JP6119282B2 - Color filter and colored resist composition for white light emitting organic EL display, and white light emitting organic EL display - Google Patents

Description

  The present invention relates to a color filter and a colored resist composition for a white light emitting organic EL display, and a white light emitting organic EL display.

  Unlike a liquid crystal display that requires a light source, an EL (electroluminescence) display has attracted attention as an alternative to a liquid crystal display in that it is a self-luminous type and has good light utilization efficiency. Among various displays, white light-emitting organic EL displays have been actively developed in terms of long life, productivity, and high definition (Patent Document 1, Patent Document 2, and Patent Document 3).

Table 1 shows a liquid crystal display using a white light emitting LED (YAG system or B-RG system) as a backlight and an organic EL display (OLED) that emits three colors of red, green and blue by the organic EL element itself. Each of the three-color light emission method (also referred to as “3C-OLED”) and the white light-emitting method (also referred to as “W-OLED”) that combines a white light-emitting organic EL element and a color filter. It is a comparison of performance.
The three-color light emission method is also referred to as a three-color painting method.

  In the white light emitting LED, the YAG system is an LED that generates white light by combining a blue LED and an yttrium / aluminum / garnet phosphor, and the B-RG system includes a blue LED, a red phosphor, and a green phosphor. It is an LED that generates white light in combination.

In this specification, both an organic EL device (Organic Electroluminescence Device (or Element)) that emits white light and an organic EL display (Organic Electroluminescence Display) that enables color display by combining a color filter with a white light emitting organic EL device. Also referred to as “W-OLED”.
In addition, since organic EL is similar in structure to LED (Light Emitting Diode), it is generally called OLED (Organic Light Emitting Diode). According to this, an organic EL display is an OLED Display, and an organic EL element that is combined with a color filter to form a display is an OLED Element or an OLED Device. However, organic EL displays are also often simply referred to as OLEDs.

  As shown in Table 1, the white light emitting organic EL display (W-OLED) is superior in productivity and resolution to the three-color light emitting method (3C-OLED).

Japanese Patent No. 3366401 JP 2003-272857 A Japanese Patent No. 4590825

However, white light-emitting organic EL elements differ in the blue light emission spectrum on the short wavelength side, in contrast to the conventional cold cathode fluorescent lamp (CCFL) as a light source for liquid crystal displays or the white light-emitting LED that has recently been widely used. , Shifted to the long wavelength side.
FIG. 6 shows emission spectra of a cold cathode fluorescent lamp (CCFL), a white light emitting LED (YAG-LED), and a white light emitting organic EL element (W-OLED).
Therefore, when the conventional color filter that has been used for a liquid crystal display is applied as it is to a white light emitting organic EL element (W-OLED), the emission spectrum in the blue region of the light source, particularly in the transmission spectrum on the short wavelength side. And the amount of transmitted light in the blue region is reduced and the luminance is lowered. If the luminance is simply maintained, the decrease in luminance may be compensated by increasing the light amount of the light source, but this is not preferable because it increases power consumption. Further, even if the thickness of the color layer of the color filter is reduced or the color material concentration in the color layer is lowered, the amount of transmitted light can be increased and the luminance can be maintained, but the color density is lowered, which is not preferable. It is desirable to maintain luminance while maintaining color density.

Table 2 shows the cold-cathode tube (CCFL), white light-emitting LED (YAG-LED), and white light-emitting organic EL element (W-OLED). The chromaticity (x, y) and Y value in the CIE Yxy color system when the thickness is adjusted so as to be the same, the Y value, and the thickness of the blue colored layer are shown.
The Yxy color system is a color system based on the XYZ color system defined by JIS Z8701: 1999 (which is also the CIE 1931 XYZ color system defined by the International Commission on Illumination (CIE)).
As shown in Table 2, when the light source is a white light-emitting organic EL element (W-OLED), the x value of chromaticity (x, y) is lower and the blue color is on the cyan side than CCFL or white light-emitting LED. In addition to shifting, the Y value decreases and the luminance decreases.

  Therefore, the problem of the present invention is that the color filter and coloring resist composition for the white light emitting organic EL display, and the white light emitting organic EL display, while maintaining the color density even if the light source is a white light emitting organic EL element, This is to suppress a decrease in luminance.

  In this invention, it was set as the color filter and colored resist composition for white light emission organic EL displays of the following structures, and a white light emission organic EL display.

(1) A color filter for a white light-emitting organic EL display, wherein the colored layer of at least one color includes a triarylmethane color material and a fluorescent color material.
(2) The color filter for white light-emitting organic EL display according to (1), wherein the triarylmethane color material is a blue color material and the fluorescent color material is a rhodamine-based purple color material.
(3) A colored resist composition for a white light-emitting organic EL display, comprising a triarylmethane color material, a fluorescent color material, and a photosensitizer having sensitivity to light having a wavelength of 370 to 450 nm.
(4) A white light-emitting organic EL comprising the color filter for white light-emitting organic EL display according to (1) or (2) and a white light-emitting organic EL element that supplies white light to the color filter for white light-emitting organic EL display. display.

  According to the present invention, even in a white light emitting organic EL display, even if the light source is a white light emitting organic EL element, a decrease in luminance is suppressed while maintaining a color density as compared with a conventional cold cathode tube or white light emitting LED. be able to.

A partially enlarged cross-sectional view (a) showing an embodiment of a color filter for white light-emitting organic EL display and a white light-emitting organic EL display according to the present invention, a partially enlarged plan view (b) showing only this color filter, and a partially enlarged cross section FIG. The figure which illustrates the excitation spectrum and light emission spectrum of a rhodamine type | system | group dye. The figure which illustrates the transmission spectrum of a triphenylmethane type | system | group blue dye and a rhodamine type | system | group purple dye as a triarylmethane type | system | group color material and a fluorescent color material. The figure which compares the absorption wavelength of a photoinitiator with the absorption wavelength of a rhodamine type | system | group coloring material. The figure which shows the transmission spectrum of the blue colored layer of an Example and a comparative example. The figure which illustrates the emission spectrum of various light sources.

Hereinafter, embodiments of the present invention will be described with reference to the drawings. Note that the drawings are conceptual diagrams, and the scale relations, aspect ratios, and the like of components may be exaggerated as appropriate for convenience of explanation.

<< A >> Color filter 10 for white light-emitting organic EL display:
An embodiment of a color filter 10 for white light emitting organic EL display according to the present invention will be described.

FIG. 1 shows an embodiment of a color filter 10 for white light emitting organic EL display according to the present invention and a white light emitting organic EL display 30 according to the present invention.
1A is a partially enlarged sectional view, FIG. 1B is a partially enlarged plan view, and FIG. 1C is a partially enlarged sectional view. The partial enlarged cross-sectional views of FIGS. 1A and 1C are cross-sectional views in the thickness direction along line CC in the partial enlarged plan view of FIG. 1B.

