JP2003203775A - Electroluminescence element and light wavelength conversion method - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide an electroluminescence element and a light wavelength conversion method using the element having excellent film stability and durability and an excellent radiation at low voltage, and capable of facilitating production. <P>SOLUTION: In this electroluminescence element, electrodes are installed on both faces of a laminated body formed of a photoelectric transducing layer and an electroluminescence layer. In this light wavelength conversion method, electrodes are installed on both faces of the laminated body formed of the photoelectric transducing layer and the electroluminescence layer containing the electroluminescence element and charge generating material characterized in that a compound expressed by the following expression 1 is contained in the photoelectric transducing layer, light in a charge generating material absorbing area is radiated on the electrodes, and a voltage is applied to the electrodes to generate light from light emitting substances. The light wavelength conversion method uses the electroluminescence element. <P>COPYRIGHT: (C)2003,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to an electroluminescent device and a light wavelength conversion method, and more particularly, it has excellent flexibility and durability, has a good light emitting property at a low voltage, and is easy to manufacture. The present invention relates to an electroluminescent device and a light wavelength conversion method using the electroluminescent device.

[0002]

2. Description of the Related Art Conventionally, various types of electroluminescent elements or light conversion elements used in various display systems are known. For example, as a light conversion element, a stack of amorphous silicon and an electroluminescent layer is laminated. A wavelength conversion element has been proposed in which a voltage is applied to the body and a current is caused to flow by light irradiation in the absorption wavelength range of amorphous silicon to cause light emission of another wavelength from the electroluminescent layer (Miyao, Hiramoto, Yokoyama, '
90 Spring Society of Applied Physics Proceedings 31a-Q-7 and 28a
-PB-12).

However, this amorphous silicon has drawbacks such as high manufacturing cost and lack of flexibility. In addition, other conventional electroluminescent devices are basically devices that emit light by applying an electric field to a layer containing a substance that emits light by an electric field. There has been a problem that a decrease in emission luminance with time due to a decrease in injected charge density is observed. Therefore, in order to stabilize the light emission characteristics, when the light emission efficiency becomes low, it is necessary to further apply a voltage, and in this case, it is unavoidable to apply a voltage that is several times that at the time of initial driving. It was a cause of shortening the life. In order to solve this problem, light input type organic light emitting devices have been proposed (Japanese Patent Laid-Open Nos. 5-13170 and 7-175420), but these devices use a low molecular weight material. It is reported that Joule heat is generated by energization, and the heat causes the recrystallization of the organic layer, the diffusion of the low molecular weight material due to the progress of aggregation, etc., and the change of the film body over time for a long time. Therefore, there is an essential problem regarding the stability of the membrane. Further, since the low molecular weight material used has a low solubility in a solvent, the element is formed by a complicated operation such as vapor deposition, so that it cannot be easily manufactured.

[0004]

DISCLOSURE OF THE INVENTION The present invention provides an electroluminescent device which is excellent in film stability and durability, has a good light emitting property at a low voltage, and is easy to manufacture, and an optical device using this electroluminescent device. It is an object of the present invention to provide a wavelength conversion method.

[0005]

In order to solve the above problems, the inventors of the present invention have completed the present invention as a result of intensive trials by paying attention to the compound contained in the photoelectric conversion layer through trial and error. Came to. That is, according to the present invention, the following electroluminescent device and optical wavelength conversion method are provided. (1) An electroluminescent device in which electrodes are provided on both sides of a laminate including a photoelectric conversion layer and an electroluminescent layer, wherein the photoelectric conversion layer and / or the electroluminescent layer contains a polycarbonate resin, and the resin is An electroluminescent device comprising an aromatic carbonate structural unit represented by the following general formula (1) in a molecular main chain.

[Chemical 3] (In the formula, Ar₁, Ar₂, Ar₃, Ar_FourIs unsubstituted or substituted
Represents an arylene group, R ₁, R₂Is an unsubstituted or substituted ally
Group) (2) The polycarbonate resin has the following general formula (2)
Characterized by containing a carbonate structural unit represented
The electroluminescent element as described in (1) above.

[Chemical 4] (In the formula, X represents a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group or a divalent organic group containing at least two aromatic groups.) (3) The photoelectric conversion The electroluminescent element as described in (1) or (2) above, wherein the layer contains a charge generating material. (4) The photoelectric conversion layer has a laminated structure of a charge generation layer and a charge transport layer, and the polycarbonate resin is contained in the charge transport layer.
The electroluminescent element according to any one of (3). (5) The photoelectric conversion layer has a laminated structure composed of a charge generation layer and a charge transport layer, and the polycarbonate resin is contained in both layers of the charge generation layer and the charge transport layer. The electroluminescent element as described in any one of (1) to (3) above. (6) Light is emitted from the electroluminescent layer by irradiating the electroluminescent element having electrodes on both surfaces of the laminate including the photoelectric conversion layer and the electroluminescent layer, and further applying a voltage from the electrodes. A light wavelength conversion method for generating light, wherein the electroluminescence device according to any one of (1) to (5) is used as the electroluminescence device.

[0006]

BEST MODE FOR CARRYING OUT THE INVENTION The electroluminescent element of the present invention has a structure in which electrodes are provided on both surfaces of a laminate of a photoelectric conversion layer and an electroluminescent layer, and either the photoelectric conversion layer or the electroluminescent layer is provided. One or both of them contains a polycarbonate resin. The polycarbonate resin used in the present invention is characterized by having an aromatic carbonate structural unit represented by the following general formula (1) in its molecular main chain.

[0007]

[Chemical 5] In the above formula, Ar ₁ , Ar ₂ , Ar ₃ and Ar ₄ represent an unsubstituted or substituted arylene group, and R ₁ and R ₂ represent an unsubstituted or substituted aryl group.

