Electroluminescent devices comprising diketopyrrolopyrroles

Electroluminescence device containing diketopyrrolylpyrrolidine

The present invention relates to an electroluminescent device comprising (a) an anode (b) a hole transfer layer (c) a light emitting layer (d) a selective electron transfer layer and (e) a cathode and a light emitting layer in the following order Substances, where the luminescent substance is a diketopyrrolopyrrole ("DPP") represented by formula I or formula III

<chemistry general="n"><img file="TW503255B_D0001.tif" /></chemistry>

Where R ₁ And R ₂ Respectively represent C ₁ -C ₂₅ Alkyl, can be one to three C ₁ -C ₃ Alkyl or Ar ₃ Substituted allyl, or -CR ₃ R ₄ -(CH ₂ ) _m -Ar ₃ ; Where R ₃ And R ₄ Each represents hydrogen or C ₁ -C ₄ Alkyl group, or one to three C ₁ -C ₃ Alkyl substituted phenyl, Ar ₃ Represents phenyl or can be one to three C ₁ -C ₈ Alkyl, C ₁ -C ₈ Alkoxy group, halogen atom or phenyl group (one to three C ₁ -C ₈ Alkyl or C ₁ -C ₈ Alkoxy substituted) to substituted 1- or 2-naphthyl, and m represents 0, 1, 2, 3 or 4, Ar _l And Ar ₂ Each represents an aryl group, preferably represents

<chemistry general="n"><img file="TW503255B_D0002.tif" /></chemistry>

Where R ₅ , R ₆ And R ₇ Each represents hydrogen, cyano group, halogen atom, C ₁ -C ₆ Alkyl, -NR ₈ R ₉ , -OR ₁₀ , -S(O) _n R ₈ , -Se(O) _n R ₈ Or can be one to three C ₁ -C ₈ Alkyl or C ₁ -C ₈ Alkoxy substituted phenyl, where R ₈ And R ₉ Each represents hydrogen, phenyl, C ₁ -C ₂₅ -Alkyl, C ₅ -C ₁₂ -Cycloalkyl, -CR ₃ R ₄ -(CH ₂ ) _m- Ph, R ₁₀ ; Where R ₁₀ Means C ₆ -C ₂₄ -Aryl or saturated or unsaturated heterocyclic group containing 5 to 7 ring atoms, wherein the ring system is composed of carbon atoms and 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur Structure, where Ph, aryl and heterocyclic group can be one to three C ₁ -C ₈ Alkyl, C ₁ -C ₈ Alkoxy or halogen atom substitution; or R ₈ And R ₉ Represents -C(O)R ₁₀ , Where R ₁₁ Is C ₁ -C ₂₅ -Alkyl, C ₅ -C _l2 -Cycloalkyl, R ₁₀ , -OR ₁₂ Or -NR ₁₃ R ₁₄ , Where R ₁₂ , R ₁₃ And R ₁₄ Means C ₁ -C ₂₅ -Alkyl, C ₅ -C ₁₂ -Cycloalkyl, C ₆ -C ₂₄ -Aryl, or a saturated or unsaturated heterocyclic group containing 5 to 7 ring atoms, wherein the ring system is composed of carbon atoms and 1 to 3 heteroatoms selected from the group consisting of nitrogen, oxygen and sulfur; The aryl and heterocyclic groups can be one to three C ₁ -C ₈ Alkyl or C ₁ -C ₈ Alkoxy substitution; or -NR ₈ R ₉ Represents a five- or six-membered heterocyclic group, where R ₈ And R ₉ Commonly expressed tetramethylene, pentamethylene, -CH ₂ -CH ₂ -O-CH ₂ -CH ₂ -Or-CH ₂ -CH ₂ -NR ₅ -CH ₂ -CH ₂ -; and n represents 0, 1, 2, or 3.

And Z represents a dibasic group, which is selected from a single bond, and can be one to three C ₁ -C ₄ Alkyl, C ₁ -C ₄ Alkoxy or phenyl substituted C ₂ -C ₆ The group consisting of alkylene, phenylene or naphthylene.

Thin-film electroluminescence devices usually mainly consist of a pair of electrodes and at least one charge transfer layer interposed therebetween. There are usually two charge transfer layers, a hole transfer layer (next to the anode) and an electron transfer layer (next to the cathode). According to its properties, it is a hole transfer material or an electron transfer material, one of which contains an inorganic or organic fluorescent substance as a luminescent material. It is also common for luminescent materials to be used as an additional layer between the hole transfer layer and the electron transfer layer.

Currently, it is common to prepare organic electroluminescence ("EL") devices that contain organic fluorescent substances formed by a vacuum evaporation process, as described in Letters of Applied Physics, 51,913 (1987), for example. Generally, two types of vacuum evaporation methods are used according to the composition of the luminescent material: one-component method and two-component method (or "guest-host" or "binary system") (for example, as described in the Journal of Applied Physics, 65, 3610 (1989)).

In order to emit red, green or blue light in a one-component system, the luminescent material itself must emit strong red, green or blue fluorescence. Further, the vacuum evaporation method must form a deposited film of consistent quality, and the film thus formed must be endowed with appropriate positive hole and/or electron ("carrier") mobility, that is, semiconductor properties.

Countless materials that emit light in the green or blue zone are known.

JP-B22,749,407 (Pioneer Electronics Co., Ltd. and Nippon Kayaku Co., Ltd.) describes N,N'-two (2,5-di-tertiary butylphenyl)-3,4,9,10-perylene Carboximide is used as a luminescent material. However, its illuminance is as low as 27 candles/square meter, which is not enough for commercial use.

JP-A2 2,296,891 (Ricoh) requests an electroluminescent device comprising a positive electrode, a negative electrode and an organic compound layer or a plurality of organic compound layers sandwiched between the positive electrode and the negative electrode, but does not contain a hole transfer material. At least one organic compound layer contains a pyrrolopyrrole compound represented by the following formula II.

<chemistry general="n"><img file="TW503255B_D0003.tif" /></chemistry>

Where Y ₁ And Y ₂ Each represents a substituted or unsubstituted alkyl, cycloalkyl or aryl group, Y ₃ And Y ₄ Each represents a hydrogen atom or a substituted or unsubstituted alkyl group or an aryl group, and X represents an oxygen atom or a sulfur atom. Only clearly state the four compounds, that is, X in each case represents oxygen and (a) Y ₃ =Y4=methyl and Yl=Y2=p-tolyl, (b) Y3=Y4=methyl and Yl=Y2=hydrogen, (c) Y3=Y4=hydrogen and Y1=Y2=p-tolyl and (d) Y3=Y4=Y1=hydrogen and Y2=p-chlorophenyl. However, according to JP-A 2 5,320,633 (see below), subsequent research conducted by the inventor showed that DPP compound II only emits light when it is used in conjunction with other compounds. This observation is confirmed by Comparative Example 2 of JP-A2 5,320,633, which shows that if DPP II is used alone, that is, without adding ginseng (8-quinolinate) aluminum ("Alq ₃ ") No light is seen.

JP-A2 5,320,633 (Sumitomo Corporation) requests an organic EL device with a light-emitting layer containing 0.005 to 15 parts by weight of a DPP compound light-emitting material between a pair of electrodes, at least one of which is transparent or semi-transparent. Although the main patent item does not describe the use of Alq ₃ , But it is obvious from the patent specification and examples, especially from Comparative Example 2 that Alq ₃ It is a necessary feature of the requested EL element or device.

JP-A 2 9003448 (Toyo Ink Co., Ltd.) requests an organic EL element which has a light-emitting layer containing a DPP compound as an electron transfer material between a pair of electrodes, or an organic compound thin film layer including a light-emitting layer and an electron injection layer, wherein the electron injection layer Contains DPP compounds as electron transfer materials. In addition, any EL element that further includes a hole injection layer is requested. The disadvantage of the requested EL device is that according to the examples, Alq must be used often ₃ And phenanthrene diamine (as a hole injection material).

EP-A 499,0ll requests an organic EL device containing DPP compounds, but only a system that does not contain an electron transfer layer is confirmed. Furthermore, it is only necessary to use highly crystalline organic pigments as luminescent materials. However, one of the requirements of the luminescent material is its stable shape. The tendency of crystalline materials is to modify the morphology of the vapor-deposited film. It becomes a disadvantage in ensuring the durability of the device.

Usually in the guest-host type luminescent material, the sensitized fluorescence caused by the Foster-type excitation energy transferred from the host to the guest is used. In addition to the aforementioned conditions, this type of material must meet the condition that the solid-state main fluorescent spectrum overlaps the absorption spectrum of the solution-state guest.

As for green light emission, through the use of Alq ₃ As the host and quinacridone derivatives as guests, the EL luminous efficiency can be as high as more than 10 lumens/watt. This type of system is actually used in monochrome displays.

Regarding blue light emission, Letters of Applied Physics, 67,3853 (1995) reported that a high EL luminous efficiency of 1.5 lumens/watt can be achieved by using stilbene derivatives as the main and amino-substituted stilbene derivatives as the guest. As mentioned above, the guest material does not need to have high carrier mobility, and therefore does not need to be a semiconductor.

Many orange, red or yellow fluorescent dyes known to be used as dye lasers have high fluorescence quantum yields in solution. But its Stoke displacement is usually small. In other words, 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. In this way, if yellow, orange or red fluorescent dyes are regarded as guests, the main material must be solid-state emitting yellow, orange or red fluorescent dyes if required to achieve sensitized fluorescence that can be transferred by Foster-type excitation. Light material.

Furthermore, in addition to the conditions similar to those required for one-component luminescent materials, compatibility with guests must also be considered.

In summary, the main material must be a yellow, orange to red solid fluorescent material to achieve yellow, orange or red organic EL light emission in a two-component system. However, at this stage, for the same reason as the single-component system, no satisfactory yellow, orange or red luminescent material is known.

EP-A 648770 describes solid fluorescent and soluble latent pigments. However, latent pigments cannot be used in the aforementioned vacuum evaporation process because they are converted into insoluble non-fluorescent DPP pigments when heated.

Thus, the object of the present invention is to provide an electroluminescent device emitting yellow, orange or red light, in which organic light-emitting materials must be used to meet the requirements of the single-component system in the solid state and/or binary system and in the binary system to the guest Strong luminescence in liquid state, -Carrier mobility to positive holes and/or electrons, -Required properties for vacuum evaporation and deposition (such as sublimation or volatilization), -Ability to form homogeneous thin films, -Pure Color properties,-electronic potential matching electrodes and/or matching neighboring substances,-in the case of a binary system, the solid host is compatible with the molecular guest,-high durability (heat, electricity, etc.) and dimensional stability.

Thus, the aforementioned electroluminescent device was found. In addition, its preparation method and novel luminescent materials have also been discovered.

The composition of a typical potential organic electroluminescence device is: (i) anode/hole transfer layer/electron transfer layer/cathode, where compound I is used as a positive hole transfer compound, which forms a light-emitting layer and a hole transfer layer, or As an electron transfer compound, it can be used to form a light-emitting layer and an electron transfer layer, and (ii) anode/hole transfer layer/light-emitting layer/electron transfer layer/cathode, where compound I forms the light-emitting layer, and whether it is different from the rest of this composition It has nothing to do with positive holes or electron transfer properties.

The light-emitting layer can be composed of two or more fluorescent substances of formula I as energy donors and/or energy receivers.

The device can be prepared in several ways. It is usually prepared by vacuum evaporation. Preferably, the organic layer is laminated in the aforementioned order on a commercially available indium tin oxide ("ITO") glass substrate maintained at room temperature, and the glass substrate and composition serve as the anode. The film thickness is preferably 1 to 10,000 nanometers, more preferably 1 to 5,000 nanometers, more preferably 1 to 1,000 nanometers, and still more preferably 1 to 500 nanometers. Cathode metals such as magnesium/silver alloy and a lithium-aluminum binary system with a thickness of about 200 nanometers are laminated on top of the organic layer. The vacuum during deposition is preferably less than 0.1333 Pa (1×10- ³ Tort), better than 1.333×+0- ³ Pa (1×10- ⁵ Torr), and better than 1.333×10- ⁴ Pa (1×10- ⁶ Tor).