In the color filter 10 for white light-emitting organic EL display according to the present invention, the colored layer 3 of at least one color contains a triarylmethane color material and a fluorescent color material.
The color filter 10 for white light emitting organic EL display of the embodiment illustrated in FIG. 1 includes a transparent substrate 1, a black matrix 2 formed on one surface 1p of the transparent substrate 1, and a surface of one surface 1p. It includes a colored layer 3 of three colors formed on the opening formed on the top and not having the black matrix 2 formed thereon. In the present embodiment, the colored layer 3 is composed of three colors, a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B. Of these, the blue colored layer 3B is a tria colored layer 3 as at least one colored layer 3B. The structure includes a reel methane color material and a fluorescent color material. Furthermore, in the present embodiment, a blue dye is used as the triarylmethane color material, and a rhodamine purple dye is used as the fluorescent color material.
On the other hand, the blue coloring layer 3B and the green coloring layer 3G other than the blue coloring layer 3B include the same color material as that of the conventional color filter.

  By adopting such a configuration, the color filter 10 for white light emitting organic EL display in the present embodiment is used for white light emitting organic EL display as compared with the case where a conventional cold cathode tube (CCFL) or white light emitting LED is used as a light source. Thus, a decrease in luminance can be suppressed while maintaining the blue color density of the blue colored layer 3B. As a result, in the present embodiment, a blue color having a high color density and a high luminance can be obtained.

As in the present embodiment, when the color of the colored layer 3 is composed of three colors of red, green, and blue, the color of the colored layer 3 containing the triarylmethane color material and the fluorescent color material is blue. Is preferred. This is because the triarylmethane colorant is an excellent colorant particularly for the three primary colors of blue. However, in the present invention, a triarylmethane color material may be used as a color material of a color other than blue.
This is because, in the present invention, the white light emitting organic EL display 30 is not limited to a full color display, and may be a display that displays an arbitrary mixed color of two colors, for example.

  In this embodiment, although the color of the colored layer 3 consists of three colors of red, green, and blue, in this invention, the color and the number of colors of the colored layer 3 are not limited to this. For example, in addition to the three colors red, green, and blue, there may be colors such as yellow and magenta.

The color filter 10 for white light-emitting organic EL display according to the embodiment shown in FIG. 1 further has one surface of the transparent substrate 1 on which the colored layer 3 is formed, as shown in FIGS. 1 (b) and 1 (c). The overcoat layer 4 is formed on the entire surface of the 1p surface, and the spacer 5 is formed on the overcoat layer 4 and on a part of the black matrix 2.
Thus, in this invention, the color filter 10 for white light emission organic electroluminescent displays can be set as the structure which further contains the various elements in a conventionally well-known color filter.

  Hereinafter, the color filter 10 for white light-emitting organic EL display according to the present invention will be described in detail from the triarylmethane color material and the fluorescent color material contained in the blue colored layer 3B.

《Triarylmethane colorants》
The triarylmethane-based color material determines the color of the colored layer 3, specifically the color of the blue colored layer 3B in the present embodiment, and the fluorescent color material has the color of the triarylmethane-based color material. Has a function to adjust.

Examples of triarylmethane colorants include C.I. I. Basic Blue 1, C.I. I. Basic Blue 6, C.I. I. Basic Blue 22, C.I. I. Basic Blue 75, C.I. I. Basic Blue 159;
C. I. Basic Violet 1, C.I. I. Basic Violet 3, C.I. I. Acid Violet 3, C.I. I. Acid Violet 15, C.I. I. Acid Violet 17, C.I. I. Acid Violet 24, C.I. I. Acid Violet 49;
Dyes, etc.
C. I. Pigment blue 1, C.I. I. Pigment blue 1: 2, C.I. I. Pigment blue 9, C.I. I. Pigment blue 14, C.I. I. Pigment blue 24, C.I. I. Pigment blue 56, C.I. I. Pigment blue 56: 1, C.I. I. Pigment blue 61, C.I. I. Pigment blue 61: 1, C.I. I. Pigment blue 62, C.I. I. Pigment blue 78;
C. I. Pigment green 1, C.I. I. Pigment green 2, C.I. I. Pigment green 4;
C. I. Pigment violet 3, C.I. I. Pigment violet 3: 1, C.I. I. Pigment violet 3: 3, C.I. I. Pigment violet 27, C.I. I. Pigment violet 39;
And the like.
Note that triphenylmethane dyes are included in these triarylmethane colorants.

  When the colored layer 3 containing the triarylmethane color material is the blue colored layer 3B as in the present embodiment, a blue color material is used as the triarylmethane color material. The reel methane color material is a preferable color material in that it is superior in performance to suppress a decrease in luminance while maintaining the color density as compared with the same blue conventional phthalocyanine color material. This can also be seen from the evaluation results of Comparative Example 1 (without combined use of fluorescent color material) with respect to Comparative Example 2 in Table 3 described later.

  In the present invention, the triarylmethane color material may be either a dye or a pigment. Triarylmethane colorants can be used alone or in combination of two or more of dyes and pigments.

  In the present invention, in the colored layer 3 containing the triarylmethane color material and the fluorescent color material, a known material other than the triarylmethane color material is used to adjust the color of the triarylmethane color material. These color materials may be used in combination in a mass ratio range smaller than that of the triarylmethane color material.

《Fluorescent color material》
The fluorescent color material can apparently increase the amount of transmitted light by emitting fluorescence, suppress the decrease in luminance while maintaining the color density, and adjust the color of the triarylmethane-based color material.

Examples of fluorescent color materials include rhodamine color materials such as C.I. I. Basic Violet 10 (Rhodamine B), C.I. I. Basic Violet 11, C.I. I. Basic violet 11: 1, C.I. I. Basic Violet 49, C.I. I. Acid Violet 9;
C. I. Basic Red 1 (Rhodamine 6G), C.I. I. Basic Red 1: 1, C.I. I. Basic Red 3, C.I. I. Basic Red 8, C.I. I. Basic Red 11 (Rhodamine S), C.I. I. Basic Red 108, C.I. I. Solvent red 49;
Dyes, etc.
C. I. Pigment violet 1, C.I. I. Pigment violet 1: 1, C.I. I. Pigment violet 2, C.I. I. Pigment violet 2: 2;
C. I. Pigment red 81, C.I. I. Pigment red 81: 1, C.I. I. Pigment red 81: 2, C.I. I. Pigment red 81: 3, C.I. I. Pigment red 81: 4, C.I. I. Pigment red 169, C.I. I. Pigment red 173;
And the like.

Examples of fluorescent color materials other than rhodamine color materials include:
Cyanine colorants such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran (DCM);
Pyridine-based coloring materials such as 1-ethyl-2- (4- (p-dimethylaminophenyl) -1,3-butadienyl) -pyridinium-perchlorate (pyridine 1);
Stilbene color materials such as 1,4-bis (2-methylstyryl) benzene and trans-4,4′-diphenylstilbene (DPS);
7-hydroxy-4-methylcoumarin (coumarin 4), 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidino (9,9a, 1-gh) coumarin (coumarin 153), Coumarin-based color materials such as 3- (2′-benzothiazolyl) -7-diethylaminocoumarin (coumarin 6) and 3- (2′-benzimidazolyl) -7-N, N-diethylaminocoumarin (coumarin 7);
C. I. Solvent Yellow 11, C.I. I. Naphthalimide-based colorants such as Solvent Yellow 116;
Alternatively, a perylene color material, an oxazine color material, and the like can be given.

  As the fluorescent color material, either a dye or a pigment may be used. The fluorescent color material can be used alone or in combination of two or more of dyes and pigments.

