Display device

Abstract

To provide a method for achieving both a wide color gamut and excellent energy efficiency in a display that comprises a blue light source, a wavelength conversion layer comprising a first wavelength conversion layer that emits green and a second wavelength conversion layer that emits red, and a light absorption layer.SOLUTION: A display 100 has a blue light source (A) 110, a wavelength conversion layer (B) 120, and a light absorption layer (C) 130. The wavelength conversion layer (B) has a first wavelength conversion layer (B1) 121 containing a compound (Q1) that absorbs blue and emits red, and a second wavelength conversion layer (B2) 122 containing a compound (Q2) that absorbs blue and emits green. The display satisfies 0.7≤X1 and 0.7≤X2. X1 is a value obtained by dividing a product of a thickness T1(μm) of (B1) and a content W1(mass%) of the compound (Q1) by 100, and X2 is a value obtained by dividing a product of a thickness T2(μm) of (B2) and a content W2(mass%) of the compound (Q2) by 100.SELECTED DRAWING: Figure 1

Description

Technical Field

[0001] The present invention relates to a display device including a light source, a wavelength conversion layer, and a light absorption layer, and further relates to a film that can be used for the wavelength conversion layer.

Background Art

[0002] Patent Document 1 proposes a display device including a light conversion unit containing quantum dots and a color filter.

[0003] Patent Document 2 proposes a light-emitting device using a curable film-forming composition containing a binder polymer, a polymerizable compound, semiconductor quantum dots, and a dispersant. Further, Patent Document 3 proposes a color filter manufactured using a photosensitive resin composition containing a quantum dot dispersion.

Prior Art Documents

Patent Documents

[0004]

Patent Document 1

Patent Document 2

Patent Document 3

Summary of the Invention

Problems to be Solved by the Invention

[0005] In a conventional display device including a wavelength conversion layer containing quantum dots and a light absorption layer, there are cases where a wide color gamut and excellent energy efficiency cannot be obtained simultaneously.

[0006] An object of the present invention is to achieve both a wide color gamut and excellent energy efficiency in a display device including a blue light source, a wavelength conversion layer having a first wavelength conversion layer that emits green light and a second wavelength conversion layer that emits red light, and a light absorption layer. Another object of the present invention is to provide a film that can be used as a wavelength conversion layer that emits green light and can achieve both a wide color gamut and excellent energy efficiency in a display device. Still another object of the present invention is to provide a film that can be used as a wavelength conversion layer that emits red light and can achieve both a wide color gamut and excellent energy efficiency in a display device.

Means for Solving the Problems

[0007] The present invention provides the following display device and film. [1] A display device having a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C), wherein the wavelength conversion layer (B) has a first wavelength conversion layer (B1) containing a compound (Q1) that absorbs blue light and emits red light, and a second wavelength conversion layer (B2) containing a compound (Q2) that absorbs blue light and emits green light, A display device that satisfies the following conditions (1) and (2). (1) 0.7 ≦ X1 (2) 0.7 ≦ X2 [However, X1 is a value obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content W1 [mass%] of the compound (Q1) in the first wavelength conversion layer (B1) by 100 [X1 = (T1 × W1) / 100], X2 is a value obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content W2 [mass%] of the compound (Q2) in the second wavelength conversion layer (B2) by 100 [X2 = (T2 × W2) / 100]. [2] The display device according to [1], wherein the blue light source (A) emits light having a peak at a wavelength of 600 nm or less. [3] The display device according to [1] or [2], wherein the compound (Q1) contains at least one selected from the group consisting of indium compounds and cadmium compounds. [4] The display device according to any one of [1] to [3], wherein the compound (Q2) contains at least one selected from the group consisting of indium compounds and cadmium compounds. [5] The display device according to any one of [1] to [4], wherein the first wavelength conversion layer (B1) further contains a light scattering agent (S) and satisfies the following condition (3). (3) X3 ≤ 1.6 [However, X3 is a value obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content rate W3 [mass%] of the light scattering agent (S) in the first wavelength conversion layer (B1) by 100 [X3 = (T1 × W3) / 100]. [6] The display device according to any one of [1] to [5], wherein the second wavelength conversion layer (B2) further contains a light scattering agent (S) and satisfies the following condition (4). (4) X4 ≤ 1.6 [However, X4 is a value obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content rate W4 [mass%] of the light scattering agent (S) in the second wavelength conversion layer (B2) by 100 [X4 = (T2 × W4) / 100]. [7] The display device according to [1] to [6], wherein the light absorption layer (C) has a first light absorption layer (C1) and a second light absorption layer (C2), the first light absorption layer (C1) is disposed on the first wavelength conversion layer (B1), and the second light absorption layer (C2) is disposed on the second wavelength conversion layer (B2). [8] A film containing a compound (Q1) that absorbs blue light and emits red light and satisfies the following condition (5). (5) 0.7 ≤ X5 [However, X5 is a value obtained by dividing the product of the thickness T5 [μm] of the film and the content rate W5 [mass%] of the compound (Q1) in the film by 100 [X5 = (T5 × W5) / 100]. [9] A film containing a compound (Q2) that absorbs blue light and emits green light and satisfies the following condition (6). (6) 0.7 ≤ X6 [However, X6 is a value obtained by dividing the product of the thickness T6 [μm] of the film and the content rate W6 [mass%] of the compound (Q2) in the film by 100 [X6 = (T6 × W6) / 100]. [Advantages of the Invention]

