JP2006344544A - Method for producing full-color organic electroluminescence device - Google Patents

Abstract

An object of the present invention is to provide an electroluminescent device capable of full-color display on a large screen with a low driving voltage and high luminous efficiency.
SOLUTION: Red, green, and blue are formed on a transparent substrate that includes partition walls that divide light emitting areas for red, green, and blue and transparent pixel electrodes for red, green, and blue. Each hole injection layer is formed, each light emitting layer for red, green, and blue is formed on each hole injection layer, and a hole blocking layer is formed on the light emitting layer, A full color organic electroluminescent device, wherein an electron transport layer is formed on the hole blocking layer, and an anode is formed on the electron transport layer.
[Selection] Figure 1

Description

  The present invention relates to an organic electroluminescence (EL) device capable of full color display and a method for manufacturing the same.

  An EL element has been attracting attention as a promising display element because it can emit light with high luminance at a low voltage.

Specifically, an organic electroluminescent element in which a thin film containing an organic compound having high fluorescence quantum efficiency that emits light at a low voltage of 10 V or less has been reported (Non-Patent Document 1). This method uses a metal chelate complex as a light emitting layer and an amine compound as a hole injection layer to obtain green light emission with high luminance. The luminance reaches several 10000 cd / m ² at a DC voltage of 6 to 7V. ing. However, the production of an organic electroluminescent device involving an organic compound vapor deposition operation has a problem in productivity, and it is desirable to create a coating-type device from the viewpoint of simplifying the manufacturing process and increasing the area.

  In the inkjet method, there is no limitation on the substrate size, and life-size posters and the like are printed in the printing industry. Therefore, many reports have been made since it will be possible to produce large-area organic electroluminescent televisions and posters using large substrates in the future (Patent Documents 1 to 3). Both high-definition printing and photo-quality printers have already been put into practical use, and RGB formation of about 200ppi is possible. In particular, the inkjet method has accumulated considerable technology as a general printing technology, and this point can also be said to be advantageous for development in organic electroluminescence devices. In addition, the material utilization efficiency is high as compared with the mask vapor deposition method used for forming the RGB pattern of the low molecular organic electroluminescence device.

  As a coating type phosphorescent light emitting device, an example in which a device is prepared by coating a hole transport layer and a light emitting layer has been reported (Non-patent Document 2). For the hole transport layer, PEDOT / PSS was used, and for the light emitting layer, a compound having a pendant host portion and a light emitting portion on the side chain of the nonconjugated polymer was used. However, there is a problem that the drive voltage becomes high due to the two-layer structure of the hole transport layer and the light emitting layer.

  In addition, for the partition wall component, when ink is filled in the gap divided by the partition wall, the ink spreads over the partition wall, and the phenomenon of color mixing that impairs the hue of the filter segment due to ink mixing into the adjacent region occurs. Conventionally, a film having good wettability with respect to ink has been formed, and a film having poor wettability with respect to ink has been formed between the plurality of color filters (Patent Document 4). Further, by providing a silicon rubber layer on the upper part of the partition wall, ink repellency is imparted to prevent ink color mixing (Patent Document 5).

  In the partition wall (Patent Document 6) formed using the partition wall composition containing a vinyl polymer having an ethylenically unsaturated double bond and a fluoroalkyl group, the polymer having a fluoroalkyl group is oriented on the upper surface. Thereby, the upper surface has ink repellency. Furthermore, since the vinyl polymer having fluoroalkyl groups constituting the partition walls is set in the network structure of the partition walls by a crosslinking reaction by active energy, the vinyl polymer having fluoroalkyl groups from the partition walls to the base material is bleeded. There is nothing to do.

C. W. Tang and S. A. Van Slyke, Appl. Phys. Lett. 51, 913 (1987) FY2003 Opening of Technical Research Lecture / Panel Discussion Research Presentation Proceedings P52-56 Japanese Patent Laid-Open No. 10-12377 Japanese Patent Laid-Open No. 10-153967 Japanese Unexamined Patent Publication No. 11-24604 JP 59-75205 A JP 4-123005 A JP 2005-60515 A

  A full-color organic electroluminescent device using the above-described organic dye emits red, green, and blue light. However, as is well known, in order to realize a full-color display body, it is necessary to dispose organic electroluminescent layers that emit three primary colors for each pixel. Conventionally, a technique for patterning a light emitting layer has been considered extremely difficult. The cause was that the patterning accuracy of vapor deposition was not achieved, and the polymer and precursor forming the hole injection layer and the organic electroluminescent layer were not resistant to the patterning process such as photolithography. However, in recent years, high-definition has become possible by the inkjet method.

  However, when a full color coating type phosphorescent light emitting device is produced by this ink jet method, there is a problem that the driving voltage becomes high due to the two-layer structure of the hole transport layer and the light emitting layer.

  The present invention solves the above-described problems, and its purpose is to pattern a red, green, and blue organic electroluminescent layer for each pixel by an inkjet method, and to form a hole blocking layer and a layer on the layer. An object of the present invention is to provide an electroluminescent element having a low driving voltage capable of full color display and a high luminous efficiency by forming an electron transport layer by a vacuum deposition method or the like.

The present invention provides a red substrate, a green substrate, and a blue substrate on a transparent substrate that includes red, green, and blue light emitting regions and transparent pixel electrodes for red, green, and blue. Each hole injection layer is formed,
On each hole injection layer, each light emitting layer for red, green, and blue is formed,
A hole blocking layer is formed on the light emitting layer,
An electron transport layer is formed on the hole blocking layer,
The present invention relates to a full-color organic electroluminescence device, wherein an anode is formed on the electron transport layer.

  The present invention also relates to the above-described full-color organic electroluminescent device, wherein the partition wall comprises a vinyl polymer having a fluoroalkyl group.

  In the present invention, the hole injection layer forming material for forming the hole injection layer is PEDOT · PSS (poly (3,4-ethylenedioxy) -2,5-thiophene · polystyrenesulfonic acid). The present invention relates to an organic electroluminescent element.

Further, in the present invention, at least one of the light emitting layer forming materials forming the light emitting layers for red, green, and blue,
A copolymer of a unit represented by the following general formula [1] and a unit having an amino group; and
The present invention relates to the above-described full-color organic electroluminescent device comprising a luminescent material.

General formula [1]

[Wherein A represents a non-conjugated trivalent organic residue, B represents a direct bond, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. Represents one or more divalent organic residues selected from the group consisting of:
C represents a monovalent organic residue represented by the following general formula [2] or general formula [3]. ]

General formula [2]

[Wherein R ^{1 to} R ⁷ each independently represents a bonding site, a hydrogen atom or a substituent,
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR ⁸ — (R ⁸ represents an alkyl group or an aryl group), —S (═O) ₂ —, — ( CO) -, - COO -, - OCO -, - CH 2 - indicates,
R ^{1 to} R ⁸ may be bonded to each other to form an aryl ring, and further the aryl ring may have a substituent. ]

General formula [3]

[Wherein R ^{9 to} R ¹⁷ each independently represent a bonding site, a hydrogen atom or a substituent. ]

  The present invention also relates to the above-described full-color organic electroluminescent device, wherein the hole blocking layer forming material for forming the hole blocking layer is an oxadiazole derivative.

The present invention also relates to the above-described full-color organic electroluminescence device, wherein the electron transport material forming the electron transport layer is an aluminum quinoline complex (Alq ₃ ).

  The present invention also relates to a method for producing a full-color organic electroluminescent device, wherein each hole injection layer and each light-emitting layer of the full-color organic electroluminescent device are formed by an ink jet method.

  The present invention also relates to the above-described method for producing a full-color organic electroluminescent element, wherein the hole blocking layer and / or the electron transport layer are formed by a vacuum deposition method.

  According to the present invention, it is possible to provide a full-color electroluminescent device having a low driving voltage and high luminous efficiency even when an inkjet method is used.

  In order to solve the problem of the present invention, as shown in FIG. 1, a hole injection layer 5 is formed on a transparent electrode 3, and a red light emitting layer 6, a green light emitting layer 7, a blue light emitting layer are formed thereon. 8, the hole blocking layer 10 and the electron transport layer 11 are further formed, and the counter electrode 12 is formed thereon.

  In addition, the hole injection layer and the light emitting layer are formed by applying each material by patterning by an ink jet method, and the hole blocking layer and / or the electron transport layer are formed by a vacuum vapor deposition method. The display is realized.

