JPH09245511A - Fluorescent conversion filter and manufacture thereof - Google Patents

Abstract

PROBLEM TO BE SOLVED: To convert light in a plurality of specific regions, emitted from an emitter, high efficiently in good balance into emission of a plurality of specific regions, by arranging a plurality of fluorescent conversion films, emitting specific fluorescence, separately in a plane manner respectively on a transparent substrate. SOLUTION: Light in a blue or blue green color region is absorbed, a light hardening type or thermally hardening resist dissolving or dispersing emitting coloring matter of fluorescent pigment emitting fluorescence in a green color region is film molded on a transparent substrate, a resist film is formed. Next, after the light hardening resist film is exposed through a mask of a pattern, the film is developed, a pattern of the light hardening resist is formed, to be hardened by heat treating, a pattern of a fluorescent conversion film is formed. Light in a blue or blue green color region is absorbed, non-reaction resin dissolving or dispersing emitting coloring matter or fluorescent pigment emitting fluorescence in a red color region is film molded on a substrate, on an obtained non- reaction resin film a light soluble resist or the light hardening type resist film is film molded and layered. As a result, a prescribed fluorescent conversion filter can be safely manufactured.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a fluorescence conversion filter and a method for manufacturing the same, and more specifically, it efficiently converts light emitted from a light-emitting element in a blue to blue-green region into light in a green region or a red region to emit light. TECHNICAL FIELD The present invention relates to a fluorescence conversion filter suitable for use in consumer or industrial display devices such as a multi-color or full-color type display and a display panel, and a method for manufacturing the same.

[0002]

BACKGROUND OF THE INVENTION Electronic display devices are commonly m
Called an-machine-interface
Information from various devices (machine)
An electronic device that transmits to humans through vision
Therefore, an important bridging role that connects humans and devices (in
terface). To this electronic device
Includes a light emitting type and a light receiving type. Examples of the light emitting type include
CRT (cathode ray tube), PDP (plasma display)
B), ELD (electroluminescence display)
B), VFD (fluorescent display tube), LED (light emitting diode)
Do) and the like. On the other hand, as the light receiving type, for example,
LCD (liquid crystal display), ECD (electrochemistry
Cull display), EPID (electrophoretic display)
B), SPD (dispersed particle oriented display), TBD
(Rotating colored particles display), PLZT (Transparent display)
Electrical PLZT [(Pb, La) (Zr, Ti) O _Three]
Lamix display) and the like.

Here, as a method of full color electronic display devices, there are a method of arranging light emitting portions of multicolors (for example, three primary colors of red, blue and green) in a plane and emitting light respectively, and a method of backlighting. There is known a method of separating white light into multiple colors using a color filter. Further, a method is known in which the light emitted from the light-emitting body is absorbed by fluorescent materials arranged in a plane and separated, and multicolor fluorescence is emitted from each fluorescent material. Here, for a method of emitting multicolor fluorescence from a certain light-emitting body using a phosphor, see CRT, PDP,
It is applied to VFD. However, in this case, it is necessary that the light emission of the light-emitting body is high in energy such as an electron beam or deep ultraviolet rays. Therefore, LED and EL
When the emission from the light emitter is low in energy such as near-ultraviolet rays or visible light like D, CRT, PD
Inorganic phosphors used in P and VFD [usually, a rare earth oxyhalide or the like is used as a matrix, and this matrix is inactivated by an inactivating agent (for example, Y ₂ O ₃ : Eu
Etc.) is not excited and does not emit fluorescence.

Therefore, an organic fluorescent dye or fluorescent pigment such as a laser dye is used as a substance that fluoresces with respect to low energy rays such as near ultraviolet rays or visible light. For example, as a multicolor light emitting element using an organic electroluminescence element (hereinafter abbreviated as an organic EL element), a phosphor containing a fluorescent dye (hereinafter, referred to as a fluorescence conversion film) is laminated or arranged in parallel with the organic EL element. The arrangement is proposed (Japanese Patent Laid-Open No. 3-15)
2897). By patterning a fluorescent conversion film containing such a fluorescent dye or fluorescent pigment with high precision, a full-color light emitting display can be constructed even with a low energy ray such as near-ultraviolet or visible light of a light emitting body.
Therefore, as a method of patterning the fluorescence conversion film, as in the case of the inorganic phosphor, a fluorescent dye is dispersed in a liquid resist (photosensitive resin), and the film is formed by a spin coating method or the like, followed by photolithography. A method of patterning by a lithography method (Japanese Patent Laid-Open Nos. 5-198921 and 5-258860) can be easily analogized. Especially,
In Japanese Patent Laid-Open No. 5-258860, a patterned fluorescent medium that emits green light by absorbing the light emission (light emission in the blue to blue-green region) having a peak wavelength of less than 480 nm of the organic EL device in the above method, and red. A configuration in which a patterned fluorescent medium that emits light is arranged in a plane to be separated (hereinafter, may be abbreviated as "fluorescence conversion filter").
Is disclosed.

However, it is well known that fluorescent dyes are easily affected by the surrounding environment, and depending on the type of medium such as solvent or resin, the fluorescent wavelength changes or quenching occurs. In particular, when a fluorescent dye is dispersed in a liquid resist, a photoinitiator (polymerization initiator) and a reactive polyfunctional monomer are present in the resist, so that an exposure step or a heat treatment (post-baking) step in the photolithography process is performed. In the above, there arises a problem that the fluorescent dye is often decolorized or quenched by the radical species or ionic species generated from the photoinitiator or the reactive polyfunctional monomer (JP-A-7-26801).
No. 0). In addition, the fluorescence conversion film that absorbs light in the blue or blue-green region of the light emitter and emits fluorescence in the green region has a small Stokes shift (difference between the absorption wavelength and the emission wavelength) and also reduces the light emitted from the light emitter. Since the light can be partially transmitted, the light of the light emitting body can be converted with relatively high efficiency. However, since the fluorescence conversion film that emits fluorescence in the red region has a large Stokes shift and hardly uses the light of the light emitting body,
Remarkably low conversion efficiency. Therefore, the conventional technique (Japanese Patent Laid-Open No.
However, when the fluorescence conversion filter according to JP-A-258860) is used, the emission brightness of blue, green, and red is poorly balanced, including the problems of decolorization and extinction, and the red brightness is low. There was a problem that it was inevitable that the color display was of poor brightness and low brightness.

[0006]

SUMMARY OF THE INVENTION Under such circumstances, the present invention provides a fluorescent conversion capable of converting light emitted from a light-emitting body in the blue to blue-green range into light in the green range or red range with high efficiency and in good balance. The purpose is to provide a filter.

[0007]

As a result of intensive studies to develop a fluorescence conversion filter having the above-mentioned preferable function, the present inventor has absorbed light in the blue to blue-green region emitted from a light-emitting body and specified it. It was found that the objective can be achieved by arranging the fluorescence conversion film that emits fluorescence in the green region and the fluorescence conversion film that emits fluorescence in the red region in a plane on a transparent substrate. The present invention has been completed based on such findings. That is, the present invention absorbs light in the blue to blue-green region emitted from the light-emitting body, and emits fluorescence in the green region consisting of a fluorescent dye or fluorescent pigment and a photocurable or thermosetting resin cured product,
And, a fluorescence conversion filter characterized in that the fluorescence conversion film which emits fluorescence in the red region consisting of a fluorescent dye or a fluorescent pigment and a non-reactive resin, is separately arranged in a plane on a transparent substrate. is there.

Further, according to the present invention, a fluorescent conversion film that absorbs light in the blue to blue-green region emitted from the light-emitting body and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region are respectively provided on the transparent substrate. In the production of a fluorescence conversion filter characterized by being arranged in a plane, (1) light in which a fluorescent dye or fluorescent pigment that absorbs light in the blue to blue-green region and emits fluorescence in the green region is dissolved or dispersed A step of forming a curable or thermosetting resist on a transparent substrate to obtain the resist film; (2) exposing the photocurable resist film through a pattern mask, and then developing the resist to form a photocurable resist film. A step of forming a pattern, (3) a step of curing the photo-curable resist film by heat treatment to form a pattern of the fluorescence conversion film, (4) absorption of light in the blue or blue-green region, Obtaining a non-reactive resin film a non-reactive resin dissolved or dispersed a fluorescent dye or fluorescent pigment emits light to form a film on a substrate after the step (3),
(5) A step of forming a photo-solubilizing resist or a photo-curing resist film on the non-reactive resin film and laminating the resist film, and (6) a photo-solubilizing resist through a pattern mask. After exposing the resist or the photocurable resist film, and simultaneously with or after the development to form the pattern of the resist film,
The present invention also provides a method for manufacturing a fluorescence conversion filter, which comprises the step of etching the non-reactive resin film. In the present invention, the light in the blue to blue-green region refers to any one of the lights reaching the region from blue to blue-green or a light in any combination. Hereinafter, the present invention will be described in more detail.

[0009]

BEST MODE FOR CARRYING OUT THE INVENTION First, fluorescent dyes and fluorescent pigments used in the fluorescence conversion filter of the present invention will be described.
Examples of the fluorescent dye or fluorescent pigment that absorbs light in the blue to blue-green region emitted from the light-emitting body and emits fluorescence in the green region include, for example, 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethyl. Quinolidine (9,9a, 1
-Gh) Coumarin (coumarin 153); 3- (2'-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6); 3- (2'-benzimidazolyl) -7-
N, N-diethylaminocoumarin (coumarin 7); 3-
(2'-N-methylbenzimidazolyl) -7-N, N
A coumarin-based dye such as diethylaminocoumarin (coumarin 30), or a coumarin-based dye, Basic Yellow 51, and Solvent Yellow 11,
Examples thereof include naphthalimide-based dyes such as Solvent Yellow 116. Further, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used if they have fluorescence.

Further, as a fluorescent dye or fluorescent pigment that absorbs light emitted from the light-emitting body in the blue to blue-green region and emits fluorescence in the red region, for example, 4-dicyanomethylene-
2-methyl-6- (p-dimethylaminostyryl) -4
Cyanine dye such as H-pyran (DCM), 1-ethyl-2- [4- (p-dimethylaminophenyl) -1,
Pyridine-based dyes such as 3-butadienyl) -pyridinium-perchlorate (pyridine 1), rhodamine-based dyes such as rhodamine B, rhodamine 6G, rhodamine 3B, rhodamine 101, rhodamine 110, sulforhodamine, basic violet 11, and basic red 2, Alternatively, an oxazine dye or the like may be used. Further, various dyes (direct dyes, acid dyes, basic dyes, disperse dyes, etc.) can be used if they have fluorescence.

