JP2002231450A - Fluorescent converting film, resin composition for fluorescent converting film and organic electroluminescence display device - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a technique for improving continuous driving durability while keeping high light emitting intensity. SOLUTION: At least one or more kinds of fluorescent coloring matters and an additive for capturing energy from the fluorescent coloring matters are contained, and when a minimum exciting triplet energy level of the additive is '3Eq', and a minimum exciting triplet energy level of a main light emitting fluorescent coloring matter having a fluorescent peak wave length of the longest wave length among the fluorescent coloring matters is '3Ed', the relationship of '3Eq<3Ed' is satisfied.

Description

DETAILED DESCRIPTION OF THE INVENTION

[0001]

The present invention relates to a fluorescence conversion film, a resin composition for a fluorescence conversion film, and an organic electroluminescent display device. More specifically, a fluorescence conversion film excellent in continuous driving durability while maintaining high fluorescence conversion efficiency, a resin composition for a fluorescence conversion film for obtaining the same, and the fluorescence conversion film and an organic electroluminescent device (hereinafter, referred to as “ Organic EL
Also referred to as an "element." ) And an organic electroluminescent display device (hereinafter referred to as “organic EL display device”)
Also called. ).

[0002]

2. Description of the Related Art Organic EL devices are completely solid devices.
It is excellent in visibility, can be reduced in weight and thickness, and can be driven at a low voltage of only a few volts. For this reason, organic EL elements are expected to be used as displays, and are being actively studied at present. In order to realize a color display using an organic EL element, it is necessary to finely arrange light emission of three primary colors of blue, green and red in a two-dimensional direction. Therefore, the following methods have been proposed.

[0003] Three-color coating method Color filter method Fluorescence conversion film method

The above-described three-color coating method is disclosed in, for example, Japanese Patent Application Laid-Open No. 57-157487. According to this method, one color pixel is constituted by three pixels using light emission sources of three primary colors. However, it is difficult for an organic EL element to perform wet patterning. For this reason,
With this method, it is difficult to create a high definition display.

The above color filter method is disclosed in, for example, Japanese Patent Application Laid-Open No. Hei 1-315988. According to this method, three primary colors are obtained by using a white light source and performing color conversion with a color filter. However, with this method, although patterning is easy, the luminance of the three primary colors obtained is significantly lower than the luminance of the white light source.

[0006] The above-mentioned fluorescence conversion film method is disclosed in, for example, Japanese Patent Application Laid-Open No. 3-152897. According to this method, three primary colors are obtained by using a blue light source and performing color conversion with a fluorescence conversion film. That is, in the fluorescence conversion film, blue light is irradiated to excite the fluorescent dye, and green light and red light having longer wavelengths are generated. For this reason, this method has an advantage that a decrease in luminance is small as compared with the above-described color filter method. However, this fluorescence conversion film method has a problem that the curing process of the resin composition for a fluorescence conversion film by light or heat causes a decrease in the fluorescence conversion rate and a change in chromaticity.

A method for solving such a problem of driving durability is disclosed in, for example, Japanese Patent Application Laid-Open No. 2000-256565. According to the technique disclosed in this publication, an antioxidant and a light stabilizer are added to the resin composition for a fluorescence conversion film. Thereby, it is possible to suppress a decrease in the fluorescence conversion rate and a change in chromaticity in the curing step of the resin composition by light or heat.

[0008]

However, in the above method, although the stability of the fluorescence conversion film itself in the curing step is improved, the fluorescence intensity of the fluorescence conversion film tends to gradually decrease by continuous driving of the organic EL element. There was room for technical improvement.

The present invention has been made in view of the above circumstances, and has a fluorescent conversion film excellent in continuous driving durability while maintaining high luminous intensity, a resin composition for obtaining the same, and
Organic E combining the fluorescence conversion film and the organic EL element
It is intended to provide an L display device.

[0010]

In order to achieve the above object, the present inventor has conducted various experiments and studies. As a result, when the fluorescent dye is excited to an excited triplet state having a long excitation lifetime, the present invention is particularly effective. It has been found that a fluorescent dye reacts with a binder resin and the like, and the fluorescence intensity decreases. In addition, the inventor
Addition of an additive whose lowest excitation triplet energy level is lower than that of the fluorescent dye to remove energy from the fluorescent dye in the excited triplet state causes a decrease in fluorescence intensity even when the fluorescence conversion film is exposed to excitation light for a long time. I found that it became difficult. The present invention has been completed based on such knowledge, and the gist is as follows.

According to a first aspect of the present invention, there is provided a fluorescence conversion film comprising at least one kind of fluorescent dye and an additive for removing energy from the fluorescent dye, and the lowest excitation triplet energy of the additive. The level is lower than the lowest excitation triplet energy level of the main emission fluorescent dye having the longest fluorescent peak wavelength among the fluorescent dyes.

When a fluorescent dye in a ground state absorbs excitation light, it is excited to an excited singlet state. The excitation lifetime of the excited singlet state is only a few nanoseconds to several hundred nanoseconds. For this reason, the fluorescent dye excited to the excited singlet quickly emits fluorescence and returns to the ground state. Due to this phenomenon, the excitation light is efficiently converted into light having a longer wavelength.

The excited state is an electronically active state. However, the excited singlet state has a short excitation lifetime.
For this reason, the fluorescent dye excited to the excited singlet state tends to hardly interact with the surrounding binder resin and the like.

However, the fluorescent dye excited to the excited singlet state always transitions to the excited triplet state with a certain probability. The excited triplet state has a long excitation lifetime of hundreds of nanoseconds to thousands of microseconds. As a result, the fluorescent dye excited to the excited triplet state easily interacts with the surrounding binder resin and the like to easily change the dye structure. For this reason,
When the excitation light is continuously irradiated on the fluorescence conversion film containing the fluorescent dye for a long time, a phenomenon occurs in which the fluorescence conversion efficiency gradually decreases and the fluorescence intensity decreases.

Therefore, in order to suppress a decrease in the fluorescence conversion efficiency, energy is taken from the fluorescent dye in the excited triplet state to shorten the time in the excited triplet state. For this purpose, an additive that receives energy from a fluorescent dye in an excited triplet state may be added. In order for the additive to receive energy, it is necessary that the lowest excited triplet energy level of the energy scavenging additive be lower than the lowest triplet energy level of the fluorescent dye. Here, the lowest excited triplet energy level is
It means the energy level of the ground vibration state among the excited triplet states.

When the fluorescent conversion film contains a plurality of fluorescent dyes, the energy absorbed by the fluorescent dye having the highest lowest singlet energy level is equal to the energy of the other fluorescent dye having the lowest lowest singlet energy level. Move to. Here, the lowest excited singlet energy level means the energy level of the ground vibration state among the excited singlet states.

Then, the fluorescent dye having the lowest lowest excited singlet energy level emits the strongest fluorescence as a result and becomes the main luminescent fluorescent dye. In other words, the main emission fluorescent dye is a fluorescent dye having the longest wavelength fluorescence peak among a plurality of types of fluorescent dyes included in the fluorescence conversion film.

Thus, according to the present invention, as an additive for energy scavenging, an additive having a lowest excited triplet energy level lower than that of the main emission fluorescent dye is added. That is, the lowest excited triplet energy level of the additive ^"3 E
q ", among the fluorescent dye, if indicated as" ³ Ed "the lowest excited triplet energy level of the main light-emitting fluorescent dye, in the present invention, the additive and the fluorescent dye satisfies the relationship of" ³ Eq ^<3 Ed. " It is a requirement.

The additive receives energy from the main emission fluorescent dye in the excited triplet state. As a result, the interaction between the excited triplet state fluorescent dye and surrounding molecules can be suppressed. Thereby, continuous driving durability can be improved while the fluorescence conversion efficiency of the fluorescence conversion film is high.

When a plurality of types of additives are contained in the fluorescence conversion film, the lowest excited triplet energy level of all the types of additives contained is the lowest excited triplet energy level of the main luminescent fluorescent dye. It is desirable to be lower.

In general, oxygen is known as a substance which receives energy from excited triple-state molecules. This is because the ground state of oxygen is a triplet state. However, oxygen is also a substance that promotes deterioration of the organic EL element. For this reason, an organic EL display element in which an organic EL element and a fluorescence conversion film are combined is usually hermetically sealed to shield it from oxygen and water. As a result, in the organic EL display element, it is difficult to actively use oxygen in order to suppress deterioration of the fluorescence conversion film with time. Therefore, the present invention is particularly suitable for application to an organic EL display element.