  Specifically, in the organic electroluminescence device shown in FIG. 1, in order to efficiently recombine electrons (charges) injected into the device from the cathode with holes (holes) injected from the anode, A layer that serves to efficiently inject electrons into the device (electron transport layer) and a hole blocking layer that retains holes injected from the anode inside the light emitting layer are required.

The hole blocking layer plays this role, and the hole blocking material forming the hole blocking layer has an ionization potential (HOMO level) higher than that of the light emitting layer by 0.1 eV or more. Plays the function of staying inside the layer.
The holes are closely related to the HOMO level of the substance, and move from the anode (for example, ITO) through the hole injection layer and the light emitting layer. On the other hand, electrons are closely related to the LUMO level of the substance, and move from the cathode to the electron transport layer / light emitting layer. At this time, if the energy barrier at the HOMO level or LUMO level is large between the layers, holes or electrons remain in the energy barrier layer and are difficult to move to the next layer. The hole blocking layer plays a role of retaining holes in the light emitting layer by utilizing this function.

  The most important function of this hole blocking layer is that the HOMO level is higher than the HOMO level of the light emitting layer. Examples of the material having such a role include a compound having an oxadiazolyl group, a compound having a triazolyl group, a compound having a pyrazolyl group, and a compound having an oxazolyl group. Examples of the compound having an oxadiazolyl group include compounds represented by the following compound (1) or compound (2).

Compound (1)

Compound (2)

  The ionization potential of these compounds is 0.1 eV or more higher than the ionization potential of the light emitting layer. Specifically, the ionization potential (HOMO level) of the light emitting layer is 5.5 to 5.6 eV, whereas the compound (1) is 6.0 eV and the compound (2) is 5.8 eV. All are 0.1 eV or more higher than the light emitting layer. Therefore, any compound having a HOMO level higher than that of the light emitting layer and capable of transferring charges can be basically used as a hole blocking material.

The partition used in the present invention will be described. The partition used in the present invention is not particularly limited as long as the red, green, and blue light emitting regions can be defined, and the material for forming the partition and the method for forming the partition are also particularly limited. is not.
For example, a material for uniformly forming a partition wall may be formed on a transparent substrate, and then a portion corresponding to the light emitting region of each color may be removed by wet or dry development, laser ablation, or the like. Only an amount corresponding to the partition wall may be formed by an inkjet method or the like, or a method of transferring a separately formed partition wall onto a transparent substrate may be used.
After the barrier ribs are formed, each hole injection layer forming material or each light emitting layer forming material is discharged into the light emitting region of each color as an ink by an ink jet method. At this time, it is preferable that ink repellency is imparted so that the ejected ink does not enter the light emitting region of another color beyond the partition.
In order to impart ink repellency, for example, a partition wall composition containing a polymer having a fluoroalkyl group may be used as a material for forming the partition wall. As such a polymer, there is a vinyl polymer having a fluoroalkyl group, and when this is used to form a partition, the fluoroalkyl group is oriented on the upper surface of the partition to effectively prevent ink from entering. To work.

  In addition, when the vinyl polymer further has an ethylenically unsaturated double bond, when the active energy ray is irradiated, the oriented vinyl polymer is set in the network structure of the partition and emits light from the partition. It serves to prevent the vinyl polymer from bleeding into the area. In particular, when the vinyl polymer is prepared as an alkali development type photoresist, it is crosslinked by active energy ray exposure, so there is little film loss during alkali development, and within the transparent substrate and between the transparent substrates. There is little variation in ink repellent performance.

The vinyl polymer can be produced by a one-stage method or a two-stage method, but the two-stage method is preferred because the vinyl polymer can be produced stably.
In the one-step method, a monomer having an ethylenically unsaturated double bond and a fluoroalkyl group and, if necessary, a monomer having an ethylenically unsaturated double bond and other active energy ray-reactive functional groups Can be polymerized to produce a vinyl polymer.

Further, in the two-stage method, a monomer (a) having an ethylenically unsaturated double bond and a fluoroalkyl group and a monomer other than (a) having an ethylenically unsaturated double bond and a reactive functional group Reaction in polymer (A) with polymer (A) of (b) and monomer (c) having an ethylenically unsaturated double bond other than (a) and (b) if necessary It can manufacture by making the compound (B) which has a functional group and an ethylenically unsaturated double bond which can react with an ionic functional group react.
The monomer (a) having an ethylenically unsaturated double bond and a fluoroalkyl group is indispensable for imparting ink repellency to the upper surface of the partition wall.

Specific examples of the monomer (a) having an ethylenically unsaturated double bond and a fluoroalkyl group include 2,2,2-trifluoroethyl (meth) acrylate, 2,2,3,3,3-penta Fluoropropyl (meth) acrylate, 2- (perfluorobutyl) ethyl (meth) acrylate, 2- (perfluorohexyl) ethyl (meth) acrylate, 2- (perfluorooctyl) ethyl (meth) acrylate, 2- (perfluoro- 3-methylbutyl) ethyl (meth) acrylate, 2- (perfluoro-7-methyloctyl) ethyl (meth) acrylate, 1H, 1H, 3H-tetrafluoropropyl (meth) acrylate, 1H, 1H, 5H-octafluoropentyl (meth) ) Acrylate, 1H, 1H, 7H-dodecafluoroheptyl Meth) acrylate, 1H, 1H, 9H- hexadecafluoro nonyl (meth) acrylate.
A monomer (a) can be used 1 type or in mixture of 2 or more types according to required performance.

The copolymerization ratio of the monomer (a) in the polymer (A) is preferably 1 to 90% by weight, more preferably 5 to 60% by weight, based on the total weight of the monomers constituting the polymer. %, Particularly preferably 10 to 40% by weight. When the copolymerization ratio of the monomer (a) is less than 1% by weight, it becomes difficult to impart sufficient ink repellency to the upper surface of the partition wall, and when it exceeds 90% by weight, the photocrosslinking component Therefore, the polymer (A) bleeds on the bottom surface of the partition wall, and the ink is repelled when the ink is filled in the region divided by the partition wall, resulting in a coating film defect.
The monomer (b) other than (a) having an ethylenically unsaturated double bond and a reactive functional group is a starting point for introducing an ethylenically unsaturated double bond into the polymer (A) polymerized in the first stage. It is indispensable in order to suppress the bleeding of the vinyl polymer and form a tough partition wall by setting the partition wall composition on the base material after crosslinking the vinyl polymer with active energy rays. .
Examples of the reactive functional group include a hydroxyl group, a carboxyl group, an isocyanate group, and an epoxy group.

  Specific examples of the monomer (b) having a hydroxyl group include 2-hydroxyethyl (meth) acrylate, 1-hydroxypropyl (meth) acrylate, 2-hydroxypropyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples include acrylate, polyethylene glycol mono (meth) acrylate, polypropylene glycol mono (meth) acrylate, polytetramethylene glycol mono (meth) acrylate, and hydroxystyrene.

Specific examples of the monomer (b) having a carboxyl group include acrylic acid, methacrylic acid, crotonic acid, maleic acid, fumaric acid, itaconic acid, and citraconic acid.
Specific examples of the monomer (b) having an isocyanate group include (meth) acryloyloxyethyl isocyanate, (meth) acryloyloxypropyl isocyanate, 2-hydroxyethyl (meth) acrylate, and 4-hydroxybutyl (meth). Examples thereof include those obtained by reacting a hydroxyalkyl (meth) acrylate such as acrylate with a polyisocyanate such as toluene diisocyanate and isophorone diisocyanate.

Specific examples of the monomer (b) having an epoxy group include glycidyl (meth) acrylate glycidyl cinnamate, glycidyl allyl ether, glycidyl vinyl ether, vinylcyclohexane monoepoxide, 1,3-butadiene monoepoxide, and the like.
A monomer (b) can be used 1 type or in mixture of 2 or more types according to required performance.

  The copolymerization ratio of the monomer (b) in the polymer (A) is preferably 10 to 90% by weight, more preferably 20 to 80% by weight based on the total weight of the monomers constituting the polymer. %, Particularly preferably 25 to 70% by weight. When the copolymerization ratio of the monomer (b) is less than 10% by weight, it becomes difficult to obtain sufficient photocurability, and when it exceeds 90% by weight, the ink repellency of the partition upper surface is lowered. To do.

The monomer (c) having an ethylenically unsaturated double bond other than (a) and (b) improves the compatibility between the vinyl polymer and other components contained in the partition wall composition, and Used to impart physical properties such as hardness, toughness, and scratch resistance. Monomers (c) include (i) (meth) acrylic acid derivatives, (ii) aromatic vinyl monomers, (iii) olefinic hydrocarbon monomers, (iv) vinyl ester monomers, ( v) vinyl halide monomers, (vi) vinyl ether monomers, and the like.
(i) Specific examples of (meth) acrylic acid derivatives include alkyl (meth) acrylates such as (meth) acrylonitrile, methyl (meth) acrylate, butyl (meth) acrylate, ethylhexyl (meth) acrylate, and stearyl (meth) acrylate. , Benzyl (meth) acrylate and the like.