The fluorescent dyes that emit fluorescence in the green region or red region are polymethacrylic acid ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine. A fluorescent pigment may be obtained by kneading a resin, a benzoguanamine resin, or a mixture of these resins in advance to form a pigment. In addition, these fluorescent dyes and fluorescent pigments may be used alone or in combination of two or more as required.

Next, the photocurable or thermosetting resin cured product used in the fluorescence conversion filter of the present invention will be described. A photocurable resin or thermosetting resin composition film (resist or paste film) is subjected to light or heat treatment to generate radical species or ionic species to polymerize or crosslink to make them insoluble and infusible. . Specifically, the acrylate-based polymer means (i) a composition film composed of an acrylic-based polyfunctional molmer and an acrylate oligomer having a plurality of acrylic groups or methacrylic groups, and a photo- or thermal-polymerization initiator, which is subjected to photo- or heat-treatment, Polymerized by generating radicals or heat radicals, (ii) a composition comprising a polyvinyl cinnamate and a sensitizer, which is cross-linked by dimerization by light or heat treatment, and (iii) a chain or cyclic olefin A composition film composed of bisazide is subjected to light or heat treatment to generate nitrene and crosslinked with an olefin, and (iv) a composition film composed of a monomer having an epoxy group and a photoacid generator is treated with light or heat to generate an acid (cation ) Is generated and polymerized, and so on.

The fluorescence conversion film that emits fluorescence in the green region is composed of the above-mentioned fluorescent dye or fluorescent pigment and this light or thermosetting resin cured product. In producing a green fluorescence conversion film, a fluorescent dye or fluorescent pigment may be exposed to radical species or ionic species generated from this resin by light or heat treatment, causing quenching, decolorization, or discoloration. When the blue-green region is absorbed and fluorescence in the green region is emitted, the Stokes shift is small, so fluorescent conversion can be performed relatively efficiently by selecting a fluorescent dye or pigment that is resistant to radical species or ionic species. In addition, since the light of a part of the light emitters can be transmitted and used for the light emission in the green region, the efficiency of converting the light in the blue region to the light in the green region is high. Here, among the photo- or thermosetting resin cured products, a composition film comprising an acrylate polymer, that is, an acrylic polyfunctional molmer having a plurality of acrylic groups or methacrylic groups and an acrylate oligomer, and a photo or thermal polymerization initiator. What was polymerized by photo- or heat-treating to generate photo radicals or heat radicals is preferable in terms of reliability such as solvent resistance and heat resistance.

Next, the non-reactive resin used in the fluorescence conversion filter of the present invention will be described. Contrary to the photo-curable or thermosetting resin, the non-reactive resin is a resin that does not generate radical species or ionic species by light or heat, that is, has no reactivity. Specifically, compounds having a structure not having a reactive vinyl group, such as a polymerization initiator, a sensitizer, a bisazide and an acid generator, which decomposes by light or heat to generate a radical species or an ionic species, are used. It is a resin that does not contain. More specific examples include general-purpose polymers such as polymethylmethacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone, polyvinyl chloride, polyvinyl acetate, polystyrene, polyester, and polypyridine.

The fluorescence conversion film that emits fluorescence in the red region is composed of the fluorescent dye or fluorescent pigment and this non-reactive resin. In producing the red fluorescence conversion film, since the fluorescent dye or fluorescent pigment is not exposed to radical species or ionic species by light or heat treatment, quenching, decolorization or discoloration does not occur. When the blue to blue-green region of the illuminant is absorbed and emits fluorescence in the red region, the Stokes shift is large, so it is difficult to efficiently perform fluorescence conversion, and part of the light emitted from the illuminator is converted to green. Since it can hardly be used for light emission in the red region after being transmitted, it is important to select a non-reactive resin that does not cause quenching, decolorization, or discoloration.

In the present invention, the non-reactive resin is preferably a resin soluble in an alkaline aqueous solution or an acidic aqueous solution.
That is, this resin film can be etched with an alkaline aqueous solution or an acidic aqueous solution, and by stacking an appropriate resist pattern on the fluorescence conversion film, a highly precise pattern of the fluorescence conversion film can be formed. Specifically, as the resin soluble in the alkaline aqueous solution, a polymer containing at least one ethylenically unsaturated carboxylic acid unit as a repeating unit is used. Examples of the monomer forming the ethylenically unsaturated carboxylic acid unit include acrylic acid,
Examples thereof include monocarboxylic acids such as methacrylic acid and crotonic acid, dicarboxylic acids such as maleic acid, fumaric acid and itaconic acid, and half esters thereof. Among these, acrylic acid and methacrylic acid are particularly preferable because they can efficiently convert the light emitted from the light emitting element into fluorescence. These ethylenically unsaturated carboxylic acids may be used alone or in combination of two or more. Also,
More preferable resins include copolymers containing the above ethylenically unsaturated carboxylic acid, and examples of the monomer to be copolymerized include various esters of the ethylenically unsaturated carboxylic acid, acrylamide, methacrylamide, acrylonitrile, Examples thereof include neutral monomers having no acid group such as methacrylonitrile, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, alkyl vinyl ether and vinylpyrrolidone. Examples of various esters of ethylenically unsaturated carboxylic acids include methyl, ethyl, propyl, butyl, hexyl, 2-ethylhexyl, cyclohexyl, benzyl, diethylaminoethyl, hydroxyethyl, hydroxypropyl and glycidyl esters. These monomers may be used alone or in combination of two or more.

The content of ethylenically unsaturated carboxylic acid units in this copolymer is preferably in the range of 3 to 60 mol%.
The copolymer having a carboxyl group has some interaction with the amino group of the fluorescent dye and may quench the fluorescent dye, but the content of the ethylenically unsaturated carboxylic acid unit in the copolymer may be reduced. By controlling, the quenching of the fluorescent dye can be suppressed, and the obtained fluorescent conversion film can be etched with an alkaline aqueous solution. When the content of the ethylenically unsaturated carboxylic acid unit is less than 3 mol%, etching treatment with an alkaline aqueous solution is difficult, and when it exceeds 60 mol%, the interaction between the fluorescent dye and the copolymer becomes remarkable, and the fluorescent dye Distorts the electronic state of and accelerates decolorization or quenching of the dye. The content of the ethylenically unsaturated carboxylic acid unit is particularly preferably from 5 to 50 from the viewpoints of etching properties with an alkaline aqueous solution and suppression of decolorization and quenching of the organic fluorescent dye.
A range of mol% is preferred.

On the other hand, as the resin soluble in the acidic aqueous solution,
For example, a resin having a primary to tertiary amino group bonded to a carbon atom in the resin (including a nitrogen-containing heterocyclic resin) can be preferably mentioned. When such a resin is treated with an acidic aqueous solution, hydrogen ions of the acidic aqueous solution are coordinated with amino groups to form quaternary ammonium ions and become water-soluble. As a result, the resin is soluble in the acidic aqueous solution. As the basic resin soluble in such an acidic aqueous solution, for example,
General formula (I)

[0019]

Embedded image (In the formula, X ¹ is

[0020]

Embedded image Represents a group represented by, R ¹ is a hydrogen atom or a methyl group, m
Represents an integer of 0 to 4. ) And the general formula (II)

[0021]

Embedded image (In the formula, X ² is

[0022]

Embedded image

R is a group represented by^TwoAnd R^ThreeIs
Hydrogen atom, methyl group, ethyl group or isopropyl
Denote groups, which may be the same or different
R ^FourIs a hydrogen atom or a methyl group, and n and k are respectively
Is an integer of 0 to 4. ) Selected from the monomers
Polymer of at least one type of monomer that has been exposed, or this monomer
With other ethylenically unsaturated monomers copolymerizable with the polymer
You can list coalescence. The above general formulas (I) and (II)
Examples of the monomer represented by

[0024]

Embedded image

[0025]

[Chemical 6]

[0026]

Embedded image

Examples thereof include compounds represented by These monomers may be used alone, or may be used in combination of two or more, among these, from the viewpoint of chemical stability of the polymer and ease of production of the polymer, Particularly, the compounds represented by (1), (2) and (13) are preferable. On the other hand, other ethylenically unsaturated monomers to be copolymerized with these monomers are not particularly limited and various ones can be mentioned, for example, styrene, α-methylstyrene, vinyl acetate, vinyl chloride, methyl. Vinyl ether, N-vinyl-2-pyrrolidone, acrylamide, methacrylamide, acrylonitrile, methacrylonitrile, and further the general formula (III)

[0028]

Embedded image

(In the formula, R ⁵ is a hydrogen atom or a methyl group, and R ^5
6 represents an alkyl group having 1 to ⁶ carbon atoms, a cyclohexylethyl group, a cyclohexyl group, a benzyl group, an N, N-dimethylaminoethyl group, a 2-hydroxyethyl group or a 3-hydroxypropyl group. A preferable example is a neutral or basic monomer such as a compound represented by).
These ethylenically unsaturated monomers may be used alone,
Two or more of them may be used in combination, but among them, styrene, acrylic acid and methacrylic acid have 1 carbon atoms from the viewpoints of chemical stability of the copolymer and easiness of production of the copolymer. Particularly preferred are alkyl esters of ~ 6. When the copolymer is used, the content of the unit derived from the monomer represented by the general formula (I) and / or the general formula (II) is
From the viewpoint of easy etching of the obtained fluorescent conversion film with an acidic aqueous solution, it is preferably 20 mol% or more, and particularly preferably 40 mol% or more.

The weight average molecular weight (Mw) of the resin soluble in the alkaline aqueous solution or the acidic aqueous solution as described above may be selected according to various situations, but is usually 1,000 to 10,000.
00 is selected in the range. If the Mw is less than 1000, the crystallinity of the fluorescence conversion film may be increased, and the strength of the film may be insufficient (become brittle). In addition to the difficulty in selection, there is a tendency that the solubility of the fluorescence conversion film in an alkaline or acidic aqueous solution is lowered, and the etching property by the alkaline or acidic aqueous solution is lowered. From the viewpoint of the strength of the fluorescence conversion film, the etching property with an alkaline or acidic aqueous solution, the solubility in a solvent, and the like, the weight average molecular weight of the resin is, in particular, 10,000 to 100,000.
Is preferred.

