JP2003077668A - Organic thin film el element - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide an organic thin film EL element showing excellent light emission characteristics and having excellent durability using a high polymer material. SOLUTION: This organic thin film EL element is provided with a light emitting layer composed of at least one layer of organic compound thin film between the opposing anode and cathode, and at least one layer of the light emitting layers has electric charge carrier performance expressed by the formula (1) as a constituent component and contains aromatic polycarbonate resin having excellent resistance against heat. This organic thin film EL element shows excellent light emission characteristics and durability by using this resin. Wherein, Ar1 and Ar2 are each substituted or non-substituted allylene groups, Ar3 is a substituted or non-substituted allyl group, Z represents an allylene group or -Ar4 -Za-Ar4 -, Ar4 represents a substituted or non-substitute allylene group, Za represents single bond, oxygen atom, sulfur atom or alkylene group, Z1 represents oxygen atom or sulfur atom, and n denotes 0 or 1.

Description

Detailed Description of the Invention

[0001]

The present invention relates to a novel organic thin film EL
It is related to the element. More specifically, the present invention provides
The present invention relates to a stable organic thin film EL element having excellent light emitting characteristics.

[0002]

2. Description of the Related Art Organic thin film EL devices are self-luminous and therefore have a wide viewing angle dependency, high visibility, and further, because they are thin film type complete solid-state devices, they can save space. Has been attracting attention, and in recent years, practical research has been conducted. However, at present, there are many problems to be solved, such as further improvement of energy conversion efficiency and emission quantum efficiency, and improvement of stability of organic thin film over time.

Up to now, organic thin-film EL devices have been reported to use low molecules and high polymers. In a low molecular weight system, it has been reported that high efficiency is realized by adopting various laminated structures, and durability is improved by controlling the doping method well.
However, in the case of a low molecular weight aggregate, it has been reported that the state of the membrane changes over time for a long time, and there is an essential problem regarding the stability of the membrane. On the other hand, in the case of polymer materials, until now, mainly PPV (poly-p
-phenylenevinylene) series and poly-thiophene have been studied vigorously. However, it is difficult to increase the purity of these material systems, and the intrinsically low fluorescence quantum yield is cited as a problem, and high-performance EL devices have not yet been obtained. . However, considering that the polymer material is essentially stable in the glass state, if it is possible to provide a high fluorescence quantum efficiency, it becomes possible to construct an excellent EL device, and therefore further improvements are made in this field. ing.

[0004]

SUMMARY OF THE INVENTION The present invention has been made in view of the above-mentioned state of the art, and an organic thin film EL element using a polymer material, which has excellent light emitting characteristics and excellent durability, is provided. The purpose is to provide.

[0005]

Means for Solving the Problems As a result of intensive studies by the present inventors, an organic thin film was obtained by using a polycarbonate resin having charge transportability, heat resistance, mechanical strength, and stability over time as a constituent component. It has been found that the durability of the EL device can be improved, and further that the EL device having a light emitting layer containing the following aromatic polycarbonate resin has excellent light emitting characteristics. That is, the present invention comprises the following [1] to [9].

[1] Between the anode and the cathode facing each other,
In an organic thin film EL device having a light emitting layer composed of at least one organic compound thin film, at least one layer of the organic compound thin film is a layer containing an aromatic polycarbonate resin represented by the following general formula (1). An organic thin film EL device characterized by:

[0007]

[Chemical 7] (In the formula (1), Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, Ar ₃ represents a substituted or unsubstituted aryl group, Z represents an arylene group or —Ar ₄ —Za—Ar ₄ —, Ar ₄ is a substituted or unsubstituted arylene group, Za is a single bond, an oxygen atom, a sulfur atom or an alkylene group, Z ₁ is an oxygen atom or a sulfur atom, and n is 0 or 1.)

[2] The organic thin film EL device according to the above [1], wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin represented by the following general formula (2).

[0009]

[Chemical 8] (In the formula (2), Ra, Rb, Rc and Rd represent a substituted or unsubstituted alkyl group, and Ar ₃ , Z, Z ₁ and n are the same as defined in the general formula (1).)

[3] Between the anode and the cathode facing each other,
In an organic thin film EL device having a light emitting layer formed of at least one layer of an organic compound thin film, at least one layer of the organic compound thin film is represented by a structural unit represented by the general formula (1) and a general formula (3) below. And the composition ratio of the structural unit represented by the general formula (1) is k, the general formula (3)
Wherein the composition ratio of the structural unit represented by is j is a layer containing an aromatic polycarbonate resin having a composition ratio of 0 <k / (k + j) ≦ 1. Thin film EL device.

[0011]

[Chemical 9] [In Formula (3), X is a substituted or unsubstituted aliphatic divalent group, a substituted or unsubstituted cycloaliphatic divalent group, a substituted or unsubstituted aromatic divalent group, or these can be linked. Divalent group, or

[0012]

[Chemical 10] (Here, R ¹ , R ² , R ³ , and R ⁴ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom. Further, a and b are each independently. Is an integer of 0 to 4, and c and d are each independently 0.
Is an integer of 3 to 3, and when a plurality of R ¹ , R ² , R ³ and R ⁴ are present, they may be the same or different. Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms,
A substituted or unsubstituted branched alkylene group having 3 to 12 carbon atoms, a divalent group composed of one or more alkylene groups having 1 to 10 carbon atoms and one or more oxygen atoms and / or sulfur atoms, -O -, - S -, - SO -, - SO 2 -, -
CO-, -COO-, or the following formula

[0013]

[Chemical 11] Z ¹ and Z ^{2 each} represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, R 1
⁵ , R ⁶ and R ¹² represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and R ⁷ , R ⁸ , R ⁹ and R
¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.
R ⁶ and R ⁷ may combine to form a carbon ring having 5 to 12 carbon atoms, R ¹³ and R ¹⁴ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, e and g are integers from 0 to 4, f is 1 or 2, h
Represents an integer of 0 to 20, and i represents an integer of 0 to 2000. )
Represents ]

[4] The organic thin-film EL device as described in [3] above, wherein the constitutional unit represented by the general formula (1) is a constitutional unit represented by the general formula (2).

[5] The organic thin film EL device according to the above [3], wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin represented by the following general formula (4).

[0016]

[Chemical 12] (In the formula (4), Ra, Rb, Rc, Rd, Ar ₃ , Z,
Z ₁ , X and n are the same as defined in the above general formulas (2) and (3). )

[6] The organic thin film EL device as described in any one of [1] to [5] above, wherein the layer containing the aromatic polycarbonate resin further contains an electron transporting substance.