As anodes, commonly used anode materials have high working functions such as metals such as gold, silver, copper, aluminum, indium, iron, zinc, tin, chromium, titanium, vanadium, cobalt, nickel, lead, manganese, tungsten, etc.; metal alloys such as magnesium / Copper, magnesium/silver, magnesium/aluminum, aluminum/indium, etc.; semiconductors such as Si, Ge, GaAs, etc.; metal oxides such as indium tin oxide ("ITO"), ZnO, etc.; metal compounds such as CuI, etc.; Use conductive polymers such as polyacetylene, polyaniline, polythiophene, polypyrrole, polyparaphenylene, etc., preferably ITO, most preferably ITO on glass. Among these electrode materials, metals, metal alloys, metal oxides, and metal compounds can be converted into electrodes by, for example, sputtering. In the case of using metal or metal alloy as the electrode and material, the electrode can also be formed by a vacuum deposition method. In the case of using metal or metal alloy as the electrode material, the electrode can be formed by electroless plating (for example, refer to the Electrochemical Handbook, pages 383-387, Maruzen, 1985). In the case of using a conductive polymer, the electrode can be formed into a thin film on a substrate by an anodic oxidation polymerization method, and the substrate is provided with a conductive coating in advance. The thickness of the electrode pre-formed on the substrate is not particularly limited, but when the substrate is used as the light-emitting plane, the electrode thickness is preferably 1 nm to 100 nm, more preferably 5 to 50 nm to ensure transparency sex.

In a preferred embodiment, ITO is used on the substrate, and the thickness of the ITO film is 10 nanometers (100 angstroms) to 1 micrometer (100,000), preferably 20 nanometers (200 angstroms) to 500 nanometers (5000 angstroms). The scope. Generally, the sheet resistance of the ITO film is selected in the range of not more than 100 ohms/square centimeter, preferably not more than 50 ohms/square centimeter.

Such anodes are commercially available from, for example, Japanese manufacturers Geomatech, Sanyo Vacuum, and Japan Glass Plate.

As for the substrate, conductive or electrically insulating materials can be used. Taking the conductive substrate as an example, the light-emitting layer or the positive hole transfer layer is directly formed thereon, and in the case of using an electrically insulating substrate, the electrode is first formed on it, and then the light-emitting layer or the positive hole transfer layer is laminated on it.

The substrate can be transparent, translucent or opaque. However, in the case of using the substrate as the indicating plane, the substrate must be transparent or translucent.

Transparent electrical insulating substrates include, for example, inorganic compounds such as glass, quartz, etc., organic polymer compounds such as polyethylene, polypropylene, polymethyl methacrylate, polypropylene clear, polyester, polycarbonate, polyvinyl chloride, poly Vinyl alcohol, polyvinyl acetate, etc. The aforementioned substrates can be converted into transparent conductive substrates by providing electrodes according to one of the aforementioned methods.

As for the translucent electrical insulation substrate, there are inorganic compounds such as alumina, YSZ (aluminum stabilized zirconium oxide), etc.; organic polymer compounds such as polyethylene, polypropylene, polystyrene, epoxy resin, etc. Each substrate can be converted into a semi-transparent conductive substrate by providing an electrode according to any of the aforementioned methods.

As for opaque conductive substrates, for example, there are metals such as aluminum, indium, iron, nickel, zinc, tin, chromium, titanium, copper, silver, gold, platinum, etc.; various electroplated metals; metal alloys such as bronze, stainless steel, etc.; semiconductors such as Si , Ge, GaAS, etc.; conductive polymers such as polyaniline, polythiophene, polypyrrole, polyacetylene, polyparaphenylene and so on.

The substrate can be obtained by forming any of the aforementioned substrate materials into a predetermined size. It is preferable that the substrate has a smooth surface, but even if the substrate has a rough surface, it will not cause any problems in practical use, as long as it has a non-uniformity of a circular arc with a curvature of not less than 20 microns. As for the thickness of the substrate, there is no particular limitation as long as sufficient mechanical strength can be ensured. As the cathode, ordinary cathode materials with low processing functions 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 alloy, magnesium, magnesium-silver alloy can be used , Mg - Cu alloy, a magnesium - aluminum alloy, magnesium - indium alloy, aluminum, aluminum - oxide of aluminum, an aluminum - lithium alloy, indium, calcium, and EP-A499,011 illustration of a conductive polymer material such as polypyrrole , Polythiophene, polyaniline, polyacetylene, etc., preferably magnesium/silver alloy or lithium-aluminum composition.

In a preferred embodiment, a magnesium-silver alloy or a mixture of magnesium and silver or a mixture of lithium-aluminum alloy or lithium and aluminum can be used for 10 nanometers (100 angstroms) to 1 nanometers (10000 angstroms), preferably 20 nanometers (200 angstroms) to 500 nanometers (5000 angstroms).

Such a cathode can be deposited on the aforementioned electron transfer layer by the aforementioned known vacuum deposition technique.

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

As for the film formation method, for example, there are vacuum deposition method, spin coating method, casting method, Langmuir-Blodgett ("LB") method, and the like. Among these methods, the vacuum deposition method, spin coating method, and casting method are particularly preferred due to easy operation and cost.

In the case of using the DPP compound I to form a thin film by a vacuum deposition method, the vacuum deposition conditions are usually strongly related to the properties, shape, and crystalline state of the compound. But the most ideal conditions are, for example, a heating boat temperature of 100 to 400°C, a substrate temperature of -100 to 350°C, and a pressure of 1.33×10 ⁴ Pa (1×10 ² Tort) to 1.33×10 ^-4 Pa (1×10 ^-6 Torr) and the deposition rate are in the range of 1 micrometer to 6 nanometers per second.

For organic EL devices, the thickness of the light-emitting layer is one of the factors that determine the light-emitting properties. For example, if the light-emitting layer is not thick enough, a short circuit is likely to occur between the two electrodes sandwiching the light-emitting layer, and EL light emission cannot be obtained. On the other hand, if the light-emitting layer is too thick, the electrical resistance is high, and a large voltage drop occurs inside the light-emitting layer, so the threshold voltage of EL light emission increases. Therefore, it is necessary to limit the thickness of the organic light-emitting layer to the range of 5 nanometers to 5 micrometers. The preferred thickness is in the range of 10 nanometers to 500 nanometers.

Take the spin coating method and the casting method to form the light-emitting layer as an example. The coating system uses a solution. The solution is prepared by dissolving DPP I in a suitable organic solvent at a concentration of 0.0001 to 90% by weight. Organic solvents such as benzene, toluene, and xylene , Tetrahydrofuran, methyltetrahydrofuran, N,N-dimethylformamide, dichloromethane, dimethylsulfide and so on. Here, the higher the concentration of DPP I, the thicker the film obtained; the lower the concentration, the thinner the film obtained. However, if the concentration exceeds 90% by weight, the solution is too viscous to form a smooth homogeneous film. In principle, if the concentration is less than 0.0001% by weight, the film formation efficiency is too low and uneconomical. The preferred concentration of DPPI is in the range of 0.01 to 80% by weight.

In the case of using the aforementioned spin coating or casting method, the homogeneity and mechanical strength of the resulting layer can be further improved by adding a polymer binder to the solution forming the light-emitting layer. In principle, any polymer binder can be used as long as it is soluble in a solvent in which DPP I can be dissolved. The polymer binder is, for example, polycarbonate, polyvinyl alcohol, polymethacrylate, polymethylmethacrylate, polyester, polyvinyl acetate, epoxy resin and the like. The solution for forming the light-emitting layer can be any concentration of DPP I, polymer binder and solvent. However, if the solid content of the polymer binder and DPP I exceeds 99% by weight, the fluidity of the solution is too low to form a light-emitting layer with excellent homogeneity. On the other hand, if the DPP I content is substantially lower than the polymer binder content, the layer resistance is generally too high, so it cannot emit light unless a high voltage is applied. In addition, the DPP I concentration of this layer in this example is small, so its luminous efficiency is quite low. In this way, the preferred composition ratio of the polymer binder to DPP I is selected in the range of 10:1 to 1:50 by weight, and the solid content of the two components in the solution is preferably 0.01 to 80% by weight, and more It is preferably in the range of 0.1 to 60% by weight.

In the case of forming the light-emitting layer by the spin coating method or the casting method, the thickness of the layer can be selected in the same manner as the light-emitting layer is formed by the vacuum deposition method. In other words, the thickness of the layer is preferably selected from the range of 5 nanometers to 5 micrometers, and more preferably 10 nanometers to 500 nanometers.

As for the hole transfer layer, a known organic hole transfer compound such as polyvinylcarbazole can be used,

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The TPD of the American Chemical Society Journal 90 (1968) 3925

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Where Q ₁ And Q ₂ Each represents a hydrogen atom or a methyl group;; compounds disclosed in Physics Journal 65(9)(1989)3610

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Stilbene-based compounds

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Where T and T ₁ Indicates that the rest of the organic compound is based on hydrazone

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Wait.

The compound used as the positive hole transfer material is not particularly limited to the aforementioned compounds. Any compound with positive hole transfer properties can be used as a positive hole transfer material, such as triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolones Derivatives, phenylenediamine derivatives, arylamine derivatives, amine substituted chalcone derivatives, oxazole derivatives, stilbene onion derivatives, fluorenone derivatives, hydrazone derivatives, diphenyl Ethylene derivatives, aniline derivative copolymers, conductive oligomers, especially thiophene oligomers, pyrrolidin compounds, aromatic third amine compounds, stilbene amine compounds, etc. Particularly aromatic third amine compounds such as N,N,N',N'-tetraphenyl-4,4'-diaminobiphenyl, N,N'-diphenyl-N,N'-two (3 -Methylphenyl)-4,4'-diaminobiphenyl (TPD), 2,2'-two (two-p-tolylaminophenyl) propane, 1,1'-two (4-two Tolylaminophenyl)-4-phenylcyclohexane, two(4-dimethylamino-2-methylphenyl)phenylmethane, two(4-di-p-tolylaminophenyl) ) Phenylmethane, N,N'-diphenyl-N,N'-bis(4-methoxyphenyl)-4,4'-diaminobiphenyl, N,N,N,'N'- Tetraphenyl-4,4'-diaminodiphenyl ether, 4,4'-two (diphenylamino) fourth phenyl, N,N,N-tris(p-tolyl)amine, 4 -(Di-p-tolylamino)-4'-[4-(di-p-tolylamino)styryl]stilbene,4-N,N-diphenylamino-(2-di Phenyl vinyl) benzene, 3-methoxy-4'-N,N-diphenylamino stilbene, N-phenylcarbazole, etc.

In addition, 4,4'-two [N-(1-naphthyl)-N-phenylamino] biphenyl is disclosed in US 5,061,569, where three triphenylamine units are bonded to a nitrogen atom similar to a "starburst "Compounds of the structure such as 4,4,'4"-[N-(3-methylphenyl)-N-phenylamino]triphenylamine are disclosed in EPA508,562.

The positive hole transfer layer can be formed on the anode by preparing an organic thin film containing at least one positive hole transfer material. The positive hole transfer layer can be made by vacuum deposition method, spin coating method, casting method, LB method, etc. Among these methods, the vacuum deposition method, spin coating method, and casting method are particularly preferred in view of easy manufacturing and cost.

Taking the vacuum deposition method as an example, the deposition conditions can be selected in the same manner as the light-emitting layer (see above). If it is desired to form a positive hole transfer layer containing more than one positive hole transfer material, a co-evaporation method using a predetermined compound can be used.

Taking the spin-coating method or the casting method to form the positive hole transfer layer as an example, the layer can be formed under the same conditions as the light-emitting layer (see above).

As in the case of using a solution containing a polymer binder to form the light-emitting layer, a smoother and more homogeneous positive hole transfer layer can be formed by using a solution containing a binder and at least one positive hole transfer material. The coating using this solution can be formed in the same manner as the example of using a polymer binder to form the light-emitting layer. Any polymer binder can be used as long as it is soluble in the solvent in which at least one positive hole transfer material is dissolved. Suitable polymer binders and suitable and preferred concentrations are listed in the previous description of forming the light-emitting layer.

The thickness of the positive hole transfer layer is preferably selected in the range of 0.5 to 1000 nanometers, preferably 1 to 100 nanometers, more preferably 2 to 50 nanometers.

