Organic el display device, and method for manufacturing same

Abstract

Provided are: an organic EL display device that is provided with an optical sensor, and suppresses noise to the optical sensor, and is capable of achieving high resolution; and a method for manufacturing the same.　An organic EL display device having a near-infrared-light-receiving unit, a lower electrode, a light-emitting layer, a transparent electrode, and a color filter in this order on a substrate, wherein the color filter has a patterned colored layer and a visible-light-shielding layer provided on the near-infrared-light-receiving unit, and has, on the colored layer, a near-infrared-light-shielding layer that is located between the colored layer and the transparent electrode or is integrated with the colored layer.

Description

Organic EL display device and manufacturing method thereof

[0001] The present disclosure relates to an organic electroluminescence display device and a manufacturing method thereof.

[0002] In recent years, in electronic devices such as mobile phones and personal digital assistants, the development and mass production of display devices using organic electroluminescence (OLED), a self-emitting element, has progressed to meet the demand for thinner, lighter devices and curved displays, which are difficult to achieve with the currently mainstream liquid crystal display devices. Among these, the application of organic EL (organic electroluminescence) displays, which are high-resolution and small, measuring approximately 0.5 inches (hereinafter referred to as microdisplays), such as head-mounted displays and electronic viewfinders, is expected to take advantage of their thin and lightweight features. Meanwhile, there has been an increasing demand for display devices that incorporate biometric authentication technology, which uses automated devices to extract specific human biometric information and behavioral characteristic information to authenticate individuals, particularly in the fields of finance, healthcare, and mobile devices. Furthermore, head-mounted displays are required to incorporate eye-tracking functionality to alleviate VR sickness caused by out-of-focus images and to enhance the sense of immersion.

[0003] Patent Document 1 discloses an organic light-emitting diode (OLED) panel incorporating a near-infrared (NIR) organic photosensor, the OLED panel including a substrate, an OLED stack disposed on the substrate and emitting visible light, and an NIR photosensor stack disposed between the substrate and the OLED stack and including an NIR light-emitting section that emits NIR light and an NIR light-receiving section that receives NIR light.

[0004] Japanese Patent Application Laid-Open No. 2019-033071

[0005] In the OLED panel of Patent Document 1, as described below, visible light may be incident on the NIR organic light-receiving section. Furthermore, light emitted from the NIR organic light-emitting section may be transmitted through the pixel section and emitted. This light may become noise, resulting in a decrease in the performance of the infrared sensor. Furthermore, in order to achieve higher resolution, further miniaturization of pixel size is required. Consideration has been given to pixel formation using a color filter method, which is advantageous for forming fine pixels.

[0006] In consideration of the above-described problems, the present disclosure has an object to provide an organic EL display device that includes an optical sensor, suppresses noise in the optical sensor, and is capable of achieving high resolution, and a manufacturing method thereof.

[0007] The organic EL display device according to the present disclosure has, on a substrate, a near-infrared light receiving section, a lower electrode, a light emitting layer, a transparent electrode, and a color filter, in this order; the color filter has a patterned colored layer and a visible light blocking layer provided on the near-infrared light receiving section; and a near-infrared light blocking layer on the colored layer, between the colored layer and the transparent electrode, or integrated with the colored layer.

[0008] One aspect of the organic EL display device further includes a near-infrared emitting section between the substrate and the lower electrode, and the color filter includes a visible light blocking layer on the near-infrared emitting section.

[0009] One aspect of the organic EL display device has the near-infrared ray blocking layer on the colored layer.

[0010] In one aspect of the organic EL display device, the thickness of the visible light blocking layer is greater than the total thickness of the colored layer and the near-infrared light blocking layer.

[0011] In one aspect of the organic EL display device, the visible light-shielding layer has a maximum light transmittance of 5% or less in a wavelength range of 400 to 620 nm, a maximum light transmittance of 13% or less in a wavelength range of 620 to 730 nm, and a minimum light transmittance of 85% or more in a wavelength range of 830 to 1000 nm.

[0012] In one aspect of the organic EL display device, the near-infrared ray shielding layer has an average light transmittance of 80% or more in a wavelength range of 450 to 600 nm, has a maximum absorption wavelength in a wavelength range of 780 to 1000 nm, and has a light transmittance of 10% or less at the maximum absorption wavelength.

[0013] In one aspect of the organic EL display device, the visible light-shielding layer is a cured product of a composition for a visible light-shielding layer, which contains an organic pigment (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable compound (D), wherein the organic pigment (A) contains a blue pigment, a yellow pigment, and a violet pigment, and the contents of the organic pigments are, based on the organic pigment (A), 32 to 45% by weight of the blue pigment, 30 to 40% by weight of the yellow pigment, and 20 to 30% by weight of the violet pigment.

[0014] In one embodiment of the organic EL display device, the near-infrared ray shielding layer is a cured product of a composition for a near-infrared ray shielding layer, the composition comprising: a near-infrared ray absorbing dye (E) represented by the following general formula (1); a resin-type dispersant (F) having an amine value of 20 mgKOH / g to 200 mgKOH / g; and a binder resin (G) having a weight-average molecular weight of 5,000 to 40,000 and an acid value of 100 mgKOH / g to 130 mgKOH / g: X １ ~X １０ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, or —SO ２ NR １ R ２ , -COOR １ , -CONR １ R ２ , a nitro group, a cyano group, or a halogen atom; X １ ~X １０ may be bonded to each other to form a ring. １ and R ２ each independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0015] The method for producing an organic EL display device according to the present disclosure is characterized in that the colored layer, the visible light blocking layer, and the near-infrared light blocking layer are formed at 120° C. or less.

[0016] One aspect of the method for producing the organic EL display device includes preparing a laminated substrate including a near-infrared receiving unit, a lower electrode, a light-emitting layer, and a transparent electrode on a substrate, and forming a coating film of a composition for color layer on the laminated substrate.

[0017] According to the present disclosure, it is possible to provide an organic EL display device that includes an optical sensor, suppresses noise in the optical sensor, and enables high resolution, and a manufacturing method thereof.

[0018] FIG. 1 is a schematic cross-sectional view showing one embodiment of the organic EL display device of the present invention. FIG. 2 is a schematic cross-sectional view showing one embodiment of the organic EL display device of the present invention. FIG. 3 is a schematic cross-sectional view showing one embodiment of the organic EL display device of the present invention. FIG. 4 is a schematic cross-sectional view showing one embodiment of the organic EL display device of the present invention. FIG. 5 is a schematic front view showing one embodiment of the organic EL display device of the present invention. FIG. 6 is a schematic front view showing one embodiment of the organic EL display device of the present invention. FIG. 7 is a transmittance spectrum of the visible light-shielding layer of Production Example 1. FIG. 8 is a transmittance spectrum of the near-infrared light-shielding layer of Production Example 2.

[0019] An organic EL display device and a manufacturing method thereof will be described below. For clarity, the following descriptions and drawings have been simplified as appropriate. For clarity, the scale of each component in the drawings may differ significantly. In each drawing, identical elements are designated by the same reference numerals, and redundant descriptions are omitted as necessary. In each drawing, the +Z side is the display surface (front) of the organic EL display device. Terms used in this specification that specify shape, geometric conditions, and their degree, such as "parallel," "perpendicular," "orthogonal," and "identical," are not limited to their strict meanings but are interpreted to encompass a range within which similar functionality can be expected. In this disclosure, the symbol "to" indicating a numerical range means that the numerical values ​​before and after it are included as the lower and upper limits. In this disclosure, "(meth)acrylate" is a general term for acrylate and methacrylate, and "(meth)acrylic" and the like are also used in this disclosure. Furthermore, in this disclosure, "C.I." refers to the Color Index (C.I.).

[0020] 1. Organic EL Display Device The configuration of an organic EL display device according to a first embodiment will be described with reference to FIG. 1 . The organic EL display device 100 shown in FIG. 1 includes a substrate 10 on which a near-infrared light receiving section 21, an organic EL layer 30, and a color filter 40 are arranged in this order. The color filter 40 includes a patterned colored layer 4 (4R, 4G, 4B), a visible light-blocking layer 5 provided on the near-infrared light receiving section 21, and a near-infrared light-blocking layer 6 provided on the colored layer 4. Although not shown, the organic EL layer 30 also includes a lower electrode, a light-emitting layer, and a transparent electrode. In the example shown in FIG. 1 , the substrate 10 includes a wiring layer 50. The wiring layer 50 includes electrodes formed on the substrate, wiring electrically connecting the near-infrared light receiving section 21, and the organic EL layer 30. The wiring layer 50, the visible light-blocking layer 5, and the color filter 40 may each include a coating film 20 for purposes such as layer planarization and insulation. In the example of FIG. 1, the visible light blocking layer 5 includes a coating film 20 .

[0021] The organic EL display device of the first embodiment has a visible light blocking layer 5 on the near-infrared light receiving section 21, and a near-infrared light blocking layer 6 on the colored layer 4. Therefore, visible light 62 incident from the display surface side and near-infrared light 63 with a large incident angle are absorbed by each layer. As a result, the incidence of light that causes noise on the near-infrared light receiving section 21 is suppressed, and near-infrared light 61 with a small incident angle can be efficiently received. In the organic EL display device of the first embodiment, the optical sensor is used as a transmissive optical sensor, a reflective optical sensor that uses an external light source, or the like.

[0022] Next, the configuration of an organic EL display device according to a second embodiment will be described with reference to Fig. 2. The organic EL display device 100 shown in the example of Fig. 2 has, on a substrate 10, a near-infrared light receiving section 21, a near-infrared light emitting section 22, an organic EL layer 30, and a color filter 40, in this order. The color filter 40 has patterned colored layers 4 (4R, 4G, 4B), a visible light blocking layer 5 provided on the near-infrared light receiving section 21, and a near-infrared light blocking layer 6 provided on the colored layer 4.

[0023] The organic EL display device of the second embodiment has the configuration of the first embodiment, and also has a visible light blocking layer 5 on the near-infrared light emitting section 22 and a near-infrared light blocking layer 6 on the colored layer 4. Therefore, of the near-infrared rays emitted from the near-infrared light emitting section 22, those with a large emission angle are absorbed by the near-infrared light blocking layer 6, and only near-infrared rays 64 with a small emission angle are emitted. As a result, the near-infrared light receiving section 21 can efficiently receive light reflected from the specimen. In the organic EL display device of the second embodiment, the optical sensor is mainly used as a reflective optical sensor or the like.

[0024] The following description is common to the organic EL display devices of the first and second embodiments unless otherwise specified. Figures 3 and 4 show modified examples of the color filter 40. The organic EL display device 100 of Figure 3 includes a near-infrared ray blocking layer 6 between the transparent electrode and the colored layer 4 of the organic EL layer 30. The organic EL display device 100 of Figure 4 also includes a colored layer 7 having near-infrared ray blocking properties, in which the colored layer 4 and the near-infrared ray blocking layer 6 are integrated. The organic EL display devices shown in Figures 3 and 4 also achieve the same effects as the organic EL display devices of the first and second embodiments.

[0025] FIG. 5 shows another modified example of a color filter 40. In the color filter 40 of FIG. 5, the thickness of the visible light-shielding layer 5 is greater than the total thickness of the colored layer 4 and the near-infrared shading layer 6 (or, in the case of a colored layer 7 having near-infrared shading properties, the thickness of the colored layer 7). This configuration prevents the colored layers (4, 7) and the near-infrared shading layer 6 from covering the visible light-shielding layer 5 during manufacturing, thereby improving the stability of the quality of the organic EL display device. The thickness of the visible light-shielding layer 5 may be, for example, 10 to 1,000 nm thicker than the total thickness of the colored layer 4 and the near-infrared shading layer 6, preferably 20 to 200 nm thicker, and more preferably 25 to 150 nm thicker.

[0026] Next, the arrangement of the visible light-blocking layer 5 will be described with reference to FIGS. 6 to 8. FIGS. 6 to 8 are front views (viewed from the +Z direction) of the organic EL display device 100. The visible light-blocking layer 5 may be individually arranged on at least a portion of the near-infrared light receiving section 21 and the near-infrared light emitting section 22, as shown in FIG. 6. The visible light-blocking layer 5 may also be formed in a lattice pattern, as shown in FIG. 7. The visible light-blocking layer 5 in FIG. 7 also functions as a black matrix. Alternatively, as shown in FIG. 8, a black matrix may be formed by combining multiple visible light-blocking layers 5 with other light-blocking layers 8.

[0027] The organic EL display devices of the first and second embodiments may further include other layers and other configurations as necessary. Each configuration of the organic EL display device will be described in more detail below.

[0028] [Near-infrared receiving unit] The near-infrared receiving unit 21 is a unit that converts near-infrared rays into an electrical signal. One example of the near-infrared receiving unit is a photodiode, preferably a photodiode that receives near-infrared rays with a wavelength of 800 to 1500 nm. At least one near-infrared receiving unit may be provided in the organic EL display device, but it is preferable to have multiple near-infrared receiving units, and more preferably, they are arranged in a grid pattern. By providing multiple near-infrared receiving units, it is possible to obtain a mapping image of the measurement target (e.g., fingerprint, retina, face, etc.), which can be used for biometric authentication, etc.

[0029] [Near-infrared light emitting section] The near-infrared light emitting section 22 is a section that emits near-infrared light. One example of the near-infrared light emitting section is a light emitting diode, and a light emitting diode that emits near-infrared light with a wavelength of 800 to 1500 nm is preferable. At least one near-infrared light emitting section may be provided in the organic EL display device, but it is preferable to have multiple near-infrared light emitting sections, and it is more preferable to have them arranged in a lattice pattern.

[0030] [Color Filter] In the present disclosure, the color filter has a laminate of a colored layer 4 and a near-infrared ray blocking layer 6 arranged in a pattern, or a colored layer 7 having near-infrared ray blocking properties and the visible light blocking layer 5 provided at the predetermined position. The color filter is arranged on the organic EL layer 30 directly or via another layer.

[0031] <Colored Layer> The colored layer 4 may have at least a red layer 4R, a green layer 4G, and a blue layer 4B, and may further have a yellow layer, a cyan layer, a magenta layer, a white (colorless) layer, etc. The pattern arrangement of the colored layers is not particularly limited, but examples thereof include a stripe arrangement, a delta arrangement, a mosaic arrangement, and a honeycomb arrangement. Visible light-shielding layers 5 are arranged in at least a part of the color filter. A black matrix including the visible light-shielding layers 5 may be provided between the colored layers. The area per section of each colored layer is 1 to 50 μm from the viewpoint of high definition. ２ is preferred, and 1 to 30 μm ２ The thickness of each colored layer is preferably 0.1 to 5 μm, more preferably 0.2 to 4 μm, from the viewpoint of color reproducibility.