(ii) Specific examples of the aromatic vinyl monomer include styrenes such as styrene, methylstyrene, ethylstyrene, chlorostyrene, monofluoromethylstyrene, difluoromethylstyrene, and trifluoromethylstyrene.
(iii) Specific examples of the olefinic hydrocarbon monomer include ethylene, propylene, butadiene, isobutylene, isoprene, and 1,4-pentadiene.
Specific examples of the (iv) vinyl ester monomer include vinyl acetate.
Specific examples of the (v) vinyl halide monomer include vinyl chloride and vinylidene chloride.
(vi) Specific examples of the vinyl ether monomer include vinyl methyl ether.

These monomers may be used in combination of two or more.
The copolymerization ratio of the monomer (c) in the polymer (A) is preferably 0 to 89% by weight, more preferably 0 to 75% by weight based on the total weight of the monomers constituting the polymer. %, Particularly preferably 0 to 65% by weight. When the copolymerization ratio of the monomer (c) exceeds 89% by weight, the ink repellency is lowered and sufficient photocurability cannot be obtained.

  The polymer (A) can be synthesized by a known method, for example, solution polymerization. Solvents used during polymerization include ketones such as acetone, methyl ethyl ketone, methyl isobutyl ketone and cyclohexanone, ethers such as tetrahydrofuran, dioxane, ethylene glycol dimethyl ether and diethylene glycol dimethyl ether, aromatics such as benzene, toluene, xylene and cumene, and acetic acid. Esters such as ether and butyl acetate can be used. Two or more solvents may be mixed and used. The monomer concentration during polymerization is preferably 0 to 80% by weight.

Examples of the polymerization initiator include ordinary peroxides or azo compounds such as benzoyl peroxide, azoisobutylvalenonitrile, azobisisobutyronitrile, di-t-butyl peroxide, t-butyl perbenzoate, t-butyl. Peroctoate, cumene hydroxyperoxide and the like are used, and the polymerization temperature is preferably 50 to 140 ° C, more preferably 70 to 140 ° C.
The preferred weight average molecular weight of the resulting polymer (A) is 2,000 to 100,000.

The polymer (A) having a reactive functional group and a fluoroalkyl group thus obtained is combined with a compound (B) having a functional group capable of reacting with the reactive functional group and an ethylenically unsaturated double bond. By reacting, a vinyl polymer having an ethylenically unsaturated double bond and a fluoroalkyl group is obtained.
In the polymer (A) and the compound (B), the number of functional groups possessed by the compound (B) that can react with the reactive functional group is the number of reactive functional groups possessed by the polymer (A). The reaction is preferably performed at a ratio of 100%, but may be performed at a ratio of less than 100% if sufficient photocurability is obtained.

When leaving unreacted reactive functional groups, a crosslinking agent and a crosslinking catalyst are added, and the remaining unreacted reactive functional groups are thermally cured to increase the crosslink density of the coating film, thereby producing a color filter. It is possible to ensure the solvent resistance of the partition walls required in the subsequent process.
When the ratio of the number of reactive functional groups of the compound (B) to the number of reactive functional groups of the polymer (A) is less than 1%, the crosslinking density of the vinyl polymer by active energy ray exposure is low, and the substrate Variations in ink repellency between the inside and between the substrates occur. On the other hand, if it exceeds 50%, the effect of thermosetting is reduced, and the solvent resistance of the partition walls is lowered.

As the combination of the reactive functional group and the functional group capable of reacting with the reactive functional group, various known combinations as shown below can be adopted.
(1) When the reactive functional group is a hydroxyl group, reaction with an isocyanate group, a halogen group, a carboxyl group or an epoxy group.
(2) When the reactive functional group is a carboxyl group, reaction with an epoxy group or a hydroxyl group.
(3) When the reactive functional group is an isocyanate group, reaction with a hydroxyl group or an amino group.
(4) When the reactive functional group is an epoxy group, it reacts with a carboxyl group or a hydroxyl group.

A catalyst can be used when reacting the reactive functional group of the polymer (A) with the functional group of the compound (B) that can react with the reactive functional group.
As the catalyst, when the reactive functional group is a hydroxyl group, it is preferable to use acidic compounds and their ammonium salts, lower amine salts, polyvalent metal salts and the like. In the case of a carboxyl group, it is preferable to use acidic compounds and their ammonium salts, lower amine salts, polyvalent metal salts and the like. In the case of an isocyanate group, it is preferable to use amines, metal salt compounds and the like. In the case of an epoxy group, it is preferable to use amines.

Specific examples of the acidic compound include formic acid, acetic acid, propionic acid, itaconic acid, oxalic acid, maleic acid, phthalic anhydride, benzoic acid, p-toluenesulfonic acid, benzenesulfonic acid, dodecylbenzenesulfonic acid, trichloroacetic acid, phosphorus Examples thereof include acid, monoalkyl phosphoric acid, dialkyl phosphoric acid, phosphoric acid ester of β-hydroxyethyl (meth) acrylate, monoalkyl phosphorous acid, dialkyl phosphorous acid and the like.
Specific examples of amines include dicyclohexylamine, triethylamine, N, N-dimethylbenzylamine, N, N, N ′, N′-tetramethyl-1,3-butanediamine, diethanolamine, triethanolamine, and cyclohexylethylamine. Is mentioned.

Specific examples of metal salt compounds include sodium acetate, tin octylate, lead octylate, cobalt octylate, zinc octylate, calcium octylate, lead naphthenate, cobalt naphthenate, dibutyltin dioctate, dibutyltin dilaurate, dibutyltin Examples thereof include malate dibutyltin di (2-ethylhexoate).
Two or more kinds of catalysts may be mixed and used, and the amount used in the case of using the catalyst is 0.01 to 10 parts by weight with respect to 100 parts by weight of the total of the polymer (A) and the compound (B). Is more preferable, and the range of 0.01 to 5 parts by weight is more preferable.

When the vinyl polymer has a reactive functional group, it is preferable to contain various crosslinking agents in the partition wall composition in order to thermally crosslink the vinyl polymer. Representative crosslinking agents include hydrazines, polyamines, polyisocyanates, dicarboxylic acids, polyhydric epoxy compounds, polyhydric alcohols, polyhydric phenols, and the like.
Specific examples of hydrazines include hydrazine and adipic acid dihydrazide.

  Specific examples of polyamines include ethylenediamine, propanediamine, butanediamine, pentanediamine, hexanediamine, diaminooctane, diaminodecane, diaminododecane, 1,6-hexamethylenediamine, 2,5-dimethyl-2,5-hexamethylene. Linear diamine such as diamine, polyoxypropylene diamine, diethylenetriamine, triethylenetetramine, tetraethylenepentamine, mensendiamine, isophoronediamine, bis (4-amino-3-methyldicyclohexyl) methane, diaminodicyclohexylmethane, 3, 9-bis (3-aminopropyl) -2,4,8,10-tetraoxaspiro [5,5] undecane, 1,4-bis (2-amino-2-methylpropyl) piperazine, m-xylenediamine , Polycyclohexyl polyamine, cyclic diamines such as bis (aminomethyl) bicyclo [2 · 2 · 1] heptane, methylene bis (furanmethanamine), triethylenetetramine, tetraethylenepentamine, diethylenetriamine and the like.

Specific examples of the polyisocyanate include toluylene diisocyanate, naphthylene-1,5-diisocyanate, o-toluylene diisocyanate, diphenylmethane diisocyanate, trimethylhexamethylene diisocyanate, isophorone diisocyanate, 4,4′-diphenylmethane diisocyanate, hexamethylene diisocyanate, m. -Diisocyanates such as xylene diisocyanate, p-xylene diisocyanate, lysine diisocyanate, hydrogenated 4,4'-diphenylmethane diisocyanate, hydrogenated tolylene diisocyanate, or both-terminal isocyanate adducts of these with glycols or diamines, triphenylmethane Examples include triisocyanate and polymethylene polyphenyl isocyanate. .
Specific examples of dicarboxylic acids include oxalic acid, malonic acid, succinic acid, glutaric acid, hexanedioic acid, citric acid, maleic acid, methyl nadic acid, dodecenyl succinic acid, sebacic acid, pyromellitic acid, hexahydrophthalic acid, tetrahydrophthalic acid An acid etc. are mentioned.