[0008] According to the present invention, in a display device including a blue light source, a wavelength conversion layer having a first wavelength conversion layer that emits red light and a second wavelength conversion layer that emits green light, and a light absorption layer, a wide color gamut and energy efficiency can be achieved simultaneously. According to another aspect of the present invention, it is possible to provide a film that can be used as a wavelength conversion layer that emits green light and can achieve both a wide color gamut and excellent energy efficiency in a display device. According to still another aspect of the present invention, it is possible to provide a film that can be used as a wavelength conversion layer that emits red light and can achieve both a wide color gamut and excellent energy efficiency in a display device.

Brief Description of the Drawings

[0009]

Figure 1

Figure 2

Figure 3

Modes for Carrying Out the Invention

[0010] <Display Device> The display device includes a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C). The display device irradiates the wavelength conversion layer (B) with light from the blue light source (A) to cause the wavelength conversion layer (B) to emit light, and extracts the emitted light through the light absorption layer (C).

[0011] The wavelength conversion layer (B) is composed of a first wavelength conversion layer (B1) containing a compound (Q1) that absorbs blue light and emits red light (hereinafter also simply referred to as the light-emitting compound (Q1)), and a second wavelength conversion layer (B2) containing a compound (Q2) that absorbs blue light and emits green light (hereinafter also simply referred to as the light-emitting compound (Q2)).

[0012] "Luminescence" refers to the property of emitting light. The luminescence preferably is a property of emitting light by excitation of electrons, and more preferably is a property of emitting light by excitation of electrons by excitation light. The peak wavelength of the excitation light may be, for example, 200 nm to 800 nm, may be 250 nm to 750 nm, may be 300 nm to 700 nm, or may be 300 nm to 600 nm.

[0013] "Blue" refers to all light that is visually recognized as blue (all light having intensity in the blue wavelength region, for example, 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light that is visually recognized as green (all light having intensity in the green wavelength region, for example, 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to all light that is visually recognized as red (all light having intensity in the red wavelength region, for example, 585 nm to 780 nm), and is not limited to light of a single wavelength. "Yellow" refers to all light that is visually recognized as yellow (all light having intensity in the yellow wavelength region, for example, 560 nm to 610 nm), and is not limited to light of a single wavelength.

[0014] The display device may include layers such as a light guide plate, a reflection film, a diffusion film, a brightness enhancement unit, a prism sheet, and a medium material layer between elements, which will be described later.

[0015] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) may be directly disposed on the blue light source (A), or may be disposed on a light guide plate disposed between the blue light source (A) and the first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) in the optical path of the light from the blue light source (A).

[0016] In the optical path of the light from the blue light source (A), the display device can have the blue light source (A), the wavelength conversion layer (B), and the light absorption layer (C) in this order.

[0017] When the display device satisfies conditions (1) and (2), it can exhibit a wide color gamut and excellent energy efficiency. In a display device including a blue light source, a wavelength conversion layer containing a light-emitting compound, and a light absorption layer, a part of the light from the blue light source leaks out from the wavelength conversion layer, resulting in a decrease in the peak intensity of the light emitted from the wavelength conversion layer, and the target chromaticity and light emission intensity may not be obtained. In order to suppress such leakage of light from the blue light source, it is conceivable to increase the thickness of the wavelength conversion layer. However, when the thickness is too large, the formation of the wavelength conversion layer tends to be difficult. As a result of research, when the product of the thickness of the wavelength conversion layer and the content rate of the light-emitting compound in the wavelength conversion layer is set to a certain value or more, it becomes easier to suppress a part of the light from the blue light source from leaking out within the thickness range where the wavelength conversion layer can be formed, and it has been found that a wide color gamut and excellent energy efficiency can be obtained.

[0018] <Condition (1)> The value X1 [X1 = (T1 × W1) / 100] (hereinafter, also simply referred to as X1) obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content rate W1 [% by mass] of the light-emitting compound (Q1) in the first wavelength conversion layer (B1) by 100 is 0.7 or more. The first wavelength conversion layer (B1) is preferably 1.0 ≦ X1, more preferably 1.5 ≦ X1, and still more preferably 2.0 ≦ X1 from the viewpoints of color gamut and energy efficiency. The first wavelength conversion layer (B1) is usually X1 ≦ 4.0, and preferably X1 ≦ 3.5 from the viewpoint of ease of manufacture.