The arylene group has 6 to 20 carbon atoms, preferably 6 to 14 carbon atoms. This arylene group is an arylene group derived from benzene (phenylene group)
Other than these, arylene groups derived from condensed polycyclic aromatic hydrocarbons such as naphthalene, phenanthrene, and anthracene, and arylene groups derived from chain polycyclic aromatic hydrocarbons such as biphenyl and terphenyl are included. Various substituents may be bonded to the arylene group.

The aryl group has 6 carbon atoms.
-20, preferably 6-14. This aryl group includes aryl groups (phenyl groups) derived from benzene, aryl groups derived from condensed polycyclic aromatic hydrocarbons such as naphthalene, phenanthrene, and anthracene, and chain polycyclic aromatic compounds such as biphenyl and terphenyl. An aryl group derived from a group hydrocarbon is included. Various substituents may be bonded to the aryl group.

Although the content of the aromatic carbonate structural unit represented by the general formula (1) is not particularly limited, it is usually
5 mol% or more, preferably 30 mol% or more, more preferably 50 mol% or more, and the upper limit value is 100 mol% based on the total number of moles of the monomer units contained in the molecular main chain.
Is.

The polycarbonate resin preferably contains a carbonate structural unit represented by the following general formula (2) as a copolymerization component in the molecular main chain together with the aromatic carbonate structural unit represented by the general formula (1). can do. The content ratio of the carbonate structural unit of the general formula (2) is 90 mol% or less, preferably 70 mol% or less, more preferably the total amount of the aromatic carbonate structural unit of the general formula (1). It is 50 mol% or less.

[Chemical 6]

In the above formula, X represents a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group or a divalent organic group containing at least two aromatic groups. The divalent aliphatic group has 2 to 20 carbon atoms, preferably 4 to 10 carbon atoms. The divalent aliphatic group includes a chain aliphatic group having 2 to 20 carbon atoms, preferably 2 to 10 carbon atoms and a cyclic aliphatic group having 4 to 12 carbon atoms, preferably 6 to 8 carbon atoms.

These aliphatic groups may have one or more various substituents. Such substituents include halogen atoms (chlorine, bromine, etc.) and heteroatoms (O, N,
S, etc.) containing various substituents (alkoxy, phenoxy group,
A hydroxyl group, a carboxyl group, an acyl group, an acyloxy group, a nitro group and the like).

In the divalent aromatic group, the number of carbon atoms is
It is 6 to 20, preferably 6 to 14. This divalent aromatic
The group includes aryl having 6 to 20 carbon atoms, preferably 6 to 10 carbon atoms.
Ren group and ant having 7 to 20 carbon atoms, preferably 7 to 10 carbon atoms
-Arylene alkylene group or arylene alkylene group
Is included. The arylene group contains the various aromas described above.
Those derived from group hydrocarbons are included. Arylene Archi
The len group also includes those derived from monoalkylated aromatic hydrocarbons.
, For example, a phenylene methylene group (-PhCH ₂−)
Etc. are included. The arylene dialkylene group contains a diar
Derived from rukylated aromatic hydrocarbons, such as phenyle
Dimethylene group (-CH₂PhCH₂-) Etc. are included
It The aromatic group has one or more various substituents.
May be.

In the above-mentioned divalent organic group containing at least two aromatic groups, the skeleton structure thereof has 14 to 40 carbon atoms, preferably 20 to 30 carbon atoms. This divalent organic group may contain a hetero atom such as an oxygen atom, a nitrogen atom or a sulfur atom.

Preferred as the divalent organic group containing at least two aromatic groups are the following formulas (3) to
What is represented by (5) can be shown.

[0017]

[Chemical 7]

[0018]

[Chemical 8]

[0019]

[Chemical 9]

In the above formulas (3) to (5), R ₃ , R ₄ ,
R ₅ and R ₆ are each a halogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, or an unsubstituted or substituted aryl group (R ₃ , R ₄ , R ₅ , and R ₆ when there are a plurality of each, They may be the same or different)
o and p are integers of 0 to 4, q and r are integers of 0 to 3.
Further, Y in the formula (3) is a linear alkylene group having 2 to 12 carbon atoms, an unsubstituted or substituted branched alkylene group having 3 to 12 carbon atoms, and one or more alkylene groups having 1 to 10 carbon atoms. And a divalent group composed of one or more oxygen atoms and / or sulfur atoms, —O—, —S—, —SO—, —S
_{O 2 -, - CO -,} - COO- or the following formula (6) - (1
The divalent group represented by 5) is shown.

[0021]

[Chemical 10]

[0022]

[Chemical 11]

[0023]

[Chemical 12]

[0024]

[Chemical 13]

[0025]

[Chemical 14]

[0026]

[Chemical 15]

[0027]

[Chemical 16]

[0028]

[Chemical 17]

[0029]

[Chemical 18]

[0030]

[Chemical 19]