As for the electron transfer material for the electron transfer layer, it preferably has high electrode injection efficiency from the cathode and high electron activity. The following materials are examples of electron transfer materials: ginseng (8-quinolinate) aluminum (III) and its derivatives, two (10-hydroxybenzo[h] quinolinate) beryllium (II) and its derivatives, diazole derivatives such as 2-(4-biphenyl)-5-(4-tert-butylphenyl)-1,3,4-dioxazole and its binary system such as 1,3-two (4 -Tertiary butylphenyl-1,3,4-oxadiazolyl) biphenyl and 1,3-two (4-tertiary butylphenyl-1,3,4-oxadiazolyl) Phenylene, triazole derivatives, phenanthroline derivatives or perylenetetracarboxylic acid derivatives are disclosed in Letters of Applied Physics 48(2) (1986)183, for example.

The electron transfer layer can be formed on the hole transfer layer or the light emitting layer by preparing an organic thin film containing at least one electron transfer material. The electron transfer layer can be made by vacuum deposition method, spin coating method, casting method, LB method, etc.

As in the case of using a polymer-containing binder solution to form a light-emitting layer or a positive hole transfer layer, a smoother and more homogeneous electron transfer layer can be made by using a solution containing a binder and at least one electron transfer material.

The thickness of the electron transfer layer is preferably selected from the range of 0.5 to 1000 nanometers, preferably 1 to 100 nanometers, and more preferably 2 to 50 nanometers.

The yellow to red fluorescent luminescent compound means that the luminescent compound used preferably has a fluorescence emission peak in the range of 500 to 780, more preferably from 520 to 750, and more preferably in the range of 540 to 700 nanometers. In addition, the compound of the present invention preferably has an absorption peak in the range of 450 to 580 nanometers.

The luminescent compound I usually has a fluorescence quantum yield ("FQY") in the range of 1&gt;FQY0.3 (measured in vented toluene or DMF). In addition, generally speaking, the compound I of the present invention has a molar absorption coefficient in the range of 5,000 to 100,000.

The preferred embodiment relates to DPP compound I, wherein R ₁ =R ₂ And Ar ₁ =Ar ₂ ;Particularly good for which in addition to the foregoing, R ₃ =R ₄ =H, m=0 and n=0; the best is DPP compound where (a)R ₁ =R ₂ =C ₁ -C ₈ Alkyl, Ar ₁ =Ar ₂ = Phenyl or stilbene, R ₇ =-NR ₈ R ₉ At position 4, R ₅ =R ₆ = Hydrogen and R ₈ =R ₉ =C ₁ -C ₈ Alkyl or phenyl, or (b) R ₁ =R ₂ =C ₁ -C ₈ Alkyl, -(CH ₂ ) _m -Ph,Ar ₁ =Ar ₂ = Phenyl or stilbene, R ₅ =R ₆ = Hydrogen, R ₇ =-SR ₇ ,-OR ₁₀ ,-N(R ₈ ) ₂ Or unsubstituted or substituted phenyl in the para position and R ₈ =C ₁ -C ₈ Alkyl, phenyl or heterocyclic group, including unsubstituted or substituted or C ₅ -C ₁₂ Cycloalkyl, or (c)R ₁ =R ₂ =-CH ₂ -Ph where phenyl can be phenyl, naphthyl or C ₁ -C ₄ Alkyl substituted up to two times, Ar ₁ =Ar ₂ =Phenyl or 1- or 2-naphthyl, R ₅ =R ₆ = Hydrogen, R ₇ = Hydrogen or -OMe (here Ar ₁ =Ar ₂ =1- or 2-naphthyl) or in all other cases C ₇ Equal to C ₁ -C ₈ Alkyl or phenyl.

Particularly good DPP compound I is the following compounds:

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C ₁ -C ₂₅ Alkyl groups are typically straight or branched, and may be methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl Base, 3-pentyl, 2,2-dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl, n-nonyl Base, Decyl, Undecyl, Twelve, Fourteen, Fifteen, Sixteen, Seventeen, Eighteen, Twenty, Twenty-One, Twenty-two, Twenty-four or Twenty-Five Base; preferably C ₁ -C ₈ Alkyl groups such as methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, 2 ,2-Dimethylpropyl, n-hexyl, n-heptyl, n-octyl, 1,1,3,3-tetramethylbutyl and 2-ethylhexyl; more preferably C ₁ -C ₄ Alkyl groups are typically methyl, ethyl, n-propyl, isopropyl, n-butyl, sec-butyl, isobutyl, and tert-butyl; C ₁ -C ₆ Alkyl means methyl, ethyl, n-propyl, isopropyl, n-butyl, second butyl, isobutyl, tertiary butyl, n-pentyl, 2-pentyl, 3-pentyl, 2 ,2-Dimethylpropyl, n-hexyl; C ₁ -C ₃ Alkyl represents methyl, ethyl, n-propyl or isopropyl.

C ₁ -C ₈ Alkoxy is typically methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, tertiary butoxy, n-pentoxy, 2-pentyloxy, 3-pentoxy, 2,2-dimethylpropoxy, n-hexyloxy, n-heptyloxy, n-octyloxy, 1,1,3,3-tetramethylbutoxy Group and 2-ethylhexyloxy; preferably C ₁ -C ₄ Alkoxy groups such as methoxy, ethoxy, n-propoxy, isopropoxy, n-butoxy, second butoxy, isobutoxy, and tertiary butoxy.

C ₆ -C ₂₄ The aryl group is typically phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl, phenanthryl, 2- or 9-fluorenyl or anthracenyl; preferably C ₆ -C ₁₂ Aryl groups such as phenyl, 1-naphthyl, 2-naphthyl, 4-biphenyl.

C ₇ -C ₂₄ Aralkyl is typically benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenylbutyl, ω, ω-dimethyl -ω-phenyl-butyl, ω-phenyl-dodecyl, ω-phenyl-octadecyl, ω-phenyl-docosyl or ω-phenyl-docosyl; preferably C ₇ -C ₁₈ Aralkyl groups such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α, α-dimethylbenzyl, ω-phenylbutyl, ω, ω-dimethyl- ω-phenyl-butyl, ω-phenyl-dodecyl or ω-phenyl-octadecyl; and particularly preferably C ₇ -C ₁₂ Aralkyl groups such as benzyl, 2-benzyl-2-propyl, β-phenyl-ethyl, α,α-dimethylbenzyl, ω-phenylbutyl or ω,ω-dimethyl- ω-phenyl-butyl.

C ₅ -C ₁₂ Cycloalkyl is typically cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, cyclononyl, cyclodecyl, cycloundecyl, cyclododecyl; preferably cyclopentyl, cyclohexyl, cycloheptyl Base, cyclooctyl.

Heteroaryl groups containing 5 to 7 ring atoms where nitrogen, oxygen or sulfur are possible heteroatoms, typically unsaturated heterocyclic groups containing 5 to 18 atoms with at least 6 conjugated π electrons such as thiophene Group, benzo[b]thienyl, dibenzo[b,d]thienyl, thioindenyl, furanyl, furfuryl, 2H-piperanyl, benzofuranyl, isobenzofuranyl, diphenyl M-furyl, phenoxythienyl, pyrrolyl, imidazolyl, pyrazolyl, pyridyl, bipyridyl, trisyl, pyrimidinyl, pyrazyl, stilbyl, indolyl, isoindole Group, indolyl, indazolyl, purinyl, quinolinyl, quinolinyl, isoqolinyl, phthalolinyl, naphthyridinyl, quinolinyl, quinolinyl, quinolinyl, pterinyl Pyridinyl, carbazolyl, carbachol, benzotrioxyl, benzoxazolyl, phenanthridinyl, acridinyl, perylene phenyl, phenanthridinyl, phenoxyl, isothiazolyl , Phenothiionyl, isoxazolyl, furuzanyl or phenoxonyl; preferably the aforementioned monocyclic or bicyclic heterocyclic group.

The DPP compound I of the present invention can be synthesized according to well-known methods in the industry, such as described in EP-A133,156, such as similar to Example 15.

The preferred embodiment of the present invention relates to a method for preparing compound I or III of the present invention by treating the DPP derivative of formula Va or Vb with alkali in the first step

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Then in the second step, the reaction mixture obtained in the first step is treated with an ordinary alkylating agent, wherein in the first step the base is a hydride, an alkali metal alkoxide or carbonate and the alkylating agent is a sulfonate, tosylate , Methanesulfonate, carbonate, sulfate or formula (R ₁ ) ₁ or ₂ X halogen compound, where X represents SO ₃ -, (p-methyl-phenyl) SO ₂ -, (2,4,6-trimethyl-phenyl)SO ₂ -, -CO ₃ -, -SO ₄ -Or a halogen atom such as chlorine, bromine or iodine, preferably chlorine, bromine or iodine, particularly preferably bromine or iodine or (R ₁ ) ₁ or ₂ X and (R ₂ ) ₁ or ₂ Mixture of X.

As for the hydride, an alkali metal hydride such as sodium hydride, lithium hydride or potassium hydride is generally used; as for the alkali metal alkoxide, an alkali metal C is generally used. ₁ -C ₄ Alkoxides such as sodium or potassium tertiary butoxide and sodium valerate; and as carbonates, sodium or potassium carbonates are generally used, preferably sodium hydride.

Generally, the first step of the preferred preparation method of compound I or III starts with compound Va or Vb and is carried out at a temperature range of -25 to 100, preferably 0 to 25°C.

Preferably, the reaction is carried out in the presence of a solvent. The solvent is preferably a bipolar aprotic solvent such as carboxyamides, lactamines, urea derivatives, sulfides and nitrobenzenes such as dimethylformamide (" DMF"), dimethylacetamide ("DMA"), N-methylpyrrolidone ("NMP"), N,N'-dimethylethylene urea and N,N'-dimethyl Propylene urea.

If a solvent is used, the weight ratio of the solvent to the DPP compound is selected in the range of 100:1 to 5:1, preferably 25:1 to 10:1.

It is also preferred to carry out the first step in the presence of a phase transfer catalyst such as a tetraalkylammonium halide such as tetraethylammonium bromide.

Generally, the molar ratio of the base to the DPP compound Va or Vb is selected from the range of 10:1 to 2:1, preferably from 4:1 to 2:1.

Preferably, the molar ratio of the DPP compound Va or Vb to the phase transfer catalyst is selected from the range of 100:1 to 5:1, preferably from 25:1 to 10:1.

Usually the reaction time is determined by the reactivity of the selected reactants and the selected temperature. For example, if room temperature is selected as the reaction temperature, in principle, the reaction time is in the range of 0.5 to 24 hours.

Preferred halogen compound R ₁ -X (or the aforementioned mixture) is added to the reaction mixture obtained in the first step with the same solvent used in the aforementioned first step.

The reaction temperature of the second method step is usually selected in the range of 0 to 160, preferably 25 to 110°C, depending on the required reaction pressure used and the solvent used.

The reaction time is usually selected in the range of 0.5 to 120, preferably 12 to 60 hours.

In principle R ₁ The molar ratio of -X to DPP compound Va or Vb is selected in the range of 10:1 to 2:1, preferably 4:1 to 2:1.

If a solvent is used, the amount of solvent is usually a halogen compound R ₁ -X weight is based on the range of 100:1 to 5:1, preferably 25:1 to 10:1. Furthermore, if a solvent is used in the first step, it is preferable to use the same solvent as in the first step. If no solvent is used in the first step, the same solvent as described above can be used.

The resulting reaction mixture can be processed using well-known methods in the industry, such as precipitation of the product in the presence of a suitable solvent such as water, and recrystallization in a suitable solvent such as ethanol if necessary. Other methods such as quenching excess alkali by adding alcohol followed by filtration.

Compound Va, for example, is described in US 4,579,949 and/or prepared according to the method described therein, wherein the appropriate nitrile is reacted with the corresponding dialkyl or diaryl succinate such as NC-Ar ₁ Reaction with sodium tertiary amylate, followed by addition of diisopropyl succinate. This method is better than Ar ₁ And/or Ar ₂ Represents a biphenyl group (that is, R ₅ And/or R ₆ It is preferred when it represents a phenyl group or a substituted phenyl group at the 4 position) or the following compound (DPPVIa).

Compound Vb can be prepared, for example, by the following route

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Of course instead of using R ₁ Hal can use R ₁ -Hal and R ₂ -Hal mixture, resulting in general formula Vb. Usually R ₁ Hal or R ₁ Hal and R ₂ The molar amount of the mixture of Hal relative to the starting DPP derivative is in the range of 0.4-0.6:1. Therefore, the molar system of Hal-Z-Hal/intermediate is selected in the range of 0.4-0.6:1.