[0019] <Condition (2)> The value X2 [X2 = (T2 × W2) / 100] (hereinafter, also simply referred to as X2) obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content rate W2 [% by mass] of the light-emitting compound (Q2) in the second wavelength conversion layer (B2) by 100 is 0.7 or more. The first wavelength conversion layer (B2) is preferably 1.0 ≦ X2, more preferably 1.5 ≦ X2, and still more preferably 2.0 ≦ X2 from the viewpoints of color gamut and energy efficiency. The first wavelength conversion layer (B1) is usually X2 ≦ 4.0, and preferably X2 ≦ 3.5 from the viewpoint of ease of manufacture.

[0020] The thickness T1 of the first wavelength conversion layer (B1) may be, for example, 1 μm or more and 20 μm or less, preferably 1.5 μm or more and 15 μm or less, and more preferably 2 μm or more and 10 μm or less from the viewpoint of ease of manufacture. The thickness T1 [μm] of the first wavelength conversion layer (B1) is measured according to the method described in the column of Examples below.

[0021] The thickness T2 of the second wavelength conversion layer (B2) may be, for example, 1 μm or more and 20 μm or less, preferably 1.5 μm or more and 15 μm or less, and more preferably 2 μm or more and 10 μm or less from the viewpoint of ease of manufacture. The thickness T2 [μm] of the second wavelength conversion layer (B2) is measured according to the method described in the column of Examples below.

[0022] The thickness T1 of the first wavelength conversion layer (B1) and the thickness T2 of the second wavelength conversion layer (B2) may be the same or different from each other.

[0023] The content W1 of the luminescent compound (Q1) in the first wavelength conversion layer (B1) may be, for example, 10% by mass or more and 80% by mass or less, preferably 15% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 40% by mass or less from the viewpoints of color gamut and energy efficiency. The content W1 of the luminescent compound (Q1) in the first wavelength conversion layer (B1) is determined as the mass ratio of the luminescent compound (Q1) to the mass of the solid content of the curable resin composition (Q1) described below for forming the first wavelength conversion layer (B1).

[0024] The content W2 of the luminescent compound (Q2) in the second wavelength conversion layer (B2) may be, for example, 10% by mass or more and 80% by mass or less, preferably 15% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 40% by mass or less from the viewpoints of color gamut and energy efficiency. The content W2 of the luminescent compound (Q2) in the second wavelength conversion layer (B2) is determined as the mass ratio of the luminescent compound (Q2) to the mass of the solid content of the curable resin composition (Q2) described below for forming the second wavelength conversion layer (B2).

[0025] In order to satisfy conditions (1) and (2), for example, methods such as adjusting the types, average particle diameters, and contents of the light-emitting compounds (Q1) and (Q2) in the curable resin composition (Q) described later, the types and contents of the polymer, and the method of adjusting the thickness of the wavelength conversion layer can be mentioned.

[0026] <Blue light source> The blue light source (A) can be a light source that emits at least blue light capable of causing the light-emitting compounds (Q1) in the first wavelength conversion layer (B1) and the light-emitting compounds (Q2) in the second wavelength conversion layer (B2) to emit light. As the blue light source (A), for example, known light sources such as light-emitting diodes (LEDs) such as blue light-emitting diodes, lasers, and ELs can be used. The blue light source (A) is preferably a light source that emits light having a peak at 600 nm or less from the viewpoints of color gamut and energy efficiency. The peak of the light emitted from the blue light source (A) is measured according to the method described in the column of the examples described later.

[0027] The blue light source (A) can be used as a backlight in combination with the wavelength conversion layer (B). The backlight may include a light guide plate.

[0028] <Wavelength conversion layer> The wavelength conversion layer (B) is composed of a first wavelength conversion layer (B1) and a second wavelength conversion layer (B2). The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) are each preferably capable of converting the wavelength of blue light from the blue light source (A) into the wavelength of red light and the wavelength of green light.

[0029] The first wavelength conversion layer (B1) can absorb a part of the light from the blue light source (A) and emit red light. Another part of the light from the blue light source (A) may pass through the first wavelength conversion layer (B1), but it is preferable that the amount of light transmitted from the blue light source (A) is small.

[0030] The light emitted from the first wavelength conversion layer (B1) has a peak in the wavelength range of 620 nm to 650 nm, and the full width at half maximum of the peak is 15 nm to 80 nm. More preferably, it has a peak in the wavelength range of 625 nm to 645 nm, and the full width at half maximum of the peak is 15 nm to 45 nm. The wavelength range of the peak and the full width at half maximum are measured by the method described in the column of the examples below.

[0031] The second wavelength conversion layer (B2) can absorb part of the light from the blue light source (A) and emit green light. The second wavelength conversion layer (B2) may allow another part of the light from the blue light source (A) to pass through, but preferably, the amount of light transmitted from the blue light source (A) is less.