[7] The organic thin film as described in any one of [1] to [5] above, wherein the layer containing the aromatic polycarbonate resin further contains an electron transporting substance and a light emitting substance. EL element.

[8] The light emitting layer is a light emitting layer composed of a plurality of organic compound thin films including at least one hole injecting and transporting layer, and at least one of the hole injecting and transporting layers contains the aromatic polycarbonate resin. The organic thin film EL device according to any one of the above [1] to [7].

[9] The light emitting layer comprises a layer containing the aromatic polycarbonate resin, at least one hole injecting and transporting layer, at least one electron injecting and transporting layer, and at least one both injecting and transporting layers. [1] to [7], characterized in that it is composed of at least one selected
5. The organic thin film EL device according to any one of 1.

The aromatic polycarbonate resin used in the organic thin film EL device of the present invention will be described in detail below.
First, a method for manufacturing the polycarbonate resin will be described. The polycarbonate resin used in the present invention can be produced by the same method as the polymerization of bisphenol and a carbonic acid derivative, which is conventionally known as a method for producing a polycarbonate resin. That is, at least one diol having a charge-transporting ability represented by the following general formula (A) or (B) is used, or these diols represented by the following general formula (5) are used in combination, It is produced by a transesterification method with a bisaryl carbonate, a solution or an interfacial polymerization method with a carbonyl halide compound such as phosgene, or a method using a chloroformate such as bischloroformate derived from a diol.

[0022]

[Chemical 13] (In the formula (A), Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, Ar ₃ represents a substituted or unsubstituted aryl group, Z represents an arylene group or —Ar ₄ —Za—Ar ₄ —, Ar ₄ is a substituted or unsubstituted arylene group, Za is a single bond, an oxygen atom, a sulfur atom or an alkylene group, Z ₁ is an oxygen atom or a sulfur atom, and n is 0 or 1.)

[0023]

[Chemical 14] (In the formula (B), Ra, Rb, Rc and Rd represent a substituted or unsubstituted alkyl group, and Ar ₃ , Z, Z ₁ and n are the same as defined in the general formula (A).)

HO-X-OH (5) (In the formula (5), X has the same definition as X in the general formula (3).)

In the method using the above-mentioned carbonyl halide compound in the production of the polycarbonate resin, the carbonyl halide compound is trichloromethylchloroformate, which is a dimer of phosgene, or a trimer of phosgene, instead of phosgene. Bis (trichloromethyl)
Carbonates are also useful, and carbonyl halide compounds derived from halogens other than chlorine, such as carbonyl bromide, carbonyl iodide, carbonyl fluoride. These known production methods are described in, for example, the Polycarbonate Resin Handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun).

As described above, the diol represented by the above general formula (5) is used in combination with at least one diol having the charge transporting ability represented by the general formula (A) or (B), It can be a copolymer having improved physical properties. In this case, the diol represented by the general formula (5) is 1
You may use together or multiple types. The ratio of the diol having the charge-transporting ability represented by the general formula (A) or (B) to the diol represented by the general formula (5) can be selected from a wide range according to desired characteristics.

By selecting an appropriate polymerization operation, random copolymers, alternating copolymers, among copolymers,
A block copolymer, a random alternating copolymer, a random block copolymer, etc. can be obtained. For example, if the diol having the charge transporting ability represented by the general formula (A) or (B) and the diol represented by the general formula (5) are uniformly mixed from the beginning and the condensation reaction with phosgene is carried out, a random copolymer is obtained. A polymer is obtained. A random block copolymer can be obtained by adding some kinds of diols during the reaction. In addition, if a bischloroformate derived from a diol represented by the general formula (5) and a diol having a charge transporting ability represented by the general formula (A) or (B) are subjected to a condensation reaction, alternating co-polymerization will occur. A coalescence is obtained. In this case, conversely, the same applies to the condensation reaction between the diol represented by the general formula (A) or (B) and having the charge-transporting ability, and the diol represented by the general formula (5). An alternating copolymer is obtained. In addition, a random alternating copolymer can be obtained by using a plurality of bischloroformates and diols in the condensation reaction of these bischloroformates and diols.

Details of the polymerization conditions and the like are disclosed in Japanese Patent Application No. 2000-60722, which has been already proposed by the present inventors, entitled "Aromatic Polycarbonate Resin and Electrophotographic Photoreceptor".

The polycarbonate resin obtained as described above removes catalysts and antioxidants used during polymerization, unreacted diols and terminal terminators, and impurities such as inorganic salts generated during polymerization. Then used. For these purification operations, conventionally known methods described in the above-mentioned polycarbonate resin handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun) can be used.

The preferred aromatic polycarbonate resin used in the present invention has a polystyrene-equivalent number average molecular weight of 1,000 to 500,000, and more preferably 10.
It is 000-200000. Further, additives such as antioxidant, light stabilizer, heat stabilizer, lubricant, plasticizer and the like can be added to the aromatic polycarbonate resin produced according to the above method, if necessary.

Next, general formulas (A) and (B) which are the main units of the aromatic polycarbonate resin of the present invention will be described in more detail. Ar in the general formulas (A) and (B)
₃ represents a substituted or unsubstituted aryl group. Examples of the substituted or unsubstituted aryl group for Ar ₃ include the following. Phenyl group, naphthyl group, biphenylyl group, terphenylyl group, pyrenyl group, fluorenyl group, 9,9-dimethyl-2-fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [A, d] cycloheptenylidenephenyl group, thienyl group, benzothienyl group, furyl group, benzofuranyl group,
Examples thereof include a carbazolyl group, a pyridinyl group, a pyrrolidyl group, an oxazolyl group, etc., and these include a substituted or unsubstituted alkyl group, an alkoxy group having a substituted or unsubstituted alkyl group, a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. May have a halogen atom and / or an amino group represented by the following general formula as a substituent.

[0032]

[Chemical 15] In the formula, R ¹⁷ and R ¹⁸ are substituted or unsubstituted alkyl groups,
It represents a substituted or unsubstituted aryl group defined by Ar ₃ , and R ¹⁷ and R ¹⁸ may jointly form a ring, or may jointly form a ring with a carbon atom on the aryl group. Specific examples thereof include a piperidino group, a morpholino group, and a julolidyl group.

In the general formula (A), Ar ₁ and Ar ₂ each represent a divalent group derived from the aryl group represented by Ar ₃ .

[0034] In general formula (A) and (B), Z is an arylene group or -Ar ₄ -Za-Ar ₄ - represents a. Examples of the arylene group are phenylene, naphthylene, biphenylylene, terphenylylene, pyrene-1,6-diyl, fluorene-2,7-diyl, 9,9-dimethylfluorene-2,7-diyl, thiophene-2,5-diyl and furan. -2,5-diyl, N-ethylcarbazole-3,6
-Diyl and the like, which may have a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group and a halogen atom as a substituent.