In the present invention, as the non-reactive resin, a resin soluble in an alkaline or acidic aqueous solution is used. Such a resin is soluble in the alkaline or acidic aqueous solution at a temperature of room temperature to about 80 ° C. Any substance that has a solubility of 0.1% by weight or more may be used. As the alkali used in this alkaline aqueous solution, there are usually used alkali metal hydroxides such as sodium hydroxide and potassium hydroxide, alkali metal carbonates such as sodium carbonate and potassium carbonate, and tetramethylammonium hydroxide and the like. Examples thereof include graded ammonium hydroxide.
The alkaline concentration in the alkaline aqueous solution is greater than 7.0 as the hydrogen ion concentration (pH), or 0.1 to 1
Advantageously, it is of the order of 0% by weight. Such an alkaline aqueous solution is non-corrosive and easily disposable, and is easily handled. On the other hand, as the acidic aqueous solution, for example, hydrochloric acid,
Aqueous solution of inorganic acid (mineral acid) such as hydrobromic acid, nitric acid, sulfuric acid, carbonic acid, aqueous solution of organic acid such as formic acid, acetic acid, propionic acid, oxalic acid, or mixed acid solution containing two or more of these acids. The aqueous solution of hydrochloric acid and the aqueous solution of acetic acid are usually used. The concentration is less than 7.0 as hydrogen ion concentration (pH), or 0.01 to 50
A material having a concentration of about wt% is used. If desired, a surfactant may be added to the above alkaline aqueous solution or acidic aqueous solution in order to improve the wettability to the fluorescence conversion film.

Next, the composition of the fluorescence conversion film constituting the fluorescence conversion filter of the present invention will be described. The fluorescence conversion film that emits fluorescence in the green region is composed of the fluorescent dye or fluorescent pigment and the photocurable or thermosetting resin cured product. On the other hand, the fluorescence conversion film that emits fluorescence in the red region is
It is composed of the fluorescent dye or fluorescent pigment and the non-reactive resin. At this time, the fluorescent dye is preferably used in a ratio of 0.0001 to 1 mol per 1 kg of each resin.
If this amount is less than 0.0001 mol, the thickness of the fluorescence conversion film is 100 μm in order to sufficiently absorb the light emitted from the luminescent material.
It is necessary to make m or more, and high-definition patterning (etching) becomes difficult. On the other hand, if it exceeds 1 mol, the concentration of the fluorescent dye is too high, the association between the dyes becomes remarkable, and concentration quenching may occur. From the viewpoints of absorption of light emitted from the light-emitting body and prevention of association between dyes, the fluorescent dye is particularly preferably used in a proportion of 0.001 to 0.1 mol per 1 kg of the binder resin. Further, in the fluorescent pigment containing the fluorescent dye in the resin, the amount of the fluorescent dye is set to the above ratio per 1 kg of the resin in the fluorescent pigment, or the amount of the fluorescent dye is the fluorescent pigment. It is preferable to use a fluorescent pigment whose content is preferably 0.1 to 10% by weight, more preferably 0.5 to 7% by weight, based on the resin inside. For the same reason as in the case of the molar ratio, if the amount of the fluorescent dye is less than 0.1% by weight, fine patterning may be difficult, and if it exceeds 10% by weight, concentration quenching may occur.

When such a fluorescent pigment is used, the weight ratio of the fluorescent pigment to the binder resin is 1:20 to 4: 1.
It is preferred that More preferably 1:10 to 3: 7
And When the ratio of the fluorescent pigment is less than 1:20,
The thickness of the fluorescence conversion film must be 100 μm or more in order to sufficiently absorb the light emitted from the light emitter, and the thickness is 4: 1.
When the ratio of the fluorescent pigment increases, the binder resin component soluble in the alkaline or acidic aqueous solution decreases,
As a result, in either case, it becomes difficult to pattern (etch) the fluorescence conversion film with high precision.

Next, the structure of the fluorescence conversion filter of the present invention will be described. The fluorescence conversion filter includes a fluorescence conversion film 2 that absorbs light 1 in the blue to blue-green region emitted from the light-emitting body and emits fluorescence in the green region, and a fluorescence conversion film 3 that emits fluorescence in the red region on the transparent substrate 10. In addition, the configuration in which they are separated and arranged in a plane is the minimum configuration (FIG. 1). The light 1 may be absorbed from the transparent substrate 10 side (FIG. 5). Further, in addition to the above configuration, by arranging the green color filter 4 and the red color filter 5 between the green conversion film 2, the red conversion film 3 and the transparent substrate 10, respectively, the green light emitted from each phosphor is emitted. 12, the color purity of the red light 13 can be adjusted to improve the color purity (FIG. 2). When the light 1 is absorbed from the transparent substrate 10 side as shown in FIG. 5, the color filters 4 and 5 are arranged above the conversion films 2 and 3 (on the side opposite to the transparent substrate 10). Further, a blue color filter 6 may be installed in parallel with the green conversion film 2 and the red conversion film 3 to adjust the color of the luminescent color of the luminescent material to enhance the color purity (FIG. 3). Also,
As shown in FIG. 4, a black matrix 7 is arranged at least in the gap between the fluorescence conversion film and / or the color filter to block the leaked light of the light emission 1 of the organic EL element to further enhance the visibility of multicolor light emission. You can also Further, a transparent protective film may be laminated on the filter, if necessary. The thickness of each fluorescence conversion film of the fluorescence conversion filter is 0.1 μm to 100 μm, preferably 1 μm to 60 μm.
It is. If it is less than 0.1 μm, it is necessary to make the concentration of the fluorescent dye or fluorescent pigment extremely high, and the concentration quenching due to the association between the dyes causes the fluorescence of the fluorescence conversion film to be lost, so that the emission from the luminescent material is efficiently converted. You cannot do it. On the other hand, 1
When it exceeds 00 μm, it becomes difficult to pattern the fluorescence conversion film with high precision.

Next, the color filter, the black matrix, and the protective film, which are arranged if necessary, will be described. (I) Color Filter and Black Matrix For the color filter and black matrix used in the present invention, a known material is selected, for example, and a desired pattern is formed at a desired position by a method such as a photolithography method or a printing method. Can be formed by performing. (Ii) Protective Film In the present invention, the protective film used as necessary only flattens the film thickness step (unevenness) of the fluorescence conversion film or the color filter (including the black matrix) arranged as necessary. Instead, it is used to protect the fluorescence conversion film from chemical factors such as external light, chemicals and solvents, and physical factors such as impact. The material is preferably a transparent (50% or more visible light) material. Specific examples thereof include those having an acrylate-based or methacrylate-based reactive vinyl group such as a photocurable resin and / or a thermosetting resin. Also, melamine resin,
Phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin monomer, oligomer, polymer, polymethylmethacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinylpyrrolidone,
Examples include transparent resins such as hydroxyethyl cellulose and carboxymethyl cellulose.

The protective film is formed by spin coating, roll coating, cast dipping or the like when the above material is in a liquid state, and the photo-curable resin is heat-cured as necessary after irradiation with light to form a heat-curable resin. Is heat-cured as it is after film formation. In the case of a film, an adhesive may be applied and adhered as it is. The thickness of the protective film is preferably about 0.5 μm to 100 μm, and the thickness of the protective film is made as small as possible in order to limit the emission leakage of the light emitter due to the gap between the fluorescence conversion film and the light emitter (improvement of the viewing angle). It is preferable. However, if the film thickness is made too small, the effect of protecting the fluorescence conversion film is lost. For further transparent substrates, for example,
A transparent material (visible light transmittance of 50% or more) such as a glass plate, a plastic plate (polycarbonate, acrylic, etc.), a plastic film (polyethylene terephthalate, polyether sulfide, etc.), and a quartz plate is preferable.

Next, a method for manufacturing the fluorescence conversion filter of the present invention will be described. The fluorescence conversion filter of the present invention, the fluorescent dye or fluorescent pigment constituting the fluorescence conversion film emitting fluorescence in the green region, and the photocurable or thermosetting resin composition is patterned on a transparent substrate, Alternatively, it is cured by heat treatment to obtain a cured product. Next, the fluorescent dye or fluorescent pigment constituting the fluorescence conversion film emitting fluorescence in the red region and the non-reactive resin composition are aligned in parallel with the pattern of the fluorescence conversion film emitting fluorescence in the green region. Patterning is performed so as to be separated in a plane. The patterning method may be a printing method or a photolithography method, but the photolithography method is generally used to obtain a high-definition pattern.

The manufacturing method of the present invention is a method for manufacturing a fluorescence conversion filter using a photolithography method.
Specifically, (1) a photocurable or thermosetting resist in which a fluorescent dye or fluorescent pigment that absorbs light in the blue to blue-green region and emits fluorescence in the green region is dissolved or dispersed is formed on a transparent substrate. A step of forming a film to obtain the resist film, (2) after exposing the photocurable resist film through a pattern mask,
Developing to form a pattern of the photocurable resist film, (3) curing the photocurable resist film by heat treatment to form a pattern of the fluorescence conversion film, (4) light in the blue or blue-green region A step of forming a non-reactive resin in which a fluorescent dye or a fluorescent pigment that emits fluorescence in the red region is dissolved or dispersed to obtain a non-reactive resin film on the substrate that has undergone the step (3), (5) A step of forming a photo-solubilizing resist or a photo-curing resist film on the non-reactive resin film and laminating the resist film, and (6) a photo-solubilizing resist through a pattern mask. After the resist or the photo-curable resist film is exposed, it is developed to form a pattern of the resist film, and at the same time or after that, the non-reactive resin film is etched.

In the step (1), the fluorescent dye or fluorescent pigment is dissolved or dispersed in the photocurable resist so that the cured product finally has the composition of the fluorescence conversion film. The photocurable resist is a liquid, paste or film of the composition described in the photocurable or thermosetting resin cured product, and may be a commercially available material. Next, the film is formed on a transparent substrate, and the liquid one is spin-coated, roll-coated,
It is performed by a method such as dipping, bar coating, casting or the like, and a paste-like material is subjected to a printing method such as screen printing, and a resist dry film is obtained by heat treatment from room temperature air drying to about 150 ° C. The film-like material is attached to a transparent substrate and heated as necessary to be brought into close contact with the substrate. The film thickness is 0.1 μm to 100 μm, preferably 1 μm to 6 as described in the description of the fluorescence conversion filter.
0 μm.