[0032] In order to obtain an organic EL display device with high brightness, high resolution, and excellent color reproducibility, it is preferable that each colored layer has the following spectral characteristics. Red layer: The maximum transmittance of light in the wavelength range of 450 nm to 560 nm is 0.5% or less, the 50% transmittance wavelength is 593 nm to 603 nm, and the average transmittance of light in the wavelength range of 600 nm to 700 nm is 80% or more and 100%. Green layer: The maximum transmittance of light in the wavelength range of 400 nm to 470 nm is 2% or less, the maximum transmittance of light in the wavelength range of 525 nm to 535 nm is 67% or more, the 50% transmittance wavelength on the short wavelength side is 497 to 507 nm, and the 50% transmittance wavelength on the long wavelength side is 554 to 581 nm. Blue layer: The maximum transmittance of light in the wavelength range of 500 nm to 560 nm is less than 20%.

[0033] <Visible Light Shielding Layer> The visible light shielding layer 5 is a layer that absorbs visible light and preferably transmits near-infrared light. The visible light shielding layer 5 preferably has, for example, the following spectral characteristics: - A maximum light transmittance of 5% or less in the wavelength range of 400 to 620 nm. - A maximum light transmittance of 13% or less in the wavelength range of 620 to 730 nm. - A minimum light transmittance of 85% or more in the wavelength range of 830 to 1000 nm.

[0034] <Near-infrared shading layer> The near-infrared shading layer 6 is preferably a layer that absorbs near-infrared rays and transmits visible light. The near-infrared shading layer 6 preferably has the following spectral characteristics, for example: - An average light transmittance in the wavelength range of 450 to 600 nm of 80% or more. - A maximum absorption wavelength in the wavelength range of 780 to 1000 nm, and a light transmittance at the maximum absorption wavelength of 10% or less.

[0035] <Materials of Each Layer> Next, the materials of each layer constituting the color filter will be described. When the present organic EL display device is used in a high-resolution microdisplay with a pixel size of 1 μm to 5 μm, for example, each layer is preferably formed by photolithography, since this allows for further miniaturization. Furthermore, when the organic EL element and the color filter are formed on separate substrates and then bonded together, there is a risk of misalignment, which is particularly significant in microdisplays. Therefore, it is preferable to form the color filter directly on the organic EL element. When forming a color filter using this on-chip method, it is necessary to form a sufficiently cured layer by baking at 120°C or less due to the heat resistance of the light-emitting layer, etc. Below, compositions for forming each layer that satisfy these conditions will be described.

[0036] (1) Composition for Visible Light Shielding Layer The composition for visible light shielding layer contains an organic pigment (A), a binder resin (B), a photopolymerization initiator (C), and a photopolymerizable compound (D), wherein the organic pigment (A) contains a blue pigment, a yellow pigment, and a violet pigment, and the organic pigment contents are preferably 32 to 45 wt % of the blue pigment, 30 to 40 wt % of the yellow pigment, and 20 to 30 wt % of the violet pigment, based on the organic pigment (A). The proportions of each pigment in the organic pigment (A) are more preferably 33 to 38 wt % of the blue pigment, 35 to 40 wt % of the yellow pigment, and 25 to 30 wt % of the violet pigment. This composition satisfies the above spectral characteristics and the above film-forming conditions.

[0037] (Organic Pigment (A)) The organic pigment (A) contains at least a blue pigment, a yellow pigment, and a purple pigment, and may further contain pigments of other colors.

[0038] Specific examples of blue pigments include C.I. Pigment Blue 1, 1:2, 9, 14, 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 17, 19, 25, 27, 28, 29, 33, 35, 36, 56, 56:1, 60, 61, 61:1, 62, 63, 66, 67, 68, 71, 72, 73, 74, 75, 76, 78, and 79.

[0039] Specific examples of yellow pigments include C.I. Pigment Yellow (PY) 1, 1:1, 2, 3, 4, 5, 6, 9, 10, 12, 13, 14, 16, 17, 24, 31, 32, 34, 35, 35:1, 36, 36:1, 37, 37:1, 40, 41, 42, 43, 48, 53, 55, 61, 62, 62:1, 63, 65, 73, 74, 75, 81, 83, 87, 93, 94, 95, 97, 100, 101, 104, 105, 108, 109, 110, 111, 116, 117, 119, 120, 126, 127, 127:1, 128, 129, 133, 134, 136 , 138, 139, 142, 147, 148, 150, 151, 153, 154, 155, 157, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 169, 170, 172, 173, 174, 175, 176, 180, 181, 182, 183, 184, 185, 188, 189, 190, 191, 191:1, 192, 193, 194, 195, 196, 197, 198, 199, 200, 202, 203, 204, 205, 206, 207, 208, etc.

[0040] Specific examples of purple pigments include C.I. Pigment Violet (PV) 1, 1:1, 2, 2:2, 3, 3:1, 3:3, 5, 5:1, 14, 15, 16, 19, 23, 25, 27, 29, 31, 32, 37, 39, 42, 44, 47, 49, and 50.

[0041] In the organic pigment (A) used in the composition for visible light-shielding layer, the blue pigment is preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6 from the viewpoint of visible light-shielding properties, and more preferably C.I. Pigment Blue 15:3 or C.I. Pigment Blue 15:6. In the organic pigment (A), the yellow pigment is preferably C.I. Pigment Yellow 83, 117, 129, 138, 139, 150, 154, 155, 180 or 185 from the viewpoint of visible light-shielding properties, and more preferably C.I. Pigment Yellow 83, 138, 139, 150 or 185. In addition, in the organic pigment (A), the purple pigment is preferably C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4 or 15:6 from the viewpoint of visible light-shielding properties. C.I. Pigment Violet 19 or 23 is preferred, and C.I. Pigment Violet 23 is more preferred.

[0042] From the viewpoint of obtaining sufficient light-shielding properties, the total concentration of the organic pigment (A) in the composition for visible light-shielding layer is preferably 10 to 90% by weight, more preferably 15 to 85% by weight, and even more preferably 20 to 80% by weight, based on the non-volatile components in the composition for visible light-shielding layer.

[0043] The organic pigment (A) is preferably used in a finely divided form. The primary particle diameter of the organic pigment (A) is preferably 20 to 100 nm, more preferably 25 to 85 nm. The primary particle diameter of the pigment is measured by directly measuring the size of the primary particles from an electron micrograph of the pigment taken with a TEM (transmission electron microscope). Specifically, the minor axis diameter and major axis diameter of the primary pigment particles are measured, and the average is taken as the particle diameter of the pigment particles. This is determined for 100 or more pigment particles, and the average is taken as the average primary particle diameter.

[0044] (Binder Resin (B)) The binder resin (B) contributes to the dispersion stability of the organic pigment (A) and suppresses aggregation of the organic pigment (A) in the visible light-shielding layer. In addition, the use of the binder resin (B) results in excellent developability and shape stability in photolithography.

[0045] The binder resin (B) is preferably a thermoplastic resin, and when the composition for visible light-shielding layer is used as an alkali-developable resist, an alkali-soluble resin having an acidic group is preferred. In order to further improve photosensitivity, the binder resin (B) may be an active energy ray-curable resin having an ethylenically unsaturated double bond. Among these, an alkali-soluble active energy ray-curable resin is preferred.

[0046] Examples of thermoplastic resins include acrylic resins, butyral resins, styrene-maleic acid copolymers, chlorinated polyethylene, chlorinated polypropylene, polyvinyl chloride, vinyl chloride-vinyl acetate copolymers, polyvinyl acetate, polyurethane resins, polyester resins, vinyl resins, alkyd resins, polystyrene resins, polyamide resins, rubber resins, cyclized rubber resins, celluloses, polyethylene (HDPE, LDPE), polybutadiene, polyimide resins, etc. Among these, acrylic resins are preferred.

[0047] Examples of the acidic group in the alkali-soluble resin include a carboxy group and a sulfo group. Specific examples of the alkali-soluble resin include an acrylic resin having an acidic group, an α-olefin / maleic acid (anhydride) copolymer, a styrene / styrene sulfonic acid copolymer, an ethylene / (meth)acrylic acid copolymer, or an isobutylene / maleic acid (anhydride) copolymer. Among these, an acrylic resin having an acidic group or a styrene / styrene sulfonic acid copolymer is preferred, and an acrylic resin having an acidic group is more preferred from the viewpoints of heat resistance and transparency.

[0048] Examples of the alkali-soluble active energy ray-curable resin include resins produced by the following methods (i) and (ii).

[0049] Method (i): A carboxylic acid having an ethylenically unsaturated double bond is subjected to an addition reaction with the side-chain epoxy group of a copolymer obtained by copolymerizing a monomer having an epoxy group with another monomer, and the resulting hydroxyl group is then reacted with a polycarboxylic acid (anhydride) to introduce an ethylenically unsaturated double bond and a carboxy group.

[0050] Examples of the monomer having an epoxy group include glycidyl (meth)acrylate, methyl glycidyl (meth)acrylate, 2-glycidoxyethyl (meth)acrylate, 3,4-epoxybutyl (meth)acrylate, and 3,4-epoxycyclohexyl (meth)acrylate. From the viewpoint of reactivity with a carboxylic acid having an ethylenically unsaturated double bond in the next step, glycidyl (meth)acrylate is preferred.

[0051] Examples of the carboxylic acid having an ethylenically unsaturated double bond include (meth)acrylic acid, crotonic acid, and vinylbenzoic acid.

[0052] The polycarboxylic acid may be an anhydride, and examples thereof include tetrahydrophthalic anhydride, phthalic anhydride, hexahydrophthalic anhydride, succinic anhydride, maleic anhydride, trimellitic anhydride, and pyromellitic dianhydride.

[0053] As a modification of the method (i), a compound having an ethylenically unsaturated double bond and an epoxy group may be added to the side chain carboxy group of a copolymer obtained by copolymerizing a monomer having a carboxy group with another monomer, and the resulting hydroxyl group may be reacted with a polycarboxylic acid (anhydride) to introduce an ethylenically unsaturated double bond and a carboxy group.

[0054] Method (ii): A monomer having a hydroxyl group, a monomer having a carboxyl group, and, if necessary, other monomers are copolymerized to obtain a copolymer, and an ethylenically unsaturated monomer having an isocyanate group is reacted with the side chain hydroxyl group of the copolymer to introduce an ethylenically unsaturated double bond.

[0055] Examples of monomers having a hydroxyl group include hydroxyalkyl (meth)acrylates such as 2-hydroxyethyl (meth)acrylate, hydroxypropyl (meth)acrylate, hydroxybutyl (meth)acrylate, glycerol (meth)acrylate, and cyclohexanedimethanol mono(meth)acrylate. Polyether mono(meth)acrylates obtained by addition polymerization of ethylene oxide, propylene oxide, and / or butylene oxide to the above-mentioned hydroxyalkyl (meth)acrylates, and (poly)ester mono(meth)acrylates obtained by addition of (poly)γ-valerolactone, (poly)ε-caprolactone, (poly)12-hydroxystearic acid, and the like, can also be used. 2-Hydroxyethyl (meth)acrylate or glycerol (meth)acrylate are preferred from the viewpoint of suppressing the generation of foreign matter when a coating film is formed.

[0056] Examples of the monomer having a carboxy group include the same monomers as those described above as the carboxylic acid having an ethylenically unsaturated double bond.

[0057] Examples of the monomer having an isocyanate group include 2-(meth)acryloyloxyethyl isocyanate and 1,1-bis[(meth)acryloyloxy]ethyl isocyanate.

[0058] From the viewpoint of dispersibility of the organic pigment (A), the weight average molecular weight (Mw) of the binder resin (B) is preferably in the range of 10,000 to 100,000, more preferably 10,000 to 80,000. The number average molecular weight (Mn) is preferably in the range of 5,000 to 50,000, and the value of Mw / Mn is preferably 10 or less.

[0059] The acid value of the binder resin (B) is preferably from 20 to 300 mgKOH / g from the viewpoints of pigment dispersibility, developability, and resistance of the cured film.

[0060] The proportion of the binder resin (B) in the composition for visible light shielding layer is preferably 20 to 1000 parts by weight per 100 parts by weight of the organic pigment (A) in terms of film-forming properties and durability of the cured film.

[0061] (Photopolymerization Initiator (C)) Examples of the photopolymerization initiator (C) include acetophenone-based compounds such as 4-phenoxydichloroacetophenone, 4-t-butyl-dichloroacetophenone, diethoxyacetophenone, p-dimethylaminoacetophenone, 1-(4-isopropylphenyl)-2-hydroxy-2-methylpropan-1-one, 1-hydroxycyclohexyl phenyl ketone, 2-methyl-1-[4-(methylthio)phenyl]-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one, and 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone; and benzoin-based compounds such as benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzyl dimethyl ketal. Benzophenone-based compounds such as benzophenone, benzoylbenzoic acid, methyl benzoylbenzoate, 4-phenylbenzophenone, hydroxybenzophenone, acrylated benzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, and 3,3',4,4'-tetra(t-butylperoxycarbonyl)benzophenone; thioxanthone-based compounds such as thioxanthone, 2-chlorothioxanthone, 2-methylthioxanthone, isopropylthioxanthone, 2,4-diisopropylthioxanthone, and 2,4-diethylthioxanthone; Triazine compounds such as 2,4,6-trichloro-s-triazine, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(p-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-(p-tolyl)-4,6-bis(trichloromethyl)-s-triazine, 2-piperonyl-4,6-bis(trichloromethyl)-s-triazine, 2,4-bis(trichloromethyl)-6-styryl-s-triazine, 2-(naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxy-naphth-1-yl)-4,6-bis(trichloromethyl)-s-triazine, 2,4-trichloromethyl-(piperonyl)-6-triazine, and 2,4-trichloromethyl(4'-methoxystyryl)-6-triazine;Acetophenone, benzophenone, 4,4'-bis(diethylamino)-benzophenone, 4-(methylphenylthio)-phenyl phenyl ketone, benzil dimethyl ketal, 2-methyl-1-methylthiophenyl-2-morpholinopropan-1-one, 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)butan-1-one, ethyl p-diethylaminobenzoate, thioxanthone, 2,5-diethylthioxanthone, 2-chloroxanthone, isopropyl Thioxanthone, 1-chloro-4-propoxy-thioxanthone, 2-(o-chlorophenyl)-4,5-diphenylimidazole dimer, 2-(o-fluorophenyl)-4,5-diphenylimidazole dimer, 2-(o-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(p-methoxyphenyl)-4,5-diphenylimidazole dimer, 2-(o-chlorophenyl)-4,5-di(o-methoxyphenyl)imidazole dimer, 9-phenylacrylamide 9-(p-toluyl)acridine, 1,7-bis(9,9'-acridinyl)heptane, N-phenylglycine, bis(η5-cyclopentadienyl)bis[2,6-difluoro-3-(1H-pyrrol-1-yl)phenyl]titanium, 2-ethylanthraquinone, 1-chloroanthraquinone, 2-phenyl-4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxyphenyl)-4,6-bis(trichloromethyl)-s-triazine, 2-naphthyl oxime ester compounds such as 4,6-bis(trichloromethyl)-s-triazine, 2-(4-methoxynaphthyl)-4,6-bis(trichloromethyl)-s-triazine, 2-methyl-4,6-bis(trichloromethyl)-s-triazine, 1,2-octanedione, 1-[4-(phenylthio)phenyl-,2-(O-benzoyloxime)], O-(acetyl)-N-(1-phenyl-2-oxo-2-(4'-methoxy-naphthyl)ethylidene)hydroxylamine;Phosphine compounds such as bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and 2,4,6-trimethylbenzoyl-diphenyl-phosphine oxide; imidazole compounds such as 2,2'-bis(o-chlorophenyl)-4,5,4',5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(o-methoxyphenyl)-4,4',5,5'-tetraphenylbiimidazole, and 2,2'-bis(o-chlorophenyl)-4,4',5,5'-tetra(p-methylphenyl)biimidazole; 2-dimethylamino-2-methyl-1-phenylpropan-1-one, 2-diethylamino-2-methyl-1-phenylpropan-1-one, 2-methyl-2-morpholino-1-phenylpropan-1-one, 2-dimethylamino-2-methyl-1-(4-methylphenyl)propan-1-one, 2-dimethylamino-1-(4-ethylphenyl)-2-methylpropan-1-one, 2-dimethylamino-1-(4-isopropylphenyl)-2-methylpropan-1-one, 1-(4-butylphenyl)-2-dimethylamino-2-methylpropan-1-one, 2-dimethylamino-1-(4-methoxyphenyl)-2-methylpropan-1-one Aminoketone compounds such as pan-1-one, 2-dimethylamino-2-methyl-1-(4-methylthiophenyl)propan-1-one, 2-methyl-1-(4-methylthiophenyl)-2-morpholinopropan-1-one (IRGACURE 907), 2-benzyl-2-dimethylamino-1-(4-morpholinophenyl)-butan-1-one (IRGACURE 369), 2-benzyl-2-dimethylamino-1-(4-dimethylaminophenyl)-butan-1-one, 2-dimethylamino-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]-1-butanone (IRGACURE 379); quinone compounds such as 9,10-phenanthrenequinone, camphorquinone, and ethylanthraquinone; borate compounds, carbazole compounds, and titanocene compounds;