When Z is represented by —Ar ₄ —Za—Ar ₄ —, Ar ₄ includes phenylene, naphthylene, biphenylylene, terphenylylene and the like, which are substituted or unsubstituted alkyl groups, substituted or unsubstituted. It may have the alkoxy group and the halogen atom as a substituent.

Ra, Rb, Rc and Rd in the general formula (B) are substituted or unsubstituted alkyl groups, and include the following.

It is a linear or branched alkyl group having 1 to 5 carbon atoms, and these alkyl groups are further fluorine atom, cyano group, phenyl group or halogen atom or 1 to 5 carbon atoms.
It may contain a phenyl group substituted with a linear or branched alkyl group. Specifically, a methyl group, an ethyl group, an n-propyl group, an i-propyl group, a t-butyl group,
s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2-cyanoethyl group, benzyl group, 4-
Examples thereof include a chlorobenzyl group and a 4-methylbenzyl group.

The method for producing the diol having the charge transporting ability represented by the general formula (A) or (B) is disclosed in the above-mentioned Japanese Patent Application No. 2000-60722.

Typical examples of the diol when X in the general formula (5) is an aliphatic divalent group or a cycloaliphatic divalent group include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, poly Tetramethylene ether glycol, 1,3-propanediol, 1,4-butanediol, 1,5-pentanediol, 3-methyl-1,5-pentanediol, 1,
6-hexanediol, 1,5-hexanediol,
1,7-Heptanediol, 1,8-octanediol, 1,9-nonanediol, 1,10-decanediol, 1,11-undecanediol, 1,12-dodecanediol, neopentyl glycol, 2-ethyl-
1,6-hexanediol, 2-methyl-1,3-propanediol, 2-ethyl-1,3-propanediol, 2,2-dimethyl-1,3-propanediol,
1,3-cyclohexanediol, 1,4-cyclohexanediol, cyclohexane-1,4-dimethanol, 2,2-bis (4-hydroxycyclohexyl) propane, xylylenediol, 1,4-bis (2-hydroxyethyl) ) Benzene, 1,4-bis (3-hydroxypropyl) benzene, 1,4-bis (4-hydroxybutyl) benzene, 1,4-bis (5-hydroxypentyl) benzene, 1,4-bis (6- Hydroxyhexyl) benzene, isophoronediol and the like.

When X in the general formula (5) is an aromatic divalent group, it is derived from a substituted or unsubstituted aryl group defined as Ar ₃ in the general formulas (A) and (B). The divalent group can be mentioned. X also represents a divalent group shown below.

[0041]

[Chemical 16]

In the above formula, R¹, R², R³, R^FourIndependently
Substituted or unsubstituted alkyl group, substituted or unsubstituted
Represents an aryl group or a halogen atom. Also, a and b are
Each independently an integer from 0 to 4, c and d each independently
And is an integer from 0 to 3, and R ¹, R², R³, R^FourIs that
When there is more than one, they may be the same or different
Yes. Y is a single bond, a linear alkyl group having 2 to 12 carbon atoms.
Ren group, substituted or unsubstituted 3 to 12 carbon atoms
A wide variety of alkylene groups, one or more C1-C10 al
From a xylene group and one or more oxygen and / or sulfur atoms
Constituted divalent group, -O-, -S-, -SO-, -SO
₂-, -CO-, -COO-, or the following general formula

[0043]

[Chemical 17] Z ¹ and Z ^{2 each} represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, and R ⁵ , R ⁶ and R ¹² are halogen atoms or substituted Or an unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group,
R ⁷ , R ⁸ , R ⁹ , R ¹⁰ and R ¹¹ are each independently a hydrogen atom,
It represents a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group. R ⁶ and R ⁷ are bonded to each other and have 5 to 5 carbon atoms.
12 may form a carbon ring, R ¹³ and R ¹⁴ each represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ each independently represent a substituted or unsubstituted alkyl group or a substituted alkyl group. Or, it represents an unsubstituted aryl group, e and g are integers of 0 to 4, f is 1 or 2, h is an integer of 0 to 20, and i is 0 to 20.
Represents an integer of 00.

Specific examples of the divalent group consisting of one or more alkylene groups having 1 to 10 carbon atoms of Y and one or more oxygen atoms and / or sulfur atoms include OCH ₂ CH ₂
O, OCH ₂ CH ₂ OCH ₂ CH ₂ O, OCH ₂ CH ₂ OCH
₂ CH ₂ OCH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ O, OCH ₂
CH ₂ CH ₂ CH ₂ O, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH
₂ O, OCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH
₂ O, CH ₂ O, CH ₂ CH ₂ O, CHEtOCHEtO, C
HCH ₃ O, SCH ₂ OCH ₂ S, CH ₂ OCH ₂ , OCH ₂
OCH ₂ O, SCH ₂ CH ₂ OCH ₂ OCH ₂ CH ₂ S, OC
H ₂ CHCH ₃ OCH ₂ CHCH ₃ O, SCH ₂ S, SCH ₂
CH ₂ S, SCH ₂ CH ₂ CH ₂ S, SCH ₂ CH ₂ CH ₂ C
H ₂ S, SCH ₂ CH ₂ CH ₂ CH ₂ CH ₂ CH ₂ S, SCH ₂
CH ₂ SCH ₂ CH ₂ S, SCH ₂ CH ₂ OCH ₂ CH ₂ OC
H ₂ CH ₂ S and the like.

As the substituent for modifying the branched alkylene group having 3 to 12 carbon atoms of Y, there may be mentioned a substituted or unsubstituted aryl group or a halogen atom.

In these Y, a substituted or unsubstituted alkyl group and a substituted or unsubstituted aryl group are all substituted or unsubstituted alkyl groups, substituted or unsubstituted aryl groups defined in the present specification. It is the same as the group.
Further, when Z ¹ and Z ² in the above Y is a substituted or unsubstituted aliphatic divalent group, a diol in the case where the above X is an aliphatic divalent group or a cycloaliphatic divalent group And a divalent group obtained by removing the hydroxy group can be mentioned. or,
When Z ¹ and Z ² are a substituted or unsubstituted arylene group, a divalent group derived from a substituted or unsubstituted aryl group defined in the present specification can be mentioned.