Compound I or III can also be obtained in a similar manner as described in EP-A353,184, including the DPP compound of reaction formula VIa or VIb

<chemistry general="n"><img file="TW503255B_D0021.tif" /></chemistry>

Where Hal represents a halogen atom such as fluorine, chlorine, bromine or iodine, preferably chlorine or bromine, and a nucleophile such as a second amine HNR ₈ R ₉ , Thiol HSR ₈ Or HS(O) _n R ₈ , Alcohol HOR ₁₀ , Diselenide R ₈ (O) _n Se-Se(O) _n R ₈ , Preferably DPP VIa or VIb: the molar ratio of the nucleophile is in the range of 1.2:1 to 0.8:1; or if R ₂ Defined as R ₁ It is in the range of 1:2.5 to 1:1; the reaction is in the presence of an anhydrous bipolar aprotic solvent and an anhydrous base. The amount is usually 0.1 to 15 mol per mol of nucleophile, and usually 100 to The temperature is in the range of 220°C and the pressure is usually in the range of 100 to 300 kPa.

Suitable anhydrous bipolar aprotic solvents are, for example, carboxamides, lactamines, urea derivatives, turquoises and nitrobenzenes such as DMF, DMA, NMP, N,N'-dimethylethylene urea and N,N'-Dimethylpropylene urea.

Suitable anhydrous bases are, for example, anhydrous organic bases such as quinoline, or preferably an excess of a second amine for the amination reaction. The aforementioned carbonates such as sodium or potassium carbonate and alkali metal hydrides such as sodium hydride are used in the case of diselenide. R ₇ (O) _n Se-Se(O) _n R ₇ , An alkali metal hydride, preferably sodium hydride, must be used as the base.

The corresponding 1- and 2-naphthyl derivatives can be prepared in a similar manner.

DPP compounds VIa and VIb are known and/or can be prepared, for example, according to the manner described in US 4,579,949. The method comprises the reaction of a dialkyl or diaryl succinate with a nitrile, such as dimethyl succinate and p-chloro Benzoonitrile was reacted according to Example 6 of US 4,579,949 to obtain the corresponding DPP compound VIa, where Hal represents chlorine.

Compound R ₁ -X is commercially available or can be prepared by methods well known in the industry.

Another specific embodiment of the present invention relates to a method for preparing compound I or III of the present invention (a) In the first step, the DPP derivative of formula VIa or VIb is treated with a nucleophile, such as a second amine HNR ₈ R ₉ , Thiol HSR ₈ Or HS(O) _n R ₈ , Alcohol HOR ₁₀ , Diselenide R ₈ (O) _n Se _- Se(O) _n R ₈ , Preferably DPP VIa or VIb: the molar ratio of the nucleophile is in the range of 1.2:1 to 0.8:1; or if R ₂ Defined as R ₁ It is in the range of 1:2.5 to 1:1; the reaction is in the presence of an anhydrous bipolar aprotic solvent, and the amount of anhydrous base is usually 0.1 to 15 mol per mol of nucleophile, and usually 100 to The temperature is in the range of 220°C and the pressure is usually in the range of 100 to 300 kPa, and the obtained compound V is selectively separated. (b) Then the obtained compound Va or Vb is treated with a base, and then an ordinary alkylating agent is used in the second step Treat the reaction mixture obtained in the first step of (b), wherein in the first step of (b), the base is a hydride, the alkali metal alkoxide or carbonate or the alkylating agent is sulfonate, tosylate, methanesulfonate Acid salt, carbonate, sulfate or formula (R ₁ ) ₁ or ₂ Halogen compound of X, where X represents SO ₃ -, (p-methyl-phenyl) SO ₂ -(2,4,6-trimethyl-phenyl)SO ₂ -,-CO ₃ -,-SO ₄ -Or halogen atom or (R ₁ ) ₁ or ₂ X and (R ₂ ) ₁ or ₂ Mixture of X [obviously (R ₁ ) ₁ or ₂ X in R ₁ The unit (1 or 2) is determined by the nature of the selected residue X, that is, if X represents a divalent anion such as -CO ₃ -,-SO ₄ -There are only two Rs at the same time ₁ unit].

The water-soluble compound I or III, that is, the compound I or III of the present invention, has a functional group that can increase the solubility in water, such as the third amino group SO ₃^- Or PO ₄^2- Instead, it can be prepared by a method well known in the industry. The following approaches are representative examples, so the present invention is not limited to these examples:

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Wherein r represents an integer usually from 2 to 25; instead of linear alkyl, branched alkyl or aralkyl such as Br-(CH ₂ ) _r1 -Aryl-(CH ₂ ) _r2 -Br,r ₁ And r ₂ Usually an integer from 0 to 10;

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Where M represents a metal ion such as sodium or potassium and t is 1 or 2

The corresponding compound III can be obtained through this way.

Another specific embodiment of the present invention relates to a method known in the industry to combine the fluorescent DPP compound I or III of the present invention to color high-molecular-weight organic materials (molecular weight is usually less than 10 ³ To 10 ⁷ G/mol range) method.

As for high molecular weight organic materials, the following materials such as biopolymers and plastic materials such as fibers can be used.

The present invention preferably relates to the use of the DPP I or III of the present invention to prepare printing inks for the printing process, for offset printing, screen printing, packaging printing, security ink printing, gravure printing or offset printing, and for front presses Stage and use for textile printing, for office, home use or drawing purposes such as paper products such as ball pens, brushes, fiber tip pens, cards, wood, (wood) dyeing, metal ink pads or impact printing processes Ink (using impact pressure ink ribbon); used to prepare colorants, for coating materials, for industrial or commercial use, for textile decoration and industrial marking, for roller coating or powder coating or automotive light It is used for high-solid (low solvent) water-containing or metal coating materials or additive pigment formulations for water-based coatings; used for the preparation of pigmented plastics for coatings, fibers, records or mold carriers; used for the preparation of non-impact printing The material is used for digital printing, thermal wax transfer, inkjet printing or thermal transfer; and also for the preparation of color filters, especially for the visible light range of 400 to 700 nanometers, for liquid crystal displays (LCD) Or charge combination device (CCD); or for the preparation of cosmetics or for the preparation of polymer ink particles, toner, dry copy toner, liquid copy toner or photocopy toner.

Can use the fluorescent DPP of the present invention Appropriate high-molecular-weight organic materials for coloring I or III such as vinyl polymers, such as polystyrene, poly-αmethylstyrene, poly-p-methylstyrene, poly-p-hydroxystyrene, poly-p-hydroxyphenyl styrene, poly Methyl methacrylate and polyacrylamide; and the corresponding methacrylic compounds, polymethyl maleate, polyacrylonitrile, polymethacrylonitrile, polyvinyl chloride, polyvinyl fluoride, and polyvinyl fluoride Vinyl chloride, polyvinylidene fluoride, polyvinyl acetate, polymethyl vinyl ether and polybutyl vinyl ether, polymers derived from maleimine and/or maleic anhydride such as maleic anhydride and benzene Copolymers of ethylene; polyvinylpyrrolidone; ABS; ASA; Substances; polyurethanes, polyureas; polycarbonates; polyarylenes; polyarylene sulfides; polyepoxides; polyolefins such as polyethylene and polypropylene; poly Alkadienes; biopolymers and their derivatives such as cellulose, cellulose ethers and esters such as ethyl cellulose, nitrocellulose, cellulose acetate and cellulose butyrate, starch, chitin, several Butane, gelatin, zein; natural resins; synthetic resins such as alkyd resins, acrylic resins, phenolic resins, epoxy resins, amino-formaldehyde resins such as urea/formaldehyde resins and melamine/formaldehyde resins; vulcanized rubber; phenolic resins Protein; polysiloxane and polysiloxane resin; rubber, chlorinated rubber; and also polymers. For example, novolac resins are used as binders in coating systems. Novolac resins are derived from C ₁ -C ₆ -Aldehydes such as formaldehyde and acetaldehyde, and dinuclear or mononuclear preferably mononuclear, phenol, if necessary, 1 or 2 C ₁ -C ₉ Alkyl group, 1 or 2 halogen atoms or 1 benzene ring substitution such as o-, m- or p-cresol, xylene, p-tert-butylphenol, o-, m- or p-nonanol, p-chlorophenol or Phenol, or compounds containing more than one phenolic group such as resorcinol, two (4-hydroxyphenyl) methane or 2,2-two (4-hydroxyphenyl) propane; and appropriate mixtures of these materials .

Especially good high molecular weight organic materials are especially used in the preparation of coating systems. 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. (Polymerization or condensation resins) such as amino plastics, especially urea/formaldehyde and melamine/formaldehyde resins, alkyd resins, phenolic plastics, polycarbonates, polyolefins, polystyrene, polyvinyl chloride, polyamides Amines, polyurethanes, polyesters, ABS, ASA, polyphenylene oxide, vulcanized rubber, casein, silicone and silicone resins and possible mixtures of each other.

High molecular weight organic materials in dissolved form can also be used as film forming agents such as boiled linseed oil, nitrocellulose, alkyd resins, phenolic resins, melamine/formaldehyde and urea/formaldehyde resins and acrylic resins.

The high-molecular-weight organic materials can be obtained individually or in combination, for example, in the form of particles, plastic materials, melts or solutions, and are especially used for preparing spin coating solutions, coating systems, coating materials, inks or printing inks.

In a particularly preferred embodiment of the present invention, the fluorescent DPP I or III of the present invention can be used for a large amount of colored polyvinyl chloride, polyimines, especially polyolefins such as polyethylene and polypropylene, and for the preparation of coating systems including Powder coating, ink, printing ink, color filter and coating pigment.

Illustrative examples of better binders for coating systems include alkyd/melamine resin coatings, acrylic/melamine resin coatings, cellulose acetate/cellulose butyrate coatings, and two-pack type based on acrylic resins that can be cross-linked with polyisocyanate System varnish.

According to the observations so far, the fluorescent DPP I or III of the present invention can be added to the coloring material in any predetermined amount, depending on the final use requirements. Taking high molecular weight organic materials as an example, for example, the amount of fluorescent DPP I or III prepared according to the present invention is in the range of 0.01 to 40, preferably 0.01 to 5% by weight based on the colored high molecular weight organic material.

Thus, another specific embodiment of the present invention relates to a composition comprising (a) based on the total weight of the high molecular weight organic material to be colored, 0.01 to 50, preferably 0.01 to 5, particularly preferably 0.01 to 2% by weight according to the present invention The fluorescent DPP I or III, and (b) based on the total weight of the high molecular weight organic material to be colored, 99.99 to 50, preferably 99.99 to 95 and particularly preferably 99.99 to 98% by weight of the high molecular weight organic material, and (c) If there is an effective amount required, such as 0 to 50% by weight based on the total weight of (a) and (b), conventional additives such as rheology modifiers, dispersants, fillers, coating aids, desiccants, increase Plasticizers, ultraviolet light stabilizers and/or other pigments or corresponding precursors.

In order to produce a non-brittle molded part or reduce its brittleness, for example, a so-called plasticizer can be added to a high molecular weight organic material before molding. Examples of plasticizers include esters of phosphoric acid, phthalic acid, and sebacic acid. The plasticizer can 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.

In order to obtain different chromaticities, the fluorescent DPP I or III of the present invention is preferably mixed with fillers, transparent and unidentified white and/or black pigments and conventional glossy pigments in the required amount.

In order to prepare coating systems, coating materials, color filters, inks and printing inks, corresponding high-molecular-weight organic materials such as binders, synthetic resin dispersions, etc. and the fluorescent DPP I or III of the present invention are usually co-dispersed or dissolved, if necessary Together with conventional additives such as dispersants, fillers, paint aids, desiccants, plasticizers and/or additional pigments or pigment precursors, they are dissolved or dispersed in common solvents or solvent mixtures. It can be achieved by dispersing or dissolving individual ingredients, or by dissolving several ingredients together, and then combining all the ingredients together or adding all the ingredients at once.

Thus, another specific embodiment of the present invention relates to a method for preparing dispersions and corresponding dispersions using the fluorescent DPP I or III of the present invention, as well as coating systems, coating materials, and coating materials containing the fluorescent DPP I or III of the present invention. Color filters, inks and printing inks.