In the above formulas (6) to (15), Z ¹ is an unsubstituted or substituted divalent aliphatic group having 2 to 20 carbon atoms, an unsubstituted or substituted arylene group having 6 to 20 carbon atoms, or at least 2 2 to 14 carbon atoms containing one aromatic group
Represents a valent organic group, Z ² is an unsubstituted or substituted C 2
To 20 divalent aliphatic groups or unsubstituted or substituted arylene groups. R ₇ is a halogen atom, an unsubstituted or substituted C 6-20 C 1-6 alkyl group, an unsubstituted or substituted C 1-6 alkoxy group, an unsubstituted or substituted C 6-20 1 to 14 carbon atoms containing an aryl group, an unsubstituted or substituted heteroaryl group having 4 to 15 carbon atoms or at least two aromatic groups.
A valent organic group is shown. R ₈ and R ₉ are hydrogen atom, halogen atom,
Unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, unsubstituted or substituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted carbon number 4 ~ 15 heteroaryl groups or monovalent organic groups containing at least two aromatic groups.
R ₈ and R ₉ may combine to form a carbon ring having 5 to 12 carbon atoms, and R ₁₀ , R ₁₁ , R ₁₂ and R ₁₃ are hydrogen atoms, halogen atoms, unsubstituted or substituted carbon atoms. 1 to 6 alkyl group, unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, unsubstituted or substituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted heteroaryl group having 4 to 15 carbon atoms, or A monovalent organic group having 14 to 40 carbon atoms containing at least two aromatic groups is shown. R ₁₄ is a halogen atom,
Unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, unsubstituted or substituted aryl group having 6 to 20 carbon atoms, unsubstituted or substituted carbon number 4 A monovalent organic group having 14 to 40 carbon atoms in the skeleton structure containing a heteroaryl group of 15 to 15 or at least two aromatic groups. R ₁₅ and R ₁₆ represent a single bond or an alkylene group having 1 to 4 carbon atoms. R ₁₇ , R ₁₈ , R
₁₉ , R ₂₀ is an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted aryl group having 6 to 20 carbon atoms, an unsubstituted or substituted heteroaryl group having 4 to 15 carbon atoms, or at least 2 A monovalent organic group having 14 to 40 carbon atoms containing one aromatic group is shown. s is an integer from 0 to 4, t
Is 1 or 2, u is an integer of 0 to 4, v is an integer of 0 to 20,
w represents 0 to 2000.

Specific examples of the various substituents shown above are shown below, but unless otherwise specified, the same notation has the same meaning in other general formulas. 1 to 6 carbon atoms
Examples of the alkyl group include a linear, branched or cyclic alkyl group. These alkyl groups may contain a fluorine atom or a cyano group as a substituent, and further, a phenyl group or a halogen atom or a carbon number of 1 to 6
It may contain a phenyl group substituted with a linear, branched or cyclic alkyl group.

Specifically, methyl group, ethyl group, n-propyl group, i-propyl group, t-butyl group, s-butyl group, n-butyl group, i-butyl group, trifluoromethyl group, 2 -Cyanoethyl group, benzyl group, 4-chlorobenzyl group, 4-methylbenzyl group, cyclopentyl group, cyclohexyl group and the like can be mentioned. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

Specific examples of the unsubstituted or substituted aryl group having 6 to 20 carbon atoms include the following. Phenyl group, naphthyl group as condensed polycyclic group, pyrenyl group, 2-fluorenyl group, 9,9-dimethyl-2
-Fluorenyl group, azulenyl group, anthryl group, triphenylenyl group, chrysenyl group, fluorenylidenephenyl group, 5H-dibenzo [a, d] cycloheptenylidenephenyl group, biphenylyl group as a non-condensed polycyclic group, terphenylyl group and the like.

As the monovalent organic group having 14 to 40 carbon atoms in the skeleton structure containing at least two aromatic groups, the monovalent group of the following formula (16) and the above-mentioned formulas (4) and (5) can be used. A monovalent group having a skeletal structure can be shown.

[Chemical 20] In the formula (16), W is -O-, -S-, -SO-,
—SO ₂ —, —CO— or the following general formula (17), (1
It is selected from the divalent group represented by 8).

[0036]

[Chemical 21]

[0037]

[Chemical formula 22]

In the above formulas (17) and (18), R ₂₁ is a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, Halogen atom, unsubstituted or substituted, having 6 to 2 carbon atoms
An aryl group of 0, a heteroaryl group having 4 to 15 carbon atoms,
A substituted or unsubstituted arylamino group having 6 to 20 carbon atoms, a nitro group or a cyano group, R ₂₂ represents a hydrogen atom, an unsubstituted or substituted alkyl group having 1 to 6 carbon atoms, an unsubstituted or substituted carbon group Represents an aryl group of the formula 6 to 20, h
Is an integer of 1 to 12, and i is an integer of 1 to 3. Examples of the heteroaryl group having 4 to 15 carbon atoms include a thienyl group, a benzothienyl group, a furyl group, a benzofuranyl group and a carbazolyl group. The above aryl group, heteroaryl group, and the like may have the following groups as substituents.

Halogen atom, trifluoromethyl group, cyano group, nitro group. An unsubstituted or substituted alkyl group having 1 to 6 carbon atoms. Unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms (as an unsubstituted or substituted alkoxy group having 1 to 6 carbon atoms, an alkyl group as defined above is replaced with an alkoxy group, a methoxy group, an ethoxy group, n-propoxy group, i-propoxy group, n-butoxy group, i-butoxy group, s-butoxy group, t-butoxy group, 2-hydroxyethoxy group, 2-cyanoethoxy group, benzyloxy group, 4-methylbenzyl An oxy group, a trifluoromethoxy group, etc.), an aryloxy group (an aryloxy group includes an aryl group having a phenyl group or a naphthyl group. A 6-alkyl group, an unsubstituted or substituted C1-C6 alkoxy group, or a halogen atom may be contained as a substituent. . Specifically, phenoxy group, 1-naphthyloxy group, 2-naphthyloxy group, 4
-Methylphenoxy group, 4-methoxyphenoxy group, 4
-Chlorophenoxy group, 6-methyl-2-naphthyloxy group and the like). Substituted mercapto group or aryl mercapto group (specifically, examples of the substituted mercapto group or aryl mercapto group include a methylthio group, an ethylthio group, a phenylthio group and a p-methylphenylthio group). Alkyl-substituted amino group (specifically, diethylamino group, N-methyl-N-phenylamino group, N, N-diphenylamino group, N, N-di (p-tolyl) amino group, dibenzylamino group, piperidino Group, morpholino group, julolidyl group and the like). Acyl group (specifically, an acyl group includes an acetyl group, a propionyl group, a butyryl group, a malonyl group, a benzoyl group, etc.).