Representative examples of preferred diols when X in the general formula (5) is an aromatic divalent group are bis (4-hydroxyphenyl) methane and bis (2-methyl-4-hydroxyphenyl). ) Methane, bis (3-methyl-4-hydroxyphenyl) methane, 1,1-bis <4
-Hydroxyphenyl) ethane, 1,2-bis (4-hydroxyphenyl) ethane, bis (4-hydroxyphenyl) phenylmethane, bis (4-hydroxyphenyl) diphenylmethane, 1,1-bis (4-hydroxyphenyl)- 1-phenylethane, 1,3-bis (4-
Hydroxyphenyl) -1,1-dimethylpropane,
2,2-bis (4-hydroxyphenyl) propane, 2
-(4-hydroxyphenyl) -2- (3-hydroxyphenyl) propane, 1,1-bis (4-hydroxyphenyl) -2-methylpropane, 2,2-bis (4-hydroxyphenyl) butane, 1, 1-bis (4-hydroxyphenyl) -3-methylbutane, 2,2-bis (4
-Hydroxyphenyl) pentane, 2,2-bis (4-
Hydroxyphenyl) -4-methylpentane, 2,2-
Bis (4-hydroxyphenyl) hexane, 4,4-bis (4-hydroxyphenyl) heptane, 2,2-bis (4-hydroxyphenyl) nonane, bis (3,5-dimethyl-4-hydroxyphenyl) Methane, 2,2-bis (3-methyl-4-hydroxyphenyl) propane,
2,2-bis (3-isopropyl-4-hydroxyphenyl) propane, 2,2-bis (3-sec-butyl-4)
-Hydroxyphenyl) propane, 2,2-bis (3-
tert-butyl-4-hydroxyphenyl) propane,
2,2-bis (3-cyclohexyl-4-hydroxyphenyl) propane, 2,2-bis (3-allyl-4-hydroxyphenyl) propane, 2,2-bis (3-phenyl-4-hydroxyphenyl) propane 2,2-bis (3,5-dimethyl-4-hydroxyphenyl) propane, 2,2-bis (3-chloro-4-hydroxyphenyl) propane, 2,2-bis (3,5-dichloro-4)
-Hydroxyphenyl) propane, 2,2-bis (3-
Bromo-4-hydroxyphenyl) propane, 2,2-
Bis (3,5-dibromo-4-hydroxyphenyl) propane, 2,2-bis (4-hydroxyphenyl) hexafluoropropane, 1,1-bis (4-hydroxyphenyl) cyclopentane, 1,1- Bis (4-hydroxyphenyl) cyclohexane, 1,1-bis (3-methyl-4-hydroxyphenyl) cyclohexane, 1,1
-Bis (3,5-dimethyl-4-hydroxyphenyl)
Cyclohexane, 1,1-bis (3,5-dichloro-4)
-Hydroxyphenyl) cyclohexane, 1,1-bis (4-hydroxyphenyl) -3,3,5-trimethylcyclohexane, 1,1-bis (4-hydroxyphenyl) cycloheptane, 2,2-bis (4-hydroxy) Phenyl) norbornane, 2,2-bis (4-hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-
Dimethyl diphenyl ether, ethylene glycol bis (4-hydroxyphenyl) ether, 1,3-bis (4-hydroxyphenoxy) benzene, 1,4-bis (3-hydroxyphenoxy) benzene, 4,4'-dihydroxydiphenyl sulfide, 3 , 3'-dimethyl-4,4'-dihydroxydiphenyl sulfide, 3,
3 ', 5,5'-tetramethyl-4,4'-dihydroxydiphenyl sulfide, 4,4'-dihydroxydiphenyl sulfoxide, 3,3'-dimethyl-4,4'-
Dihydroxydiphenyl sulfoxide, 4,4'-dihydroxydiphenyl sulfone, 3,3'-dimethyl-
4,4'-dihydroxydiphenyl sulfone, 3,3 '
-Diphenyl-4,4'-dihydroxydiphenyl sulfone, 3,3'-dichloro-4,4'-dihydroxydiphenyl sulfone, bis (4-hydroxyphenyl) ketone, bis (3-methyl-4-hydroxyphenyl) ketone, 3,3,3 ', 3'-tetramethyl-6,6'-
Dihydroxyspiro (bis) indane, 3,3 ', 4
4'-tetrahydro-4,4,4 ', 4'-tetramethyl-2,2'-spirobis (2H-1-benzopyran)
-7,7'-diol, trans-2,3-bis (4-
Hydroxyphenyl) -2-butene, 9,9-bis (4
-Hydroxyphenyl) fluorene, 9,9-bis (4
-Hydroxyphenyl) xanthene, 1,6-bis (4
-Hydroxyphenyl) -1,6-hexanedione,
α, α, α ′, α′-tetramethyl-α, α′-bis (4-hydroxyphenyl) -p-xylene, α, α,
α ', α'-tetramethyl-α, α'-bis (4-hydroxyphenyl) -m-xylene, 2,6-dihydroxydibenzo-p-dioxin, 2,6-dihydroxythianthrene, 2,7-dihydroxy Phenoxathine,
9,10-Dimethyl-2,7-dihydroxyphenazine, 3,6-dihydroxydibenzofuran, 3,6-dihydroxydibenzothiophene, 4,4'-dihydroxybiphenyl, 1,4-dihydroxynaphthalene, 2,
7-dihydroxypyrene, hydroquinone, resorcin, 4-hydroxyphenyl-4-hydroxybenzoate, ethylene glycol-bis (4-hydroxybenzoate), diethylene glycol-bis (4-hydroxybenzoate), triethylene glycol-bis (4-hydroxybenzoate) ), P-phenylene-bis (4-hydroxybenzoate), 1,6-bis (4
-Hydroxybenzoyloxy) -1H, 1H, 6H,
6H-perfluorohexane, 1,4-bis (4-hydroxybenzoyloxy) -1H, 1H, 4H, 4H-
Examples include perfluorobutane, 1,3-bis (4-hydroxyphenyl) tetramethyldisiloxane, and phenol-modified silicone oil. An aromatic diol compound containing an ester bond, which is produced by the reaction of 2 mol of diol and 1 mol of isophthaloyl chloride or terephthaloyl chloride is also useful.

The general formula (5) has been described above, but the same symbols have the same definitions in other general formulas.

Since the aromatic polycarbonate resin described above has both hole transporting property and fluorescent property, the organic thin film E
In the L element, it can be used as both a charge transport material and a light emitting material.

