JPH08259938A - Luminous display element and its production - Google Patents

Abstract

PURPOSE: To produce a luminous display element the electrodes of which can be processed into a display pattern without complexity, in which the electrode parts connected to the display pattern are inconspicuous and which can display a complicated pattern by composing the luminous layer of a specified compound. CONSTITUTION: A luminous display element provided with transparent bases with transparent electrodes and metallic electrodes formed on the transparent electrodes, wherein the luminous layer is made of a polysilane derivative the main chain of which partially consists of anthrylene groups and which comprises structural units A represented by formula I (wherein R<1> and R<2> are each 1-6 C linear alkyl, provided that the total number of carbon atoms of R<1> and R<2> is within 8) and structural units B represented by 34 formula II (wherein R<3> and R<4> are each 1-6 C alkyl, aryl or aralkyl) and has a molar ratio structural units A/ structural units B of 0.5-10 and a weight-average molecular weight of 1000-1000000. The hole transport function of this element can be eliminated by irradiating it with ultraviolet rays. Therefore, the pattern not irradiated with ultraviolet rays forms a pattern which does not luminesce under applied voltage, whereas the pattern not irradiated with ultraviolet rays forms a pattern which luminesces under applied voltage.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a light emitting display device and a method of manufacturing the same, more specifically, there is no complexity of processing electrodes into a display pattern, and an electrode portion connecting a predetermined display pattern is not conspicuous. The present invention relates to a light emitting display device capable of displaying a complicated pattern and a manufacturing method thereof. INDUSTRIAL APPLICABILITY The present invention is widely used for an organic EL device having an organic light emitting material as a light emitting layer, a light emitting diode type light emitting display device, and the like.

[0002]

2. Description of the Related Art An organic EL element uses an organic material as a light emitting material and electrically emits it, and is expected to be a new type of light emitting display element that can be made large in area and thinned, and earnestly studied. Development is in progress. A typical example of such an organic EL element is Applied Physics Letters (Applied Physics).
Letters), Vol. 51, No. 12, pp. 913 to 915 (1987). That is,
Aluminum quinolinoleate complex (hereinafter,
It is called "Alq3". ), A diamine derivative is used as the hole transport auxiliary electrode material, and a glass substrate / transparent electrode (ITO) / diamine derivative is formed on a glass substrate coated with an indium tin oxide alloy (hereinafter, also referred to as “ITO”) as a transparent electrode. / Alq3 / magnesium aluminum alloy electrode formed by laminating in this order (metal electrode), an ITO electrode negative, voltage application pressure to the to the magnesium aluminum alloy electrode to a positive result, a layer of Alq3 emits light, from the glass substrate side The luminescence can be observed.

As another example, Applied Physics, Vol. 61, No. 10, pp. 1044 to 1047 (1992), coumarin 6 as a light emitting material and oxadiazole derivative as an electron transport auxiliary material ( Bu-PBD) and a hole transport auxiliary material, poly (N-vinylcarbazole) (PVK), are mixed to form a material for the light emitting layer, and a glass substrate is coated with indium tin oxide alloy (ITO) as a transparent electrode. Coumarin 6 emits light when a voltage is applied with the ITO electrode minus and the magnesium aluminum alloy electrode plus, in the order of substrate / transparent electrode (ITO) / mixed light-emitting layer material / magnesium-aluminum alloy electrode. There is. The organic EL element as shown above is obtained by sandwiching an organic light emitting material together with a material for assisting the transport of electrons and holes between a transparent electrode such as ITO which is a positive electrode and an electrode of aluminum or an aluminum-magnesium alloy which is a negative electrode. Then, the structure is such that light emitted from the light emitting material is taken out from the glass substrate side to which the transparent electrode is applied.

[0004]

The above-mentioned conventional organic EL device is expected to be a large-sized thin film display device.
To make a display element that displays and transmits information such as characters,
Like a display element using a conventional inorganic light emitting diode,
Light emitting element segments are arranged in an XY matrix, and wiring is performed to realize the light emission of the character pattern, or the electrode shape of the light emitting segment is processed into the character pattern in advance to realize the light emission of the character pattern. I had to resort to the complicated method of doing.

The present inventors have conducted intensive studies on a method for easily manufacturing a light emitting display device for transmitting character information, and as a result, have found a material and a manufacturing method which meet such an object and completed the present invention. did. The present invention provides a light-emitting display element capable of displaying a complicated pattern without the complexity of processing electrodes into a display pattern, the electrode portion connecting a predetermined display pattern is not conspicuous, and a method for manufacturing the same. With the goal.

[0006]

A light emitting display device of the first invention comprises a transparent substrate with a transparent electrode, a light emitting layer formed on the transparent electrode, and a metal electrode formed on the light emitting layer. It is characterized in that the light emitting layer is composed of a polysilane derivative containing an anthrylene group in a part of the main chain as shown in the claims. The light emitting display device of the second invention is such that the light emitting layer constituting the light emitting display device of the first invention is irradiated with ultraviolet rays in a predetermined irradiation pattern, and the irradiation pattern is the ultraviolet irradiation and the voltage is applied. With a predetermined non-emission pattern that does not emit light,
It is characterized in that a non-irradiation pattern in which the ultraviolet ray irradiation is not performed and a predetermined light emission pattern which emits light when a voltage is applied are directly formed in the light emitting layer.

