JP2003277369A - Nile red-type compound emitting red light, method for producing the same and light-emitting element utilizing the same - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a nile red-type new compound capable of emitting red light near to magenta, and to provide a new method for producing the compound, and a high-intensity element emitting the red light near to the magenta. <P>SOLUTION: The nile red-type compound emitting the red light is represented by general formula (1). The new method for producing the compound involves reacting a nile red type coloring matter with an electron-attracting aromatic acetonitrile. The high-intensity light-emitting element contains a composition containing the nile red-type compound emitting the red light. <P>COPYRIGHT: (C)2004,JPO

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a Nile red-based red light-emitting compound, a method for producing the same, and a light-emitting device. More specifically, Nile red capable of emitting red light close to crimson with high brightness when electric energy is applied. TECHNICAL FIELD The present invention relates to a red-light-emitting compound, a novel method for producing the same, and a light-emitting device using the same.

[0002]

2. Description of the Related Art Conventionally, various organic compounds have been proposed as an organic electroluminescence device (also referred to as an organic electroluminescence device or an organic EL device).

However, under the present circumstances, an organic compound capable of emitting red light, having high emission brightness and stable to heat and light has not yet been developed.

[0004]

The object of the present invention is to provide a high emission luminance and / or a red emission in which the X coordinate in CIE chromaticity exceeds 0.62, and particularly 0.63. An object of the present invention is to provide an organic red light emitting compound that is stable to heat and light, a method for producing the same, and a light emitting device using the organic red light emitting compound.

[0005]

A first invention for solving the above-mentioned problems is a Nile red-type red light-emitting compound characterized by having a structure represented by the following general formula (1).

[0006]

[Chemical 8] However, in the formula, R¹Is a lower alkyl group having 1 to 5 carbon atoms
Shown and also R¹Is R ^ThreeIn collaboration with -CH_TwoCH_Two-C
R⁶R⁷-(However, -CR⁶R⁷The carbon at − is
Bound to the Nzen ring, R⁶And R⁷Is hydrogen atom or carbon number
1 to 5 represents a lower alkyl group, R⁶And R⁷Is the same
It may be one or different. ) Is formed.

R ² represents a lower alkyl group having 1 to 5 carbon atoms, and R ² in cooperation with R ⁵ is —CH ₂ CH ₂ —C.
R ⁸ R ⁹ - (However, ^-CR 8 ^{R 9} - carbon bonded to the benzene ring in, ^{R 8} and ^{R 9} represents a hydrogen atom or a lower alkyl group of 1 to 5 carbon atoms, ^{R 8} and ^{R 9} , Which may be the same or different).

R ³ represents a hydrogen atom, the above-mentioned bond formed in cooperation with R ¹ , or a naphthalene ring formed in cooperation with R ⁴ and containing an adjacent benzene ring.

R ⁴ represents a hydrogen atom or a naphthalene ring formed by including an adjacent benzene ring in cooperation with R ³ .

R ⁵ represents a hydrogen atom or the above-mentioned bond formed in cooperation with R ² .

Ar is represented by the general formulas (2), (4) and (5).
Indicates either

[0012]

[Chemical 9] However, R ¹⁰ represents a single bond or a methylene group.

R ¹¹ represents a hydrogen atom or —CF ₂ —O—CF ₂ — which is formed in cooperation with R ¹² .

R ¹² is a fluorine atom, a cyano group, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms, —CF ₂ —O—CF ₂ — formed in cooperation with R ¹¹ , or R.
¹³ _-CF 2 are formed in association with -O-CF ₂ - shows a.

R ¹³ is a hydrogen atom, a cyano group, a fluorine atom, a lower alkyl group containing a fluorine atom having 1 to 5 carbon atoms, or —CF ₂ —O—CF which is formed in cooperation with R ^12.
_2- , or a group represented by the general formula (3) is shown.

[0016] R ¹⁴ is, R ¹³ represents a hydrogen atom or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms when a hydrogen atom, a hydrogen atom when R ¹³ is a group other than a hydrogen atom.

[0017]

[Chemical 10] However, R ¹⁵ represents a hydrogen atom or —CF ₂ —O—CF ₂ — which is formed in cooperation with R ¹⁶ .

R ¹⁶ is a fluorine atom, a cyano group, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms, —CF ₂ —O—CF ₂ — or R formed in cooperation with R ^15.
_{-CF 2} -O-CF 2 which is formed in association with ¹⁷ - shows the.

R ¹⁷ is a hydrogen atom, a cyano group, a fluorine atom, a lower alkyl group containing a fluorine atom having 1 to 5 carbon atoms, or —CF ₂ —O—CF ₂ — formed in cooperation with R ^16.
Indicates.

R ¹⁸ represents a hydrogen atom or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms when R ¹⁷ is a hydrogen atom, and represents a hydrogen atom when R ¹⁷ is a group other than a hydrogen atom.

[0021]

[Chemical 11] However, R ¹⁹ represents a fluorine atom, a cyano group, or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms. k shows the integer of 1-4, m shows the integer of 1-3. R ¹⁹ of the total number of m and k may be the same or different.

[0022]

[Chemical 12] However, R ¹⁹ represents a fluorine atom, a cyano group, or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms. k shows the integer of 1-4, m shows the integer of 1-3. R ¹⁹ of the total number of m and k may be the same or different.

Another means for solving the above problems is to react the Nile red dye compound represented by the general formula (6) with the electron-withdrawing aromatic acetonitrile represented by the general formula (7). A method for producing a Nile red-based red light emitting compound represented by the general formula (1).

[0024]

[Chemical 13] However, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as described above.

[0025]

[Chemical 14] However, Ar has the same meaning as described above.

Still another means for solving the above-mentioned problems is that a light-emitting layer containing a Nile red-based red light-emitting compound represented by the general formula (1) is provided between a pair of electrodes. It is a light emitting element.

In a preferred embodiment of the light emitting device, a hole transport layer is interposed between an anode, which is one of a pair of electrodes, and the light emitting layer. In an embodiment, the light emitting layer comprises a Nile red-based red light emitting compound and a host dye, the light emitting device, in a preferred embodiment thereof, the light emitting layer and the hole transport layer are formed by a vapor deposition method,
In a preferred embodiment of the light emitting device, the light emitting layer comprises the Nile red red light emitting compound, an electron transporting substance, and a hole transporting polymer, and the light emitting device is in a preferred embodiment thereof. In the preferred embodiment of the light emitting device, the light emitting layer is formed by a coating method, and the light emitting layer is at least selected from the group consisting of a diphenylvinylbiphenol blue light emitting compound and a stilbene blue light emitting compound. One kind and at least one kind selected from the group consisting of a coumarin type green light emitting compound, an indophenol type green light emitting compound and an indigo type green light emitting compound.

[0028]

BEST MODE FOR CARRYING OUT THE INVENTION The Nile red red light emitting compound according to the present invention is represented by the general formula (1).

[0029]

[Chemical 15] In general formula (1), R ¹ may be a lower alkyl group having 1 to 5 carbon atoms. Examples of the lower alkyl group represented by R ¹ include a methyl group, an ethyl group, a propyl group, a butyl group and a pentyl group.

R ² may be a lower alkyl group having 1 to 5 carbon atoms. The lower alkyl group represented by R ² is the same as the above R ¹ . R ¹ and R ² may be the same lower alkyl group or different lower alkyl groups.

R¹Is R^ThreeIn collaboration with -CH_TwoCH
_Two-CR⁶R⁷-(However, -CR ⁶R⁷At charcoal
The element is bonded to the benzene ring and R⁶And R⁷Is a hydrogen atom or
Represents a lower alkyl group having 1 to 5 carbon atoms, R⁶And R⁷
May be the same or different. ) Form
It

When R ¹ and R ² are lower alkyl groups, preferred —NR ¹ R ² includes diethylamino group, di-n-propylamino group, di-i-propylamino group, butyl group and the like. Can be mentioned.

