JP5194353B2 - Color filter substrate for organic electroluminescence device - Google Patents

Description

  The present invention relates to a color filter substrate for an organic EL element used in an organic electroluminescence (hereinafter abbreviated as EL) display device.

  In principle, the organic EL element has a structure in which a light emitting layer is sandwiched between an anode and a cathode. Actually, when an organic EL display device is configured using organic EL elements, (1) a method of arranging light emitting layers that emit light of each of the three primary colors, and (2) a light emitting layer that emits white light, and coloring of the three primary colors. There are a color filter system combining layers, and (3) a color conversion system combining a light emitting layer emitting blue light and a color conversion layer converting blue to green, and blue to red.

  In the method (1), it is necessary to make the characteristics of the light emitting layers that emit light of the respective colors uniform, and there is a problem that high-definition patterning is difficult. Therefore, the color filter method (2) and the color conversion method (3) are attracting attention. Since these methods need only use a single type of light-emitting layer, there is no problem like the method (1).

  Research has been actively conducted on a method for obtaining a light emitting layer that emits white light used in the color filter method of (2) above. For example, a method using a light emitting material that emits white light, or light emission of a plurality of colors having a complementary color relationship. A method using a material has been proposed. Among these, since there are few light emitting materials that emit white light, a method using a plurality of colors of light emitting materials having a complementary color relationship has become the mainstream.

  When using light emitting materials of a plurality of colors, it is known to select a blue light emitting material and an orange light emitting material that is a complementary color thereof (see, for example, Patent Document 1). The emission spectrum of white light obtained by this method has two wavelength peaks of blue and red derived from a blue light emitting material and an orange light emitting material. For this reason, when such white light is transmitted through the colored layer, red light and blue light are actually strongly observed and green light is hardly observed. Therefore, an organic EL using a light emitting layer that emits white light is used. The display device has a problem that the color characteristics of the three primary colors are not well balanced.

JP-A-9-63770

  The present invention has been made in view of the above problems, and can be applied to an organic EL display device having a white light emitting layer, and provides a color filter substrate for an organic EL element that has an excellent balance of color characteristics of three primary colors. The main purpose.

  In order to achieve the above object, the present invention provides a transparent base material, a colored layer formed in a pattern on the transparent base material, and having a red colored portion, a green colored portion and a blue colored portion, and the green colored portion. A color filter substrate for an organic EL element having a color conversion layer having at least a green color conversion part formed thereon, wherein the area of the green color conversion part is formed on the red color part There is provided a color filter substrate for an organic EL element, which is larger than each area of the blue color conversion part formed on the part and the blue coloring part.

  When the color filter substrate for an organic EL element of the present invention is used for an organic EL display device having a white light emitting layer, for example, the white light emitted from the white light emitting layer is generally composed of red light and blue light, and the green light component is small. However, in the present invention, a green color conversion unit that converts incident light into green light is formed, and the area of the green color conversion unit is made larger than the areas of the red color conversion unit and the blue color conversion unit, respectively. Thus, the green light component can be increased. Therefore, by using the color filter substrate for an organic EL element of the present invention, it is possible to provide an organic EL display device excellent in the balance of the color characteristics of the three primary colors.

  In the said invention, it is preferable that the said red color conversion part and the said blue color conversion part are not formed. That is, it is preferable that the color conversion layer has only a green color conversion part formed on the green coloring part. This is because it is not necessary to repeat the patterning process, which is advantageous in terms of cost and simplifies the manufacturing process.

  In this case, it is preferable that the difference between the thickness of the red coloring portion, the thickness of the green coloring portion and the green color conversion portion combined, and the thickness of the blue coloring portion is 2.0 μm or less. This is because if the difference in thickness is too large, a step (unevenness) due to the configuration of the colored layer and the color conversion layer becomes large, and it becomes difficult to flatten the surface.

  In this case, it is preferable that the thickness of the red colored portion, the thickness of the green colored portion and the green color converting portion combined, and the thickness of the blue colored portion are in the range of 1 μm to 3 μm. This is because it is difficult to form red colored portions and blue colored portions that are too thick, and it is also difficult to form green color converting portions that are too thin. In particular, if the concentration of the green conversion phosphor in the green color conversion portion is too high in order to form a thin green color conversion portion, concentration quenching may occur.

  Furthermore, in this invention, the green color conversion part may be formed on the said red coloring part. Most of the green light emitted from the green color converter cannot pass through the red colored part, but the long wavelength component of the green light passes through the red colored part as the short wavelength component of the red light. This is because the hue can be adjusted with such a configuration.

  Furthermore, in the present invention, it is preferable that a planarizing layer is formed on the color conversion layer. This is because the colored layer and the color conversion layer can be protected by forming the planarizing layer. Moreover, when the color filter substrate for organic EL elements of the present invention is used in an organic EL display device, it is possible to reduce the influence at the time of forming the transparent electrode layer and prevent the occurrence of thickness unevenness at the time of forming the organic EL layer. Because it can.

  In the present invention, a gas barrier layer is preferably formed on the color conversion layer. Due to the formation of the gas barrier layer, when the color filter substrate for organic EL elements of the present invention is used in an organic EL display device, it is vulnerable to water vapor, oxygen, or desorbed gas from a colored layer, a color conversion layer, or the like. This is because the organic EL layer as a member can be protected from such a gas.

  Furthermore, in this invention, the light shielding part may be formed between each said colored part on the said transparent base material. This is because the formation of the light-shielding portion partitions areas that emit light for each pixel, prevents reflection of external light at the boundaries between the areas that emit light, and increases contrast.

  The present invention is also formed on the transparent electrode layer, the color filter substrate for organic EL elements described above, the transparent electrode layer formed on the color conversion layer side surface of the color filter substrate for organic EL elements, An organic EL display device comprising: an organic EL layer including at least a white light emitting layer that emits white light from a two-wavelength light source; and a counter electrode layer formed on the organic EL layer.

  The organic EL display device of the present invention has a white light-emitting layer that emits white light. However, since the above-described color filter substrate for an organic EL element is used, the organic EL display device has an advantage of excellent balance of color characteristics of the three primary colors.

  When the color filter substrate for an organic EL element of the present invention is used in an organic EL display device having a white light emitting layer that emits white light, for example, the area of the green color conversion unit is larger than the area of each of the red color conversion unit and the blue color conversion unit. By increasing the value, the green light component can be increased. Therefore, in the organic EL display device using the color filter substrate for organic EL elements of the present invention, there is an effect that the balance of the color characteristics of the three primary colors is excellent.

  Hereinafter, the color filter substrate for organic EL elements of the present invention and the organic EL display device using the same will be described in detail.

A. Color filter substrate for organic EL elements The color filter substrate for organic EL elements of the present invention is formed in a pattern on a transparent base material and the transparent base material, and has a red coloring portion, a green coloring portion, and a blue coloring portion. A color filter substrate for an organic EL element having a layer and a color conversion layer having at least a green color conversion part formed on the green coloration part, wherein the area of the green color conversion part is on the red coloration part The area of each of the red color conversion part formed on the blue color conversion part and the blue color conversion part formed on the blue coloration part is larger.