  Specific examples of the polyvalent epoxy compound include ethylene glycol diglycidyl ether, propylene glycol diglycidyl ether, polyethylene glycol diglycidyl ether, polypropylene glycol diglycidyl ether, tripropylene glycol diglycidyl ether, neopentyl glycol diglycidyl ether, 1, Bisepoxy compounds such as 6-hexanediol diglycidyl ether and phthalic acid diglycidyl ester, trade name Epicoat 801, 802, 807, 815, 827, 828, 834, 815X, 815XA1, 828EL, 828XA manufactured by Yuka Shell Epoxy Co., Ltd. , 1001, 1002, 1003, 1055, 1004, 1004AF, 1007, 1009, 1010, 1003F, 1004F, 100 F, 1100L, 834X90, 1001B80, 1001X70, 1001X75, 1001T75, 5045B80, 5046B80, 5048B70, 5049B70, 5050T60, 5050, 5051, 152, 154, 180S65, 180H65, 1031S, 1032H60, 604, 157S70, etc. .

Specific examples of the polyhydric alcohol include diols such as 1,4-butanediol and 2,3-butanediol, 1,1,1-trimethylolpropane ethylene glycol, diethylene glycol, glycerin, erythritol, arabitol, xylitol, sorbitol, Examples include dulcitol and mannitol.
Specific examples of the polyhydric phenol include catechol, resorcin, hydroquinone, guaiacol, hexyl resorcin, pyrogallol, trihydroxybenzene, phloroglucin, and dimethylolphenol.

When the reactive functional group of the vinyl polymer is a hydroxyl group or a carboxyl group, it is preferable to use a polyisocyanate, a polyvalent epoxy compound, or the like as a crosslinking agent. In the case of an isocyanate group, it is preferable to use a polyhydric alcohol, dicarboxylic acid or the like as a crosslinking agent.
In the case of an epoxy group, it is preferable to use dicarboxylic acid, polyhydric alcohol, polyhydric phenol, polyamine or the like as a crosslinking agent.
Two or more types of crosslinking agents may be mixed and used. When the crosslinking agent is contained, the amount used is 0.1 to 30 parts by weight with respect to 100 parts by weight of the nonvolatile content of the partition wall composition. More preferably, it is the range of 0.1-10 weight part.

Further, in the partition wall composition, when the vinyl polymer has a reactive functional group, in order to promote the reaction between the reactive functional groups or the reaction between the reactive functional group and the crosslinking agent, Depending on the functional group, various crosslinking catalysts can be included. As the crosslinking catalyst, a metal complex compound can be used in addition to the acidic compound exemplified above and its ammonium salt, lower amine salt or polyvalent metal salt, amine metal salt compound.
Specific examples of metal complex compounds include aluminum triacetylacetonate, iron triacetylacetonate, manganese tetraacetylacetonate, nickel tetraacetylacetonate, chromium hexaacetylacetonate, titanium tetraacetylacetonate, and cobalt tetraacetylacetonate. Etc.

Among these cross-linking catalysts, when the reactive functional group of the vinyl polymer is a hydroxyl group, it is preferable to use acidic compounds and their ammonium salts, lower amine salts, polyvalent metal salts and the like. In the case of a carboxyl group, it is preferable to use acidic compounds and their ammonium salts, lower amine salts, polyvalent metal salts and the like.
In the case of an isocyanate group, it is preferable to use amines, metal salt compounds and the like.
In the case of an epoxy group, it is preferable to use amines.
Two or more types of crosslinking catalysts may be used as a mixture. The amount of the crosslinking catalyst used is 0.01 to 10 parts by weight with respect to 100 parts by weight of the nonvolatile content of the partition wall composition. More preferably, it is the range of 0.01-5 weight part.

Moreover, the compound for partition can also be made to contain the compound which has an ethylenically unsaturated double bond. As a result, it is possible to increase the crosslinking density of the coating film and ensure the solvent resistance of the partition walls required in the subsequent steps of color filter production.
As the compound having an ethylenically unsaturated double bond, monomers, oligomers, photosensitive resins and the like can be used.
Monomers include monofunctional monomers such as 2-hydroxy (meth) acrylate and β- (meth) acryloyloxyethyl hydrogen succinate, ethylene glycol di (meth) acrylate, 1,6-hexanediol di (meth) acrylate, neo Bifunctional monomers such as pentyl glycol di (meth) acrylate, 2,2-bis [4- (methacryloxyethoxy) phenyl] propane, 2,2-bis [4-acryloxydiethoxy] phenyl] propane, trimethylolpropane tri Trifunctional or higher functional monomers such as (meth) acrylate and tetramethylolmethanetetra (meth) acrylate are exemplified. On the other hand, examples of the oligomer include dipentaerythritol hexaacrylate, hexaacrylate of caprolactone adduct of dipentaerythritol, melamine acrylate, epoxy (meth) acrylate prepolymer, and the like. These may be used in combination of two or more.

  In addition, when forming the pixel forming substrate using the partition wall composition, when the vinyl polymer in the partition wall composition is crosslinked by ultraviolet irradiation, a photopolymerization reaction of an ethylenically unsaturated double bond. In order to promote this, it is preferable to contain a photoinitiator in the partition wall composition.

  As photoinitiators, 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1one, 1-hydroxycyclohexyl Acetophenone photoinitiators such as phenyl ketone, 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butan-1-one, benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzyl Benzoin series such as dimethyl ketal, benzophenone series photoinitiator, benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4 Benzophenone photoinitiators such as benzoyl-4'-methyldiphenyl sulfide, thioxanthone photoinitiators such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone Agent, 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis (trichloromethyl) -s-triazine, 2- (p-methoxyphenyl) -4,6-bis (trichloromethyl) -S-triazine, 2- (p-tolyl) -4,6-bis (trichloromethyl) -s-triazine, 2-piperonyl--4,6-bis (trichloromethyl) -s-triazine, 2,4- Bis (trichloromethyl) -6-styryl s-triazine, 2- (naphth-1-yl) -4,6-bis (to Chloromethyl) -s-triazine, 2- (4-methoxy-naphth-1-yl) -4,6-bis (trichloromethyl) -s-triazine, 2,4-trichloromethyl- (piperonyl) -6-triazine Triazine photoinitiators such as 2,4-trichloromethyl (4′-methoxystyryl) -6-triazine, carbazole photoinitiators, imidazole photoinitiators and the like are used.

The photoinitiator may be used in combination of two or more, but as a sensitizer, α-acyloxy ester, acylphosphine oxide, methylphenylglyoxylate, benzyl, 9,10-phenanthrene Compounds such as quinone, camphorquinone, ethylanthraquinone, 4,4′-diethylisophthalophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, 4,4′-diethylaminobenzophenone Can also be used together.

When the partition walls are colored, the partition wall composition includes carbon black, titanium black, aniline black, anthraquinone black pigment, perylene black pigment, specifically CI pigment black 1, 6, 7, 12, 20, Black pigments such as 31, 32 can be contained. Among black pigments, carbon black is preferably used from the viewpoint of cost and light shielding properties. Carbon black may be surface-treated with a resin or the like.
The black pigment content in the partition wall composition is preferably 3 to 80% by weight based on the nonvolatile content of the partition wall composition. When the content of the black pigment is less than 3% by weight, the light shielding property per unit film thickness is lowered, and when it exceeds 80% by weight, it is difficult to form a thin film.

  In addition, the partition wall composition includes an azo pigment other than a black pigment, a phthalocyanine pigment, a selenium pigment, an indigo pigment, a perinone pigment, a perylene pigment, and a phthalone pigment for the purpose of improving dispersibility and adjusting the hue. , Dioxazine pigments, quinacridone pigments, isoindolinone pigments, metal complex pigments, methine / azomethine pigments, diketopyrrolopyrrole pigments, derivatives of these pigments, extender pigments, and dyes.

  The composition ratio of the vinyl polymer in the partition wall composition is such that the content of the monomer (a) is 0.01 to 10% by weight, particularly 0.01 to 0% based on the nonvolatile content of the partition wall composition. The ratio is preferably 4% by weight. When the content of the monomer (a) is less than 0.01% by weight, it becomes difficult to impart sufficient ink repellency to the upper surface of the partition wall. When the composition is prepared as an alkali development type photosensitive resist and partition walls are formed on the substrate, uneven development and defects in the partition walls are likely to occur.