In the step (2), exposure is performed by a method such as a contact method, a proximity method, a projection method or the like through a mask that can obtain a desired pattern of the fluorescence conversion film on the resist film. Although the light source varies depending on the resist film, a high pressure mercury lamp is usually used to irradiate ultraviolet rays. The exposure energy is applied in such an amount that the resist film becomes less soluble in the developing solution. The developing solution is selected so that the resist film in the unexposed portion is dissolved. For the acrylic or methacrylic acid type resist film, in the step (3) where an alkaline aqueous solution is usually used, the heat treatment is applied to such an extent that the resist film pattern is hardened and becomes insoluble in the solvent. But usually 150 ℃ ~ 2
Heat treatment at about 50 ° C. is performed. In the step (4),
A fluorescent dye or fluorescent pigment is dissolved or dispersed in a non-reactive resin so as to have the composition of the fluorescent conversion film. The non-reactive resin may be dissolved or dispersed in an appropriate solvent to form a liquid or paste, or a dry film in the form of a film. Then, film formation is performed in the same manner as (1). (5)
In the step of (1), a commercially available liquid or film material is used as the photosolubilizing resist or the photocuring resist. As the photosolubilizing resist, a novolak resin-naphthoquinonediazide material is usually used. On the other hand, as the photocurable resist, the material of the composition described for the photocurable resin cured product or the like is used. The film forming method is the same as in (1). The step (6) is performed in the same manner as the step (2), but if the non-reactive resin film is dissolved in a developing solution that dissolves the resist film, the non-reactive resin film is developed simultaneously with the development of the resist film. To etch. If the non-reactive resin film does not dissolve in the developing solution for the resist film, the resist film is developed and then etched with an etchant that dissolves the non-reactive resin film. The dry etching such as reactive ion etching (RIE) can be applied to the development and etching in the above (2) and (6).

The fluorescence conversion filter can be produced as described above. Preferably, in addition to the step (6), the resist film laminated on the non-reactive resin film is peeled off with an appropriate peeling solution. The light absorption of the resist film is eliminated, and the fluorescence conversion efficiency is improved. If the non-reactive resin (film) is soluble in an alkaline aqueous solution or an acidic aqueous solution, the same water-based etchant can be used, so it is non-ignitable, easy to handle, and safe. The advantages of the method for manufacturing the fluorescence conversion filter as described above are shown below. By using a solvent-insoluble cured product of the fluorescence conversion film pattern that emits fluorescence in the green region, the previous fluorescence conversion film in the patterning of the fluorescence conversion film that emits fluorescence in the next red region may be dissolved or swollen,
It is possible to prevent defects of the fluorescence conversion filter without being contaminated and to improve the production yield. Further, in the method of patterning the fluorescence conversion film that emits fluorescence in the red region, since the resist film and the fluorescence conversion film are layer-separated, the fluorescence in the fluorescence conversion film is changed by the radical species or ionic species generated from the resist film. The dye does not bleach or quench.

The light-emitting body in the present invention is not particularly limited as long as it emits light in the blue to blue-green region, and examples thereof include EL, LED, VFD, and PDP. Among these elements, an organic EL element capable of efficiently emitting light in the blue or blue-green region is suitable. Even if the type of light-emitting body is different, if a fluorescent conversion film capable of emitting fluorescence of a desired color is arranged by aligning with a light-emitting body of one color separated and arranged in a plane, as many as the organic EL element, Color emission is possible. This organic EL
The element basically holds a light emitting layer between a pair of electrodes,
It has a structure with a hole injection layer and an electron injection layer interposed as necessary. Specifically, (i) anode / light emitting layer / cathode (ii) anode / hole injection layer / light emitting layer / cathode (iii) anode / light emitting layer / electron injection layer / cathode (iv) anode / hole injection layer There are structures such as / emission layer / electron injection layer / cathode.

The light emitting layer (1) has an injection function capable of injecting holes from the anode or the hole injection layer and injecting electrons from the cathode or the electron injection layer when an electric field is applied, (2) It has the function of transporting the injected charges (electrons and holes) by the force of the electric field, and (3) the function of providing a field for recombination of electrons and holes inside the light-emitting layer and connecting it to light emission. ing. However, there may be a difference between the ease of injecting holes and the ease of injecting electrons, and the transport function represented by the mobility of holes and electrons may be large or small. It is preferable to use a material having a function of transferring the charge. There is no particular limitation on the type of light emitting material used in the light emitting layer, and a known light emitting material in an organic EL element can be used. Such a light emitting material is mainly an organic compound, and specific examples thereof include the following compounds according to a desired color tone.

To obtain light emission in the blue to blue-green region,
Examples thereof include benzothiazole-based, benzimidazole-based, and benzoxazole-based optical brighteners, metal chelated oxinoid compounds, and styrylbenzene-based compounds. In addition, aromatic dimethylidyne compounds (European Patent No. 388768, JP-A-3-231)
Those disclosed in Japanese Patent Publication No. 970) can also be preferably used. Examples of this aromatic dimethylidyne compound include 1,4-phenylenedimethyridin; 4,4'-biphenylenedimethyridin;2,5-xylylenedimethyridin;2,6-naphthylenedimethyridin; 1,4
-P-Terephenylenedimethylidene; 4,4'-bis (2,2-di-t-butylphenylvinyl) biphenyl (DTBPVBi); 4,4'-bis (2,2-diphenylvinyl) biphenyl (DPVBi) ) And the like and derivatives thereof.

Furthermore, the general formula (IV) (RQ) ₂ -Al-OL ... (IV) described in JP-A-5-258862 and the like (wherein L represents a benzene ring) A hydrocarbon group containing 6 to 24 carbon atoms, OL is a phenolate ligand, Q is a substituted 8-quinolinolato ligand, and R is an aluminum atom with more than two substituted 8-quinolinolato ligands bonded. The compound represented by the formula (8-quinolinolate ring substituent selected so as to sterically hinder the reaction) is also included. An example of this compound is bis (2-methyl-8-
(Quinolinolate) (p-phenylphenolate) aluminum (III) (hereinafter PC-7), bis (2-methyl-)
8-quinolinolato) (1-naphtholate) aluminum (III) (hereinafter PC-17) and the like.

In addition, in order to obtain highly efficient mixed light emission of blue and green, there may be mentioned one obtained by adding a dopant to the above-mentioned light emitting material which is a host (JP-A-6-9953, etc.). Examples of the dopant include fluorescent dyes in the blue region or green region, specifically, coumarin-based or the same fluorescent dyes as those used as the above host. In particular, a luminescent material of an aromatic dimethylidyne compound as a host, preferably DPVBi,
Those having a diphenylaminostyrylarylene skeleton as a dopant, preferably 1,4-bis [4-
[N, N-diphenylamino) styryl] benzene (D
Preference is given to the combination with PAVB).
As a method for forming a light emitting layer using the above materials, for example, the light emitting layer can be formed by thinning by a known method such as an evaporation method, a spin coating method, a casting method, and an LB method. Preferably, there is. Here, the molecular deposition film is a thin film formed by depositing the compound in a vapor phase state, or a film formed by solidifying a molten state or a liquid phase state of the compound. Usually, this molecular deposition film is a thin film (molecular cumulative film) formed by the LB method.
Can be distinguished by the difference in aggregation structure, higher-order structure, and functional difference caused by them.

Further, this light emitting layer is disclosed in JP-A-57-517.
As described in No. 81, after dissolving the luminescent material in a solvent together with a binder such as a resin to form a solution,
This can be formed into a thin film by a spin coating method or the like. The thickness of the light emitting layer formed in this way is not particularly limited and can be appropriately selected depending on the situation, but is usually in the range of 5 nm to 5 μm. As the anode in this EL element, a metal, an alloy, an electrically conductive compound, or a mixture thereof having a large work function (4 eV or more) as an electrode material is preferably used. Specific examples of such an electrode material include metals such as Au, CuI, indium tin oxide (ITO), and Sn.
Conductive transparent materials such as O ₂ and ZnO are mentioned. The anode may be formed by forming a thin film of these electrode materials by a method such as vapor deposition or sputtering, and forming a pattern of a desired shape by a photolithography method, or (100 μm Above), a pattern may be formed via a mask having a desired shape at the time of vapor deposition or sputtering of the electrode material.
When light emission is extracted from this anode, the transmittance is 10%.
It is desirable to make it larger, and the sheet resistance as the anode is preferably several hundred Ω / □ or less. The film thickness depends on the material, but is usually 10 nm to 1 μm, preferably 10 nm.
Is selected in the range of up to 200 nm.

On the other hand, as the cathode, a metal having a low work function (4 eV or less) (referred to as an electron injecting metal), an alloy, an electrically conductive compound, or a mixture thereof is used as an electrode material. Specific examples of such an electrode material include sodium, sodium-potassium alloy, magnesium, lithium, magnesium / copper mixture, magnesium / silver mixture, magnesium / aluminum mixture, magnesium / indium mixture, aluminum /
Aluminum oxide (Al ₂ O ₃ ) mixture, indium,
Examples include lithium / aluminum mixtures and rare earth metals. Among these, from the viewpoint of electron injecting property and durability against oxidation, etc., a mixture of an electron injecting metal and a second metal which is a stable metal having a larger work function value, such as a magnesium / silver mixture or magnesium. Aluminium / aluminum mixture, magnesium / indium mixture, aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, lithium / aluminum mixture and the like are suitable. The cathode can be produced by forming a thin film of these electrode substances by a method such as vapor deposition or sputtering. The sheet resistance of the cathode is several hundred Ω / □
The following is preferred, and the film thickness is usually selected in the range of 10 nm to 1 μm, preferably 50 to 200 nm. In order to transmit the emitted light, it is convenient that either the anode or the cathode of the organic EL element is transparent or semi-transparent and the luminous efficiency is improved.

Next, the hole injection layer, which is provided as necessary, has a function of transmitting the holes injected from the anode to the light emitting layer, and the hole injection layer is interposed between the anode and the light emitting layer. By doing so, many holes are injected into the light-emitting layer at a lower electric field, and moreover, the electrons injected from the cathode or the electron-injection layer into the light-emitting layer are separated from the electrons existing at the interface between the light-emitting layer and the hole-injection layer. Due to the barrier, the element is excellent in light emission performance because it is accumulated at the interface in the light emitting layer and the light emission efficiency is improved. Regarding the material of the hole injection layer (hereinafter, referred to as a hole injection material),
There is no particular limitation as long as it has the above preferable properties. Conventionally, in photoconductive materials, those commonly used as a hole charge injection / transport material and known materials used for a hole injection layer of an EL element are used. Any of them can be selected and used.

The above hole injecting material has one of hole injecting property and electron blocking property, and may be either an organic substance or an inorganic substance. As this hole injection material,
For example, triazole derivatives, oxadiazole derivatives,
Imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives and pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, aniline-based copolymers Coalescing,
Further, a conductive polymer oligomer, particularly a thiophene oligomer, may be used. As the hole injection material, those described above can be used.
Aromatic tertiary amine compounds and styrylamine compounds,
It is particularly preferable to use an aromatic tertiary amine compound.