Further, according to the second aspect of the invention, at least one or more of the lowest excited singlet energy level of the additive ⁽¹ Eq) is the main light-emitting fluorescent dye lowest excited singlet energy level ⁽¹ Ed) When the ratio is higher than this, the ratio of the molar concentration of the additive to the molar concentration of the main light-emitting fluorescent dye is in the range of 0.01 to 100.

[0023] In the case of ^"1 Eq> ¹ Ed", (additives) /
(Fluorescent dye) molar ratio of 0.01 to 100
The reason why the range is desirable is as follows. That is, when the molar concentration ratio is lower than 0.01, a substantial effect of suppressing the decrease in fluorescence intensity cannot be obtained. Also,
If the molar concentration ratio is higher than 100 times, the additives aggregate, and a substantial effect of suppressing the decrease in fluorescence intensity cannot be obtained.

Further, according to the third aspect of the present invention, the lowest excited singlet energy level of at least one or more of the additives ⁽¹ Eq) is the main emission lowest excited singlet energy level ⁽¹ Ed fluorochrome ), The ratio of the molar concentration of this additive to the molar concentration of the main emission fluorescent dye is in the range of 0.01 to 5.

When “ ¹ Eq < ¹ Ed”, (additive) /
The reason why the molar ratio of (fluorescent dye) is preferably in the range of 0.01 to 5 is as follows. That is, when the molar concentration ratio is lower than 0.01, a substantial effect of suppressing the decrease in fluorescence intensity cannot be obtained. Also, in this case, when the molar concentration ratio is higher than 5 times, energy transfer from the fluorescent dye in the excited singlet state to the additive is likely to occur, and as a result, the additive is converted from the fluorescent dye to the energy that should contribute to light emission. This is because they will be robbed.
In particular, when the molar concentration ratio exceeds 10 times, the emission intensity of the fluorescence conversion film becomes low from the beginning, which is not practical.

[0026] According to the fourth aspect of the present invention, the lowest excited triplet energy level of the additive ⁽³ Eq) is the main light-emitting fluorescent dye lowest excited triplet energy level of ⁽³ E
It is configured to be higher than the level obtained by multiplying d) by 0.7.

As described above, “0.7 × ³ Ed < ³ Eq < ³
If the relationship of "Ed" is satisfied, the overlap between the energy bands of the additive and the fluorescent dye becomes large. As a result, energy transfer from the fluorescent dye to the additive easily occurs.
As a result, the additive can more efficiently take energy from the fluorescent dye in the excited triplet state.

When a plurality of types of additives are contained in the fluorescence conversion film, “0.7 × ³ Ed < ³ Eq < ³ Ed” for all the types of additives contained therein.
It is desirable that the following relationship be satisfied.

According to the fifth aspect of the invention, the transition probability of the additive from the lowest excited singlet energy level to the lowest excited triplet energy level is 0.5 or more. Thus, the transition probability is 0.5
When the value is higher than the above, the additive is easily excited to the excited triplet state by receiving energy from the fluorescent dye in the excited triplet state. As a result, the additive can more efficiently take energy from the fluorescent dye in the excited triplet state.

According to the invention of claim 6, the fluorescent dye contains at least one kind of rhodamine-based dye, and the additives include anthracene derivative, azulene derivative, thiobenzophenone derivative, porphine derivative and C60 derivative. And one or more additives selected from the group consisting of: By combining such kinds of fluorescent dyes and additives, it is possible to realize a red fluorescence conversion film capable of maintaining a particularly high fluorescence intensity for a long time.

According to the seventh aspect of the present invention, the composition includes a binder resin in addition to the fluorescent dye and the additive. The binder resin functions as a dispersion medium for the fluorescent dye and the additive. When the fluorescent conversion film is formed from the fluorescent conversion film resin composition containing the fluorescent dye, the additive, and the binder resin, the fluorescent conversion film also contains the binder resin.

Further, according to the resin composition for a fluorescence conversion film according to claim 8 of the present invention, the resin composition contains at least one kind of fluorescent dye, an additive for removing energy from the fluorescent dye, and a binder resin, The additive has the lowest excitation triplet energy level ³ Eq lower than the lowest excitation triplet energy level ³ Ed of the main emission fluorescent dye having the longest fluorescence peak wavelength among the fluorescent dyes.

When a fluorescence conversion film is formed using the resin composition for a fluorescence conversion film of the present invention, the additive can receive energy from the main emission fluorescent dye in the excited triplet state. As a result, the interaction between the excited triplet state fluorescent dye and surrounding molecules can be suppressed. Thereby, continuous driving durability can be improved while the fluorescence conversion efficiency of the fluorescence conversion film is high.

According to the ninth aspect of the present invention, the content of the fluorescent dye in the resin composition for a fluorescence conversion film is 0.0
The composition is in the range of 1 to 1% by weight.

The reason why the content of the fluorescent dye is preferably in the range of 0.01 to 1% by weight is as follows. That is, when the content is lower than 0.01% by weight, it becomes difficult for the fluorescence conversion film to sufficiently absorb the excitation light, and the fluorescence intensity decreases. On the other hand, if the content is higher than 1% by weight, the distance between the fluorescent dye molecules in the fluorescence conversion film becomes too short, and the fluorescence intensity decreases due to concentration quenching.

Further, according to the organic electroluminescent display device according to the tenth aspect of the present invention, there is provided an organic electroluminescent display device in which an organic electroluminescent element and a fluorescent conversion film are sequentially arranged in a light extraction direction. The fluorescence conversion film is constituted by the fluorescence conversion film according to any one of claims 1 to 7.

The organic EL element and the fluorescent conversion film of the organic EL display device are usually hermetically sealed to shield them from oxygen and water. Therefore, in the organic EL display device, it is difficult to actively use oxygen to suppress the deterioration of the fluorescence conversion film with time. Therefore, in the present invention, a film obtained by adding an additive that receives energy from the main emission fluorescent dye in the excited triplet state is used as the fluorescence conversion film. Thereby, the interaction between the excited triplet state fluorescent dye and surrounding molecules can be suppressed. As a result, continuous driving durability can be improved while the fluorescence conversion efficiency of the fluorescence conversion film is high.

[0038]

BEST MODE FOR CARRYING OUT THE INVENTION Hereinafter, embodiments of a fluorescence conversion film, a resin composition for a fluorescence conversion film, and an organic EL display device of the present invention will be described. In the present embodiment, first, 1. 1. The resin composition for a fluorescence conversion film will be described, and subsequently formed from the resin composition for a fluorescence conversion film. The fluorescence conversion film will be described. And, using this fluorescence conversion film,
3. The organic EL display will be described. In addition, the kind and content ratio of the fluorescent dye and the additive in the resin composition for a fluorescence conversion film are the same as the kind and content ratio in the fluorescence conversion film.

1. Resin composition for fluorescence conversion film The fluorescence conversion film resin composition of the present embodiment comprises (1) a fluorescent dye, and (2) an additive for depriving energy from the fluorescent dye,
And (3) a binder resin serving as a dispersion medium for the fluorescent dye. Hereinafter, (1) a fluorescent dye, (2) an additive, and (3) a binder resin will be sequentially described.

(1) Fluorescent Dye In the present embodiment, a single type of fluorescent dye may be used, or a plurality of types of fluorescent dyes may be used according to a desired emission color. For example, when converting blue to blue-green excitation light into red light, a rhodamine-based dye having a fluorescence peak in a wavelength region of 600 nm or more may be used. Further, it is more preferable to use a fluorescent dye having an absorption band in the wavelength region of the excitation light and inducing energy transfer or re-absorption to the rhodamine-based dye.

The content of the fluorescent dye with respect to the whole of the resin composition for a fluorescence conversion film is desirably in the range of 0.01 to 1% by weight. When the content is lower than 0.01% by weight, it becomes difficult for the fluorescence conversion film to sufficiently absorb the excitation light, and the fluorescence intensity is reduced. On the other hand, if the content is higher than 1% by weight, the distance between the fluorescent dye molecules in the fluorescence conversion film becomes too short, and the fluorescence intensity decreases due to concentration quenching.