The color filter substrate for organic EL elements of the present invention will be described with reference to the drawings.
FIG. 1 is a schematic cross-sectional view showing an example of a color filter substrate for an organic EL element of the present invention. As shown in FIG. 1, in the color filter substrate 10 for organic EL elements of the present invention, a colored layer 2 composed of a red colored portion 2R, a green colored portion 2G, and a blue colored portion 2B on the transparent substrate 1, Color conversion composed of a red color conversion unit 3R formed on the red coloring unit 2R, a green color conversion unit 3G formed on the green coloring unit 2G, and a blue color conversion unit 3B formed on the blue coloring unit 2B A layer 3 is sequentially formed, and a planarizing layer 5 is formed so as to cover the colored layer 2 and the color conversion layer 3. A black matrix 4 is formed between the colored portions 2R, 2G, and 2B of the colored layer 2. Further, the area of the green color conversion unit 3G is larger than the area of the red color conversion unit 3R and larger than the area of the blue color conversion unit 3B.

  When such a color filter substrate for an organic EL element is used for an organic EL display device having a white light emitting layer, for example, a transparent electrode layer, a white light emitting layer and a counter electrode layer are sequentially laminated on the planarizing layer 5. . In general, white light emitted from the white light emitting layer is composed of red light and blue light, and there are many cases where the component of green light is small. When this white light passes through the colored layer, almost no green light is observed. On the other hand, in the present invention, the area of the green color conversion unit 3G that converts incident light into green light is made larger than the areas of the red color conversion unit 3R and the blue color conversion unit 3B, so that the green light component Can be increased. Therefore, by using the color filter substrate for an organic EL element of the present invention, it is possible to provide an organic EL display device excellent in the balance of the color characteristics of the three primary colors.

  In the present invention, if the area of the green color conversion unit is larger than the areas of the red color conversion unit and the blue color conversion unit, the areas of the red color conversion unit and the blue color conversion unit are particularly limited. It is not a thing. Further, as described above, since the white light emitted from the white light emitting layer includes components of red light and blue light, in principle, the red color conversion unit and the blue color conversion unit do not need to perform color conversion. Therefore, the red color conversion portion and the blue color conversion portion may or may not be formed. For example, when the red color conversion unit 3R and the blue color conversion unit 3B are formed as shown in FIG. 1, there is an advantage that the hues of red and blue can be adjusted. On the other hand, for example, when the red color conversion unit and the blue color conversion unit are not formed as shown in FIG. 2, only the green color conversion unit 3G needs to be formed. There is no need to repeat the patterning process using a photolithographic method or the like, which is advantageous in terms of cost and that the manufacturing process is simple. In the present invention, among the above, it is preferable that the red color conversion portion and the blue color conversion portion are not formed.

  When the red color conversion portion and the blue color conversion portion are not formed, for example, as shown in FIG. 2, the thickness d1 of the red coloring portion 2R, the thickness d2 that combines the green coloring portion 2G and the green color conversion portion 3G, The difference h from the thickness d3 of the blue colored portion 2B is preferably 2.0 μm or less, more preferably 0.5 μm or less, and most preferably 0.2 μm or less. This is because if the difference in thickness is too large, a step (unevenness) due to the configuration of the colored layer and the color conversion layer becomes large, and it becomes difficult to flatten the surface. When an organic EL display device is produced using the color filter substrate for an organic EL element of the present invention, a transparent electrode layer and an organic EL layer are formed on the color conversion layer side surface. If the surface unevenness due to the configuration of the color conversion layer is large, it may cause dark areas.

  In general, the thickness of the color conversion layer is larger than the thickness of the colored layer. In the present invention, in order to make the difference in thickness within a predetermined range, for example, the thickness of the red colored portion and the blue colored portion may be increased, or the thickness of the green color converting portion may be decreased. Specifically, it is possible to increase the thickness of the red coloring portion and the blue coloring portion by reducing the concentration of the colorant in each coloring portion, and to increase the concentration of the green conversion phosphor in the green color conversion portion. By doing so, the thickness of the green color conversion portion can be reduced. However, it is difficult to form red colored portions and blue colored portions that are too thick, and it is also difficult to form green color converting portions that are too thin. In particular, if the concentration of the green conversion phosphor in the green color conversion portion is too high in order to form a thin green color conversion portion, concentration quenching may occur.

  Accordingly, the thickness d1 of the red coloring portion 2R, the thickness d2 of the green coloring portion 2G and the green color conversion portion 3G, and the thickness d3 of the blue coloring portion 2B are all in the range of 1 μm to 3 μm. More preferably, it is in the range of 1 μm to 2 μm, and most preferably in the range of 1.2 μm to 1.8 μm.

  Hereinafter, each structure of the color filter substrate for organic EL elements of this invention is demonstrated.

1. Color Conversion Layer The color conversion layer used in the present invention has at least a green color conversion portion formed on the green coloring portion. Moreover, the area of this green color conversion part is larger than each area of the red color conversion part formed on a red coloring part and the blue color conversion part formed on a blue coloring part.

  The area ratio of the color conversion units is not particularly limited as long as the area of the green color conversion unit is larger than the areas of the red color conversion unit and the blue color conversion unit.

  Here, the “area” means an area on a plane that is horizontal with respect to the transparent substrate surface. Further, it can be confirmed by observation with an optical microscope or the like that the area of the green color conversion unit is larger than the areas of the red color conversion unit and the blue color conversion unit.

  In the present invention, as described above, the red color conversion unit and the blue color conversion unit may or may not be formed.

  When the red color conversion unit and the blue color conversion unit are formed, for example, as shown in FIG. 1, the red color conversion unit 3R and the blue color conversion unit 3B are part of the red color unit 2R and the blue color unit 2B. As a result, the area of the green color conversion section can be made larger than the areas of the red color conversion section and the blue color conversion section. In this case, the formation position of the red color conversion portion and the blue color conversion portion is not particularly limited as long as it is a part on each coloring portion. For example, a red color conversion portion or a blue color conversion is provided at the center of each coloring portion. A part may be formed, and a red color conversion part or a blue color conversion part may be formed on each colored part.

  Moreover, when the red color conversion part and the blue color conversion part are not formed, a transmission part that transmits incident light may be formed on each colored part. This transmissive part transmits red light when formed on the red colored part, and transmits blue light when formed on the blue colored part.

  In the present invention, for example, as shown in FIG. 3, a green color conversion section 3G may be formed on the red coloring section 2R. Most of the green light emitted from the green color conversion unit 3G cannot pass through the red coloring unit 2R, but the component on the long wavelength side of the green light is used as the component on the short wavelength side of the red light. This is because the hue can be adjusted.

  Therefore, a red color conversion unit may be formed on the red coloring unit, a green color conversion unit may be formed, or both the red color conversion unit and the green color conversion unit may be formed. In addition, neither the red color conversion unit nor the green color conversion unit may be formed.

  The green color conversion unit used in the present invention is obtained by dispersing or dissolving a green conversion phosphor that absorbs incident light and emits green fluorescence.

  Specific examples of the green conversion phosphor include 2,3,5,6-1H, 4H-tetrahydro-8-trifluoromethylquinolidino (9,9a, 1-gh) coumarin, 3- (2′-benzothiazolyl). ) -7-diethylaminocoumarin, or coumarin dyes such as 3- (2′-benzimidazolyl) -7-N, N-diethylaminocoumarin; coumarin dyes such as basic yellow 51; solvent yellow 11 or solvent yellow 116 And a fluorescent pigment such as a yellow-green pigment (for example, FA005 (trade name) manufactured by Shin-Helloy Co., Ltd.) or a pigment such as a ZnS phosphor such as ZnS: Tb.