A method of manufacturing a light emitting display device according to the third aspect of the present invention comprises:
On the transparent electrode of the transparent substrate with a transparent electrode, a light emitting layer composed of a polysilane derivative containing an anthrylene group in a part of the main chain is formed on the transparent electrode, and then the transparent electrode / light emitting layer is attached. From one surface of the transparent substrate, the light emitting layer is irradiated with ultraviolet rays so as to have a predetermined irradiation pattern, and a predetermined non-light emitting pattern which is an irradiation pattern subjected to the ultraviolet irradiation and does not emit light by voltage application,
It is characterized in that a non-irradiation pattern in which the ultraviolet irradiation is not performed and a predetermined light emission pattern which emits light by applying a voltage are directly formed in the light emitting layer, and then a metal electrode is formed on the light emitting layer. .

A method of manufacturing a light emitting display device according to the fourth invention is
A light emitting layer composed of a polysilane derivative containing an anthrylene group in a part of its main chain as shown in claim 1 is formed on the transparent electrode of a transparent substrate with a transparent electrode, and then a metal electrode is formed on the light emitting layer. Then, from the transparent substrate side of the transparent electrode / light emitting layer / metal electrode-attached transparent substrate, the light emitting layer was irradiated with ultraviolet rays so as to have a predetermined irradiation pattern, and the ultraviolet rays were irradiated. A predetermined non-light emitting pattern that is an irradiation pattern and does not emit light when a voltage is applied, and a predetermined light emitting pattern that is a non-irradiation pattern that is not irradiated by ultraviolet rays and that emits light when a voltage is applied are formed directly in the light emitting layer. Is characterized by.

The above polysilane derivative used in the present invention
In the structural unit A, which is one of the structural units of¹as well as
R²Are the same or different straight-chain alkanes having 1 to 6 carbon atoms.
Is a kill group and R¹And R²The total number of carbons in
It is within. Preferred R¹Or R²Has 1 to 4 carbon atoms
A linear alkyl group of¹Over
And R²Either of these is a methyl group. R¹Or R²
Is branched or R ¹Or R²Carbon number of exceeds 6
Or R¹And R²If the total number of carbons in
Due to the steric hindrance, the raw material is represented by the following formula [1].
And a compound represented by the following formula [2]:
Reactivity in the presence of liquid metals or alkaline earth metals
Lowers the yield of the polysilane derivative of the present invention.
It has a long industrial disadvantage. R¹And R²As concrete
Specifically, methyl group, ethyl group, n-propyl group, n-butyl group
Group, n-pentyl group and n-hexyl group.
It

[0010]

Embedded image

[0011]

[Chemical 4]

In the structural unit B which is the other structural unit of the polysilane derivative used in the present invention, R ³ and R ⁴
May be the same or different and have 1 to 10 carbon atoms.
Is a linear or branched alkyl group, aryl group or aralkyl group. The alkyl group preferably has 1 to 6 carbon atoms.
Is a linear or branched alkyl group, and specific examples thereof include a methyl group, an n-propyl group, an i-propyl group, an n-butyl group, and a sec-butyl group. In addition, examples of the alkylene group in the aralkyl group include a methylene group and an ethylene group. The aryl group and the aralkyl group each have a substituent that does not react with a silane compound represented by the formula [2] and an alkali metal or an alkaline earth metal in the polymerization described below for producing the polysilane derivative,
Those having on the aromatic ring are also included, and examples of such a substituent include a linear or branched alkyl group having 1 to 6 carbon atoms, preferably 1 to 4 carbon atoms (eg, methyl group, ethyl group, n-propyl group). Group, i-propyl group, etc.), carbon number 1 to
6, preferably 1 to 4 linear or branched alkoxy groups (eg, methoxy group, ethoxy group, etc.) and the like.
Specific examples of the aryl group include a phenyl group, a tolyl group,
Examples thereof include a xylyl group, a mesityl group, a cumenyl group, a methoxyphenyl group, an ethoxyphenyl group and a naphthyl group. Further, as the aralkyl group, specifically, a benzyl group, a tolylmethyl group, a xylylmethyl group, a cumenylmethyl group, a phenethyl group, a diphenylmethyl group, a trityl group, a tritolylmethyl group, a tri (dimethylphenyl) methyl group, a methoxyphenylmethyl group, Examples thereof include a diethoxyphenylmethyl group.

The combination of R ³ and R ⁴ is not particularly limited, but any one of them is a linear or branched alkyl group having 1 to 6 carbon atoms, more preferably 1 to 4 carbon atoms, and particularly a methyl group, and the other is It is preferably a linear or branched alkyl group having 1 to 6 carbon atoms, particularly 1 to 4 carbon atoms, an aryl group or an aralkyl group. A particularly preferred combination of R ³ and R ^{4 is} a combination of one of which is a methyl group and the other of which is a linear alkyl group having 1 to 4 carbon atoms or an aryl group.