The layer containing the above-mentioned aromatic polycarbonate resin in the light emitting layer in the organic thin film EL device of the present invention can be thinned by a known method such as a spin coating method or a casting method. The aromatic polycarbonate resin is easily dissolved in an organic solvent such as dichloromethane or tetrahydrofuran. Therefore, a thin film can be prepared by preparing a solution having a suitable concentration with a suitable solvent capable of dissolving the aromatic polycarbonate resin, and using the solution to apply the solution by the above method. When a mixed film with an electron transporting substance or a light emitting substance is produced, it can be produced by dissolving the substances together in the aromatic polycarbonate resin solution and applying the solution. Further, by utilizing the property that different kinds of polymers are hard to be compatible with each other, it is possible to prepare a film in which a polymer micro-dispersed phase of another kind is formed in one kind of polymer medium. In this case, a mixed solution in which the combination of resin species and the mixing ratio are changed is prepared, and the mixed solution may be applied by the same wet film forming method.
In such a film, the aromatic polycarbonate resin represented by the above general formula (1) may be used as a polymer medium or as a fine dispersed phase. Since these films are thin, usually less than 20 μm, the pore size should be 0.4
The solution is preferably used after being filtered with a filter having a pore size of 5 μm or less, more preferably 0.1 μm or less. When the light emitting layer in the organic thin film EL element is composed of a plurality of organic compound thin films and has a low molecular compound layer, a dry film forming method such as a vacuum vapor deposition method or a sputtering method can be used in addition to the wet film forming method.

The light emitting layer of the organic thin film EL element may be composed of a single organic compound thin film layer or a plurality of layers. When the light emitting layer is composed of a single organic compound thin film layer, the layer may be composed of a polycarbonate resin alone, or a low molecular compound having an electron transporting property may be dispersed in this layer, or other polymer may be used. The compounds may be blended and other charge transporting polymers may be blended. Further, a small amount of fluorescent molecules (light-emitting substance) having extremely high fluorescence quantum efficiency can be doped in this layer, which is effective for increasing the efficiency of light emission.

As the electron transporting substance, an existing material having the ability to transport electrons can be used. For example, fluorenone, anthraquinodimethane, diphenoquinone, thiopyran dioxide, perylene tetracarboxylic acid, fluorenylidene methane, anthraquinodimethane,
It is possible to use anthrone and its derivatives and oxadiazole and triazole derivatives which have been reported to have excellent electron transporting properties.

As a fluorescent molecule having extremely high fluorescence quantum efficiency, use should be made of a laser dye or the like which exhibits strong fluorescence in a solution state and an existing low molecular weight fluorescent material which has been used as a light emitting material in an organic thin film EL device so far. Is possible. For example, anthracene, naphthalene, phenanthrene, pyrene, tetracene, coronene, chrysene, fluorescein, perylene, phthaloperylene, naphthaloperylene, perinone, phthaloperinone, naphthaloperinone, diphenylbutadiene, tetraphenylbutadiene, coumarin, oxadiazole, aldazine, bisbenzoxazoline, Bisstyryl, pyrazine, cyclopentadiene, quinoline metal complex, aminoquinoline metal complex, benzoquinoline metal complex, imine, diphenylethylene, vinylanthracene, diaminocarbazole, pyran, thiopyran, polymethine, merocyanine, imidazolequinolated oxinoid compound, quinacridone, rubrene Etc. and their derivatives.

Further, in the organic thin film EL device of the present invention, the light emitting layer can be composed of a plurality of layers. That is, an electron injecting and transporting layer, a layer containing a light emitting material, and the like can be further laminated on the polycarbonate resin-containing layer by a spin coating method or a vacuum vapor deposition method. Further, forming the hole injecting and transporting layer before forming the polycarbonate resin-containing layer may be effective in improving the performance.

As the material for forming the hole injecting and transporting layer, it has been reported that it functions in an organic thin film EL device, a phthalocyanine compound, a porphyrin compound, an oxadiazole, a triazole, a triphenylamine compound, Existing materials such as polysilane can be used.

The thickness of the light emitting layer formed as described above is not particularly limited and is usually selected in the range of 5 nm to 20 μm. More preferably, it is in the range of 5 nm to 0.2 μm. The film thickness is adjusted in consideration of occurrence of film defects such as pinholes, optical interference within the device at the emission wavelength, and increase in applied voltage due to increase in film thickness.

As the anode of the organic thin film EL device of the present invention, a metal, an alloy, a metal oxide, etc. having a work function of 4 eV, preferably greater than 4.8 eV is used. Specific examples of such electrode materials include gold, platinum, palladium,
Silver, tungsten, nickel, cobalt, ITO, Cu
The use of transparent electrodes such as I, SnO ₂ and ZnO can be mentioned. In particular, an ITO substrate is suitable. In the case of an ITO substrate, one having a smooth surface is preferable, and the surface is thoroughly cleaned before use. As a cleaning method, a known method may be used, but it is preferable to perform ultraviolet irradiation in an ozone atmosphere or plasma treatment in an oxygen atmosphere.

On the other hand, as the cathode, a metal, an alloy or the like having a work function smaller than 4 eV is used. Specific examples of such substances include sodium, calcium, magnesium, lithium, aluminum, samarium, and alloys thereof.

When the organic thin film EL device is used as a surface emitting device, at least one of these electrodes is sufficiently transparent in the emission wavelength region of the device, and the opposite side thereof has a sufficiently high reflectance in the emission wavelength region. desired.
The above-mentioned ITO is preferably used as the transparent electrode, and a transparent glass plate or plastic plate is also used as the substrate. On the other hand, the electrodes need not be transparent when used as an edge emitting device.

Further, a protective layer may be provided on the surface of the obtained organic thin film EL element in order to improve the stability against the temperature and humidity of the environment and the atmosphere, or silicon oil or the like may be enclosed to protect the entire element. It is valid.

When the positive electrode and the negative electrode of the organic thin film EL element of the present invention thus obtained are connected to the positive electrode and the negative electrode is connected to the electrode, a voltage can be applied to observe EL emission.

In the organic thin film EL element, Joule heat is generated by energization, and the heat causes recrystallization of the light emitting layer, progress of agglomeration, etc., and diffusion of low molecular weight materials, all of which reduce the durability of the element. In the organic thin film EL device of the present invention, since a stable aromatic polycarbonate resin having a high melting point temperature in an amorphous state is used for the light emitting layer, device deterioration due to crystallization or aggregation and device deterioration due to diffusion can be suppressed, which is excellent. An element having durability can be obtained.

[0063]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, Production Examples 1 to 11 of a diphenol compound used to produce an aromatic polycarbonate resin used in an organic thin film EL element of the present invention, and Production Examples 1 to 18 of an aromatic polycarbonate resin will be described. The present invention will be described more specifically.