[0062] Among these, it is more preferable to use an oxime ester compound as the photopolymerization initiator. Oxime ester compounds have very high sensitivity, which allows pattern formation with low exposure dose and also provides excellent adhesion during the development process.

[0063] As the oxime ester photopolymerization initiator, among others, oxime ester photopolymerization initiators represented by the following general formulas (8) to (10) are preferred, oxime ester photopolymerization initiators represented by the following general formula (8) or (9) are more preferred, and oxime ester photopolymerization initiators represented by general formula (8) are even more preferred.

[0064] Oxime ester photopolymerization initiator represented by general formula (8) In formula (8), Z represents a direct bond or a —C(═O)— group, and R １１ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R １２ represents an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, R １３ ~R ２０ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R ２１ represents a —C(═O)— group. ２１ represents an aryl group which may have a substituent.

[0065] R １１ ~R ２０ Examples of the alkyl group having 1 to 20 carbon atoms in R include linear alkyl groups such as methyl, ethyl, propyl, butyl, hexyl, octyl, and dodecyl groups. １２ ~R ２１ Examples of the aryl group in the formula (8) include a phenyl group, a naphthyl group, an anthracenyl group, etc. Note that when Z is a direct bond, this means that Z does not have any atoms, and the two atoms connected to Z in general formula (8) are directly bonded.

[0066] The substituents that the alkyl group and aryl group may have refer to the fact that the alkyl group or aryl group may have a substituent in place of a hydrogen atom that the alkyl group or aryl group has. Examples of the substituent include halogen atoms such as a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom; alkoxy groups such as a methoxy group, an ethoxy group, and a tert-butoxy group; aryloxy groups such as a phenoxy group and a p-tolyloxy group; alkoxycarbonyl groups such as a methoxycarbonyl group, a butoxycarbonyl group, and a phenoxycarbonyl group; acyloxy groups such as an acetoxy group, a propionyloxy group, and a benzoyloxy group; acyl groups such as an acetyl group, a benzoyl group, an isobutyryl group, an acryloyl group, a methacryloyl group, and a methoxalyl group; alkylsulfanyl groups such as a methylsulfanyl group and a tert-butylsulfanyl group; arylsulfanyl groups such as a phenylsulfanyl group and a p-tolylsulfanyl group; alkylamino groups such as a methylamino group and a cyclohexylamino group; arylamino groups such as a phenylamino group and a p-tolylamino group; alkyl groups such as a methyl group, an ethyl group, a tert-butyl group, a dodecyl group, a cyclopropyl group, a cyclobutyl group, a cyclopentyl group, a cyclohexyl group, a cycloheptyl group, a cyclooctyl group, and a cyclooctadecyl group; aryl groups such as a phenyl group, a p-tolyl group, a xylyl group, a cumenyl group, a naphthyl group, an anthryl group, and a phenanthryl group; heterocyclic groups such as a furyl group and a thienyl group, as well as a hydroxy group, a carboxy group, a formyl group, a mercapto group, a sulfo group, a mesyl group, a p-toluenesulfonyl group, an amino group, a nitro group, a cyano group, a trifluoromethyl group, a trichloromethyl group, a trimethylsilyl group, a phosphinico group, a phosphono group, a trimethylammonium group, a dimethylsulfoniumyl group, and a triphenylphenacylphosphoniumyl group. Furthermore, one or more of these substituents may be present, or one or more types of these substituents may be present, and furthermore, the hydrogen atoms of these substituents may be further substituted with other substituents.

[0067] Among the oxime ester photopolymerization initiators represented by general formula (8), Z is a direct bond or a —C(═O)— group, and R １１is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R １２ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R １３ ~R ２０ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, a nitro group, or R ２１ A —CO— group is preferred. １４ ~R １６ and R １８ ~R ２０ is a hydrogen atom, and R １７ is a hydrogen atom, or R ２１ is a —CO— group, and R ２１ However, it is more preferably an aryl group which may have a substituent.

[0068] Of the oxime ester photopolymerization initiators represented by general formula (8), compounds represented by the following chemical formula (8-1) or (8-2) are preferred.

[0069]

[0070] Oxime ester photopolymerization initiator represented by general formula (9) In formula (9), W １ and W ２ each independently represents a carbonyl bond (—CO—) or a single bond, W １ and W ２ At least one of R is a carbonyl bond (—CO—). ａ is an alkyl group having 2 to 6 carbon atoms, and R ｂ is an alkyl group having 4 to 10 carbon atoms, and R ｃ is a group that contains at least a hydrocarbon ring or a heterocyclic ring and may further contain at least one divalent linking group selected from an alkylene chain having 1 to 4 carbon atoms, a thioether bond (—S—), an ether bond (—O—), and a carbonyl bond (—CO—), and R ｂ and R ｃ are different substituents. ｄ and R ｅ are each independently an alkyl group having 1 to 6 carbon atoms.

[0071] R ａ Examples of the alkyl group in R include linear alkyl groups such as an ethyl group, a propyl group, a butyl group, and a hexyl group. ｂ Examples of the alkyl group in R include a straight-chain alkyl group such as a butyl group, a hexyl group, an octyl group, and a dodecyl group. ｃ Examples of the hydrocarbon ring in R include an aliphatic hydrocarbon ring such as a cyclohexyl group, and an aromatic hydrocarbon ring such as a phenyl group, a naphthyl group, and an anthracenyl group. ｃ Examples of the heterocyclic ring in R include a ring in which one or more carbon atoms of the hydrocarbon ring are replaced with a nitrogen atom, an oxygen atom, or a sulfur atom. ｄ and R ｅ Examples of the alkyl group include a straight-chain alkyl group such as a methyl group, an ethyl group, a propyl group, a butyl group, and a hexyl group.

[0072] Of the oxime ester photopolymerization initiators represented by general formula (9), compounds represented by the following chemical formula (9-1) are preferred.

[0073]

[0074] Oxime ester photopolymerization initiator represented by general formula (10) In formula (10), R ３１ and R ３２ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R ３３ and R ３４ are each independently a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, or an aryl group which may have a substituent, and R ３５ is a hydrogen atom, an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or R ３６ is a —CO— group, and R ３６ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, an aryl group which may have a substituent, or a heterocyclic group.

[0075] R ３１ ~R３６ The alkyl group having 1 to 20 carbon atoms in the R １１ ~R ２０ The alkyl group may be the same as the alkyl group having 1 to 20 carbon atoms in R ３１ ~R ３６ The aryl group in １２ ~R ２１ The aryl group in R ３６ Examples of the heterocyclic ring in the heterocyclic group include furan, thiophene, pyrrole, oxazole, thiazole, imidazole, pyrazole, pyran, pyrone, pyridine, pyrone, pyridazine, pyrimidine, pyrazine, benzofuran, thionaphthene, indole, carbazole, coumarin, quinoline, phthalazine, quinoxaline, etc. The substituents that the alkyl group and aryl group may have may be the same as the substituents in the general formula (8).

[0076] The oxime ester photopolymerization initiator represented by general formula (10) is R ３１ is an aryl group which may have a substituent, and R ３２ is an alkyl group having 1 to 20 carbon atoms which may have a substituent, and R ３３ and R ３４ is a hydrogen atom, and R ３５ is a hydrogen atom, or R ３６ A —CO— group is preferred.

[0077] Of the oxime ester photopolymerization initiators represented by general formula (10), compounds represented by the following chemical formula (10-1) are preferred.

[0078]

[0079] The proportion of the photopolymerization initiator (C) in the composition for visible light-shielding layer is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, per 100 parts by weight of the organic pigment (A), from the viewpoints of curability and developability.

[0080] (Photopolymerizable Compound (D)) Examples of the photopolymerizable compound (D) include monomers and oligomers that are cured by ultraviolet light or the like to produce a transparent resin. Specific examples of the photopolymerizable compound (D) include methyl (meth)acrylate, ethyl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, cyclohexyl (meth)acrylate, β-carboxyethyl (meth)acrylate, polyethylene glycol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, triethylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, trimethylolpropane tri(meth)acrylate, trimethylolpropane PO-modified tri(meth)acrylate, trimethylolpropane EO-modified tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, and 1,6-hexanediol diglycidyl ether. Examples of the acrylic acid esters and methacrylic acid esters include methylol di(meth)acrylate, bisphenol A diglycidyl ether di(meth)acrylate, neopentyl glycol diglycidyl ether di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol penta(meth)acrylate, tricyclodecanyl (meth)acrylate, ester acrylate, (meth)acrylic acid ester of methylolated melamine, epoxy (meth)acrylate, and urethane acrylate; (meth)acrylic acid, styrene, vinyl acetate, hydroxyethyl vinyl ether, ethylene glycol divinyl ether, pentaerythritol trivinyl ether, (meth)acrylamide, N-hydroxymethyl (meth)acrylamide, N-vinylformamide, and acrylonitrile.

[0081] Further, as the photopolymerizable compound (D), an esterification product of a compound in which (meth)acrylic acid is introduced into a part of a polyhydric alcohol with a dicarboxylic acid; an esterification product of a polycarboxylic acid with a monohydroxy(meth)acrylate; or the like may be used. Specific examples include monoesters of monohydroxy oligoacrylates or monohydroxy oligomethacrylates, such as trimethylolpropane diacrylate, trimethylolpropane dimethacrylate, pentaerythritol triacrylate, pentaerythritol trimethacrylate, dipentaerythritol pentaacrylate, and dipentaerythritol pentamethacrylate, with dicarboxylic acids, such as malonic acid, succinic acid, glutaric acid, and terephthalic acid; and esters of tricarboxylic acids, such as propane-1,2,3-tricarboxylic acid (tricarballylic acid), butane-1,2,4-tricarboxylic acid, benzene-1,2,3-tricarboxylic acid, benzene-1,3,4-tricarboxylic acid, and benzene-1,3,5-tricarboxylic acid, with monohydroxy monoacrylates or monohydroxy monomethacrylates, such as 2-hydroxyethyl acrylate, 2-hydroxyethyl methacrylate, 2-hydroxypropyl acrylate, and 2-hydroxypropyl methacrylate.

[0082] Further, polyfunctional monomers having 3 to 12 ethylenically unsaturated bonds per molecule are exemplified, and it is preferable to include a polyfunctional monomer. Examples of the polyfunctional monomer include, in addition to the above, phenoxytetraethylene glycol (meth)acrylate, phenoxyhexaethylene glycol (meth)acrylate, EO-modified phthalic acid (meth)acrylate, PO-modified phthalic acid (meth)acrylate, acrylated isocyanurate, bis(acryloxyneopentyl glycol) adipate, polyethylene glycol 200 di(meth)acrylate, polyethylene glycol 400 di(meth)acrylate, tetraethylene glycol di(meth)acrylate, EO-modified trimethylolpropane triacrylate, PO-modified trimethylolpropane tri(meth)acrylate, and tripropylene glycol. Examples of the di(meth)acrylate include di(meth)acrylate, tris(acryloxyethyl)isocyanurate, caprolactone-modified tris(acryloxyethyl)isocyanurate, hydroxypivalic acid neopentyl glycol di(meth)acrylate, pentaerythritol tri(meth)acrylate, dicyclopentanyl di(meth)acrylate, EO-modified bisphenol A di(meth)acrylate, dipentaerythritol hexa(meth)acrylate, dipentaerythritol monohydroxypenta(meth)acrylate, alkyl-modified dipentaerythritol penta(meth)acrylate, and caprolactone-modified dipentaerythritol hexa(meth)acrylate.

[0083] The photopolymerizable compound (D) may contain a compound represented by the following general formula (7) in order to achieve both adhesion to other layers and high resolution of the resist pattern. ２ =CHC(=O)-(OC ｍ H ２ｍ ) ｎ -OCH ２ ] ３ -CR (In the general formula (1), m represents an integer of 1 to 3, n represents an integer of 0 to 2, and plural m's and n's may be the same or different. R is -CH ２ CH ３ , -CH ２ OH, -CH ２OC(=O)C=CH ２ represents a substituent selected from the following.) Examples of the compound represented by general formula (7) include trimethylolpropane triacrylate, trimethylolpropane EO-modified triacrylate, trimethylolpropane PO-modified triacrylate, pentaerythritol triacrylate, and pentaerythritol tetraacrylate.

[0084] The proportion of the photopolymerizable compound (D) in the composition for visible light-shielding layer is preferably 5 to 400 parts by weight, more preferably 10 to 300 parts by weight, per 100 parts by weight of the organic pigment (A), from the viewpoints of curability and developability.