Specific examples of the divalent group represented by X in the general formula (2) include ethylene glycol, diethylene glycol, triethylene glycol, polyethylene glycol, polytetramethylene 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, 1,1
2-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-di Methanol, 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, Examples thereof include divalent groups obtained by removing two hydroxy groups from a diol such as 4-bis (5-hydroxypentyl) benzene, 1,4-bis (6-hydroxyhexyl) benzene, and isophoronediol.

One or more represented by Y in the general formula (3)
An alkylene group having 1 to 10 carbon atoms and one or more oxygen atoms
And / or as a specific example of a divalent group composed of a sulfur atom,
OCH₂CH₂O, OCH₂CH₂OCH₂CH₂O, O
CH₂CH₂OCH₂CH₂OCH₂CH₂O, OCH₂CH₂
CH₂O, OCH₂CH₂CH₂CH₂O, OCH₂CH₂C
H₂CH₂CH₂CH₂O, OCH₂CH₂CH₂CH₂CH₂
CH₂CH₂CH₂O, CH₂O, CH₂CH₂O, CHEt
OCHEtO, CHCH₃O, SCH₂OCH₂S, CH₂
OCH₂, OCH₂OCH₂O, SCH₂CH₂OCH₂OC
H₂CH₂S, OCH₂CHCH₃OCH₂CHCH₃O, S
CH₂S, SCH₂CH₂S, SCH₂CH ₂CH₂S, SC
H₂CH₂CH₂CH₂S, SCH₂CH₂CH₂CH₂CH₂
CH₂S, SCH₂CH₂SCH₂CH₂S, SCH₂CH₂
OCH₂CH₂OCH₂CH₂S etc. are mentioned.

Examples of the substituent bonded to the branched alkylene group having 3 to 12 carbon atoms include an unsubstituted or substituted aryl group and a halogen atom. When Z ¹ and Z ² are an unsubstituted or substituted aliphatic divalent group, examples of the divalent group include the aliphatic divalent group represented by X and the cycloaliphatic divalent group. it can.

When Z ¹ and Z ² in the general formulas (7) and (8) are an unsubstituted or substituted arylene group, the group is a divalent group derived from the above unsubstituted or substituted aryl group. Can be mentioned.

Specific preferred examples of the case where X in the general formula (2) is an aromatic divalent group include diols shown below from which two hydroxyl groups have been removed.
Bis (4-hydroxyphenyl) methane, 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-
Hydroxyphenyl) norbornane, 2,2-bis (4
-Hydroxyphenyl) adamantane, 4,4'-dihydroxydiphenyl ether, 4,4'-dihydroxy-3,3'-dimethyldiphenyl 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'-spirobi (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-dihydroxyphenoxathiin, 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-perfluorobutane, 1,3-bis (4-
Hydroxyphenyl) tetramethyldisiloxane and the like.

The polycarbonate resin containing an aromatic carbonate structural unit represented by the above general formula (1) used in the present invention is described in, for example, JP-A-9-3020.
The details are described in Japanese Patent Publication No. 84.

The polycarbonate resin having the aromatic carbonate structure represented by the general formula (1) used in the present invention can be produced by the same method as the conventionally known method of polymerizing a bisphenol compound and a carbonic acid derivative. The manufacturing method thereof is described in, for example, the Polycarbonate Resin Handbook (editor: Seiichi Homma, published by Nikkan Kogyo Shimbun). The preferred molecular weight of this polycarbonate resin is 1000 to 100 in terms of polystyrene equivalent number average molecular weight.
0000, and more preferably 2000-50000
It is 0. If the molecular weight is too low, it will be cracked during film formation, making it less practical, and if the molecular weight is too high, the solubility in general solvents will be poor and the viscosity of the solution will be high, resulting in coating. Becomes difficult, and similarly, it becomes less practical.

The polycarbonate resin may be used alone or in the form of a mixture with other resins. Examples of other resins include poly-N
-Carbazole derivative, poly-γ-carbazolylethylglutamate derivative, pyrene-formaldehyde condensate derivative, polyvinylpyrene, polyvinylphenanthrene, oxazole derivative, imidazole derivative, acetophenone derivative (described in JP-A-7-325409), distyryl Benzene derivative, diphenethylbenzene derivative (described in JP-A-9-127713), α
-Phenylstilbene derivative (Japanese Patent Laid-Open No. 9-297419)
JP-A-9-807.
83), diphenylcyclohexane derivative (described in JP-A-9-80772), distyryltriphenylamine derivative (described in JP-A-9-222740), diphenyldistyrylbenzene derivative (described in JP-A-9-772). Nos. 265197 and 9-265201), stilbene derivatives (described in JP-A-9-212877), m-phenylenediamine derivatives (described in JP-A-9-304956 and 9-304957), Resorcin derivatives (described in JP-A-9-329907), triarylamine derivatives (JP-A-64-
No. 9964, JP-A-7-199503, and JP-A-8-1.
76293, JP-A-8-208820, JP-A-8-
253568, JP-A-8-269446, JP-A-3
-221522, JP-A-4-11627, JP-A-4
-183719, JP-A-4-124163, JP-A-4-320420, JP-A-4-316543, JP-A-5-310904, JP-A-7-56374, JP-A-8-62864, U.S. Pat. 5,428,09
No. 0, 5, 486, 439, etc.) and the like.