Typical examples of the aromatic tertiary amine compound and the styrylamine compound are N, N, N ', N'.
N-tetraphenyl-4,4′-diaminophenyl;
N'-diphenyl-N, N'-bis (3-methylphenyl)-[1,1'-biphenyl] -4,4'-diamine (TPD); 2,2-bis (4-di-p-tolyl Aminophenyl) propane; 1,1-bis (4-di-p-tolylaminophenyl) cyclohexane; N, N, N ′,
N'-tetra-p-tolyl-4,4'-diaminobiphenyl; 1,1-bis (4-di-p-tolylaminophenyl) -4-phenylcyclohexane; bis (4-dimethylamino-2-methylphenyl ) Phenylmethane; bis (4-di-p-tolylaminophenyl) phenylmethane; N, N'-diphenyl-N, N'-di (4-methoxyphenyl) -4,4'-diaminobiphenyl;
N, N ', N'-tetraphenyl-4,4'-diaminodiphenyl ether; 4,4'-bis (diphenylamino) quadriphenyl; N, N, N-tri (p-tolyl) amine; 4- ( Di-p-tolylamino) -4'-
[4- (di-p-tolylamino) styryl] stilbene; 4-N, N-diphenylamino- (2-diphenylvinyl) benzene; 3-methoxy-4′-N, N-diphenylaminostilbenzene; N-phenyl Carbazoles, as well as those having in the molecule two fused aromatic rings as described in U.S. Pat. No. 5,061,569, such as 4,4'-bis [N- (1-naphthyl) -N
-Phenylamino] biphenyl (NPD);
No. 3,068,688, in which three triphenylamine units are linked in a star-burst form.
4 ', 4''-tris [N- (3-methylphenyl) -N
-Phenylamino] triphenylamine (MTDAT
A) and the like.

Further, the above-mentioned aromatic dimethylidyne compound, p-type-Si, p-type-Si shown as the material of the light emitting layer.
An inorganic compound such as C can also be used as the hole injection material. The hole injection layer can be formed by thinning the hole injection material by a known method such as a vacuum deposition method, a spin coating method, a casting method, and an LB method. The thickness of the hole injection layer is not particularly limited, but is usually about 5 nm to 5 μm. The hole injection layer may have a single-layer structure composed of one or more of the above-mentioned materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. Further, the electron injection layer used as necessary may have a function of transmitting electrons injected from the cathode to the light emitting layer, and any material may be selected from conventionally known compounds. Can be used.

Materials used for this electron injection layer (hereinafter,
Examples of the electron injection material) include nitro-substituted fluorene derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthalene perylene, carbodiimide, fluorenylidene methane derivatives, anthraquinodimethane and Examples include anthrone derivatives and oxadiazole derivatives. Further, a series of electron-transporting compounds described in JP-A-59-194393 are disclosed as materials for forming a light-emitting layer in the publication. It has been found that it can be used as a material. Further, in the oxadiazole derivative, a thiadiazole derivative in which an oxygen atom of the oxadiazole ring is substituted with a sulfur atom, and a quinoxaline derivative having a quinoxaline ring known as an electron withdrawing group can also be used as the electron injecting material.

Also, metal complexes of 8-quinolinol derivatives, such as tris (8-quinolinol) aluminum (Alq), tris (5,7-dichloro-8-quinolinol) aluminum, tris (5,7-dibromo-8-).
Quinolinol) aluminum, tris (2-methyl-8)
-Quinolinol) aluminum, tris (5-methyl-)
8-quinolinol) aluminum, bis (8-quinolinol) zinc (Znq), etc., and the central metal of these metal complexes is In, Mg, Cu, Ca, Sn, Ga or Pb.
The metal complex replaced with can also be used as an electron injection material. In addition, metal-free or metal phthalocyanine, or those whose terminals are substituted with an alkyl group, a sulfonic acid group, or the like, can also be preferably used as an electron injection material. Further, the distyrylpyrazine derivative exemplified as the material for the light emitting layer can also be used as the electron injecting material, and like the hole injecting layer,
Inorganic semiconductors such as n-type-Si and n-type-SiC can also be used as the electron injection material.

This electron injection layer can be formed by forming the above compound into a film by a known thin film forming method such as a vacuum vapor deposition method, a spin coating method, a casting method and an LB method. The thickness of the electron injection layer is not particularly limited, but is usually selected in the range of 5 nm to 5 μm. The electron injection layer may have a single-layer structure composed of one or more of these electron injection materials, or may have a laminated structure composed of a plurality of layers having the same composition or different compositions. next,
A preferred example of producing the organic EL element will be described. As an example, a method of manufacturing an EL device composed of the above-mentioned anode / hole injection layer / light-emitting layer / electron injection layer / cathode will be described. First, a thin film made of a desired electrode material, for example, an anode material, is formed on a suitable substrate. Is 1 μm or less, preferably 10 to 200 n
An anode is formed by a method such as vapor deposition or sputtering so that the film thickness is in the range of m. Next, a thin film made of the material of the hole injection layer, the light emitting layer, and the electron injection layer, which are element materials, is formed on this.

As the thinning method, there are the spin coating method, the casting method, the vapor deposition method and the like as described above, but the vacuum vapor deposition is preferred because a uniform film is easily obtained and pinholes are not easily generated. Method is preferred. When this vapor deposition method is employed for thinning the film, the vapor deposition conditions vary depending on the type of compound used, the target crystal structure of the molecular deposition film, the association structure, and the like.
50 ° C., degree of vacuum 10 ^-6 to 10 ^-3 Pa, deposition rate 0.01 to
50 nm / sec, substrate temperature -50 to 300 ° C, film thickness 5 nm
It is desirable to select an appropriate value within a range of from 5 μm to 5 μm.

After forming these layers, a thin film made of a substance for the cathode is formed thereon and has a thickness of 1 μm or less, preferably 50 to 200 n.
A desired EL element can be obtained by forming a film having a thickness in the range of m by, for example, a method such as vapor deposition or sputtering and providing a cathode. In order to fabricate this organic EL device, it is preferable to consistently fabricate from the hole injecting layer to the cathode by pulling once, but the production order is reversed, and the cathode, electron injecting layer, light emitting layer, and hole injecting layer are injected. It is also possible to fabricate the layers and the anode in this order. When a direct current voltage is applied to the EL device thus obtained, light emission can be observed by applying a voltage of about 5 to 40 V with the anode having a positive polarity and the cathode having a negative polarity. Also, even if a voltage is applied with the opposite polarity, no current flows and no light emission occurs. Further, when an AC voltage is applied, light is emitted only when the anode is in the + state and the cathode is in the-state. The waveform of the applied alternating current may be arbitrary.

[0058]

Next, the present invention will be described in more detail with reference to examples, but the present invention is not limited to these examples. Production Example 1 (Fabrication of blue light emitting organic EL device as a light emitting body) A glass substrate (Corning 7059) of 25 mm × 75 mm × 1.1 mm was sputtered over the entire surface to 120 n.
After forming an ITO film with a film thickness of m, a novolak / quinonediazide photosolubilizing resist, that is, a positive resist (HPR204 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is spin-coated and laminated, dried at 80 ° C., and then a glass substrate. Contact exposure was performed using a high pressure mercury lamp as a light source at 100 mJ / cm ² through a mask that gives an ITO solid pattern in an area of 15 mm × 50 mm □, and 2.38% T
After developing with MAH (tetramethylammonium hydroxide) and baking at 130 ° C., the exposed ITO film is etched with a hydrobromic acid aqueous solution, and finally, the positive resist is peeled off to form an ITO pattern serving as an anode of the organic EL element. Obtained.

Next, this substrate was subjected to IPA cleaning and UV cleaning, and then fixed to a substrate holder of a vapor deposition apparatus (manufactured by Nippon Vacuum Technology). As a vapor deposition source, MTDATA and NPD as a hole injection material, DPVBi as a light emitting material, and Alq as an electron injection material were charged in a resistance heating boat made of molybdenum, and Ag was used as a second metal of the cathode in a tungsten filament and electrons of the cathode were used. Mg as an injectable metal was mounted on a molybdenum boat. After that, the vacuum chamber is 5 × 10
After reducing the pressure to -7 torr, the layers were sequentially laminated in the following order. Vacuuming was performed once without breaking the vacuum on the way from the hole injection layer to the cathode. First, as the hole injection layer, M
Vapor deposition rate of TDATA 0.1-0.3 nm / s, film thickness 60n
m, NPD deposition rate 0.1-0.3nm / s, film thickness 20n
m, DPVBi for the light emitting layer, vapor deposition rate 0.1 to 0.3n
m / s, film thickness 50 nm, vapor deposition rate of 0.1 to 0.3 nm / s for the electron injection layer, film thickness 20 nm, and cathode 15 mm x 50 mm in the glass substrate so as to intersect the ITO anode pattern. □ Area through a mask Mg and A
g was co-deposited. That is, Mg has a deposition rate of 1.3 to
The film thickness of 1.4 nm / s and Ag was 200 nm at a vapor deposition rate of 0.1 nm / s. In this way, when an organic EL device was produced and a voltage of 12 V DC was applied to the anode and the cathode, the intersection of the anode and the cathode emitted light. The emission brightness is 200 cd / m ² , C with a color difference meter (CS100 manufactured by Minolta).
The IE chromaticity coordinates were x = 0.16 and y = 0.15, and it was confirmed that blue light was emitted.

Example 1 A carbon black-containing photocurable resist (CK2000 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on a transparent substrate (blue glass manufactured by Geomatec) having a thickness of 100 mm × 100 mm × 1.1 mm, and the coating was performed at 80 ° C. After baking, an oxygen barrier film of polyvinyl alcohol (CP manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated and baked at 80 ° C. Next, the substrate was set in a contact type exposure machine using a high pressure mercury lamp as a light source, and
100 mJ / cm ² (36 μm) through a mask that gives a stripe pattern of 0 μm line and 250 μm gap.
Exposure at 5 nm). Further, after development with a 1N sodium carbonate aqueous solution, post-baking was performed at 200 ° C. to obtain a black matrix (film thickness 1.5 μm). Next, 0.33 g of coumarin 6 at a ratio of 0.02 mol / kg (relative to solid content) as a fluorescent dye, and 2% by weight of Solvent Yellow 116 and 6% by weight of Solvent Yellow as a fluorescent pigment with respect to a benzoguanamine resin. 44 was previously kneaded (naphthalimide-based fluorescent pigment) to the solid content of 3
Prepare 100 g of solution (solid content 47% by weight) by mixing 14.1 g of 0% by weight and 85.6 g of acrylate photo-curable resist (JNPC06 manufactured by Japan Synthetic Rubber Co., solid content 38% by weight). To do.

