. .. A 20V bias was applied to the device by using the ITO side as the anode and the aluminum side as the cathode. 1410cd / m²Luminescence, which indicates the brightness of the EL emission peak at an EL emission peak wavelength of 560 nm, was confirmed as the average value of the five elements. In order to evaluate the brightness and emission spectrum, TOPCON's luminometer BM-8 and Otuka Electronics' multi-channel photodetector IMUC-7000 were used, respectively.

Example 69 was repeated using the compounds shown in Table 7 below (including the results of Example 69) summarizing the performance of Examples 70-101EL in place of the luminescent material.

[0273] [Table 7]<img file="JP3854792B2_D0025.tif" />Example 102 Examples The compounds of 14, 15, 16, 17, 19, 21 and 39 were accurately weighed on the order of 0.1 mg and toluene (ventilated) using a volumetric flask to obtain the correct molar concentration of solution. Dissolved in 50 ml. The optical absorption spectrum was measured using a HITACHI U-3300 spectrophotometer to evaluate the molar absorption coefficient. Then, using a measuring pipette and a volumetric flask, the solution was diluted exactly 10-fold with aerated toluene. FQY was evaluated by measuring the optical absorption spectrum and photoluminescence spectrum of the diluted solution using U-3300 and HITACHI F-4500 fluorescence spectrophotometers, respectively.

[0275] The above compound is vacuum-deposited to 6.665 × 10.^-4Pa (5.0 × 10^-6A transparent film was formed by vapor deposition on a slide glass substrate to a film thickness of 50 nm at a vapor deposition rate of 0.05 nm / sec under reduced pressure of Torr). The optical absorption spectrum and photoluminescence spectrum of the film were evaluated using U-3300 and F-4500 spectrophotometers, respectively. The results are summarized in the table below. These compounds absorb light at about 480 nm both in solution and in the vapor-deposited membrane, fluoresce in the green region in solution and in the orange-red region in the vapor-deposited membrane. These properties prove that these compounds are applicable to the discoloration medium.

[0276] [Table 8]<img file="JP3854792B2_D0026.tif" />Example 103 A membrane co-deposited with the compound described in Example 34 and Rhodamine 19 (0.50% by weight) and a cathode co-deposited with magnesium and silver (Mg: Ag, 20: 1), respectively. Example 69 was repeated using the luminescent material as well as the cathode instead. Co-deposition is 6.665 × 10 for the compound of Example 34^-4Pa (5.0 × 10^-6Torr) and 0.13 nm / s (1.3 Å / s), 0.66 pm / s (0.0066 Å / s) for rhodamine 19, 200 pm / s (2.0 Å / s) for magnesium and silver Was carried out under vapor deposition conditions of 10 pm / s (0.1 Å / s). For comparison, devices using the compound of Example 34 as the luminescent material were manufactured using a Mg / Ag (20: 1) cathode.

[0278] The device having the co-deposited light emitting layer began to emit light at 4 V. The wavelength of the EL emission spectrum was 558 nm. This suggests that luminescence was induced by the resonance energy transfer from the compound of Example 34 to Rhodamine 19. The element of the one-component light emitting layer began to emit light at 7 V, and the maximum EL light emission wavelength was 529 nm. The EL emission performance is summarized in the table below.

[0279] [Table 9]<img file="JP3854792B2_D0027.tif" />The above results demonstrate that the compounds of the present invention are useful for host-guest luminescent materials.

Example 104 Potassium tert-butoxide 28 g (0.25 mol), 4- (diphenylamino) benzonitrile 62.5 g (0.23 mol) and 300 ml of tert-amyl alcohol were heated to 100 ° C. under a nitrogen atmosphere. Immediately after reaching this temperature, a solution of 26.7 g (0.12 mol) of di-n-butyl succinate and 70 ml of tert-amyl alcohol was added over 1 hour using a dropping funnel. When the addition was complete, the reaction mixture was maintained at 100 ° C. for 16 hours, cooled to 65 ° C., neutralized with 20 ml glacial acetic acid and boiled for a short time at reflux temperature. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was isolated again by filtration, and finally washed with methanol and water until the wash was colorless and dried under reduced pressure at 100 ° C. 4-Diketo-3,6-bis- (4-diphenylaminophenyl) -pyrrolo- (3,4-c) -pyrrole pure pigment 10.8 g (15% of the logical value based on dibutyl succinate) Obtained.