The molar ratio (%) of structural unit A / structural unit B constituting the polysilane derivative used in the present invention is 0.5.
-10%. When the molar ratio (%) is less than 0.5%, the proportion of anthrylene group becomes too small, light emission in the visible region does not occur or is too weak, and the light emission efficiency becomes poor. If it is more than 10%, the number of repeating structural units B is not sufficient, and the function as polysilane, for example, the energy band and hole (hole) transportability cannot be obtained. Sufficient energy band for polysilane (σ-σ band)
To have a hole transporting property and to be conjugated with π electrons of the anthrylene moiety, the molar ratio (%) is preferably 5% or less, and sufficient visible light emission function is obtained. It is preferable that the molar ratio (%) is 1% or more. The molar ratio (%) of the structural units means the molar ratio (%) obtained by the following method.

This is calculated by the following procedures. The standard absorbance for anthracene is determined as follows. A standard solution in which a predetermined molar amount of anthracene is dissolved in a chloroform solvent is prepared, and the molar absorbance at λmax of UV absorption is measured, and this is used as the standard absorbance. The number of moles of structural unit A in the desired product is determined as follows. Target product (polymer) with the same solvent as the standard solution and the same molar concentration (converted from the number average molecular weight of the entire polymer)
A solution is prepared, and the molar absorptivity of λmax attributed to anthracene in UV absorption is measured and divided by the standard absorbance described above to obtain the number of moles of the anthrylene group in the target product. This value is equal to the number of moles of structural unit A.

The weight of the structural unit A in the desired product is calculated by the following formula. Weight of structural unit A = (molecular weight of structural unit A obtained by subtracting halogen atoms X ¹ and X ² from bissilylanthracene compound [1] used as a raw material) × (number of moles of structural unit A) Structure in target product The number of moles of unit B is calculated by the following formula. Number of moles of structural unit B = (weight of target product used for measurement of molar absorbance−weight of structural unit A) / (structure obtained by subtracting halogen atoms X ³ and X ⁴ from silane compound [2] used as a raw material Molecular Weight of Unit B) The molar ratio (%) of structural unit A / structural unit B in the target product is calculated by the following formula. Structural unit A / structural unit B [molar ratio (%)] = (number of moles of structural unit A determined by) × 100 / (number of moles of structural unit B determined by)

The polysilane derivative has a weight average molecular weight of 1,000 to 1,000,000, preferably 2,000.
It is 0 to 500,000. Weight average molecular weight is 100
When it is less than 0, it is difficult to isolate and purify the polymer, and the produced polymer is a polymer that is difficult to mold and process.
On the other hand, if it exceeds 1,000,000, when it is dissolved in a solvent, the viscosity becomes too high, and the film forming performance by spin coating, casting method or the like deteriorates. The weight average molecular weight means the weight average molecular weight determined by the GPC method (in terms of polystyrene). The polysilane derivative is used in various organic solvents, especially aprotic organic solvents such as benzene, toluene, xylene, n-hexane and n-hexane.
It dissolves in octane, tetrahydrofuran, etc.

The polysilane derivative is represented by the above formula [1] and the 9,10-bis (dialkylhalosilyl) anthracene represented by the above formula [1] (hereinafter referred to as the bissilylanthracene compound [1]). Can be obtained by reacting a silane compound (hereinafter referred to as silane compound [2]) in the presence of an alkali metal or an alkaline earth metal in an inert solvent.

The above bissilylanthracene compound [1]
Is a novel compound, and its manufacturing method will be described later. R ¹ and R ² of this bissilylanthracene compound [1] are as described for the above polysilane derivative. Also X
^The halogen atom represented by ¹ or X ² is preferably a chlorine atom or a bromine atom, and particularly preferably a chlorine atom.

The above bissilylanthracene compound [1]
As preferred examples of 9,10-bis (dimethylchlorosilyl) anthracene, 9,10-bis (diethylchlorosilyl) anthracene, 9,10-bis (di-n-propylchlorosilyl) anthracene, 9,10-bis ( Di-n-butylchlorosilyl) anthracene, 9,10-bis (methylethylchlorosilyl) anthracene, 9,1
0-bis (methyl n-propylchlorosilyl) anthracene, 9,10-bis (methyl n-butylchlorosilyl) anthracene, 9,10-bis (methyl n-pentylchlorosilyl) anthracene, 9,10-bis (methyl) n-hexylchlorosilyl) anthracene, 9,10
-Bis (ethyl n-propylchlorosilyl) anthracene, 9,10-bis (ethyl n-butylchlorosilyl)
Anthracene, 9,10-bis (ethyl n-pentylchlorosilyl) anthracene, 9,10-bis (ethyl n
-Hexylchlorosilyl) anthracene, 9,10-bis (n-propyl n-butylchlorosilyl) anthracene, 9,10-bis (n-propyl n-pentylchlorosilyl) anthracene, and particularly preferable examples are 9 , 10-bis (dimethylchlorosilyl) anthracene, 9,10-bis (methylethylchlorosilyl) anthracene, 9,10-bis (methyl n-propylchlorosilyl) anthracene, 9,10-bis (methyl n-
Butylchlorosilyl) anthracene, 9,10-bis (methyl n-pentylchlorosilyl) anthracene,
Mention may be made of 9,10-bis (methyl n-hexylchlorosilyl) anthracene.