[0085] (Optional Components) The composition for visible light-shielding layer may further contain other components, such as a sensitizer, a solvent, a chain transfer agent, an antioxidant, a leveling agent, a storage stabilizer, an adhesion improver, an ultraviolet absorber, and a polymerization inhibitor.

[0086] Sensitizers improve the photocurability of the composition and the development stability of the cured product. Examples of sensitizers include unsaturated ketones such as chalcone derivatives and dibenzalacetone; 1,2-diketone derivatives such as benzil and camphorquinone; polymethine dyes such as benzoin derivatives, fluorene derivatives, naphthoquinone derivatives, anthraquinone derivatives, xanthene derivatives, thioxanthene derivatives, xanthone derivatives, thioxanthone derivatives, coumarin derivatives, ketocoumarin derivatives, cyanine derivatives, merocyanine derivatives, and oxonol derivatives; acridine derivatives, azine derivatives, thiazine derivatives, oxazine derivatives, indoline derivatives, azulene derivatives, azulenium derivatives, and squaryliridines. Examples of suitable ruthenium derivatives include ruthenium derivatives, porphyrin derivatives, tetraphenylporphyrin derivatives, triarylmethane derivatives, tetrabenzoporphyrin derivatives, tetrapyrazinoporphyrazine derivatives, phthalocyanine derivatives, tetraazaporphyrazine derivatives, tetraquinoxalylporphyrazine derivatives, naphthalocyanine derivatives, subphthalocyanine derivatives, pyrylium derivatives, thiopyrylium derivatives, tetraphyrin derivatives, annulene derivatives, spiropyran derivatives, spirooxazine derivatives, thiospiropyran derivatives, metal arene complexes, organic ruthenium complexes, and Michler's ketone derivatives. Among these, thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives are preferred as sensitizers, and more specifically, 2,4-diethylthioxanthone, 2-chlorothioxanthone, 2,4-dichlorothioxanthone, 2-isopropylthioxanthone, 4-isopropylthioxanthone, 1-chloro-4-propoxythioxanthone, 4,4'-bis(dimethylamino)benzophenone, 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, N-ethylcarbazole, 3-benzoyl-N-ethylcarbazole, and 3,6-dibenzoyl-N-ethylcarbazole are preferred. When a sensitizer is used, the amount of the sensitizer is preferably 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator (C), from the viewpoints of curability and developability.

[0087] Solvent The solvent improves the dispersibility of the organic pigment (A) and the coatability and film-forming properties of the composition. Examples of the solvent include ester solvents (solvents that contain -COO- in the molecule but do not contain -O-), ether solvents (solvents that contain -O- in the molecule but do not contain -COO-), ether ester solvents (solvents that contain -COO- and -O- in the molecule), ketone solvents (solvents that contain -CO- in the molecule but do not contain -COO-), alcohol solvents (solvents that contain OH in the molecule but do not contain -O-, -CO-, or -COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

[0088] Specific examples of the solvent include 1,2,3-trichloropropane, 1,3-butanediol, 1,3-butylene glycol, 1,3-butylene glycol diacetate, 1,4-dioxane, 2-heptanone, 2-methyl-1,3-propanediol, 3,5,5-trimethyl-2-cyclohexen-1-one, 3,3,5-trimethylcyclohexanone, ethyl 3-ethoxypropionate, 3-methyl-1,3-butanediol, 3-methoxy-3-methyl-1-butanol, 3-methoxy-3-methylbutyl acetate, 3-methoxybutanol, 3-methyl-2-methyl-1-propanediol, 2-methyl-1,3-propanediol, 2 ... butyl acetate, 4-heptanone, m-xylene, m-diethylbenzene, m-dichlorobenzene, N,N-dimethylacetamide, N,N-dimethylformamide, n-butyl alcohol, n-butylbenzene, n-propyl acetate, N-methylpyrrolidone, o-xylene, o-chlorotoluene, o-diethylbenzene, o-dichlorobenzene, p-chlorotoluene, p-diethylbenzene, sec-butylbenzene, tert-butylbenzene, γ-butyrolactone, isobutyl alcohol, isophorone, ethylene glycol diethyl ether ether, ethylene glycol dibutyl ether, ethylene glycol monoisopropyl ether, ethylene glycol monoethyl ether, ethylene glycol monoethyl ether acetate, ethylene glycol monotertiary butyl ether, ethylene glycol monobutyl ether, ethylene glycol monobutyl ether acetate, ethylene glycol monopropyl ether, ethylene glycol monohexyl ether, ethylene glycol monomethyl ether, ethylene glycol monomethyl ether acetate, diisobutyl ketone, diethylene glycol diethyl ether, diethylene glycol dimethyl ether, diethylene glycol monoisopropyl ether, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether, diethylene glycol monobutyl ether acetate, diethylene glycol monomethyl ether, cyclohexanol, cyclohexanol acetate, cyclohexanone, dipropylene glycol dimethyl ether, dipropylene glycol methyl ether acetate, dipropylene glycol monoethyl ether,Examples of suitable solvents include dipropylene glycol monobutyl ether, dipropylene glycol monopropyl ether, dipropylene glycol monomethyl ether, diacetone alcohol, triacetin, tripropylene glycol monobutyl ether, tripropylene glycol monomethyl ether, propylene glycol diacetate, propylene glycol phenyl ether, propylene glycol monoethyl ether, propylene glycol monoethyl ether acetate, propylene glycol monobutyl ether, propylene glycol monopropyl ether, propylene glycol monomethyl ether, propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether propionate, benzyl alcohol, methyl isobutyl ketone, methylcyclohexanol, n-amyl acetate, n-butyl acetate, isoamyl acetate, isobutyl acetate, propyl acetate, dibasic acid esters, and ethyl lactate. Among these, solvents having a boiling point of 120°C or higher and 245°C or lower at 1 atm are preferred in terms of coatability and drying properties. In the composition for visible light-shielding layer, the content of the solvent is preferably 100 to 10,000 parts by weight, more preferably 500 to 5,000 parts by weight, per 100 parts by weight of the organic pigment (A).

[0089] Chain Transfer Agent The chain transfer agent improves the photocurability of the composition. As the chain transfer agent, a polyfunctional thiol is preferred. Specific examples of polyfunctional thiols include hexanedithiol, decanedithiol, 1,4-butanediol bisthiopropionate, 1,4-butanediol bisthioglycolate, ethylene glycol bisthioglycolate, ethylene glycol bisthiopropionate, trimethylolpropane tristhioglycolate, trimethylolpropane tristhiopropionate, trimethylolethane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), trimethylolpropane tris(3-mercaptobutyrate), and Examples of suitable chain transfer agents include pentaerythritol tetrakis(3-mercaptopropionate), pentaerythritol tetrakisthioglycolate, pentaerythritol tetrakisthiopropionate, pentaerythritol tetrakis(3-mercaptopropionate), dipentaerythritol hexakis(3-mercaptopropionate), trimercaptopropionic acid tris(2-hydroxyethyl)isocyanurate, 1,4-dimethylmercaptobenzene, 2,4,6-trimercapto-s-triazine, and 2-(N,N-dibutylamino)-4,6-dimercapto-s-triazine. When a chain transfer agent is used, the amount of the chain transfer agent is preferably 0.05 to 100 parts by weight, and more preferably 1 to 50 parts by weight, per 100 parts by weight of the organic pigment (A), from the viewpoint of development resistance after curing.

[0090] Antioxidants: Antioxidants suppress yellowing due to oxidation of each component during the heating process. Examples of antioxidants include hindered phenol-based, hindered amine-based, phosphorus-based, sulfur-based, benzotriazole-based, benzophenone-based, hydroxylamine-based, salicylic acid ester-based, and triazine-based compounds. From the viewpoint of achieving both transmittance and sensitivity of the coating film, hindered phenol-based antioxidants, hindered amine-based antioxidants, phosphorus-based antioxidants, and sulfur-based antioxidants are preferred, and hindered phenol-based antioxidants, hindered amine-based antioxidants, and phosphorus-based antioxidants are more preferred. When an antioxidant is used, the content of the antioxidant is preferably 0.5 to 5.0 parts by weight per 100 parts by weight of the non-volatile components of the composition for visible light-shielding layer.

[0091] Leveling Agents Leveling agents improve the leveling properties of coating films. As leveling agents, dimethylsiloxanes having a polyether structure or polyester structure in the main chain are preferred. Specific examples of dimethylsiloxanes having a polyether structure in the main chain include FZ-2122 manufactured by Dow Corning Toray Co., Ltd. and BYK-333 manufactured by BYK-Chemie. Specific examples of dimethylsiloxanes having a polyester structure in the main chain include BYK-310 and BYK-370 manufactured by BYK-Chemie. Also preferred as leveling agents are dimethylpolysiloxanes having polyalkylene oxide units. Examples of polyalkylene oxide units include polyethylene oxide units and polypropylene oxide units. Examples of dimethylpolysiloxanes having polyalkylene oxide units include FZ-2110, FZ-2122, FZ-2130, FZ-2166, FZ-2191, FZ-2203, and FZ-2207 manufactured by Dow Corning Toray Co., Ltd. When a leveling agent is used, the content of the leveling agent is preferably 0.003 to 1.0 part by weight relative to the total weight of the nonvolatile content of the composition for visible light-shielding layer.

[0092] Furthermore, anionic, cationic, nonionic, or amphoteric surfactants may be added as an auxiliary in combination with the leveling agent. Examples of anionic surfactants include polyoxyethylene alkyl ether sulfates, sodium dodecylbenzenesulfonate, alkali salts of styrene-acrylic acid copolymers, sodium alkylnaphthalenesulfonates, sodium alkyldiphenyletherdisulfonates, monoethanolamine lauryl sulfate, triethanolamine lauryl sulfate, ammonium lauryl sulfate, monoethanolamine stearate, sodium stearate, sodium lauryl sulfate, monoethanolamine styrene-acrylic acid copolymers, and polyoxyethylene alkyl ether phosphate esters. Examples of cationic surfactants include alkyl quaternary ammonium salts and their ethylene oxide adducts. Examples of nonionic surfactants include alcohol ethoxylates such as polyoxyethylene oleyl ether, polyoxyethylene lauryl ether, polyoxyethylene nonylphenyl ether, polyoxyethylene alkyl ether phosphate esters, polyoxyethylene sorbitan monostearate, and polyethylene glycol monolaurate; alkyl betaines such as alkyl dimethylaminoacetic acid betaine, and amphoteric surfactants such as alkyl imidazolines, as well as fluorine-based and silicone-based surfactants.

[0093] Storage stabilizer A storage stabilizer is used to stabilize the viscosity of the composition for the visible light-shielding layer. Examples of storage stabilizers include quaternary ammonium chlorides such as benzyl trimethyl chloride and diethylhydroxyamine, organic acids such as lactic acid and oxalic acid and their methyl ethers, organic phosphines such as t-butylpyrocatechol, tetraethylphosphine and tetraphenylphosphine, and phosphites. The storage stabilizer can be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the organic pigment (A).

[0094] Adhesion improvers are used to improve adhesion to other layers. Examples of adhesion improvers include vinyl silanes such as vinyltris(β-methoxyethoxy)silane, vinylethoxysilane, and vinyltrimethoxysilane, (meth)acrylic silanes such as γ-methacryloxypropyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltrimethoxysilane, β-(3,4-epoxycyclohexyl)methyltrimethoxysilane, β-(3,4-epoxycyclohexyl)ethyltriethoxysilane, β-(3,4-epoxycyclohexyl)methyltriethoxysilane, γ-glycidoxypropyltrimethoxysilane, and γ-glycidoxypropyltriethoxysilane. Examples of suitable silane coupling agents include epoxy silanes such as N-β(aminoethyl)γ-aminopropyltrimethoxysilane, N-β(aminoethyl)γ-aminopropyltriethoxysilane, N-β(aminoethyl)γ-aminopropylmethyldiethoxysilane, γ-aminopropyltriethoxysilane, γ-aminopropyltrimethoxysilane, N-phenyl-γ-aminopropyltriethoxysilane, and thiosilanes such as γ-mercaptopropyltrimethoxysilane and γ-mercaptopropyltriethoxysilane. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the total amount of the organic pigment (A) in the composition for visible light-shielding layer.

[0095] Ultraviolet absorbers and polymerization inhibitors: Ultraviolet absorbers and polymerization inhibitors improve the solubility contrast of the composition after curing. Examples of ultraviolet absorbers include hydroxyphenyltriazine-based compounds such as 2-[4-[(2-hydroxy-3-(dodecyl and tridecyl)oxypropyl)oxy]-2-hydroxyphenyl]-4,6-bis(2,4-dimethylphenyl)-1,3,5-triazine and 2-(2-hydroxy-4-[1-octyloxycarbonylethoxy]phenyl)-4,6-bis(4-phenylphenyl)-1,3,5-triazine; benzotriazole-based compounds such as 2-(5-methyl-2-hydroxyphenyl)benzotriazole, 2-(2H-benzotriazol-2-yl)-4,6-bis(1-methyl-1-phenylethyl)phenol and 2-(3-t-butyl-5-methyl-2-hydroxyphenyl)-5-chlorobenzotriazole; Benzophenone-based compounds such as 4-dihydroxybenzophenone, 2-hydroxy-4-octoxybenzophenone, and 2,2',4,4'-tetrahydroxybenzophenone; salicylate-based compounds such as phenyl salicylate and p-tert-butylphenyl salicylate; cyanoacrylate-based compounds such as ethyl-2-cyano-3,3'-diphenylacrylate; and hindered amine-based compounds such as 2,2,6,6-tetramethylpiperidine-1-oxyl (triacetone-amine-N-oxyl), bis(2,2,6,6-tetramethyl-4-piperidyl)-sebacate, and poly[[6-[(1,1,3,3-tetrabutyl)amino]-1,3,5-triazine-2,4-diyl][(2,2,6,6-tetramethyl-4-piperidinyl)imino].Examples of the polymerization inhibitor include hydroquinone derivatives and phenol compounds such as methylhydroquinone, t-butylhydroquinone, 2,5-di-t-butylhydroquinone, 4-benzoquinone, 4-methoxyphenol, 4-methoxy-1-naphthol, and t-butylcatechol; amine compounds such as phenothiazine, bis-(1-dimethylbenzyl)phenothiazine, and 3,7-dioctylphenothiazine; copper and manganese salt compounds such as copper dibutyldithiocarbamate, copper diethyldithiocarbamate, manganese diethyldithiocarbamate, and manganese diphenyldithiocarbamate; nitroso compounds such as 4-nitrosophenol, N-nitrosodiphenylamine, N-nitrosocyclohexylhydroxylamine, and N-nitrosophenylhydroxylamine, and the ammonium salts or aluminum salts thereof. When an ultraviolet absorber and / or a polymerization inhibitor is used, the total content thereof is preferably 0.01 to 20 parts by weight, more preferably 0.05 to 10 parts by weight, per 100 parts by weight of the organic pigment (A).