[0282] 1,4-Diketo-3,6-bis- (4-diphenylaminophenyl) -pyrrolo- (3,4-c) -pyrrole 1.02 g (1.64 mmol), 1-methyl-2-pyrrolidinone 20 ml Slurryed at room temperature for 2 hours. 0.57 g (5.09 mmol) of potassium tert-butoxide was added to the slurry under nitrogen. After stirring for 2 hours, 1.37 g (4.84 mmol) of 3,5-di-tert-butylbenzyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The reaction mixture was poured into 50 ml of water, and the obtained solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.444 g (26%) of a red solid was obtained.

[0283] The compounds obtained above exhibited the optical properties summarized in the table below.

[0284] [Table 10]<img file="JP3854792B2_D0028.tif" />Next, a film co-deposited using tris- (8-hydroxyquinolinato) aluminum (III) (manufactured by Wako Pure Chemicals Industries) and the compound (0.50% by mass) produced above was used as a luminescent material. The EL element was manufactured by repeating Example 103 using the alternative. Co-deposited is 6.665 × 10 in the case of aluminum complex^-4Pa (5.0 × 10^-6It was carried out under vapor deposition conditions of Torr) and 300 pm / s (3.0 Å / s) and in the case of the above compounds 1.5 pm / s (0.015 Å / s). For comparison, an element using an aluminum complex as a luminescent material was manufactured.

[0286] Devices using a light emitting layer consisting only of an aluminum complex began to emit green EL light at 8V. The maximum emission value is 520 nm, and the brightness is 6980 cd / m at 25 V.²Met. Devices using light emitting layers containing complexes and compounds began to emit light at 4V (see table below for device performance). The wavelength of the maximum EL emission was 590 nm. That is, the light emission was orange, which was different from the light emission of the one-component element. This suggests that luminescence was induced by the resonance energy transfer from the aluminum complex to the compound of the present invention.

[0287] [Table 11]<img file="JP3854792B2_D0029.tif" />The above results demonstrate that the compounds of the present invention are useful as energy receptors for host-guest luminescent materials.

Example 1051,4-Diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 2.09 g (4.75 mmol) in 30 ml of 1-methyl-2-pyrrolidinone. , Slurryed at room temperature for 2 hours. 1.29 g (11.52 mmol) of potassium tert-butoxide was added to the slurry under a nitrogen atmosphere. After stirring for 1 hour, 1.21 g (10 mmol) of allyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was then poured into 50 ml of water and the resulting red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 1.13 g (60%) of a red solid was obtained.

Example 105 was repeated except that Example 1061,4-diketo-3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as a starting material. A red solid (54%) was obtained.

Example 107 Example 105 was repeated except that 3,3-dimethylallyl bromide was used in place of allyl bromide. A red solid (42%) was obtained.

Example 108 Example 105 was repeated except that 3-phenylallyl bromide was used in place of allyl bromide. A red solid (55%) was obtained.

Example 109 A mixture of 45 g (0.4 mol) of potassium tert-butoxide, 82 g (0.373 mol) of 9-ethyl-3-cyanocarbazole and 300 ml of tert-amyl alcohol was heated to 110 ° C. under a nitrogen atmosphere. Immediately after reaching this temperature, a solution of 43 g (0.18 mol) of di-n-butyl succinate and 100 ml of tert-amyl alcohol was added over 1.5 hours using a dropping funnel. Upon completion of the addition, the reaction mixture was maintained at 110 ° C. for 16 hours, cooled to 65 ° C., neutralized with 40 ml glacial acetic acid and boiled for a short time at reflux temperature. The obtained pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was isolated by filtration, and finally washed with methanol and water until the washing liquid became colorless, and dried at 100 ° C. under a reduced pressure atmosphere. 10.5 g (11%) of 1,4-diketo-3,6-bis- (3-9-ethylcarbazole) -pyrrolo- (3,4-c) -pyrrole was obtained.

Example 1101,4-Diketo-3,6-bis- (2-naphthyl) -pyrrolo- (3,4-c) -pyrrole and the use of 3,5-di-tert-butylbenzyl bromide. Example 105 was repeated except for. A red solid (36%) was obtained.