R ³ and R ⁴ of the silane compound [2] are as described for the polysilane derivative of the present invention. The halogen atom represented by X ³ or X ⁴ is preferably a chlorine atom or a bromine atom, particularly preferably a chlorine atom. Preferred examples of the silane compound [2] include dimethyldichlorosilane, diethyldichlorosilane, dipropyldichlorosilane, dibutyldichlorosilane, dipentyldichlorosilane, dihexyldichlorosilane, methylethyldichlorosilane, methylpropyldichlorosilane, methylbutyldichlorosilane. , Methylpentyldichlorosilane, methylhexyldichlorosilane, ethylpropyldichlorosilane, ethylbutyldichlorosilane, ethylpentyldichlorosilane, ethylhexyldichlorosilane, propylbutyldichlorosilane, methylphenyldichlorosilane, ethylphenyldichlorosilane, methyltolyldichlorosilane, Ethyltolyldichlorosilane, methylxylyldichlorosilane, ethylxylyldichlorosilane, methyl Naphthyl dichlorosilane, methyl Baie emissions Jill dichlorosilane, ethyl benzyl dichlorosilane, include methyl phenethyl dichlorosilane, etc., dimethyldichlorosilane, methyl ethyl dichlorosilane Particularly preferred examples,
Examples thereof include methyl n-propyldichlorosilane, methyl n-butyldichlorosilane, and methylphenyldichlorosilane. The polysilane derivative used in the present invention is obtained by reacting the bissilylanthracene compound [1] with the silane compound [2] in the presence of an alkali metal or an alkaline earth metal, particularly preferably an alkali metal, in an inert solvent. The alkali metal includes lithium, sodium, potassium, and the like. Lithium and sodium are preferable, and sodium is particularly preferable. Magnesium as an alkaline earth metal,
Examples include calcium.

Since the optimum ratio of the bissilylanthracene compound [1] and the silane compound [2] used as the raw materials differs depending on the reactivity of the two raw materials, the molar ratio of structural unit A / structural unit B of the target polysilane derivative. It is desirable to confirm the required amount experimentally after setting (%) before use. The proportion of alkali metal or alkaline earth metal used is preferably 2 to 5 mol based on 1 mol of the total amount of the bissilylanthracene compound [1] and the silane compound [2]. If it is less than 2 moles, the yield of the reaction product is reduced, and if it exceeds 5 moles, the corresponding effect cannot be expected and it is uneconomical, and the amount of excess alkali metal or alkaline earth metal increases. , Then the processing becomes difficult. An aprotic solvent is preferable as the inert solvent, and specifically, benzene, toluene, xylene,
Examples include n-hexane, n-octane, and tetrahydrofuran. The inert solvent is preferably used so that the concentration of the silane compound [2] is 100 mmol / L to 1 mol / L.

The reaction temperature is preferably 0 ° C. or higher and not higher than the boiling point of the reaction solvent. The reaction is preferably carried out under an inert gas atmosphere. The reaction time varies depending on the reaction solvent used and the reaction temperature, but the reaction is usually completed within 24 hours.
After completion of the reaction, the reaction solution is filtered to remove the by-product metal salt, and the filtrate is dropped into a poor solvent such as methanol to precipitate the product, whereby the target polysilane derivative can be obtained. The bissilylanthracene compound [1], which is one of the raw materials for producing the above-mentioned polymer, is also a novel compound, and is represented by the formula [3]

[0024]

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9,10-dilithioanthracene represented by the formula or the formula [4]

[0026]

[Chemical 6]

A Grignard reagent represented by the formula (wherein X ⁵ is a halogen atom), that is, 9,10-dimagnesium halogenoanthracene, and a compound of the formula [5]

[0028]

[Chemical 7]

(In the formula, R ¹ and R ² are the same as above, and X ⁶ is the same as X ¹ or X ² of the compound [1].) By reacting in an active solvent in an inert gas atmosphere, it can be easily obtained in high yield. The halogen atom represented by X ⁵ is preferably a chlorine atom or a bromine atom. The halogen atom represented by X ⁶ is preferably a chlorine atom or a bromine atom,
Particularly preferred is a chlorine atom. An aprotic organic solvent is preferable as the inert solvent, and specific examples thereof include diethyl ether, tetrahydrofuran, n-hexane, and n.
-Octane, n-pentane, benzene, toluene, xylene and the like. The inert solvent has a concentration of 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] of 100 mmol / L.
It is preferable to use it in an amount of about 2 mol / L. Examples of the inert gas include argon and nitrogen. The reaction ratio of dialkyldihalosilane [5] and 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] is 9,10-dilithioanthracene [3] or 9,10 -The dialkyl bahalosilane [5] is preferably 2 to 10 equivalents, more preferably 2 to 6 equivalents, based on the dimagnesium halogenoanthracene [4]. The reaction temperature is preferably -30 to 70 ° C, more preferably 0 to 50 ° C, most preferably 10 to 50 ° C. If the reaction temperature is too low, the yield of the bissilylanthracene compound [1] may decrease. The reaction time varies depending on the reaction temperature, the reaction solvent and the like, but the reaction is usually completed within 24 hours.