This solution was spin-coated on the substrate,
After baking at 80 ° C., the substrate was set in a contact type exposure machine using a high pressure mercury lamp as a light source, and the 280 μm line 6 was used.
Align the mask that gives a 20 μm gap stripe pattern with the black matrix and
Exposure was performed at J / cm ² (365 nm). Furthermore, 2.38
% Tetramethylammonium hydroxide aqueous solution and post-baked at 200 ° C. to obtain a pattern A (film thickness 6.0 μm) of the fluorescence conversion film. Next, as the fluorescent pigment, the above-mentioned naphthalimide-based fluorescent pigment was added in an amount of 7 g, which was 20% by weight based on the solid content, and 4% based on the benzoguanamine resin.
10.5 g of a basic violet 11% by weight and a rhodamine 6G of 4% by weight kneaded in advance (rhodamine fluorescent pigment) to be 30% by weight based on the solid content.
And a weight average molecular weight (Mw) 40 as a non-reactive resin,
Solution of 17.5 g of 000 poly (2-vinylpyridine) and 65 g of ethyl cellosolve acetate 10
0 g (solid content 35% by weight) was prepared.

This solution was spin-coated on the above substrate, baked at 80 ° C., and then a novolac resin-naphthoquinone diazide photo-soluble resist (HPR20 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was formed on the film.
4) was spin-coated and baked at 80 ° C. to form a resist film. Next, the substrate is set in a contact type exposure machine using a high pressure mercury lamp as a light source, and a 280 μm line 620 is set.
The resist film was exposed at 100 mJ / cm ² (365 nm) by aligning the mask for obtaining a stripe pattern with a μm gap with the position adjacent to the previously formed fluorescence conversion film pattern A. Further, after developing the resist film with a 2.38% tetramethylammonium hydroxide aqueous solution, the exposed film of the fluorescent pigment and the non-reactive resin is etched with a 20% by weight acetic acid aqueous solution to form a 2% sodium hydroxide aqueous solution. The laminated resist film was peeled off. As a result,
A pattern B (film thickness 19.8 μm) of the fluorescence conversion film was obtained.

Here, when the organic EL element of the luminescent material produced in Production Example 1 and the fluorescent conversion film pattern A are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element by a colorimeter. 184 cd / m for ^2
2 (conversion efficiency 92%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that yellowish green (yellowish green) light was emitted at 0.25 and y = 0.62. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern B are overlapped, the luminance emitted from the fluorescent conversion film is 66 cd / m ² (conversion efficiency 33%) with respect to the luminance of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.61, y =
It was observed that red light emission was emitted at 0.32. That is, a fluorescent conversion film that absorbs light in the blue region and that emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region are provided on a transparent substrate (with a black matrix) at a pitch of 300 μm. It is possible to produce a fluorescence conversion filter that is separated and arranged in a high-definition plane.
By transmitting the blue light of the light emitter as it is, multicolor emission of the three primary colors becomes possible.

Example 2 As a fluorescent dye, 0.02 mol / kg (based on solid content)
0.098 g of Marine 6 and the naphthalimide of Example 1
Amount of 30% by weight based on solid content of fluorescent pigment 4.2g
And a polyvinyl cinnamate-based photocurable resist
(Tokyo Ohka Kogyo Co., Ltd. TPR, solid content 10% by weight) 95.7
Prepare 100 g of a solution mixed with g (solid content 14% by weight).
To make. This solution was added to the black matrix of Example 1.
Spin coat on the formed transparent substrate and bake at 80 ℃
After that, the next is the contact type that uses a high-pressure mercury lamp as the light source for the substrate.
Set it on the exposure machine and set the 280 μm line and 620 μm line.
Black mask to obtain a stripe pattern
300 mJ / cm, aligned with the tricks ^Two(3
Exposure at 65 nm). Furthermore, it is currently used in ethyl cellosolve.
After the image, post-baking at 180 ℃, the pattern of the fluorescence conversion film
Cone (film thickness: 6.3 μm) was obtained. Next, as a fluorescent dye
0.02 mol / kg (vs solid content) of coumarin 6
45 g and the rhodamine-based firefly of Example 1 as a fluorescent pigment
The amount of photo pigment is 30% by weight based on the solid content, 10.5 g
And a weight average molecular weight (Mw) of 50 as a non-reactive resin,
24.5 g of poly (4-vinyl pyridine)
Solution 10 mixed with 65 g of chill cellosolve acetate
0 g (solid content 35% by weight) was prepared. Example 1 below
Similarly, the pattern D of the fluorescence conversion film (film thickness 20.8 μ
m).

Here, when the organic EL element of the luminescent material produced in Production Example 1 and the fluorescent conversion film pattern C are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element by a colorimeter. 176 cd / m for ^2
2 (conversion efficiency 88%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that yellowish green (yellowish green) light was emitted at 0.25 and y = 0.61. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern D are overlapped, the luminance emitted from the fluorescent conversion film is 60 cd / m ² (conversion efficiency 30%) with respect to the luminance of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.61, y =
It was observed that red light emission was emitted at 0.31. That is, a fluorescent conversion film that absorbs light in the blue region and that emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region are provided on a transparent substrate (with a black matrix) at a pitch of 300 μm. It is possible to produce a fluorescence conversion filter that is separated and arranged in a high-definition plane.
By transmitting the blue light of the light emitter as it is, multicolor emission of the three primary colors becomes possible.

Example 3 A fluorescent conversion film pattern A was produced in the same manner as in Example 1 on the transparent substrate on which the black matrix of Example 1 was formed. Next, in the same manner as in Example 1, the amount of the above naphthalimide-based fluorescent pigment as the fluorescent pigment was 7 g, which was 20% by weight based on the solid content, and 4% by weight based on the benzoguanamine resin.
Of basic violet 11 and 4% by weight of rhodamine 6G (rhodamine-based fluorescent pigment), which is 30% by weight based on the solid content of 10.5 g,
Weight average molecular weight (Mw) 40,00 as non-reactive resin
100 g of a solution (solid content: 35% by weight) was prepared by mixing 17.5 g of poly (2-vinylpyridine) of 0 and 65 g of ethyl cellosolve acetate. The solution was spin-coated on the above substrate, baked at 80 ° C., and then a cyclized rubber-based photocurable resist (IC28-T3 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on this film. The resist film was laminated by baking at 80 ° C. Next, the substrate is set in a contact type exposure machine using a high-pressure mercury lamp as a light source, and a mask for obtaining a stripe pattern with a 280 μm line and a 620 μm gap is aligned with a position adjacent to the previously formed fluorescence conversion film pattern.
The resist film was exposed at 00 mJ / cm ² (365 nm). Further, after developing the resist film with a xylene-based solvent (WNRD manufactured by Fuji Hunt Electronics Technology Co., Ltd.), the film made of the fluorescent pigment and the non-reactive resin exposed in a 20 wt% acetic acid aqueous solution was etched. As a result, a pattern E of the fluorescence conversion film (thickness: 21.5 μm) was obtained.

Here, when the organic EL element of the luminescent material produced in Production Example 1 and the fluorescence conversion film pattern A were overlaid, Example 1
On the other hand, when the organic EL element of the luminescent material and the fluorescent conversion film pattern E are overlapped with each other, the luminance emitted from the fluorescent conversion film is 60 cd / m ^{2 with} respect to the luminance of 200 cd / m ² of the organic EL element. ² (conversion efficiency 30%) was obtained, and CI
E chromaticity coordinates are red (red) with x = 0.61 and y = 0.32.
It was observed that the luminescence was emitted. That is, a fluorescent conversion film that absorbs light in the blue region and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region on a transparent substrate (with a black matrix)
In addition, it was possible to fabricate a high-definition, two-dimensionally separated fluorescence conversion filter with a pitch of 300 μm, and by transmitting the blue light of the light emitter as it was, multi-color emission of three primary colors became possible.

Production Example 2 (Blue-green light-emitting organic E as a light-emitting body
Fabrication of L element) 120 n by sputtering on the entire surface of a 25 mm × 75 mm × 1.1 mm glass substrate (Corning 7059).
After forming an ITO film with a film thickness of m, a photo-solubilizing resist, a novolak / quinonediazide positive resist (HPR20 manufactured by Fuji Hunt Electronics Technology Co., Ltd.
4) was spin-coated, laminated, dried at 80 ° C., and then contact-exposed with a high-pressure mercury lamp as a light source at 100 mJ / cm ² through a mask that gives an ITO solid pattern in a 15 mm × 50 mm square area in a glass substrate. , 2.3 more
After developing with 8% TMAH (tetramethylammonium hydroxide) and baking at 130 ° C., the exposed ITO film is etched with an aqueous solution of hydrobromic acid, and finally the photosolubilizing resist is peeled off to form the anode of the organic EL element. The following ITO pattern was obtained. Next, the substrate was subjected to IPA cleaning and UV cleaning, and then fixed to a substrate holder of a vapor deposition device (manufactured by Nippon Vacuum Technology). The evaporation source was prepared by charging MTDATA and NPD as hole injection materials, DPVBi as a light emitting material, DPAVB as a dopant, and Alq as an electron injection material into a resistance heating boat made of molybdenum, and Ag as a second metal of the cathode into a tungsten filament. As a cathode electron-injecting metal, Mg was mounted on a molybdenum boat.

After that, the pressure in the vacuum chamber was reduced to 5 × 10 ⁻⁷ torr, and the layers were sequentially laminated in the following order. Vacuuming was performed once without breaking the vacuum on the way from the hole injection layer to the cathode. First, as the hole injecting layer, MTDATA is vapor deposition rate 0.1 to 0.3 nm / s, film thickness 60 nm, NPD is vapor deposition rate 0.1 to 0.3 nm / s, film thickness 20 nm, and DPVBi is used as the light emitting layer. Vapor deposition rate 0.1-0.3nm / s, DPAV
B was simultaneously vapor-deposited at a vapor deposition rate of 0.05 nm / s to obtain a total film thickness of 40 nm (the weight ratio of the dopant to the host material is
1.2 to 1.6), the electron injection layer was Alq with a deposition rate of 0.1 to 0.3 nm / s, the film thickness was 20 nm, and the cathode was in a glass substrate so as to intersect with the ITO anode pattern. Mg and A through the mask in the area of 15mm x 50mm
g was co-deposited. That is, Mg has a deposition rate of 1.3 to
The film thickness of 1.4 nm / s and Ag was 200 nm at a vapor deposition rate of 0.1 nm / s. In this way, when an organic EL element was produced and a voltage of 8 V DC was applied to the anode and the cathode, the intersection of the anode and the cathode emitted light. The emission brightness was 200 cd / m ² and CI with a colorimeter (CS100 manufactured by Minolta).
The E chromaticity coordinates were x = 0.16 and y = 0.24, and it was confirmed that the light emission was bluish green, which was greener than in Production Example 1.