[0032] The light emitted from the second wavelength conversion layer (B2) has a peak in the wavelength range of 520 nm to 545 nm, and the full width at half maximum of the peak is 15 nm to 80 nm. More preferably, it has a peak in the wavelength range of 525 nm to 535 nm, and the full width at half maximum of the peak is 15 nm to 45 nm.

[0033] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) each can be a layer including a cured product of a curable resin composition containing a luminescent compound (Q1) (hereinafter, also referred to as curable resin composition (D1)) and a layer including a cured product of a curable resin composition containing a luminescent compound (Q2) (hereinafter, also referred to as curable resin composition (D2)). Hereinafter, curable resin composition (D1) and curable resin composition (D2) are also collectively referred to as curable resin composition (D).

[0034] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) each may have a single-layer structure or may have a multilayer structure composed of a plurality of layers. When the first wavelength conversion layer (B1) has a multilayer structure composed of a plurality of layers, the first wavelength conversion layer (B1) may have two or more layers including a cured product of curable resin composition (D1).

[0035] The light transmittance (450 nm) of the first wavelength conversion layer (B1) may be, for example, 85% or less, preferably 60% or less, more preferably 40% or less, still more preferably 30% or less, particularly preferably 20% or less, and even more particularly preferably 10% or less, from the viewpoints of color gamut and energy efficiency. The light transmittance (450 nm) of the second wavelength conversion layer (B2) may be, for example, 90% or less, preferably 75% or less, more preferably 60% or less, still more preferably 40% or less, particularly preferably 30% or less, and even more particularly preferably 20% or less, from the viewpoints of color gamut and energy efficiency.

[0036] [Luminescent compound] The emission spectrum (peak) of the red light emitted by the luminescent compound (Q1) preferably has a maximum value in the wavelength range of 610 nm to 750 nm. When the maximum value is in the wavelength range of 610 nm to 750 nm, the color purity of the red light corresponding to the peak is particularly high, so that the luminance of the red light of the display device can be further improved. The above maximum value more preferably exists in the wavelength range of 620 nm to 650 nm. The emission spectrum of the luminescent compound (Q1) is measured according to the method described in the column of Examples below.

[0037] The emission spectrum of the luminescent compound (Q1) preferably has a full width at half maximum of 20 nm to 80 nm. When the full width at half maximum is 80 nm or less, the color purity of the red light in the emission from the first wavelength conversion layer (B1) is high, so that the luminance of the red light of the display device can be further improved. On the other hand, when the full width at half maximum is 20 nm or more, the transmission amount of the red light can be further increased, so that the luminance of the red light can be further improved. The full width at half maximum of the emission spectrum of the red light is more preferably 20 nm to 60 nm, and still more preferably 20 nm to 50 nm.

[0038] The emission spectrum (peak) of the green light emitted by the luminescent compound (Q2) preferably has a maximum value in the wavelength range of 500 nm to 560 nm. When the maximum value is in the wavelength range of 500 nm to 560 nm, the color purity of the green light corresponding to the peak is particularly high, so the luminance of the green light of the display device can be further improved. The above maximum value more preferably exists in the wavelength range of 500 nm to 560 nm. The emission spectrum of the luminescent compound (Q2) is measured according to the method described in the column of the examples described later.

[0039] The emission spectrum of the luminescent compound (Q2) preferably has a full width at half maximum of 20 nm to 80 nm. When the full width at half maximum is 80 nm or less, the color purity of the green light in the emission from the second wavelength conversion layer (B2) is high, so the luminance of the green light of the display device can be further improved. On the other hand, when the full width at half maximum is 20 nm or more, the transmission amount of the green light can be further increased, so the luminance of the green light can be further improved. The full width at half maximum of the emission spectrum of the above green light is more preferably 20 nm to 60 nm, and even more preferably 20 nm to 50 nm.

[0040] As the luminescent compound (Q1) and the luminescent compound (Q2), quantum dots are preferred. Examples of quantum dots include particles of indium compounds having luminescence and particles of cadmium compounds having luminescence.

[0041] Examples of indium compounds include III-V group indium compounds, III-VI group indium compounds, and I-III-VI group indium compounds. Preferably, they are III-V group indium compounds, and more preferably indium compounds containing a phosphorus element in group V.

[0042] Examples of cadmium compounds include II-VI group cadmium compounds and II-V group cadmium compounds.

[0043] The indium compound does not contain cadmium element, and the cadmium compound does not contain indium element.

[0044] [III-V Group Indium Compounds] III-V group indium compounds are compounds containing a Group III element and a Group V element, and containing at least an indium element. Here, Group III means Group 13 of the periodic table, and Group V means Group 15 of the periodic table (the same applies hereinafter). In this specification, the "periodic table" means the long-period type periodic table.

[0045] III-V group indium compounds may be binary, ternary, or quaternary.