R^TwoIs R⁵In collaboration with -CH_TwoCH
_Two-CR⁸R⁹-(However, -CR ⁸R⁹At charcoal
The element is bonded to the benzene ring and R⁸And R⁹Is a hydrogen atom or
Represents a lower alkyl group having 1 to 5 carbon atoms, R⁸And R⁹
May be the same or different. ) Form
It

The above R ¹ cooperates with R ³ to --CH ₂ CH ₂
-CR ⁶ R ⁷ - and is, -C wherein ^{R 2} taken together with ^{R 5
_{H 2 CH 2 -CR 8 R 9}} - a general formula when it (1)
Can be represented by the general formula (8).

[0035]

[Chemical 16] R ⁴ , R ⁶ , R ⁷ , R ⁸ and R in this general formula (8)
⁹ and Ar have the same meanings as described above.

In the general formula (1), R ³ and R ⁴ are both hydrogen atoms, or may jointly include adjacent benzene rings to form a naphthalene ring. R ³ and R ⁴
A red light-emitting compound formed by forming a naphthalene ring by containing adjacent benzene rings together is represented by the general formula (9).

[0037]

[Chemical 17] R ¹ , R ² and Ar in the general formula (9) have the same meanings as described above.

Ar in the general formula (1) has a structure represented by the general formula (2), (4) or (5).

[0039]

[Chemical 18] However, R ¹⁰ represents a single bond or a methylene group.

R ¹¹ represents a hydrogen atom or —CF ₂ —O—CF ₂ — which is formed in cooperation with R ¹² .

R ¹² is a fluorine atom, a cyano group, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms (in other words,
A fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms in the entire group and containing a fluorine element in the group),
_{-CF 2} -O-CF 2 which is formed in conjunction with the ^{R 11}
-, or _-CF 2 -O-C which is formed in conjunction with ^{R 13}
F ₂ − is shown. Here, the "fluorine atom-containing lower alkyl group" is understood to mean a lower alkyl group containing a fluorine atom as a substituent.

R ¹³ is a hydrogen atom, a cyano group, a fluorine atom, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms, or —CF ₂ —O—CF formed in cooperation with R ^12.
_2- , or a group represented by the general formula (3) is shown.

R ¹⁴ represents a hydrogen atom or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms when R ¹³ is a hydrogen atom, and represents a hydrogen atom when R ¹³ is a group other than a hydrogen atom.

[0044]

[Chemical 19] However, R ¹⁵ represents a hydrogen atom or —CF ₂ —O—CF ₂ — which is formed in cooperation with R ¹⁶ .

R ¹⁶ is a fluorine atom, a cyano group, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms, —CF ₂ —O—CF ₂ — or R formed in cooperation with R ^15.
_{-CF 2} -O-CF 2 which is formed in association with ¹⁷ - shows the.

R ¹⁷ is a hydrogen atom, a cyano group, a fluorine atom, a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms, or —CF ₂ —O—CF ₂ — which is formed in cooperation with R ^16.
Indicates.

R ¹⁸ represents a hydrogen atom or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms when R ¹⁷ is a hydrogen atom, and represents a hydrogen atom when R ¹⁷ is a group other than a hydrogen atom.

The above R ¹² , R ¹³ , R ¹⁶ and R ¹⁷
Examples of the fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms represented by are fluorine atom-containing methyl groups such as trifluoromethyl group, difluoromethyl group, and monofluoromethyl group, fluorine atom-containing ethyl group such as pentafluoroethyl group Examples thereof include a fluorine atom-containing propyl group such as a hexafluoropropyl group and a fluorine atom-containing pentyl group. Among these, a lower alkyl group containing a fluorine atom is preferably a methyl group containing a fluorine atom.

In Ar in the general formula (1), (8) or (9), when R ¹⁰ is a single bond or a methylene group, a suitable combination of R ¹¹ , R ¹² , R ¹³ and R ¹⁴ is obtained. An example is shown in Table 1.

[0050]

[Table 1]

In addition to the preferred examples shown in Table 1, 2,4
Fluorinated phenyl groups such as difluorophenyl group, 2,5-difluorophenyl group, 2,6-difluorophenyl group, 3,4-difluorophenyl group, and 3,5-difluorophenyl group, 3-trifluoromethylphenyl Group, 4-trifluoromethylphenyl group, and 3,5-
A trifluoromethylphenyl group such as a bis (trifluoromethyl) phenyl group and a fluorotrifluoromethylphenyl group such as a 4-fluoro-3-trifluoromethylphenyl group or a 6-fluoro-2-trifluoromethylphenyl group It can be mentioned as a suitable example of Ar.

One of Ar is represented by the general formula (4).

[0053]

[Chemical 20] However, R ¹⁹ represents a fluorine atom, a cyano group, or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms. k shows the integer of 1-4, m shows the integer of 1-3. R ¹⁴ of the total number of m and k may be the same or different.

One of Ar is represented by the general formula (5).

[0055]

[Chemical 21] However, R ¹⁹ represents a fluorine atom, a cyano group, or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms. k shows the integer of 1-4, m shows the integer of 1-3. R ¹⁹ of the total number of m and k may be the same or different.

The naphthyl group represented by the general formula (4) or (5) has an electron-withdrawing group called a fluorine atom, a cyano group, or a fluorine atom-containing lower alkyl group having 1 to 5 carbon atoms. The π electron in the Nile red skeleton and the fluorine-based substituent or the cyano group exhibit a superconjugation effect to facilitate red light emission.

The C1-C5 fluorine atom-containing lower alkyl group bonded to the naphthyl group is the same as the C1-C5 fluorine atom-containing lower alkyl group in the general formula (2). Among the fluorine atom-containing lower alkyl groups having 1 to 5 carbon atoms which are bonded to the naphthyl group, a trifluoromethyl group is preferable.

Of the naphthyl groups represented by the general formula (4),
Regarding the 1-naphthyl group, for example, one trifluoromethyl group is bonded to the 2-position, 3-position, 4-position, 5-position, 6-position, 7-position or 8-position (trifluoromethyl) -1-naphthyl group. , A fluorine atom bonded to the 2-position, 3-position, 4-position, 5-position, 6-position, 7-position or 8-position by a fluoro-1-naphthyl group, and two trifluoromethyl groups having 2-position, 3-position and 2-position. And 4th,
2nd and 5th, 2nd and 6th, 2nd and 7th, 2nd and 8th, 3rd and 4th, 3rd and 5th, 3rd and 6th, 3rd
3rd and 8th, 4th and 5th, 4th and 6th
4th and 7th, 4th and 8th, 5th and 6th, 5th and 7th, 5th and 8th, 6th and 7th, 6th and 8th
Position, or a bis (trifluoromethyl) -1-naphthyl group bound to the 7- and 8-positions, two fluorine atoms being 2- and 3-positions, 2- and 4-positions, 2- and 5-positions, 2- and 6th, 2
7th, 7th, 2nd and 8th, 3rd and 4th, 3rd and 5th
3rd and 6th, 3rd and 7th, 3rd and 8th, 4th and 5th, 4th and 6th, 4th and 7th, 4th and 8th
Position, 5 and 6 position, 5 position and 7 position, 5 position and 8 position, 6 position and 7 position, 6 position and 8 position, or difluoro-1-naphthyl group bonded to 7 position and 8 position, 3 The trifluoromethyl group of is in the 2-position, 3-position and 4-position, 2-position, 3-position and 5-position, 2
3rd and 6th, 2nd, 3rd and 7th, 2nd, 3rd and 8th, 2nd, 4th and 5th, 2nd, 4th and 6th, 2nd
4th and 7th, 2nd, 4th and 8th, 2nd, 5th and 6th, 2nd, 5th and 7th, 2nd, 5th and 8th, 2nd
6th and 7th, 2nd, 5th and 8th, 3rd, 4th and 5th, 3rd, 4th and 6th, 3rd, 4th and 7th, 3rd
4th, 8th, 3rd, 5th and 6th, 3rd, 5th and 7th, 3rd, 5th and 8th, 3rd, 6th and 7th, 3rd
4th, 6th and 8th, 4th, 7th and 8th, 4th, 5th and 6th, 4th, 5th and 7th, 4th, 5th and 8th, 4th
5th, 6th and 7th, 4th, 6th and 8th, 4th, 7th and 8th, 5th, 6th and 7th, 5th, 6th and 8th, 5th
Position, 7-position and 8-position, and tri (trifluoromethyl) -1-naphthyl group bonded to 6-position, 7-position and 8-position, 3 fluorine atoms are 2-position, 3-position and 4-position, 2-position, 3rd and 5th
2nd, 3rd and 6th, 2nd, 3rd and 7th, 2nd,
3rd and 8th, 2nd, 4th and 5th, 2nd, 4th and 6th
2nd, 4th and 7th, 2nd, 4th and 8th, 2nd,
5th and 6th, 2nd, 5th and 7th, 2nd, 5th and 8th
2nd, 6th and 7th, 2nd, 5th and 8th, 3rd,
4th and 5th, 3rd, 4th and 6th, 3rd, 4th and 7th
3rd, 4th and 8th, 3rd, 5th and 6th, 3rd,
5th and 7th, 3rd, 5th and 8th, 3rd, 6th and 7th
3rd, 6th and 8th, 4th, 7th and 8th, 4th,
5th and 6th, 4th, 5th and 7th, 4th, 5th and 8th
4th, 6th and 7th, 4th, 6th and 8th, 4th,
7th and 8th, 5th, 6th and 7th, 5th, 6th and 8th
Trifluoro-1-naphthyl group attached to the 5-position, 5-position, 7-position and 8-position, and 6-position, 7-position and 8-position, and 2,
Mention may be made of the 3,4,5,6,7,8-heptafluoro-1-naphthyl group.