A particularly preferred embodiment relates to the use of the DPP I or III of the present invention to prepare fluorescent tracers, such as fluid leakage monitoring such as lubricants, cooling systems, etc., and fluorescent tracers or lubricants containing DPP I or III of the present invention . Generally, lubricant compositions, such as refrigerants, contain oils selected from naphthenic oils, paraffin oils, alkylated benzene oils, polyalkyl silicate oils, polyethylene glycols, esters, and polyether polyols. Classes, polyvinyl ethers, polycarbonates, fluorinated polysiloxanes, perfluoroethers, aromatic compounds with fluoroalkoxy or fluoroalkylthio substituents. The content of DPP I or III in the lubricant of the present invention is usually selected from 100 to 1000 ppm. If the compound I of the present invention is water-soluble, it can also be used as a tracer in water.

The specific embodiment of the present invention relates to an inkjet ink containing the fluorescent composition of the present invention.

The ink contains up to 30% by weight of the fluorescent composition, but it is usually used in most thermal inkjet printing applications in the range of 0.1 to 10, preferably 0.1 to 8% by weight of the total ink composition.

Further inks usually contain polymeric dispersants such as random, block, branched or grafted polymers or copolymers. The most preferred is a polymer dispersant prepared via a group transfer polymerization method, because it usually does not contain higher molecular weight species, which easily clog the nozzles of inkjet pens.

In AB or BAB block copolymers, the A segment is usually a hydrophobic homopolymer or copolymer which is used to connect the fluorescent composition of the present invention, and the B segment is usually a hydrophilic homopolymer or copolymer, or its salt. To disperse the pigment in the preferred aqueous medium. Such polymer dispersants and their synthesis are known, for example, from US 5,085,698.

ABC triblock can also be used as a dispersant. In the ABC triblock, the A segment is usually a water-compatible polymer, the B segment is a polymer that can be bound to the fluorescent composition, and the C segment is a polymer compatible with organic solvents. Preferably, sections A and C are terminal sections. The ABC triblock and its synthesis are disclosed in EP-A 556,649, for example. Suitable graft polymers are disclosed in US 5,231,131.

Useful representative compounds for this project include, for example, polyvinyl alcohol polymers, cellulose and ethylene oxide modified polymers, and dissociable group-containing dispersant compounds such as acrylic acid, maleic acid or sulfonic acid.

The polymer dispersant is usually present in an amount ranging from 0.1 to 30, preferably 0.1 to 8% by weight of the total ink composition.

In addition to or instead of the preferred polymer dispersant, a surfactant can be used as a dispersant. It can be anionic, nonionic or amphoteric surfactants. Non-polymer dispersants and some polymer dispersants are listed in detail in Manufacture Pastry Publishing Company (1990) page 110-129, McCutcheon's Functional Materials, North American Edition Dispersant Section B.

Generally, the ink contains 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 are disclosed in, for example, US 5,085,698. The selection of a suitable mixture of water and water-soluble organic solvents is based on specific application requirements, such as predetermined surface tension and viscosity, ink drying time, and the medium substrate of the ink to be printed.

Particularly preferred is a water-soluble solvent mixture having at least two hydroxyl groups, such as diethylene glycol and water, especially deionized water. If a mixture of water and a water-soluble organic solvent is used as the aqueous medium, water usually accounts for 30 to 95 and preferably 60 to 95% by weight of the total weight of the aqueous medium.

The content of the aqueous medium is usually 70 to 99.8 and preferably 84 to 99.8% of the total weight of the ink.

The ink contains other ingredients well known in the industry such as surfactants to change the surface tension and achieve maximum penetration. However, since the surfactant may destabilize the dispersion, care must be taken to ensure that the surfactant is compatible with other ink components. Generally, in water-based inks, the surfactant is present in an amount of 0.01 to 5 and preferably 0.2 to 3% by weight of the total weight of the ink.

Biocides can be used in the ink composition to inhibit the growth of microorganisms. Barriers such as EDTA can also be included to eliminate the adverse effects of heavy metal impurities. Other known additives such as viscosity modifiers can also be added.

Another specific embodiment relates to the use of the fluorescent compound I of the present invention in a phase change inkjet ink. The preparation of this ink is well known in the industry, for example, it is described in detail in EP-A 816,410.

For pigmentation of high-molecular-weight organic materials, the DPP I or III of the present invention is usually in the form of a master batch, usually using a roller mill, a mixing device or a grinding device to mix the high-molecular-weight organic materials. Pigment materials are usually added and then adjusted to a predetermined final form by conventional methods, such as calendering, compression molding, extrusion, expansion, casting or injection molding. In order to prepare non-rigid molded parts or reduce brittleness, it is often necessary to mix so-called plasticizers with high molecular weight organic materials in the molded parts. Useful compounds are for example plasticizers such as esters of phosphoric acid, phthalic acid or sebacic acid. The plasticizer can be added before or after the DPP I or III of the present invention is added to the polymer.

In order to achieve different shades, it is also possible to add a required amount of white or black pigments to high molecular weight organic materials in addition to the DPP I or III of the present invention.

Used to add pigments to varnishes, coating materials and printing inks, high molecular weight organic materials and DPP I or III of the present invention alone or together with additives such as fillers, other pigments, desiccants or plasticizers are generally dissolved or dispersed in common organic solvents Or solvent mixture. In this case, a procedure can be used such that individual components are dispersed or dissolved separately, or two or more of them are dispersed or dissolved together, and then all the ingredients are combined.

The present invention additionally relates to an ink containing the pigment dispersion of the DPP I or III of the present invention in an effective amount for coloring.

The preparation method of ink, especially inkjet printing ink, is generally known and described in, for example, US 5,106,412.

The ink can be prepared, for example, by mixing a pigment dispersion containing the DPP I or III of the present invention and a polymer dispersant.

The mixing of the pigment dispersion and the polymer dispersant is preferably carried out according to general mixing methods such as stirring or mechanical mixing; it is recommended to preferably use a powerful mechanical mixer such as the so-called so-called Stefen, Kunke and Qiang company (Kunkel ml Jahn ) ULTRATURAX mixer.

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

The weight ratio of the pigment dispersion to the ink is usually selected to be 0.001 to 75% by weight and preferably 0.01 to 50% by weight based on the total weight of the ink.

Suitable polymer dispersants are, for example, carboxyl group-containing polyacrylic resins, such as polymers of methacrylic acid or crotonic acid, especially obtained by addition polymerization of acrylic acid or acrylic acid with other acrylic monomers such as acrylates.

Depending on the field of use or when using DPP I or III, if necessary, a small amount of water-miscible organic solvent from 0.01 to 30% by weight of the total ink weight can be mixed, and/or mixed water and/ Or alkali to obtain a pH of 7 to 11. It is also preferable to add preservatives, defoamers, surfactants, light stabilizers and pH adjusters (for example) to the ink of the present invention, depending on the field of use.

Suitable pH adjusting agents are inorganic salts such as lithium hydroxide or lithium carbonate, fourth ammonium hydroxide or ammonium carbonate. The preservative and defoaming agent are, for example, dehydrated sodium acetate, 2,2-dimethyl-6-acetoxydioxane or ammonium thioglycolate. Known chemical agents that can adjust viscosity or surface tension can also be used and are described in, for example, US 5,085,698.

The water-miscible organic solvent is, for example, aliphatic C ₁ -C ₄ Alcohols such as methanol, ethanol, n-propanol, isopropanol, n-butanol, tertiary butanol; ketones such as acetone, isobutyl ketone, methyl isobutyl ketone or diacetone alcohol; and polyols; cellosolve Vegetables and carbitols such as ethylene glycol, diethylene glycol, triethylene glycol, glycerin, propylene glycol, ethylene glycol monomethyl or monoethyl ether, propylene glycol methyl ether, dipropylene glycol methyl ether, tripropylene glycol methyl ether Ether, ethylene glycol phenyl ether, propylene glycol phenyl ether, diethylene glycol monomethyl or monoethyl ether, diethylene glycol monobutyl ether, triethylene glycol monomethyl ether or monoethyl ether and N-methyl 2-pyrrolidone, 2-pyrrolidone, N,N'-dimethylformamide or N,N'-dimethylacetamide.

If necessary, the aforementioned ink can also be processed further. The subsequent processing of the ink can be used to separate coarse particles from the resulting dispersion using a separation technique such as sieving or centrifugation by the conventional subsequent processing method of the dispersion. It has been found that it is also preferable to perform centrifugation in two stages of different intensities, for example, in the first stage at 2000 to 4000 rpm for 10 minutes to one hour, and in the second stage at 6000 to 10000 rpm for 10 minutes to 1 hour.

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

The present invention additionally relates to a method of manufacturing a color filter, comprising a transparent substrate and applying red, blue and green layers on it in any predetermined order using red compound I and known blue and green compounds. Different color layers preferably have patterns so that at least 5% of their individual surfaces do not overlap, and it is particularly preferred that they do not overlap at all.

The preparation and use of color filters or pigmented high molecular weight organic materials are well known in the industry, for example, as described in Display 14/2,1151 (1993), EP-A 784085 or GB-A 2,310,072.

The color filter can, for example, be coated with an ink, a special printing ink, containing a pigment dispersion containing DPP I or III of the present invention, or can, for example, be mixed with a pigment dispersion containing DPP I or III with a high molecular weight chemical, thermal or photodecomposable structure Preparation of organic materials (so-called resists). The subsequent preparation, for example, can be applied to a substrate such as LCD in a similar manner to EP-A 654711, followed by photostructuring and imaging preparation.

The manufacturing method of the special color filter is to pigment the dispersion liquid containing DPP I or III, the dispersion liquid contains a non-aqueous solvent or a polymer dispersion medium.

In addition, the present invention relates to a toner containing DPP I or III or a high molecular weight organic material to color an effective amount of DPP 4 or III added pigment pigment dispersion.

In a specific embodiment of the method of the present invention, the toner, coating material, ink or colored plastic is prepared by using a roller mill, mixing device or grinding device to produce the toner, coating material, ink or colored plastic master batch .

The present invention additionally relates to colorants, colored plastics, polymer ink particles or non-impact printing materials containing the DPP I or III pigments of the present invention, preferably in the form of dispersions or high molecular weight organic materials with effective amount of DPP I or III added for coloring And pigmentation.

According to the effective amount of coloring, the pigmented dispersion liquid of the present invention contains 0.0001 to 99.99% by weight of the DPP I or III of the present invention in the total weight of the pigment material, preferably 0.001 to 50% by weight and particularly preferably 0.01 to 50% by weight .

Furthermore, the compound I of the present invention can be used in textile applications and in paper dyeing.

Another preferred embodiment relates to the use of the compounds of the present invention for color-changing media. There are three major technologies for realizing full-color organic electroluminescence devices: (i) using the three primary colors of blue, red and green by electroluminescence, (ii) using a color-changing medium which absorbs the aforementioned electroluminescence blue and emits green and red fluorescence to convert electrons The luminous blue is converted into luminous green and red, and (iii) the electroluminescent white light is converted into blue, green and red by traditional color filters.

The compounds of the present invention can be used in the EL materials of the aforementioned category (i). In addition, the compounds of the present invention can also be used in the aforementioned technique (ii). The reason is that the compound of the present invention has strong photoluminescence and electroluminescence.

Technology (ii) is known, for example, from US 5,126,214, which describes a method in which EL blue with a maximum wavelength of about 480 nm uses coumarin, 4-(dicyanomethylene)-2-methyl-6- (P-dimethylamino styryl)-4H-piperan, pyridine, rhodamine 6G, phenohydrazone and other dyes are converted into green, yellow-green, orange and red.

Contrary to the known red fluorescent dye (thioisatin), the DPP I or III of the present invention can be applied to colored polyimines because it does not decompose during mixing with polyimine. In addition, it has extra good light fastness and excellent heat resistance, especially for plastics.

Instance

The solid-state absorption spectrum was measured by Perkin-Elmer λ9UV/VIS spectrometer, and the solid-state fluorescence spectrum was measured by Perkin-Elmer MPF 66 with a 5 cm Ulbricht ball. The measurement was performed using soft PVC containing 0.02% by weight of the compound of the present invention.

Example 1: Sodium hydride (60% in mineral oil dispersion 47 g, 1.175 mol) was divided into several portions and added in 30 minutes without external cooling and added to 1,4-diketo-3,6 under nitrogen -II-(4'-tert-butylphenyl)pyrrolo[3,4-c]pyrrole (140g, 0.33mole) in a slurry of 1-methyl-2-pyrrolidone (2L) . After 2 hours, the reaction mixture was cooled in an ice-water bath for 30 minutes and then benzyl bromide (216 g, 1.263 mol) was added dropwise (over a period of 30 minutes). Then the reaction mixture was slowly warmed to room temperature (maintain the reaction flask in a cooling bath and allow the ice in the bath to melt) and stirred at this temperature for 10 hours. Then add acetic acid (50 ml), water (50 ml) and acetone (1.5 ml) in sequence. After stirring for 1 hour, the red solid was filtered out, washed with acetone (500 ml), water (4 liters), ethanol (1 liter), hexane (1 liter) and acetone (500 ml) and then at 50°C in a reduced pressure atmosphere Dehydrate for 24 hours. Yield: 104 g (53%) bright red solid 1,4-diketo-2,5-dibenzyl-3,6-two-(4'-tert-butylphenyl)pyrrolo[3, 4-c] pyrrole.