[0046] Binary III-V group indium compounds may be any compounds containing an indium element (the first element) and a Group V element (the second element), and examples include InN, InP, InAs, and InSb.

[0047] Ternary III-V group indium compounds may be compounds containing an indium element (the first element) and two types of elements selected from Group V (the second elements), or may be compounds containing two types of elements selected from Group III with one type being an indium element (the first elements) and one type of element selected from Group V (the second element).

[0048] Examples of ternary III-V group indium compounds include InPN, InPAs, InPSb, InGaP, etc.

[0049] Quaternary III-V group indium compounds are compounds containing two types of elements selected from Group III with one type being an indium element (the first elements) and two types of elements selected from Group V (the second elements).

[0050] Examples of quaternary III-V group indium compounds include InGaPN, InGaPAs, and InGaPSb, etc.

[0051] Semiconductors containing III-V indium compounds may contain elements other than those in Group 13 and Group 15 of the periodic table (excluding the element cadmium) as doping elements.

[0052] [III-VI indium compounds] III-VI indium compounds are compounds containing a Group III element and a Group VI element, and at least containing an indium element. Here, Group VI means Group 16 of the periodic table (the same applies hereinafter).

[0053] III-VI indium compounds may be binary systems, ternary systems, or quaternary systems.

[0054] Binary III-VI indium compounds may be compounds containing an indium element (the first element) and an element in Group VI (the second element), such as In2S3, In2Se3, and In2Te3.

[0055] Ternary III-VI indium compounds may be compounds containing an indium element (the first element) and two types of elements selected from Group VI (the second element), or may be compounds containing two types of elements selected from Group III (the first element) with one type being an indium element and one type of element selected from Group VI (the second element).

[0056] Examples of ternary III-VI indium compounds include InGaS3, InGaSe3, InGaTe3, In2SSe2, and In2TeSe2.

[0057] Quaternary III-VI indium compounds are compounds containing two types of elements selected from Group III (the first element) with one type being an indium element and two types of elements selected from Group VI (the second element).

[0058] Examples of quaternary III-VI indium compounds include InGaSSe2, InGaSeTe2, and InGaSTe2.

[0059] Semiconductors containing III-VI group indium compounds may contain elements other than those in Group 13 and Group 16 of the periodic table (excluding the element cadmium) as doping elements.

[0060] [I-III-VI group indium compounds] I-III-VI group indium compounds are compounds containing a Group I element, a Group III element, and a Group VI element, and are compounds containing at least an indium element. Here, Group I means Group 11 of the periodic table (the same applies hereinafter).

[0061] I-III-VI group indium compounds may be ternary systems or quaternary systems.

[0062] Ternary I-III-VI group indium compounds are compounds containing an element selected from Group I (the first element), an indium element (the second element), and an element selected from Group VI (the third element).

[0063] Examples of ternary I-III-VI group indium compounds include CuInS2.

[0064] Semiconductors containing I-III-VI group indium compounds may contain elements other than those in Group 11, Group 13, and Group 16 of the periodic table (excluding the element cadmium) as doping elements.

[0065] From the viewpoint of obtaining sufficient emission intensity, indium compounds are preferably InP, CuInS2, InNP, and GaInNP, and more preferably InP and CuInS2.

[0066] [II-VI group cadmium compounds] II-VI group cadmium compounds are compounds containing a Group II element and a Group VI element, and are compounds containing at least a cadmium element. Here, Group II means Group 2 or Group 12 of the periodic table (the same applies hereinafter).

[0067] II-VI cadmium compounds may be binary, ternary, or quaternary systems.

[0068] The binary II-VI cadmium compound may be a compound containing a cadmium element (the first element) and an element of Group 16 (the second element). Examples include CdS, CdSe, and CdTe.

[0069] The ternary II-VI cadmium compound may be a compound containing a cadmium element (the first element) and two types of elements selected from Group VI (the second elements), or it may be a compound containing two types of elements selected from Group II (the first elements) with one type being a cadmium element and one type of element selected from Group VI (the second element).

[0070] Examples of ternary II-VI cadmium compounds include CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, and CdHgTe.

[0071] The quaternary II-VI cadmium compound is a compound containing two types of elements selected from Group II (the first elements) with one type being a cadmium element and two types of elements selected from Group VI (the second elements).

[0072] Examples of quaternary II-VI cadmium compounds include CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, and CdHgSTe.

[0073] The semiconductor containing the II-VI cadmium compound may contain elements other than those in Groups 2, 12, and 16 of the periodic table (excluding indium) as doping elements.

[0074] [II-V cadmium compound] The II-V cadmium compound is a compound containing a Group II element and a Group V element, and is a compound containing at least a cadmium element.

[0075] II-V cadmium compounds may be binary, ternary, or quaternary systems.

[0076] A binary II-V cadmium compound may be a compound containing a cadmium element (the first element) and an element of Group V (the second element). Examples include Cd3P2, Cd3As2, and Cd3N2.