Of the naphthyl groups represented by the general formula (5),
For example, one trifluoromethyl group may have 1-position, 3-position, 4-position
Position, 5-position, 6-position, 7-position or 8-position (trifluoromethyl) -2-naphthyl group, fluorine atom is 1-position, 3
A fluoro-2-naphthyl group bonded to the 4-position, 5-position, 6-position, 7-position or 8-position and 2 trifluoromethyl groups are 1
1st and 3rd, 1st and 4th, 1st and 5th, 1st and 6th
1st and 7th, 1st and 8th, 3rd and 4th, 3rd and 5th, 3rd and 6th, 3rd and 7th, 3rd and 8th
4th and 5th, 4th and 6th, 4th and 7th, 4th and 8th, 5th and 6th, 5th and 7th, 5th and 8th
Position, 6-position and 7-position, 6-position and 8-position, or bis (trifluoromethyl) -2-naphthyl group bonded to 7-position and 8-position, two fluorine atoms are 1-position and 3-position, 1-position and 4th place,
1st and 5th, 1st and 6th, 1st and 7th, 1st and 8th, 3rd and 4th, 3rd and 5th, 3rd and 6th, 3rd
3rd and 8th, 4th and 5th, 4th and 6th
4th and 7th, 4th and 8th, 5th and 6th, 5th and 7th, 5th and 8th, 6th and 7th, 6th and 8th
Difluoro-2-naphthyl group bonded to the 7-position or the 7-position and the 8-position, three trifluoromethyl groups are bonded to the 1-position, 3-position and 4-position, 1-position, 3-position and 5-position, 1-position, 3-position and 6th, 1
1st, 3rd and 7th, 1st, 3rd and 8th, 1st, 4th and 5th, 1st, 4th and 6th, 1st, 4th and 7th, 1st
1st, 4th and 8th, 1st, 5th and 6th, 1st, 5th and 7th, 1st, 5th and 8th, 1st, 6th and 7th, 1st
5th, 8th, 3rd, 4th and 5th, 3rd, 4th and 6th, 3rd, 4th and 7th, 3rd, 4th and 8th, 3rd
5th and 6th, 3rd, 5th and 7th, 3rd, 5th and 8th, 3rd, 6th and 7th, 3rd, 6th and 8th, 4th
4th, 7th and 8th, 4th, 5th and 6th, 4th, 5th and 7th, 4th, 5th and 8th, 4th, 6th and 7th, 4th
6th and 8th, 4th, 7th and 8th, 5th, 6th and 7th, 5th, 6th and 8th, 5th, 7th and 8th, and 6th and 7th And a tri (trifluoromethyl) -2-naphthyl group bonded to the 8-position, three fluorine atoms at the 1-position,
3rd and 4th, 1st, 3rd and 5th, 1st, 3rd and 6th
1st, 3rd and 7th, 1st, 3rd and 8th, 1st,
4th and 5th, 1st, 4th and 6th, 1st, 4th and 7th
1st, 1st, 4th and 8th, 1st, 5th and 6th, 1st,
5th and 7th, 1st, 5th and 8th, 1st, 6th and 7th
1st, 5th and 8th, 3rd, 4th and 5th, 3rd,
4th and 6th, 3rd, 4th and 7th, 3rd, 4th and 8th
3rd, 5th and 6th, 3rd, 5th and 7th, 3rd,
5th and 8th, 3rd, 6th and 7th, 3rd, 6th and 8th
4th, 7th and 8th, 4th, 5th and 6th, 4th,
5th and 7th, 4th, 5th and 8th, 4th, 6th and 7th
4th, 6th and 8th, 4th, 7th and 8th, 5th,
6th and 7th, 5th, 6th and 8th, 5th, 7th and 8th
Position, and trifluoro-2-naphthyl groups bonded to the 6, 7 and 8 positions, and 1,3,4,5,6,7,8
-Heptafluoro-2-naphthyl group may be mentioned.

In the Nile red red light emitting compound represented by the general formula (1), —NR ¹ R ² is an electron donating group,
Since -Ar is an electron-withdrawing group, H in -CH- adjacent to this Ar- becomes δ ⁺ , and the bond between this CH and C in the adjacent benzene ring becomes a double bond, resulting in excess surplus. The conjugation effect is exhibited, and as a result, the π electron cloud in the Nile red skeleton spreads, and it is speculated that red light emission is facilitated with a small amount of energy.
The novel Nile red-based red light-emitting compound according to the present invention has an electron-donating group R ¹ —N—R ² that donates an electron to a π-electron cloud in the Nile red skeleton, and is an aromatic electron-withdrawing group Ar. It is characterized by a structure that attracts electrons. Since this Nile red-based red light emitting compound has a stable Nile red skeleton structure, it is chemically stable and exhibits the peculiarity that it does not deteriorate even under severe use conditions.

The Nile red type red light emitting compound represented by the general formula (1) can be produced as follows.

That is, the Nile red compound represented by the general formula (6) is reacted with the electron-withdrawing aromatic acetonitrile represented by the general formula (7).

The Nile Red compound and the electron-withdrawing aromatic acetonitrile react easily by heating in a solvent. As the solvent, acetic anhydride, acetic acid, acid anhydrides having 5 or less carbon atoms, aromatic solvents such as benzene and toluene, dioxane and the like can be used. The reaction temperature is generally 100 to 250 ° C, preferably 100 to 170 ° C. After completion of the reaction, the desired Nile red-type red light-emitting compound can be obtained by performing purification and separation operations according to a conventional method.

The Nile red type red light emitting compound according to the present invention can be easily produced by simply heating the Nile red type compound and the electron-withdrawing aromatic acetonitrile. Such a simple method for producing a Nile red-based red light emitting compound is an industrial production method.