Example 2: Repeat Example 1 but use 1,4-diketo-3,6-two-(4'-chlorophenyl)pyrrolo[3,4-c]pyrrole, and then obtain 1,4-diketo -2,5-Dibenzyl-3,6-bis-(4'-chloro-phenyl)pyrrolo[3,4-c]pyrrole. Yield: 58%

Example 3: Sodium hydride (60% by weight in mineral oil 3.84 g, 0.088 mol) was added to bis-(4-chlorophenyl) diselenide (16.76 g, 0.044 mol) under nitrogen atmosphere at room temperature. ) In DMF (200 ml). Then the reaction mixture was heated in an oil bath at 70°C for 1 hour, and then 1,4-diketo-2,5-dibenzyl-3,6-bis-(4'-chloro-phenyl)pyrrolo[3 ,4-c]pyrrole (obtained according to Example 2) (21.5 g, 0.040 mol), and the reaction mixture was heated to 140°C for 5 hours. After cooling to room temperature, water (500 ml) was added, and the reaction mixture was heated to 100°C for 30 minutes. The obtained solid was filtered out, washed with water and then ethanol, and finally dehydrated at 50°C under reduced pressure for 24 hours.

Yield: 96% (32.44 g, 0.038 mol) dark red solid 1,4-diketo-2,5-dibenzyl-3,6-bis-(4'-(4"-chlorophenyl selenium) Alkyl)phenyl)pyrrolo[3,4-c]pyrrole, melting point 248 to 250°C.

Example 4: Repeat Example 1 but use n-butyl iodide as the alkylating agent. Yield: 33%.

Example 5: Repeat Example 4 but use 1,4-diketo-3,6-two-(4'-methylphenyl)pyrrolo[3,4-c]pyrrole. Yield: 54%.

Example 6: Repeat Example 5 but use 1,4-diketo-3,6-two-(4'-biphenyl)pyrrolo[3,4-c]pyrrole. Yield: 58%.

Example 7: Repeat Example 6 but use 2-naphthylmethyl bromide as the alkylating agent. Yield: 51%.

Example 8: Repeat Example 1 but use 1,4-diketo-3,6-two-(4-(4-morpholinyl)phenyl)pyrrolo[3,4-c]pyrrole (according to EP-A 353,184 Example 4 obtained). Yield: 64%.

Example 9: Repeat Example 7 but use 1,4-diketo-3,6-two-(4-(4-morpholinyl)phenyl)pyrrolo[3,4-c]pyrrole. Yield: 19%.

Example 10: (a) Triphenylamine (98.32 g, 0.393 mol) was suspended in DMF (280 ml). Phosphorus chloride (66.24 g, 0.432 mol) was added dropwise over a period of 30 minutes without external cooling. After stirring for another hour, the reaction was heated to 80°C (tank temperature) for 2 1/2 hours. After cooling to room temperature, the reaction was slowly poured into ice-cold water (8 liters) with vigorous stirring. After 30 minutes, an aqueous sodium hydroxide solution (5N, 250 mL) was added to the reaction, and stirring was continued for 1 hour. The resulting precipitate was filtered, washed with water (2 liters), then washed with methanol (2 liters) and dehydrated to obtain 4-diphenylamine benzaldehyde as a serge colored solid (90.47 g, 0.331 mol, 84%). Further purification is used in the next step.

(B) 48.7 g of 4-diphenylamine benzaldehyde (0.178 mol) obtained above was suspended in formic acid (400 ml). Hydroxylamine sulfate (16.08 g, 0.098 mol) was added followed by sodium formate (14.15 g, 0.214 mol). The reaction was heated at reflux for 3 hours. Then the solvent was removed in vacuo. The residue was suspended in toluene (800 ml). The remaining solid was filtered out and discarded. The solvent was evaporated and the residue was dissolved in a minimum amount of dichloromethane. The solution was filtered through a silicone pad using dichloromethane as a solvent. Then the solvent was evaporated under vacuum. The resulting solid was taken in toluene (350 ml) and heated to reflux in the presence of charcoal. After hot filtration, the solvent was removed from the filtrate to obtain 4-diphenylaminobenzonitrile (42.01 g, 0.155 mol, 87%) as a serge colored solid, which was used in the next step without further purification.

(c) Sodium tablets (24.5 g, 1.064 mol) were added to tertiary amyl alcohol (400 ml). Then add 20 grams of anhydrous ferric chloride. The reaction mixture was slowly heated until a gentle reflux was obtained. All the sodium reacted after 2 hours. 134.54 g of 4-diphenylaminobenzonitrile (0.501 mol) obtained as above was added portion by portion over a period of 15 minutes. Then add di-tert-butyl succinate (79.5 g, 0.346 mol) to tertiary amyl alcohol (300 ml) over 1.75 hours. After heating at reflux for another hour, the reaction mixture was cooled to room temperature and stirred overnight. Then the reaction mixture was slowly added to a mixture of water (1200 ml) and methanol (600 ml) and stirred for 3 hours. The solid thus obtained was filtered, first washed with water and then ethanol and then dehydrated at 50°C overnight. 70.96 grams (0.114 mol, 46%) of 1,4-diketo-3,6-two-(4-diphenylaminophenyl)pyrrolo[3,4-c]pyrrole was obtained as a purple powder. 1H-NMR(300MHz,d ⁶ -DMSO): 6.91(d,4H,J=9Hz);7.15-7.22(m,12H):7.38-7.43(m,8H);8.32(d,4H,J=9Hz);11.02(wide S,2H ).

(d) Example 1 Example 1 was repeated but the 1,4-diketo-3,6-two-(4-diphenylaminophenyl)pyrrolo[3,4-c]pyrrole obtained as above was used. Yield: 56%.

Example 11: 1.02 g (2.3 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole in 15 ml of 1-methyl-2 -Pyrolidone was slurried at room temperature for 2 hours. 0.35 g of sodium hydride (60-72% in mineral oil dispersion) is 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 out and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.327 g (18%) of a red solid was obtained.

Example 12: Repeat Example 11 but use 4-tert-butylbenzyl bromide as the alkylating agent. Red solid (yield: 63%).

Example 13: 2.09 g (4.75 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole in 30 ml of 1-methyl-2 -Pyrolidone was slurried at room temperature for 2 hours. 1.29 grams of sodium hydride (11.52 millimoles) potassium tertiary 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 introduced into 50 ml of water, the red solid was filtered out and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 1.89 g (61%) of a red solid was obtained.

Example 14: Repeat Example 11 but using 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole as starting material. Red solid (yield: 18%).

Example 15: Repeat Example 14 but use 4-tert-butylbenzyl bromide as the alkylating agent. Red solid (yield: 13%).

Example 16: Repeat Example 14 but use 2-methylbenzyl bromide as the alkylating agent. Red solid (yield: 27%).

Example 17: Repeat Example 14 but use 3-methylbenzyl bromide as the alkylating agent. Red solid (yield: 9.3%).

Example 18: Repeat Example 13 but use 3,5-dimethylbenzyl bromide as the alkylating agent. Red solid (yield: 24%).

Example 19: Repeat Example 14 but use 3,5-dimethylbenzyl bromide as the alkylating agent. Red solid (yield: 54%).

Example 20: Repeat Example 13 but use 4-methylbenzyl bromide as the alkylating agent. Red solid (yield: 62%).

Example 21: Repeat Example 14 but use 4-methylbenzyl bromide as the alkylating agent. Red solid (yield: 57%).

Example 22: 24.6 grams of potassium tert-butoxide, 30 grams of 2-naphthalenecarbonitrile and 200 ml of tertiary amyl alcohol were heated to 100°C under a nitrogen atmosphere. Once this temperature is reached, use an addition funnel to add 23 grams of di-n-butyl succinate and 70 milliliters of tertiary amyl alcohol solution over a period of 1 hour. When the addition is complete, the reaction mixture is maintained at 100°C for 16 hours, then cooled to 65°C, neutralized with 20 ml of glacial acetic acid and briefly boiled to reflux. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol and the pigment was separated by filtration again, and then finally washed with methanol and water until the washing liquid was colorless, and dehydrated at 100°C under reduced pressure to obtain 26.1 g (69% of theoretical value, based on succinic acid). Butyl ester) pure pigment 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole.

Then Example 18 was repeated but using 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole as the starting material. Red solid (yield: 36%).

Example 23: Repeat Example 22 but use benzyl bromide as the alkylating agent. Orange solid (yield: 30%).

Example 24: Repeat Example 22 but use 2-methylbenzyl bromide as the alkylating agent. Orange solid (yield: 30%).

Example 25: Repeat Example 22 but use 2-phenylbenzyl bromide as the alkylating agent. Red solid (yield: 8%).

Example 26: Repeat Example 13 but use 4-phenylbenzyl bromide as the alkylating agent. Red solid (yield: 50%).

Example 27: 2.0 g (4.54 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole in 30 ml of 1-methylpyrrole at room temperature The 2-pyrrolidone was mixed into a slurry for 2 hours, and 2.07 g (11.2 millimoles) of potassium tertiary 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 then the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water and the red solid was filtered out, and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.866 g (29%) of a red solid was obtained.

Example 28: Repeat Example 27 but use 3-phenylbenzyl bromide as the alkylating agent. Red solid (yield: 38%).

Example 29: Repeat Example 22 but use 3-methylbenzyl bromide and 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole respectively as the alkylation Agents and starting materials. Red solid (yield: 30%).

Example 30: Repeat Example 29 but use 4-methylbenzyl bromide as the alkylating agent. Red solid (yield: 36%).

Example 31: Repeat Example 29 but use 4-phenylbenzyl bromide as the alkylating agent. Orange solid (yield: 30%).

Example 32: Example 31 was repeated but using 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole as the starting material. Red solid (yield: 30%).

Example 33: Repeat Example 27 but use 1-bromoethylbenzene as the alkylating agent. Yellow solid (yield: 11.4%).

Example 34: Example 33 was repeated but using 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole as starting material. Yellow solid (yield: 35%).

Example 35: 9.2 grams of potassium tert-butoxide, 15 grams of 6-methoxy-2-naphthocarbonitrile and 80 ml of tertiary amyl alcohol were heated to 100°C under a nitrogen atmosphere. Once this temperature is reached, use a dropping funnel to add 9.4 g of di-n-butyl succinate and 20 ml of tertiary amyl alcohol solution. When the addition is complete, the reaction mixture is maintained at 100°C for 12 hours and then cooled to 65°C, neutralized with 20 ml of glacial acetic acid and briefly boiled to reflux. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol and the pigment was separated again by filtration, and then finally washed with methanol and water until the washing liquid was colorless, and dehydrated at 100°C under reduced pressure to obtain 4.2 g (23% of theoretical value, based on butadiene disulfide). Dibutyl ester) 1,4-diketo-3,6-two-(2-(6-methoxynaphthyl))pyrrolo(3,4-c)pyrrole.

Example 29 was repeated but using 1,4-diketo-3,6-two-(6-methoxy-2-naphthyl)pyrrolo(3,4-c)pyrrole as the starting material. Yellow solid (yield: 21%).

Example 36: Repeat Example 35 but using 3,5-dimethylbenzyl bromide as the alkylating agent. Yellow solid (yield: 38%).

Example 37: 2.2 g (5.0 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole at room temperature in 20 ml of 1-methyl Al-2-pyrrolidone was mixed into a slurry for 2 hours. 1.4 grams (13.0 millimoles) of potassium tertiary 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 another 3 hours. After cooling to room temperature, the mixture was poured into 50 ml of water and the red solid was filtered out, and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.16 g (5% 0 red solid) was obtained.

Example 38: Repeat Example 37 but use 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole as the starting material (yield: 29%).

Example 39: Repeat Example 32 but use 3-methoxybenzyl bromide as the alkylating agent. Yellow solid (yield: 38%).