  The use amount of the fluorescent color material is preferably less than the use amount of the triarylmethane color material, for example, 5% by mass or more and less than 50% by mass, preferably 5 to 40% by mass with respect to the use amount of the triarylmethane color material. %, More preferably 10 to 30% by mass. If the use amount of the fluorescent color material is less than the above range, the combined effect of the fluorescent color material may not be sufficiently obtained. If the use amount of the fluorescent color material exceeds the above range, the fluorescent color as the auxiliary color material may be obtained. This is because it deviates from the combined effect of the materials, and the color due to the triarylmethane color material itself is impaired, and good color characteristics may not be obtained.

  FIG. 2 is a diagram illustrating an example of the excitation spectrum of a fluorescent color material in the case of a rhodamine dye. As shown in the figure, the fluorescent color material emits light having a wavelength longer than the absorbed excitation light as fluorescence. For this reason, in the transmission spectrum of the color of the colored layer 3 containing the fluorescent color material, light in a wavelength band unnecessary for the color is used as excitation light, and light in the wavelength band necessary for the color is used as emission light. As described above, by using a fluorescent color material, it is possible to transmit light that has been absorbed in the past as light in another wavelength band. As a result, it is possible to increase the amount of transmitted light and to suppress the decrease in luminance while maintaining the color density. At the same time, the color of the triarylmethane color material can be adjusted by using the fluorescent color material together.

  As in this embodiment, when a blue color material is used as the triarylmethane color material and a purple rhodamine fluorescent color material is used as the fluorescent color material, light in the absorption wavelength band of the triarylmethane color material is excited as light. As a result of light emission on the longer wavelength side than this, light that was absorbed by the triarylmethane colorant and did not contribute to luminance was effectively used as light on the longer wavelength side, and apparently transmitted light amount was reduced. It is possible to increase the luminance by that amount.

  Therefore, when the colored layer 3 containing the triarylmethane color material and the fluorescent color material is the blue colored layer 3B as in this embodiment, the blue color material is used as the triarylmethane color material, and the fluorescent color material is used as the fluorescent color material. By using a purple fluorescent color material (in this embodiment, a rhodamine dye), it is possible to suppress a decrease in luminance while maintaining a blue color density due to the triarylmethane color material.

<Combination example of triarylmethane color material and fluorescent color material>
FIG. 3 is a diagram showing an example of a transmission spectrum of each of triphenylmethane blue dye as a triarylmethane colorant and rhodamine purple dye as a fluorescent colorant. The rhodamine-based purple dye has a higher transmittance in a long wavelength region having a wavelength of 600 nm or more than the triphenylmethane-based blue dye, and as a result, exhibits a purple color. Further, the rhodamine-based purple dye has an effect of increasing the blue color density as compared with the case where the triphenylmethane-based blue dye alone is used to form the color material of the blue colored layer 3B.

<< Total content in coloring layer 3 of coloring material >>
The total content of the triarylmethane colorant and the fluorescent colorant in the colored layer 3 is, for example, 10 to 75% by mass, preferably 20 to 60% by mass, based on the total solid content of the colored layer 3. is there. If the content of the coloring material is out of the above range, good color characteristics may not be obtained.

<< Other colored layer 3 not containing a triarylmethane color material and a fluorescent color material >>
In the present invention, the colored layer 3 is a specific colored layer 3 in which at least one of the colored layers 3 includes a triarylmethane-based color material and a fluorescent color material. The triarylmethane color material and the fluorescent color material may not be included, or the triarylmethane color material and the fluorescent color material may be included.
As the configuration of the colored layer 3 that does not include the triarylmethane-based color material and the fluorescent color material, there can be the following three types of configurations.
a) A structure including a triarylmethane-based color material but not including a fluorescent color material.
b) A configuration that does not include a triarylmethane colorant but includes a fluorescent colorant.
c) A structure containing neither a triarylmethane color material nor a fluorescent color material.

The color material included in the colored layer 3 in the three types of configurations a), b), and c) is not particularly limited as to the color material other than the triarylmethane color material and the fluorescent color material. Various conventionally known color materials can be appropriately employed.
For example, color materials other than triarylmethane colorants include red pigments such as diketopyrrolopyrrole, anthraquinone and perylene, green pigments such as phthalocyanine and isoindoline, blue phthalocyanine and anthraquinone Pigments such as pigments, isoindoline-based, anthraquinone-based yellow pigments, quinacridone-based purple pigments,
Examples include dyes such as red dyes such as anthraquinone and perylene, green dyes such as phthalocyanine, and blue dyes such as methine, anthraquinone, and azo.

Furthermore, if it shows by a specific example,
C. I. Pigment blue 15: 1, C.I. I. Pigment blue 15: 6, C.I. I. Pigment blue 16;
C. I. Pigment green 7, C.I. I. Pigment green 36;
C. I. Pigment red 177, C.I. I. Pigment red 254;
C. I. Pigment violet 23, C.I. I. Pigment violet 37;
C. I. Pigment yellow 138, C.I. I. Pigment yellow 139, C.I. I. Pigment yellow 150;
Etc.

<< Formation Method of Colored Layer 3 >>
The formation method of the colored layer 3 containing a triarylmethane color material and a fluorescent color material and the colored layer 3 not containing a triarylmethane color material and a fluorescent color material are not particularly limited, and a known formation method is appropriately selected. Can be adopted. Any colored layer 3 can be formed of a colored resist composition containing a coloring material, a binder resin, and a solvent. When the colored resist composition is photosensitive, the colored resist composition further contains a photosensitizer and can be formed by a photolithography method. On the other hand, when the colored resist composition is not photosensitive, the photosensitive agent can be omitted and can be formed by a printing method such as an inkjet method.
The thickness of the colored layer 3 is, for example, 1 to 6 μm.

  About the colored layer 3 containing a triarylmethane type | system | group coloring material and a fluorescent coloring material, it can form suitably with the coloring resist composition for white light emission organic EL displays by this invention mentioned later.

<< Black Matrix 2 >>
A known material and a forming method can be employed for the black matrix 2. For example, a metal material such as chromium or a chromium compound, or a resin resist containing a photosensitive resin and a black color material can be used. In the case of chromium, the black matrix 2 is formed by forming a chromium thin film on the entire surface of the transparent substrate 1 by vapor deposition, applying a resin resist, exposing and developing, and then removing unnecessary chromium thin film by etching. Can do.
The plan view shape of the black matrix 2 is not limited to the shape shown in FIG. It can take various known shapes.

  As the resin resist, a resist containing a black color material such as carbon black or titanium black and a photosensitive resin can be used. The resin resist may be either a negative type or a positive type. In the case of a negative type, it is possible to use a negative type colored resist composition, which will be described later, in which the color material is changed to a black color material. In the case of the positive type, it is possible to use a positive type colored resist composition, which will be described later, in which the color material is changed to a black color material.

<< Transparent substrate 1 >>
A known material can be used for the transparent substrate 1. For example, as a material of the transparent substrate 1, in addition to an inorganic material such as glass or quartz, a resin can be used. Examples of the resin include a polyester resin, an acrylic resin, and a polycarbonate resin.

<< Other constituent layers; overcoat layer 4, spacer 5, etc. >>
In the present invention, the color filter 10 for white light-emitting organic EL display can further include other components known in the color filter, in addition to the transparent substrate 1, the black matrix 2, and the colored layer 3 described above. For example, the overcoat layer 4, the spacer 5, the transparent conductive layer, and the like.