  In addition, the green conversion phosphor is prepared by combining the fluorescent dye with, for example, polymethacrylate, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin, and the like. It may be a fluorescent pigment kneaded in advance in these resin mixtures.

  The fluorescent dyes and fluorescent pigments may be used alone or in combination of two or more in order to adjust the hue of fluorescence.

  Specific examples of the resin used in the green color conversion part include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, Illustrative examples include transparent resins such as phenol resins, alkyd resins, epoxy resins, polyurethane resins, polyester resins, maleic acid resins, and polyamide resins. Examples of the resin include ionizing radiation curable resins having a reactive vinyl group such as acrylate, methacrylate, polyvinyl cinnamate, or cyclized rubber (actually, an electron beam curable resin or an ultraviolet ray). It is also possible to use a curable resin, which is often the latter.

  The ratio of the resin in the green color conversion part and the green conversion phosphor is preferably about 100: 0.3 to 100: 5 (mass basis). This is because if the ratio of the green conversion phosphor is too small, sufficient color conversion efficiency may not be obtained, and if the ratio is too large, concentration quenching may occur.

  The thickness of the green color conversion part can be set to about 1 μm to 10 μm. Among them, as described above, the thickness of the red colored portion, the thickness of the combined green colored portion and the green color converting portion, and the thickness of the blue colored portion are within a predetermined range, and further green colored It is preferable that the combined thickness of the part and the green color conversion part be a predetermined range. Specifically, although the thickness varies depending on the thickness of the green coloring portion, the thickness of the green color conversion portion is preferably in the range of 1.5 μm to 5 μm, more preferably in the range of 1.8 μm to 2.5 μm. It is.

  When the thickness of the green color conversion part is set to be relatively thin in order to set the difference in thickness and the combined thickness of the green coloring part and the green color conversion part within a predetermined range, for example, in the green color conversion part By increasing the content of the green conversion phosphor, it is possible to reduce the thickness of the green color conversion portion without reducing the color conversion efficiency. However, if the content of the green conversion phosphor in the green color conversion part is too large, concentration quenching may occur. Therefore, when the content of the green color conversion phosphor in the green color conversion part is increased to reduce the thickness of the green color conversion part, the thickness is appropriately selected in consideration of concentration quenching.

  In the present invention, when a red color conversion part is formed, the red color conversion part is obtained by dispersing or dissolving a red conversion phosphor that absorbs incident light and emits red fluorescence.

  Specific examples of the red conversion phosphor include cyanine dyes such as 4-dicyanomethylene-2-methyl-6- (p-dimethylaminostyryl) -4H-pyran, 1-ethyl-2- [4- (p- Pyridine dyes such as dimethylaminophenyl) -1,3-butadienyl] -pyridium-perchlorate; Rhodamine dyes such as rhodamine B or rhodamine 6G; Oxazine dyes; ZnS: Mn, ZnS: Mn / ZnMgS and other ZnS Fluorescent pigments such as phosphors or fluorescent pigments such as orange pigments (for example, FA001 (trade name) manufactured by Shinhiro Corporation) can be exemplified.

  In addition, the red conversion phosphor is obtained by combining the fluorescent dye with, for example, polymethacrylic ester, polyvinyl chloride, vinyl chloride-vinyl acetate copolymer resin, alkyd resin, aromatic sulfonamide resin, urea resin, melamine resin, benzoguanamine resin, and the like. It may be a fluorescent pigment kneaded in advance in these resin mixtures.

  The fluorescent dyes and fluorescent pigments may be used alone or in combination of two or more in order to adjust the hue of fluorescence.

  In addition, about resin used for a red color conversion part, it is the same as that of resin used for the green color conversion part mentioned above. The ratio of the resin and the red conversion phosphor in the red color conversion part is the same as that in the case of the green color conversion part.

  The thicknesses of the red color conversion unit and the blue color conversion unit are preferably approximately the same as the thickness of the green color conversion unit.

  Further, when the transmissive part is formed, the transmissive part transmits red light when formed on the red colored part, and transmits blue light when formed on the blue colored part. The material is not particularly limited as long as it transmits light. For example, it can be made of the above-described resin without including a color conversion phosphor.

  As a method for forming a color conversion layer, for example, each color conversion phosphor and resin are mixed with a solvent, a diluent or an appropriate additive as necessary to prepare a color conversion part forming coating solution. A method of patterning by a photolithography method using a conversion part forming coating solution, or a method of patterning by a printing method using each of the above color conversion part forming coating solutions is used.

2. Colored layer The colored layer used in the present invention is formed in a pattern on a transparent substrate, and has a red colored portion, a green colored portion, and a blue colored portion. Each coloring part is regularly arranged corresponding to each pixel, and when the light shielding part is formed, it is provided corresponding to the opening part of the light shielding part.

  Each colored portion used in the present invention is obtained by dispersing or dissolving a colorant such as a pigment or dye of each color in a binder resin.

  Examples of the colorant used in the red coloring part include perylene pigments, lake pigments, azo pigments, quinacridone pigments, anthraquinone pigments, anthracene pigments, and isoindoline pigments. These pigments may be used alone or in combination of two or more.

  Examples of the colorant used in the green coloring portion include phthalocyanine pigments such as halogen polysubstituted phthalocyanine pigments or halogen polysubstituted copper phthalocyanine pigments, triphenylmethane basic dyes, isoindoline pigments, and isoindolinone pigments. Etc. These pigments or dyes may be used alone or in combination of two or more.

  Examples of the colorant used in the blue coloring portion include copper phthalocyanine pigments, anthraquinone pigments, indanthrene pigments, indophenol pigments, cyanine pigments, dioxazine pigments and the like. These pigments may be used alone or in combination of two or more.

  A transparent resin is used as the binder resin used for each colored portion.

  When a printing method is used as a method for forming the colored layer, examples of the binder resin include polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, and polyvinyl chloride resin. Melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin, maleic acid resin, polyamide resin and the like.

In addition, when a photolithography method is used as a method for forming a colored layer, the binder resin is usually an ionizing radiation curable resin having a reactive vinyl group such as an acrylate, methacrylate, polyvinyl cinnamate, or cyclized rubber. Is used. Usually, an electron beam curable resin or an ultraviolet curable resin is used.
When using an ultraviolet curable photopolymer, a photopolymerization initiator is used alone or in combination with a binder resin. When an ultraviolet curable resin is used, a sensitizer, a coatability improver, a development improver, a crosslinking agent, a polymerization inhibitor, a plasticizer, a flame retardant, and the like may be used as necessary.

  The content of the colorant described above is preferably in the range of 5 to 50% by weight in each colored portion. The binder resin content is preferably in the range of 30 to 100 parts by weight with respect to 100 parts by weight of the colorant.

  As described above, the thickness of the green colored portion is such that the difference between the thickness of the red colored portion, the combined thickness of the green colored portion and the green color converting portion, and the thickness of the blue colored portion is within a predetermined range. Further, it is preferable that the total thickness of the green coloring portion and the green color conversion portion is within a predetermined range. Specifically, although it varies depending on the thickness of the green color conversion portion, the thickness of the green coloring portion is preferably about 1 μm to 3 μm, more preferably in the range of 1.2 μm to 2 μm, most preferably It is in the range of 1.5 μm to 1.8 μm.