Example 111 Example 110 was repeated except that 3,3-dimethylbenzyl bromide was used in place of 3,5-di-tert-butylbenzyl bromide. A red solid (30%) was obtained.

Example 1129 Except for the use of 1- (4-cyanophenyl) -2- (3,5-di-tert-butylphenyl) -trans-ethylene instead of ethyl-3-cyanocarbazole. 109 was repeated. A red solid (5%) was obtained.

Example 113 Example 112 was repeated except that 3,5-dimethylbenzyl bromide was used as the alkylating agent. A red solid (8%) was obtained.

Example 114 Example 10 was repeated except that 3-bromobenzyl bromide was used as an alkylating agent. A red solid (23%) was obtained.

Example 115 Example 10 was repeated except that methyl iodide was used as an alkylating agent. A red solid (40%) was obtained.

Example 116 Example 10 was repeated except that 3-methylbenzyl bromide was used as an alkylating agent. A red solid (45%) was obtained.

Example 117 (a) 1,4-Diketo-3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 4.04 g (10 mmol), 1-methyl-2- Slurry was made in 30 ml of pyrrolidinone at room temperature for 2 hours. 1.23 g (11 mmol) of potassium tert-butoxide was added to this slurry under a nitrogen atmosphere. After stirring for 1 hour, 2.83 g (10 mmol) of 3,5-di-tert-butylbenzyl bromide was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 1,4-diketo-2- (di-tert-butylbenzyl) -3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 1.61 g (25%) ) Was obtained.

(B) Obtained 1,4-diketo-2- (di-tert-butylbenzyl) -3,6-bis- (4-biphenyl) -pyrrolo- (3,4-c) -pyrrole 1.61 g was slurried in 20 ml of 1-methyl-2-pyrrolidinone at room temperature for 15 minutes. 0.32 g (2.8 mmol) of potassium tert-butoxide was added to the slurry under a nitrogen atmosphere. After stirring for 1 hour, 3.38 g (1.2 mmol) of 1,2-diiodoethane was added to the reaction mixture and the mixture was stirred for another 2 hours. The mixture was then poured into 50 ml of water, the red solid was filtered off and purified by column chromatography (silica gel, dichloromethane as eluent). After drying, 0.58 g of a red solid of formula IV was obtained.

[0303] [Chemical 29]<img file="JP3854792B2_D0030.tif" />Example 118 (a) Example 117 except that 1,4-diketo-3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole was used as the starting compound. (a) was repeated to obtain 1,4-diketo-2- (di-tert-butylbenzyl) -3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole. (32%).

(B) 1,4-Diketo-2- (di-tert-butylbenzyl) -3,6-bis- (4-methylphenyl) -pyrrolo- (3,4-c) -pyrrole and α, Example 117 (b) was repeated except that α'-dibromo-p-xylene was used. A red solid of the following formula V was obtained.

[0306] [Chemical 30]<img file="JP3854792B2_D0031.tif" />Example 104 was repeated using the compounds listed in Table 9 below, which summarizes the EL performance of Examples 119 to 129, in place of the guest material in the binary system.

[0308] [Table 12]<img file="JP3854792B2_D0032.tif" />Examples 130-134 The compounds listed in Table 10 below summarizing the EL performance were used in place of the luminescent material and Example 69 was repeated.

[0310] [Table 13]<img file="JP3854792B2_D0033.tif" />Example 135 Tetrahydrofuran Recrystallized Alq₃(Manufactured by Tokyo Kasei Organic Chemicals) 294 mg and 1,4-diketo-2,5-bis- (3,5-di-tert-butylbenzyl) -3,6-bis- (4-diphenylaminophenyl) -pyrrole -(3,4-c)-Pyrrole 6 mg was dissolved in 50 ml of dichloromethane. The solution thus obtained was slowly poured into 500 ml of boiling water, and the obtained precipitate was collected and dried. The obtained precipitate is 6.65 / 10^-4Pa (5 10^-6Purified by sublimation by heating in a reduced pressure atmosphere of Torr). A red host / guest complex 250 mg (5%) was obtained.

Next, the host / guest complex obtained above was used instead of the luminescent material, and Example 103 was repeated to manufacture an EL device.

[0313] Examples 136-138 Example 136 was repeated without exchanging guest concentrations listed in Table 11 below.

[0314] [Table 14]<img file="JP3854792B2_D0034.tif" />