[0096] Each component in the composition for a visible light-shielding layer may be used independently as a single type, or as a combination of two or more types.

[0097] (2) Composition for Near-Infrared Light-Shielding Layer The composition for near-infrared light-shielding layer contains a near-infrared absorbing dye (E) represented by the following general formula (1), a resin-type dispersant (F) having an amine value of 20 mgKOH / g to 200 mgKOH / g (hereinafter also simply referred to as resin-type dispersant (F)), and a binder resin (G) having a weight-average molecular weight of 5,000 to 40,000 and an acid value of 100 mgKOH / g to 130 mgKOH / g (hereinafter also simply referred to as binder resin (G)). By using such a composition, a composition that satisfies the above-mentioned spectral characteristics and film-forming conditions is obtained. X １ ~X １０each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, or —SO ２ NR １ R ２ , -COOR １ , -CONR １ R ２ , a nitro group, a cyano group, or a halogen atom; X １ ~X １０ may be bonded to each other to form a ring. １ and R ２ each independently represents a hydrogen atom or an alkyl group which may have a substituent.

[0098] (Near-infrared absorbing dye (E)) The near-infrared absorbing dye represented by the general formula (1) has little absorption of visible light (wavelength 400 to 700 nm), and is excellent in near-infrared absorbing ability and durability.

[0099] X １ ~X １０ Examples of the alkyl group which may have a substituent in the formula (I) include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, a tert-butyl group, a tert-amyl group, a 2-ethylhexyl group, a stearyl group, a chloromethyl group, a trichloromethyl group, a trifluoromethyl group, a 2-methoxyethyl group, a 2-chloroethyl group, a 2-nitroethyl group, a cyclopentyl group, a cyclohexyl group, and a dimethylcyclohexyl group. Among these, in terms of durability of the compound and ease of synthesis, a methyl group, an ethyl group, or an n-propyl group is preferred, and a methyl group is more preferred.

[0100] X １ ~X １０Examples of the alkenyl group which may have a substituent include a vinyl group, a 1-propenyl group, an allyl group, a 2-butenyl group, a 3-butenyl group, an isopropenyl group, an isobutenyl group, a 1-pentenyl group, a 2-pentenyl group, a 3-pentenyl group, a 4-pentenyl group, a 1-hexenyl group, a 2-hexenyl group, a 3-hexenyl group, a 4-hexenyl group, and a 5-hexenyl group. Of these, a vinyl group or an allyl group is preferred in terms of durability of the compound and ease of synthesis.

[0101] X １ ~X １０ Examples of the aryl group which may have a substituent in the formula (I) include a phenyl group, a naphthyl group, a 4-methylphenyl group, a 3,5-dimethylphenyl group, a pentafluorophenyl group, a 4-bromophenyl group, a 2-methoxyphenyl group, a 4-diethylaminophenyl group, a 3-nitrophenyl group, and a 4-cyanophenyl group. Of these, a phenyl group or a 4-methylphenyl group is preferred in terms of durability of the compound and ease of synthesis.

[0102] X １ ~X １０ Examples of the aralkyl group which may have a substituent include a benzyl group, a phenethyl group, a phenylpropyl group, and a naphthylmethyl group. Of these, a benzyl group is preferred in terms of durability of the compound and ease of synthesis.

[0103] X １ ~X １０ Examples of the alkoxy group which may have a substituent in the formula (I) include a methoxy group, an ethoxy group, an n-propoxy group, an isopropoxy group, an n-butoxy group, an n-octyloxy group, a 2-ethylhexyloxy group, a trifluoromethoxy group, a cyclohexyloxy group, and a stearyloxy group. Among these, a methoxy group, an ethoxy group, or a trifluoromethoxy group is preferred in terms of durability of the compound and ease of synthesis.

[0104] X １ ~X １０Examples of the optionally substituted aryloxy group in the formula (I) include a phenoxy group, a naphthyloxy group, a 4-methylphenyloxy group, a 3,5-chlorophenyloxy group, a 4-chloro-2-methylphenyloxy group, a 4-tert-butylphenyloxy group, a 4-methoxyphenyloxy group, a 4-diethylaminophenyloxy group, and a 4-nitrophenyloxy group. Among these, a phenoxy group or a naphthyloxy group is preferred in terms of durability of the compound and ease of synthesis.

[0105] X １ ~X １０ Examples of the substituted amino group in include a methylamino group, an ethylamino group, an isopropylamino group, an n-butylamino group, a cyclohexylamino group, a stearylamino group, a dimethylamino group, a diethylamino group, a dibutylamino group, an N,N-di(2-hydroxyethyl)amino group, a phenylamino group, a naphthylamino group, a 4-tert-butylphenylamino group, a diphenylamino group, and an N-phenyl-N-ethylamino group. Of these, a dimethylamino group or a diethylamino group is preferred in terms of the durability of the compound and ease of synthesis.

[0106] X １ ~X １０ Examples of the halogen atom in the formula include fluorine, bromine, chlorine, and iodine.

[0107] X １ ~X １０ Examples of structures in which are bonded to each other to form a ring include the following structures, where * indicates the bonding position.

[0108]

[0109] Also, R １ and R ２ The alkyl group which may have a substituent in X １ ~X １０ The same applies to the preferred embodiments.

[0110] Among them, X １ ~X １０ preferably contains an unsubstituted alkyl group, and X ３ , X ４ , X７ and X ８ It is more preferable that at least one of X is an unsubstituted alkyl group. ３ and X ７ is more preferably an unsubstituted alkyl group, and the unsubstituted alkyl group is particularly preferably a methyl group.

[0111] The content of the near-infrared absorbing dye (E) in the composition for near-infrared ray shielding layer is preferably from 0.01 to 50% by weight, and more preferably from 0.1 to 30% by weight, based on the non-volatile components in the composition for near-infrared ray shielding layer, from the viewpoint of the near-infrared ray absorption ability of the cured product.

[0112] The near-infrared absorbing dye (E) is preferably used in a finely divided form. The primary particle size of the near-infrared absorbing dye (E) is preferably 1 to 200 nm, more preferably 10 to 150 nm, and even more preferably 10 to 100 nm. When the average primary particle size is 1 nm or more, aggregation of the near-infrared absorbing dye (E) is suppressed, resulting in excellent dispersibility and dispersion stability. On the other hand, when the primary particle size is 200 nm or less, the influence of particle scattering is reduced, resulting in a sharp absorption spectrum. The particle size can be measured by the same method as for the organic pigment (A).

[0113] The near-infrared absorbing dye (E) may be a commercially available product or may be synthesized. The synthesis method is not particularly limited, but as an example, it can be synthesized based on the following scheme 1. Specifically, 1,8-diaminonaphthalene (the following formula (2)) and a compound of the following formula (3) are heated and refluxed together with a catalyst in a solvent to synthesize a compound of the following formula (4), and 3,4-dihydroxy-3-cyclobutene-1,2-dione is added and the mixture is further heated and refluxed to obtain a compound of formula (1) (near-infrared absorbing dye (E)).

[0114]

[0115] (Resin-type Dispersant (F)) The composition for near-infrared shielding layer contains a resin-type dispersant (F) having an amine value of 20 mgKOH / g to 200 mgKOH / g from the viewpoint of dispersibility and dispersion stability of the near-infrared absorbing dye (E). The amine value is preferably 60 to 150 mgKOH / g, and more preferably 60 to 120 mgKOH / g.

[0116] The resin-type dispersant (F) has an affinity moiety that adsorbs to the dye (E) and a moiety that is compatible with a carrier such as the binder resin (G), and adsorbs to the dye (E) to stabilize the dispersion. In particular, resins with controlled structures such as graft (comb) and block structures are preferred. Specific examples of the main chain and / or side chain skeleton of the resin-type dispersant include polyurethane, polycarboxylate esters such as polyacrylate, unsaturated polyamides, polycarboxylic acids, polycarboxylic acid (partial) amine salts, polycarboxylate ammonium salts, polycarboxylate alkylamine salts, polysiloxanes, long-chain polyaminoamidophosphate salts, hydroxyl group-containing polycarboxylate esters, modified products thereof, oil-based dispersants such as amides formed by the reaction of poly(lower alkyleneimines) with polyesters having free carboxyl groups and salts thereof, water-soluble resins and water-soluble polymer compounds such as (meth)acrylic acid-styrene copolymers, (meth)acrylic acid-(meth)acrylic acid ester copolymers, styrene-maleic acid copolymers, polyvinyl alcohol, and polyvinylpyrrolidone, polyesters, modified polyacrylates, ethylene oxide / propylene oxide adducts, and phosphate esters. Among these, those having a (meth)acrylic copolymer as the main chain and / or side chain are preferred. Specific examples of the dye-adsorbing group of the resin-type dispersant (F) include acidic adsorbing groups such as aromatic carboxyl groups and phosphate groups, and basic adsorbing groups such as primary amino groups, secondary amino groups, tertiary amino groups, and quaternary ammonium salts. Among these, resin-type dispersants having aromatic carboxyl groups, tertiary amino groups, and quaternary ammonium salts as dye-adsorbing groups are preferred from the viewpoints of near-infrared absorption ability and durability, and resin-type dispersants having tertiary amino groups or quaternary ammonium salts are more preferred, with resin-type dispersants having tertiary amino groups and quaternary ammonium salts being even more preferred. When the resin-type dispersant contains both a tertiary amino group and a quaternary ammonium salt group, it is preferred not only from the viewpoints of visible transmittance, near-infrared absorption ability, durability, and patterning ability, but also from the viewpoints of storage stability.

[0117] Examples of the resin-type dispersant (F) include Disperbyk-106, 108, 109, 112, 116, 130, 140, 142, 145, 166, 180, 187, 2001, 2010, 2020, 2025, 2050, 2070, 6919, etc., manufactured by BYK Japan Co., Ltd., SOLSPERSE-13240, 13650, 13940, 20000, 24000, 26000, 32000, 33000, 39000, 56000, 71000, etc., manufactured by The Lubrizol Corporation, and Ajisper PB711 manufactured by Ajinomoto Fine-Techno Co., Ltd. Further, the resin-type dispersant (F) can be produced by a known method such as the method described in JP-A-2010-506016. When the resin-type dispersant (F) is a block copolymer, it can be produced by copolymerizing a monomer having a tertiary amino group or a quaternary amino group with another monomer, and when the resin-type dispersant (F) is a graft copolymer, it can be produced by grafting a monomer having a tertiary amino group or a quaternary amino group onto a reactive group in the side chain of the main chain polymer.

[0118] The content of the resin-type dispersant (F) in the composition for near-infrared ray shielding layer is preferably from 5 to 200% by weight, more preferably from 10 to 150% by weight, based on the weight of the near-infrared absorbing dye (E), from the viewpoints of optical properties and durability.

[0119] (Binder Resin (G)) From the viewpoints of storage stability, alkali developability, and the like, the composition for near-infrared shading layer contains a binder resin (G) having a weight-average molecular weight of 5,000 to 40,000 and an acid value of 100 mgKOH / g to 130 mgKOH / g. The binder resin (G) preferably has a spectral transmittance of 80% or more, and more preferably 95% or more, over the entire wavelength range of the visible light region (wavelengths of 400 to 700 nm). Among these, an acrylic copolymer containing methacrylic acid and hydroxyethyl methacrylate as monomers is preferred from the viewpoint of storage stability of the composition. Furthermore, from the viewpoints of further improving photosensitivity and solvent resistance, the weight-average molecular weight of the binder resin (G) is more preferably 10,000 to 30,000. The acid value is more preferably 100 mgKOH / g to 120 mgKOH / g. The binder resin (G) may be an active energy ray-curable resin having an ethylenically unsaturated double bond, and among these, an alkali-soluble active energy ray-curable resin is preferred.

[0120] Specific examples of the active energy ray-curable resin having an ethylenically unsaturated double bond and the alkali-soluble active energy ray-curable resin are the same as those described above for the binder resin (B), and therefore, description thereof will be omitted here.

[0121] The number average molecular weight (Mn) of the binder resin (G) is preferably in the range of 50,000 to 25,000, and the value of Mw / Mn is preferably 10 or less, from the viewpoint of dispersibility of the near-infrared absorbing dye (E).

[0122] The proportion of the binder resin (G) in the composition for near-infrared ray shielding layer is preferably 30 to 500 parts by weight per 100 parts by weight of the near-infrared absorbing dye (E) from the viewpoints of film-forming properties and durability of the cured film.

[0123] (Optional Components) The composition for a near-infrared ray shielding layer may further contain other components, such as a photopolymerizable monomer, a photopolymerization initiator, a solvent, a sensitizer, a chain transfer agent, an antioxidant, an amine compound, a leveling agent, a curing agent, a curing accelerator, other near-infrared ray absorbing dyes, a storage stabilizer, and an adhesion improver.

[0124] Photopolymerizable Monomer The photopolymerizable monomer may be any of those exemplified as the photopolymerizable compound (D) above, and preferably contains a polyfunctional monomer.

[0125] When a photopolymerizable monomer is used, the proportion of the photopolymerizable monomer is preferably 5 to 400 parts by weight, more preferably 10 to 300 parts by weight, relative to 100 parts by weight of the near-infrared absorbing dye (E) from the viewpoint of curability and developability.

[0126] Photopolymerization Initiator Examples of the photopolymerization initiator include the same ones as those exemplified as the photopolymerization initiator (C) above, and from the viewpoints of sensitivity and resolution, oxime ester compounds and aminoketone compounds are preferred.

[0127] When a photopolymerization initiator is used, the proportion of the photopolymerization initiator is preferably 5 to 200 parts by weight, more preferably 10 to 150 parts by weight, relative to 100 parts by weight of the near-infrared absorbing dye (E), from the viewpoints of curability and developability.

[0128] The solvent may be the same as those exemplified in the composition for visible light-shielding layer. The content of the solvent in the composition for near-infrared light-shielding layer is preferably 500 to 4,000 parts by weight per 100 parts by weight of the near-infrared absorbing dye (E).

[0129] Sensitizer The same sensitizers as those exemplified in the composition for visible light-shielding layer can be used. When a sensitizer is used, the amount of the sensitizer to be added is preferably 3 to 60 parts by weight, more preferably 5 to 50 parts by weight, per 100 parts by weight of the photopolymerization initiator, from the viewpoints of curability and developability.

[0130] Chain Transfer Agent The chain transfer agent may be the same as those exemplified in the composition for visible light-shielding layer. When a chain transfer agent is used, the amount of the chain transfer agent is preferably 0.1 to 30 parts by weight, and more preferably 1 to 20 parts by weight, relative to 100 parts by weight of the total amount of nonvolatile components of the composition for near-infrared light-shielding layer, from the viewpoint of development resistance after curing.