When a bissilylanthracene compound [1] in which X ¹ and X ² are different from each other is obtained, for example, X ⁶
A dialkyldihalosilane [5] wherein X is X ¹ and X ⁶ is X
² , using a mixture of dialkyldihalosilanes [5], or reacting both compounds with 9,10-dilithioanthracene [3] or 9,10-dimagnesium halogenoanthracene [4] sequentially at different times, etc. Can be taken. To obtain the produced bissilylanthracene compound [1] from the reaction solution obtained by the above reaction,
A method in which the precipitate of by-produced lithium halide or magnesium halide is removed from the reaction solution by filtration, decantation, etc., the reaction solvent is then distilled off under reduced pressure, and the residue is recrystallized from an inert solvent such as pentane. It may be purified by. The obtained bissilylanthracene compound [1] is a yellow solid. The bissilylanthracene compound [1] does not necessarily have to be purified for the next polymerization, and may be subjected to the polymerization at a stage after the reaction solvent is distilled off under reduced pressure, for example.

Further, dialkyldihalosilane [5] used for the production of bissilylanthracene compound [1]
And the silane compound [2] that reacts with the produced bissilylanthracene compound [1] are the same compound, when the bissilylanthracene compound [1] is produced,
One reaction can be achieved by coexisting an alkali metal or an alkaline earth metal and using the dialkyldihalosilane [5] in a sufficient amount not only for the production of the bissilylanthracene compound [1] but also for the production of the next polymer. In the system, the polysilane derivative used in the present invention can be obtained.

[0032]

The organic EL device (light-emitting display device) having a conventional structure is manufactured by using the above-mentioned light-emitting material used in the present invention. That is, as shown in FIG. 1, a light emitting layer 3 is formed by spin coating this light emitting material on a glass substrate 1 on the surface of which an indium tin oxide alloy (ITO) is applied as a transparent electrode 2. , On this, aluminum (Al)
The electrode 4 was laminated using a vacuum evaporation technique. This light emitting layer 3
The thickness is preferably 50 to 100 nanometers.
When the ITO transparent electrode 2 is made positive and the Al electrode 4 is made negative and a voltage is applied from the lead wires 5a, 5b, a light emitting pattern 32 corresponding to the electrode shape can be observed from the glass substrate 1 side as shown in FIG. In the case of displaying a character pattern or the like by light emission, a method of arranging a large number of light emitting elements of FIG. 1 in a character pattern and connecting electrodes with lead wires or the like can be used.

Still another simple method is to make the shape of the electrode similar to the character pattern beforehand. That is, as shown in FIG. 3, aluminum electrodes are formed in the character pattern 4a. When the lead wire 5b is connected to the character pattern electrode portion 4a and a voltage is applied in the same manner as described above, the light emission of the character pattern 32 can be observed from the glass substrate 1 side as shown in FIG. Similar results can be obtained by forming the ITO electrode having the character pattern. In addition, in the method of forming the electrode pattern,
There are a method of forming the electrode into a character pattern by the photolithography technique, a method of using a vapor deposition mask in which the character pattern is already removed, and the like. The former requires the addition of multiple strokes. In the latter case, it may be difficult to form a complicated character pattern.

On the other hand, the polysilanes are cleaved at the silicon-silicon bond and the silicon oxide is cleaved by the irradiation of light having a characteristic absorption wavelength of the polysilane or less (for example, in the case of poly (methylphenylsilane), irradiation of ultraviolet light of 350 nm or less). It is known that the formation of polysilanes causes the hole transport function of polysilanes to disappear. [References: (1) Synthesis and application of organosilicon polymers, supervised by Hideki Sakurai, published by CMC Co., Ltd.] 128 to 148 (1989), (2) Applied Physics Letters, Volume 55, 2141 (1990)
Year)]. When the light emitting layer having a film thickness of 50 to 100 nanometers is irradiated with ultraviolet rays, an irradiation time of 1 to 5 minutes is appropriate.

Since the luminescent material used in the present invention is the above-mentioned polysilane derivative, the hole transport function disappears when the ultraviolet light of 350 nm or less is similarly irradiated. Therefore, the following experiment was conducted. First, as shown in FIG. 5, the above-mentioned light emitting material is applied onto a glass substrate 1 on the surface of which an indium tin oxide alloy (ITO) is applied as a transparent electrode 2 in accordance with the above-described procedure for manufacturing an organic EL element. The light emitting layer 3 was formed by spin coating. Next, a part of the light emitting layer 3 is covered with a mask 6 and 350 nm
The following ultraviolet light was applied. After that, aluminum (A
l) The electrode 4 was laminated using the vacuum evaporation technique (FIG. 6).
When the ITO transparent electrode 2 is made positive and the Al electrode 4 is made negative and a voltage is applied from a lead wire (not shown), only the non-irradiated portion 32 where the hole transport function has not disappeared by masking at the time of ultraviolet irradiation. (31 illuminated parts)
It was possible to observe luminescence from.

Similarly, as shown in FIG. 7, the light emitting layer 3 and the metal electrode 4 were sequentially formed on the glass substrate 1 with the transparent electrode 2 to produce an organic EL device (FIG. 7). Then, as shown in FIG. 8, even when a part of the glass substrate 1 side is covered with a mask 6 and is irradiated with ultraviolet rays, the hole transport function of the irradiated portion 31 disappears due to the ultraviolet ray components passing through the glass substrate 1, Light emission could be observed only from the non-irradiated portion 32 in which the hole transport function did not disappear.