The Nile red type red light emitting compound according to the present invention is used for a light emitting device. This light emitting device has a structure including an anode, a light emitting layer containing a Nile red red light emitting compound, and a cathode formed on the surface of the light emitting layer. This light emitting device can employ various types of structures as long as it has a light emitting layer containing the Nile red red light emitting compound between the anode and the cathode. As the light-emitting device, for example, a single-layer organic material having a light-emitting layer containing an electron-transporting substance that transports electrons, a Nile red-based red light-emitting compound, and a hole-transporting substance that transports holes between an anode and a cathode. Two-layer organic light-emitting device comprising a light-emitting device, a hole-transporting layer containing a hole-transporting substance, and an electron-transporting light-emitting layer containing a Nile red-based red light-emitting compound, which are laminated between an anode and a cathode (for example, A two-layer type dye-doped light-emitting device comprising a hole-transporting layer and a light-emitting layer containing a Nile red red light-emitting compound as a guest dye and a host dye between the anode and the cathode), the anode and the cathode And a hole transporting light emitting layer containing the electron transporting substance and a hole transporting light emitting layer containing the Nile red-based red light emitting compound. A two-layer dye-doped organic light-emitting device, which is formed by stacking an electron-transporting layer and a light-emitting layer containing a Nile red-based red light-emitting compound as a guest dye and a host dye between the cathode and the anode), and an anode and a cathode. A three-layer organic light-emitting device in which a hole-transporting layer, a light-emitting layer containing a Nile red-based red light-emitting compound, and an electron-transporting layer are laminated between these layers can be given. In the above various organic light-emitting devices, a single light-emitting layer and a laminate composed of two layers and three layers may be referred to as an organic layer.

The light emitting device can be usually formed on a substrate. As this substrate, for example, a transparent substrate such as glass or plastic can be used.

As the anode, various materials can be adopted as long as they have a large work function and are transparent, and holes can be injected into the film by applying a voltage. Specifically, as the anode, ITO, In ₂ O ₃ ,
It can be formed of an inorganic transparent conductive material such as SnO ₂ , ZnO, CdO, or a compound thereof, a conductive polymer material such as polyaniline, or the like.

The film thickness of this anode is usually 100 to 200.
μm, and the surface resistance is 10 to 20 Ω / □.

This anode is formed on the substrate by chemical vapor deposition, spray pyrolysis, vacuum evaporation, electron beam evaporation, sputtering, ion beam sputtering, ion plating, ion assisted evaporation, and others. Can be formed by the above method.

A material having a small work function is used for the cathode, and it can be formed of a simple metal or an alloy of metals such as MgAg, aluminum alloy, and metal calcium. A preferred cathode is an alloy electrode of aluminum and a small amount of lithium. This cathode can be easily formed, for example, on the surface of the organic layer including the light emitting layer formed on the substrate by a vapor deposition technique.

Examples of the electron-transporting substance include:
2,5-bis (1-naphthyl) -1,3,4-oxadiazole (BND), and 2- (4-tert-butylphenyl) -5- (4-biphenylyl) -1,3,4- Oxadiazole derivatives such as oxadiazole, and 2,
5-bis (5'-tert-butyl-2'-benzoxazolyl) thiophene and the like can be mentioned. Further, as the electron transporting substance, for example, quinolinol aluminum complex (Al
q3), benzoquinolinol beryllium complex (Bebq
A metal complex material such as 2) can also be preferably used.

Examples of the hole transport material include triphenylamine compounds such as N, N'-diphenyl-N,
Examples thereof include N′-di (m-tolyl) -benzidine (TPD) and α-NPD, hydrazone compounds, stilbene compounds, heterocyclic compounds, π-electron starburst hole transporting substances and the like.

The organic layer in this light emitting device is formed by a vapor deposition method,
In addition, it can be formed by any one of a coating method such as a spin casting method, a coating method and a dipping method.

Whether a vapor deposition method or a coating method is adopted, it is preferable to interpose a buffer layer between the electrode and the organic layer.

As a material capable of forming the buffer layer formed between the cathode and the organic layer, for example, an alkali metal compound such as lithium fluoride, an alkaline earth metal compound such as magnesium fluoride, Examples thereof include oxides such as aluminum oxide and 4,4′-biscarbazole biphenyl (Cz-TPD). As a material for forming a buffer layer formed between an anode such as ITO and an organic layer, for example, m-MTDATA is used.
(4,4 ′, 4 ″ -tris (3-methylphenylphenylamino) triphenylamine), phthalocyanine, polyaniline, polythiophene derivatives, inorganic oxides such as molybdenum oxide, ruthenium oxide, vanadium oxide and lithium fluoride. You can By appropriately selecting the material of these buffer layers, the driving voltage of the light emitting element can be lowered, the quantum efficiency of light emission can be improved, and the emission brightness can be improved.

A preferable light emitting element that can be formed by the vapor deposition method is a hole transport layer formed by the vapor deposition method on the surface of an anode such as ITO formed by the vapor deposition method, preferably via a buffer layer, An electron-transporting light-emitting layer containing a host dye such as Alq3 or Bebq2 and a Nile red-based red light-emitting compound as a guest dye, which was formed by vapor deposition on the surface of the hole-transporting layer, and the electron-transporting light-emitting layer. It is formed by laminating the surface of the layer, preferably a cathode formed by a vapor deposition method via a buffer layer.

The content of the Nile red type red light emitting compound contained in the electron transporting light emitting layer in this light emitting device is usually 0.001 to 50% by weight, preferably 0.01 to 10% by weight based on the host dye. % By weight. When the content of the Nile red-based red light emitting compound is within the above range,
In particular, red light emission vividly occurs.

The thickness of this electron-transporting light-emitting layer is usually 3
It is 0 to 300 nm, preferably 50 to 200 nm.
When the thickness of the electron-transporting light emitting layer is within the above range, there is an advantage that light emission with high brightness can be achieved at a low voltage.

A suitable light emitting element that can be formed by a coating method is IT formed by a vapor deposition method on the surface of a substrate.
An anode such as P, and an organic layer formed by applying a solution containing a Nile red-based red light-emitting compound, an electron-transporting material and a hole-transporting polymer on the surface of the anode and drying the solution. On the surface of this organic layer, preferably, a cathode formed by vapor deposition via a buffer layer is laminated.

The content of the Nile red type red light emitting compound contained in the organic layer is usually 0.01 to 10% by weight, preferably 0.1 to 5% by weight. When the content of the Nile red-based red light emitting compound is within the above range, particularly red light emission occurs vividly.

Examples of the hole transporting polymer include polyvinyl carbazole and poly (3-alkylenethiophene). Further, rubrene is preferably contained as a sensitizer in this organic layer, and particularly, rubrene and Alq3 are preferably contained.

The thickness of the electron-transporting light-emitting layer is usually 3
It is 0 to 300 nm, preferably 50 to 200 nm.
When the thickness of the electron-transporting light emitting layer is within the above range, there is an advantage that a high luminance can be obtained at a low voltage.

The light emitting device according to the present invention can be generally used as, for example, a DC drive type device, and can also be used as a pulse drive type device and an AC drive type device. Conventional Nile Red emits only orange light, but since the light emitting device according to the present invention contains a Nile red-based red light emitting compound, it emits red light close to deep red with high brightness.

If the light emitting layer of the light emitting device according to the present invention contains only the above-mentioned Nile red type red light emitting compound as a light emitting substance, the light emitting layer emits red light. In this light emitting layer, a Nile red-based red light emitting compound,
When the blue light emitting compound and the green light emitting compound are contained, this light emitting layer emits white light.

Examples of the blue light emitting compound include a diphenyl vinyl biphenol type blue light emitting compound and a stilbene type blue light emitting compound. Examples of suitable diphenylvinylbiphenol-based blue light emitting compounds include DPVBi represented by the general formula (10).

[0086]

[Chemical formula 22] Examples of the green light emitting compound include a coumarin green light emitting compound, an indophenol green light emitting compound and an indigo green light emitting compound, and the coumarin green light emitting compound represented by the general formula (11) is preferable.

[0087]

[Chemical formula 23] In order to make the light emitting device according to the present invention emit white light, the compounding ratio of the Nile red-based red light emitting compound, the blue light emitting compound and the green light emitting compound in the light emitting layer is usually 5 to 200: 10 to 100 by weight. : 50 to 20000, preferably 10 to 100: 50 to 500: 100 to
It is 10,000.

The element that emits red light and the light emitting element that emits white light can be used for an illumination device such as a fluorescent lamp and a display device.