  In the embodiment illustrated in FIGS. 1A and 1C, the overcoat layer 4 and the spacer 5 are provided. About the overcoat layer 4 and the spacer 5, it can form with a well-known material and a formation method. For example, the overcoat layer 4 and the spacer 5 can be formed by a photolithography method using a transparent resist composition containing a transparent photosensitive resin.

<< B >> Colored resist composition for white light-emitting organic EL display:
The colored resist composition for white light-emitting organic EL display according to the present invention is a photosensitive resin composition containing a triarylmethane colorant, a fluorescent colorant, and a photosensitive agent sensitive to light having a wavelength of 370 to 450 nm. .

  Hereinafter, the “colored resist composition for white light-emitting organic EL display” may be simply referred to as “colored resist composition”.

  The colored resist composition according to the present invention may be either a negative type or a positive type. In the negative type, the unexposed part is removed by development, and the exposed part remains after development, and becomes the colored layer 3. In the positive type, the exposed portion is removed by development, and the unexposed portion remains after development, and becomes the colored layer 3.

  Furthermore, the colored resist composition according to the present invention may include a binder resin, a solvent, an additive, and the like. Among the constituent components of the colored resist composition according to the present invention, among the binder resin and the photosensitizing agent, the photosensitizing agent is used properly depending on whether it is a negative type or a positive type.

  Hereinafter, the components of the colored resist composition for white light-emitting organic EL display will be described in the case of the negative type, and then the case of the positive type will be described.

《Coloring material》
The triarylmethane color material, the fluorescent color material, and other color materials, which are the color materials contained in the colored resist composition according to the present invention as essential components, have already been described above, and a description thereof will be omitted.

<Binder resin>
When the colored resist composition according to the present invention is a negative type, the binder resin usually contains a photopolymerizable compound such as a monomer and a prepolymer, and a polymer.

In the present invention, the binder resin for the colored resist composition includes a photopolymerizable compound such as a monomer before becoming a polymer. When the binder resin is referred to after the colored layer 3 is formed, the photopolymerizable compound such as a monomer is polymerized into a polymer.
In the colored resist composition, a “resin binder” is a mixture of a binder resin, a solvent, a photosensitizer, an additive, and the like, which are constituents other than the color material. That is, the “resin binder” is a composition that includes at least a binder resin that is a component other than a color material, and may further include various additives such as a solvent, a photosensitive agent, and a dispersant.
Therefore, the “resin binder” in the present invention contains a coloring material and a specific photosensitive agent as essential components.

<Photopolymerizable compound>
As the photopolymerizable compound, one or more compounds of monomers and prepolymers can be used. Here, the prepolymer means a polymer having a plurality of repeating structural units and having photopolymerizability. Although some monomers include a plurality of repeating structural units, here, the prepolymer is a compound having a molecular weight of 2000 or more. An oligomer is also a compound containing a plurality of repeating structural units, but in the present invention, it is classified into either the above monomer or prepolymer according to its molecular weight.

〔monomer〕
Examples of the monomer include, for example, allyl acrylate, benzyl acrylate, butoxyethyl acrylate, butoxyethylene glycol acrylate, cyclohexyl acrylate, dicyclopentanyl acrylate, 2-ethylhexyl acrylate, glycerol acrylate, glycidyl acrylate, and 2-hydroxyethyl. Acrylate, 2-hydroxypropyl acrylate, isobornyl acrylate, isodexyl acrylate, isooctyl acrylate, lauryl acrylate, 2-methoxyethyl acrylate, methoxyethylene glycol acrylate, phenoxyethyl acrylate, stearyl acrylate, phenol-ethylene oxide modified acrylate, Phenol-propylene oxa De-modified acrylate, tetrahydrofurfuryl acrylate, dicyclopentenyl acrylate, dicyclopentenyl oxyethyl acrylate;
Among the bifunctional monomers, ethylene glycol diacrylate, diethylene glycol diacrylate, 1,3-propanediol acrylate, 3-butanediol diacrylate, 1,4-butanediol diacrylate, 1,5-pentanediol diacrylate, 1,6 -Hexanediol diacrylate, 1,10-decanediol diacrylate, 1,4-cyclohexanediol diacrylate, 2,2-dimethylolpropane diacrylate, glycerol diacrylate, butylene glycol diacrylate, neopentyl glycol diacrylate, tetra Ethylene glycol diacrylate, triethylene glycol diacrylate, tripropylene glycol diacrylate, polyethylene glycol diacrylate, Polypropylene glycol diacrylate, bisphenol A- ethylene oxide-modified diacrylate, 2,2,4-trimethyl-1,3-pentanediol diacrylate, pentaerythritol diacrylate monostearate, hydroxypivalic acid ester neopentyl glycol diacrylate;
For three monofunctional monomers, glycerol triacrylate, trimethylolpropane triacrylate, 1,2,4-butanetriol triacrylate;
Polyoxyethylated trimethylolpropane triacrylate, pentaerythritol triacrylate, polyoxypropyltrimethylolpropane triacrylate, trimethylolpropane ethylene oxide modified triacrylate, trimethylolpropane propylene oxide modified triacrylate, isocyanuric acid ethylene oxide modified triacrylate ;
4 For monofunctional or higher polyfunctional monomers, pentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate;
Acrylate monomers such as
And a monomer in which an acrylate group in the monomer is substituted with a methacrylate group;
Or diallyl fumarate, N-vinyl-2-pyrrolidone (1-vinyl-2-pyrrolidone), 2-hydroxyethylacryloyl phosphate, γ-methacryloxypropyltrimethoxysilane,
And other monomers.

  The content of the monomer is, for example, 1 to 40% by mass with respect to the total solid content of the colored resist composition.

[Prepolymer]
Examples of the prepolymer include a urethane acrylate prepolymer, a polyester acrylate prepolymer, an epoxy acrylate prepolymer, and a compound in which an acrylate group in these compounds is substituted with a methacrylate group.
The content of the prepolymer is, for example, 1 to 40% by mass with respect to the total solid content of the colored resist composition.

<Polymer>
Examples of the polymer include ethylene-vinyl acetate copolymer, ethylene-vinyl chloride copolymer, ethylene-vinyl alcohol copolymer, polystyrene, acrylonitrile-styrene copolymer, ABS resin (acrylonitrile-butadiene-styrene copolymer). ), Polymethacrylic acid resin, ethylene-methacrylic acid copolymer, vinyl chloride resin, chlorinated vinyl chloride resin, polyvinyl alcohol, cellulose acetate propionate, cellulose acetate butyrate, nylon (registered trademark) 6, nylon (registered trademark) ) 66, nylon (registered trademark) 12, polyethylene terephthalate, polybutylene terephthalate, polycarbonate, polyvinyl acetal, polyether ether ketone, polyether sulfone, polyphenylene sulfide Polyarylate, polyvinyl butyral, epoxy resins, phenoxy resins, polyimide resins, polyamide-imide resins, polyamic acid resins, polyether imide resins, phenolic resins, urea resins, and the like.