  In addition, about the thickness of a red coloring part and a blue coloring part, it is as above-mentioned.

  In order to set the difference in thickness and the thickness of each colored portion within a predetermined range, for example, the content of the colorant in each colored portion may be adjusted.

  The arrangement of the colored portions is not particularly limited as long as the colored portions are arranged on an average when viewed macroscopically, and examples thereof include a stripe arrangement, a mosaic arrangement, and a delta arrangement. Moreover, each coloring part may be formed for every opening part of the light-shielding part.

  As a method for forming a colored layer, for example, each coloring agent is mixed, dispersed or solubilized in a binder resin to prepare each colored portion forming coating solution, and a photolithography method using this colored portion forming coating solution. The method of patterning by the above, or the method of patterning by the printing method using each of the above colored portion forming coating liquids is used.

3. Transparent base material The transparent base material used for this invention is a support body which supports the color filter substrate for organic EL elements. Moreover, when an organic EL display device is configured using the color filter substrate for organic EL elements of the present invention, it is disposed on the observation side and is also a support that supports the entire organic EL display device.

  As the transparent substrate, for example, an inorganic plate-like transparent substrate such as glass or quartz glass, an organic (for example, synthetic resin) plate-like transparent substrate such as acrylic resin, or a synthetic resin-made transparent film-like substrate Materials can be used. A very thin glass can also be used as the transparent film substrate.

  Moreover, as a transparent base material, it is preferable that the smoothness of the surface at the side which forms a colored layer, a color conversion layer, etc. is high. Specifically, it is preferable to use one having an average surface roughness (Ra) of 0.5 nm to 3.0 nm (5 μm □ region).

  Specific examples of the synthetic resin constituting the transparent substrate include polycarbonate resin, polyarylate resin, polyethersulfone resin, acrylic resin such as methyl methacrylate resin, cellulose resin such as triacetyl cellulose resin, epoxy resin, or cyclic Examples thereof include olefin resins and cyclic olefin copolymer resins.

4). Light Shielding Part In the present invention, a light shielding part (also referred to as a black matrix) may be formed between the colored parts on the transparent substrate. The light shielding section is provided to partition the light emitting area for each pixel, prevent reflection of external light at the boundary between the light emitting areas, and increase the contrast of images and videos. Therefore, the light-shielding portion is not necessarily provided. However, in addition to improving the contrast, the light-shielding portion is formed when the colored layer, the color conversion layer, or the like is formed corresponding to the opening of the light-shielding portion. preferable. Further, when the organic EL display device is formed using the color filter substrate for the organic EL element of the present invention, the light shielding portion is formed because the light emitting layer and the like are formed corresponding to the opening of the light shielding portion. It is preferable.

  The light-shielding portion is usually formed in a black line shape, and is formed in a pattern shape having openings such as a matrix shape or a stripe shape. When an organic EL display device is formed using the color filter substrate for organic EL elements of the present invention, light emission from the light emitting layer reaches the observer side via the opening of the light shielding portion.

  The light-shielding part used in the present invention may be insulating or non-insulating, but preferably has insulating properties. If the light-shielding part has an insulating property, even when the light-shielding part and the transparent electrode layer are in contact with each other when the organic EL element color filter substrate of the present invention is used to form an organic EL display device, the light-shielding part is light-shielded. This is because it is possible to avoid electrical conduction between the portion and the transparent electrode layer.

  Examples of the material for forming the light-shielding portion having insulating properties include a resin composition containing a black colorant such as carbon black. Examples of the resin used in the resin composition include ionizing radiation curable resins having reactive vinyl groups such as acrylate-based, methacrylate-based, polyvinyl cinnamate, or cyclized rubber, particularly electron beam curable resins or An ultraviolet curable resin can be used. Also, for example, polymethyl methacrylate resin, polyacrylate resin, polycarbonate resin, polyvinyl alcohol resin, polyvinyl pyrrolidone resin, hydroxyethyl cellulose resin, carboxymethyl cellulose resin, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin Examples thereof include a polyester resin, a maleic acid resin, and a polyamide resin.

In addition, examples of a material for forming a light-shielding portion having no insulating property include metals such as chromium or metal oxides such as chromium oxide. At this time, the light-shielding part having no insulating property may be a laminate of two layers of a CrO _x film (x is an arbitrary number) and a Cr film, and a CrO _x film with a further reduced reflectance. (X is an arbitrary number), a CrN _y film (y is an arbitrary number), and a three-layered Cr film may be laminated.

  As a method for forming a light-shielding portion having insulating properties, a method of applying the above resin composition on a substrate and patterning it by a photolithography method can be used. Also, a printing method or the like can be used.

  As a method for forming a light-shielding portion having no insulating property, a method of forming a thin film by a vapor deposition method, an ion plating method, a sputtering method, or the like, and patterning using a photolithography method can be used. Further, an electroless plating method or the like can also be used.

  The film thickness of the light-shielding portion is about 0.2 μm to 0.4 μm when formed by vapor deposition, ion plating, sputtering, or the like, and is about 0.2 μm when formed by coating or printing. It is about 5 μm to 2 μm.

5. Flattening layer In the present invention, a flattening layer may be formed on the color conversion layer. This flattening layer has a role of protecting the colored layer and the color conversion layer, and when the thickness of the colored layer and the color conversion layer is not constant, the surface of the layer is smoothed to obtain a flat surface. When used in a display device, it is provided for the purpose of reducing the influence when forming a transparent electrode layer or the like. In addition, when there is a level difference (unevenness) due to the configuration of the color layer or the color conversion layer, the leveling layer eliminates the level difference to achieve leveling, and forms the organic EL layer at the time of manufacturing the organic EL display device. It is a flattening action that prevents the occurrence of uneven thickness.

  As a material for forming the planarization layer used in the present invention, a transparent resin can be used. Specifically, a photocurable resin or a thermosetting resin having an acrylate-based or methacrylate-based reactive vinyl group can be used. In addition, as the transparent resin, polymethyl methacrylate, polyacrylate, polycarbonate, polyvinyl alcohol, polyvinyl pyrrolidone, hydroxyethyl cellulose, carboxymethyl cellulose, polyvinyl chloride resin, melamine resin, phenol resin, alkyd resin, epoxy resin, polyurethane resin, polyester resin A maleic acid resin, a polyamide resin, or the like can be used.

  As the method for forming the flattening layer, when the flattening layer forming coating liquid containing the transparent resin is a liquid, it is applied by spin coating, roll coating, cast coating, etc. In the case of a curable resin, there may be mentioned a method in which the resin is thermally cured as necessary after irradiation with ultraviolet rays, and in the case of a thermosetting resin, it can be directly heat-cured after film formation. Moreover, when the transparent resin mentioned above is shape | molded in the film form, a planarization layer can be formed by sticking directly or via an adhesive.

  The thickness of such a planarization layer can be set to about 1 to 5 μm, for example.

6). Gas Barrier Layer In the present invention, a gas barrier layer may be formed on the color conversion layer. For example, as shown in FIG. 4, when the planarizing layer 5 is formed on the green color conversion unit 3 </ b> G, the gas barrier layer 6 is formed on the planarizing layer 5. When this gas barrier layer is used in an organic EL display device, it blocks the permeation of water vapor or oxygen from the color filter substrate for organic EL elements or the desorbed gas from a colored layer or color conversion layer to the organic EL layer. It is provided for this purpose.