[0089]

EXAMPLES Example 1 Synthesis of Nile Red Red Light-Emitting Compound A In a 100 ml eggplant flask, 0.50 g of Nile Red was added.
(1.57 mmol), 3,5-bis (trifluoromethyl) phenylacetonitrile 0.40 g (1.57 m)
mol) and acetic anhydride 25 ml were charged. The solution in the eggplant flask was heated to 135 ° C. in a silicon oil bath and reacted for 4 hours. Acetic anhydride was distilled off using an evaporator and dissolved in chloroform. This chloroform solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes for dehydration. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to obtain 30 mg of a blue-violet solid. The yield of the synthesized compound was 12%, and the melting point was 257 to 260 ° C. The ¹ H-NMR and IR spectra of this compound are as shown in FIGS. 1 and 2. From these results, the obtained compound was identified as the compound represented by the formula (12).

[0090]

[Chemical formula 24] Example 2 Synthesis of Nile Red Red Light Emitting Compound B In a 100 ml eggplant flask, 0.50 g of Nile Red was added.
(1.57 mmol), 2,3-difluoro-4- (trifluoromethyl) phenylacetonitrile 0.35 g
(1.57 mmol) and 25 ml of acetic anhydride were charged. Use a silicone oil bath to put the solution in the eggplant flask 13
The mixture was heated to 5 ° C. and reacted for 3 hours. Acetic anhydride was distilled off using an evaporator and dissolved in chloroform.
This chloroform solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes for dehydration. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to obtain 10 mg of a blue-violet solid.
The yield of the synthesized compound was 6.4%, and the melting point was 17
It was 2-174 degreeC. The IR spectrum of this compound is as shown in FIG. From these results, the obtained compound was identified as the compound represented by the formula (13).

[0091]

[Chemical 25] (Example 3) 70 mg of polyvinylcarbazole (hereinafter referred to as PVK, manufactured by Kanto Chemical Co., Inc.), 2,5-bis (1-naphthyl) -in a 5 ml volumetric flask.
29 mg of 1,3,4-oxadiazole (hereinafter referred to as BND. Synthetic product) and 1 mg of Nile red-based red light emitting compound A were weighed, and dichloroethane was added to the mixture so as to be 5 ml. A solution was prepared. This Nile Red-based red light emitting compound-containing solution is an ultrasonic cleaner (manufactured by SND Corp., US
It was made sufficiently uniform by irradiating ultrasonic waves for 2 minutes in -2). An ITO substrate (50 × 50 mm, manufactured by Sanyo Vacuum Industrial Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, blown with nitrogen and dried. After that, UV irradiation was performed for 30 seconds with a UV irradiation device (manufactured by MDI Excimer Co., Ltd., wavelength 172 nm) to wash. The prepared Nile Red-based red light-emitting compound-containing solution was dropped onto an ITO substrate that had been washed and dried using a spin coater (1H-D7 manufactured by Mikasa Co., Ltd.), and the rotation speed was 1,500 rp.
m and the rotation time was 3 seconds to form a film by spin coating. The film-formed substrate was dried in a constant temperature bath at 50 ° C. for 30 minutes, and then a vacuum deposition apparatus (VDS-M manufactured by Daia Vacuum Giken Co., Ltd.).
2-46 type) aluminum alloy (Al: Li = 99: 1 weight ratio, manufactured by Kojundo Chemical Laboratory Co., Ltd.) electrodes 4 × 10 ⁻⁶ To
The EL element was manufactured by vapor deposition to a thickness of about 1,500 Å at rr.

This EL device is a Fastcon manufactured by Topcon Corporation.
Luminance and chromaticity were measured while gradually increasing the voltage with BM-7. The results are shown in Table 2.

Example 4 A 5 ml volumetric flask was charged with P
VK 68 mg, 2- (4-tert-butylphenyl-5)
31.2 mg of-(4-biphenylyl) -1,3,4-oxadiazole (hereinafter referred to as PBD) and 0.8 mg of Nile red red light-emitting compound A were weighed, and dichloroethane was added to make 5 ml. Thus, a solution containing a Nile red-based red light emitting compound was prepared. Regarding the solution containing the Nile red-based red light-emitting compound, the above-mentioned Example 3 was used.
An EL device was prepared in the same manner as in, and the luminance and chromaticity were measured in the same manner as in Example 3 above. The results are shown in Table 2.

(Example 5) P was added to a 5 ml volumetric flask.
VK 63.7 mg, 2,5-bis (5'-Tert-butyl-2'-benzoxazolyl) thiophene (hereinafter referred to as BBOT) 35.5 mg, and Nile red red light-emitting compound A 0.8 mg were weighed. Then, dichloroethane was added thereto to prepare a solution containing a Nile red-based red light emitting compound so as to have a volume of 5 ml. An EL device was prepared in the same manner as in Example 3 using this Nile Red red light emitting compound-containing solution, and the luminance and chromaticity were measured in the same manner as in Example 3. The results are shown in Table 2.

(Example 6) In a 5 ml volumetric flask, P
VK 64.0 mg, BBOT 35.6 mg, and Nile red type red light emitting compound A 0.4 mg were weighed, and dichloroethane was added thereto to prepare a Nile red type red light emitting compound-containing solution to be 5 ml. An EL device was prepared in the same manner as in Example 3 using the solution containing the Nile red-based red light emitting compound, and the luminance and chromaticity were measured in the same manner as in Example 3. The results are shown in Table 2.

(Comparative Example 1) A 5 ml volumetric flask was charged with P
VK 68.2 mg, PBD 31.3 mg, and Nile red 0.5 mg were weighed, and dichloroethane was added to prepare a Nile red-containing solution so as to be 5 ml.
An EL device was prepared from this Nile Red-containing solution in the same manner as in Example 3, and the luminance and chromaticity were measured in the same manner as in Example 3. The results are shown in Table 2.

[0097]

[Table 2]

Example 7 Polyvinylcarbazole (hereinafter referred to as PVK) was placed in a 5 ml volumetric flask.
Kanto Chemical Co., Ltd.) 70.1 mg, 2,5-bis (1-
29.3 mg of naphthyl) -1,3,4-oxadiazole (hereinafter referred to as BND. Synthetic product) and 0.61 mg of Nile red red light-emitting compound A were weighed,
A solution containing a Nile red-based red light emitting compound was prepared by adding dichloroethane to a volume of 5 ml. This Nile Red-based red light emitting compound-containing solution was made sufficiently uniform by irradiating ultrasonic waves for 20 minutes with an ultrasonic cleaner (manufactured by SND, US-2). I
A TO substrate (50 × 50 mm, manufactured by Sanyo Vacuum Industrial Co., Ltd.) was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with 2-propanol for 10 minutes, blown with nitrogen and dried. After that, UV irradiation was performed for 30 seconds with a UV irradiation device (manufactured by MDI Excimer Co., Ltd., wavelength 172 nm) to wash. Spin coater (Mikasa Co., Ltd., 1H-
The prepared solution containing the Nile red-based red light-emitting compound was dropped onto the ITO substrate that had been washed and dried using D7), and spin-coated at a rotation speed of 1,500 rpm for a rotation time of 3 seconds to form a film. did. The film-formed substrate was dried in a constant temperature bath at 50 ° C. for 30 minutes, and then an aluminum alloy (Al: Li = 99: was manufactured by a vacuum vapor deposition apparatus (VDS-M2-46 type manufactured by Daia Vacuum Giken Co., Ltd.)). Electrodes were manufactured by vapor-depositing an electrode having a weight ratio of 1; manufactured by Kojundo Chemical Laboratory Co., Ltd. at a thickness of about 1,500Å at 1 × 10 ^-6 Torr.

This EL device is manufactured by Topcon Co., Ltd.
The maximum brightness and chromaticity were measured while gradually increasing the voltage with Fast BM-7. The results are shown in Table 3.