Moreover, as a polymer, as a copolymer,
Methyl acrylate, ethyl acrylate, n-propyl acrylate, isopropyl acrylate, sec-butyl acrylate, isobutyl acrylate, tert-butyl acrylate, n-pentyl acrylate, n-hexyl acrylate, 2-ethylhexyl acrylate, n-octyl acrylate, n-decyl One or more of acrylate, 2-hydroxyethyl acrylate, glycidyl acrylate, benzyl acrylate, styrene, α-methyl styrene, N-vinyl-2-pyrrolidone, and monomers obtained by substituting acrylate groups in these acrylate monomers with methacrylate groups A monomer of
Examples thereof include acrylic acid, methacrylic acid, a dimer of acrylic acid, itaconic acid, crotonic acid, maleic acid, fumaric acid, vinyl acetic acid, and copolymers with one or more of these acid anhydrides.

  Among them, a typical polymer is an alkali-soluble resin that is soluble in an alkaline developer at least during development after exposure. Examples of the alkali-soluble resin include a resin having a carboxyl group, and specific examples include methacrylic acid ester copolymers such as benzyl methacrylate-methacrylic acid copolymer.

  The content of the polymer is, for example, 1 to 40% by mass with respect to the total solid content of the colored resist composition.

"solvent"
Examples of the solvent include alcohols such as methanol, ethanol, n-propanol, isopropanol, ethylene glycol and propylene glycol, terpenes such as α- or β-terpineol, acetone, methyl ethyl ketone, cyclohexanone, N-methyl-2- Ketones such as pyrrolidone, aromatic hydrocarbons such as toluene, xylene, tetramethylbenzene, cellosolve, methyl cellosolve, ethyl cellosolve, carbitol, methyl carbitol, ethyl carbitol, butyl carbitol, propylene glycol monomethyl ether, propylene Glycol monoethyl ether, dipropylene glycol monomethyl ether, dipropylene glycol monoethyl ether, triethylene glycol monomethyl ether, Glycol ethers such as reethylene glycol monoethyl ether, ethyl acetate, butyl acetate, cellosolve acetate, ethyl cellosolve acetate, butyl cellosolve acetate, carbitol acetate, ethyl carbitol acetate, butyl carbitol acetate, propylene glycol monomethyl ether acetate, propylene glycol mono Examples thereof include acetates such as ethyl ether acetate and 3-methoxybutyl acetate.

  Among them, representative ones are 3-trimethoxybutyl acetate (MBA), propylene glycol monomethyl ether acetate (PGMEA), diethylene glycol dimethyl ether (DMDG), diethylene glycol methyl ethyl ether and the like.

  The content of the solvent is, for example, 20 to 90% by mass with respect to the total amount (including the solvent) of the colored resist composition.

<Sensitive agent>
When the colored resist composition is a negative type, a photopolymerization initiator is used as a photosensitive agent. Photopolymerization with a photopolymerization initiator means that a polymerization reaction occurs upon irradiation with energy rays such as visible light, ultraviolet rays, electron beams, and X-rays. The polymerization reaction is not particularly limited, such as radical polymerization, cationic polymerization, and anionic polymerization, but radical polymerization is common.
As the energy ray, ultraviolet rays are usually used, and visible light is also used. In particular, when using a color material that also absorbs in the ultraviolet region and may impair the sensitivity of the photopolymerization initiator, a photosensitizer having sensitivity in the visible light region with little overlap with the absorption band of the color material is preferable. .
In addition, when using an electron beam and X-ray | X_line, a photoinitiator can be abbreviate | omitted.

  In the present invention, the “photosensitive agent” includes a “photosensitive agent system” composed of a combination of a plurality of compounds including a sensitizer. Therefore, the colored resist composition may contain a sensitizer. For example, in the case of radical polymerization, the sensitizer does not initiate radical polymerization by itself generating radicals, but a photopolymerization initiator that can generate radicals and initiate radical polymerization (radical generator). In contrast, the compound is capable of initiating photopolymerization by transferring light energy. For this reason, the sensitizer absorbs light on the long wavelength side that cannot be absorbed by the photopolymerization initiator, and the photopolymerization initiator can start photopolymerization by this sensitizer.

(Photopolymerization initiator)
Examples of the photopolymerization initiator include diethoxyacetophenone, 4- (2-hydroxyethoxy) phenyl- (2-hydroxy-2-propyl) ketone, 2-hydroxy-2-methyl-1-phenylpropan-1-one 1-hydroxycyclohexyl-phenyl ketone, 1- (4-isopropylphenyl) -2-hydroxy-2-methylpropan-1-one, 2-methyl-2-morpholino (4-thiomethylphenyl) propan-1-one Acetophenone compounds such as 2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone;
Benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, benzoin isobutyl ether, benzyl dimethyl ketal;
Benzophenone, 4,4′-dichlorobenzophenone, 3,3 ′, 4,4′-tetra (t-butylperoxycarbonyl) benzophenone, methyl o-benzoylbenzoate, hydroxybenzophenone, Michler's ketone (4,4′-dimethylamino) Benzophenone), 4-phenylbenzophenone, 4-benzoyl-4′-methyl-diphenyl sulfide, 4,4′-diethylaminobenzophenone, 4,4′-dichlorobenzophenone, alkylated benzophenone, and the like;
Ketone compounds such as 2-ethylanthraquinone, 9,10-phenanthrenequinone, camphorquinone, α-acyloxime ester (1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime);
2,2,2-trichloro [1,4 ′-(1,1-dimethylethyl) phenyl] ethanone, 2,2-dichloro-1,4- (phenoxyphenol) ethanone, α, α, α-tribromo Halogen compounds such as methylphenylsulfone;
2,4,6-tris (trichloromethyl) -triazine, 2,4-trichloromethyl- (4'-methoxyphenyl) -6-triazine, 2,4-trichloromethyl- (1 ', 3'-dioxo-5 Trichloromethyltriazine compounds such as' -indanyl) -6-triazine, 2,4-trichloromethyl- (4'-methoxystyryl) -6-triazine;
Acylphosphine oxides such as 2,4,6-trimethylbenzoyldiphenylphosphine oxide, bis (2,4,6-trimethylbenzoyl) -phenylphosphine oxide (manufactured by BASF Japan, LUCIRIN (registered trademark) TPO) Compounds;
1.2-octanedione, 1- [4- (phenylthio)-, 2- (O-benzoyloxime)] (BASF Japan, Irgacure (registered trademark) OXE 01), ethanone, 1- [9-ethyl Oxime ester compounds such as -6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (manufactured by BASF Japan Ltd., Irgacure (registered trademark) OXE 02) ;
Iron arene complex compounds such as Irgacure (registered trademark) 261 manufactured by BASF Japan Ltd .;
Bis (η5-2,4-cyclopentadien-1-yl) -bis (2,6-difluoro-3- (1H-pyrrol-1-yl) -phenyl) titanium (manufactured by BASF Japan Ltd., Irgacure (registered trademark) ) 784) titanocene compounds;
Diphenyl sulfide compounds such as Optomer (ADEKA, registered trademark) SP150 and Optomer (ADEKA, registered trademark) SP170;
10-butyl-2-chloroacridone, 9-phenylacridine and the like.

Furthermore, if a photoinitiator is mentioned by a commercial item, it will be Irgacure (BASF Japan Ltd., registered trademark) 2959 (1- [4- (2-hydroxyethoxy) -phenyl] -2-hydroxy which is a hydroxyalkyl phenone series. -2-methyl-1-propan-1-one),
Irgacure (BASF Japan K.K., registered trademark) 907 (2-methyl-1- (4-methylthiophenyl) -2-morpholinopropan-1-one), Irgacure (BASF Japan K.K. Registered trademark) 369 (2-benzyl-2-dimethylamino-1- (4-morpholinophenyl) -butanone-1),
And so on.