Here, preferred fluorescent dyes are illustrated for each combination of the following excitation light colors and emission colors. Examples of fluorescent dyes that change near-ultraviolet light to blue-violet excitation light into blue light emission • Stilbene dyes: 1,4-bis (2-methylstyryl) benzene, trans-4,4-diphenylstilbene • Coumarin dyes : 7-hydroxy-4-methylcoumarin (also referred to as “coumarin 4”)

Examples of fluorescent dyes that convert blue, blue-green, or white excitation light into green light emission Coumarin-based dyes: 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidine ( 9, 9a,
1-gh) coumarin (also referred to as "coumarin 153"), 3- (2'-benzothiazolyl) -7-diethylaminocoumarin (also referred to as "coumarin 6"), 3-
(2'-benzimidazolyl) -7-N, N-diethylaminocoumarin (also referred to as "coumarin 7") Naphthalimide dyes: Basic Yellow 51, Solvent Yellow 11, Solvent Yellow 116

Examples of fluorescent dyes that convert blue, green or white excitation light into orange to red light emission (i) Cyanine dye: 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostillyl) ) -4H-
Pyran (ii) pyridine dye: 1-ethyl-2- [4- (p-
Dimethylaminophenyl) -1,3-butadienyl]-
Pyridinium-perchlorate (iii) Rhodamine dyes: rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, basic violet 11, sulforhodamine 101 In addition, rhodamine dyes inhibit the formation of aggregates A compound having at least one sterically hindered group in the molecule may be used. Examples of such rhodamine-based dyes are described in JP-A-11-279426.

(2) Additives Basic Requirements of Additives The additives of the present embodiment are the lowest excited triplet energy of the fluorescent dye having the longest fluorescence peak wavelength (main emission fluorescent dye) among the fluorescent dyes. The basic requirement is to have a lowest excited triplet energy level below the level. That is, the lowest excited triplet energy level of the additive ^"3 Eq", among the fluorescent dye, if indicated the lowest excited triplet energy level of the main light-emitting fluorescent dye and ^"3 Ed", in the present invention, an additive fluorescent dye and is a fundamental requirement to satisfy the relationship of ^"3 Eq ^<3 Ed".

As described above, since the additive for energy scavenging contains an additive having the lowest excited triplet energy level lower than that of the main emission fluorescent dye, the additive is removed from the main emission fluorescent dye in the excited triplet state. Can receive energy. As a result, the interaction between the excited triplet state fluorescent dye and surrounding molecules can be suppressed. Thereby, continuous driving durability can be improved while the fluorescence conversion efficiency of the fluorescence conversion film is high. That is, high fluorescence intensity can be maintained for a long time.

When a plurality of types of additives are contained in the resin composition for a fluorescence conversion film, the lowest excitation triplet energy level of all the types of additives contained is the lowest excitation triplet energy level of the main emission fluorescent dye. Desirably lower than the triplet energy level.

Preferred Additive Amount of Additive to Fluorescent Dye Minimum Excited Singlet Energy Level of Additive ( ¹ Eq)
And the lowest excitation singlet energy level ( ¹ Ed) of the main emission fluorescent dye, the suitable amount of the additive to the fluorescent dye is different.

[0049] (i) in the case of ^"1 Eq> ¹ Ed", as a molar concentration ratio of (additive) / (a fluorescent dye), 0.01
A range of 100 is desirable. If the molar concentration ratio is lower than 0.01, a substantial effect of suppressing a decrease in fluorescence intensity cannot be obtained. If the molar concentration ratio is higher than 100 times, the additives aggregate, and the effect of substantially suppressing the decrease in fluorescence intensity cannot be obtained.

(Ii) When “ ¹ Eq < ¹ Ed”, the molar ratio of (additive) / (fluorescent dye) is 0.01 to
The range of 5 is desirable. If the molar concentration ratio is lower than 0.01, a substantial effect of suppressing a decrease in fluorescence intensity cannot be obtained. In this case, when the molar concentration ratio is higher than 5 times, energy transfer from the excited singlet state fluorescent dye to the additive is likely to occur. As a result, the additive deprives the fluorescent dye of the energy that should contribute to light emission. In particular, when the molar concentration ratio exceeds 10 times, the emission intensity of the fluorescence conversion film is low from the beginning, which is not practical.

When a plurality of types of additives are contained in the resin composition of the fluorescence conversion film, the lowest excited triplet energy level of all the types of additives contained is the lowest excited triplet of the main light emitting fluorescent dye. Desirably lower than the term energy level.

Lower Limit of Minimum Excited Triplet Energy Level of Additives Minimum Excited Triplet Energy Level of Additives ( ³ Eq)
However, it is desirable to be higher than 0.7 times the lowest excitation triplet energy level ( ³ Ed) of the main emission fluorescent dye. That is, it is desirable to satisfy the relationship of “0.7 × ³ Ed < ³ Eq < ³ Ed”.

As described above, “0.7 × ³ Ed < ³ Eq < ³
If the relationship of "Ed" is satisfied, the overlap between the energy bands of the additive and the fluorescent dye becomes large. As a result, energy transfer from the fluorescent dye to the additive easily occurs.
As a result, the additive can more efficiently take energy from the fluorescent dye in the excited triplet state.

When a plurality of types of additives are contained in the resin composition of the fluorescence conversion film, “0.7 × ³ Ed < ³ Eq” for all the types of additives contained therein.
It is desirable that the relationship of < ³ Ed ”be satisfied.

Transition Probability in Additive The transition probability from the lowest excited singlet energy level to the lowest excited triplet energy level in the additive is 0.5
It is desirable that this is the case. When the transition probability is as high as 0.5 or more, the additive is easily excited to the excited triplet state by receiving energy from the fluorescent dye in the excited triplet state. As a result, the additive can more efficiently take energy from the fluorescent dye in the excited triplet state.

Specific Examples of Additives Specific examples of the additives include the following. 2,4,6,8,10-dodecapentaenal,
1,8-diphenyl-1,3,5,7-octatetraene, pheophytin b, methylene blue cation, tetraphenylporphine, (all-E) retinol, chlorophyll b zinc (II), dibenzo [def, mno]
Chrysene

1,3-diphenylisobenzofuran, tetraphenylporphine magnesium (II), benzo [c] tinoline, dibenzo [b, def] chrysene,
(E) - azobenzene, C _70, perylene, 1,6-diphenyl-1,3,5-hexatriene, tetra benzo porphine zinc (II), 5-methyl-7- (2,6,6
Trimethyl-1-cyclohexen-1-yl) (E,
E, E) -2,4,6-heptatrienal, 7,12
-Diethenyl 3,8,13,17-tetramethylporphine-2,18-dipropanoic acid dimethyl ester,
C _60, porphine, 7,12 diethenyl -3,8,1
3,17-tetramethylporphine-2,18-dipropanoic acid, 2,4,6,8-decatetraenal, tetraphenylporphine zinc (II), 7,12-diethyl-
3,8,13,17-tetramethyl-porphine-2,
18-dipropanoic acid, 7,12-diethyl-3,8,1
3,17-tetramethyl-porphine-2,18-dipropanoic acid dimethyl ester, octaethylporphine

2,7,12,17-tetraethyl-3,
8,13,18-tetramethylporphine, tetrakis (4-chlorophenyl) porphine zinc (II), tetrakis (2-methylphenyl) porphine zinc (II), tetrakis (2-chlorophenyl) porphine zinc (I
I), cycloheptatriene, ferrocene, thiofluorenone, 5-methylbenzo [rst] pentaphene,
2,7,12,17-tetraethyl-3,8,13,1
8-tetramethylporphine, azulene, thionine cation, 9,9-dimethylanthrathion, 3,4,5
6-tetrachloro-2 ', 4', 5 ', 7'-tetraiodofluorescein dianion, porphine magnesium (II), 3,3'-diethyl-2,2'-thiacarbocyanine, thiobenzophenone, 1,5 , 10-Trichloroanthracene, tetrabenzoporphine magnesium (II), thioxanthion, 2-methyl-1-aceanthrlenone, porphine zinc (II), 2 ', 4',
5 ', 7'-tetrabromo-3,4,5,6-tetrachlorofluorescein dianion