[0077] A ternary II-V cadmium compound may be a compound containing a cadmium element (the first element) and two types of elements selected from Group V (the second elements), or may be a compound containing two types of elements selected from Group II (the first elements) with one type being a cadmium element and one type of element selected from Group V (the second element).

[0078] Examples of ternary II-V cadmium compounds include Cd3PN, Cd3PAs, Cd3AsN, Cd2ZnP2, Cd2ZnAs2, and Cd2ZnN2.

[0079] A quaternary II-V cadmium compound is a compound containing two types of elements selected from Group II (the first elements) with one type being a cadmium element and two types of elements selected from Group V (the second elements).

[0080] Examples of quaternary II-V cadmium compounds include CdZnPN, CdZnPAs, and Cd2ZnAsN.

[0081] A semiconductor containing an II-V cadmium compound may contain an element other than those in Groups 2, 12, and 15 of the periodic table (excluding indium) as a doping element.

[0082] From the viewpoint of obtaining sufficient luminescence intensity, the cadmium compound is preferably CdS, CdSe, ZnCdS, CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, ZnCdSSe, CdZnSeS, CdZnSeTe, and CdZnSTe; more preferably CdS, CdSe, ZnCdS, CdSeS, CdZnS, CdZnSe, ZnCdSSe, and CdZnSeS; still more preferably CdS, CdSe, ZnCdS, ZnCdSSe, CdZnSeS; and particularly preferably CdSe, CdZnSeS.

[0083] The particles of the indium compound and the particles of the cadmium compound may have an inorganic protective layer on the particle surface from the viewpoints of luminescence intensity and durability. The inorganic protective layer may be two or more layers, or may be a single layer. Examples of the inorganic material capable of forming the inorganic protective layer include, but are not limited to, semiconductors having a larger band gap than the indium compound and / or the cadmium compound. The inorganic protective layer is formed of a known inorganic material such as ZnS, ZnSe, and CdS.

[0084] The particles of the indium compound and the particles of the cadmium compound can be synthesized by a wet chemical process, a metalorganic chemical vapor deposition process, or a molecular beam epitaxy process. The wet chemical process is a method of growing particles by putting a precursor substance in an organic solvent. When the crystal grows, the organic solvent is naturally coordinated on the surface of the quantum dot crystal and serves as a dispersant to regulate the crystal growth. Therefore, the growth of nanoparticles can be controlled through a process that is easier and less expensive than vapor deposition methods such as metal organic chemical vapor deposition (MOCVD) and molecular beam epitaxy (MBE).

[0085] [Light Scattering Agent] The first wavelength conversion layer (B1) and / or the second wavelength conversion layer (B2) may further contain a light scattering agent (S) from the viewpoint of efficiently absorbing the incident light. The light scattering agent (S) is not particularly limited, but a light scattering agent having translucency is preferable from the viewpoint of extracting the emitted light, and may be, for example, light scattering particles such as inorganic oxide particles. Examples of the inorganic oxide particles include titanium oxide particles.

[0086] [Condition (3)] When the first wavelength conversion layer (B1) further contains the light scattering agent (S), preferably, the value X3 obtained by dividing the product of the thickness T1 of the first wavelength conversion layer (B1) and the content rate W3 of the light scattering agent (S) in the first wavelength conversion layer (B1) by 100 [X3 = (T1 × W3) / 100] (hereinafter, also simply referred to as X3) is 1.6 or less (Condition 3) from the viewpoints of color gamut and energy efficiency, more preferably X3 ≦ 1.2, and even more preferably X3 ≦ 1.0. When the first wavelength conversion layer (B1) further contains the light scattering agent (S), usually, 0.1 ≦ X3, and preferably 0.5 ≦ X3 from the viewpoints of color gamut and energy efficiency.

[0087] When the first wavelength conversion layer (B1) further contains the light scattering agent (S), the content rate of the light scattering agent (S) in the first wavelength conversion layer (B1) may be, for example, 1% by mass or more and 20% by mass or less, and preferably 3% by mass or more and 15% by mass or less from the viewpoints of color gamut and energy efficiency.

[0088] [Condition (4)] When the second wavelength conversion layer (B2) further contains a light scattering agent (S), the second wavelength conversion layer (B2) preferably satisfies the condition 4 that the value X4 obtained by dividing the product of the thickness T2 of the second wavelength conversion layer (B2) and the content rate W4 of the light scattering agent (S) in the second wavelength conversion layer (B2) by 100 [X4 = (T2 × W4) / 100] (hereinafter also simply referred to as X4) is 1.6 or less, more preferably X4 ≤ 1.2, and even more preferably X4 ≤ 1.0, from the viewpoints of color gamut and energy efficiency. When the second wavelength conversion layer (B2) further contains a light scattering agent (S), usually 0.1 ≤ X4, and preferably 0.3 ≤ X4 from the viewpoints of color gamut and energy efficiency.