For the purpose of improving electrical characteristics,
The photoelectric conversion layer may contain a low molecular weight charge transport material together with a polycarbonate resin. As such a material, a conventionally known low molecular weight charge transport material can be used, and these low molecular weight charge transport materials can be used alone or in combination of two or more kinds. Examples of conventionally known low molecular weight charge transport materials include α-phenylstilbene derivatives (described in JP-A-57-73075) and hydrazone derivatives (JP-A-55-154955 and 55-15695).
No. 4, No. 55-52063, No. 56-81850, etc.), triphenylmethane derivative (Japanese Patent Publication No.
-10983), anthracene derivative (described in JP-A-51-94829), oxazole derivative, oxadiazole derivative (described in JP-A-52-1390).
No. 65, No. 52-139066), imidazole derivatives, triphenylamine derivatives (JP-A-3-
285960), benzidine derivatives (described in JP-B-58-32372), styryl derivatives (described in JP-A-56-29245 and JP-A-58-198043), and carbazole derivatives (JP-A-58). -5
No. 8552), pyrene derivatives (Japanese Patent Laid-Open No. 2-9)
No. 4812).

Next, the structure of the photoelectric conversion layer will be described. The photoelectric conversion layer can contain the polycarbonate resin. When a polycarbonate resin is used as the photoelectric conversion layer material, this can be used alone, but at this time, it is excited by using a light source such as a nitrogen laser. Further, typically, a charge transfer complex composed of poly-N-vinylcarbazole and 2,4,7-trinitro-9-fluorenone can also be used for the photoelectric conversion layer. Further, a dye-sensitized photoelectric conversion layer can also be used.

As the sensitizing dye, triarylmethane dyes such as Brilliant Green, Victoria Blue B, Methyl Violet, Crystal Violet, Acid Violet 6B, Rhodamine B, Rhodamine 6 are used.
G, rhodamine G extra, eosin S, erythrosine, rose bengal, xanthene dyes such as fluorescein, thiazine dyes such as methylene blue, and cyanine dyes such as cyanine.

In order to form the photoelectric conversion layer in the present invention, known methods such as a spin coating method, a casting method and an inkjet method can be used, whereby a thin photoelectric conversion layer can be obtained. Polycarbonate resin is easily dissolved in an organic solvent such as dichloromethane or tetrahydrofuran. Therefore, it is possible to prepare a thin-film photoelectric conversion layer by preparing a solution having an appropriate concentration with an appropriate solvent capable of dissolving this substance, and applying the solution using the above method or the like.

In the present invention, the photoelectric conversion layer may further contain a charge generating material. Examples of the charge generation material include inorganic materials such as selenium, selenium-tellurium, cadmium sulfide, cadmium sulfide-selenium, and α-silicon, and examples of the organic material include CI Pigment Blue 25 (color index CI21).
180), CI Pigment Red 41 (CI212
00), CI Acid Red 52 (CI4510
0), CI Basic Red 3 (CI4521)
0), an azo pigment having a carbazole skeleton (JP-A-53-53
-95033), an azo pigment having a distyrylbenzene skeleton (JP-A-53-133445), an azo pigment having a triphenylamine skeleton (described in JP-A-53-132347), and dibenzothiophene. Azo pigments having a skeleton (described in JP-A-54-21728), azo pigments having an oxadiazole skeleton (described in JP-A-54-12742), azo pigments having a fluorenone skeleton (JP-A-54). No. 22834), an azo pigment having a bisstilbene skeleton (described in JP-A-54-17733), and an azo pigment having a distyryloxadiazole skeleton (JP-A-54-21).
29), azo pigments having a distyrylcarbazole skeleton (described in JP-A-54-14967).
Azo pigments such as CI Eye Bat Brown 5 (CI
73410), sea butt die (CI73030)
And indigo-based pigments such as Argos Scarlet B (manufactured by Bayer) and Indense Scarlet R (manufactured by Bayer).

A phthalocyanine pigment represented by the following formula (19) is also useful as a charge generating substance. In the formula, M
(Central metal) represents metal or hydrogen.

[0054]

[Chemical formula 23]

This M (central metal) is H, Li, Be,
Na, Mg, Al, Si, K, Ca, Sc, Ti, V,
Cr, Mn, Fe, Co, Ni, Cu, Zn, Ga, G
e, Y, Zr, Nb, Mo, Tc, Ru, Rh, Pd,
Ag, Cd, In, Sn, Sb, Ba, Hf, Ta,
W, Re, Os, Ir, Pt, Au, Hg, Tl, L
a, Ce, Pr, Nd, Pm, Sm, Eu, Gd, T
b, Dy, Ho, Er, Tm, Yb, Lu, Th, P
It consists of a simple substance such as a, U, Np and Am or two or more kinds of elements such as oxides, chlorides, fluorides, hydroxides and bromides.
The central metal is not limited to these elements.

The charge generating substance having a phthalocyanine skeleton in the present invention is required to have at least the basic skeleton of the general formula (19), a substance having a multimeric structure such as a dimer or trimer, and a higher one. It may have the following polymer structure. Further, the basic skeleton may have various substituents. Among these various phthalocyanines, oxotitanium phthalocyanine having TiO as the central metal and metal-free phthalocyanine having H as the central metal are particularly preferable in terms of photoreceptor characteristics.

It is also known that these phthalocyanines have various crystal forms. For example, in the case of oxotitanium phthalocyanine, α, β, γ, m, y type, etc., in the case of copper phthalocyanine, α, It has crystal polymorphisms such as β and γ. Even in phthalocyanines having the same central metal, various characteristics change due to the change in crystal type. Among them, it has been reported that the characteristics of the photoconductor also change with such a crystal type change.
Vol. 29, No. 4 (1990)]. From this, each phthalocyanine has an optimal crystal form in terms of photoreceptor characteristics, and particularly in oxotitanium phthalocyanine,
The y-type crystal form is preferred. Further, two or more kinds of the charge generating substances described above may be mixed and used.

In the case of the electroluminescent device of the present invention, considering the photoelectric conversion efficiency and the like, it is preferable to form a function-separated photoelectric conversion layer composed of a charge generating material and a charge transporting material. That is, the photoelectric conversion layer in the electroluminescent element of the present invention is preferably a laminate of a charge generation layer and a charge transport layer containing a polycarbonate resin.