2,8,12,18-tetraethyl-3,
7,13,17-tetramethylporphine magnesium (II), benzo [rst] pentaphene, 9,10-dibromoanthracene, dibenzo [a, d] cycloheptene 5-thione, 2,6-dimethyl-2,4,6- Octatriene, 1,10-dichloroanthracene 71.9-
Benzoyl-10-bromoanthracene, 9.10-dichloroanthracene, 1,4,5,8-tetrachloroanthracene, 9-benzoyl-10-chloroanthracene, zinc (II) octaethylporphine, 2,7,1
2,17-tetraethyl-3,8,13,18-tetramethylporphine zinc (II), 7,12-diethyl-
3,8,13,17-tetramethylporphine-2,1
8 dipropanoic acid, 9,10-diphenylanthracene,
5,12-dihydro-2,9-dimethylquine [2,
3-b] acridine, 4,4'-dimethoxythiobenzophenone, 9-bromoanthracene, 9-methylanthracene, 2-methylanthracene, 1,5-dichloroanthracene, 9,10-dicyanoanthracene, pyronin B cation

Sulforhodamine B salt, 9-nitroanthracene, benzo [a] pyrene, 9-naphthoylanthracene, 2,5-dimethyl-2,4-hexadiene
4,4'-bis ({methylamino) thiobenzophenone, 9-acetylanthracene, 9-benzoylanthracene, 9-propionylanthracene, 1-chloroanthracene, 9-cinnamoylanthracene, 9-anthracenecarboxylic acid, 1,4-diphenyl- 1,3-butadiene, 2 ', 4', 5 ', 7'-tetrabromofluorescein dianion, anthracene-9-carboxamide, anthracene, benz [g] isoquinoline, rhodamine 3G cation, rhodamine B salt, 10-methyl-9
-Acridinethione, pyronin cation, 1-pyrenecarboxaldehyde, di-tert-butylthioketene, benzo [g] quinoline,

Rhodamine 6G cation, 2,6-dimethyl-1-benzothiopyran-4-thione, 9-xanthion, anthracene-9-carboxaldehyde,
4,6-octatrienal, N, N'-diethylrhodamine salt, 9-chloroacridine, 1-aminoanthracene, 2-aminoanthracene, 9-aminoanthracene, 2 ', 4', 5 ', 7'-tetra Iodofluorescein dianion, ovalene, 7,12-dimethylbenz [a] anthracene, dibenzo [b, g] phenanthrene, 4-cholesten-3-thione, phenazine, 4-bromo-2,3-dihydro-2,2,3 , 3-Tetramethylindene-1-thione, 1,1-dimethyl-2-naphthalenthione, benzo [a] phenazinium, naphtho [2,3-a] coronene, 9-methyl-acridine, 9
-Propyl acridine, colchicine,

3-methyl-5- (2,6,6-trimethyl-1-cyclohexen-1-yl) (E, E) -2,
4 pentadienone knurl, 4,4'-dinitro (E) - stilbene, Jinafusu [1,2-a; 1 ', 2'-h] anthracene, acridine, acridine -d _9, benzo [b] chrysene, 4 ', 5'-Dibromo-2', 7'-
Dinitrofluorescein dianion, 2,2,4,4-
Tetramethyl-3-pentanethione, 4-cyano-4 '
-Methoxy- (E) -stilbene, 2,3-dihydro-2,2,3, -tetramethylindene-1-thione,
Rhodamine salt, Benz [b] acridin-12-one,
Benzuanthrone, 2 ', 7'-dichlorofluorescein dianion, 4,4'-dicyano- (E) -stilbene, 9-aminoacridine, dibenzo [h, rst] pentaphene, benzo [ghi] perylene, hexabenzo [a, d , G, j, m, p] coronene, 12-methylbenz [a] anthracene, 1,2-dihydro-3-methylbenz [j] aceanthrylene, 3,5,5-trimethyl2-cyclohexcentione, porphine Platinum (I
I),

4-nitro- (E) -stilbene, dibenz [a, e] acetylene, (E) -1,3,5-hexatriene, benz [a] anthracene, fluorescein dianion, naphtho [1,2, 3,4-def] chrysene, 2-nitro- (E) -stilbene, 4-benzoyl- (E) -stilbene, 4-cyano- (E) -stilbene, 9-methylbenz [a] anthracene, 10-
Methylbenz [a] anthracene, tetrabenzo [a,
c, j, l] naphthacene, indeno [2,1-a] indene, 2-methylbenz [a] anthracene, 8-methylbenz [a] anthracene, 4-methylbenz [a]
Anthracene, dibenzo [a, j] coronene, tribenzo [a, d, g] coronene, 5-methylbenz [b] acridin-12-one, 4-acetyl- (E) -stilbene, 4-iodo- (E) -Stilbene, 3-methylbenz [a] anthracene, 11-methylbenz [a] anthracene, 2,2,4,4-tetramethyl-1,3-
Cyclobutanedithione

(E) -Stilbene-d ₁₂ , 4-bromo-
(E) -Stilbene, tropolone, 5-methylbenz [a] anthracene, tevenidine, 4-chloro- (E)
-Stilbene, pentaphene, pyrene, 1-methylbenz [a] anthracene, 6-methylbenz [a] anthracene, 1-naphthalene methyl acrylate,
4,4′-dimethoxy- (E) -stilbene, 3-methoxy- (E) -stilbene, 3-nitro- (E) -stilbene, β- (3-pyridyl)-(E) -styrene,
2-methoxy-2,4,6-cycloheptatriene-1
-One, 3,3'-dibromo- (E) -stilbene, 4
-Fluoro- (E) -stilbene, 3-methyl- (E)
-Stilbene, β- (2-pyridyl)-(E) -styrene, diphenyloctatetraine, acridine orange, tetrachloro-1,4-benzoquinone, 3,3′-
Bis (1,2-ethenediyl)-(E) -pyridine,

(E) -Stilbene, 10-methylbenzo [g] pteridine-2,4-dione, dibenzo [g,
p] chrysene, hexahydro (E) -2-indanthion, pyrone-4-thione, (E) -2,2 '-(1,
2-ethenedyl) bispyridine, thioacetone, 3,1
0-dimethylbenzo [g] pteridine-2,4-dione, 7- (diethylamino) -3,3′-carbonylbiscoumarin, β- (4-pyridyl)-(E) -styrene, benz [a] acridine, 7,8,10-trimethylbenzo [g] pteridine-2,4-dione, tetraphenylethene, riboflavin, triphenylethylene,
Diadamantylethanedione, benzo [a] phenazine, dibenzo [hi, uv] hexacene, hexabenzo [bc, ef, hi, kl, no, qr] coronene,
-Methoxy- (E) -stilbene, benzo [k] fluoranthene, 2,2'-bibenzo [b] thiophene, 7-
(Diethylamino) -5,7'-dimethoxy-3,3 '
-Carbonylbiscoumarin, dibenzo [c, m] pentaphene

9-fluorenone, 2-phenylindene, α-methyl- (E) -stilbene, 9-methylbenz [c] acridine, 4.4′-bis (1,2-entenediyl)-(E) -bispyridine Thiocoumarin, benzo [b] triphenylene, benz [c] acridine,
3- (2-benzofuroyl) -7-diethylaminocoumarin, 3-benzoyl-7-diethylaminocoumarin,
3,3'-carbonylbis (7-diethylamino) coumarin, 2,6-dimethylpyran-4-thione, 2,4
6-tris (4-methoxyphenyl) pyrylium, 3,6
-Diaminoacridine, 3,6-diamino-10-methylacridinium, 6-nitrochrysene, 1,7,7-
Trimethylbicyclo [2,2,1] heptane-2,3-
Dione, 2,2,5,5-tetramethyl-3,4-hexanedione, benzo [a] coronene, 1,4-dionenaphthalene, dicyclohexylethanedione, 2-bromotricycloquinazoline, 1,2-dinitro Naphthalene, benzo [b] carbazole,

7- (diethylamino) -3-thenoylcoumarin, dibenz [a, h] anthracene, 2,4,6
-Triphenylthiopyrylium, 3-phenylcoumarin, 1,3-cyclohexadiene, 1-phenyl-1,
2-propanedione, acridine yellow, dinaphtho [2,1-b: 1 ′, 2′-d] thiophene, adamantanethione, dibenzo [fg, ij] phenanthro [9,10,1,2,3-pqrest] pentaphene Fluoranthene, dibenzo [a, g] coronene, benzo [e] pyrene, dibenz [a, j] anthracene,
Tricycloquinazoline, 7- (diethylamino) -3
-(4-dimethylaminobenzoyl) coumarin, 2,
4,6-triphenylpyrylium, dibenz [a, j]
Acridine, tribenzo [b, n, pqr] perylene,
Dibenzo [a, c] phenazine, benzo [b] naphtho [2,3-d] thiophene, benzyl, 1,4-benzoquinone, 1,3,5,7-octatetraindiol