  The partition wall composition is a mixture of a vinyl polymer having a fluoroalkyl group and, if necessary, a crosslinking agent, a crosslinking catalyst, a compound having an ethylenically unsaturated double bond, a photoinitiator, a pigment, an additive, etc. in a solvent. It is obtained by dissolving. Solvents include acetone, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone and other ketones, tetrahydrofuran, dioxane, ethylene glycol dimethyl ether, diethylene glycol dimethyl ether, and other ethers, hexane, heptane, octane and other hydrocarbons, benzene, toluene, xylene, cumene. Are selected according to the monomer composition of the polymer from among aromatics such as ethers and esters such as ether acetate and butyl acetate. Two or more solvents may be mixed and used.

When the partition wall composition is not colored, the method for manufacturing the partition wall composition is not particularly limited, but usually, a vinyl polymer polymerization solution and an additive component such as a cross-linking agent are mixed, and a stirring blade and a shaker are mixed. What is necessary is just to stir with a stirrer, a rotary stirrer, etc.
When coloring the barrier rib composition, disperse the pigment, the polymer solution of vinyl polymer, and if necessary, the resin-type or surfactant-type pigment dispersant, the pigment derivative, the anthraquinone derivative, the triazine derivative, etc. And the pigment is dispersed until it has a desired average particle size and particle size distribution. The raw materials may be mixed and dispersed all at once, or may be mixed and dispersed separately in consideration of the characteristics and economics of each raw material.

As the disperser, a sand mill, a bead mill, an agitator mill, a dyno mill, a ball mill and the like are suitable. If there is a viscosity region suitable for pigment dispersion in each disperser, the viscosity is adjusted by changing the ratio of the polymer and the pigment.
The partition wall composition is preferably filtered by a filter or a centrifugal method for the purpose of removing coarse particles and foreign matters after being dispersed by a disperser.

Further, in order to improve the coating property of the partition wall composition, the viscosity may be adjusted by adding a solvent and stirring or concentrating uniformly.
In the composition for partition walls, the filler, thixotropy imparting agent, anti-aging agent, antioxidant, antistatic agent, flame retardant, thermal conductivity improver, plasticizer, anti-sagging are within the range that does not interfere with the effect of the present invention. Various additives such as an agent, an antifouling agent, an antiseptic, a bactericidal agent, an antifoaming agent, a leveling agent, and an ultraviolet absorber may be contained.

Next, a pixel forming substrate having a partition formed of a partition wall composition on the substrate will be described.
As the substrate, a glass plate, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, a resin film, or the like can be used. When the obtained pixel forming substrate is used for manufacturing a color filter, a transparent substrate having a transmittance of 80% or more, particularly preferably 95% or more in the entire wavelength region of the visible light region (400 to 700 nm) is used. preferable.
The partition walls can be formed on the substrate by a gravure offset printing method, a waterless offset printing method, a silk screen printing method, a photolithography method using a solvent developing type or an alkali developing type photosensitive resist, or a colloidal particle made of a vinyl polymer. Electrodeposition method in which partition walls are electrodeposited on a transparent conductive film by electrophoresis, and a transfer method in which a partition layer formed in advance on the surface of a transfer base sheet is transferred onto a substrate.

Since the printing method can be patterned only by repeating printing and drying, the partition wall manufacturing method is low in cost and excellent in mass productivity. Furthermore, it is possible to print a fine pattern having high dimensional accuracy and smoothness by the development of printing technology. When manufacturing a partition by a printing method, control of the fluidity | liquidity of the composition for a partition on a printing machine is important.
The photolithographic method using a solvent development type or alkali development type photosensitive resist is a method in which a partition wall resist is applied on a substrate by a coating method such as spin coating, slit coating, roll coating, and then exposed to ultraviolet rays through a photomask. In this method, the unexposed area is washed away with a solvent or an alkali developer to form a desired pattern to form a partition wall. According to this method, the partition wall can be formed with higher accuracy than the above printing method.

Next, in the general formula [1], which is a material for forming the light emitting layer, A represents an arbitrary trivalent organic residue capable of forming a non-conjugated main chain skeleton having B and C in the side chain. Examples are shown in E-1 to E-12, but are not limited thereto.

  The light emitting layer forming material used in the present invention is preferably a low molecular light emitting material or a copolymer of a unit represented by the general formula [2] and other units. Examples of other units include a unit having an amino group and a unit having an electron transporting skeleton.

  The polymerization mode of the non-conjugated main chain skeleton monomer in forming the copolymer is to perform copolymer formation by vinyl polymerization such as radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, ring-opening polymerization, and various polymerization reactions. The polymerization method is not particularly limited, but in the present invention, a copolymer formation reaction by polymerization of a vinyl polymerization monomer is particularly preferable.

  In addition, the monovalent organic residue composed of B and C in the general formula [2], or the organic residue containing an amino group when the amino group of the unit having an amino group is in the side chain is a non-conjugated main group. Even if it is not introduced at the stage of the chain skeleton monomer, it may be introduced / modified after the non-conjugated main chain skeleton is formed.

In the copolymer of the unit represented by the general formula [2] and the unit having an amino group, the amino group of the unit having an amino group is present in the main chain or side chain of the copolymer.
Preferably, the unit has a structure represented by the following general formula [4].

General formula [4]

[Wherein E and F are each independently a divalent group selected from one or more selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. Represents an organic residue (however, when an ethenylene group is selected, it is a case between two arylene groups or heteroarylene groups). ]

Further, a unit having a structure represented by the following general formula [5] is preferable.
General formula [5]

[Wherein D, E and F are each independently divalent selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, a substituted or unsubstituted ethenylene group. (However, when an ethenylene group is selected, it is a case between two arylene groups or heteroarylene groups.) ]

The unit having an amino group is more preferably represented by the following general formula [6].
General formula [6]

[Wherein D represents a divalent organic residue selected from the group consisting of a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group (provided that And an ethenylene group is a case between two arylene groups or heteroarylene groups.) And H and I are substituted or unsubstituted aryl groups or substituted or unsubstituted heteroaryl groups 1 or 2 selected from the group represents a monovalent organic residue, and G represents a non-conjugated trivalent organic residue. ]
Examples of G in the general formula [6] are the same as those in A in the above general formula [1].

  More preferably, examples of the unit having an amino group include, but are not limited to, the structures shown in H-1 to H-12 below.

  The arylene group in the general formulas [1] to [6] is preferably a monocyclic or condensed arylene group having 6 to 60 carbon atoms, more preferably 6 to 40 carbon atoms, and still more preferably 6 to 30 carbon atoms. An arylene group. Specific examples include phenylene, biphenylene, naphthalenediyl, anthracenediyl, phenanthroline diyl, pyrenediyl, triphenylenediyl, benzophenanthroline diyl, perylenediyl, pentaphenylenediyl, pentacenediyl, and the like. good.

  The heteroarylene group in the general formulas [1] to [2] is preferably a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms, more preferably at least a nitrogen atom, an oxygen atom or a sulfur atom. It is a monocyclic or condensed aromatic heterocyclic group having 4 to 60 carbon atoms containing one, and more preferably a 5- or 6-membered aromatic heterocyclic group having 4 to 30 carbon atoms. Specific examples of the aromatic heterocyclic group include pyrrole diyl, furanyl, thienylene, pyridinediyl, pyridazinediyl, pyrimidinediyl, pyrazinediyl, quinolinediyl, isoquinolinediyl, cinnolinediyl, quinazolinediyl, quinoxalinediyl, phthalazinediyl, pteridinediyl, acridinediyl, phenidinediyl Examples thereof include diyl and phenanthroline diyl, and these groups may have a substituent.

  Examples of the ethenylene group in the general formulas [1] to [2] include an ethenylene group, a 1-methylethenylene group, and a 1-ethylethenylene group.

  The substituent of the compound in the present invention is a halogen atom (for example, fluorine atom, chlorine atom, bromine atom, iodine atom, etc.), substituted or unsubstituted alkyl group, substituted or unsubstituted alkoxy group, substituted or unsubstituted. Substituted thioalkoxy group, cyano group, amino group, mono- or di-substituted amino group, hydroxyl group, mercapto group, substituted or unsubstituted aryloxy group, substituted or unsubstituted arylthio group, substituted or unsubstituted aryl group, substituted Alternatively, it represents an unsubstituted heteroaryl group, and the substituents may form a substituted or unsubstituted ring with adjacent substituents.