The charge generating layer used in the electroluminescent device of the present invention can be provided by dissolving or dispersing the charge generating material in a suitable solvent, if necessary, with a binder resin, coating and drying. Any conventionally known binder resin having good insulating properties can be used as the binder resin, and there is no particular limitation. Examples of the binder resin include polyethylene, polyvinyl butyral, polyvinyl formal, polystyrene resin, phenoxy resin, polypropylene, acrylic resin,
Methacrylic resin, vinyl chloride resin, vinyl acetate resin, epoxy resin, polyurethane resin, phenol resin, polyester resin, alkyd resin, polycarbonate resin, polyamide resin, silicone resin, melamine resin, etc. Condensation-type resins and copolymer resins containing two or more of repeating units of these resins, for example, vinyl chloride-vinyl acetate copolymer, styrene-acrylic copolymer, vinyl chloride-vinyl acetate-maleic anhydride copolymer In addition to insulating resins such as polymer resins, polymer organic semiconductors such as poly-N-vinylcarbazole may be mentioned.

These binder resins can be used alone or as a mixture of two or more kinds. The amount of the binder resin is 0 to 5 parts by weight, preferably 0.1 to 3 parts by weight, based on 1 part by weight of the charge generating material.

Examples of the solvent used for preparing the dispersion or solution for forming the charge generating layer include N, N-dimethylformamide, toluene, xylene, monochlorobenzene, 1,2-dichloroethane, 1,1, 1-Trichloroethane, dichloromethane, 1,1,2-trichloroethane, trichloroethylene, tetrahydrofuran, methyl ethyl ketone, methyl isobutyl ketone, cyclohexanone, ethyl acetate, butyl acetate, dioxane and the like can be mentioned.

The dispersion method of the charge generation layer dispersion liquid is as follows:
Examples thereof include a ball mill, ultrasonic waves, a homomixer, and the like, and examples of the coating means include a dipping coating method, a blade coating method, a spray coating method, an inkjet coating method, and the like.

The luminescent material used in the electroluminescent layer of the electroluminescent device of the present invention is a laser dye or the like which exhibits strong fluorescence in a solution state, and existing low molecular weight compounds which have been used as luminescent materials in organic thin film EL devices. It is possible to utilize fluorescent materials.

Examples of the low molecular weight fluorescent material include:
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, and derivatives thereof.

Further, two or more kinds of the above-mentioned light emitting materials may be mixed and used, or these may be laminated to form an electroluminescent layer. As a method for forming an electroluminescent layer containing the above light emitting material, the same film forming method as in the case of forming the above photoelectric conversion layer can be used. Other than that, a dry film forming method such as a vacuum evaporation method or a sputtering method can also be used.

In the electroluminescent device of the present invention, the electroluminescent layer may also contain a polycarbonate resin.

The electroluminescent device and the light wavelength conversion method of the present invention will be described below with reference to the drawings. Figure 1
FIG. 3 is a cross-sectional view of a typical electroluminescent device according to the present invention. 1
Is a photoelectric conversion layer, 2 is an electroluminescent layer which emits light by an electric field, 3
Is an electrode, 4 is an upper electrode, and 5 is a support. The photoelectric conversion layer contains a polycarbonate resin. In this electroluminescent device, the thickness of the photoelectric conversion layer is 10 nm to 50 μm.
m, preferably 50 nm to 30 μm, and the thickness of the electroluminescent layer is 5 nm to 20 μm.

FIG. 2 is a cross-sectional view of a typical electroluminescent device of the present invention in which the photoelectric conversion layer 1 is composed of a charge generation layer 12 and a charge transport layer 11. A polycarbonate resin is contained in the charge transport layer. In this electroluminescent device, the thickness of the charge generation layer is 5 nm to 5 μm, preferably 10 nm.
nm to 1 μm, and the thickness of the charge transport layer is 0.1 μm.
m to 50 μm, preferably 1 μm to 30 μm.

FIG. 3 is a sectional view showing an example of the electroluminescent device of the present invention, in which the electroluminescent layer 6 contains a polycarbonate resin. The polycarbonate resin can be contained in both the photoelectric conversion layer and the electroluminescent layer. FIG. 4 is a cross-sectional view of the electroluminescent device of the present invention showing this example, in which both the electroluminescent layer 6 and the photoelectric conversion layer 7 contain a polycarbonate resin. It is desirable that the photoelectric conversion layer simultaneously contains a charge generation material. Furthermore, the photoelectric conversion layer can also be configured by laminating a charge generation layer and a charge transport layer containing a polycarbonate resin. FIG. 5 is a cross-sectional view of the electroluminescent device of the present invention showing this example, in which the photoelectric conversion layer is formed by stacking the charge generation layer 12 and the charge transport layer 71, and the charge transport layer 71 contains a polycarbonate resin. .

When a DC voltage is applied to the electroluminescent device of the present invention, the electrode 3 serves as a positive electrode and the electrode 4 serves as a negative electrode. For the purpose of radiating the light emitted from the electroluminescent layer to the outside through the electrode 3 and the support 5, the electrode 3 and the support preferably have high transparency, and the absorption of the charge-generating substance is More light can be extracted to the outside if it does not overlap the emission wavelength.

On the other hand, when the light emitted through the electrode 4 is used, the electrode 4 should be as transparent as possible (a transparent electrode or aluminum is vapor-deposited thinly). The transparent support may be attached to the electrode 4 side. When used as an electroluminescent element for display, light is not particularly radiated from the outside,
The room illumination light may be used. Further, if the charge generating layer is made thin, electroluminescence can be performed especially in a dark place.
Further, as shown in FIG. 2, it is also possible to provide a charge transport layer between the light emitting layer and the counter electrode side. Also, a charge generation layer can be provided on the counter electrode side.