<Production Example 1 of diphenol compound> (Production of dimethoxy compound) 2.54 g of p-toluidine, 4
-Iodo-4'-methoxydiphenyl ether 17.0
g, anhydrous potassium carbonate 7.20 g and copper powder 0.83 g were taken in 40 ml of nitrobenzene and heated under reflux for 9 hours under a nitrogen stream. After cooling to room temperature, the insoluble portion was removed by filtration, and the solvent was evaporated under reduced pressure to give a pale brown oily substance. This was subjected to silica gel column chromatography treatment (eluent: toluene / n-hexane = 5/1 vol.) And then recrystallized from a mixed solvent of ethanol-toluene to give 4-methyl- colorless plate crystals.
3.87 g of 4 ', 4''-bis (4-methoxyphenoxy) triphenylamine was obtained. Melting point 115.5-116.5 ° C ¹ H-NMR (CDCl ₃ ); δ (ppm) 2.29 (CH ₃ , 3H) 3.78 (OCH ₃ , 6H) 6.82 to 7.04 (Aromatic, 20H)

(Production of diphenol compound) Obtained 4
7.90 g of -methyl-4 ', 4''-bis (4-methoxyphenoxy) triphenylamine was dissolved in 50 ml of dry methylene chloride, and 8.40 g of boron tribromide was added to 25 ml of methylene chloride under a nitrogen stream. 0 for dissolved solution
It was added dropwise at -3 ° C over 50 minutes. 3 at room temperature after dropping
After stirring for 0 minutes, water was added and the mixture was extracted with ethyl acetate. The organic layer was washed with a 5% aqueous sodium hydrogen carbonate solution and then with water, and the solvent was evaporated under reduced pressure to give a pale brown oil. This was subjected to silica gel column chromatography treatment (eluent; toluene / ethyl acetate = 5/1 vol.) To give colorless glassy 4-methyl-4 ′, 4 ″ -bis (4-hydroxyphenoxy) triphenylamine 6. 30 g was obtained.

<Production Examples 2 to 4 of Diphenol Compound> Dimethoxy compounds were obtained according to the method of Production Example 1 of diphenol compound, and then the diphenol compounds shown in Table 1 were obtained.

[0067]

[Table 1]

<Production Example 5 of diphenol compound> (Production of dimethoxy compound) N, N'-bis [4- (4-methoxyphenoxy) phenyl] diphenyl ether-
4,3'-diamine 8.62 g, iodobenzene 50.
0 g, 15.5 g of potassium carbonate and 0.96 g of copper powder were heated under reflux for 18 hours under a nitrogen stream. After cooling to room temperature, the insoluble portion was removed by filtration, and the solvent was evaporated under reduced pressure to give a pale brown oily substance. This is subjected to silica gel column chromatography (eluent;
Toluene / n-hexane = 4/1 vol. ) And colorless oil N, N'-diphenyl-N, N'-bis [4- (4
There was obtained 9.8 g of -methoxyphenoxy) phenyl] diphenyl ether-4,3'-diamine. In the infrared absorption spectrum (liquid film method), stretching vibration of ether was observed at 1220 cm ^-1 , 1040 cm ^-1 .

(Production of diphenol compound) The obtained N, N'-diphenyl-N, N'-bis [4- (4-methoxyphenoxy) phenyl] diphenyl ether-4,
A solution of 9.8 g of 3'-diamine dissolved in 50 ml of dry methylene chloride and 6.56 g of boron tribromide dissolved in 20 ml of methylene chloride was added dropwise at 0 to 2 ° C over 40 minutes under a nitrogen stream. After dropping, the mixture was stirred at room temperature for 4 hours, water was added, the organic layer was washed with water, 5% aqueous sodium hydrogen carbonate solution, and then with water, and then the solvent was distilled off under reduced pressure to obtain a light brown oily substance. This was subjected to silica gel column chromatography treatment (eluent; toluene / ethyl acetate = 5/1 vol.) To give N, N′-diphenyl-N, N′-bis [4 as colorless glass.
6.12 g of-(4-hydroxyphenoxy) phenyl] diphenyl ether-4,3'-diamine was obtained.

<Production Example 6 of diphenol compound> (Production of dimethoxy compound) 7.40 g of N, N'-diphenylbenzidine, 16.00 g of 4-iodo-3'-methoxydiphenyl ether, 15.43 g of potassium carbonate and activation. Orthodichlorobenzene 45 with 0.78 g of copper powder
The mixture was taken in ml and heated under reflux for 30 hours while removing water under a nitrogen stream from the system. After being discharged to room temperature, the insoluble portion was removed using a filter aid, and the filtrate was dried under reduced pressure, followed by silica gel column chromatography treatment (eluent: toluene / hexane = 4 /
1) Then, 13.40 g of colorless powder N, N'-diphenyl-N, N'-bis [4- (3-methoxyphenoxy) phenyl] benzidine was obtained. Melting point glassy

(Production of diphenol compound) The obtained N, N'-diphenyl-N, N'-bis [4- (3-methoxyphenoxy) phenyl] benzidine was removed according to the method shown in Production Example 5. Methylation was performed to obtain N, N'-diphenyl-N, N'-bis [4- (3-hydroxyphenoxy) phenyl] benzidine. Melting point 212.0 ° C. (TG-GTA endothermic peak) Elemental analysis value (%) Actual value (calculated value) C 81.52 (81.79) H 5.02 (5.16) N 3.78 (3.98) )

<Production Examples 7 to 11 of Diphenol Compound>
A dimethoxy compound was obtained by a method similar to that of Production Example 6 of diphenol compound, and then the diphenol compound shown in Table 2 was obtained.

[0073]

[Table 2]

<Production Example 1 of Polycarbonate Resin> 2.69 g of the diphenol compound obtained in Production Example 1 of diphenol compound, 1.97 g of 1,1-bis (4-hydroxyphenyl) cyclohexane and 4-tert-butylphenol 39 mg of sodium hydroxide 2.60 g and sodium hydrosulfite 83 mg of water 33 ml
Was stirred at room temperature for 20 minutes under a nitrogen stream. 2.32 g of bis (trichloromethyl) carbonate at 28 ° C with vigorous stirring and 28 ml of methylene chloride
The solution dissolved in was added all at once and stirred for 15 minutes, then 1 drop of triethylamine was added and stirred at room temperature for 1 hour. After diluting the contents with methylene chloride, the organic layer was separated, washed with 3% sodium hydroxide aqueous solution and 2% hydrochloric acid aqueous solution in that order, and then the conductivity of the aqueous layer was that of distilled water. It was washed with distilled water until it became almost equal to. The organic layer was dropped into a large amount of methanol, filtered and dried to obtain colorless polycarbonate resin No. 4.18 g of 1 was obtained.