1,3,3-trimethylbicyclo [2,
2,1] heptane-2-thione, dibenz [a, h] acridine, 2-methyltricycloquinazoline, 3,
5,7,9-dodecatetraine, 1-[(1-naphthyl) amino] naphthalene, 2,3′-bibenzo [b] thiophene, benzo [g] chrysene, benzo [ghi] fluoranthene, 6-benzoylchrysene, 2,3-pentanedione, 1-methylbenzo [c] phenanthrene,
4-methyltinoline, dibenz [a, c] acridine,
2-benzoyl-N-methyl-β-naphthiazoline,
(Z) -stilbene, 1-anilinonaphthalene, coronene, benzo [b] fluoranthene, 1,3-diazaazulene, hexahelicene, 1-naphthalenecarboxylic thioic acid-O-ethyl ester, 3,4-dichloro-2,5 -Thiophenedione, l-aminonaphthalene, tetrabenzo [fg, lm, uv, a, b] heptacene

Methyl cinnamate, (E) -diethyldiazene, β-ionone, 1,5-dinitronaphthalene, N, N-dimethyl-4-nitroaniline, benzo [def] carbazole, benzo [b] naphtho [ Two, three
-D] furan, benzo [c] fluorene, 3,3,8,
8-tetramethylcyclooctane-1,2-dione, 1,
3-dibromonaphthalene, 1-nitronaphthalene, naphtho [1,2-b] triphenylene, diphenylhexatriin, 4-nitroaniline, 7,8-dimethylbenzo [g] pteridine, 1,2-cyclodecanedione,
(E) -dimethyl diazene, (E) -dipropyl diazene, 2,3,5,6-tetraphenyl 1,4-dioxin, 3,4-dichloro-2,5-furandione, 1,4
-Dicyanonaphthalene, 2,2 '-(1,4-phenylene) bis [5-phenyl] oxazole, 3,4-dichloropyrrol-2,5-dione, pentacene-6,13-
Zeon,

1,8-dihydroxyanthrone, benzo [c] chrysene, 2,2'-binaphthyl, 2,3-dihydro-2-methylnaphtho [1,8-de] -1,
3,2-diazabolin, tetrabenzo [a, c, hi,
qr] pentacene, 3- (4-cyanobenzoyl)-
5,7-dimethoxycoumarin, 5,7-dimethoxy-
3,3'-carbonylbiscoumarin, octafluoronaphthalene, 2-methyl-4,6-diphenylpyrylium, 1-naphthalaldehyde, N-methyl-4-nitroaniline, dibenzo [c, g] carbazole, 5,12- Tetracenequinone, 6-methylbenzo [c] phenanthrene, 2-[(2-naphthyl) amino] naphthalene, 3,
3'-carbonylbis (5,7-dimethoxy) coumarin, biacetyl, 5,7,7'-trimethoxy-3,
3'-carbonylbiscoumarin, 1-acetylnaphthalene, 4-methylbenzo [c] phenanthrene, 5-methylbenzo [c] phenanthrene, 10,15-dihydrodiindeno [1,2-a: 2 ', 1'- c] fluorene, 2-methylbenzo [c] phenanthrene, 3-methylbenzo [c] phenanthrene

(E) -Diisopropyldiazene, 5-nitroaceneaphthene, 1-methoxy-1,3-butadiene, pentahelicene, benzo [c] phenanthrene, 1
-Chloro-1,3-butadiene, 3-benzoyl-5,
7-dimethoxycoumarin, 2-nitronaphthalene, 2,
2 '-(1,3-phenylene) bisthiophene, 1,5
-Dibenzoylnaphthalene, 2-aminonaphthalene, chrysene, 3,3'-carbonylbis (7-methoxy) coumarin, 3- (4-cyanobenzoyl) -7-methoxycoumarin, (S) -dinaphtho [2,1- d: 1 ', 2'
-F] [1,3] dioxepin, 1,8-dinitronaphthalene, 5,7-dimethoxy-3- (4-methoxybenzoyl) coumarin, 3,3,7,7-tetramethylcycloheptane-1,2- Zion, Zinaphtho [1,2-b:
1 ', 2'-d] thiophendinaphtho, 2-anilinonaphthalene, naphtho [1,2-c] [1,2,5] thiadiazole, (Z) -piperylene, benzo [b] fluorene, 5,7 -Dimethoki-3-thenoylcoumarin

5-nitro-2-froic acid, 1-cyano naphthalene, picene, benzo [a] fluorene,
2-cycloheptanedione, 1-benzoylnaphthalene, 1-naphthalenecarboxylic acid, 3-acetyl-6-bromocoumarin, 1,4-naphthoquinone, 1,5-dihydroquinaphthalene, 2-bromo-9-acridinone,
4,4'-dinitrobiphenyl, 4,4'-dibenzoylbiphenyl, 2,6-dithiocaffeine, diphenylbutadiyne, 3,3'-carbonylbiscoumarin, nitrobenzene, 9- (1-naphthoyl) carbazole,
-Benzoyl-7-methoxycoumarin, cyclopentadiene, dicyclopropylethanedione, 1,4-dibromonaphthalene, 1- (dimethylamino) naphthalene, dibenzo [fg, op] naphthacene

9-acridinone, 3- (4-cyanobenzoyl) coumarin, 7-methoxy-3- (4-methoxybenzoyl) coumarin, 3-thenoyl-7-methoxycoumarin, 4,4-di (1-naphthyl) -2,5-cyclohexadien-1-one, 2-methyl-5-nitroimidazole-1-ethanol, 9-acetylphenanthrene, quinoline-4-carboxylic acid ethyl ester, p-terphenyl, 10-phenyl- 9-acridinone, 1-
Chloronaphthalene, 1- (2-naphthoyl) aziridine, 4 ', 5'-diamino-2-phenylbenzoxazole, 4-nitrobiphenyl, 2-chloro-1,3-butadiene, 9- (2-naphthoyl) carbazole , 2,
4-hexadiene, 1-hydroxynaphthalene, 1-
Iodonaphthalene, 2-phenylnaphthalene, thioxanthen-9-one-3-carboxylic acid ethyl ester, 9
-Chlorophenanthrene, tetrabenz [a, c, h,
j] anthracene, 4 ', 6'-diamino-2-phenylbenzoxazole

2,3-dichloro-1,3-butadiene,
3-benzoylcoumarin, 4,4-di (2-naphthyl)
-2,5-cyclohexadien-1-one, 2-nitrofluorene, 1-[(methylsulfonyl) methyl] naphthalene, 1-phenylnaphthalene, 7,8-benzoflavanone, 6-methoxyflavanone, maleonitrile, 3
-Acetylphenanthrene, 2,4,6-tris (4-
(Methoxyphenyl) -N-methylpyridinium, α-phenylstyrene, 2-nitrothiophene, 2,2′-biquinoline, 10-methyl-9-acridinone, indolo [3,2-b] carbazole, 9-bromophenanthrene , 1-bromonaphthalene, dibenzo [a, g] carbazole, dinaphtho [1,2-b: 2 ', 1'-d] thiophene, benzo [c] carbazole, (E) -piperylene, 3- (4-methoxy Benzoyl) coumarin, 1-phenyl-1-cyclopentene, 1-phenyl-3-acetylcyclopentene, 4,5-dichloro-4-cyclopentene-1,3-dione

Among these additives, those particularly suitable for suppressing deterioration of the red fluorescence conversion film when a rhodamine dye is used as the fluorescent dye are exemplified below. The following additives have an appropriate energy level "0.7 to the lowest excited triplet state energy level of the rhodamine-based dye.
× ³ Ed has a ^<3 Eq ^<3 Ed ", and the transition probability to these excited triplet state is 0.5 or more.

(I) Anthracene derivatives: anthracene, 9-chloroanthracene, 9,10-dibromoanthracene, 9,10-dichloroanthracene, 9,10
-Dicyanoanthracene, 9-methylanthracene, 9
-Phenylanthracene (ii) Azulene derivative: The azulene derivative has the following chemical formula.