(Example 8) In a 5 ml volumetric flask, P
VK 70.1 mg, BND 29.3 mg, and Nile red red luminescent compound A 0.61 mg were added, and dichloroethane was further added to prepare a Nile red luminescent compound-containing solution so that the total amount became 5 ml.
In a ml volumetric flask, PVK 69.9 mg, BND
29.1 mg, 0.4 mg of rubrene and 0.6 mg of Nile red type red light emitting compound A were added, and dichloroethane was further added to prepare a solution containing Nile red type red light emitting compound so that the total amount became 5 ml. An EL device was manufactured in the same manner as in Example 7.

Maximum luminance and chromaticity were measured in the same manner as in Example 7. The results are shown in Table 3.

Example 9 An EL device was manufactured in the same manner as in Example 7 except that the Nile red red light emitting compound A was used in place of the Nile red red light emitting compound A. Luminance and chromaticity of this EL device were measured in the same manner as in Example 7. The results are shown in Table 3.

Example 10 Synthesis of Nile Red Red Light Emitting Compound C 2,5-bis (trifluoromethyl) phenylacetonitrile 1.57 mm instead of 3,5-bis (trifluoromethyl) phenylacetonitrile 1.57 mmol
A Nile red luminescent compound C represented by the formula (14) was synthesized in the same manner as in Example 1 except that ol was used.

^{1 of} this Nile red-based red light-emitting compound C
1 H-NMR is shown in FIG.

[0105]

[Chemical formula 26] An EL device was manufactured in the same manner as in Example 7 except that the Nile red type red light emitting compound C was used in place of the Nile red type red light emitting compound A. Luminance and chromaticity of this EL device were measured in the same manner as in Example 7. The results are shown in Table 3.

[0106]

[Table 3]

(Embodiment 11) An ITO substrate washed in the same manner as in Embodiment 7 is set in a vacuum vapor deposition device and 1 × 10.
N, N'-diphenyl-N, under reduced pressure of ^-6 torr or less.
N-di (m-tolyl) -benzidine (TPD) 60n
vapor deposited to a thickness of m and then Tris (8-quinolinate)
A mixture of aluminum (Alq3) and a Nile red-based red light-emitting compound A, which was weighed so as to be 1.7% by weight, was vapor-deposited on the surface of the TPD vapor-deposited film so as to have a thickness of 31 nm. An EL device was manufactured by vapor-depositing the electrodes so as to have a thickness of 150 nm.

The maximum luminance and chromaticity of this EL device were measured in the same manner as in Example 7. The results are shown in Table 4.

(Example 12) The film thickness of TPD was set to 60 nm, and Nq.
Example 1 except that the mixture obtained by mixing so as to have a ratio of 6% by weight was vapor-deposited so as to have a thickness of 40 nm.
An EL device was manufactured in the same manner as in 1.

The results are shown in Table 4.

[0111]

[Table 4]

Example 13 In a 5 ml volumetric flask,
Poly (N-vinylcarbazole) (hereinafter referred to as PVK. Manufactured by Kanto Chemical Co., Inc.) 70.0 mg, 2,5-bis (1-naphthyl) -1,3,4-oxadiazole (hereinafter referred to as BND) Made by Lancaster) 14.85m
g, Nile red red light-emitting compound A 0.05 mg,
0.10 mg of the green luminescent dye (dye B) having the structural formula represented by the above formula (9) and 15.0 mg of the blue luminescent dye (DPVBi) having the structure represented by the above formula (8) are weighed and dichloroethane is added. A solution was prepared so that the total volume became 5 ml. The solution was sufficiently dissolved by applying ultrasonic waves with an ultrasonic cleaner US-2 manufactured by SND Co., Ltd. for 20 minutes.

The ITO substrate was ultrasonically cleaned with acetone for 10 minutes, then ultrasonically cleaned with IPA for 10 minutes, blown with nitrogen and dried. Photosurface processor PL manufactured by Sen Special Light Source Co., Ltd. over 5 minutes after drying
UV cleaning was performed with 16-110. After cleaning and drying the ITO substrate, spin coater 1H- manufactured by Mikasa Co., Ltd.
The solution was set to D7 and the prepared solution was dropped to form a film. The substrate after the film formation was dried in a constant temperature layer at 50 ° C. for 30 minutes, and then was placed on an aluminum electrode (Al: Li = 9) with a high vacuum deposition device VDS-M2-46 type manufactured by Daia Vacuum Giken Co., Ltd.
9: 1 wt% of Co. Kojundo Chemical Laboratory), ^10-6
An EL device was manufactured by depositing about 150 nm below Torr.

The manufactured EL element is F manufactured by Topcon Co., Ltd.
The optical characteristics were measured with ast BM-7. The results are shown in Table 4. As shown in Table 4, by combining the Nile red-based red light-emitting compound according to the present invention with the green light-emitting dye and the blue light-emitting dye, it is possible to emit white light.
The device could be completed.

Example 14 In a 5 ml volumetric flask,
PVK 70.1 mg, BND 14.85 mg, the Nile red red luminescent compound A 0.04 mg, and the same type of green luminescent dye as used in Example 13 above.
10 mg and 15.0 mg of the same type of blue luminescent dye as used in Example 13 were weighed out, and dichloroethane was added to the solution to prepare a solution of 5 ml. An EL element was manufactured in the same manner as in Example 13 below, and the optical characteristics were measured. The results are shown in Table 5. As shown in Table 5, an EL device capable of emitting white light could be completed by combining the Nile red-based red light emitting compound according to the present invention with the green light emitting dye and the blue light emitting dye.

Example 15 In a 5 ml volumetric flask,
PVK 70.0 mg, BND 20.0 mg, Nile red red light-emitting compound A 0.02 mg, Example 1 above.
0.03m of the same type of green luminescent pigment used in 3
g and 9.95 mg of the same type of blue luminescent dye as used in Example 13 were weighed out, and dichloroethane was added to the solution to prepare a solution of 5 ml. Thereafter, an element was manufactured in the same manner as in Example 1 and its optical characteristics were measured. The results are shown in Table 5. As shown in Table 5, an EL device capable of emitting white light could be completed by combining the Nile red-based red light emitting compound according to the present invention with the green light emitting dye and the blue light emitting dye.

[0117]

[Table 5]

Example 16 In a 100 ml round-bottomed flask, 0.92 g (2.89 mmol) of Nile Red,
Fluorinated phenylacetonitrile represented by formula (15)
(1) 1.0 g (4.33 mmol) and acetic anhydride 5
0 ml was added. 13 this solution in a silicone oil bath
The mixture was heated to 5 ° C. and reacted for 1 hour. Acetic anhydride was distilled off using an evaporator, and the residue was dissolved in chloroform. The chloroform solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, and sodium sulfate was added to the solution to 30
It was left still for a minute and dehydrated. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to give a blue-purple solid (40 mg).
Got The melting point of this blue-violet solid was 235 to 240 ° C. The NMR of this blue-violet solid is shown in FIG. From these results, this blue-violet solid was identified as a Nile red-based red light-emitting compound D having a structure represented by the formula (16).

[0119]

[Chemical 27]

[0120]

[Chemical 28]

Example 17 In a 100 ml eggplant-shaped flask, 0.92 g (2.89 mmol) of Nile Red,
Fluorinated phenylacetonitrile represented by formula (17)
(2) 1.0 g (4.33 mmol) and acetic anhydride 5
0 ml was added. 13 this solution in a silicone oil bath
The mixture was heated to 5 ° C. and reacted for 1.5 hours. Acetic anhydride was distilled off using an evaporator, and the residue was dissolved in chloroform. This solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes for dehydration. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to obtain 50 mg of a blue-purple solid.
The melting point of this blue-violet solid was 250 to 252 ° C.
The NMR of this blue-violet solid is shown in FIG. From these results, this blue-violet solid was identified as a Nile red red light-emitting compound E having a structure represented by the formula (18).

[0122]

[Chemical 29]

[0123]

[Chemical 30] Polyvinylcarbazole (hereinafter referred to as PVK. Manufactured by Kanto Chemical Co., Inc.) 70.
0 mg, BND 29.7 mg, and Nile red red light-emitting compound D 0.3 mg represented by the formula (16).
Was weighed, dichloroethane was added, and a solution containing Nile red-type red light-emitting compound was prepared so as to be 5 ml. An EL device was manufactured in the same manner as in Example 7 using the solution containing the Nile red-based red light emitting compound.