The electrode 3 is 4 eV, preferably 4.
A metal, an alloy, a metal oxide having a work function larger than 8 eV is used. Specific examples of such an electrode material include gold, platinum, palladium, silver, tungsten, nickel, cobalt, ITO, CuI, SnO ₂ , ZnO and the like. In particular, an ITO substrate is suitable. In the case of an ITO substrate, one having a smooth surface is preferable, and the surface should be 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, the electrode 4 has a work function of 4 eV.
Smaller metals, alloys, etc. are utilized. Specific examples of such substances include sodium, calcium, magnesium, lithium, aluminum, samarium and alloys thereof. At least one of the materials used for the electrode 1 and the electrode 4 is preferably sufficiently transparent in the emission wavelength region of the device. A glass plate or a synthetic resin sheet is usually used as the substrate 5, and
It is preferably transparent to the light emitted from the light emitting layer.

Next, the operation of the electroluminescent device of the present invention will be described with reference to FIG. When this electroluminescent element is to function as a light conversion element, first, the electrodes 3 and 4 are
An electric field is applied between them, and at the same time, for example, light in the absorption wavelength region of the photoelectric conversion layer 1 is irradiated from below. The voltage between the electrodes 3 and 4 is 30 V or less, preferably 10 V or less. The charges (for example, holes) generated in the photoelectric conversion layer 1 are generated in the light emitting layer 2
To the interface with. When the light emitting layer 2 has electron mobility,
Electrons injected from the upper electrode 4 into the electroluminescent layer 2 meet the holes, and light having a wavelength different from that of the irradiation light based on the light emitting material in the electroluminescent layer occurs. In the electroluminescent device of the present invention, charges are injected from the metal electrode to the light emitting portion through the photoelectric conversion layer, and therefore deterioration at the joint between the metal electrode and the light emitting layer is unlikely to occur, and the light emitting characteristics are stable. Is. The electroluminescent element of the present invention contains a photoconductive polycarbonate resin having excellent charge transporting ability and mechanical strength in the photoelectric conversion layer and / or the electroluminescent layer. It has the following advantages as compared with JP-A-5-13170. (1) Since the electroluminescent device of the present invention is configured to contain a polymer material containing a polycarbonate resin, recrystallization of an organic layer due to energization, progress of aggregation, etc. hardly occur, and film stability over time is achieved. Excellent in. (2) Further, it has a relatively high solubility in a solvent, a film can be formed by coating, and it can be easily manufactured.

[0075]

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

Example 1 A glass substrate provided with an ITO film having a thickness of 150 nm was washed with boiling alcohol, and the surface was further surface-treated with oxygen plasma. X-type copper phthalocyanine 5 on this substrate
After vapor-depositing 0 nm, a 1.5 wt% dichloromethane solution of an aromatic polycarbonate resin having a structural unit represented by the following formula (20) was prepared as a polycarbonate resin used in the present invention, and a membrane filter having a pore diameter of 0.1 μm was prepared. Filtered through. Using this solution, a 100-nm-thick film was formed on the X-type copper phthalocyanine film by spin coating to form a photoelectric conversion layer. After sufficiently drying, 50 n of 1,4-bis (4-di-p-tolylaminostyryl) benzene as a light emitting layer was formed on the photoelectric conversion layer.
m is vapor-deposited, and then 2- (4-ter
t. -Butylphenyl) -5- (4-biphenylyl)-
1,3,4-oxadiazole was vapor-deposited to a thickness of 100 nm to form an electroluminescent layer. Further, a MgAg alloy layer having a thickness of 200 nm was formed thereon. In the electroluminescent device thus produced, ITO was connected to the anode and MgAg was connected to the cathode,
When a laser beam of 780 nm was irradiated from the ITO side at an applied voltage of 10 V, blue-green light emission was observed.

[0077]

[Chemical formula 24]

Example 2 The light emitting layer used in Example 1 was formed of tris (8) represented by the following formula (21)
-Hydroxyquinolyl) aluminium, except
An electroluminescence device was prepared in the same manner as in Example 1. When this element was connected to ITO as an anode and MgAg as a cathode and irradiated with a laser beam of 780 nm from the ITO side at an applied voltage of 10 V, green light emission was observed.

[0079]

[Chemical 25]

Example 3 A glass substrate provided with an ITO film having a thickness of 150 nm was washed with boiling alcohol, and the surface was surface-treated with oxygen plasma. A charge generation layer forming liquid consisting of Y-type titanyl phthalocyanine / silicone resin (trade name KR5240, manufactured by Shin-Etsu Chemical Co., Ltd.) / 2-butanone was applied onto this substrate by a doctor blade and dried to form a 100 nm photoelectric conversion layer. 1.5w of an aromatic polycarbonate resin comprising a structural unit represented by the following formula (22) on the photoelectric conversion layer
2- (4-tert.-butylphenyl) -5- (4-biphenylyl) -1,3,3 in a t% dichloromethane solution.
30 wt% of solid content of 4-oxadiazole and a small amount of 3w of solid content of perylene derivative represented by the following formula (23).
Dissolve t%, apply doctor blade, dry, and
An electroluminescent layer of 0 nm was formed. When the electroluminescent device thus produced was connected to ITO as an anode and MgAg as a cathode and irradiated with a laser beam of 780 nm from the ITO side at an applied voltage of 10 V, orange light emission was observed.

[0081]

[Chemical formula 26]

[0082]

[Chemical 27]

Example 4 In place of the X-type copper phthalocyanine vapor deposited film in Example 1, 3.6 g of a bisazo pigment represented by the following formula (24) was pulverized and mixed with 65.63 g of cyclohexanone in a ball mill to obtain a dispersion liquid. Same as Example 1 except that 1 part by weight of the solution was further mixed with 4 parts by weight of cyclohexanone to form a 100 nm charge generation layer on the ITO film treated in the same manner as in Example 1 by an immersion coating method. Then, a charge transport layer and an electroluminescent layer were provided to prepare an electroluminescent device.
The device manufactured in this manner was prepared by using ITO as an anode and Mg.
When Ag was connected to the cathode and light of 580 nm was irradiated from the ITO side at an applied voltage of 10 V, blue-green light emission was observed.