Example 40: Repeat Example 27 but use 3-methoxybenzyl bromide as the alkylating agent. Yellow solid (yield: 38%).

Example 41: Repeat Example 32 but use 3-phenylbenzyl bromide as the alkylating agent. Yellow solid (yield: 33%).

Example 42: Repeat Example 29 but use 3-methoxybenzyl bromide as the alkylating agent. Orange solid (yield: 35%).

Example 43: Repeat Example 27 but use 3-chlorobenzyl bromide as the alkylating agent. Yellow solid (yield: 52%).

Example 44: Repeat Example 27 but use 3,4-dichlorobenzyl bromide as the alkylating agent. Yellow solid (yield: 36%).

Example 45: Repeat Example 29 but use 3-methoxybenzyl bromide as the alkylating agent. Orange solid (yield: 30%).

Example 46: 50.4 grams (0.45 moles) of potassium tertiary butoxide, 50 grams of 3-toluonitrile and 300 ml of tertiary amyl alcohol were heated to 100°C under a nitrogen atmosphere. Once this temperature is reached, use a dropping funnel to add 50.6 g (0.22 mmol) of di-n-butyl succinate and 50 ml of tertiary amyl alcohol solution over a period of 1 hour. When the addition is complete, the reaction mixture is maintained at 100°C for 19 hours and then cooled to 65°C, neutralized with 40 ml of glacial acetic acid and briefly boiled to reflux. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigment was separated again by filtration, and then finally washed with methanol and water until the washing liquid became colorless, and dehydrated at 100°C under reduced pressure to obtain 28.8 g (42% of the theoretical value, with succinic acid). Based on dibutyl ester) 1,4-diketo-3,6-two-(3-methylphenyl)pyrrolo(3,4-c)pyrrole.

Example 29 was repeated but using 1,4-diketo-3,6-two-(3-methylphenyl)pyrrolo(3,4-c)pyrrole as the starting material. Yellow solid (yield: 34%).

Example 47: Repeat Example 46 but use 3,5-dimethylbenzyl bromide as the alkylating agent. Yellow solid (yield: 42%).

Example 48: 53 g (0.47 mol) of potassium tertiary butoxide, 50 g (0.38 mol) of 3-methoxybenzonitrile and 250 ml of tertiary amyl alcohol were heated to 100°C under a nitrogen atmosphere. Once this temperature is reached, use a dropping funnel to add 50.6 g (0.22 mol) of di-n-butyl succinate and 50 ml of tertiary amyl alcohol solution over a period of 1 hour. When the addition is complete, the reaction mixture is maintained at 100°C for 20 hours and then cooled to 65°C, neutralized with 35 ml of glacial acetic acid and briefly boiled to reflux. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 500 ml of water and the pigment was separated by filtration again, and then finally washed with methanol and water until the washing liquid became colorless, and dehydrated at 100°C under reduced pressure to obtain 42.3 g (65% of the theoretical value, with succinic acid). Based on dibutyl ester) 1,4-diketo-3,6-two-(3-methoxyphenyl)pyrrolo(3,4-c)pyrrole.

Example 29 was repeated but using 1,4-diketo-3,6-two-(3-methoxyphenyl)pyrrolo(3,4-c)pyrrole as the starting material. Yellow solid (yield: 45%).

Example 49: Example 48 was repeated but using 3,5-dimethylbenzyl bromide as the alkylating agent. Yellow solid (yield: 38%).

Example 50: Repeat Example 32 but use 3,5-di-tert-butylbenzyl bromide as the alkylating agent. Yellow solid (yield: 27%).

Example 51: 2.2 g (5.0 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole in 20 ml of 1-methylpyrrole at room temperature Al-2-pyrrolidone was mixed into a slurry for 2 hours. 1.46 grams (13.0 millimoles) of potassium tertiary 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 another 12 hours. After cooling to room temperature, the mixture was poured into 50 ml of water and the red solid was filtered out, and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.13 g (4%) of orange solid was obtained.

Example 52: 1.87 g (5.0 millimoles) of 1,4-diketo-3,6-two-(4-dimethylaminophenyl)pyrrolo(3,4-c)pyrrole at room temperature Make a slurry in 60 ml 1-methyl-2-pyrrolidone for 2 hours. 1.68 g (15.0 millimoles) of potassium tertiary 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 another 2 hours. After cooling to room temperature, the mixture was poured into 50 ml of water and the red solid was filtered out, and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.2 g (10%) of a red solid was obtained.

Example 53: Repeat Example 52 but use 3,5-di-tert-butylbenzyl bromide as the alkylating agent. Red solid (yield: 33%).

Example 54: Repeat Example 52 but use 3,5-bromobenzyl bromide as the alkylating agent. Yellow solid (yield: 23%).

Example 55: Repeat Example 53 but using 1,4-diketo-3,6-two-(6-methoxy-2-naphthyl)pyrrolo(3,4-c)pyrrole as starting material. Red solid (yield: 25%).

Example 56: Repeat Example 53 but using 1,4-diketo-3,6-two-(4-chlorophenyl)pyrrolo(3,4-c)pyrrole as starting material. Yellow solid (yield: 25%).

Example 57: Example 53 was repeated but using 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole as the starting material. Red solid (yield: 23%).

Example 58: Repeat Example 53 but use 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole and 1-bromo-n-propylbenzene as starting materials, respectively Starting material and alkylating agent. Red solid (yield: 5%).

Example 59: 6.7 grams (60 millimoles) of potassium tertiary butoxide, 10.7 grams (52 millimoles) of 4-cyano-trans-stilbene and 100 ml of tertiary amyl alcohol were heated to 100°C under a nitrogen atmosphere . Once this temperature is reached, 5.98 g (26 mmol) of di-n-butyl succinate and 50 ml of tertiary amyl alcohol solution are added over 1 hour using a dropping funnel. When the addition is complete, the reaction mixture is maintained at 100°C for 16 hours, then cooled to 65°C, neutralized with 20 ml of glacial acetic acid and briefly boiled to reflux temperature. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 100 ml of methanol, the pigment was separated by filtration, and then finally washed with methanol and water until the washing liquid became colorless, and dehydrated at 100 °C under reduced pressure atmosphere to obtain 2.5 g (20% of the theoretical value, with succinic acid). Based on butyl ester) 1,4-diketo-3,6-two-(4-trans-stilbene)pyrrolo(3,4-c)pyrrole pure pigment.

Example 53 was repeated but using 1,4-diketo-3,6-two-(4-trans-stilbene)pyrrolo(3,4-c)pyrrole as the starting material. Red solid (yield: 20%).

Example 60: Repeat Example 59 but use 3,5-dimethylbenzyl bromide as the alkylating agent. Red solid (yield: 33%).

Example 61: Sodium hydride (60% in mineral oil dispersion 47 g, 1.175 mol) was added to 1,4-diketo-3,6-two-by-piece under nitrogen without external cooling for 30 minutes (4'-Biphenyl)pyrrolo[3,4-c]pyrrole (140 g, 0.318 mol obtained according to US 4,579,949 Example 19) in 1-methyl-2-pyrrolidone (2 liters) slurry. After 2 hours, the reaction mixture was cooled in an ice-water bath for 30 minutes, and then benzyl bromide (216 g, 1.263 mol) was added dropwise (over a period of 30 minutes). Then the reaction mixture was slowly warmed to room temperature (by keeping the reaction flask in a cooling bath and allowing the ice in the bath to melt) and stirred at this temperature for 60 hours. Then add acetic acid (50 ml), water (50 ml) and acetone (1.5 liters) in sequence. After stirring for 1 hour, the red solid was filtered out, washed with acetone (500 ml), water (4 liters), ethanol (1 liter), hexane (1 liter) and acetone (500 ml), and then at 50°C in a reduced pressure atmosphere Dehydrate for 24 hours. Yield: 129.50 g (66%) bright red solid 1,4-diketo-2,5-dibenzyl-3,6-two-(4'-biphenyl)pyrrolo[3,4-c] Pyrrole.

Elemental analysis: C: 83.05% (calculated value 85.14%), H: 5.36% (calculated value 5.20%), N: 4.15% (calculated value 4.51%), maximum absorption (solid state): 497 nm; maximum fluorescence ( Solid): 557 nm; absorption in toluene (ventilated) (maximum): 492 nm; fluorescence in toluene (ventilated) (maximum): 557 nm; molar absorption coefficient (in toluene): 27579; quantum Yield (in toluene): 0.50.

Example 62: Repeat Example 61 but using 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo[3,4-c]pyrrole as starting material. Red solid (yield: 42%).

Example 63: Repeat Example 53 but using 1,4-diketo-3,6-two-(4-cisstilbene)pyrrolo[3,4-c]pyrrole as starting material. Red solid (yield: 36%).

Example 64: Repeat Example 36 but use 3-phenylbenzyl bromide as the alkylating agent. Red solid (yield: 25%).

Example 65: Repeat Example 46 but use 1-phenylethyl bromide as the alkylating agent. Red solid (yield: 11%).

Example 66: Repeat Example 61 but use 3,5-di-tert-butylbenzyl bromide as the alkylating agent. Red solid (yield: 42%).

Example 67: Repeat Example 48 but use 3,5-di-tert-butylbenzyl bromide as the alkylating agent. Red solid (yield: 42%).

Example 68: Add the compound of the present invention (0.12 g each) to the paint shaker in the following engineering plastic (400 g each) and shake for 90 seconds. Subsequently, the sheet containing the adhesive compound of the present invention was molded using BA400 Battenfeld injection molding agent at the temperature specified in Table 1 below.

<tables><img file="TW503255B_D0025.tif" /></tables>

HIPS: Highly impact-resistant polystyrene (825P1 obtained from Fina Oil and Chemical Company; Melt flow rate (g/10 minutes): 8 (refer to ASTM test 200/5.0D-1238)) ABS: Acrylic- Butadiene-styrene copolymer (natural ABS 3501-002 available from Diamond Polymer Corporation: Melt flow rate (g/10 minutes): 7.5 (refer to ASTM method D-1238)) Nylon 6,12: Polyimide ZYTEL 158L was obtained from DuPont Engineering Polymers; Intrinsic Viscosity 1.15)) PMMA: Polymethyl methacrylate PLEXIGLAS V825 was obtained from Atohaas; melt Body flow rate (g/10 minutes): 3.7 (refer to ASTM method D-1238) Collect five pieces from the injection molding machine (from the same series) after the color is evenly distributed.

Then the color flake was set up on the C135A Atlas xenon weatherometer, and the last part of the flake was exposed (0.31 cm (0.122 inch)). The weatherometer parameters are shown in Table 2.

The color flakes were then exposed to the weatherometer for 100, 250, 500, 750 and 1000 hours. Color flakes are rated after each fade interval is reached. Light fastness is subjectively evaluated using a gray scale rating of 1-5. A rating of 5 indicates no fading or color difference. When the color flakes become darker, the gray scale rating is rated as d. When a color flake loses most of its color, the application rating f fades to a grayscale rating.

<tables><img file="TW503255B_D0026.tif" /></tables>

Automatic voltage: control illuminance (similar to the average illuminance in South Florida on a sunny day) 1) Temperature is measured by the sensor attached to the specimen holder; any heating caused by the chamber air and xenon light provides a temperature reading 2) Air temperature The difference between the temperature of the wet bubble (measured by the so-called dry bubble sensor) and the temperature of the wet bubble (measured by the wet bubble sensor). Bubble reading value (except 100% relative humidity).

result

<tables><img file="TW503255B_D0027.tif" /></tables>

By comparing the commercially available sulfur isatin Vat barrel red 41 Hostasol Red 5B obtained from Clariant Company in nylon decomposition, that is, the nylon flakes produced have no color.