  The gas barrier layer used in the present invention is not particularly limited as long as it can exhibit gas barrier properties against gases such as water vapor, oxygen, and desorption gas. For example, a transparent inorganic film, a transparent resin A film or an organic-inorganic hybrid film is used. Among these, a transparent inorganic film is preferable because of its high gas barrier property.

  The material used for the transparent inorganic film is not particularly limited as long as it can exhibit gas barrier properties. For example, oxides such as aluminum oxide, silicon oxide, and magnesium oxide; nitriding such as silicon nitride A nitride oxide such as silicon nitride oxide; Among these, silicon nitride oxide is preferable because pinholes and protrusions hardly occur and the gas barrier property is high.

  Further, the gas barrier layer may be a single layer or a multilayer. For example, when the gas barrier layer is a multilayer in which a plurality of silicon nitride oxide films are stacked, the gas barrier property can be further improved. Moreover, when a gas barrier layer is a multilayer, you may use a different material for each layer, respectively.

  The thickness of the gas barrier layer is not particularly limited, and differs depending on the base material to be used, the type of material used for the gas barrier layer, or whether the gas barrier layer is a single layer or a multilayer, and cannot be specified unconditionally. However, it is generally about 50 nm to 2 μm for the entire gas barrier layer. This is because if the thickness of the gas barrier layer is too thin, the gas barrier property may be insufficient, and if the thickness of the gas barrier layer is too thick, a phenomenon such as a crack due to the film stress of the thin film tends to occur.

  When the gas barrier layer is a transparent inorganic film, the method for forming the transparent inorganic film is not particularly limited as long as it is a film forming method that can be formed in a vacuum state. For example, sputtering, chemical vapor deposition ( CVD) method, ion plating method, vacuum deposition method such as electron beam (EB) deposition method and resistance heating method, laser ablation method and the like. Among these, considering the productivity of the color filter substrate for an organic EL element, the sputtering method, the ion plating method, and the CVD method are preferable, and the sputtering method is more preferable. This is because by using the sputtering method, a gas barrier layer having high productivity and excellent quality stability can be formed.

7). Method for Manufacturing Color Filter Substrate for Organic EL Element Hereinafter, an example of a method for manufacturing a color filter substrate for an organic EL element of the present invention will be described.
First, a black matrix is formed by depositing a metal such as chromium or a metal oxide such as chromium oxide on the entire surface of the transparent substrate and patterning it using a photolithography method. Next, a red colored portion forming coating solution in which a red colorant is dispersed or dissolved in a binder resin is applied on a transparent base material on which a black matrix is formed, and then patterned by using a photolithography method. A colored part is formed. A green colored portion and a blue colored portion are formed by the same procedure. At this time, each colored portion is formed so that its thickness falls within a predetermined range.
Next, a green color conversion part is formed by applying a green color conversion part forming coating liquid in which a green conversion phosphor is dispersed or dissolved in a resin and patterning the green color part using a photolithography method. . At this time, the green color conversion part is formed such that the thickness of the red color part, the thickness of the green color part and the green color conversion part, and the thickness of the blue color part are within a predetermined range.
And a planarization layer is formed so that a green color conversion part and each coloring part may be covered as needed.
In this way, a color filter substrate for an organic EL element can be produced.

B. Organic EL Display Device Next, the organic EL display device of the present invention will be described. The organic EL display device of the present invention includes the above-described color filter substrate for organic EL elements, the transparent electrode layer formed on the color conversion layer side surface of the color filter substrate for organic EL elements, and the transparent electrode layer. It has an organic EL layer that is formed and includes at least a white light-emitting layer that emits white light from a two-wavelength light source, and a counter electrode layer formed on the organic EL layer.

  The organic EL display device of the present invention has a white light-emitting layer that emits white light. However, since the above-described color filter substrate for an organic EL element is used, the organic EL display device has an advantage of excellent balance of color characteristics of the three primary colors.

FIG. 4 is a schematic sectional view showing an example of the organic EL display device of the present invention. In FIG. 4, the color filter substrate 10 for organic EL elements has a colored layer having three primary color coloring portions 2R, 2G, 2B and a green color conversion portion 3G corresponding to the green coloring portion 2G on the transparent substrate 1. A color conversion layer is formed, a light shielding portion 4 is formed between the colored portions 2R, 2G, and 2B. A planarizing layer 5 is formed so as to cover the colored layer and the color conversion layer, and a gas barrier is formed thereon. The layer 6 is formed. In the organic EL display device 20 of the present invention, the transparent electrode layer 11, the organic EL layer 12 including the white light emitting layer, and the counter electrode layer 13 are formed on the gas barrier layer 6 of the color filter substrate 10 for organic EL elements. An insulating layer 14 is formed between the transparent electrode layers 11 on the gas barrier layer 6, and a partition wall (cathode separator) 15 is formed thereon.
Hereinafter, each configuration of the organic EL display device of the present invention will be described.

1. Organic EL Layer The organic EL layer used in the present invention is composed of one or more organic layers including at least a white light emitting layer. That is, the organic EL layer is a layer including at least a white light-emitting layer, and the layer configuration refers to a layer having one or more organic layers. Usually, when an organic EL layer is formed by a wet method by coating, it is often difficult to stack a large number of layers in relation to a solvent, so that it is often formed of one or two organic layers. However, it is possible to further increase the number of layers by devising an organic material so that the solubility in a solvent is different or by combining a vacuum deposition method.

Examples of the organic layer formed in the organic EL layer other than the white light emitting layer include charge injection layers such as a hole injection layer and an electron injection layer. In addition, examples of the other organic layers include charge transport layers such as a hole transport layer that transports holes to the white light-emitting layer and an electron transport layer that transports electrons to the light-emitting layer. In many cases, the layer is formed integrally with the charge injection layer by providing the layer with a charge transport function. In addition, as an organic layer formed in the organic EL layer, it prevents holes or electrons from penetrating like a carrier block layer and further prevents diffusion of excitons and confines excitons in the light emitting layer. And a layer for increasing the recombination efficiency.
Hereinafter, each structure of such an organic EL layer will be described.

(1) White light-emitting layer The white light-emitting layer used in the present invention has a function of emitting light by providing a recombination field between electrons and holes, and emits white light.

  White light emission by the white light emitting layer can be obtained by superimposing light emitted from a plurality of light emitters. The white light emitting layer in the present invention may be one that obtains white light emission by superimposing two-color light emission of two kinds of light emitters having a predetermined fluorescence peak wavelength, and three kinds of light emission layers having a predetermined fluorescence peak wavelength. White light emission may be obtained by superimposing three-color light emission of the light emitter. Especially, it is preferable that a white light emitting layer shows white light emission with few components of green light. For example, by forming the green color conversion part partially on the green coloring part, a good green display can be obtained and the brightness of the green light can be improved. This is because an EL display device can be obtained.

The white light-emitting layer in the present invention preferably emits white light by a so-called two-wavelength light source that obtains white light by superimposing two-color light emission of two kinds of light emitters having a predetermined fluorescence peak wavelength. In particular, the white light emitting layer preferably contains a blue light emitter and a small amount of a red light emitter and emits white light from a two-wavelength light source. The white light emission obtained by such a white light emitting layer has a small component of green light, but as described above, for example, a green color conversion part is partially formed on the green coloring part to obtain a good green display. This is because the luminance of green light can be improved, and an organic EL display device having an excellent balance of the color characteristics of the three primary colors can be obtained.
Note that the “two-wavelength light source” here includes not only complete two-wavelength light emission but also main light emission having two wavelengths.