This EL device was manufactured by Topcon Corporation.
The maximum brightness and chromaticity were measured while gradually increasing the voltage with Fast BM-7. When the voltage is 17 V and the current is 9.07 mA, the luminance is 1575 Cd / m ² and the CIE chromaticity is X-coordinate is 0.
6552, voltage 18 V and current 11.84 mA, brightness 1815 Cd / m ² and CIE chromaticity, X coordinate is 0.65.
63, voltage 19V and current 13.98mA, brightness 17
X-coordinate is 0.655 at 02 Cd / m ² and CIE chromaticity
Brightness of 150 at 9, voltage 20V and current 16.84mA
The X coordinate was 0.6517 at 5 Cd / m ² and CIE chromaticity.

ITO washed as in Example 7
The substrate was set in a vacuum evaporator, and N, N′-diphenyl-N, N-di (m-tolyl) -benzidine (TPD) was evaporated to a thickness of 60 nm under reduced pressure of 1 × 10 ⁻⁶ torr or less, Then, a mixture of tris (8-quinolinato) aluminum (Alq3) and Nile red red light-emitting compound E having a structure represented by formula (18), which was weighed so as to be 2% by weight, was added to the TPD. Evaporate to a thickness of 31 nm on the surface of the evaporated film, and finally,
An EL element was manufactured by depositing an aluminum electrode so as to have a thickness of 150 nm.

The luminance and chromaticity of this EL device were measured in the same manner as in Example 7. Brightness of 3660 Cd / m ² and CI at voltage of 27 V and current of 15.37 mA
The X coordinate was 0.6266 in E chromaticity.

Example 18 In a 100 ml eggplant-shaped flask, 0.92 g (2.89 mmol) of Nile Red,
Fluorinated phenylacetonitrile represented by formula (19)
(3) 1.0 g (4.33 mmol) and acetic anhydride 60
ml was added. 135 this solution in a silicone oil bath
The mixture was heated to ℃ and reacted for 3.5 hours. Acetic anhydride was distilled off using an evaporator, and the residue was dissolved in chloroform. This solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes.
Dehydrated. Concentrate this solution using an evaporator,
The obtained solid was purified by column chromatography using silica gel and benzene to obtain 10 mg of a blue-violet solid. The NMR of this blue-violet solid is shown in FIG. 7. From these results, this blue-violet solid was identified as a Nile red-based red light emitting compound F having a structure represented by the formula (20).

[0128]

[Chemical 31]

[0129]

[Chemical 32] (Example 19) 1.04 g (3.28 mmol) of Nile red, 1.0 g (4.92 mmol) of 3-fluoro-4- (trifluoromethyl) phenylacetonitrile and 50 ml of acetic anhydride were placed in a 100 ml eggplant flask.
I put. This solution was heated to 135 ° C. in a silicon oil bath and reacted for 2.5 hours. Acetic anhydride was distilled off with an evaporator, and the residue was dissolved in chloroform. This solution was washed with a 5% aqueous sodium hydroxide solution and water in this order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes for dehydration. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to obtain 40 mg of a blue-violet solid. The melting point of the blue-violet solid was 215 to 220 ° C. NMR of blue-violet solid
Is shown in FIG. From these results, this blue-violet solid was identified as the Nile red-based red light-emitting compound G having the structure represented by the formula (21).

[0130]

[Chemical 33] Polyvinylcarbazole (hereinafter referred to as PVK. Manufactured by Kanto Chemical Co., Inc.) 70.
0 mg, BND 29.8 mg, and Nile red red light-emitting compound G 0.2 mg represented by the formula (21).
Was weighed, dichloroethane was added, and a solution containing Nile red-type red light-emitting compound was prepared so as to be 5 ml. An EL device was manufactured in the same manner as in Example 7 using the solution containing the Nile red-based red light emitting compound.

This EL element is manufactured by Topcon Corp.
The maximum brightness and chromaticity were measured while gradually increasing the voltage with Fast BM-7. At a voltage of 16 V and a current of 6.16 mA, the luminance is 1087 Cd / m ² and the CIE chromaticity is 0, and the X coordinate is 0.
Brightness is 1 at 6776, voltage 17V and current 9.32mA
The X coordinate is 0.678 at 444 Cd / m ² and CIE chromaticity.
0, voltage 18V, current 12.71mA, brightness 162
2Cd / m ² and CIE chromaticity have an X coordinate of 0.6787,
Brightness of 1455C at voltage of 19V and current of 15.73mA
The X-coordinate is 0.6790 at d / m ² and CIE chromaticity, the brightness is 1120 Cd / at a voltage of 20 V and a current of 18.28 mA.
The X coordinate was 0.6710 in m ² and CIE chromaticity.

ITO washed in the same manner as in Example 7
The substrate is set in a vacuum vapor deposition device, and N, N′-diphenyl-N, N-di (m-tolyl) -benzidine (TPD) is vapor-deposited to a thickness of 60 nm under a reduced pressure of 1 × 10 ⁻⁶ torr or less, Then, a mixture of tris (8-quinolinato) aluminum (Alq3) and Nile red red light-emitting compound G having a structure represented by the formula (29), which was weighed to be 1.7% by weight, was added. The TPD
An EL device was manufactured by vapor-depositing a film having a thickness of 31 nm on the surface of the vapor-deposited film and finally depositing an aluminum electrode so as to have a thickness of 150 nm.

The luminance and chromaticity of this EL device were measured in the same manner as in Example 7. Brightness of 6043 Cd / m ² and CI at voltage of 27 V and current of 18.53 mA
The X coordinate was 0.6326 in E chromaticity.

(Example 20) <Synthesis of 6-amino-3- (diisopropylamino) phenol> In a 500 ml three-necked flask, 26 g (115 mmol) of tin chloride dihydrate and 28 ml of concentrated hydrochloric acid were added.
Then, the mixture was heated and boiled. 5- (diisopropylamino) -2-nitrophenol 5.5 g (2
60 ml of acetic acid solution (3.1 mmol) was added dropwise, and after completion of the addition, reaction was carried out at reflux temperature for 1 hour. After cooling to room temperature, water and acetic acid were completely distilled off. 200 ml water residue
Was dissolved in water and the pH was adjusted to 3 to 4 with a 5% aqueous sodium hydroxide solution, and the precipitated solid was filtered off. The filtrate was concentrated and the precipitated solid was washed with ether and vacuum dried to give 16.9 g of a skin-colored solid.
(Containing salt). The NMR chart of this flesh-colored solid is shown in FIG. 6-amino-
It was identified as 3- (diisopropylamino) phenol.

<Synthesis of Nile Red Derivative> 500 ml
In a round bottom flask, 16.9 g of 6-amino-3- (diisopropylamino) phenol and 2-hydroxy-
1,4-naphthoquinone 4.0 g (23.1 mmo
l), 150 ml of ethanol and boiling stones,
The reaction was carried out under reflux for 21 hours. The reaction solution was concentrated with an evaporator, made alkaline with 200 ml of a 10% aqueous sodium hydroxide solution, extracted with chloroform, and washed with water. After dehydration with anhydrous sodium sulfate, chloroform was distilled off, and the residue was purified by column chromatography using silica gel,
0.50 g of the target Nile Red derivative was obtained. The NMR chart of this Nile Red derivative is shown in FIG.