Table 3 shows the analysis results. The composition ratios in the table represent k and j shown in this specification. The molecular weights in the table represent polystyrene-equivalent number average molecular weights and weight average molecular weights measured by gel permeation chromatography. The glass transition temperatures obtained from the differential scanning calorimetry are also shown in Table 3.

<Production Examples 2 to 18 of Polycarbonate Resin
> An aromatic polycarbonate resin used in the present invention was obtained according to Production Example 1 of Polycarbonate Resin except that the diphenol compound and the diol compound used in Production Example 1 of polycarbonate resin were replaced with those shown in Table 3. The analysis results are also shown in Table 3.

[0077]

[Table 3]

[Table 4]

[Table 5]

[0078]

EXAMPLES The present invention will be described in more detail with reference to examples below, but the present invention is not limited to these examples.

Example 1 An ITO substrate etched in a 2 mm stripe shape was washed with boiling alcohol, and the surface was further surface-treated with oxygen plasma. Resin No. A 1.0 wt% dichloromethane solution of the aromatic polycarbonate resin of 1 was prepared and filtered with a membrane filter having a pore size of 0.1 μm. Using this solution, a light emitting layer of an organic compound thin film having a film thickness of 100 nm was formed on an ITO substrate by a spin coating method. Then, after sufficiently drying, the substrate was set inside the vapor deposition apparatus, and a MgAg alloy layer was formed to a thickness of 200 nm through a mask at a vacuum degree of 10 ⁻⁴ Pa. The size of the light emitting surface was 2 mm × 2 mm. E produced in this way
When ITO was connected to the anode and MgAg was connected to the cathode of the L element, green light emission was observed at an applied voltage of 10V. Further, this light emitting layer did not undergo alteration such as crystallization.

Example 2 In a dichloromethane solution of the polycarbonate resin in Example 1, 2- (4-Biphenylyl) -5- (4-t-bu shown below was further added.
tylphenyl) -1,3,4-oxadiazole (PBD) 3% solids
An EL element was produced in the same manner as in Example 1 except that the EL element was dissolved so that the concentration became 0 wt%. When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus manufactured, green light emission was observed at an applied voltage of 10V. Further, this light emitting layer did not undergo alteration such as crystallization.

[0081]

[Chemical 18]

Example 3 2- (4-Biphenylyl) -5- (4-t-butylphenyl) -1,3,4 was added to a solution of the polycarbonate resin in Example 1 in dichloromethane.
An EL device was produced in the same manner as in Example 1 except that 30 wt% of solid content of -oxadiazole (PBD) and 3 wt% of solid amount of perylene derivative (C) having the following structure were dissolved. When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus manufactured, the applied voltage was 10 V.
An orange emission was observed at. Further, this light emitting layer did not undergo alteration such as crystallization.

[0083]

[Chemical 19]

Example 4 On a ITO substrate treated in the same manner as in Example 1, a dichloromethane solution of the same polycarbonate resin as in Example 1 was used and a film similar to that in Example 1 was formed by dipping method.
It was formed to 0 nm. Then, after sufficiently drying, the substrate is set inside the vapor deposition apparatus, an Alq molecule deposition film of the following structure (D) having a thickness of 50 nm is formed at a vacuum degree of 10 ⁻⁴ Pa, and a MgAg alloy layer is further formed through a mask. Having a thickness of 200 nm. The size of the light emitting surface was 2 mm × 2 mm. In the EL device thus manufactured, ITO was used as an anode and MgAg was used.
Was connected to the cathode, green emission was observed at an applied voltage of 10V. Further, this light emitting layer did not undergo alteration such as crystallization.

[0085]

[Chemical 20]

Example 5 Resin No. 1 was used as the polycarbonate resin. EL as in Example 2 except that the aromatic polycarbonate resin of 2 was used.
A device was produced. The EL device thus manufactured has I
When TO was connected to the anode and MgAg was connected to the cathode, green light emission was observed at an applied voltage of 10V. Further, this light emitting layer did not undergo alteration such as crystallization.

Examples 6 to 21 Resin Nos. Resin No. 2 instead of the aromatic polycarbonate resin of No. 2 3, 4, 5,
6, 7, 8, 9, 10, 11, 12, 13, 14, 1
An EL device was produced in the same manner as in Example 5 except that 5, 16, 17 and 18 aromatic polycarbonate resins were used. When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus manufactured, the applied voltage was 10 V.
A green emission was observed at. In addition, these aromatic polycarbonate resin Nos. The light emitting layer using 3 to 18 did not undergo alteration such as crystallization.

Example 22 An ITO substrate etched in a 2 mm stripe shape was washed with boiling alcohol, and the surface was further surface-treated with oxygen plasma. A copper phthalocyanine layer as a hole injecting and transporting layer was formed thereon by vacuum vapor deposition with a film thickness of 10 nm. On top of this, the resin No. used in Example 1 was used.
90 nm using 1 aromatic polycarbonate resin solution
An organic compound thin film was formed by the spin coating method with a film thickness of. Then, after sufficiently drying, the substrate is set inside the vapor deposition apparatus, and a vacuum degree of 10 ⁻⁴ Pa is applied to the substrate through a mask.
A 200 nm thick gAg alloy layer was formed. The size of the light emitting surface was 2 mm × 2 mm. EL manufactured in this way
When ITO was connected to the anode and MgAg was connected to the cathode of the device, green light emission was observed at an applied voltage of 10V. Also,
This light emitting layer did not undergo alteration such as crystallization.

Example 23 In the same manner as in Example 22, a copper phthalocyanine layer and a resin No. An organic compound thin film using the aromatic polycarbonate resin of 1 was prepared. On top of this, an Alq molecule deposition film of 50 nm is formed by vacuum deposition in the same manner as in Example 4.
Then, a MgAg alloy layer is further formed on the surface of the mask through a mask.
nm formed. The size of the light emitting surface was 2 mm × 2 mm. When ITO was connected to the anode and MgAg was connected to the cathode of the EL device thus manufactured, the applied voltage was 10 V.
A green emission was observed at. Further, this light emitting layer did not undergo alteration such as crystallization.

Example 24 First, a copper phthalocyanine layer was formed on an ITO substrate in the same manner as in Example 22. On top of this, the resin No. An organic compound thin film was prepared by spin coating using the mixed solution of the aromatic polycarbonate resin of No. 1, PBD, and the perylene derivative (C). Furthermore, the following structure (E)
The oxadiazole compound of
An electron transport layer of nm was prepared. In addition, M through the mask
A 200 nm thick gAg alloy layer was formed. The size of the light emitting surface was 2 mm × 2 mm. EL manufactured in this way
When ITO was connected to the anode and MgAg was connected to the cathode of the device, orange light emission was observed at an applied voltage of 10V. Further, this light emitting layer did not undergo alteration such as crystallization.