  The blue phosphor used for the white light emitting layer preferably has a fluorescence peak wavelength of 380 nm or more and less than 480 nm, more preferably 420 nm or more and less than 475 nm. As such a blue light emitter, among the compounds described in, for example, JP-A-3-231970, International Publication No. WO92 / 05131 or JP-A-7-26254, the above-mentioned fluorescence condition is satisfied. To do. Specific examples include compounds described in JP-A-6-207170.

  Moreover, it is preferable that the red light-emitting body used for a white light emitting layer has a fluorescence peak wavelength of 575 nm or more and 650 nm or less, and more preferably 580 nm or more and 620 nm or less. Examples of such red light emitters include dicyanomethylene pyran derivatives, dicyanomethylene thiopyran derivatives, fluorescein derivatives, and perylene derivatives used as red starting laser dyes described in European Patent Publication No. 0283381. The content of the red light emitter is set in a range in which concentration quenching does not occur.

  Although it does not specifically limit as thickness of a white light emitting layer, For example, it can be set as about 5 nm-1 micrometer.

  The method for forming the white light emitting layer is not particularly limited as long as it is a method capable of high-definition patterning. For example, vapor deposition method, printing method, inkjet method, spin coating method, casting method, dipping method, bar coating method, blade coating method, roll coating method, gravure coating method, flexographic printing method, spray coating method, and self-assembly method (Alternate adsorption method, self-assembled monolayer method) and the like. Among these, it is preferable to use a vapor deposition method, a spin coating method, and an ink jet method. Moreover, when patterning a white light emitting layer, it may coat and vapor-deposit by a masking method, or may form a partition part between white light emitting layers.

(2) Hole injection layer In the present invention, a hole injection layer may be formed between the white light emitting layer and the anode (transparent electrode layer or counter electrode layer). This is because by providing the hole injection layer, the injection of holes into the white light emitting layer is stabilized and the light emission efficiency can be increased.

  As a constituent material of the hole injection layer used in the present invention, a material generally used for a hole injection layer of an organic EL element can be used. The constituent material of the hole injection layer may be any material that has either a hole injection property or an electron barrier property, and may be an organic material or an inorganic material.

  Specifically, the constituent material of the hole injection layer includes triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives. And styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based, aniline-based copolymers, or conductive polymer oligomers such as thiophene oligomers. Furthermore, examples of the constituent material of the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, and styrylamine compounds.

  Examples of the porphyrin compound include porphine, 1,10,15,20-tetraphenyl-21H, 23H-porphine copper (II), aluminum phthalocyanine chloride, copper octamethylphthalocyanine, and the like.

  Examples of the aromatic tertiary amine compound include N, N, N ′, N′-tetraphenyl-4,4′-diaminophenyl, N, N′-diphenyl-N, N′-bis- ( 3-methylphenyl)-[1,1′-biphenyl] -4,4′-diamine, 4- (di-p-tolylamino) -4 ′-[4 (di-p-tolylamino) styryl] stilbene, 3- Methoxy-4'-N, N-diphenylaminostilbenzene, 4,4'-bis [N- (1-naphthyl) -N-phenylamino] biphenyl, or 4,4 ', 4 "-tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine and the like.

  The thickness of such a hole injection layer is not particularly limited, but can be, for example, about 5 nm to 0.5 μm.

(3) Electron Injection Layer In the present invention, an electron injection layer may be formed between the white light emitting layer and the cathode (transparent electrode layer or counter electrode layer). This is because by providing the electron injection layer, the injection of electrons into the white light emitting layer is stabilized, and the light emission efficiency can be increased.

  As the constituent material of the electron injection layer used in the present invention, for example, nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyrandioxide derivatives, heterocyclic tetracarboxylic anhydrides such as naphthaleneperylene, carbodiimide, Fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, or thiazole derivatives in which the oxygen atom of the oxadiazole ring of the oxadiazole derivative is substituted with a sulfur atom, quinoxaline known as an electron withdrawing group Examples thereof include quinoxaline derivatives having a ring, metal complexes of 8-quinolinol derivatives such as tris (8-quinolinol) aluminum, phthalocyanine, metal phthalocyanine, or distyrylpyrazine derivatives.

  Although it does not specifically limit as thickness of the said electron injection layer, For example, it can be set as about 5 nm-0.5 micrometer.

2. Transparent electrode layer The transparent electrode layer used in the present invention is for applying a voltage to the organic EL layer sandwiched between the counter electrode layer and causing light emission at a predetermined position. The transparent electrode layer is formed on the color conversion layer side surface of the color filter substrate for the organic EL element described above. For example, as shown in FIG. It is formed in a stripe shape having a width corresponding to the width. In this case, the pitch of the striped transparent electrode layer 11 is the same as the pitch of the openings of the light shielding portion 4.

  The transparent electrode layer in the present invention is usually composed of a metal oxide thin film having transparency and conductivity. Examples of such a metal oxide include indium tin oxide (ITO), indium oxide, zinc oxide, and stannic oxide.

  As a method for forming such a transparent electrode layer, for example, a method of forming a thin film of metal oxide by, for example, vapor deposition or sputtering and then patterning by photolithography is preferably used.

3. Counter Electrode Layer The counter electrode layer used in the present invention forms the other electrode for causing the organic EL layer to emit light, and is an electrode having a charge opposite to that of the transparent electrode layer. This counter electrode layer is formed on the organic EL layer.

The counter electrode layer in the present invention is usually composed of a metal, an alloy, or a mixture thereof having a work function as small as about 4 eV or less. Specifically, 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, Or a lithium / aluminum mixture, a rare earth metal, etc. can be illustrated. More preferable examples include a magnesium / silver mixture, a magnesium / aluminum mixture, a magnesium / indium mixture, an aluminum / aluminum oxide (Al ₂ O ₃ ) mixture, or a lithium / aluminum mixture.

The counter electrode layer preferably has a sheet resistance of several hundred Ω / cm or less.
The thickness of the counter electrode layer is preferably about 10 nm to 1 μm, more preferably about 50 to 200 nm.

  As a method for forming such a counter electrode layer, a method of forming a thin film by an evaporation method or a sputtering method and then patterning by a photolithography method is preferably used.

4). Others In the present invention, an insulating layer may be formed between the striped transparent electrode layers so as to correspond to the light shielding portion.

  In addition, a partition wall functioning as a mask for forming a light emitting layer or the like may be formed on the insulating layer. As a material for forming the partition wall, for example, a photocurable resin such as a photosensitive polyimide resin or an acrylic resin, a thermosetting resin, an inorganic material, or the like can be used. In this case, you may perform the process which changes the surface energy (wetting property) of a partition part.

  The driving method of the organic EL display device of the present invention may be either a passive matrix or an active matrix.

  The present invention is not limited to the above embodiment. The above-described embodiment is an exemplification, and the present invention has substantially the same configuration as the technical idea described in the claims of the present invention, and any device that exhibits the same function and effect is the present invention. It is included in the technical scope of the invention.