  Content of a photoinitiator is 1-20 mass% with respect to solid content whole quantity of a colored resist composition, for example, Preferably it is 5-10 mass%.

[Suitable photopolymerization initiator]
Among the various photopolymerization initiators, in the colored resist composition according to the present invention, it is preferable that the absorption band of the photopolymerization initiator is as small as possible with the absorption band of the coloring material to be added.
For example, when a rhodamine-based color material is used as the fluorescent color material, it may have absorption in the ultraviolet region with a wavelength of 400 nm or less, as in the excitation spectrum illustrated in FIG.
However, this excitation spectrum has little absorption in the visible light region near the wavelength of 400 to 450 nm.
For this reason, when using such a coloring material, it is preferable that the photopolymerization initiator has sensitivity to light having a wavelength of 370 to 450 nm.
Here, having sensitivity to light having a wavelength of 370 to 450 nm means that photopolymerization can be initiated by light within a wavelength range of 370 to 450 nm.

More specifically, the meaning of having a sensitivity is such that the molar extinction coefficient [L / (mol · cm)] is 100 or more, preferably 400 or more, more preferably 1000 with respect to light in the wavelength range of 370 to 450 nm. The above can be shown. Therefore, the molar extinction coefficient need not be equal to or greater than the above value at all wavelengths within the wavelength range of 370 to 450 nm. Of course, it is preferable that the molar extinction coefficient is not less than the above value at all wavelengths within the wavelength range of 370 to 450 nm.
As the molar extinction coefficient, a measured value when ethyl acetate is used as a solvent for dissolving the photopolymerizable compound can be adopted.

Here, FIG. 4 is a diagram comparing the absorption spectrum of the photopolymerization initiator with the excitation spectrum R of the rhodamine-based fluorescent color material.
In the figure, A, B, C, D, E, and F are absorption spectra of general photopolymerization initiators, and are examples that do not have sufficient sensitivity at wavelengths of 370 to 450 nm. For example, F is the absorption spectrum of Irgacure (BASF Japan Ltd., registered trademark) 184. C is the absorption spectrum of Irgacure (BASF Japan Ltd., registered trademark) 907.
On the other hand, the absorption spectrum G is an example having sensitivity at a wavelength of 370 to 450 nm.

As described above, it is preferable that ultraviolet rays have sensitivity on the long wavelength side, and those having sensitivity to visible light are preferable.
Note that having sensitivity to light with a wavelength of 370 to 450 nm means having sensitivity to at least light in this range, and may have sensitivity to light outside this range.
Moreover, if it is a photoinitiator which has a sensitivity also in the visible light region to wavelength 400-450 nm, even when the sensitivity in an ultraviolet region is inhibited, photopolymerization can be started.

  Examples of such photopolymerization initiators sensitive to light having a wavelength of 370 to 450 nm include acylphosphine oxide compounds, oxime ester compounds, iron arene complex compounds, titanocenes among the above-mentioned photopolymerization initiators. Such a compound is a preferred photopolymerization initiator.

"Additive"
The colored resist composition according to the present invention can contain various additives. As the additive, known ones can be used, and examples thereof include a dispersant, an antioxidant, a stabilizer, and an adhesion improver.

<< When the colored resist composition is positive type >>
It has already been mentioned that the colored resist composition according to the present invention may be positive. Even when the colored resist composition is a positive type, the colored resist composition includes a triarylmethane colorant, a fluorescent colorant, and a photosensitive agent sensitive to light having a wavelength of 370 to 450 nm. Resins, solvents, additives and the like can be included.

  Since the color material and the solvent are the same as those of the negative type, description thereof will be omitted, and materials specific to the positive type will be described below.

<< Positive binder resin >>
An alkali-soluble resin can be used as the binder resin.

<Alkali-soluble resin>
The alkali-soluble resin is not particularly limited as long as it is a resin that is soluble in an alkaline developer and has film-forming properties at least during development after exposure.
Examples of the alkali-soluble resin include a resin having a phenolic hydroxyl group and a resin having a carboxyl group.
Examples of the resin having a phenolic hydroxyl group include a phenol resin, a novolak resin, or a copolymer of hydroxystyrene and p-acetomethoxystyrene, which is a resin having a hydroxystyrene repeating unit.
As resin which has a carboxyl group, an acrylic acid copolymer, a methacrylic acid copolymer, a maleic acid copolymer etc. are mentioned, for example.

<Positive photosensitizer>
In the present invention, a positive-type photosensitive agent is a photosensitive agent having sensitivity to light having a wavelength of 370 to 450 nm.
Here, “having sensitivity” is the same as that described for the photopolymerization initiator in the negative type.
In the positive type, a quinonediazide compound, a photoacid generator, a photobase generator and the like can be used as the photosensitizer.

Examples of the quinonediazide compound include o-naphthoquinonediazide-4-sulfonic acid ester and o-naphthoquinonediazide-5-sulfonic acid ester. The quinonediazide sulfonate ester component includes, for example, 2,2-bis (4-hydroxyphenyl) propane and a bisphenol A derivative obtained by adding a hydroxyl group to the phenyl group, 1,1,1-tri (4-hydroxyphenyl) Examples include ethane and compounds obtained by adding a hydroxyl group to the phenyl group.
Content of a quinonediazide compound is 5-50 mass% with respect to alkali-soluble resin, for example.

Examples of the photoacid generator include onium salts, halogen-containing compounds, diazomethane compounds, sulfone compounds, sulfonic acid ester compounds, sulfonimide compounds, and diazo ketone compounds. Specifically, for example, 2-benzoylmethylene-3-methylnaphtho (1 · 2 · d) thiazoline, 1-phenyl-1,2-propanedione-2- (o-ethoxycarbonyl) oxime, 3,6-bis (2-methyl-2-morpholinopropanol) -9-butylcarbazole, and the like.
Content of a photo-acid generator is 1-30 mass% with respect to alkali-soluble resin, for example.

Examples of the photobase generator include transition metal complexes, orthonitrobenzyl carbamates, α, α-dimethyl-3,5-dimethoxybenzyl carbamates, acyloxyiminos and the like.
Content of a photobase generator is 1-30 mass% with respect to alkali-soluble resin, for example.

<Suitable photosensitizer>
As such a positive photosensitive agent having sensitivity to light having a wavelength of 370 to 450 nm, a quinonediazide compound is a preferable photosensitive agent among the above-described photosensitive agents.

《Curing agent》
In the positive coloring resist composition, a melamine resin, an epoxy compound, a novolac resin, an oxetane compound, an alkoxide compound, or the like can be contained as a curing agent. The resolution, thermosetting property, heat resistance and the like can be improved by the curing agent. For example, examples of the melamine resin include hexamethoxymethylol melamine.
Content of a hardening | curing agent is 5-50 mass% with respect to alkali-soluble resin, for example.

<< C >> White light emitting organic EL display:
A white light-emitting organic EL display according to the present invention includes an organic color display for white light-emitting organic EL display according to the present invention described above and a white light-emitting organic EL element that supplies white light to the color filter for white light-emitting organic EL display. It is an EL display.

  According to the present invention, by including the color filter 10 for white light emitting organic EL display according to the present invention described above as the color filter, even if the light source is a white light emitting organic EL element, a conventional cold cathode tube or white light emitting device can be used. As compared with the LED, it is possible to suppress a decrease in luminance while maintaining the color density.