[0077]

Embedded image

However, as the R ^{1 to} R ⁸ groups in the above chemical formula, for example, a hydrogen group, an alkyl group, a substituted alkyl group,
Aralkyl group, substituted aralkyl group, alkenyl group, substituted alkenyl group, CN group, COR ⁹ group, COOR ⁹ group, SO
₂ R ⁹ group, SO ₃ R ⁹ groups, and sulfonic acid base. Further, as the above R ⁹ group, for example, a hydrogen group,
Examples include an alkyl group, a substituted alkyl group, an aralkyl group, a substituted aralkyl group, an amino group, and a substituted amino group.

Further, examples of the substituents exemplified as the groups R ^{1 to} R ⁹ include a hydroxy group, a halogen group, a carboxyl group, an amino group and an alkoxyl group.
Examples of such an azulene derivative include those represented by the following chemical formula.

[0080]

Embedded image

(Iii) Thiobenzophenone derivative / thiobenzophenone, 4,4'-bis (dimethylamine)-
Thiobenbenzophenone, 4,4'-dimethoxy-thiobenzophenone (iv) porphine derivative: polyfin, tetraphenylpolyfin (v) C60 derivative: C60 (vi) C70 derivative: C70 (vii) thionin derivative: thionin, Azure A, Azure B

(3) Binder Resin In this embodiment, a non-curable resin or a photo-curable resin can be used as the binder resin. Further, one kind of the binder resin may be used alone, or a plurality of kinds may be mixed and used. In a full-color display, a fluorescent conversion film in which phosphor layers separated from each other are arranged in a matrix is formed. Therefore, it is preferable to use a photosensitive resin to which a photolithography method can be applied as the binder resin.

Here, a photosensitive resin and a non-curable resin will be sequentially described as the binder resin. Photosensitive resin (i) Examples of the photosensitive resin include a photosensitive resin having a reactive vinyl group such as an acrylic resin, a methacrylic resin, a polyvinyl cinnamate resin, and a hard rubber resin (a photocurable resist material). ) One or more mixtures are preferred.

Such a photosensitive resin is composed of a reactive oligomer, a polymerization initiator, a polymerization accelerator, and monomers as a reactive diluent. The reactive oligomer suitable for use herein includes the following.

(Ii) Epoxy acrylates obtained by adding acrylic acid to a biphenol type epoxy resin or a novolak type epoxy resin. (iii) polyfunctional isocyanate, equimolar amounts of 2-hydroxyethyl acrylate and polyfunctional alcohol,
Polyurethane acrylates reacted at any molar ratio. (iv) Polyester acrylates obtained by reacting an equimolar amount of acrylic acid and a polyfunctional carboxylic acid with a polyfunctional alcohol at an arbitrary molar ratio. (v) Polyether acrylates obtained by reacting polyols with acrylic acid. (vi) Reactive polyacrylates obtained by reacting acrylic acid with a side chain epoxy group such as poly (methyl methacrylate-CO-glycidyl methacrylate). (vii) Carboxyl-modified epoxy acrylates obtained by partially modifying epoxy acrylates with a dihydrochloric acid-based carboxylic anhydride. (viii) Carboxyl-modified reactive polyacrylates obtained by partially modifying reactive polyacrylates with dihydrochloric acid-based carboxylic anhydride. (ix) Polybutadiene acrylates having an acrylate group on the side chain of the polybutadiene oligomer. (x) Silicon acrylates having a polysiloxane bond in the main chain. (xi) Aminoplast resin acrylates obtained by modifying an aminoplast resin.

The polymerization initiator for the photosensitive resin includes:
Those commonly used in polymerization reactions can be used, and there is no particular limitation on the type. For example, vinyl monomers, benzophenones, acetophenones,
Benzoins, thioxanthones, anthraquinones,
Organic peroxides such as azobisisobutyronitrile and benzoyl peroxide can be mentioned.

As the polymerization accelerator for the photosensitive resin,
For example, triethanolamine, 4,4'-dimethylaminobenzophenone (Michler's ketone), ethyl 4-dimethylaminobenzoate and the like are preferred. Further, examples of monomers as a reactive diluent for the photosensitive resin include the following in a radical polymerization system. (i) Monofunctional monomers: acrylates and methacrylic esters (ii) Polyfunctional monomers: trimethylolpropane triacrylate and pentaerythri (iii) Oligomers: tall triacrylate, dipentaerythritol hexaacrylate, polyester acrylate, epoxy Acrylate, urethane acrylate, polyether acrylate

Examples of Non-Curable Resins Non-curable binder resins include, for example, polymethacrylates, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer, alkyd resins, aromatic sulfonamide resins, urea resins, melamine Resins and benzoguanamine resins are preferred. Among these binder resins, benzoguanamine resin, melamine resin and vinyl chloride resin are particularly preferred. Further, these binder resins may be used alone or in combination of two or more.

Further, in addition to the above binder resin,
A binder resin for dilution may be used. For example, one kind of polymethyl methacrylate, polyacrylate, polycarbonate, polyester, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyamide, silicone, and epoxy resin, or a mixture of plural kinds thereof may be used.

2. Fluorescence conversion film The fluorescence conversion film can be formed from a resin composition for fluorescence conversion. Note that the types and content ratios of the fluorescent dye and the additive in the fluorescence conversion film of the present embodiment are the same as the types and content ratios in the above-described resin composition for a fluorescence conversion film. Further, the fluorescence conversion film can also be formed without using the resin composition for a fluorescence conversion film. For example, a fluorescent dye and an additive can be co-evaporated on a glass substrate or the like to form a fluorescent conversion film.

(1) Material for Film Formation When forming the fluorescence conversion film, the resin composition for the fluorescence conversion film may be dissolved in a solvent in order to enhance the dispersibility of the fluorescent dye and the additive. Suitable solvents for use herein include, for example, ethylene glycol monomethyl ether,
Preferred are ethylene glycol monoethyl ether, 2-acetoxy-1-methoxypropane, 1-acetoxy-2-ethoxyethane, cyclohexane, toluene, propylene glycol monoethyl ether acetate, 1,2-dichloroethane, acetone and ethanol.

(2) Supporting substrate The substrate for supporting the fluorescence conversion film has a wavelength of 400 to 70
It is preferable that the transmittance of the light in the 0 nm visible light region is 50% or more and the plate is flat.

As such a translucent substrate, for example,
A glass substrate or a synthetic resin plate can be used. As the glass substrate, for example, soda-lime glass, barium
Strontium-containing glass, lead glass, aluminum silicate glass, borosilicate glass, barium borosilicate glass,
Quartz is mentioned. Examples of the synthetic resin plate include a polycarbonate resin, an acrylic resin, a polyethylene terephthalate resin, a polyether sulfide resin, and a polysulfonic acid resin.

(3) Method for Depositing Resin Composition and Desirable Film Thickness The method for depositing the resin composition for a fluorescence conversion film includes, for example,
Spin coating, printing, and coating are preferred, and in particular,
Spin coating is preferred. The film thickness of the fluorescence conversion film resin composition may be a film thickness necessary for converting incident light into a desired wavelength. This film thickness is preferably 1 to 100 μm
, More preferably within the range of 1 to 20 μm.

(4) Etching process In order to obtain a full-color organic EL display device (display) having a fluorescence conversion film, it is necessary to two-dimensionally arrange the RGB three-color fluorescence conversion films on a glass substrate. For that purpose, for example, it is preferable to form the fluorescence conversion film by etching the formed resin composition by a photolithography method, and further heating and curing the resin composition. The heating temperature here has a suitable temperature depending on the type of the binder resin. For example, the heat treatment may be performed at 70 to 240 ° C. for 0.5 to 3 hours.

3. Organic EL Display Device The organic EL display device of the present embodiment has a basic configuration in which an organic electroluminescence element as a light source and the above-mentioned fluorescence conversion film are sequentially arranged in a light extraction direction. INDUSTRIAL APPLICABILITY The present invention is particularly suitable when applied to a sealed organic EL display element in which it is difficult to use oxygen to suppress the deterioration of the fluorescence conversion film over time.

The combination of the light source and the fluorescence conversion film includes:
There are various forms. Here, the following (1) to (10)
A typical combination is illustrated below. (1) Light source / fluorescence conversion film (2) Light source / light transmission substrate / fluorescence conversion film (3) Light source / fluorescence conversion film / light transmission substrate (4) Light source / light transmission substrate / fluorescence conversion film / light transmission (5) Light source / fluorescent conversion film / color filter (6) Light source / translucent substrate / fluorescent conversion film / color filter (7) Light source / fluorescent conversion film / translucent substrate / color filter (8) light source / (9) light source / light-transmitting substrate / fluorescent conversion film / color filter (10) light source / fluorescent conversion film / color filter / light-transmitting substrate The respective components such as the fluorescence conversion film and the translucent substrate of the organic EL display device may be formed by sequentially laminating, or may be formed by bonding.