Hereinafter, the present invention will be specifically described using examples and comparative examples.
[Example 1]
(Formation of black matrix)
As a transparent substrate, soda glass (manufactured by Central Glass Co., Ltd.) having a thickness of 370 mm × 470 mm and a thickness of 0.7 mm was prepared. A thin film (thickness 0.2 μm) of oxynitride composite chromium was formed on this transparent substrate by sputtering. A photosensitive resist is applied on the oxynitride composite chrome thin film, mask exposure, development, and etching of the oxynitride composite chrome thin film are sequentially performed, and an 80 μm × 280 μm rectangular opening has a length of 100 μm in the short side direction. A black matrix arranged in a matrix at a pitch of 300 μm in the long side direction was formed.

(Formation of colored layer)
A coating solution for forming colored portions of red, green and blue was prepared. Condensed azo pigments (manufactured by Ciba Specialty Chemicals, Chromophthalred BRN) as red colorants, phthalocyanine green pigments (Lionol Green 2Y-301, manufactured by Toyo Ink Co., Ltd.), and blue as green colorants As the colorant, anthraquinone pigment (Ciba Specialty Chemicals, Chromophthal Blue A3R) was used. As the binder resin, an acrylic UV curable resin composition (acrylic UV curable resin 20%, acrylic UV curable resin monomer 20%, additive 5%, propylene glycol monomethyl ether acetate (PGMEA ) 55%). For each 10 parts of the acrylic UV curable resin composition, each colorant is blended in a ratio of 1 part (all parts are based on mass), and sufficiently mixed and dispersed. Obtained.

Each colored part was formed using the above-described coating liquid for forming colored parts. That is, on the transparent substrate on which the black matrix was formed, a red colored portion forming coating solution was applied by a spin coating method, and prebaked at 120 ° C. for 2 minutes. Then, it exposed using the photomask (integrated exposure amount 300mJ / cm < ² >), and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at 230 ° C. for 60 minutes to synchronize with the pattern of the black matrix, and the striped red colored portion having a width of 85 μm and a thickness of 1.5 μm is arranged in the direction of the short side of the opening of the black matrix. It formed so that it might become. Thereafter, a green colored portion forming coating solution and a blue colored portion forming coating solution are sequentially used to form a striped green colored portion having a width of 85 μm and a thickness of 1.6 μm, and a stripe shape having a width of 85 μm and a thickness of 1.6 μm. The blue colored part of was formed. This formed a colored layer in which the colored portions of the three primary colors were repeatedly arranged in the width direction.

(Formation of color conversion layer)
An alkali-soluble negative photosensitive resist in which a green conversion phosphor (manufactured by Aldrich, Coumarin 6) is dispersed is used as a green color conversion part forming coating liquid, and this green color conversion part forming coating liquid is black matrix and colored After the layer was formed, it was applied by spin coating and prebaked at 100 ° C. for 5 minutes. Next, after patterning by photolithography, post baking was performed at 200 ° C. for 60 minutes. As a result, a striped green color conversion portion having a width of 85 μm and a thickness of 3.3 μm was formed on the green coloring portion.

(Formation of planarization layer)
Next, a flattened layer formed by diluting an acrylate-based photocurable resin (manufactured by Nippon Steel Chemical Co., Ltd., trade name: “V-259PA / PH5”) with propylene glycol monomethyl ether acetate on the color conversion layer formed A coating solution was prepared, applied by spin coating, and prebaked at 120 ° C. for 5 minutes. Next, after patterning by photolithography, post baking was performed at 200 ° C. for 60 minutes to form a transparent flattening layer covering the entire color layer and the color conversion layer with a thickness of 2 μm on the color conversion layer.

(Formation of gas barrier layer)
Next, a Si ₃ N ₄ target (3N) is used on the above planarized layer by sputtering to form an argon gas introduced amount: 40 sccm, RF power: 430 kW, substrate temperature: 100 ° C., and a thickness of 150 nm. A silicon oxynitride film was laminated to form a transparent gas barrier layer.
A color filter substrate for an organic EL element was produced by the series of operations described above.

(Formation of transparent electrode layer)
Next, an indium tin oxide (ITO) electrode film having a film thickness of 150 nm is formed by ion plating on the gas barrier layer of the color filter substrate for the organic EL element, and a photosensitive resist is applied on the ITO electrode film, Mask exposure, development, and etching of the ITO electrode film were performed to form a transparent electrode layer.

(Formation of auxiliary electrode)
Next, a chromium thin film (thickness 0.2 μm) is formed by sputtering on the entire surface of the gas barrier layer so as to cover the transparent electrode layer, a photosensitive resist is applied on the chromium thin film, mask exposure, development, The auxiliary electrode was formed by etching the chromium thin film. This auxiliary electrode was a striped pattern formed on the transparent electrode layer so as to run on the color conversion layer from the transparent substrate.

(Formation of insulating layer and partition wall)
Using a coating solution for forming an insulating layer obtained by diluting a norbornene-based resin (JSR, ARTON) having an average molecular weight of about 100,000 with toluene, it was applied on the gas barrier layer so as to cover the transparent electrode layer by spin coating. Then, baking (100 degreeC, 30 minutes) was performed, and the insulating film (thickness 1 micrometer) was formed. Next, a photosensitive resist was applied on the insulating film, mask exposure, development, and etching of the insulating film were performed to form an insulating layer. This insulating layer was a stripe-like pattern (width 20 μm) intersecting the transparent electrode layer at a right angle, and was located on the black matrix.
Next, a partition wall coating (manufactured by Nippon Zeon Co., Ltd., photoresist, ZPN1100) was applied over the entire surface by spin coating so as to cover the insulating layer, and prebaked (70 ° C., 30 minutes). Then, it exposed using the predetermined | prescribed photomask, developed with the developing solution (Nippon-Zeon company make, ZTMA-100), and then post-baked (100 degreeC, 30 minutes). Thereby, the partition part was formed on the insulating layer. The partition wall had a shape with a height of 10 μm, a lower portion (insulating layer side) width of 15 μm, and an upper portion width of 26 μm.

(Formation of organic EL layer)
Next, an organic EL layer composed of a hole injection layer, a white light emitting layer, and an electron injection layer was formed by vacuum deposition using the partition wall as a mask.

That is, first, 4,4 ′, 4 ″ -tris [N- (3-methylphenyl) -N-phenylamino] triphenylamine is 200 nm through a photomask having an opening corresponding to the image display region. By depositing 4,4′-bis [N- (1-naphthyl) -N-phenylamino] biphenyl to a thickness of 20 nm to form a film, the partition wall becomes a mask pattern. The material for forming the hole injection layer passed only between the partition walls, and the hole injection layer was formed on the transparent electrode layer.
Similarly, 4,4′-bis (2,2′-diphenylvinyl) biphenyl (fluorescence peak wavelength: 465 nm (solid)) was deposited to 40 nm to form a film. At the same time, a small amount of rubrene (manufactured by Aldrich Co., Ltd., fluorescence peak wavelength: 585 nm (dimethylformamide 0.1 wt% solution)) was contained. This formed the white light emitting layer.
Thereafter, tris (8-quinolinol) aluminum was deposited to a thickness of 20 nm to form an electron injection layer. The organic EL layer thus formed exists between the partition walls as a stripe pattern having a width of 280 μm, and a dummy organic EL layer is formed on the upper surface of the partition wall with the same layer structure. It was done.