Example 4 A copper phthalocyanine-containing photocurable resist (CK2 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was formed on a substrate in which a black matrix was formed on the transparent substrate of Example 1.
000) is spin-coated and baked at 80 ° C., and then an oxygen barrier film of polyvinyl alcohol (CP manufactured by Fuji Hunt Electronics Technology Co., Ltd.) is spin-coated,
Bake at 80 ° C. Next, the substrate was set in a contact type exposure machine using a high-pressure mercury lamp as a light source, a mask for obtaining a stripe pattern with a 280 μm line and a 620 μm gap was aligned with a black matrix, and 100
It was exposed to mJ / cm ² (365 nm). Furthermore, 1N
After development with an aqueous sodium carbonate solution, post-baking was performed at 200 ° C. to obtain a blue color filter (film thickness 0.7 μm).
Thereafter, as in Example 1, the fluorescence conversion films were separated and arranged in a plane, and a fluorescence conversion filter could be produced.

Here, when the organic EL element of the luminous body produced in Production Example 2 and the fluorescent conversion film pattern A are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element by a colorimeter. 180 cd / m for ^2
2 (conversion efficiency 90%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that yellowish green light (yellowish green) was emitted at 0.24 and y = 0.62. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern B are overlapped, the luminance emitted from the fluorescent conversion film is 50 cd / m ² (conversion efficiency 25%) with respect to the luminance of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.62, y =
It was observed that red light emission was emitted at 0.32. In addition, when the organic EL element of the luminescent material and the blue color filter are overlapped, the brightness transmitted through the color filter is 86 cd / m ² relative to the brightness of the organic EL element of 200 cd / m ² .
m ² (conversion efficiency 43%) is obtained, and the CIE chromaticity coordinate is x
It was observed that at = 0.13 and y = 0.16, luminescence with increased blue purity was emitted. That is, a fluorescent conversion film that absorbs light in the blue region and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region, and a blue color filter on a transparent substrate (with a black matrix). ), It was possible to manufacture a fluorescence conversion filter with a high resolution of 300 μm pitch and two-dimensionally separated, and it became possible to emit light of three primary colors.

Example 5 Next, 0.47 g of coumarin 7 at 0.03 mol / kg (relative to solid content) was used as a fluorescent dye, and the naphthalimide-based fluorescent pigment of Example 1 was added at 30% by weight based on the solid content. Amount of 14.1g, and acrylate photo-curable resist 8
101 g of a solution (47% by weight of solid content) mixed with 6.6 g (JNPC06 manufactured by Japan Synthetic Rubber Co., Ltd., 38% by weight of solid content) is prepared. This solution was spin-coated on the substrate on which the black matrix and blue color filter of Example 4 had been prepared, baked at 80 ° C., and then the substrate was set in a contact type exposure machine using a high pressure mercury lamp as a light source and set to 280 μm.
A mask capable of obtaining a stripe pattern with a m-line 620 μm gap was aligned with a black matrix and exposed at 300 mJ / cm ² (365 nm). Further, after development with a 2.38% tetramethylammonium hydroxide aqueous solution, post-baking was performed at 200 ° C. to obtain a pattern F (film thickness 5.0 μm) of the fluorescence conversion film.

Next, as the fluorescent pigment, the above-mentioned naphthalimide-based fluorescent pigment was added in an amount of 7 g, which was 20% by weight based on the solid content.
And 4% by weight of basic violet 11 and 4% by weight of Rhodamine 6G with respect to the benzoguanamine resin
Was mixed in advance (rhodamine-based fluorescent pigment) in an amount of 10.5 g, which is 30% by weight based on the solid content, and a methylmethacrylate-methacrylic acid copolymer having a weight average molecular weight (Mw) of 34,000 as a non-reactive resin. Polymer (Methyl methacrylate unit: Methacrylic acid unit molar ratio = 75:25)
100 g of a solution (solid content: 35% by weight) obtained by mixing 17.5 g and 65 g of ethyl cellosolve acetate was prepared. This solution is spin-coated on the above substrate and heated to 80 ° C.
After baking with, an acrylate-based photocurable resist (V259PA manufactured by Nippon Steel Chemical Co., Ltd.) was spin-coated on this film, and baked at 80 ° C. to form a resist film. Then, the substrate was set in a contact type exposure machine using a high pressure mercury lamp as a light source, and a mask for obtaining a stripe pattern of 280 μm lines and 620 μm gaps was aligned with a position adjacent to the fluorescence conversion film pattern previously formed, and then 300 m.
The resist film was exposed with J / cm ² (365 nm). Further, the resist film was developed with a 2.38% tetramethylammonium hydroxide aqueous solution, and at the same time as the development, the film made of the fluorescent pigment and the non-reactive resin exposed was etched to form a pattern G (film thickness 24.0 μm) of the fluorescent conversion film. Obtained.

Here, when the organic EL element of the luminescent material produced in Production Example 1 and the fluorescent conversion film pattern F are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element by a color difference meter. 175 cd / m for ^2
2 (conversion efficiency 88%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that a yellowish green (yellowish green) emission was emitted at 0.26 and y = 0.61. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern G are overlapped, the brightness emitted from the fluorescent conversion film is 40 cd / m ² (conversion efficiency 20%) with respect to the brightness of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.62, y =
It was observed that red light emission was emitted at 0.31. That is, a fluorescent conversion film that absorbs light in the blue region and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region, and a blue color filter on a transparent substrate (with a black matrix). )
In addition, it was possible to manufacture a fluorescence conversion filter with a 300 μm pitch and which was separated and arranged in a plane with high precision, and it became possible to emit light of three primary colors.

Example 6 A fluorescent conversion film pattern A was produced in the same manner as in Example 1 on the substrate on which the black matrix and blue color filter of Example 4 were produced. Next, as the fluorescent pigment, the above-mentioned naphthalimide-based fluorescent pigment was added in an amount of 7 g, which was 20% by weight based on the solid content, and 4% based on the benzoguanamine resin.
Rhodamine 110% by weight and rhodamine 6G 4% by weight were previously kneaded (rhodamine-based fluorescent pigment) in an amount of 10.5 g, which was 30% by weight based on the solid content, and a weight average molecular weight as a non-reactive resin ( Mw) 60,000 poly (p-N, N-dimethylaminostyrene) 17.5 g
And 65 g of ethyl cellosolve acetate were mixed to prepare 100 g of a solution (solid content: 35% by weight). Thereafter, in the same manner as in Example 1, a pattern H of the fluorescence conversion film was produced (film thickness 20.1 μm). When the organic EL element of the light emitting body and the fluorescent conversion film pattern H are overlapped, the luminance emitted from the fluorescent conversion film is 4 with respect to the luminance of 200 cd / m ² of the organic EL element.
It was observed that 5 cd / m ² (conversion efficiency 23%) was obtained, CIE chromaticity coordinates were x = 0.61, y = 0.31, and red light emission was observed. That is, the organic E of the luminous body
A fluorescent conversion film that absorbs light in the blue region emitted from the L element and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region, and a blue color filter are mounted on a transparent substrate (with a black matrix) at a pitch of 300 μm. It is possible to produce a fluorescence conversion filter that is finely separated and arranged in a plane.
Multi-color emission of three primary colors is now possible.

Example 7 A fluorescent conversion film pattern A was prepared in the same manner as in Example 1 on the substrate on which the black matrix and blue color filter of Example 4 were prepared. Next, as the fluorescent pigment, 7 g of the above naphthalimide-based fluorescent pigment was added to the solid content in an amount of 20% by weight, and 4% by weight of Rhodamine 110 and 4% by weight of Rhodamine 6G were kneaded in advance with respect to the benzoguanamine resin. Damono (rhodamine fluorescent pigment)
In an amount of 10.5 g, which is 30% by weight based on the solid content, and a weight average molecular weight (Mw) of 110,000 as a non-reactive resin.
2-vinylpyridine-styrene copolymer of (2-vinylpyridine unit: styrene unit molar ratio = 70: 30) 1
100 g of a solution (solid content 35% by weight) in which 7.5 g and 65 g of ethyl cellosolve acetate were mixed was prepared.
Thereafter, in the same manner as in Example 1, a pattern I of the fluorescence conversion film was produced (film thickness 21.3 μm).

When the organic EL element of the light emitting body and the fluorescent conversion film pattern I are overlapped, the luminance emitted from the fluorescent conversion film is 44 cd / m with respect to the luminance of 200 cd / m ² of the organic EL element.
² (conversion efficiency 22%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that red light was emitted at 0.61 and y = 0.32. That is, a fluorescent conversion film that absorbs light in the blue region and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region, and a blue color filter on a transparent substrate (with a black matrix). ), It was possible to manufacture a fluorescence conversion filter with a high resolution of 300 μm pitch and two-dimensionally separated, and it became possible to emit light of three primary colors.

Example 8 0.34 g of coumarin 6 at 0.02 mol / kg (based on solid content) as a fluorescent dye, and 2% by weight of Solvent Yellow 116 and 6% by weight of Solvent Yellow as a fluorescent pigment with respect to a benzoguanamine resin. 44 kneaded in advance (naphthalimide fluorescent pigment) in an amount of 14.6 g, which is 30% by weight with respect to the solid content, and an epoxy-based one-component thermosetting resin ink (Sericol ME manufactured by Teikoku Ink Co., Ltd.).
G, solid content 40% by weight) 85.1 g mixed solution 10
0 g (solid content 49% by weight) was prepared. This solution was screen-printed on the substrate on which the black matrix and the blue color filter of Example 4 were prepared by aligning a mask for screen printing, which gives a stripe pattern of 280 μm lines and 620 μm gaps, on the black matrix, After that, it is baked at 150 ° C. and heat-cured, and the pattern J (film thickness 7.1 μ) of the fluorescence conversion film is formed.
m). Next, as the fluorescent pigment, the above naphthalimide-based fluorescent pigment was added in an amount of 7.5% by weight based on the solid content of 7.5%.
g, and 4% by weight of basic violet 11 and 4% by weight of rhodamine 6 relative to the benzoguanamine resin.
An amount of 11.5 g of a mixture of G (rhodamine-based fluorescent pigment) which is 23% by weight based on the solid content, and polyvinyl chloride having a weight average molecular weight (Mw) of 20,000 as the non-reactive resin 31. 100 g of a solution obtained by mixing 0 g and 50 g of ethyl cellosolve acetate (solid content: 50% by weight)
Was prepared. This solution is 280 μm line 620 μm
The solution is screen-printed by aligning a screen-printing mask that provides a stripe pattern of the gap with a position adjacent to the previously formed fluorescent conversion film pattern J, and then baked at 80 ° C. to form a fluorescent conversion film pattern K ( A film thickness of 22.1 μm) was obtained.