[0131] Antioxidant The same antioxidants as those exemplified in the composition for visible light-shielding layer can be used. When an antioxidant is used, the content of the antioxidant is preferably 0.5 to 5.0 parts by weight per 100 parts by weight of the non-volatile components of the composition for near-infrared light-shielding layer.

[0132] Amine Compounds Amine compounds are used to reduce oxygen dissolved in the composition for a near-infrared shielding layer. Examples of such amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, and N,N-dimethyl-p-toluidine.

[0133] Leveling Agent The same leveling agents as those exemplified in the composition for visible light shielding layer can be used. When a leveling agent is used, the content of the leveling agent is preferably 0.003 to 1.0 parts by weight based on the total weight of the nonvolatile content of the composition for near-infrared ray shielding layer.

[0134] Storage stabilizer The storage stabilizer may be the same as those exemplified in the composition for visible light-shielding layer. The storage stabilizer may be used in an amount of 0.1 to 10 parts by weight per 100 parts by weight of the total amount of the near-infrared absorbing dye (E).

[0135] Adhesion improver The same adhesion improver as exemplified in the composition for visible light-shielding layer can be used. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the total amount of the near-infrared absorbing dye (E).

[0136] Other Near-Infrared Absorbing Dyes The composition for near-infrared shielding layer may contain a near-infrared absorbing dye other than the near-infrared absorbing dye (E). Examples of the near-infrared absorbing dye include cyanine compounds, squarylium compounds, phthalocyanine compounds, naphthalocyanine compounds, aminium compounds, diimmonium compounds, croconium compounds, azo compounds, quinoid complex compounds, and dithiol metal complex compounds.

[0137] Each component in the composition for a near-infrared ray shielding layer may be used independently as a single type, or as a combination of two or more types.

[0138] (3) Composition for Colored Layer The composition for colored layer contains at least a colorant (H), a photopolymerizable compound (I), and a photopolymerization initiator (J), and may contain other components as necessary.

[0139] (Colorant (H)) The colorant (H) is used so that each colored layer has the desired spectral characteristics, and can be appropriately selected from known pigments and dyes. As the pigment, both organic pigments and inorganic pigments can be suitably used. In addition, since the composition for colored layer described later has excellent low-temperature curing properties, even dyes having lower heat resistance than pigments can be suitably used.

[0140] Examples of inorganic pigments include metal oxide powders such as barium sulfate, zinc white, lead sulfate, yellow lead, zinc yellow, red iron oxide (red iron (III) oxide), cadmium red, ultramarine, Prussian blue, chromium oxide green, cobalt green, umber, titanium black, synthetic iron black, titanium oxide, and iron tetroxide, as well as metal sulfide powders and metal powders. Inorganic pigments are preferably used in combination with organic pigments to ensure good coatability, sensitivity, developability, and the like while maintaining a balance between saturation and brightness. Dyes that can be used include acid dyes, direct dyes, basic dyes, salt-forming dyes, oil-soluble dyes, disperse dyes, reactive dyes, mordant dyes, vat dyes, and sulfide dyes. Derivatives of these dyes and lake pigments obtained by converting dyes into lakes may also be used.

[0141] The colorant (H) preferably contains a pigment, and more preferably an organic pigment, from the viewpoint of high color development, excellent heat resistance, and particularly excellent resistance to thermal decomposition. The colorant (H) will be described in more detail below for each color. Note that, for each color, the colorant (H) may be used alone or in combination of two or more types.

[0142] Red Layer The colorant for the red layer preferably contains a red pigment, and may further contain an orange pigment, a yellow pigment, or the like.

[0143] Specific examples of red pigments include C.I. Pigment Red (PR) 1, 2, 3, 4, 5, 6, 7, 8, 9, 12, 14, 15, 16, 17, 21, 22, 23, 31, 32, 37, 38, 41, 47, 48, 48:1, 48:2, 48:3, 48:4, 49, 49:1, 49:2, 50:1, 52:1, 52:2, 53, 53:1, 53:2, 53:3, 57, 5 7:1, 57:2, 58:4, 60, 63, 63:1, 63:2, 64, 64:1, 68, 69, 81, 81:1, 81:2, 81:3, 81:4, 83, 88, 90:1, 101, 101:1, 104, 108, 108:1, 109, 112, 113, 114, 122, 123, 144, 146, 147, 149, 151, 166, 168, 169, 170, 172, 173, 174, 175, 176, 177, 178, 179, 181, 184, 185, 187, 188, 190, 193, 194, 200, 202, 206, 207, 208, 209, 210, 214, 216, 220, 221, 224, 230, 231, 232, 233, 234 5, 236, 237, 238, 239, 242, 243, 245, 247, 249, 250, 251, 253, 254, 255, 256, 257, 258, 259, 260, 262, 263, 264, 265, 266, 267, 268, 269, 270, 271, 272, 273, 274, 275, 276, etc.

[0144] Specific examples of orange pigments include C.I. Pigment Orange 36, 38, 43, 51, 55, 59, and 61. Specific examples of yellow pigments include the same pigments as those exemplified for the organic pigment (A).

[0145] From the viewpoints of high brightness and high color reproducibility, the colorant for the red layer preferably contains Pigment Red 177, and more preferably contains Pigment Red 139, Pigment Red 177, and Pigment Red 254. When PY139, PY177, and PY254 are used in combination, it is preferable that the content of PY177 in the red colorant be 55% by weight to 65% by weight, the content of PY254 be 15% by weight to 25% by weight, and the content of PY139 be 15% by weight to 25% by weight.

[0146] Green Layer The colorant for the green layer preferably contains a green pigment or a blue pigment, and may further contain a yellow pigment or the like.

[0147] Specific examples of the green pigment include C.I. Pigment Green (PG) 1, 2, 4, 7, 8, 10, 13, 14, 15, 17, 18, 19, 26, 36, 45, 48, 50, 51, 54, 55, 58, 59, 62, and 63. Specific examples of blue pigments and yellow pigments include the same pigments as those exemplified for the organic pigment (A).

[0148] From the viewpoint of high brightness and high color reproducibility, the colorant for the green layer preferably contains Pigment Yellow 185, and further preferably contains any of Pigment Green 36, Pigment Green 58, and Pigment Blue 15:3. The content of PY185 in the colorant for the green layer is preferably 49% by weight to 59% by weight. The total content of PG36 and PG58 in the colorant for the green layer is preferably 33% by weight to 43% by weight. The content of PB15:3 in the colorant for the green filter is preferably 3% by weight to 13% by weight.

[0149] Blue Layer The colorant for the blue layer preferably contains a blue pigment, and may further contain a violet pigment, a xanthene dye, etc. Specific examples of the blue pigment and the violet pigment include those similar to those exemplified for the organic pigment (A).

[0150] Xanthene dyes may be any of oil-soluble dyes, acid dyes, direct dyes, and basic dyes, and may be used as lake pigments.Specific examples of xanthene oil-soluble dyes include C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 42, C.I. Solvent Red 43, C.I. Solvent Red 44, C.I. Solvent Red 45, C.I. Solvent Red 46, C.I. Solvent Red 47, C.I. Solvent Red 48, C.I. Solvent Red 49, C.I. Solvent Red 72, C.I. Solvent Red 73, C.I. Solvent Red 109, C.I. Solvent Red 140, C.I. Examples of the xanthene-based basic dye include C.I. Solvent Red 141, C.I. Solvent Red 237, C.I. Solvent Red 246, C.I. Solvent Violet 2, and C.I. Solvent Violet 10. From the viewpoint of color development, C.I. Solvent Red 35, C.I. Solvent Red 36, C.I. Solvent Red 49, C.I. Solvent Red 109, C.I. Solvent Red 237, C.I. Solvent Red 246, and C.I. Solvent Violet 2 are preferred. Specific examples of the xanthene-based basic dye include C.I. Basic Red 1 (Rhodamine 6GCP), 8 (Rhodamine G), and C.I. Basic Violet 10 (Rhodamine B). From the viewpoint of excellent color development, C.I. Basic Red 1 and C. I. Basic Violet 10 is preferred.Specific examples of xanthene acid dyes include C.I. Acid Red 51 (Erythrosine (Food Red No. 3)), C.I. Acid Red 52 (Acid Rhodamine), C.I. Acid Red 87 (Eosin G (Food Red No. 103)), C.I. Acid Red 92 (Acid Phloxine PB (Food Red No. 104)), C.I. Acid Red 289, C.I. Acid Red 388, Rose Bengal B (Food Red No. 5), Acid Rhodamine G, and C.I. Acid Violet 9. From the viewpoint of heat resistance and light fastness, C.I. Acid Red 87, C.I. Acid Red 92, C.I. Acid Red 388, C.I. Acid Red 52 (Acid Rhodamine), C.I. More preferred are C.I. Acid Red 289, Acid Rhodamine G, and C.I. Acid Violet 9, and more preferred are C.I. Acid Red 52 and C.I. Acid Red 289.

[0151] The colorant for the blue layer preferably contains Pigment Blue 15:6, and further preferably contains Pigment Violet 23 or a xanthene dye. The content of PB15:6 in the colorant for the blue layer is preferably 58% by weight to 64% by weight. The content of PV23 in the colorant for the blue layer is preferably 12% by weight to 20% by weight. Furthermore, the content of the xanthene dye in the colorant for the blue layer is preferably 17% by weight to 25% by weight.

[0152] When a pigment is used as a colorant of each color, it is preferable to make the pigment finer. The method of making the pigment finer and the preferred particle size are the same as those for the organic pigment (A).

[0153] (Photopolymerizable Compound (I)) Examples of the photopolymerizable compound (I) include the same compounds as those described above for the photopolymerizable compound (D). From the viewpoint of achieving both good adhesion to other layers and high resolution of the resist pattern, the photopolymerizable compound (I) preferably contains a compound represented by the general formula (7).

[0154] The content of the photopolymerizable compound (I) relative to the total nonvolatile content in the colored layer composition is preferably 5 to 40 wt %. Within this range, the adhesion of the fine pattern is excellent, and taper expansion is suppressed, resulting in a high-definition display device. Furthermore, the content of the compound represented by the general formula (1) contained in the photopolymerizable compound (I) is preferably 50 to 100 wt %, more preferably 60 wt % or more, relative to the total amount of the photopolymerizable compound (I). Within this range, the coating film adhesion to the substrate and chemical resistance during the manufacturing process are excellent.

[0155] (Photopolymerization initiator (J)) The photopolymerization initiator (J) can be appropriately selected from those that promote the polymerization reaction of the photopolymerizable compound by the action of light. In the present disclosure, it is preferable to include an oxime ester-based photopolymerization initiator in view of excellent UV curability, color properties, chemical resistance, and developability.

[0156] The content of the photopolymerization initiator (J) is preferably 0.5 to 50 parts by weight relative to 100 parts by weight of the colorant (H), and more preferably 1 to 30 parts by weight from the viewpoint of photocurability and developability. When the content of the photopolymerization initiator (J) is 1 part by weight or more, the adhesion to the substrate is excellent. Furthermore, when the content of the photopolymerization initiator (J) is 30 parts by weight or less, the resolution is excellent.

[0157] The color layer composition may further contain other components, such as a sensitizer, a resin, a thermosetting compound, an antioxidant, an adhesion improver, a leveling agent, a curing agent, a curing accelerator, a storage stabilizer, a solvent, a dispersing aid, and a chain transfer agent.

[0158] Sensitizer Examples of the sensitizer include those similar to those in the composition for the visible light-shielding layer. Among the above sensitizers, particularly suitable sensitizers that can sensitize include thioxanthone derivatives, Michler's ketone derivatives, and carbazole derivatives. When a sensitizer is used, the content of the sensitizer is preferably 3 to 60 parts by weight, and more preferably 5 to 50 parts by weight, relative to 100 parts by weight of the photopolymerization initiator (J), from the viewpoints of photocurability and developability.

[0159] Resin The colored layer composition may further contain a resin. The resin is preferably a transparent resin that has a transmittance of 80% or more in the entire wavelength range of 400 to 700 nm when a 2 μm-thick coating is formed, and the transmittance is preferably 95% or more. Examples of the resin include active energy ray-curable resins and thermoplastic resins. From the viewpoint of patterning properties by photolithography, the resin preferably contains an alkali-soluble resin. Examples of the resin include the same as the binder resin (B) described above.

[0160] The content of the resin is preferably 20 to 400 parts by weight, more preferably 50 to 250 parts by weight, per 100 parts by weight of the colorant (H). When the resin is contained in an appropriate amount, a coating can be easily formed and good color characteristics can be easily obtained.

[0161] Antioxidant The color layer composition may contain an antioxidant. Examples of antioxidants include those described above. When an antioxidant is used, the antioxidant is preferably contained in an amount of 0.5 to 5.0% by weight of the total nonvolatile content of the color layer composition from the viewpoints of brightness and sensitivity.

[0162] The color layer composition may contain an adhesion improver. Examples of the adhesion improver include those described above. The adhesion improver can be used in an amount of 0.01 to 10 parts by weight, preferably 0.05 to 5 parts by weight, per 100 parts by weight of the colorant in the color layer composition.

[0163] Leveling Agent The color layer composition may contain a leveling agent. Examples of the leveling agent include those mentioned above. The leveling agent is preferably used in an amount of 0.003 to 0.5% by weight based on the total nonvolatile content of the color layer composition.

[0164] Solvent The color layer composition may contain a solvent. This makes it easier to adjust the viscosity of the color layer composition, making it easier to form a coating with a smooth surface. The same solvents as those exemplified for the visible light-shielding layer composition can be used. The solvent is preferably used in an amount of 200 to 900 parts by weight, and more preferably 300 to 570 parts by weight, per 100 parts by weight of the nonvolatile content of the color layer composition, since it allows the color layer composition to be adjusted to an appropriate viscosity and allows the formation of a coating film with the desired uniform thickness. The viscosity of the color layer composition is preferably 2.4 to 7.2 mPa·s, and more preferably 3.4 to 6.4 mPa·s.

[0165] Dispersion Aid The color layer composition may contain a dispersing aid such as a dye derivative, a resin-type dispersing agent, a surfactant, etc. as needed to disperse the colorant in the colorant. The dispersing aid has a significant effect of preventing reagglomeration of the colorant after dispersion, and therefore the color layer composition obtained by dispersing the colorant in the colorant carrier using the dispersing aid has good brightness and viscosity stability.

[0166] ((Dye Derivatives)) Examples of dye derivatives include compounds in which a basic substituent, an acidic substituent, or a phthalimidomethyl group which may have a substituent has been introduced into an organic pigment, an anthraquinone, an acridone, or a triazine, and for example, those disclosed in JP-A-63-305173, JP-B-57-15620, JP-B-59-40172, JP-B-63-17102, JP-B-5-9469, and JP-A-2001-335717 Those described in JP-A-2003-128669, JP-A-2004-091497, JP-A-2007-156395, JP-A-2008-094873, JP-A-2008-094986, JP-A-2008-095007, JP-A-2008-195916, Japanese Patent No. 4585781, etc. can be used, and these can be used alone or in combination of two or more types.