[0091]

[Chemical 21]

[0092]

Industrial Applicability According to the present invention, by containing an aromatic polycarbonate resin having a high charge transporting ability and excellent heat resistance, it is possible to obtain a stable organic compound which exhibits excellent luminescent characteristics and does not change properties such as crystallization. A thin film EL device can be provided.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Kazuyoshi Nagai             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Lee Honggu             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Shinichi Kawamura             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Susumu Suzuka             2 Kowa, 66 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa             Kawasaki West Building 11th floor Hodogaya Chemical Co., Ltd.             In-house (72) Inventor Katsuhiro Morooka             2 Kowa, 66 Horikawa-cho, Saiwai-ku, Kawasaki-shi, Kanagawa             Kawasaki West Building 11th floor Hodogaya Chemical Co., Ltd.             In-house F term (reference) 3K007 AB04 AB11 CA01 CB01 DA01                       DB03 EB00                 4J029 AA09 AB01 AC02 AD01 AE04                       BA01 BA02 BA03 BA04 BA05                       BA07 BA10 BB04A BB05A                       BB06A BB10A BB12A BB13A                       BB13B BC05A BC07A BD03A                       BD04A BD05A BD07A BD09A                       BD09B BD09C BE05A BE05B                       BE07 BF08 BF09 BF14A                       BF14B BF20 BF25 BF30                       BG08X BG08Y BH02 BH04                       DA09 DA13 DB11 DB13 DB17                       HA01 HC01 HC05 KE09 KE11

Claims (9)

[Claims] 1. An organic thin film EL device comprising a light emitting layer comprising at least one layer of an organic compound thin film between an anode and a cathode facing each other, wherein at least one layer of the organic compound thin film is represented by the following general formula (1): An organic thin film EL element, which is a layer containing an aromatic polycarbonate resin represented. [Chemical 1] (In the formula (1), Ar ₁ and Ar ₂ represent a substituted or unsubstituted arylene group, Ar ₃ represents a substituted or unsubstituted aryl group, Z represents an arylene group or —Ar ₄ —Za—Ar ₄ —, Ar ₄ is a substituted or unsubstituted arylene group, Za is a single bond, an oxygen atom, a sulfur atom or an alkylene group, Z ₁ is an oxygen atom or a sulfur atom, and n is 0 or 1.) 2. The organic thin film EL device according to claim 1, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin represented by the following general formula (2). [Chemical 2] (In the formula (2), Ra, Rb, Rc and Rd represent a substituted or unsubstituted alkyl group, and Ar ₃ , Z, Z ₁ and n are the same as defined in the general formula (1).) 3. An organic thin film EL device comprising a light emitting layer made of at least one layer of an organic compound thin film between an anode and a cathode facing each other, wherein at least one layer of the organic compound thin film has the above-mentioned general formula (1). And a constituent unit represented by the following general formula (3), the composition ratio of the constituent unit represented by the general formula (1) is k, and the general formula (3)
Wherein the composition ratio of the structural unit represented by is j is a layer containing an aromatic polycarbonate resin having a composition ratio of 0 <k / (k + j) ≦ 1. Thin film EL device. [Chemical 3] [In Formula (3), X is a substituted or unsubstituted aliphatic divalent group, a substituted or unsubstituted cycloaliphatic divalent group, a substituted or unsubstituted aromatic divalent group, or these can be linked. A divalent group, or (Here, R ¹ , R ² , R ³ , and R ⁴ are independently a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group or a halogen atom. Further, a and b are each independently. Is an integer of 0 to 4, and c and d are each independently 0.
Is an integer of 3 to 3, and when a plurality of R ¹ , R ² , R ³ and R ⁴ are present, they may be the same or different. Y is a single bond, a linear alkylene group having 2 to 12 carbon atoms,
A substituted or unsubstituted branched alkylene group having 3 to 12 carbon atoms, a divalent group composed of one or more alkylene groups having 1 to 10 carbon atoms and one or more oxygen atoms and / or sulfur atoms, -O -, - S -, - SO -, - SO 2 -, -
CO-, -COO-, or the following formula: Z ¹ and Z ^{2 each} represent a substituted or unsubstituted aliphatic divalent group or a substituted or unsubstituted arylene group, R 1
⁵ , R ⁶ and R ¹² represent a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, a substituted or unsubstituted aryl group, and R ⁷ , R ⁸ , R ⁹ and R
¹⁰ and R ¹¹ each independently represent a hydrogen atom, a halogen atom, a substituted or unsubstituted alkyl group, a substituted or unsubstituted alkoxy group, or a substituted or unsubstituted aryl group.
R ⁶ and R ⁷ may combine to form a carbon ring having 5 to 12 carbon atoms, R ¹³ and R ¹⁴ represent a single bond or an alkylene group having 1 to 4 carbon atoms, and R ¹⁵ and R ¹⁶ Each independently represent a substituted or unsubstituted alkyl group, a substituted or unsubstituted aryl group, e and g are integers from 0 to 4, f is 1 or 2, h
Represents an integer of 0 to 20, and i represents an integer of 0 to 2000. )
Represents ] 4. The organic thin film EL element according to claim 3, wherein the constitutional unit represented by the general formula (1) is a constitutional unit represented by the general formula (2). 5. The organic thin film EL device according to claim 3, wherein the aromatic polycarbonate resin is an aromatic polycarbonate resin represented by the following general formula (4). [Chemical 6] (In the formula (4), Ra, Rb, Rc, Rd, Ar ₃ , Z,
Z ₁ , X and n are the same as defined in the above general formulas (2) and (3). ) 6. The organic thin film EL device according to claim 1, wherein the layer containing the aromatic polycarbonate resin further contains an electron transporting substance. 7. The organic thin film EL element according to claim 1, wherein the layer containing the aromatic polycarbonate resin further contains an electron transporting substance and a light emitting substance. 8. The light emitting layer is a light emitting layer composed of a plurality of organic compound thin films including at least one hole injecting and transporting layer, and at least one layer of the hole injecting and transporting layer contains the aromatic polycarbonate resin. It is a layer, The organic thin film EL in any one of Claims 1-7 characterized by the above-mentioned.
element. 9. The light emitting layer is selected from a layer containing the aromatic polycarbonate resin, at least one hole injecting and transporting layer, at least one electron injecting and transporting layer, and at least one both injecting and transporting layers. 8. The organic thin film EL element according to claim 1, wherein the organic thin film EL element is composed of one or more of the following.