From this experiment, it was found that an organic EL element for pattern display could be easily manufactured by the following manufacturing process. That is, as in the present invention, the light emitting layer 3 is formed from a light emitting material that loses its hole transport function by irradiation with ultraviolet rays and emits light in the visible region. Therefore, this light emitting layer is irradiated with ultraviolet rays so as to have a predetermined irradiation pattern, and a predetermined non-light emitting pattern 31 that does not emit light by voltage application and that is the irradiation pattern that has been subjected to the ultraviolet irradiation and the ultraviolet irradiation is performed. A non-irradiated pattern that is not exposed and a predetermined light emitting pattern 32 that emits light when a voltage is applied can be formed directly in the light emitting layer. This makes it possible to easily obtain a light emission pattern by applying a voltage, particularly a complicated light emission pattern, without forming a complicated electrode pattern.

[0038]

EXAMPLES The present invention will be specifically described below based on Examples and Reference Examples. Synthesis of Light-Emitting Material The light-emitting material composed of the polysilane derivative used in this example was synthesized as follows. Monomer 1 [9,10 bis (methylpropylchlorosilylanthracene)] shown in the following (a) and monomer 2 [methylphenyldichlorosilane] shown in the following b were changed in the charging ratio as shown in Table 1, and Table 1 Polymer 3 (Sample Nos. R1 to R4) shown in the following (c) having the following characteristics was synthesized.

[0039]

Embedded image

[0040]

[Chemical 9]

[0041]

[Chemical 10]

[0042]

[Table 1]

The synthesis conditions are as follows. That is,
Sodium and toluene were charged into a container in an argon atmosphere, heated to the boiling point of this toluene, and the sodium was melted in a reflux atmosphere and vigorously stirred to finely disperse the sodium. After that, the content temperature is kept near the boiling point of the solvent while stirring, and a predetermined amount of the monomers (a) and (b) is added.
The mixture was slowly added dropwise, and the mixture was reacted for 3 hours. After completion of the polymerization reaction, the mixture was cooled to room temperature, sodium chloride produced as a by-product and excess metal sodium were filtered off, and the filtrate was dropped into methanol to precipitate the polymer. Collect this,
The desired product was obtained by drying. Any of the polymers 3 could be used for an organic EL device, but when the charging ratio of the monomer [monomer 2 / monomer 1] was about 12 to 24, preferable light emission characteristics were obtained. According to the emission spectrum, each of these polymers showed emission of 480 nm. Further, the emission efficiency of each of these polymers was about 15%, which was about 1.5 times that of Alq3.
Further, the most preferable was sample R3 having a charging ratio of 24. It was confirmed from the optical absorption characteristics that the content ratio of the anthrylene group was almost equal to the charging ratio of the monomer. Therefore, this charging ratio is shown in Table 1. Moreover, the weight average molecular weight and the number average molecular weight in Table 1 were calculated | required by GPC method (polystyrene conversion). Furthermore,
The above luminous efficiency is calculated as a standard substance in chloroform.

[0044]

[Chemical 11] Was measured using Alq ₃ (emission efficiency 10.1%).

Example 1 First, the sheet resistance was 20 to 30 ohm / cm ² , and the transmittance was 8
A glass substrate 1 (FIG. 9) 1 having a thickness of 1 mm coated with a transparent electrode 2 of 0 to 90% indium tin oxide alloy (ITO) is prepared. Then, on the transparent electrode 2, the toluene solvent of the above-mentioned polysilane derivative containing an anthrylene group (toluene 300 per 3 mg of polysilane derivative) was used.
It was dissolved with a microliter. ) Is spin coated,
A light emitting layer 3 having a thickness of 50 nanometers was formed (FIG. 10).
After that, a mask 6 is prepared by printing a reverse-looking pattern (mask portion) 61 of the character pattern “EL” desired to be displayed on a polyethylene sheet (commercial OHP sheet) (FIG. 11). Then, after covering the light emitting layer 3 with this mask 6 (FIG. 11), it was exposed to the radiant light of a lamp containing an ultraviolet light component for 60 seconds at a distance of 30 cm from a 150 W high pressure mercury xenon lamp. As a result, the light-irradiated portion (pattern) 31 of the light emitting layer 3 is oxidized and the hole transport function is lost (FIG. 12). In the figure, 32
Indicates a non-irradiated portion (pattern). Next, an aluminum electrode (having a thickness of 0.
2 μm) 4 was formed to produce an organic EL device (light emitting display device) (FIG. 13). A lead wire (not shown) was attached to this organic EL element, the ITO electrode 2 was set to be positive, the aluminum electrode 4 was set to be negative, and a voltage was applied.
However, it could be observed from the glass substrate 1 side (FIG. 14). The same experiment was conducted by changing the thickness of the light emitting layer 3 in the range of 30 nanometers to 150 nanometers.
When the thickness was nanometer, a good organic EL device was obtained.