<Synthesis of Nile Red Red Compound> 10
In a 0 ml eggplant flask, the Nile Red derivative
46 g (1.33 mmol), 3,5-bis (trifluoromethyl) phenylacetonitrile 0.50 g
(1.99 mmol), and add 50 ml of acetic anhydride,
Heat this solution to 135 ° C in a silicone oil bath,
The reaction was carried out for 2 hours. Acetic anhydride was distilled off using an evaporator, and the residue was dissolved in chloroform. Add this solution to 5
% Sodium hydroxide aqueous solution and water in that order, sodium sulfate was added, and the mixture was allowed to stand for 30 minutes for dehydration. This solution was concentrated with an evaporator, and the obtained solid was purified by column chromatography using silica gel and benzene to obtain 14 mg of a blue-violet solid. The melting point of this blue-violet solid was 183 to 185 ° C. The NMR of this blue-violet solid is shown in FIG. From these results, this blue-violet solid was identified as a Nile red-based red light-emitting compound represented by the formula (22).

[0137]

[Chemical 34]

[0138]

EFFECTS OF THE INVENTION According to the present invention, a heat- and light-stable Nile, which is a novel substance which has not been obtainable hitherto, is capable of emitting red light having a peak wavelength closer to that of deep red with high brightness. A red-based red light emitting compound can be provided.

According to the present invention, it is possible to provide a novel Nile red-based red light emitting compound capable of producing a device capable of emitting white light.

[Brief description of drawings]

FIG. 1 is a ¹ H-NMR chart of Nile red-based red light-emitting compound A in Example 1.

FIG. 2 is an IR chart of Nile red-based red light-emitting compound A in Example 1.

FIG. 3 is an IR chart of a Nile red-based red light emitting compound A in Example 1.

FIG. 4 is an NMR chart of the Nile red-type red light-emitting compound in Example 16.

FIG. 5 is an NMR chart of the Nile red-type red light-emitting compound in Example 17.

FIG. 6 is an NMR chart of the Nile red-type red light-emitting compound in Example 10.

FIG. 7 is an NMR chart of the Nile red-type red light-emitting compound in Example 18.

FIG. 8 is an NMR chart of the Nile red-type red light-emitting compound in Example 19.

FIG. 9 is 6-amino-3-in Example 20.
N of (diisopropylamino) -2-nitrophenol
It is an MR chart.

FIG. 10 is an NMR chart of a Nile red derivative in Example 20.

FIG. 11 is an NMR chart of the Nile red-type red light emitting compound in Example 20.

   ─────────────────────────────────────────────────── ─── Continued front page    (72) Inventor Toshiyuki Saikawa             1-33-15 Kokubunkita, Ebina City, Kanagawa Prefecture Leo             Palace BP246 A Building No. 102 (72) Inventor Akio Tajima             1-33-15 Kokubunkita, Ebina City, Kanagawa Prefecture Leo             Palace BP246 A Building No. 105 (72) Inventor Hidemasa Mori             2-6-9 Minamiseya, Seya-ku, Yokohama-shi, Kanagawa F-term (reference) 3K007 AB02 AB04 AB11 AB14 DB03                 4C056 AA02 AB01 AC03 AD08 AE03                       EA01 EB01 EC01 ED06 ED08

Claims (8)

[Claims] 1. A structure represented by the following general formula (1):
A Nile red-type red light-emitting compound characterized by the above. [Chemical 1] (However, in the formula, R¹Is a lower alkyl group having 1 to 5 carbon atoms
, And R¹Is R ^ThreeIn collaboration with -CH_TwoCH_Two−
CR⁶R⁷-(However, -CR⁶R⁷The carbon at −
R bound to the benzene ring⁶And R⁷Is a hydrogen atom or carbon
Represents a lower alkyl group of the number 1 to 5, R⁵And R⁶Is
It may be the same or different. ) Is formed. R
^TwoRepresents a lower alkyl group having 1 to 5 carbon atoms, and R
^TwoIs R⁵In collaboration with -CH_TwoCH_Two-CR⁸R⁹-(Ta
But, -CR⁸R⁹Carbon in-bonds to the benzene ring
And R⁸And R⁹Is a hydrogen atom or a lower atom having 1 to 5 carbon atoms.
R is a group, R⁸And R⁹Are the same phase
You may make a mistake. ) Is formed. R^ThreeIs a hydrogen atom,
R¹The bond or R formed in cooperation with^FourIn collaboration with
And naphtha formed by containing adjacent benzene rings
Indicates a len ring. R^FourIs a hydrogen atom or R^ThreeIn collaboration with
Naphthalene formed by containing adjacent benzene rings
Indicates a ring. R⁵Is a hydrogen atom or R^TwoIn collaboration with
The bond formed is shown. Ar is the general formula (2),
Either (4) or (5) is shown. ) [Chemical 2] (However, R¹⁰Represents a single bond or a methylene group. R
¹¹Is a hydrogen atom or R ¹²Formed in collaboration with
CF_Two-O-CF_Two-Indicates. R¹²Is a fluorine atom,
Cyano group, C1-C5 fluorine atom-containing lower alkyl
Group, said R¹¹Formed in collaboration with -CF_Two-OC
F_Two-Or R^ThirteenFormed in collaboration with -CF_Two-O
-CF_Two-Indicates. R^ThirteenIs a hydrogen atom, cyano group,
Fluorine atom-containing lower alkyl having 1 to 5 carbon atoms
Group, said R¹²Formed in collaboration with -CF_Two-OC
F_Two-Or a group represented by the general formula (3) is shown. R¹⁴
Is R ^ThirteenIs a hydrogen atom or a hydrogen atom or carbon
R 1 represents a fluorine atom-containing lower alkyl group represented by the formula
^ThirteenRepresents a hydrogen atom when is a group other than a hydrogen atom.
You ) [Chemical 3] (However, R¹⁵Is a hydrogen atom or R¹⁶Formed in collaboration with
Made-CF_Two-O-CF_Two-Indicates. R¹⁶Is
Fluorine atom-containing, cyano group, fluorine atom with 1 to 5 carbon atoms
Primary alkyl group, R¹⁵Formed in collaboration with -CF
_Two-O-CF_Two-Or R¹⁷Formed in collaboration with
CF_Two-O-CF_Two-Indicates. R¹⁷Is a hydrogen atom,
Ano group, fluorine atom, fluorine atom containing 1 to 5 carbon atoms low
Primary alkyl group, R¹⁶Formed in collaboration with -CF
_Two-O-CF_Two-Indicates. R¹⁸Is R¹⁷Is a hydrogen atom
Is hydrogen atom or a fluorine atom having 1 to 5 carbon atoms
Represents a lower alkyl group contained, R¹⁷Is a group other than hydrogen atom
Is a hydrogen atom. ) [Chemical 4] (However, R¹⁹Is a fluorine atom, a cyano group, and 1 to 5 carbon atoms
Represents a fluorine atom-containing lower alkyl group. k is 1 to 4
An integer is shown and m shows an integer of 1-3. sum of m and k
Number of R¹⁹May be the same or different. ) [Chemical 5] (However, R¹⁹Is a fluorine atom, a cyano group, and 1 to 5 carbon atoms
Represents a fluorine atom-containing lower alkyl group. k is 1 to 4
An integer is shown and m shows an integer of 1-3. sum of m and k
Number of R¹⁹May be the same or different. ) 2. In the general formula (1), the Nile red dye compound represented by the general formula (6) is reacted with the electron-withdrawing aromatic acetonitrile represented by the general formula (7). A method for producing the indicated Nile red-based red light emitting compound. [Chemical 6] (However, R ¹ , R ² , R ³ , R ⁴ and R ⁵ have the same meanings as in the above claim 1.) (However, Ar has the same meaning as in claim 1.) 3. A light emitting device comprising a light emitting layer containing a Nile red red light emitting compound represented by the general formula (1), provided between a pair of electrodes. 4. The light emitting device according to claim 3, wherein a hole transport layer is interposed between an anode of the pair of electrodes and the light emitting layer. 5. The light emitting device according to claim 4, wherein the light emitting layer contains a Nile red red light emitting compound and a host dye. 6. The light emitting device according to claim 4, wherein the light emitting layer and the hole transport layer are formed by a vapor deposition method. 7. The light emitting device according to claim 3, wherein the light emitting layer contains the Nile red red light emitting compound, an electron transporting substance, and a hole transporting polymer. 8. The light emitting device according to claim 7, wherein the light emitting layer is formed by a coating method.