In the above combinations (1) to (10), various light sources such as LEDs (light emitting diodes), cold cathode tubes, inorganic electroluminescent elements, fluorescent lamps and incandescent lamps are used instead of the organic EL elements. May be used.

In the above combinations (5) to (10), a color filter is combined with the organic EL element and the fluorescence conversion film. By using a color filter in this way, the color purity can be adjusted. as a result,
The quality of light displayed by the display can be improved, and higher definition can be achieved.

The dye contained in the color filter includes:
For example, perylene pigments, lake pigments, azo pigments,
Quinacridone pigments, anthraquinone pigments, anthracene pigments, isoindoline pigments, isoindolinone pigments, phthalocyanine pigments, triphenylmethane basic dyes, indanthrone pigments, indophenol pigments, cyanine pigments, It is preferable to use one kind of dioxazine pigment alone or to mix and use a plurality of kinds. Further, those obtained by dissolving these dyes in a binder resin to form a color filter may be used.

[0101]

Next, the present invention will be described in more detail by way of examples. Here, Examples 1 to 5 having different components were used.
And adjusting the resin composition for a fluorescence conversion film of Comparative Examples 1 to 5,
A continuous irradiation test was performed on the fluorescence conversion films formed from these resin compositions. Hereinafter, 1. 1. Preparation of resin composition for fluorescence conversion film; 2. Measurement of energy level, etc. 3. Preparation of fluorescence conversion film; 4. continuous irradiation test; 5. Evaluation of fluorescence conversion performance and The results of the continuous irradiation test will be described sequentially.

1. Preparation of Resin Composition for Fluorescence Conversion Film In preparing the resin composition for fluorescence conversion film, a binder resin and a solvent (propylene glycol monoethyl ether acetate) were added to a fluorescent dye and dissolved. Further, a toluene solution of an additive was added to this solution, followed by stirring to obtain a resin composition for a fluorescence conversion film (solid content concentration: 40% by weight).

Table 1 below shows that each of the resin compositions for a fluorescence conversion film obtained in each of the examples and comparative examples obtained as described above contains
Shows the types and contents of fluorescent dyes, additives and binder resins.

[0104]

[Table 1]

As shown in Table 1 above, in each of the Examples and Comparative Examples, each of the three types of fluorescent dyes of coumarin 6, rhodamine 6G and rhodamine B was added in an amount of 0.5% by weight based on the entire resin composition. % (Wt%).

In Example 1, 9 and 9 were used as additives.
Contains 10-dibromoanthracene in a proportion of 3% by weight. Converting this, the (additive) /
The molar concentration ratio of (fluorescent dye) is 8.55.

In Example 2, azulene was added to 0.02
It is contained in the proportion of weight%. When converted, the molar ratio of (additive) / (fluorescent dye) in Example 2 is
0.15.

Further, in Example 3, C60 was contained at a ratio of 0.4% by weight. Converting this, Example 3
The molar ratio of (additive) / (fluorescent dye) is 0.5
It becomes 3.

Further, in Example 4, the content of tetraphenylpolyfin was 0.3% by weight. When converted, the molar ratio of (additive) / (fluorescent dye) in Example 4 is 0.47.

Further, in Example 5, 9,10-dibromoanthracene was contained at a ratio of 3% by weight. When converted, the molar ratio of (additive) / (fluorescent dye) of Example 5 is 8.55.

On the other hand, Comparative Example 1 does not contain any additives. In Comparative Example 2, 9,10-diphenylanthracene was contained at a ratio of 3% by weight. When converted, the molar ratio of (additive) / (fluorescent dye) in Comparative Example 2 is 8.70.

In Comparative Example 3, 1% by weight of rubrene was added.
Contains. When converted, the molar ratio of (additive) / (fluorescent dye) in Comparative Example 3 is 1.80. In Comparative Example 4, 1% by weight of azulene was contained. When converted, the molar ratio of (additive) / (fluorescent dye) in Comparative Example 4 is 7.53.

Further, Comparative Example 5 contains 1% by weight of fluoranthene as an additive. When converted, the molar ratio of (additive) / (fluorescent dye) of Comparative Example 5 is 4.74.

Further, in Examples 1 to 4 and Comparative Examples 1 to 5, a benzoguanamine resin (manufactured by Schinloich) is contained as a binder resin. In Example 5, an acrylic photosensitive resin (V259PA (trade name) manufactured by Nippon Steel Chemical Co., Ltd.) was contained as a binder resin.

[0115] 2. Measurements of Energy Level (1) a fluorescent dye and the lowest excited triplet energy level of the additive ⁽³ Eq, ³ Ed) and the lowest excited singlet energy level ⁽³ Eq, ³ Ed) were measured in the following manner . That is, as for each energy level, the absorption spectrum of each fluorescent dye and additive in the near ultraviolet to visible to near infrared wavelength region was measured, and the energy level corresponding to the wavelength was determined from the absorption peak wavelength.

Specifically, a sample solution is prepared by dissolving a fluorescent dye or an additive in an appropriate solvent to a concentration of about 10 ^-5 to 10 ^-3 mol / liter. Then, this sample solution is placed in a quartz cell, and the absorption peak wavelength is measured using a spectrometer. The thickness of the quartz cell is such that the maximum absorbance is 0.
It is preferably about 25 to 0.75. As a light source of the spectrometer, a hydrogen discharge tube or a tungsten lamp may be used.

Table 2 below shows the energy levels ( ¹ Ed and ³ Ed) of each fluorescent dye thus measured.

[0118]

[Table 2]

As shown in Table 2 above, rhodamine B
(Rh-B) has the longest fluorescent peak wavelength of 580 nm among the three types of fluorescent dyes. That is,
Lowest excited singlet energy level of Rhodamine B ¹ Ed
Is 2.21 eV, which is the lowest among the three types of fluorescent dyes. Therefore, in each of Examples and Comparative Examples, rhodamine B is a main light-emitting fluorescent dye that mainly emits fluorescence.
Table 3 below shows the energy levels ( ¹
Ed and ³ Ed) are shown.

[0120]

[Table 3]

As shown in Table 3 above, in Examples 1 to 5 and Comparative Examples 2 to 3, “0.7 × ³ Ed (= 1.
^{29eV) <3 Eq <3 Ed} (= 1.84eV) "we are satisfied. On the other hand, in Comparative Example 4, “ ³ Eq (1.
14 eV) <0.7 × ³ Ed (= 1.29 eV) ”.

In Examples 1 and 5 and Comparative Examples 2 and 3, " ¹ Eq> ¹ Ed" is satisfied. On the other hand, Examples 2 to
4 and Comparative Examples 2 and 3, “ ¹ Eq < ¹ Ed”. In addition, in Comparative Example 5, and it has a ^"3 Eq> ³ Ed".

(2) The transition probability φt of the additive from the lowest excited singlet energy level to the lowest excited triplet energy level was measured as follows. In the measurement of the transition probability φt, the same quenching time constant τf of the fluorescence from the sample was measured by the flash photolysis method using the same sample as that used for the measurement of the energy level.
The phosphorescence extinction time constant τp is obtained.

More specifically, first, the sample is continuously irradiated with excitation light having a wavelength corresponding to the energy absorption when exciting from the ground state S0 to the lowest excited singlet state S1. After the light is in the steady state, the extinction coefficient of the wavelength corresponding to the energy level difference from S1 to the second excited singlet state S2, and the change from the lowest excited triplet state T1 to the second excited triplet state T2. The extinction coefficient of the wavelength corresponding to the energy level difference is measured.

From these extinction coefficients, the molar concentration [S1] of the molecule in the S1 state and the molar concentration [T1] of the molecule in the T1 state are determined. Furthermore, the molar concentration I of the molecule that absorbs light per unit time and is excited from S0 to S1
a is determined from the irradiation intensity of the excitation light and the molar extinction coefficient of the molecule.