[0089] When the second wavelength conversion layer (B2) further contains a light scattering agent (S), the content rate of the light scattering agent (S) in the second wavelength conversion layer (B2) may be, for example, 1% by mass or more and 20% by mass or less, and preferably 3% by mass or more and 15% by mass or less from the viewpoints of color gamut and energy efficiency.

[0090] The wavelength conversion layer (B) can be used by being bonded to a substrate, a barrier layer, a light scattering layer, etc.

[0091] [Substrate] From the viewpoint of extracting light during light emission, the substrate preferably has translucency. As the substrate, for example, a thermoplastic resin film such as polyethylene terephthalate or a known material such as glass can be used. For example, in the wavelength conversion layer (B), a layer containing a cured product of the curable resin composition (Q) described later can be provided on the substrate.

[0092] [Barrier layer] In order to protect the wavelength conversion layer (B) from water vapor in the outside air and oxygen in the atmosphere, a barrier layer may be bonded. The barrier layer is not particularly limited, and a known barrier layer can be applied.

[0093] [Light scattering layer] From the perspective of efficiently absorbing the incident light, a light-scattering layer may be laminated. The light-scattering layer is not particularly limited, but from the perspective of extracting the emitted light, a light-scattering layer having translucency is preferable, and for example, a known light-scattering layer such as an amplified diffusion film can be applied.

[0094] [Method for manufacturing wavelength conversion layer] Examples of the method for manufacturing the wavelength conversion layer (B) include a manufacturing method including a step of preparing a curable resin composition (D), a step of coating the curable resin composition (D) on a substrate, and a step of removing a solvent; a manufacturing method including a step of producing a film containing a cured product of the curable resin composition (D), and a step of laminating the obtained film on a substrate; and a manufacturing method including a step of preparing a curable resin composition (D), a step of coating the curable resin composition (D) on a substrate, and a step of polymerizing a polymerizable compound.

[0095] As a method for coating the curable resin composition (D) on a substrate, for example, known coating methods such as a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dip method, and a die coating method can be used.

[0096] In the step of laminating a film containing a cured product of the curable resin composition (D) on a substrate, any adhesive can be used. The adhesive is not particularly limited as long as it does not dissolve the curable resin composition (D), and a known adhesive can be used.

[0097] The manufacturing method of the wavelength conversion layer (B) may be a manufacturing method further including a step of laminating any film. Examples of the arbitrary film to be laminated include a barrier film, a light-scattering film, a reflective film, a diffusion film, and the like. In the step of laminating any film, any adhesive can be used. The above-mentioned adhesive is not particularly limited as long as it does not dissolve the curable resin composition (Q), and a known adhesive can be used.

[0098] [Curable resin composition] The wavelength conversion layer (B) can be formed from a curable resin composition (D). The curable resin composition (D) can further contain at least one selected from the group consisting of an organic ligand (L), a light scattering agent (S), a solvent (K), a polymerizable compound (G), and a polymerization initiator (H) in addition to the luminescent compound (Q1) or the luminescent compound (Q2).

[0099] The content of the luminescent compound (Q1) in the curable composition (D1) may be, for example, 10% by mass or more and 80% by mass or less, preferably 15% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 40% by mass or less with respect to the total amount of the solid content of the curable composition (D1) from the viewpoints of color gamut and energy efficiency.

[0100] The content of the luminescent compound (Q2) in the curable composition (D2) may be, for example, 10% by mass or more and 80% by mass or less, preferably 15% by mass or more and 60% by mass or less, and more preferably 15% by mass or more and 40% by mass or less with respect to the total amount of the solid content of the curable composition (D2) from the viewpoints of color gamut and energy efficiency.

[0101] When the curable resin composition (D1) contains a light scattering agent (S), the content of the light scattering agent (S) in the curable resin composition (D1) may be, for example, 1% by mass or more and 20% by mass or less with respect to the total amount of the solid content of the curable resin composition (D1), and is preferably 3% by mass or more and 15% by mass or less from the viewpoints of color gamut and energy efficiency.

[0102] When the curable resin composition (D2) contains a light scattering agent (S), the content of the light scattering agent (S) in the curable resin composition (D2) may be, for example, 1% by mass or more and 20% by mass or less with respect to the total amount of the solid content of the curable resin composition (D2), and is preferably 3% by mass or more and 15% by mass or less from the viewpoints of color gamut and energy efficiency.

[0103] [Organic ligand] The organic ligand (L) may be either a non-polar organic ligand or a polar organic ligand. Examples of the non-polar organic ligand include linear or branched saturated or unsaturated aliphatic acids, aliphatic amines, and aliphatic thiols having 1 to 30 carbon atoms. The number of carbon atoms is preferably 6 to 20. The number of polar groups is preferably 2 or less in one molecule. The polar groups are preferably thiol groups and carboxy groups.

[0104] Examples of the polar organic ligand include a compound (La) containing a polyalkylene glycol structure represented by the following formula and having a polar group at the molecular end.