  Examples of the substituted or unsubstituted aryl group include phenyl group, biphenylenyl group, triphenylenyl group, tetraphenylenyl group, 3-nitrophenyl group, 4-methylthiophenyl group, 3,5-dicyanophenyl group, o-, m- And p-tolyl group, xylyl group, o-, m- and p-cumenyl group, mesityl group, pentarenyl group, indenyl group, naphthyl group, anthracenyl group, azulenyl group, heptaenyl group, acenaphthylenyl group, phenalenyl group, fluorenyl group, Anthryl group, anthraquinonyl group, 3-methylanthryl group, phenanthryl group, pyrenyl group, chrysenyl group, 2-ethyl-1-chrysenyl group, picenyl group, perylenyl group, 6-chloroperylenyl group, pentaphenyl group, pentacenyl group, tetra Phenylenyl group, hexaphenyl Group, hexacenyl group, rubicenyl group, coronenyl groups, trinaphthylenyl groups, heptacenyl groups, pyranthrenyl groups, there is ovalenyl group.

  Examples of the substituted or unsubstituted heteroaryl group include thionyl group, furyl group, pyrrolyl group, imidazolyl group, pyrazolyl group, pyridyl group, pyrazinyl group, pyrimidinyl group, pyridazinyl group, indolyl group, quinolyl group, isoquinolyl group, phthalazinyl group, Quinoxalinyl group, quinazolinyl group, carbazolyl group, acridinyl group, phenazinyl group, furfuryl group, isothiazolyl group, isoxazolyl group, furazanyl group, phenoxazinyl group, benzothiazolyl group, benzoxazolyl group, benzimidazolyl group, 2-methylpyridyl group, 3 -A cyanopyridyl group and the like.

  Mono- or di-substituted amino groups include methylamino, dimethylamino, ethylamino, diethylamino, dipropylamino, dibutylamino, diphenylamino, bis (acetoxymethyl) amino, bis (acetoxy) And ethyl) amino group, bis (acetoxypropyl) amino group, bis (acetoxybutyl) amino group, and dibenzylamino group.

  Substituted or unsubstituted alkyl groups include methyl, ethyl, propyl, butyl, sec-butyl, tert-butyl, pentyl, hexyl, 2-ethylhexyl, heptyl, octyl, isooctyl , Stearyl group, trichloromethyl group, trifluoromethyl group, cyclopropyl group, cyclohexyl group, 1,3-cyclohexadienyl group, 2-cyclopenten-1-yl group, 2,4-cyclopentadiene-1-ylidenyl group, etc. There is.

  Examples of substituted or unsubstituted alkoxy groups include methoxy, ethoxy, propoxy, n-butoxy, sec-butoxy, tert-butoxy, pentyloxy, hexyloxy, 2-ethylhexyloxy, stearyloxy Group, trifluoromethoxy group and the like.

  Examples of the substituted or unsubstituted thioalkoxy group include a methylthio group, an ethylthio group, a propylthio group, a butylthio group, a sec-butylthio group, a tert-butylthio group, a pentylthio group, a hexylthio group, a heptylthio group, and an octylthio group.

Examples of the substituted or unsubstituted aryloxy group include a phenoxy group, a p-tert-butylphenoxy group, and a 3-fluorophenoxy group.
Examples of the substituted or unsubstituted arylthio group include a phenylthio group and a 3-fluorophenylthio group.

  Preferred substituents are a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, or an alkoxy group. Further, adjacent substituents form an aliphatic, carbocyclic aromatic, heterocyclic aromatic or heterocyclic ring which may contain a 5- to 7-membered oxygen atom, nitrogen atom, sulfur atom, etc. It may also have a substituent at any position of these rings.

The copolymer of the unit represented by the general formula [1] of the present invention and the unit having an amino group may be a random, block, or graft copolymer, and has an intermediate structure thereof. It may be a polymer having, for example, a random copolymer having block properties.
The copolymer of the unit represented by the general formula [1] and the unit having an amino group of the present invention is further co-polymerized with styrene and its derivatives, acrylic acid and its derivatives, maleic acid and its derivatives, organic acid vinyl ester and the like. It may be a polymer.

  The weight average molecular weight of the organic electroluminescent device material of the present invention is not particularly limited considering the heat resistance and stability of the thin film state. For example, it is 1000 to 1000000 in terms of polystyrene by gel permeation chromatography measurement method, particularly 3000 to 3000. It is preferably 500,000.

B in the general formula [1] of the present invention is selected from the group consisting of a direct bond, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. This is a divalent organic residue. When the arylene group or heteroarylene group has a substituent, the substituents may be combined to form a new ring.
Although the structural example of the unit used for a polymer is specifically shown in Table 1, the polymer of this invention is not limited to the following representative examples. Table 1 shows only the structure of each unit monomer, and does not show its polymerization form. Moreover,% in a table | surface represents mol%.

The organic electroluminescent element material used in the present invention may be used alone or in combination with other organic materials or inorganic materials. The organic material used in combination may be a low molecular organic material or a high molecular organic material. Moreover, it is also possible to use it by laminating and coating with other polymer organic materials. Furthermore, it can be used by mixing with a low molecular weight compound or by laminating. In this case, the low molecular weight compound may be mixed with a polymer binder and applied, or may be laminated by a method such as vacuum deposition or sputtering. However, each hole injection layer and each light emitting layer are preferably formed by an inkjet method, and more preferably, a hole blocking layer or an electron transport layer is formed by a vacuum deposition method. Further preferably, the hole blocking layer and the electron transport layer are formed by a vacuum deposition method.
Hereinafter, although the specific example of the organic electroluminescent element material of this invention is shown, they do not limit this invention.

  The light emitting materials include those that emit light from singlet excitons, those that emit light from triplet excitons, and those that emit light from both, and any of these light emitting materials can be used in the organic electroluminescence device of the present invention. It is. As the light-emitting material or dopant material that can be used in the present invention, polyalkylfluorene derivatives, polyphenylene derivatives, polyphenylene vinylene derivatives, polythiophene derivatives, and other light-emitting polymers can be used. In addition, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bis Benzoxazoline, bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazole chelating oxinoid compound, Examples include, but are not limited to, quinacridone, rubrene, and fluorescent dyes for dye laser and sensitization. Not shall.

As the light emitting material or dopant material that can be used in the present invention, a light emitting material capable of emitting light from triplet excitons is particularly preferable. Examples of luminescent materials that can emit light from triplet excitons include triplet luminescent metal complexes, such as the iridium complex Ir (ppy) ₃ (Tris-Ortho-Metalated Complex of Iridium (III) with 2-Phenylpyridine). Are known. The green light emitting device using Ir (ppy) ₃ achieves an external quantum yield of 8%, exceeding the external quantum yield of 5%, which was previously considered the limit of organic electroluminescent devices (Applied Physics Letters 75 , 4 (1999)). Other Ir complex compounds and metal coordination porphyrin compounds can be used with the organic electroluminescent material of the present invention, but are not limited thereto.

  If necessary, a hole injection material or an electron injection material can be further used for the light emitting layer. The organic electroluminescent element can prevent a decrease in luminance and lifetime due to quenching by adopting a multilayer structure. If necessary, a light emitting material, a dopant material, a hole injection material, and an electron injection material can be used in combination. Further, with the dopant material, it is possible to improve light emission luminance and light emission efficiency and to obtain red or blue light emission. Moreover, the hole injection zone, the light emitting layer, and the electron injection zone may each be formed with a layer configuration of two or more layers. In that case, in the case of the hole injection zone, the layer that injects holes from the electrode is a hole injection layer, and the layer that receives holes from the hole injection layer and transports holes to the light emitting layer is a hole transport layer. Call. Similarly, in the case of an electron injection zone, a layer for injecting electrons from an electrode is referred to as an electron injection layer, and a layer for receiving electrons from the electron injection layer and transporting electrons to a light emitting layer is referred to as an electron transport layer. Each of these layers is selected and used depending on factors such as the energy level of the material, heat resistance, and adhesion to the organic layer or metal electrode.

  As a hole injection material, it has the ability to transport holes, has a hole injection effect from the anode, an excellent hole injection effect for the light emitting layer or light emitting material, and excitons generated in the light emitting layer. Examples thereof include a compound that prevents movement to an electron injection zone or an electron injection material and has an excellent thin film forming ability. Specifically, PEDOT, phthalocyanine derivative, naphthalocyanine derivative, porphyrin derivative, oxazole, oxadiazole, triazole, imidazole, imidazolone, imidazolethione, pyrazoline, pyrazolone, tetrahydroimidazole, hydrazone, acyl hydrazone, polyarylalkane, stilbene, Examples include but are not limited to butadiene, benzidine type triphenylamine, styrylamine type triphenylamine, diamine type triphenylamine, and their derivatives, and polymer materials such as polyvinylcarbazole, polysilane, and conductive polymers. Is not to be done.