  Hereinafter, the components of the white light emitting organic EL display according to the present invention will be described with reference to the embodiment shown in FIG.

A white light emitting organic EL display 30 illustrated in FIG. 1A includes a white light emitting organic EL display color filter 10 and a white light emitting organic EL element 20 that supplies white light to the white light emitting organic EL display color filter 10. With.
The color filter 10 for white light-emitting organic EL display has a colored layer 3 composed of three colors of a red colored layer 3R, a green colored layer 3G, and a blue colored layer 3B. Of these, the blue colored layer 3B is included in the present invention. It contains a triarylmethane color material and a fluorescent color material, which are characteristic color materials.
In the white light emitting organic EL element 20, each white light from the plurality of white organic light emitting layers 21 arranged corresponding to the red colored layer 3R, the green colored layer 3G, and the blue colored layer 3B is colored in the red color. By being supplied to and transmitted through each of the layer 3R, the green coloring layer 3G, and the blue coloring layer 3B, a full color image display is possible by mixing three colors of red, green, and blue.

<< Color filter 10 for white light emitting organic EL display >>
Since the white light emitting organic EL display color filter 10 has already been described above, further description is omitted.

<< White Light-Emitting Organic EL Element 20 >>
As the white light-emitting organic EL element 20, a known element can be used as long as a plurality of white organic light-emitting layers 21 that emit white light are arranged in a plane.
The white light-emitting organic EL element 20 is normally further laminated with a substrate 22 supporting the white organic light-emitting layer 21, a back electrode layer 23 that sandwiches the white organic light-emitting layer 21, and applies a voltage to the white organic light-emitting layer 21. It has an electrode layer 24, an insulating layer 25 that insulates them from each other, a transparent protective layer 26 that protects them, and can also have an electron transport layer, a hole transport layer, a hole injection layer, and the like.

<White organic light emitting layer 21>
As the white organic light emitting layer 21, for example,
a) one that emits white light by laminating a plurality of light emitting layers emitting different colors,
b) a single layer that emits white light,
Is mentioned.
In a) above
a-1) Stacking a red light-emitting layer, a green light-emitting layer, and a blue light-emitting layer to emit white light by mixing colors of light emitted from these layers,
a-2) Two layers of light-emitting layers whose emission colors are complementary to each other, for example, a layer in which a blue light-emitting layer and a yellow light-emitting layer are laminated to emit white light by color mixture of these light-emitting colors,
and so on.

  Examples of the material constituting the white organic light-emitting layer 21 usually include a dye-based light-emitting material, a metal complex-based light-emitting material, and a polymer-based light-emitting material.

  Examples of dye-based light emitting materials include cyclopentadiene derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine rings Examples thereof include compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, trifumanylamine derivatives, coumarin derivatives, oxadiazole dimers, pyrazoline dimers, and the like.

  Metal complex light emitting materials include aluminum quinolinol complex, benzoquinolinol beryllium complex, benzoxazole zinc complex, benzothiazole zinc complex, azomethyl zinc complex, porphyrin zinc complex, europium complex, iridium metal complex, platinum metal complex, etc. , Al, Zn, Be, Ir, Pt, etc., or a metal complex having a rare earth metal such as Tb, Eu, Dy, etc., and having an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, quinoline structure, etc. as a ligand Etc.

  Polymeric light-emitting materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyvinylcarbazole, polyfluorenone derivatives, polyfluorene derivatives, polyquinoxaline derivatives, polydialkylfluorene derivatives, and those And the like.

<Substrate 22>
As the substrate 22, an opaque metal material such as aluminum or the materials listed in the transparent substrate 1 in the color filter 10 for white light emitting organic EL display described above can be used.

<Back electrode layer 23, transparent electrode layer 24, insulating layer 25, protective layer 26>
For each of the back electrode layer 23, the transparent electrode layer 24, the insulating layer 25, and the protective layer 26, known materials and forming methods can be appropriately employed.
For example, as the back electrode layer 23, an alloy of magnesium and silver, an alloy of magnesium and aluminum, or the like can be used.
As the transparent electrode layer 24, indium tin oxide (ITO), zinc oxide, or the like can be used.
As the insulating layer 25, a transparent resist using a photosensitive resin, an inorganic material, or the like can be used.
As the protective layer 26, a transparent resist using a photosensitive resin, an inorganic material, or the like can be used.

<< Adhesive layer 31 >>
The adhesive layer 31 is a layer that adheres and laminates the color filter 10 for white light emitting organic EL display and the white light emitting organic EL element 20. Known materials and forming methods can be employed for the adhesive layer 31. For example, it can be formed by applying a photosensitive resin composition such as an acrylate or epoxy resin.

<Other components>
In addition to this, the white light emitting organic EL display 30 may include a drive circuit, a housing, and the like according to applications.

<Deformation>
In the white light emitting organic EL display 30 of the embodiment illustrated in FIG. 1, the white light emitting organic EL display color filter 10 has a transparent substrate 1, and the black matrix 2 and the colored layer 3 are formed on the transparent substrate 1. The white light-emitting organic EL element 20 has a substrate 22 that is separate from the transparent substrate 1, and the white organic light-emitting layer 21 is a form example formed on the substrate 22. However, in the present invention, the white light-emitting organic EL display color filter 10 and the white light-emitting organic EL element 20 share a substrate. For example, the black matrix 2 and the coloring are formed on the substrate 22 of the white light-emitting organic EL element 20. For example, the layer 3 may be formed.

<< D >> Usage:
The use of the color filter 10 for white light emitting organic EL display according to the present invention is for a white light emitting organic EL display.
The application of the white light emitting organic EL display 30 according to the present invention is not particularly limited. For example, a mobile phone such as a smartphone, a portable information terminal such as a tablet computer, an electronic book terminal, a personal computer, a monitor display, a digital camera, a digital photo frame, and the like.

  Hereinafter, the present invention will be described in more detail by way of examples and comparative examples.

<Synthesis of alkali-soluble resin as binder resin>
In a polymerization tank, 63 parts by mass of methyl methacrylate, 12 parts by mass of acrylic acid, 6 parts by mass of 2-hydroxyethyl methacrylate, and 88 parts by mass of diethylene glycol dimethyl ether were charged and dissolved by stirring. Thereafter, 2,2′-azobisisobutyronitrile was added to 7
Mass parts were added and dissolved uniformly. Then, it stirred at 85 degreeC under nitrogen stream for 2 hours, and also was made to react at 100 degreeC for 1 hour. The resulting solution was further added with 7 parts by mass of glycidyl methacrylate, 0.4 parts by mass of triethylamine, and 0.2 parts by mass of hydroquinone, stirred at 100 ° C. for 5 hours, and reacted to obtain an acrylic copolymer. Resin solution A (solid content 50%) containing an alkali-soluble resin consisting of

<Preparation of resin binder solution>
Next, using the resin solution A, the following materials were mixed at room temperature to prepare a resin binder solution for containing a coloring material.