When the non-radiative transition from T1 to S0 hardly occurs, the transition probability φt from S1 to T1 is obtained by the following equation (1). φt = [T1] / (Ia · τp) (1)

When the non-radiative transition from T1 to S0 cannot be ignored, the transition probability φt from S1 to T1 is obtained by the following equation (2). φt = [T1] / (Ia · τf) (2)

Each transition probability (φ
t) is shown in Table 3 above. As shown in Table 3, Example 1
5 to 5 and Comparative Examples 4 and 5, the transition probability is 0.5 or more. On the other hand, in Comparative Examples 2 and 3, the transition probability has not reached 0.5.

3. Preparation of Fluorescence Conversion Film Using a solution of the resin composition for a fluorescence conversion film, a film was formed on a 2.5 cm × 2.5 cm glass substrate by a spin coater method. The spin coater was rotated 500 revolutions per minute for 10 seconds. Further, a drying treatment was performed at a temperature of 80 ° C. for 15 minutes to produce a fluorescence conversion film having a thickness of 20 μm or less. Also,
In Example 5 using an acrylic photosensitive resin as the binder resin, ultraviolet light was further irradiated under the condition of 1500 mJ / cm ² , and then heat treatment was performed at a temperature of 180 ° C. for 30 minutes to produce a fluorescence conversion film.

[0130] 4. Continuous irradiation test In the organic EL display device, the emission intensity of the organic EL element itself as a light source has a half-life. For this reason, in the organic EL display device, it is difficult to accurately measure the change with time of the fluorescence conversion efficiency of the fluorescence conversion film. Therefore, in each of Examples and Comparative Examples, a blue light emitting LED having a peak wavelength at 470 nm was used as an excitation light source. And this blue light emission L
A fluorescence conversion film was laminated on the ED and placed in a chamber capable of being replaced with nitrogen. In the test, the inside of the chamber was set to a dry atmosphere, and the blue LED was continuously operated at 400 nit for 500 hours. The relative fluorescence intensity of the fluorescence conversion film before and after the test was compared, and the continuous use durability of the fluorescence conversion film was evaluated.

[0131] 5. Evaluation of fluorescence conversion performance The fluorescence conversion performance was evaluated by comparing the relative fluorescence intensity of the fluorescence conversion film before and after the test. In measuring the fluorescence intensity, the spectrum of the transmitted light obtained through the fluorescence conversion film laminated on the blue light emitting LED was measured. The spectrum is
The measurement was performed twice in a visual field using a spectral luminance meter (CS-1000 (trade name) manufactured by Minolta). And blue light emitting LED
, The relative fluorescence intensity of the fluorescence conversion film was defined as follows. (Relative fluorescence intensity) = (Peak intensity of transmitted light obtained through the fluorescence conversion film) / (LED peak intensity)

6. Table 4 shows the relative fluorescence intensity before the test, the relative fluorescence intensity after the test, and (after the test) /
The retention rate of the relative fluorescence intensity (before the test) is shown.

[0133]

[Table 4]

As shown in Table 4 above, in each embodiment,
In each case, a high retention of 90% or more is achieved. Therefore, in each of the examples, high continuous driving durability was realized while maintaining high fluorescence conversion efficiency. That is, it can be seen that a fluorescence conversion film having excellent long-term stability of emission intensity was obtained.
On the other hand, in each of the comparative examples, the retention rate was less than 90%, and it can be seen that the fluorescence conversion efficiency was reduced. Less than,
Each comparative example is examined individually.

Comparative Example 1 In Comparative Example 1, the holding ratio was 7
It has dropped to 0.8%. The reason is considered to be that in Comparative Example 1, no additive was added.

Comparative Example 2 In Comparative Example 2, the holding ratio was 8
It has dropped to 3.0%. It is considered that the reason is that the additive could not efficiently receive energy from the fluorescent dye excited in the excited triplet state because the transition probability φt of the additive was as low as 0.02.

Comparative Example 3 In Comparative Example 3, the holding ratio was 8
It has dropped to 5.8%. The reason is that the transition probability of the additive is low and the lowest excited triplet energy level is "
³ is considered to be because the Eq <0.7 × ³ Ed "too low.

Comparative Example 4 In Comparative Example 4, a continuous irradiation test was not performed because the emission intensity was already too low before the test. The reason why the emission intensity is low is that “ ¹ Eq < ¹
An additive satisfying “Ed” was used at a molar concentration of 7.5 of the fluorescent dye.
It is probable that, because the additive was added twice, the additive deprived the excited singlet state energy which should originally contribute to the emission of the fluorescent dye.

[Comparative Example 5] In Comparative Example 5, the holding ratio was 7
It has dropped to 2.5%. The reason is, because that is the Comparative Example 5 ^"3 Eq> ³ Ed", the additive is considered to be because it is difficult to take the energy from the fluorescent dye excited triplet state.

In the above-described embodiment, an example has been described in which the present invention is configured under specific conditions. However, the present invention can be variously modified. For example, in the above-described embodiment, an example in which the fluorescence conversion film is formed using the resin composition for a fluorescence conversion film has been described, but in the present invention, the fluorescence conversion film is formed of a resin composition. Not limited. For example, the fluorescence conversion film may be formed by co-evaporation of a fluorescent dye and an additive. In this case, the binder resin component is not contained in the fluorescence conversion film.

In each of the embodiments described above, the example of the fluorescence conversion film to which the additives are added one by one has been described.
In the present invention, the type of additive added simultaneously is not limited to one type.

[0142]

As described in detail above, according to the present invention, an additive having the lowest excited triplet energy level is lower than that of the fluorescent dye. For this reason, the additive can receive energy from the fluorescent dye in the excited triplet state. As a result, interaction between the excited triplet state fluorescent dye and surrounding molecules such as a binder resin can be suppressed. Thereby, continuous driving durability can be improved while the fluorescence conversion efficiency of the fluorescence conversion film is high.

Claims (10)

[Claims] Claims: 1. An additive comprising at least one fluorescent dye and an additive for removing energy from the fluorescent dye, wherein the lowest triplet energy level of the additive is ³ Eq.
Is lower than the lowest excited triplet energy level ³ Ed of the main emission fluorescent dye having the longest fluorescent peak wavelength among the fluorescent dyes. 2. When the lowest excited singlet energy level ¹ Eq of at least one or more of the additives is higher than the lowest excited singlet energy level ¹ Ed of the main light-emitting fluorescent dye, the main light-emitting fluorescent dye is contained. The fluorescence conversion film according to claim 1, wherein a ratio of a molar concentration of the additive to a molar concentration is in a range of 0.01 to 100. 3. When the minimum excitation singlet energy level ¹ Eq of at least one or more of the additives is lower than the minimum excitation singlet energy level ¹ Ed of the main light emitting fluorescent dye, the main light emitting fluorescent dye is contained. 3. The fluorescence conversion film according to claim 1, wherein a ratio of a molar concentration of the additive to a molar concentration is in a range of 0.01 to 5. 4. The method according to claim 1, wherein the lowest excited triplet energy level ³ Eq of the additive is higher than 0.7 times the lowest excited triplet energy level ³ Ed of the main light emitting fluorescent dye. 4. The fluorescence conversion film according to 2 or 3. 5. The method according to claim 1, wherein the transition probability of the additive from the lowest excited singlet energy level to the lowest excited triplet energy level is 0.5 or more. Fluorescence conversion film. 6. The fluorescent dye contains at least one or more rhodamine-based dyes, and the additive includes one or more selected from anthracene derivatives, azulene derivatives, thiobenzophenone derivatives, porphine derivatives and C60 derivatives. The fluorescence conversion film according to any one of claims 1 to 5, comprising a plurality of types of additives. 7. The fluorescence conversion film according to claim 1, further comprising a binder resin in addition to the fluorescent dye and the additive. 8. At least one or more kinds of fluorescent dyes, an additive for removing energy from the fluorescent dyes, and a binder resin, wherein the additive has a minimum excited triplet energy level of ³ Eq.
Is lower than the lowest excited triplet energy level ³ Ed of the main emission fluorescent dye having the longest fluorescent peak wavelength among the fluorescent dyes. 9. The resin composition for a fluorescence conversion film according to claim 8, wherein the content of the fluorescent dye in the resin composition for a fluorescence conversion film is in the range of 0.01 to 1% by weight. . 10. An organic electroluminescence display device in which an organic electroluminescence element and a fluorescence conversion film are sequentially arranged in a light extraction direction, wherein the fluorescence conversion film is any one of claims 1 to 7. An organic electroluminescence display device, characterized in that it is a fluorescent conversion film prepared.