Here, when the organic EL element of the luminous body produced in Production Example 2 and the fluorescent conversion film pattern J are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element by a color difference meter. 160 cd / m for ^2
2 (conversion efficiency 80%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that a yellowish green (yellowish green) emission was emitted at 0.28 and y = 0.62. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern K are overlapped, the luminance emitted from the fluorescent conversion film is 50 cd / m ² (conversion efficiency 25%) with respect to the luminance of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.60, y =
It was observed that red light emission was emitted at 0.31. That is, a fluorescent conversion film that absorbs light in the blue region and emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region, and a blue color filter on a transparent substrate (with a black matrix). )
In addition, it was possible to manufacture a fluorescence conversion filter with a 300 μm pitch and which was separated and arranged in a plane with high precision, and it became possible to emit light of three primary colors.

Comparative Example 1 The pattern A of the fluorescence conversion film was obtained on the substrate of Example 1 in the same manner as in Example 1. Next, as the fluorescent pigment, the above-mentioned naphthalimide-based fluorescent pigment was added in an amount of 7 g, which was 20% by weight based on the solid content, and 4% by weight based on the benzoguanamine resin.
Of basic violet 11 and 4% by weight of rhodamine 6G (rhodamine-based fluorescent pigment), which is 30% by weight based on the solid content of 10.5 g,
An acrylate-based photocurable resist (JNPC06 manufactured by Japan Synthetic Rubber Co., Ltd., solid content 38% by weight) 46.1 g and ethyl cellosolve acetate 36.4 g were mixed to prepare a solution (solid content 35% by weight) 100 g. This solution was spin-coated on the above substrate, baked at 80 ° C., and then the substrate was set in a contact type exposure machine using a high-pressure mercury lamp as a light source, and a mask on which a stripe pattern with a 280 μm line and a 620 μm gap was obtained first. 300mJ to match the position adjacent to the fluorescence conversion film pattern formed on
/ Cm ² (365 nm). Furthermore, 2.38%
After development with an aqueous solution of tetramethylammonium hydroxide, post-baking was performed at 200 ° C. to obtain a pattern L (film thickness 21.1 μm) of the fluorescence conversion film.

Here, when the organic EL element of the luminescent material produced in Production Example 1 and the fluorescent conversion film pattern A are overlapped, the luminance emitted from the fluorescent conversion film is 200 cd / m of the luminance of the organic EL element measured by a color difference meter. 184 cd / m for ^2
2 (conversion efficiency 92%) is obtained, and the CIE chromaticity coordinate is x =
It was observed that yellowish green (yellowish green) light was emitted at 0.25 and y = 0.62. On the other hand, when the organic EL element of the light emitting body and the fluorescent conversion film pattern L are overlapped, the brightness emitted from the fluorescent conversion film is 66 cd / m ² (conversion efficiency 10%) with respect to the brightness of 200 cd / m ² of the organic EL element. The obtained CIE chromaticity coordinates are x = 0.61, y =
It was observed that red light emission was emitted at 0.32. That is, a fluorescent conversion film that absorbs light in the blue region and that emits fluorescence in the green region and a fluorescent conversion film that emits fluorescence in the red region are provided on a transparent substrate (with a black matrix) at a pitch of 300 μm. We were able to produce a fluorescent conversion filter that was separated and arranged in a high-definition plane, but because a light or thermosetting resin was used for the red conversion film,
It was not possible to efficiently convert the blue light emission of the luminescent material into red light as compared with Example 1.

Comparative Example 2 Next, 0.35 g of coumarin 7 at 0.03 mol / kg (relative to solid content) was used as a fluorescent dye, and the naphthalimide-based fluorescent pigment of Example 1 was set at 30% by weight based on the solid content. And the weight average molecular weight (M
w) 24.5 g of 40,000 poly (2-vinylpyridine)
And ethyl cellosolve acetate 64.65 g were mixed to prepare a solution (solid content 35% by weight) 100 g. This solution was spin-coated on the substrate on which the black matrix and blue color filter of Example 4 were prepared,
After baking at 0 ° C., a novolak resin-naphthoquinonediazide photo-soluble resist (HPR204 manufactured by Fuji Hunt Electronics Technology Co., Ltd.) was spin-coated on the film, and baked at 80 ° C. to form a resist film. . Then, the substrate was set in a contact type exposure machine using a high-pressure mercury lamp as a light source, a mask for obtaining a stripe pattern with a 280 μm line and a 620 μm gap was aligned with a black matrix, and 100 mJ / cm 2.
^The resist film was exposed to ² (365 nm). In addition, 2.
After developing the resist film with a 38% tetramethylammonium hydroxide aqueous solution, the exposed film containing the fluorescent pigment and the non-reactive resin was etched with a 20% by weight acetic acid aqueous solution and laminated with a 2% sodium hydroxide aqueous solution. The existing resist film was peeled off. As a result, the pattern N of the fluorescence conversion film
(Film thickness 8.0 μm) was obtained.

Next, as the fluorescent pigment, the above-mentioned naphthalimide-based fluorescent pigment was added in an amount of 7 g, which was 20% by weight based on the solid content.
And 4% by weight of basic violet 11 and 4% by weight of Rhodamine 6G with respect to the benzoguanamine resin
Was mixed in advance (rhodamine-based fluorescent pigment) in an amount of 10.5 g, which is 30% by weight based on the solid content, and poly (2-vinylpyridine) having a weight average molecular weight (Mw) of 40,000 as a non-reactive resin. ) 17.5 g and ethyl cellosolve acetate 65 g were mixed to prepare a solution (solid content 35% by weight) 100 g. As a result of spin-coating this solution on the above substrate, the pattern of the fluorescence conversion film previously formed was eroded and dissolved by this solution. As a result, the desired fluorescence conversion filter could not be produced.

[0084]

Industrial Applicability The fluorescence conversion filter of the present invention is capable of efficiently converting light emitted from the light-emitting element in the blue to blue-green region into light emission in the green region or the red region in a well-balanced manner. display,
It is suitable for use in consumer and industrial display devices such as display panels and backlights. Further, according to the method for producing a fluorescence conversion filter of the present invention, the fluorescence conversion filter can be safely produced without any defect.

[Brief description of drawings]

FIG. 1 is a cross-sectional view when light emitted from a light-emitting body is transmitted through a fluorescence conversion filter of the present invention.

FIG. 2 is a cross-sectional view of a fluorescence conversion filter of the present invention in which green and red color filters are arranged.

FIG. 3 is a cross-sectional view in the case where light emitted from a light emitting body is transmitted through a fluorescence conversion filter of the present invention in which a blue color filter is arranged.

FIG. 4 is a sectional view of a fluorescence conversion filter of the present invention in which a blue color filter and a black matrix are arranged.

FIG. 5 is a cross-sectional view of the fluorescence conversion filter of the present invention in which light emitted from a light emitting body is transmitted from the transparent substrate side.

[Explanation of symbols]

 1 ... Light in the blue or blue-green range emitted from the light-emitting body 2 ... Fluorescence conversion film that emits fluorescence in the green range 3 ... Fluorescence conversion film that emits fluorescence in the red range 4 ... Green color filter 5. .. Red color filter 6 ... Blue color filter 7 ... Black matrix 10 ... Transparent substrate 11 ... Blue or blue-green light 12 ... Green light 13 ... Red light 14 ... Blue light

Claims (7)

[Claims] 1. A fluorescence conversion film that absorbs light in the blue to blue-green region emitted from a light-emitting body and emits fluorescence in the green region consisting of a fluorescent dye or fluorescent pigment and a photocurable or thermosetting resin cured product, and A fluorescent conversion filter, wherein fluorescent conversion films, each of which emits fluorescence in a red region and which is composed of a fluorescent dye or fluorescent pigment and a non-reactive resin, are two-dimensionally arranged on a transparent substrate. 2. The photocurable or thermosetting resin cured product is made of an acrylate polymer.
The described fluorescence conversion filter. 3. The non-reactive resin is a resin soluble in an alkaline aqueous solution or an acidic aqueous solution.
The described fluorescence conversion filter. 4. The fluorescence conversion filter according to claim 1, wherein the light emitting body is an organic electroluminescence element. 5. A fluorescence conversion film that absorbs light in the blue to blue-green region emitted from the light-emitting body and emits fluorescence in the green region and a fluorescence conversion film that emits fluorescence in the red region are two-dimensionally separated on a transparent substrate. In the production of a fluorescence conversion filter, which is characterized in that (1) a photo-curing type or heat solution in which a fluorescent dye or fluorescent pigment that absorbs light in the blue or blue-green region and emits fluorescence in the green region is dissolved or dispersed A step of forming a curable resist on a transparent substrate to obtain the resist film, (2) exposing the photocurable resist film through a pattern mask, and then developing it to form a photocurable resist film pattern Step, (3) a step of curing the photocurable resist film by heat treatment to form a pattern of the fluorescence conversion film,
(4) A non-reactive resin in which a fluorescent dye or fluorescent pigment that absorbs light in the blue to blue-green region and emits fluorescence in the red region is dissolved or dispersed is formed on the substrate after the above step (3). To obtain the non-reactive resin film, (5) a step of forming a photosolubilizing resist or a photocurable resist film on the non-reactive resin film, and laminating the resist film, and
(6) A step of etching the non-reactive resin film at the same time as or after forming the pattern of the resist film by exposing the photosolubilizing resist or the photocurable resist film through a pattern mask and developing the resist film, A method for producing a fluorescence conversion filter, comprising: 6. In addition to the steps (1) to (6),
(7) The method for producing a fluorescence conversion filter according to claim 5, further comprising a step of removing the photosolubilizing resist or the photocurable resist film. 7. The fluorescence conversion according to claim 5, wherein in the step (6) of etching the non-reactive resin film, the non-reactive resin film is etched by treatment with an alkaline aqueous solution or an acidic aqueous solution. Filter manufacturing method.