Example 2 In the same manner as in Example 1, a glass substrate 1 having an ITO transparent electrode 2 (FIG. 15) was spin-coated with the toluene solution containing the above polysilane derivative containing an anthrylene group to emit light. Layer 3 was formed on the transparent electrode 2 (Fig. 16).
Then, the aluminum electrode 4 was formed thereon by vacuum evaporation (FIG. 17). The respective film thicknesses, etc. are shown in Example 1.
Same as. At this stage, a normal organic EL element was completed, but in this example, as shown in FIG. 18, further, from the light emission extraction side of the glass substrate 1 (the side opposite to the side on which the electrodes and the light emitting layer were formed), It was exposed for 90 seconds through a polyethylene mask 6 (the pattern of the mask portion 61 indicates “EL”). In addition, except for this exposure time, irradiation was performed with the radiant light of a lamp containing an ultraviolet light component under the same apparatus and conditions as in Example 1 above. A lead wire (not shown) was attached to this organic EL element, and when a voltage was applied with the ITO electrode 2 being positive and the aluminum electrode 4 being negative, the light emission of the character pattern "EL" 32 was observed from about 10V. It was observed from the substrate 1 side (Fig. 19).

Reference Example 1 In this reference example, the light emitting material has a function such that the light emitting material can be easily oxidized to form a light emitting pattern by irradiation with ultraviolet light like the anthrylene group-containing polysilane derivative used in the present invention. It is an example of a manufacturing method for displaying a character pattern when a non-luminescent material is used. However, since the handling of the light emitting material is the same, the same light emitting material as that in the example was used for convenience. Similar to the above example, a glass substrate 1 with an ITO transparent electrode 2 (FIG. 20) was spin-coated with the same toluene solution to form a light emitting layer 3 (FIG. 21). Then, the character pattern "E
The light emitting layer 3 is covered with a vapor deposition mask 6 (FIG. 22) made of stainless steel and having a pattern reverse to that of “L”, and the aluminum electrode 4b having a character pattern is attached to the light emitting layer 3 by vacuum vapor deposition.
It was formed on top of (FIG. 23). In this case, the lead lead 41b is formed. Next, when a voltage is applied with the aluminum electrode 4b of the character pattern being negative and the ITO transparent electrode 2 being positive, the character pattern "EL" is obtained.
32 emitted light could be observed from the glass substrate 1 side (FIG. 2).
4). In this case, the lead lead equivalent portion 321 also emits light at the same time.

The present invention is not limited to the specific examples described above, and various modifications may be made within the scope of the present invention depending on the purpose and application. That is,
As the transparent electrode, not only the above ITO but also other transparent conductive material such as indium oxide or tin oxide can be used. The transparent substrate and the light emitting pattern may have various shapes and sizes. The material of the transparent substrate is not limited to the glass shown in the above embodiment, but a resin (for example, acrylic resin such as polyacrylic acid ester, polyester resin, polycarbonate or the like) can be used. Further, the light emitting material is not limited to the one used in the above-mentioned examples, and other polysilane derivatives having an emission wavelength in the visible region, which are shown in the scope of the present invention, can also be used.
Further, various known methods can be used for forming the light emitting layer.

[0049]

As described above, in the light emitting display device of the present invention, the conventional light emitting material can be obtained by using the light emitting material composed of the polysilane derivative, which is characterized in that the hole transporting function can be eliminated by the irradiation of ultraviolet rays. It is possible to omit the processing process such as the stainless steel mask for vapor deposition that is required when displaying a character pattern in a light emitting display element using, and the electrode part connecting the character pattern is not conspicuous, and the complicated character pattern Can also be displayed. Further, since the polysilane compound used in the present invention has an emission wavelength in the visible region and has a high emission efficiency, it is visible to humans and is excellent in efficiency as a light emitting display element. Furthermore, it is an organic solvent, preferably an aprotic organic solvent, especially benzene, toluene,
Since it is soluble in a non-polar aromatic solvent such as xylene, it can be easily formed into a film, which is excellent in forming a coating as a light emitting layer, and is very convenient for measuring the physical properties of the polymer itself. Further, according to the manufacturing method of the present invention, it is possible to extremely easily manufacture a light emitting display device which emits a character pattern (especially a complicated character pattern), particularly the useful light emitting display device described above.

[Brief description of drawings]

FIG. 1 is a perspective view of a light emitting display device in a mode in which the entire surface of a light emitting layer is made to emit light.

FIG. 2 is a perspective view showing a state in which the light emitting display element shown in FIG. 1 emits light.

FIG. 3 is an explanatory diagram showing a state in which a metal electrode having a character pattern is formed on a light emitting layer.

FIG. 4 is a perspective view showing a state in which the light emitting display element shown in FIG. 4 emits light.

FIG. 5 is an explanatory cross-sectional view showing a state in which ultraviolet rays are radiated on the light emitting layer using a mask.

6 is an explanatory cross-sectional view showing a state in which a metal electrode has been formed after the ultraviolet irradiation shown in FIG.

FIG. 7 is an explanatory cross-sectional view of a light emitting display device before irradiation with ultraviolet rays.

8 is an explanatory cross-sectional view showing a state where the light emitting display element shown in FIG. 7 is irradiated with ultraviolet rays using a mask.

9 is a perspective view of a glass substrate with a transparent electrode according to Example 1. FIG.