<tables><img file="TW503255B_D0028.tif" /></tables>

<tables><img file="TW503255B_D0029.tif" /></tables>

<tables><img file="TW503255B_D0030.tif" /></tables>

Example 69: Depositing the TPD compound of the following formula on an ITO glass substrate (obtained from Jumatic Company, ITO film thickness 200 nm, sheet resistance 10 ohm/cm²)

<chemistry general="n"><img file="TW503255B_D0031.tif" /></chemistry>

As the hole transfer material, the deposition method is vacuum evaporation in 6.665×10- ⁴ Pa (5.0×10 ^-6 Torr) was deposited to a film thickness of 50 nm at a deposition rate of 0.05 nm/sec under reduced pressure to form a hole transfer layer. Then on the hole transfer layer prepared in this way, the deposition condition is 6.665×10 ^-4 Pa (5.0×10 ^-6 The compound of Example 1 was deposited as a luminescent material to a film thickness of 50 nm under deposition conditions of 0.05 nm/sec to form a luminescent layer. Then, on the light-emitting layer, firstly, lithium and the aforementioned compound were co-deposited at a rate of 0.015 nanometers/second to form a 1 nanometer thick layer, and then aluminum as a cathode was deposited on it with a film thickness of 200 nanometers. By using the IOT side as the anode and the aluminum side as the cathode, a 20 volt bias was applied to the aforementioned element. The illuminance showed 1410 candles/square meter, and the EL emission peak wavelength was 560 nanometers, which proved to be the average of five elements. For evaluating the illuminance and luminescence spectrum, the illuminance meter BM-8 manufactured by TPOCON and the multi-channel optical detector IMUC-7000 manufactured by Otsuka Electronics are used.

Examples 70-101: Repeat Example 69 to replace the luminescent materials with the compounds shown in Table 7 below. Table 7 also summarizes the EL performance (the results of Example 69 are also included in the table).

<tables><img file="TW503255B_D0032.tif" /></tables>

Example 102: The compounds of Examples 14, 15, 16, 17, 19, 21 and 39 were accurately weighed to 0.1 mg and dissolved in 50 ml of toluene (ventilated) using a volumetric flask to obtain the correct molar concentration of the solution. The absorption spectrum was measured using Hitachi U-3300 spectrophotometer to evaluate the molar absorption coefficient. Then use a measuring burette and volumetric flask to accurately dilute the solution 10 times with ventilated toluene. The light absorption and emission spectra of the aforementioned diluted solution were also measured using U-3300 and Hitachi F-4500 fluorescent spectrophotometers to evaluate FQY.

The aforementioned compounds were deposited on 6.665×10 by vacuum evaporation ^-4 Pa (5.0×10 ^-6 Torr) and deposited on the glass slide substrate at a deposition rate of 0.05 nm/sec to a film thickness of 50 nm to form a transparent film. The light absorption and emission spectra of the film were evaluated using U-3300 and F-4500 spectrophotometers, respectively. The results are summarized in the table below. The compound absorbs about 480 nanometers of light in the solution state and the vapor-deposited film, and emits fluorescence in the green region in the solution and orange to red region in the vapor-deposited film. These properties confirm that the compound can be used in the aforementioned color-changing medium.

<tables><img file="TW503255B_D0033.tif" /></tables>

*1: At the wavelength of the maximum light absorption *2: Moore absorption coefficient *3: At the wavelength of the maximum light emission *4: FQY

Example 103: Repeat Example 69 but use the compound described in Example 34 and the film co-deposited with Rhodamine-19 (0.05% by weight) and the cathode co-deposited with magnesium and silver (magnesium:silver, 20:1) instead Luminescent materials and cathodes. The co-deposition condition is 6.665×10 ^-4 Pa (5.0×10 ^-6 Torr) and 0.13 nanometers/second (1.3 angstroms/second) for the compound of Example 34, 0.66 micrometers/second (0.0066 angstroms/second) for rhodamine -19,200 micrometers/second (2.0 angstroms/second) For magnesium and 10 micrometers/second (0.1 angstroms/second) for silver. For comparison, a device using the compound of Example 34 as a luminescent substance was prepared using a magnesium/silver (20:1) cathode.

The device with the co-deposited light-emitting layer starts to emit light at 4 volts. The wavelength of the EL emission spectrum is 558 nm. This suggests that the transfer of the compound of Example 34 to Rhodamine-19 induces luminescence through resonance. The single-component light-emitting layer device starts to emit light at 7 volts, and the maximum EL emission wavelength is 529 nanometers. The EL luminescence properties are summarized in the table below.

<tables><img file="TW503255B_D0034.tif" /></tables>

The above results verify that the compounds of the present invention can be used in guest-host type luminescent materials.

Example 104: 28 grams (0.25 mol) of potassium tertiary butoxide, 62.5 grams (0.23 mol) of 4-(diphenylamino)benzonitrile and 300 ml of tertiary amyl alcohol are heated to 100°C under a nitrogen atmosphere . Once this temperature is reached, 26.7 g (0.12 mol) of di-n-butyl succinate and 70 ml of tertiary amyl alcohol solution are added over 1 hour using an addition funnel. When the addition is complete, the reaction mixture is maintained at 100°C for 16 hours, then cooled to 65°C, neutralized with 20 ml of glacial acetic acid and boiled briefly at reflux temperature. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml methanol, the pigment was separated by filtration again, and then finally washed with methanol and water until the washing liquid was colorless, and vacuum dehydrated at 100°C to obtain 10.8 g (15% theoretical value, based on dibutyl succinate) pure Pigment 1,4-diketo-3,6-two-(4-diphenylaminophenyl)pyrrolo(3,4-c)pyrrole.

1.02 g (1.64 millimoles) of 1,4-diketo-3,6-two-(4-diphenylaminophenyl)pyrrolo(3,4-c)pyrrole in 20 ml of 1 -Methyl-2-pyrrolidone was made into a slurry for 2 hours. 0.57 g of sodium hydride (5.09 millimoles) of potassium tertiary 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 then the mixture was stirred for another 2 hours. After the reaction mixture was poured into 50 ml of water, the resulting solid was filtered out and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 0.444 g (26%) of a red solid was obtained.

The optical properties of the compound obtained above are summarized in the table below

<tables><img file="TW503255B_D0035.tif" /></tables>

*1: at the wavelength of the maximum light absorption, *2: molar absorption coefficient *3: at the wavelength of the maximum light emission, *4: FQY

Then repeat the preparation of the EL device of Example 103, but using ginseng-(8-quinolinate) aluminum (III) (manufactured by Wako Pure Chemical Industries Co., Ltd.) and the compound prepared as above (0.50% by weight) Co-deposited thin films replace luminescent materials. The co-deposited p-aluminum complex system is 6.665×10 ^-4 Pa (5.0×10 ^-6 Torr) and 300 micrometers/second (3.0 angstroms/second) and the aforementioned compounds were carried out under deposition conditions of 1.5 micrometers/second (0.015 angstroms/second). For comparison, a device using aluminum complex as a luminescent substance was prepared.

A device that uses a light-emitting layer that contains only aluminum complexes emits green EL light starting at 8 volts. The maximum luminescence is at 520 nanometers, and the intensity is 6980 candles/square meter at 25 volts. The device using the light-emitting layer containing the complex compound and the compound starts to emit light at 4 volts (refer to the device performance in the table below). The maximum thin layer of EL light emission is 590 nm, which means that it emits orange light, which is different from the aforementioned single-component device. This suggests that the luminescence system is induced by the transition from the aluminum complex to the compound of the present invention via resonance energy.

<tables><img file="TW503255B_D0036.tif" /></tables>

The above results verify that the compounds of the present invention can be used in energy acceptors of guest-host luminescent materials.

Example 105: 2.09 g (4.75 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole in 30 ml of 1-methyl-2 -Pyrolidone was stirred at room temperature for 2 hours. 1.29 grams (11.52 millimoles) of potassium tertiary 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 then the mixture was stirred for another 2 hours. The mixture was poured into 50 ml of water, and the resulting red solid was filtered out and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 1.13 g (60%) of a red solid was obtained.

Example 106: Repeat Example 105 but use 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole as starting material. A red solid (540.

Example 107: Repeat Example 105 but use 3,3-dimethylallyl bromide instead of allyl bromide. A red solid (42%) was obtained.

Example 108: Repeat Example 105 but use 3-phenylallyl bromide instead of allyl bromide. A red solid (55%) was obtained.

Example 109: A mixture of 45 grams (0.4 mol) of potassium tertiary butoxide, 82 grams (0.373 mol) of 9-ethyl-3-cyanocarbazole and 300 ml of tertiary amyl alcohol was heated to 110 under a nitrogen atmosphere °C temperature. Once this temperature is reached, use a dropping funnel to add a solution of 43 g (0.18 mol) of di-n-butyl succinate and 100 ml of tertiary amyl alcohol over a period of 1.5 hours. When the addition is complete, the reaction mixture is maintained at 110°C for 16 hours and then cooled to 65°C, neutralized with 40 ml of glacial acetic acid and boiled briefly at reflux temperature. The resulting pigment suspension was filtered at room temperature. The filter cake was suspended in 300 ml of methanol, the pigments were separated by filtration, and then finally washed with methanol and water until the washing liquid was colorless, and dehydrated at 100°C under reduced pressure. 10.5 g (11%) of pure 1,4-diketo-3,6-two-(3-9-ethylcarbazole)pyrrolo(3,4-c)pyrrole was obtained.

Example 110: Repeat Example 105 but use 1,4-diketo-3,6-two-(2-naphthyl)pyrrolo(3,4-c)pyrrole and 3,5-di-tert-butylbenzyl bromine. A red solid (36%) was obtained.

Example 111: Repeat Example 110 but use 3,5-dimethylbenzyl bromide instead of 3,5-di-tert-butylbenzyl bromide. A red solid (30%) was obtained.

Example 112: Repeat Example 109 but use 1-(4-oxyphenyl)-2-(3,5-di-tert-butylphenyl)-transethylene instead of 9-ethyl-3-oxycarbazole . A red solid (5%) was obtained.

Example 113: Repeat Example 112 but use 3,5-dimethylbenzyl bromide as the alkylating agent to obtain a red solid (8%).

Example 114: Repeat Example 10 but use 3-bromobenzyl bromide as the alkylating agent to obtain a red solid (23%).

Example 115: Repeat Example 10 but use methyl iodide as the alkylating agent to obtain a red solid (40%).

Example 116: Repeat Example 10 but use 3-methylbenzyl bromide as the alkylating agent to obtain a red solid (45%).

Example 117: (a) 4.04 g (10 millimoles) of 1,4-diketo-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole at room temperature in 30 ml The 1-methyl-2-pyrrolidone was made into a slurry for 2 hours. 1.23 g (11 millimoles) of potassium tertiary butoxide was added to the 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 and the red solid was filtered out, and purified by column chromatography (silica gel, dichloromethane as eluent). After dehydration, 1.61 g (25%) of 1,4-diketo-2-(di-tert-butylbenzyl)-3,6-two-(4-biphenyl)pyrrolo(3,4-c) ) Pyrrole.

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

<chemistry general="n"><img file="TW503255B_D0037.tif" /></chemistry>

Example 118: (a) Repeat Example 117(a) but use 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole as starting material And 1,4-diketo-2-(di-tert-butylbenzyl)-3,6-two-(4-biphenyl)pyrrolo(3,4-c)pyrrole (32%) was obtained.

(b) Repeat Example 117(b) but use 1,4-diketo-3,6-two-(4-methylphenyl)pyrrolo(3,4-c)pyrrole and a,a'-di Bromo-p-xylene. Obtain the following formula V red solid

<chemistry general="n"><img file="TW503255B_D0038.tif" /></chemistry>

Examples 119 to 129: Repeat Example 104 but only use the compounds listed in Table 9 below to replace the guest materials of the binary system. The EL properties are also summarized in the table:

<tables><img file="TW503255B_D0039.tif" /></tables>

Examples 130 to 134: Repeat Example 69 but the following Table 10 lists compounds instead of luminescent materials, and the EL performance is also summarized in the table:

<tables><img file="TW503255B_D0040.tif" /></tables>

Example 135: 294 mg of Alq recrystallized from tetrahydrofuran ₃ (Manufactured by Tokyo Kasei Organic Chemical Co., Ltd.) and 6 mg of 1,4-diketo-2,5-two-(3,5-di-tert-butylbenzyl)-3,6-two-(4-di Phenylaminophenyl)pyrrolo(3,4-c)pyrrole was dissolved in 50 ml of dichloromethane. The resulting solution was slowly poured into 500 ml of hot water, and the resulting precipitate was collected and dehydrated. The obtained precipitate was purified by sublimation, and the temperature was 6.65×10 ^-4 Pa (5×10 ^-6 Torr) Sublimation by heating under reduced pressure atmosphere. Obtained 250 mg (5%) red host/guest compound material.

Then repeat Example 103 to prepare the EL device but replace the luminescent material with the host/guest composite obtained above.

Examples 136 to 138: Repeat Example 135 but use the guest concentration substitutions listed in Table 11 below:

<tables><img file="TW503255B_D0041.tif" /></tables>