[0084]

[Chemical 28]

Example 5 Instead of the bisazo pigment in Example 4, the following formula (2
3.6 g of the trisazo pigment represented by 5) was pulverized and mixed with 65.63 g of cyclohexanone in a ball mill,
A liquid obtained by further mixing 4 parts by weight of cyclohexanone with 1 part by weight of the obtained dispersion liquid was treated in the same manner as in Example 1.
A charge transport layer and a charge light emitting layer were provided in the same manner as in Example 4 except that a 100 nm charge generation layer was provided on the TO film by an immersion coating method, to fabricate an electroluminescent device. In the device thus manufactured, ITO was connected to the anode and MgAg was connected to the cathode, and 780 nm from the ITO side at an applied voltage of 10V.
When it was irradiated with the laser light of, a blue-green light emission was observed.

[0086]

[Chemical 29]

Example 6 An electroluminescent device was produced by spin-coating the electroluminescent layer-forming resin liquid shown in Example 3 on the photoelectric conversion layer produced in Example 4. When the device thus produced was connected to ITO as an anode and MgAg as a cathode and irradiated with light of 580 nm from the ITO side at an applied voltage of 10 V, orange light emission was observed.

Example 7 2,4,7-Trinitro-9-fluorenone and poly-N
-Thickness of vinylcarbazole in a molar ratio of 1: 1 2
An electroluminescent element was produced by spin-coating the electroluminescent layer-forming resin liquid described in Example 3 on the 00 nm photoelectric conversion layer. The device thus manufactured was
TO is connected to the anode and MgAg is connected to the cathode, and the applied voltage is 10
When a xenon light was irradiated from the ITO side at V, orange light emission was observed.

Example 8 A 1.5 wt% xylene solution of an aromatic polycarbonate resin consisting of the structural unit represented by the above formula (20) was prepared and filtered with a membrane filter having a pore size of 0.1 μm. This solution was used to spin coat an ITO film to form a photoelectric conversion layer having a thickness of 250 nm. An electroluminescent element was prepared by providing the electroluminescent layer shown in Example 1 on this photoelectric conversion layer. When the device thus produced was connected to ITO as an anode and MgAg as a cathode and irradiated with nitrogen laser light from the ITO side at an applied voltage of 10 V, blue-green light emission was observed.

[0090]

According to the present invention, an electroluminescent device which is excellent in flexibility and durability, has a good light emitting property at a low voltage, and is easy to manufacture, and a light wavelength conversion using the electroluminescent device. The method is provided and contributes greatly to the fields of designing, manufacturing, etc. of the light emitting material used for various display systems.

[Brief description of drawings]

FIG. 1 is a cross-sectional view showing an electroluminescent device of the present invention.

FIG. 2 is a cross-sectional view showing another electroluminescent device of the present invention.

FIG. 3 is a cross-sectional view showing still another electroluminescent device of the present invention.

FIG. 4 is a cross-sectional view showing still another electroluminescent device of the present invention.

FIG. 5 is a cross-sectional view showing still another electroluminescent device of the present invention.

[Explanation of symbols]

1 Photoelectric Conversion Layer 11 Charge Transport Layer 12 Charge Generation Layer 2 Electroluminescent Layer 3 Electrode 4 Electrode 5 Support 6 Electroluminescent Layer Containing Polycarbonate Resin 7 Photoelectric Conversion Layer 71 Containing Polycarbonate Resin and Charge Generating Agent Containing Polycarbonate Resin Charge transport layer

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Shinichi Kawamura             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Takashi Okada             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Toshiya Kosaka             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh (72) Inventor Tamotsu Ariga             1-3-3 Nakamagome, Ota-ku, Tokyo Stocks             Company Ricoh F-term (reference) 3K007 AB02 AB06 AB11 AB18 DB03

Claims (6)

[Claims] 1. A laminate comprising a photoelectric conversion layer and an electroluminescent layer.
An electroluminescent device having electrodes on both sides of a body, comprising:
The conversion layer and / or the electroluminescent layer is a polycarbonate resin
Containing the following general formula (1) in the molecular main chain:
Containing an aromatic carbonate structural unit represented by
An electroluminescent device characterized by: [Chemical 1] (In the formula, Ar₁, Ar₂, Ar₃, Ar_FourIs unsubstituted or substituted
Represents an arylene group, R ₁, R₂Is an unsubstituted or substituted ally
Group) 2. The electroluminescent device according to claim 1, wherein the polycarbonate resin contains a carbonate structural unit represented by the following general formula (2). [Chemical 2] (In the formula, X represents a substituted or unsubstituted divalent aliphatic group, a substituted or unsubstituted divalent aromatic group, or a divalent organic group containing at least two aromatic groups) 3. The electroluminescent device according to claim 1, wherein the photoelectric conversion layer contains a charge generating material. 4. The photoelectric conversion layer has a laminated structure of a charge generating layer and a charge transporting layer, and the polycarbonate resin is contained in the charge transporting layer. 4. The electroluminescent element according to any one of 3 to 3. 5. The photoelectric conversion layer has a laminated structure composed of a charge generation layer and a charge transport layer, and the polycarbonate resin is contained in both the charge generation layer and the charge transport layer. The electroluminescent element according to claim 1. 6. An electroluminescent device having electrodes on both sides of a laminate comprising a photoelectric conversion layer and an electroluminescent layer is irradiated with light, and a voltage is applied from the electrodes, whereby the electroluminescent layer is separated from the electroluminescent layer. A light wavelength conversion method for generating light,
A light wavelength conversion method, wherein the electroluminescent device according to claim 1 is used as the electroluminescent device.