[0167] The content of the dye derivative is preferably 0.5 parts by weight or more, more preferably 1 part by weight or more, and most preferably 3 parts by weight or more, relative to 100 parts by weight of the colorant from the viewpoint of improving dispersibility, and is preferably 40 parts by weight or less, more preferably 35 parts by weight or less, from the viewpoint of heat resistance and light resistance.

[0168] ((Resin-type dispersant / surfactant)) Examples of the resin-type dispersant include those similar to the resin-type dispersant (F) described above. Examples of the surfactant include those similar to those exemplified in the composition for visible light-shielding layer described above. When a resin-type dispersant or a surfactant is added, the amount is preferably 0.1 to 55 parts by weight, more preferably 0.1 to 45 parts by weight, relative to 100 parts by weight of the colorant.

[0169] Chain Transfer Agent The color layer composition may contain a chain transfer agent. The chain transfer agent is as described above. The content of the chain transfer agent is preferably 0.5 to 10%, and more preferably 1 to 8%, of the total nonvolatile content of the color layer composition.

[0170] Near-infrared absorbing dye When the colored layer is to be the colored layer 7 having near-infrared ray blocking properties shown in Fig. 4, the composition for colored layer contains a near-infrared absorbing dye. As the near-infrared absorbing dye, the near-infrared absorbing dye (E) represented by the general formula (1) is preferred.

[0171] [Substrate] The substrate 10 is a substrate on which electrodes for driving the organic EL layer, the near-infrared light receiving section, and the near-infrared light emitting section, and electrodes for inputting electrical signals from the near-infrared light receiving section are formed, and is preferably a silicon substrate. Each of the electrodes is formed in a TFT array, for example.

[0172] [Organic EL Layer] The organic EL layer 30 is a multilayer structure formed by laminating a lower electrode, a light-emitting layer, and a transparent electrode, and may further include other layers. An example of the organic EL layer is a structure formed by laminating, in order from the substrate 10 side, a lower electrode, an organic layer including a light-emitting layer, and a transparent electrode, and airtightly covered with a sealing layer.

[0173] One of the lower electrode and the transparent electrode is an anode and the other is a cathode, and either may be the anode. The material of the anode may be, for example, nickel, silver, gold, platinum, palladium, selenium, rhodium, ruthenium, iridium, rhenium, tungsten, molybdenum, chromium, tantalum, niobium, or an alloy thereof, or tin oxide (SnO ２ Examples of the cathode material include indium tin oxide (ITO), zinc oxide, and titanium oxide. The cathode may be made of an alloy of an active metal such as Li, Mg, or Ca with a metal such as Ag, Al, or In, or a laminate of these. Alternatively, a thin compound layer of an active metal such as Li, Mg, or Ca with a halogen such as fluorine or bromine, or oxygen, may be inserted between the organic layer.

[0174] The organic layer has at least a white light-emitting layer, and is usually composed of multiple organic layers, and may have a charge injection layer such as a hole injection layer or an electron injection layer, and a charge transport layer such as a hole transport layer that transports holes to the white light-emitting layer, or an electron transport layer that transports electrons to the white light-emitting layer. The organic layer may have any configuration from among all known configurations having a white light-emitting layer.

[0175] The light-emitting layer can be any known layer that can emit white light. The white light-emitting characteristics require that the layer emit light in at least three regions: the red region (600 nm to 780 nm), the green region (475 nm to 600 nm), and the blue region (380 nm to 475 nm). Three or more emission peaks are not necessarily required; for example, two emission peaks may be sufficient as long as the layer emits light in the above-mentioned regions. However, in order to obtain a wide color reproducibility, it is preferable to use a white light-emitting layer that has three or more emission peaks, and it is preferable that the layer have an emission peak in at least one of the above-mentioned three color regions.

[0176] The material for forming such a white light-emitting layer is not particularly limited as long as it emits fluorescence or phosphorescence. The light-emitting material may have hole transport properties or electron transport properties. Examples of the light-emitting material include dye-based materials, metal complex-based materials, and polymer-based materials.

[0177] Examples of the dye-based materials include cyclopentamine derivatives, tetraphenylbutadiene derivatives, triphenylamine derivatives, oxadiazole derivatives, pyrazoloquinoline derivatives, distyrylbenzene derivatives, distyrylarylene derivatives, silole derivatives, thiophene ring compounds, pyridine ring compounds, perinone derivatives, perylene derivatives, oligothiophene derivatives, triphimanylamine derivatives, oxadiazole dimers, and pyrazoline dimers.

[0178] Examples of the metal complex material include aluminum quinolinol complexes, benzoquinolinol beryllium complexes, benzoxazole zinc complexes, benzothiazole zinc complexes, azomethyl zinc complexes, porphyrin zinc complexes, and europium complexes; and metal complexes having a central metal such as Al, Zn, or Be or a rare earth metal such as Tb, Eu, or Dy, and having an oxadiazole, thiadiazole, phenylpyridine, phenylbenzimidazole, or quinoline structure as a ligand.

[0179] Examples of the polymeric materials include polyparaphenylene vinylene derivatives, polythiophene derivatives, polyparaphenylene derivatives, polysilane derivatives, polyacetylene derivatives, polyfluorene derivatives, polyvinylcarbazole derivatives, and polymerized versions of the above-mentioned dye-based materials and metal complex-based materials.

[0180] Examples of methods for forming the white light-emitting layer include vapor deposition, printing, inkjet printing, spin coating, casting, dipping, bar coating, blade coating, roll coating, gravure coating, flexographic printing, spray coating, and self-assembly methods (layer-by-layer adsorption, self-assembled monolayer). Vapor deposition, spin coating, and inkjet printing are particularly preferred. The film thickness of the white light-emitting layer is usually about 5 nm to 5 μm.

[0181] The organic EL layer may also include a hole injection layer between the white light-emitting layer and the anode. By providing the hole injection layer, the injection of holes into the white light-emitting layer can be stabilized, thereby improving the luminous efficiency. Materials generally used for hole injection layers in organic EL elements can be used as materials for forming the hole injection layer. The material for forming the hole injection layer may be any material that has either hole injection properties or electron barrier properties.

[0182] Specific examples of materials for forming the hole injection layer include triazole derivatives, oxadiazole derivatives, imidazole derivatives, polyarylalkane derivatives, pyrazoline derivatives, pyrazolone derivatives, phenylenediamine derivatives, arylamine derivatives, amino-substituted chalcone derivatives, oxazole derivatives, styrylanthracene derivatives, fluorenone derivatives, hydrazone derivatives, stilbene derivatives, silazane derivatives, polysilane-based and aniline-based copolymers, and conductive polymer oligomers such as thiophene oligomers.

[0183] Furthermore, materials for forming the hole injection layer include porphyrin compounds, aromatic tertiary amine compounds, styrylamine compounds, etc. The thickness of the hole injection layer is usually about 5 nm to 1 μm.

[0184] The organic EL layer may further include an electron injection layer formed between the white light-emitting layer and the cathode. By providing the electron injection layer, electron injection into the white light-emitting layer can be stabilized, thereby improving luminous efficiency.

[0185] Examples of materials for forming the electron injection layer include nitro-substituted fluorene derivatives, anthraquinodimethane derivatives, diphenylquinone derivatives, thiopyran dioxide derivatives, heterocyclic tetracarboxylic acid anhydrides such as naphthalene perylene, carbodiimides, fluorenylidenemethane derivatives, anthraquinodimethane and anthrone derivatives, oxadiazole derivatives, thiazole derivatives in which the oxygen atom of the oxadiazole ring of an oxadiazole derivative is substituted with a sulfur atom, quinoxaline derivatives having a quinoxaline ring known as an electron-withdrawing group, metal complexes of 8-quinolinol derivatives such as tris(8-quinolinol)aluminum, phthalocyanines, metal phthalocyanines, and distyrylpyrazine derivatives.

[0186] 2. Manufacturing Method of Organic EL Display Device The manufacturing method of an organic EL display device according to the present disclosure is a manufacturing method of the organic EL display device according to the first and second embodiments, characterized in that the colored layer, the visible light blocking layer, and the near-infrared light blocking layer are all formed at a temperature of 120° C. or less. This manufacturing method can suppress thermal damage to the organic EL element even when a color filter is formed directly on the organic EL element, and also eliminates the need for a step of bonding the organic EL element and the color filter, thereby suppressing misalignment.

[0187] In a specific example of a method for manufacturing an organic EL display device, a laminated substrate including a near-infrared receiving unit, a lower electrode, a light-emitting layer, and a transparent electrode is first prepared on a substrate. The method for preparing the laminated substrate is not particularly limited, and it can be manufactured using a known process. A sealing layer and / or an adhesive layer may be formed on the transparent electrode. The sealing layer can be made of a known curable resin, preferably an active energy ray-curable resin, and may also be used in combination with a thermosetting resin. The ultraviolet-curable resin is not particularly limited, but an acrylic resin that is sensitive to i-rays (wavelength 365 nm) is preferred. Forming the sealing layer allows the surface on which the color filter is to be formed to be flattened.

[0188] The color filter is formed directly on the transparent electrode, the sealing layer, or the adhesive layer. The color filter is preferably formed by photolithography. In the photolithography method, the above-described composition for the visible light-shielding layer, the composition for the near-infrared light-shielding layer, and the compositions for the red, green, and blue colored layers are each prepared. Furthermore, a photosensitive composition for the black matrix may be prepared. For example, first, the composition for the visible light-shielding layer is applied to form a coating film, which is then exposed to light, developed, and heat-cured to form a patterned visible light-shielding layer. Next, the composition for the first colored layer is applied to form a coating film, which is then exposed to light, developed, and heat-cured to form a colored layer of the first color. The same process is repeated with the compositions for the second and third colored layers, thereby forming three colored layers. Next, the composition for the near-infrared light-shielding layer is applied to form a coating film, which is then exposed to light, developed, and heat-cured to form a patterned near-infrared light-shielding layer on the colored layer, thereby obtaining a color filter.

[0189] The coating method can be appropriately selected from known methods such as spray coating, dip coating, bar coating, coal coating, and spin coating. The exposure method can be performed using a light source such as ultraviolet light from a low-pressure mercury lamp, a high-pressure mercury lamp, or a metal halide lamp, or electron beams, and exposing the resulting material through a mask with a predetermined pattern. A patterned filter can be obtained by removing the uncured photosensitive composition using a developer such as an alkaline developer. From the viewpoint of protecting the organic EL layer, the heat curing temperature is preferably 120°C or less, more preferably 100°C or less. By using the photosensitive composition, sufficient curing can be achieved even at temperatures as low as 120°C or less. The film thickness of each color filter is preferably 0.1 to 5 μm, more preferably 0.5 μm to 2.0 μm, and even more preferably 1.0 to 2.0 μm. As a result, an organic EL display device with high brightness and high resolution and reduced driving power can be obtained.

[0190] [Manufacturing Examples of Visible Light Shielding Layer and Near-Infrared Light Shielding Layer] The visible light shielding layer and near-infrared light shielding layer will be described below by citing manufacturing examples. In the manufacturing examples, "parts" and "%" represent "parts by weight" and "% by weight", respectively. Furthermore, "PGMAC" means methoxypropyl acetate. Furthermore, the weight average molecular weight (Mw) of the resin was measured as follows.

[0191] (Weight-average molecular weight (Mw) of resin) The weight-average molecular weight (Mw) of the resin is the weight-average molecular weight (Mw) in terms of polystyrene measured using a TSKgel column (manufactured by Tosoh Corporation) and a GPC (manufactured by Tosoh Corporation, HLC-8120GPC) equipped with an RI detector, using THF as a developing solvent.

[0192] [Production of Composition for Visible Light Shielding Layer] <Production of Binder Resin Solution> (Preparation of Binder Resin Solution 1) A separable four-necked flask was equipped with a thermometer, a condenser, a nitrogen gas inlet tube, a dropping tube, and a stirrer to form a reaction vessel. 196 parts of cyclohexanone was charged, the temperature was raised to 80°C, and the atmosphere inside the reaction vessel was replaced with nitrogen. Then, a mixture of 20.0 parts of benzyl methacrylate, 17.2 parts of n-butyl methacrylate, 12.9 parts of 2-hydroxyethyl methacrylate, 12.0 parts of methacrylic acid, 20.7 parts of paracumylphenol ethylene oxide-modified acrylate ("Aronix M110" manufactured by Toagosei Co., Ltd.), and 1.1 parts of 2,2'-azobisisobutyronitrile was added dropwise from the dropping tube over 2 hours to polymerize. After completion of the dropwise addition, the reaction was continued for a further 3 hours, and then cooled to terminate the reaction. After cooling to room temperature, approximately 2 parts of the resin solution was sampled and dried by heating at 180°C for 20 minutes to measure the nonvolatile content, and PGMAC was added so that the nonvolatile content became 20% by weight to prepare binder resin solution 1. The weight average molecular weight (Mw) was 26,000.

[0193] <Method for producing micronized pigment> (Blue micronized pigment (B1)) 200 parts of a phthalocyanine blue pigment C.I. Pigment Blue 15:6 ("LIONOL BLUE ES" manufactured by Toyocolor Co., Ltd., hereinafter referred to as PB15:6), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was added to 8,000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 85°C overnight to obtain a blue micronized pigment (B1).

[0194] (Yellow Micronized Pigment (Y1)) 100 parts of an isoindolinone yellow pigment C.I. Pigment Yellow 139 (BASF "PALIOTOL YELLOW D1819", hereinafter referred to as PY139), 800 parts of ground salt, and 180 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (Inoue Seisakusho Co., Ltd.) and kneaded for 4 hours at 70° C. This mixture was added to 3,000 parts of warm water, and while heating to about 80° C., the mixture was stirred in a high-speed mixer for about 1 hour to form a slurry. The mixture was filtered and washed repeatedly with water to remove the salt and solvent, and then dried at 80° C. for 24 hours to obtain 96 parts of a yellow micronized pigment (Y1).

[0195] (Finely divided purple pigment (V1)) 200 parts of a dioxazine-based purple pigment C.I. Pigment Violet 23 ("LIONOGEN VIOLET RL" manufactured by Toyocolor Co., Ltd., hereinafter referred to as PV23), 1,400 parts of sodium chloride, and 360 parts of diethylene glycol were charged into a stainless steel 1-gallon kneader (manufactured by Inoue Seisakusho Co., Ltd.) and kneaded for 6 hours at 80°C. Next, this kneaded mixture was added to 8,000 parts of warm water, heated to 80°C and stirred for 2 hours to form a slurry, filtered and washed repeatedly to remove the sodium chloride and diethylene glycol, and then dried at 85°C for 24 hours to obtain a finely divided purple pigment (V1).