10 is a perspective view showing a state in which a light emitting layer is formed on the glass substrate with a transparent electrode shown in FIG.

FIG. 11 is an explanatory diagram for attempting to dispose a mask on the light emitting layer shown in FIG.

12 is an explanatory diagram showing a state where ultraviolet rays are radiated from above the mask arranged in FIG. 11. FIG.

13 is an explanatory diagram of a light emitting display device in which a metal electrode is formed on a light emitting layer irradiated with ultraviolet rays in FIG.

14 is an explanatory diagram showing a state in which the light emitting display element shown in FIG. 12 emits light.

FIG. 15 is a perspective view of a glass substrate with a transparent electrode according to a second embodiment.

16 is a perspective view showing a state in which a light emitting layer is formed on the glass substrate with a transparent electrode shown in FIG.

17 is an explanatory diagram showing a state in which a metal electrode is formed on the light emitting layer shown in FIG.

FIG. 18 is an explanatory diagram in which a mask is arranged on the glass substrate side of the glass substrate with the transparent electrode / light emitting layer / metal electrode shown in FIG. 17;

FIG. 19 is an explanatory diagram showing a state in which the light emitting display element manufactured in Example 2 is caused to emit light.

20 is a perspective view of a glass substrate with a transparent electrode according to Reference Example 1. FIG.

21 is a perspective view showing a state in which a light emitting layer is formed on the glass substrate with a transparent electrode shown in FIG.

22 is an explanatory diagram showing a state in which a mask is to be arranged to form a metal electrode having a predetermined pattern on the light emitting layer shown in FIG. 21.

23 is an explanatory diagram of a light emitting display device in which a metal electrode having a predetermined pattern is formed on a light emitting layer using the mask shown in FIG.

FIG. 24 is an explanatory diagram showing a state in which the light emitting display element shown in FIG. 23 emits light.

[Explanation of symbols]

1; glass substrate, 2; ITO transparent electrode, 3; light emitting layer, 3
1; irradiation part, 32; light emitting part, 4; aluminum electrode (metal electrode), 5a, 5b; lead wire, 6; mask, 6
1; mask part.

Claims (4)

[Claims] 1. A transparent substrate with a transparent electrode, a light-emitting layer formed on the transparent electrode, and a metal electrode formed on the light-emitting layer, wherein the light-emitting layer has a main chain shown below. A light-emitting display device comprising a polysilane derivative partially containing an anthrylene group. [The above polysilane derivative]; Formula A: (In the formula, R ¹ and R ² have the same or different carbon number 1
To 6 linear alkyl groups, and the total number of carbon atoms of R ¹ and R ² is 8 or less. ) Structural unit A represented by
And the formula B (In the formula, R ³ and R ⁴ may be the same or different and each is an alkyl group having 1 to 10 carbon atoms, an aryl group or an aralkyl group.) The molar ratio (%) of the structural unit A / the structural unit B is 0.5 to 10%, and the weight average molecular weight is 1,000 to
A polysilane derivative that is 1,000,000. 2. A transparent substrate with a transparent electrode, a light emitting layer formed on the transparent electrode, and a metal electrode formed on the light emitting layer, wherein the light emitting layer comprises the polysilane according to claim 1. The light-emitting layer is irradiated with ultraviolet rays in a predetermined irradiation pattern, and the ultraviolet-ray irradiation is performed with a predetermined non-light-emission pattern that does not emit light when a voltage is applied. A light-emitting display element, which has an unirradiated non-irradiated pattern and a predetermined light-emitting pattern which emits light when a voltage is applied, is directly formed in the light-emitting layer. 3. A light emitting layer composed of a polysilane derivative containing an anthrylene group in a part of its main chain as shown in claim 1, is formed on the transparent electrode of a transparent substrate with a transparent electrode, and then this transparent layer is formed. The light emitting layer is irradiated with ultraviolet rays from one surface of the transparent substrate with an electrode / light emitting layer in a predetermined irradiation pattern, and the ultraviolet irradiation is performed, and the predetermined non-emission does not emit light by voltage application. A pattern and a predetermined light emitting pattern which is a non-irradiated pattern in which the ultraviolet ray irradiation is not performed and which emits light when a voltage is applied are directly formed in the light emitting layer, and then a metal electrode is formed on the light emitting layer. A method for manufacturing a light-emitting display device characterized by the above. 4. A light emitting layer composed of a polysilane derivative containing an anthrylene group in a part of its main chain, which is shown in claim 1, is formed on the transparent electrode of a transparent substrate with a transparent electrode, and then the light emission is performed. A metal electrode is formed on the layer, and then, from the transparent substrate side of the transparent electrode / light emitting layer / transparent substrate with metal electrode, ultraviolet irradiation is performed on the light emitting layer in a predetermined irradiation pattern, and the ultraviolet irradiation is performed. A predetermined non-light-emission pattern that is an irradiation pattern that is performed and does not emit light when a voltage is applied, and a predetermined light-emission pattern that is a non-irradiation pattern that is not irradiated by ultraviolet light and that emits light when a voltage is applied are directly provided in the light-emitting layer A method for manufacturing a light-emitting display element, which is characterized by being formed.