(Resin binder solution)
Resin solution A (solid content 50%) 16 parts by mass Dipentaerythritol pentaacrylate 24 parts by mass (trade name SR399, manufactured by Sartomer, USA)
Orthocresol novolac-type epoxy resin 4 parts by mass (Oilized Shell Epoxy Co., Ltd., Epicoat (registered trademark) 180S70)
Photosensitizer (photopolymerization initiator) 4 parts by mass (ethanone, 1- [9-ethyl-6- (2-methylbenzoyl) -9H-carbazol-3-yl]-, 1- (0-acetyloxime) (BASF Irgacure (registered trademark) OXE 02) manufactured by Japan
Solvent (diethylene glycol dimethyl ether) 52 parts by mass

<Example 1>
The following colored resist composition for blue was prepared using the resin binder solution obtained above.

[Blue colored resist composition]
Triarylmethane-based color material: Blue dye (CI Basic Blue 1) 24 parts by mass Fluorescent color material: Rhodamine-based purple dye (CI Acid Violet 9) 6 parts by mass The above resin binder solution 300 parts by mass Dispersion 500 parts by weight of agent (Bicchemy Japan, DISPERBYK (registered trademark) 2000)
Solvent (3-methoxybutyl acetate) 2500 parts by mass

After the alkali-free glass (1737 material manufactured by Corning, USA) is washed as the transparent substrate 1, the blue colored layer 3B is formed on the transparent substrate 1 in the following manner using the above-described blue colored resist composition. Formed.
That is, the blue colored resist composition is applied onto the transparent substrate 1 by a spin coating method to form a blue resist layer on the entire surface, and then pre-baked (at 80 ° C. for 5 minutes) to form a photomask having a predetermined pattern. Used to expose UV light.
Next, spray development with a 0.1% KOH aqueous solution was performed for 60 seconds, and then post-baked (at 230 ° C. for 25 minutes) to prepare a blue colored layer 3B for evaluation.

<Example 2>
In Example 1, the blue colored layer 3B for evaluation was changed in the same manner as in Example 1 except that the blue colored resist composition was changed to the following contents in which the ratio of the rhodamine colorant was doubled. Produced.

[Blue colored resist composition]
Triarylmethane colorant: Blue dye (CI Basic Blue 1) 18 parts by weight Fluorescent colorant: Rhodamine-based purple dye (CI Acid Violet 9) 12 parts by weight The above resin binder solution 300 parts by weight Dispersion 500 parts by weight of agent (Bicchemy Japan, DISPERBYK (registered trademark) 2000)
Solvent (3-methoxybutyl acetate) 2500 parts by mass

<Comparative Example 1>
In Example 1, a blue colored layer 3B for evaluation was produced in the same manner as in Example 1 except that the blue colored resist composition was changed to the following contents in which the mixing of the rhodamine color material was omitted.

[Blue colored resist composition]
Triarylmethane-based colorant: Blue dye (CI Basic Blue 1) 30 parts by mass The above resin binder solution 300 parts by mass Dispersant 500 parts by mass (Bicchemy Japan, DISPERBYK (registered trademark) 2000)
Solvent (3-methoxybutyl acetate) 2500 parts by mass

<Comparative example 2>
Example 1 is the same as Example 1 except that the triarylmethane colorant is changed to a phthalocyanine colorant and the rhodamine colorant composition is omitted as the blue colored resist composition. In the same manner, a blue colored layer 3B for evaluation was produced.

[Blue colored resist composition]
Phthalocyanine-based color material (blue pigment, CI pigment blue 15: 6) 30 parts by mass The above resin binder solution 300 parts by mass Dispersant 500 parts by mass (manufactured by Big Chemie Japan, DISPERBYK (registered trademark) 2000)
Solvent (3-methoxybutyl acetate) 2500 parts by mass

<Performance evaluation>
The transmission spectrum of each blue colored layer 3B obtained above is shown in FIG. 5, and the chromaticity and luminance are shown in Table 3.
The measurement was performed with a microscopic spectrophotometer OSP-SP200 (manufactured by Olympus Corporation) using a standard light source C by the International Illumination Commission CIE as a light source and measuring the transmitted light transmitted through the blue colored layer 3B in each sample. First, chromaticity x and y in the CIE Yxy color system and Y [%] corresponding to luminance are obtained. Next, from this measurement result, the transmittance for each wavelength when a white light emitting organic EL element is used instead of the standard light source C is calculated using the emission spectrum of the white light emitting organic EL element. Thus, the chromaticity (x, y) in the CIE Yxy color system when the light source is a white light-emitting organic EL element, and Y [%] corresponding to the luminance were obtained.

  The Yxy color system is a color system based on the XYZ color system defined by JIS Z8701: 1999 (which is also the CIE 1931 XYZ color system defined by the International Commission on Illumination (CIE)).

Comparative Example 2 using a conventional phthalocyanine-based color material as a blue color material is a reference for luminance. In Comparative Example 2, a Y value of 3.7% when the light source is W-OLED is improved by 1. 00.
Further, in order to make the color density the same level, as shown in Table 3, each of the example and the comparative example has the same value of the chromaticity (x, y) so that the y value of the chromaticity (x, y) is the same. The thickness is adjusted.

As shown in Table 3, in Comparative Example 1 in which the blue color material was changed to the triarylmethane color material without using the fluorescent color material in combination with Comparative Example 2, the improvement rate was 1.19 and the luminance Increases by 19%.
In Example 1 in which a fluorescent color material was used in addition to the triarylmethane color material, the luminance was further increased, the improvement rate was 1.24, and the luminance was 24% higher.
Furthermore, in Example 2 in which the ratio of the fluorescent color material was increased, the improvement rate was 1.30, and the luminance was increased by 30%.
As for the combined effect of the fluorescent color material, the improvement rate is 1.30 in Example 2 including the fluorescent color material, compared with 1.19 in the comparative example 1 not including the fluorescent color material, and the luminance is 9%. It turns out that the effect to raise is acquired.

As a result, the luminance can be increased even if only the triarylmethane colorant is used under the same color density condition, but the luminance can be further increased by using the fluorescent colorant together. found.
Therefore, in Example 1 and Example 2, in the white light-emitting organic EL display, even when the light source is a white light-emitting organic EL element, the color density is maintained as compared with the conventional cold cathode tube and white light-emitting LED. As a result, a decrease in luminance can be suppressed.

DESCRIPTION OF SYMBOLS 1 Transparent substrate 1p One side 2 Black matrix 3 Colored layer 3B Blue colored layer 3G Green colored layer 3R Red colored layer 4 Overcoat layer 5 Spacer 10 Color filter for white light emitting organic EL display 20 White light emitting organic EL element 21 White organic light emitting Layer 22 Substrate 23 Back electrode layer 24 Transparent electrode layer 25 Insulating layer 26 Protective layer 30 White light emitting organic EL display 31 Adhesive layer

Claims (3)

At least one color of the colored layer, seeing containing a triarylmethane coloring material and a fluorescent coloring material,
A color filter for a white light-emitting organic EL display , wherein the triarylmethane color material is a blue color material, and the fluorescent color material is a rhodamine-based purple color material . Triarylmethane colorants, fluorescent coloring material, and, seen containing a photosensitive agent having a sensitivity to light of a wavelength 370～450Nm,
A colored resist composition for a white light-emitting organic EL display , wherein the triarylmethane color material is a blue color material, and the fluorescent color material is a rhodamine-based purple color material .   A white light emitting organic EL display comprising the color filter for white light emitting organic EL display according to claim 1 and a white light emitting organic EL element for supplying white light to the color filter for white light emitting organic EL display.