(Formation of counter electrode layer)
Next, magnesium and silver are simultaneously deposited by vacuum deposition (magnesium deposition rate) on the region where the partition wall is formed through a photomask having a predetermined opening wider than the image display region. = 1.3 to 1.4 nm / second, silver deposition rate = 0.1 nm / second). Thereby, the partition electrode portion was used as a mask to form a 200 nm-thick counter electrode layer made of a magnesium / silver compound on the organic EL layer. This counter electrode layer exists on the organic EL layer as a stripe pattern having a width of 280 μm, and a dummy counter electrode layer was also formed on the upper surface of the partition wall.
An organic EL element was produced by the series of operations described above.

(Organic EL display device)
The organic EL element was sealed to obtain an organic EL display device.

[Example 2]
In Example 1, an organic EL display device was produced in the same manner as in Example 1 except that the thickness of the green color conversion portion was 10.8 μm.

[Comparative Example 1]
An organic EL display device was produced in the same manner as in Example 1 except that the color conversion layer was not formed in Example 1.

[Evaluation]
For the organic EL display devices of Examples 1 and 2 and Comparative Example 1, chromaticity x, y and reflectance Y were measured using a spectrocolorimeter CM2500d manufactured by Minolta. The results are shown in Table 1 below.

  As can be seen from Table 1, in Examples 1 and 2, a brighter green color can be observed than in Comparative Example 1, and a wider color reproduction range can be realized.

[Example 3]
In Example 1, an organic EL display device was produced in the same manner as in Example 1 except that a colored layer and a color conversion layer were formed as shown below.

(Formation of colored layer)
First, red and blue colored portion forming coating solutions were prepared. Condensed azo pigments (Ciba Specialty Chemicals, Chromophthal Red BRN) are used as red colorants, and anthraquinone pigments (Ciba Specialty Chemicals, Chromophthal Blue A3R) are used as blue colorants. Using. As the binder resin, an acrylic UV curable resin composition (acrylic UV curable resin 20%, acrylic UV curable resin monomer 20%, additive 5%, propylene glycol monomethyl ether acetate (PGMEA) 55%) Was used. For 10 parts of the acrylic UV curable resin composition, 1 part of each colorant (parts are based on mass) are mixed and dispersed sufficiently to form red and blue colored parts. A coating solution was obtained.
Next, a green colored part forming coating solution was prepared. As the green colorant, a phthalocyanine green pigment (manufactured by Toyo Ink Co., Ltd., Lionol Green 2Y-301) was used. Moreover, said acrylic UV curable resin composition was used as binder resin. A coloring agent is blended in a ratio of 1 part (all parts are based on mass) to 10 parts of the acrylic UV curable resin composition, and sufficiently mixed and dispersed to obtain a green colored part forming coating solution. It was.

Each colored part was formed using the above-described coating liquid for forming colored parts. That is, on the transparent substrate on which the black matrix was formed, a red colored portion forming coating solution was applied by a spin coating method, and prebaked at 120 ° C. for 2 minutes. Then, it exposed using the photomask (integrated exposure amount 300mJ / cm < ² >), and developed with the developing solution (0.05% KOH aqueous solution). Next, post-baking is performed at 230 ° C. for 60 minutes to synchronize with the black matrix pattern, and stripe-shaped red colored portions having a width of 85 μm and a thickness of 3.0 μm are arranged in the short side direction of the opening portion of the black matrix. It formed so that it might become. Thereafter, a green colored portion forming coating solution and a blue colored portion forming coating solution are sequentially used to form a striped green colored portion having a width of 85 μm and a thickness of 1.6 μm, and a stripe shape having a width of 85 μm and a thickness of 3.0 μm. The blue colored part of was formed. This formed a colored layer in which the colored portions of the three primary colors were repeatedly arranged in the width direction.

(Formation of color conversion layer)
An alkali-soluble negative photosensitive resist in which a green conversion phosphor (manufactured by Aldrich, Coumarin 6) is dispersed is used as a green color conversion part forming coating liquid, and this green color conversion part forming coating liquid is black matrix and colored After the layer was formed, it was applied by spin coating and prebaked at 100 ° C. for 5 minutes. Next, after patterning by photolithography, post baking was performed at 200 ° C. for 60 minutes. As a result, a striped green color conversion portion having a width of 85 μm and a thickness of 3.3 μm was formed on the green coloring portion.

(Evaluation)
Similar to the organic EL display devices of Examples 1 and 2, the organic EL display device of Example 3 was able to observe a vivid green color and realized a wider color reproduction range.

It is a schematic sectional drawing which shows an example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows the other example of the color filter substrate for organic EL elements of this invention. It is a schematic sectional drawing which shows an example of the organic electroluminescent display apparatus of this invention.

Explanation of symbols

DESCRIPTION OF SYMBOLS 1 ... Transparent base material 2 ... Colored layer 2R ... Red colored part 2G ... Green colored part 2B ... Blue colored part 3 ... Color conversion layer 3R ... Red color conversion part 3G ... Green color conversion part 3B ... Blue color conversion part 4 ... Light shielding Part 5: Flattening layer 6 ... Gas barrier layer 10 ... Color filter substrate for organic EL element 11 ... Transparent electrode layer 12 ... Organic EL layer 13 ... Counter electrode layer 20 ... Organic EL display device

Claims (8)

At least a transparent substrate, a colored layer formed in a pattern on the transparent substrate, having a red colored portion, a green colored portion, and a blue colored portion, and a green color conversion portion formed on the green colored portion A color filter substrate for an organic electroluminescence device having a color conversion layer,
Area formed on the green colored section the green color conversion part, than each area of the blue color conversion part is formed on the red-colored red color conversion part which is formed on part and the blue colored portion on also rather large,
Further, the green color conversion part is formed on the red color part, and the component on the long wavelength side of the green light emitted from the green color conversion part is the red color as the component on the short wavelength side of the red light. A color filter substrate for an organic electroluminescence element, wherein the color filter substrate is capable of transmitting through a portion .   The color filter substrate for an organic electroluminescence element according to claim 1, wherein the red color conversion part and the blue color conversion part are not formed.   The difference between the thickness of the red coloring portion, the thickness of the green coloring portion and the green color conversion portion combined, and the thickness of the blue coloring portion is 2.0 μm or less. The color filter substrate for organic electroluminescent elements as described.   The thickness of the red colored portion, the combined thickness of the green colored portion and the green color converting portion, and the thickness of the blue colored portion are within a range of 1 μm to 3 μm. The color filter substrate for organic electroluminescent elements according to claim 3. The color filter substrate for an organic electroluminescence element according to any one of claims 1 to 4, wherein a planarization layer is formed on the color conversion layer. 6. The color filter substrate for an organic electroluminescence element according to claim 1, wherein a gas barrier layer is formed on the color conversion layer. The color filter substrate for an organic electroluminescent element according to any one of claims 1 to 6 , wherein a light-shielding portion is formed between the colored portions on the transparent base material. . Organic color filter substrate for an electroluminescent device, a transparent electrode layer formed on the color conversion layer side surface of the color filter substrate for the organic electroluminescent device according to any one of claims of claims 1 to 7 And an organic electroluminescent layer including at least a white light emitting layer that is formed on the transparent electrode layer and emits white light by a two-wavelength light source, and a counter electrode layer formed on the organic electroluminescent layer. An organic electroluminescence display device.

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