  As an electron injection material, it has the ability to transport electrons, has a hole injection effect from the cathode, and an excellent electron injection effect for the light-emitting layer or light-emitting material, and hole injection of excitons generated in the light-emitting layer Examples thereof include compounds that prevent migration to the zone and have an excellent thin film forming ability. For example, there are fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, oxazole, oxadiazole, triazole, imidazole, perylenetetracarboxylic acid, fluorenylidenemethane, anthraquinodimethane, anthrone, and their derivatives. However, it is not limited to these. Further, it can be sensitized by adding an electron accepting substance to the hole injecting material and an electron donating substance to the electron injecting material.

  As a method of forming the organic compound thin film used in the present invention, it is preferable to form each hole injection layer and each light emitting layer by an ink jet method. Solvents for this ink jet method include organic halogen solvents such as dichloroethane, dichloromethane and chloroform, ether solvents such as tetrahydrofuran and 1.4-dioxane, aromatic hydrocarbon solvents such as toluene and xylene, dimethylformamide, dimethylacetamide and the like. Amide solvents, ester solvents such as ethyl acetate and butyl acetate, or a mixed solvent thereof may be used. Although it depends on the structure and molecular weight of the polymer, the film is usually formed using a solution of 0.01 to 10% by weight, preferably 0.1 to 5% by weight, of a solvent.

As the conductive material used for the anode of the organic electroluminescence device, a material having a work function larger than 4 eV is preferable, and carbon, aluminum, cesium, vanadium, iron, cobalt, nickel, tungsten, silver, gold, platinum Further, palladium, etc. and alloys thereof, ITO substrate, metal oxide such as tin oxide and indium oxide called NESA substrate, and organic conductive resin such as polythiophene and polypyrrole are used.
As the conductive material used for the cathode, those having a work function smaller than 4.0 eV are preferable, such as magnesium, barium, calcium, cesium, tin, lead, titanium, yttrium, lithium, ruthenium, manganese, and the like. However, it is not limited to these.

  The cathode is preferably formed with a thin film transistor for driving each pixel. If necessary, the anode and the cathode may be formed of two or more layers.

The organic electroluminescent element of the present invention can be applied to flat panel displays such as wall-mounted televisions, flat light emitters, light sources such as copiers and printers, light sources such as liquid crystal displays and instruments, display boards, and indicator lights. And its industrial value is very large.

Examples of the present invention will be described below, but the present invention is not limited to the examples. In the examples, parts and% represent parts by weight and% by weight. Moreover, the weight average molecular weight of the polymer was measured by GPC (polystyrene conversion).
Hereinafter, the present invention will be described in more detail based on examples. In the description, parts represent parts by weight and% represents% by weight.
Production Example 1
(Synthesis of IPDI adduct)
After heating 222 parts of isophorone diisocyanate (IPDI) to 80 ° C. in a 1 L four-necked flask in a nitrogen stream, 116 parts of 2-hydroxyethyl acrylate and 0.13 part of hydroquinone were added dropwise over 2 hours, and then at 80 ° C. The mixture was reacted for 3 hours to obtain a compound having a liquid isocyanate group and one vinyl group (IPDI adduct molecular weight 338).

(Synthesis of Polymer A1)
4-perfluorooctylethyl methacrylate 20 parts, 2-hydroxyethyl (meth) acrylate 40 parts, butyl (meth) acrylate 40 parts, methyl ethyl ketone (MEK) 200 parts with a cooling tube, a stirrer, and a thermometer Charge to a flask, raise the temperature to 80 ° C. while stirring under a nitrogen stream, add 1.6 parts of azobisisobutyronitrile, conduct a polymerization reaction for 2 hours, and further add 0.4 part of azobisisobutyronitrile. In addition, polymerization was carried out for 2 hours. Next, 104 parts of IPDI adduct (a ratio in which the number of isocyanate groups and the number of hydroxyl groups are equal) and 1 part of tin octylate dissolved in 20 parts of methyl ethyl ketone (MEK) are dropped in about 10 minutes. The reaction was carried out at 2 ° C for 2 hours.
Cyclohexanone was added to the solution so that the non-volatile content was 10% to obtain a polymer A1 solution. The weight average molecular weight of the polymer A1 was about 20,000.

Production Example 2
Synthesis method of P-1

Under a dry nitrogen stream, p-bromoiodobenzene (15.4 g, 54.4 mmol), carbazole (10.0 g, 59.8 mmol), Cu powder 0.3 g, K ₂ CO ₃ (7.9 g, 57.0 mmol) and 1,3- 100 ml of dimethylimidazilijinone was added and stirred at 190 ° C. for 18 hours. The reaction solution was poured into 700 ml of water, and the precipitate was filtered and dried at 70 ° C. to obtain a crude product. After that, it was isolated and purified by silica gel column chromatography to obtain compound (5). Yield 55%. The structure of this compound (5) was determined by elemental analysis, mass spectrometry, infrared absorption spectrum, NMR spectrum and the like.

A condenser tube was attached to the four-necked flask, and THF (30 ml) was added to Compound (5) (2.5 g, 7.8 mmol) and 4-vinylphenylboronic acid (1.72 g, 11.6 mmol) and stirred. 2M K ₂ CO ₃ aq (30 ml) was added thereto. Tetrakistriphenylphosphine palladium (0) (Pd (PPh ₃ )) (200 mg, 174 μmol) and THF (10 ml) were added, and the mixture was cyclized at 80 ° C. for 24 hours. Purification by column chromatography and methanol reprecipitation gave compound (6). The yield was 62%. The structure of this compound (6) was determined by elemental analysis, mass spectrometry, infrared absorption spectrum, NMR spectrum and the like.

Attach a condenser tube to a four-necked flask and add THF (50 ml) to 4-bromo-N, N-ditolylamine (6.79 g, 19.27 mmol) and 4-vinylphenylboronic acid (3.0 g, 20.27 mmol) and stir. did. 2M K ₂ CO ₃ aq (50 ml) was added thereto. Tetrakistriphenylphosphine palladium (0) (Pd (PPh ₃ )) (351 mg, 304 μmol) and THF (10 ml) were added, and the mixture was cyclized at 80 ° C. for 24 hours. Purification by column chromatography and methanol reprecipitation gave compound (7). The yield was 65%. The structure of this compound (7) was determined by elemental analysis, mass spectrometry, infrared absorption spectrum, NMR spectrum and the like.

  0.8g and 0.2g of the compound (6) and the compound (7) were put in a Schlenk type flask, respectively, and vacuum degassing was repeated several times. Azobisisobutyronitrile (0.02 g) and THF (2.7 ml) were added thereto, and the mixture was stirred at 70 ° C. for 9 hours. The reaction liquid has become viscous. Purification was performed by methanol reprecipitation. The yield was 90%. The obtained white powder was subjected to elemental analysis, GPC analysis, infrared absorption spectrum, NMR spectrum and the like, and as a result, it was found to be compound P-1.

Production Example 3
Synthesis method of P-10

  0.34 g, 0.45 g, and 0.1 g of compound (8), compound (6), and compound (7) were placed in a Schlenk flask, respectively, and vacuum degassing was repeated several times. Azobisisobutyronitrile (0.02 g) and THF (2.7 ml) were added thereto, and the mixture was stirred at 70 ° C. for 9 hours. The reaction liquid has become viscous. Purification was performed by methanol reprecipitation. The yield was 90%. The obtained white powder was subjected to elemental analysis, GPC analysis, infrared absorption spectrum, NMR spectrum and the like, and as a result, it was found to be compound P-10.

    Examples of using the organic electroluminescent element material of the present invention are specifically shown below, but the present invention is not limited thereto. Compound (1) and compound (2) were synthesized according to the method described in the literature (Journal of the Chemical Society of Japan, 11, 1540 (1991)).

  The polymerization mode of the non-conjugated main chain skeleton monomer in forming the copolymer is to perform copolymer formation by vinyl polymerization such as radical polymerization, cationic polymerization, anionic polymerization, condensation polymerization, ring-opening polymerization, and various polymerization reactions. The polymerization method is not particularly limited, but in the present invention, a copolymer formation reaction by polymerization of a vinyl polymerization monomer is particularly preferable.

    Examples of using the organic electroluminescent element material of the present invention are specifically shown below, but the present invention is not limited thereto.