[0196] <Method for producing pigment dispersion> (Preparation of pigment dispersion (BP-1)) The following mixture was stirred and mixed to homogeneity, and then dispersed for 5 hours using zirconia beads with a diameter of 1 mm in a paint shaker SO400 (manufactured by Skandex). Thereafter, 30.0 parts of methoxypropyl acetate was added, and the mixture was filtered through a 5 μm filter to obtain pigment dispersion (BP-1). Blue fine pigment (B1): 14.0 parts Binder resin solution 1: 30.0 parts Methoxypropyl acetate: 26.0 parts

[0197] (Preparation of Pigment Dispersions (YP1, VP-1)) Pigment dispersions (YP1, VP-1) were obtained in the same manner as for pigment dispersion (BP-1), except that the compositions and blending amounts (parts by weight) were changed to those shown in Table 1. The blending amounts in the table are in parts by mass.

[0198]

[0199] <Production of composition for visible light-shielding layer (BLK-1)> The following mixture (total 100 parts) was stirred and mixed to become uniform, and then filtered through a 1.0 μm filter to obtain a composition for visible light-shielding layer (BLK-1). Pigment dispersion (BP-1): 22.5 parts Pigment dispersion (VP-1): 17.4 parts Pigment dispersion (YP-1): 24.4 parts Binder resin solution 1: 0.9 parts Photopolymerizable monomer A: 4.2 parts "Aronix M-309" manufactured by Toagosei Co., Ltd. Photopolymerization initiator A: 0.7 parts "Irgacure OXE-02" manufactured by BASF Leveling agent solution: 1.0 parts "FZ-2122" manufactured by Toray Dow Corning Co., Ltd. (solution obtained by diluting 1 part (100% non-volatile content) with 99 parts cyclohexanone) Solvent: 28.9 parts Methoxypropyl acetate

[0200] [Preparation of Composition for Near-Infrared Shielding Layer] <Method for Producing Near-Infrared Absorbing Dye (E)> 400 parts of toluene were mixed with 40.0 parts of 1,8-diaminonaphthalene, 25.1 parts of cyclohexanone, and 0.087 parts of p-toluenesulfonic acid monohydrate, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 3 hours. Water generated during the reaction was removed from the system by azeotropic distillation. After completion of the reaction, the dark brown solid obtained by distilling the toluene was extracted with acetone and purified by recrystallization from a mixed solvent of acetone and ethanol. The resulting brown solid was dissolved in a mixed solvent of 240 parts of toluene and 160 parts of n-butanol. Next, 13.8 parts of 3,4-dihydroxy-3-cyclobutene-1,2-dione was added, and the mixture was heated and stirred in a nitrogen gas atmosphere and refluxed for 8 hours. Water generated during the reaction was removed from the reaction system by azeotropic distillation. After completion of the reaction, the solvent was distilled off, and 200 parts of hexane was added to the resulting reaction mixture while stirring. The resulting black-brown precipitate was filtered off, washed successively with hexane, ethanol, and acetone, and dried under reduced pressure to obtain 61.9 parts of near-infrared absorbing dye (E) (yield: 92%). The compound was identified by mass spectrometry using TOF-MS.

[0201]

[0202] <Method for producing resin-type dispersant (F)> (Resin-type dispersant (F) solution): Graft copolymer A reaction vessel equipped with a gas inlet tube, thermometer, condenser, and stirrer was charged with 150 parts of PGMAC and 100 parts of n-butyl acrylate, and the atmosphere was replaced with nitrogen gas. The reaction vessel was heated to 80°C, and a solution of 0.5 parts of 2,2'-azobisisobutyronitrile dissolved in 4 parts of 2-mercaptoethanol was added and reacted for 10 hours. Measurement of the nonvolatile content confirmed that 95% or more had reacted, and a reaction product (dispersant 1a) with a number average molecular weight of 3900 and a weight average molecular weight of 7900 was obtained. 7.9 parts of 2-methacryloyloxyethyl isocyanate, 0.05 parts of methyl dibutyltin dilaurate, and 0.05 parts of methylhydroquinone were additionally charged to the reaction product, and the reaction vessel was heated to 100°C and reacted for 4 hours. Thereafter, the mixture was cooled to 40° C. to obtain a reaction product (a solution of resin-type dispersant 1b).

[0203] A reaction vessel equipped with a gas inlet tube, condenser, stirring blade, and thermometer was charged with 122 parts of PGMAC, and the temperature was raised to 100 ° C. while purging with nitrogen. 262.5 parts of the reaction product (resin-type dispersant 1b solution), 150 parts of pentamethylpiperidyl methacrylate (ADEKA Corporation, Adekastab LA-82), 10 parts of hydroxyethyl methacrylate, and 4 parts of 2,2'-azobis (2,4-dimethylbutyronitrile) were charged into a dropping vessel, stirred until homogeneous, and then added dropwise to the reaction vessel over 2 hours to carry out the reaction. The reaction was then continued at the same temperature for 3 hours, after which the reaction was terminated by cooling. After sampling to confirm the nonvolatile content, PGMAC was added to adjust the nonvolatile content to 40% by mass. In this way, a solution of resin-type dispersant (F) was obtained, which was a graft copolymer having a tertiary amino group and an amine value per nonvolatile content of 42 mg KOH / g and a weight average molecular weight (Mw) of 23,500.

[0204] <Method for producing binder resin (G) solution> A separable four-neck flask equipped with a thermometer, a cooling tube, a nitrogen gas inlet tube, and a stirrer was charged with 70.0 parts of cyclohexanone, the temperature was raised to 80 ° C., and the atmosphere in the reaction vessel was replaced with nitrogen. Then, a mixture of 12.4 parts of n-butyl methacrylate, 4.6 parts of 2-hydroxyethyl methacrylate, 4.3 parts of methacrylic acid, 7.3 parts of paracumylphenol ethylene oxide-modified acrylate (manufactured by Toagosei Co., Ltd., "Aronix M110") (weight ratio of n-butyl methacrylate / 2-hydroxyethyl methacrylate / methacrylic acid / paracumylphenol ethylene oxide-modified acrylate 10.5 / 15.5 / 17.1 / 25.0), and 0.7 parts of 2,2'-azobisisobutyronitrile was added dropwise over 2 hours to carry out the reaction. After completion of the dropwise addition, the reaction was continued for another 3 hours and then terminated by cooling. After cooling to room temperature, about 2 g of the resin solution was sampled and dried by heating at 180°C for 20 minutes, and the nonvolatile content was measured. Propylene glycol monoethyl ether acetate was added so that the nonvolatile content became 20% by weight, thereby preparing a binder resin (G) solution having an acid value of 110 mgKOH / g and a weight average molecular weight (Mw) of 10,000 b.

[0205] (Near-infrared ray-shielding dispersion (E-1)) A mixture having the following composition was uniformly stirred and mixed, and then dispersed in an Eiger mill using zirconia beads having a diameter of 0.5 mm for 3 hours. The mixture was then filtered through a 0.5 μm filter to prepare a near-infrared ray-shielding dispersion (E-1) having a nonvolatile content of 20.0%. Near-infrared ray-absorbing dye (E): 12.5 parts Resin-type dispersant (F): 9.5 parts Binder resin (G): 18.5 parts Methoxypropyl acetate: 59.5 parts

[0206] <Preparation of Composition for Near-Infrared Light-Shielding Layer> The following mixture was stirred and mixed to become uniform, and then filtered through a 1.0 μm filter to obtain a composition for near-infrared light-shielding layer (IR-1). Near-infrared light-shielding dispersion (E-1): 27.5 parts Binder resin (G) solution: 17.8 parts Photopolymerizable monomer ("Aronix M-309" manufactured by Toagosei Co., Ltd.): 6.8 parts Photopolymerization initiator (oxime ester photopolymerization initiator "OXE-02" manufactured by BASF): 0.6 parts Leveling agent "FZ-2122" manufactured by Dow Corning Toray Co., Ltd. (solution obtained by diluting 1 part (non-volatile content 100% by weight) with 99 parts of cyclohexanone) Solvent: 1.0 part Methoxypropyl acetate: 43.3 parts

[0207] [Production Example 1: Preparation of visible light-shielding layer] The obtained composition for visible light-shielding layer (BLK-1) was applied onto a glass substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm using a spin coater, and then heated at 100°C for 15 minutes and allowed to cool, thereby obtaining a test substrate 1 having a film thickness of 1.0 µm.

[0208] <Measurement of Light Transmittance of Visible Light-Shielding Layer> The light transmittance of the obtained test substrate 1 at wavelengths of 400 to 1,000 nm was measured using a microspectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Corporation). The spectral data is shown in FIG. 9. Table 2 also shows the maximum light transmittance at wavelengths of 400 to 620 nm (Tmax (400 to 620 nm)), the maximum light transmittance at wavelengths of 620 to 730 nm (Tmax (620 to 730 nm)), and the minimum light transmittance at wavelengths of 830 to 1,000 nm (Tmin (830 to 1,000 nm)).

[0209]

[0210] [Production Example 2: Preparation of near-infrared absorbing layer] The obtained composition for near-infrared shielding layer (IR-1) was applied onto a glass substrate having a length of 100 mm, a width of 100 mm, and a thickness of 0.7 mm using a spin coater, and then heated at 100°C for 15 minutes and allowed to cool, thereby obtaining a test substrate 2 having a film thickness of 0.7 µm.

[0211] <Measurement of Light Transmittance of Near-Infrared Absorption Layer> The light transmittance of the obtained test substrate 2 at wavelengths of 400 to 1000 nm was measured using a microspectrophotometer ("U-3900" manufactured by Hitachi High-Tech Science Corporation). The spectroscopic data is shown in FIG. 10. Table 3 also shows the average light transmittance at wavelengths of 450 to 600 nm, the maximum absorption wavelength, and its transmittance.

[0212]

[0213] As shown in Table 2 and Fig. 9, the visible light-shielding layer of Production Example 1 has excellent visible light-shielding properties and excellent near-infrared transmittance. Furthermore, as shown in Table 3 and Fig. 10, the near-infrared light-shielding layer of Production Example 2 has excellent near-infrared light-shielding properties and excellent visible light transmittance. The organic EL display device of the present disclosure combines such a visible light-shielding layer and a near-infrared light-shielding layer to form a color filter with the layer configuration shown in Figs. 1 to 5, thereby suppressing the incidence of light that causes noise in the near-infrared light receiving section while maintaining the high brightness, high resolution, and color reproducibility of the display device.

[0214] The organic EL display device of the present disclosure has high brightness, high resolution, excellent color reproducibility, and can reduce driving power, and can be made small and lightweight. Therefore, it is suitable for Micro-OLED, and can be suitably used as a display device for electronic devices such as smart glasses, head-mounted displays, and electronic viewfinders.

[0215] This application claims priority based on Japanese Patent Application No. 2023-149493, filed September 14, 2023, the disclosure of which is incorporated herein in its entirety by reference.

[0216] 4: Colored layer, 4B: Blue layer, 4G: Green layer, 4R: Red layer, 5: Visible light-shielding layer, 6: Near-infrared light-shielding layer, 7: Colored layer, 8: Light-shielding layer, 10: Substrate, 20: Covering film, 21: Near-infrared light-receiving section, 22: Near-infrared light-emitting section, 30: Organic EL layer, 40: Color filter, 50: Wiring layer, 61: Near-infrared light, 62: Visible light, 63: Near-infrared light, 64: Near-infrared light, 100: Organic EL display device.

Claims

1. An organic electroluminescence display device having a near-infrared receiving section, a lower electrode, a light-emitting layer, a transparent electrode, and a color filter on a substrate, in that order; the color filter having a patterned colored layer and a visible light blocking layer provided on the near-infrared receiving section; and a near-infrared light blocking layer on the colored layer, between the colored layer and the transparent electrode, or integrated with the colored layer.

2. The organic electroluminescence display device according to claim 1, further comprising a near-infrared emitting section between the substrate and the lower electrode, and the color filter having a visible light blocking layer on the near-infrared emitting section.

3. The organic electroluminescence display device according to claim 1, further comprising the near-infrared light-shielding layer on the colored layer.

4. The organic electroluminescence display device according to claim 1, wherein the thickness of the visible light blocking layer is greater than the total thickness of the colored layer and the near-infrared light blocking layer.

5. The organic EL display device according to claim 1, wherein the visible light blocking layer has a maximum light transmittance of 5% or less in a wavelength range of 400 to 620 nm, a maximum light transmittance of 13% or less in a wavelength range of 620 to 730 nm, and a minimum light transmittance of 85% or more in a wavelength range of 830 to 1000 nm.

6. The organic EL display device according to claim 3, wherein the near-infrared shading layer has an average light transmittance of 80% or more in a wavelength range of 450 to 600 nm, has a maximum absorption wavelength in a wavelength range of 780 to 1000 nm, and has a light transmittance of 10% or less at the maximum absorption wavelength.

7. The organic EL display device according to claim 1, wherein the visible light shielding layer is a cured product of a composition for visible light shielding layer containing an organic pigment (A), a binder resin (B), a photopolymerization initiator (C) and a photopolymerizable compound (D), the organic pigment (A) contains a blue pigment, a yellow pigment and a violet pigment, and the content ratios of the organic pigments, based on the organic pigment (A), are 32 to 45% by weight for the blue pigment, 30 to 40% by weight for the yellow pigment and 20 to 30% by weight for the violet pigment.

8. The organic EL display device according to claim 1, wherein the near-infrared light-shielding layer is a cured product of a composition for near-infrared light-shielding layer, the composition comprising a near-infrared absorbing dye (E) represented by the following general formula (1), a resin-type dispersant (F) having an amine value of 20 mgKOH / g to 200 mgKOH / g, and a binder resin (G) having a weight-average molecular weight of 5,000 to 40,000 and an acid value of 100 mgKOH / g to 130 mgKOH / g: X １ ~X １０ each independently represents a hydrogen atom, an alkyl group which may have a substituent, an alkenyl group which may have a substituent, an aryl group which may have a substituent, an aralkyl group which may have a substituent, an alkoxy group which may have a substituent, an aryloxy group which may have a substituent, an amino group, a substituted amino group, a sulfo group, -SO ２ N.R. １ R ２ , -COOR １ , -CONR １ R ２ , a nitro group, a cyano group, or a halogen atom; X １ ~X １０ may be bonded to each other to form a ring. １ and R ２ each independently represents a hydrogen atom or an alkyl group which may have a substituent.

9. A method for manufacturing an organic EL display device according to any one of claims 1 to 8, wherein the colored layer, the visible light shielding layer, and the near-infrared light shielding layer are formed at a temperature of 120°C or less.

10. A method for producing an organic EL display device according to claim 9, comprising: preparing a laminated substrate having a near-infrared receiving section, a lower electrode, a light-emitting layer, and a transparent electrode on a substrate; and forming a coating film of a color layer composition on the laminated substrate.

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