Example 1
As shown in FIG. 1, an ITO transparent pixel electrode 3 having a 100 μm pitch and a 0.1 μm thick pattern was formed on a 100 mm × 100 mm, 1.1 mm thick glass substrate 1 by photolithography. A partition wall 9 was formed between the ITO patterns by photolithography.
This partition wall 9 was uniformly mixed with 7.5 parts of carbon black ("Pritex 75" manufactured by Degussa), 0.5 part of a dispersant, 27.0 parts of a polymer C solution, and 32.0 parts of cyclohexanone. Were dispersed for 5 hours with a sand mill to prepare a black dispersion. To the obtained black dispersion, 2.0 parts of the polymer A1 solution, 5.4 parts of trimethylolpropane triacrylate (“NK ester ATMPT” manufactured by Shin-Nakamura Chemical Co., Ltd.), photoinitiator (“Irgacure 907” manufactured by Ciba Geigy Co., Ltd.) )) 0.6 parts, a mixture of sensitizer ("EAB-F" manufactured by Hodogaya Chemical Co., Ltd.) 0.4 parts, and cyclohexanone 24.6 parts were stirred and mixed uniformly, and then filtered through a 1 µm filter to obtain an alkali. A development type black photosensitive resist (compartment composition) was prepared, and an alkali development type black photosensitive resist obtained with a spin coater was applied on the glass substrate so that the dry film thickness was 1.0 μm. And dried at 70 ° C. for 20 minutes.
Next, using an ultra-high pressure mercury lamp, after irradiating UV light with a light quantity of 200 mJ from the resist coating surface side through a mask film, this coated substrate is immersed in a 2% aqueous sodium carbonate solution for about 20 seconds to develop, Then, it heated at 180 degreeC for 1 hour, and produced the substrate for pixel formation. The width of the partition wall obtained by this method was 20 μm, and the thickness was 1.0 μm. Next, PEDOT / PSS (polypropylene), which is the hole injection layer 5, is used in the region (the concave portion surrounded by the convex portion) divided by the partition wall of the obtained pixel forming substrate using an ink jet recording apparatus. (3,4-Ethylenedioxy) -2,5-thiophene / polystyrenesulfonic acid) was discharged and dried to a thickness of 50 nm. Next, 50 nm thick coloring layers 6, 7, and 8 were formed using a light emitting material that developed red, green, and blue color dissolved in toluene using an ink jet recording apparatus. The compound (9) was used as the red light emitting material, the compound (10) was used as the green light emitting material, the compound (11) was used as the blue light emitting material, and the compound (P-1) was used as the host material.
Next, the compound (1) is vacuum-deposited with a film thickness of 7 nm to form the hole blocking layer 10, and further an aluminum quinolinol complex is formed with a film thickness of 50 nm by a vacuum vapor deposition method, and the electron injection layer 11 is formed. Formed. Next, the anode 12 was formed by depositing LiF with a thickness of 1 nm by a vacuum deposition method, and finally with Al with a thickness of 200 nm, a full-color organic electroluminescence device (1) was produced.

Compound (9)

Compound (10)

Compound (11)

Example 2
As shown in FIG. 1, an ITO transparent pixel electrode 3 was formed on a glass substrate 1 with a pattern of 100 μm pitch and 0.1 μm thickness by photolithography. A partition wall 9 was formed between the ITO patterns by the method of Example 1. The partition wall had a width of 20 μm and a thickness of 1.0 μm. Next, PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrene sulfonic acid), which is the hole injection layer 5, is ejected to a thickness of 50 nm by an inkjet printing apparatus. Dried. Next, 50 nm thick coloring layers 6, 7, and 8 were formed using a light emitting material that developed red, green, and blue color dissolved in toluene using an ink jet recording apparatus. The compound (9) was used as the red light emitting material, the compound (10) was used as the green light emitting material, the compound (11) was used as the blue light emitting material, and the compound (P-10) was used as the host material.
Next, the compound (1) is vacuum-deposited with a film thickness of 7 nm to form the hole blocking layer 10, and an aluminum quinolinol complex is formed into a film with a film thickness of 50 nm by a vacuum vapor deposition method. Formed. Next, the anode 12 was formed by depositing LiF with a film thickness of 1 nm by a vacuum deposition method, and finally, Al was formed with a film thickness of 200 nm to produce a full-color organic electroluminescent device (2).

Comparative Example 1
As shown in FIG. 2, an ITO transparent pixel electrode 3 was formed on a glass substrate 1 with a pattern of 100 μm pitch and 0.1 μm thickness by photolithography. A partition wall 9 was formed between the ITO patterns by the method of Example 1. The partition wall had a width of 20 μm and a thickness of 1.0 μm. Next, PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrenesulfonic acid), which is the hole injection layer 5, is formed to a thickness of 50 nm using an ink jet recording apparatus. It was discharged and dried as follows. Next, 50 nm thick coloring layers 6, 7, and 8 were formed using a light emitting material that developed red, green, and blue color dissolved in toluene using an ink jet recording apparatus. The compound (9) was used as the red light emitting material, the compound (10) was used as the green light emitting material, the compound (11) was used as the blue light emitting material, and the compound (P-1) was used as the host material.
Next, the anode 12 was formed by depositing Ca with a thickness of 20 nm by a vacuum deposition method, and finally depositing Al with a thickness of 200 nm, thereby producing a full-color organic electroluminescent device (3).

The EL characteristics of Examples 1 and 2 and Comparative Example 1 are shown in Table 3.

  As can be seen from Table 2, the organic electroluminescent element (element 1) using the hole blocking layer and electron transport layer of the present invention and the organic electroluminescent element not using these (element 3) are compared with the former, which has a lower driving voltage. It can be confirmed that the light emission is highly efficient.

First Embodiment of Element Structure of the Present Invention Second Embodiment of Device Structure of Comparative Example

Explanation of symbols

1 is glass substrate 3 is cathode (ITO)
5, hole injection layer 6, red light emitting layer 7, green light emitting layer 8, blue light emitting layer 9, partition wall 10, hole blocking layer 11, electron transport layer 12, anode

Claims (8)

Each of the positive electrodes for red, green, and blue is formed on a transparent substrate having partition walls that divide the red, green, and blue light emitting regions and transparent pixel electrodes for red, green, and blue. A hole injection layer is formed,
On each hole injection layer, each light emitting layer for red, green, and blue is formed,
A hole blocking layer is formed on the light emitting layer,
An electron transport layer is formed on the hole blocking layer,
A full-color organic electroluminescent device, wherein an anode is formed on the electron transport layer. 2. The full-color organic electroluminescence device according to claim 1, wherein the partition wall comprises a vinyl polymer having a fluoroalkyl group. 3. The full color according to claim 1, wherein the hole injection layer forming material for forming the hole injection layer is PEDOT / PSS (poly (3,4-ethylenedioxy) -2,5-thiophene / polystyrenesulfonic acid). Organic electroluminescent device. At least one of the light emitting layer forming materials forming the light emitting layers for red, green, and blue,
A copolymer of a unit represented by the following general formula [1] and a unit having an amino group; and
The full-color organic electroluminescent element according to claim 1, comprising a luminescent material.
General formula [1]

[Wherein A represents a non-conjugated trivalent organic residue, B represents a direct bond, or a substituted or unsubstituted arylene group, a substituted or unsubstituted heteroarylene group, and a substituted or unsubstituted ethenylene group. Represents one or more divalent organic residues selected from the group consisting of:
C represents a monovalent organic residue represented by the following general formula [2] or general formula [3]. ]
General formula [2]

[Wherein R ^{1 to} R ⁷ each independently represents a bonding site, a hydrogen atom or a substituent,
X is a direct bond, —O—, —S—, —Se—, —NH—, —NR ⁸ — (R ⁸ represents an alkyl group or an aryl group), —S (═O) ₂ —, — ( CO) -, - COO -, - OCO -, - CH 2 - indicates,
R ^{1 to} R ⁸ may be bonded to each other to form an aryl ring, and further the aryl ring may have a substituent. ]
General formula [3]

[Wherein R ^{9 to} R ¹⁷ each independently represent a bonding site, a hydrogen atom or a substituent. ] The full-color organic electroluminescent element according to claim 1, wherein the hole blocking layer forming material for forming the hole blocking layer is an oxadiazole derivative. 6. The full color organic electroluminescence device according to claim 1, wherein the electron transport material forming the electron transport layer is an aluminum quinoline complex (Alq ₃ ). A method for producing a full-color organic electroluminescent device, wherein each hole injection layer and each light-emitting layer of the full-color organic electroluminescent device according to claim 1 are formed by an ink jet method. 8. The method for producing a full-color organic electroluminescent device according to claim 7, wherein the hole blocking layer and / or the electron transport layer is formed by a vacuum deposition method.

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