Chemical formula

[0105] Specific examples of the compound (La) include the following formula (La-1):

Chemical formula

[0106] [Resin] Resin (F) is preferably an alkali-soluble resin. Examples of resin (F) include the following resins [f1] to [f4]. Resin [f1]: A resin obtained by copolymerizing at least one kind (a) (hereinafter sometimes referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic acid anhydrides, and a monomer (c) copolymerizable with (a) (however, different from (a), hereinafter sometimes referred to as "(c)"). Resin [f2]: A resin obtained by reacting a monomer (b) (hereinafter sometimes referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenic unsaturated bond with a copolymer of (a) and (c). Resin [f3]: A resin obtained by reacting (a) with a copolymer of (b) and (c). Resin [f4]: A resin obtained by reacting (a) with a copolymer of (b) and (c), and further reacting with a carboxylic acid anhydride.

[0107] Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, o-, m-, p-vinylbenzoic acid, etc.; unsaturated dicarboxylic acids such as maleic acid, fumaric acid, citraconic acid, mesaconic acid, itaconic acid, 3-vinylphthalic acid, 4-vinylphthalic acid, 3,4,5,6-tetrahydrophthalic acid, 1,2,3,6-tetrahydrophthalic acid, dimethyltetrahydrophthalic acid, 1,4-cyclohexenedicarboxylic acid, etc.; Bicyclic unsaturated compounds containing a carboxy group such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene, etc.; Anhydrides of unsaturated dicarboxylic acids such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, etc.; Unsaturated mono[(meth)acryloyloxyalkyl] esters of polyvalent carboxylic acids with a valence of 2 or more such as succinic acid mono[2-(meth)acryloyloxyethyl], phthalic acid mono[2-(meth)acryloyloxyethyl], etc.; Examples include unsaturated acrylates such as α-(hydroxymethyl)acrylic acid that contain a hydroxy group and a carboxy group in the same molecule. Among these, acrylic acid, methacrylic acid, maleic anhydride, etc. are preferable from the viewpoints of copolymerization reactivity and solubility of the resulting resin in an alkaline aqueous solution.

[0108] (b) is a monomer having, for example, a cyclic ether structure with 2 to 4 carbon atoms (for example, at least one selected from the group consisting of an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure with 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0109] Examples of (b) include monomers having an oxirane ring and an ethylenically unsaturated bond, such as glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyloxymethyl)styrene, 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, 2,4,6-tris(glycidyloxymethyl)styrene; monomers having an oxetane ring and an ethylenically unsaturated bond, such as 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane; and monomers having a tetrahydrofuran ring and an ethylenically unsaturated bond, such as tetrahydrofurfuryl acrylate (e.g., Biscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate.

[0110] (b) has high reactivity during the production of resins [f2] to [f4], and unreacted (b) hardly remains. Therefore, as (b), monomers having an oxirane ring and an ethylenically unsaturated bond are preferred.

[0111] (c) Examples include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0 2,6 decane-8-yl (meth)acrylate (common name in the art: dicyclopentanyl (meth)acrylate or tricyclodecyl (meth)acrylate), tricyclo[5.2.1.0 2,6 decen-8-yl (meth)acrylate (common name in the art: dicyclopentenyl (meth)acrylate), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate and other (meth)acrylic acid esters; 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate and other hydroxy group-containing (meth)acrylic acid esters; Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxy-bicyclo[2.2.1]hept-2-ene, 5-ethoxy-bicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy-bicyclo[2.2.1]hept-2-ene, 5,6-diethoxy-bicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; Dicarbonylimide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl 3-maleimidobenzoate, N-succinimidyl 4-maleimidobutyrate, N-succinimidyl 6-maleimidocaproate, N-succinimidyl 3-maleimidopropionate, N-(9-acridinyl)maleimide; Examples include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, and the like. Among these, from the viewpoints of copolymerization reactivity and heat resistance, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, and the like are preferable.

[0112] In the resin [f1], the ratio of the structural units derived from each monomer is preferably such that the structural units derived from (a) are 2 mol% or more and 70 mol% or less, and the structural units derived from (c) are 30 mol% or more and 98 mol% or less, based on all the structural units constituting the resin [f1]. More preferably, the structural units derived from (a) are 10 mol% or more and 70 mol% or less, and the structural units derived from (c) are 30 mol% or more and 90 mol% or less. When the ratio of the structural units of the resin [f1] is within the above range, the storage stability of the curable composition, the developability when forming a cured pattern, and the solvent resistance of the obtained cured pattern tend to be excellent.

[0113] The resin [f1] can be produced, for example, with reference to the methods described in the literature "Experimental Methods of Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Publishing Co., Ltd., 1st edition, 1st printing, issued on March 1, 1972) and the cited references described in the literature.

[0114] Specifically, a method includes putting predetermined amounts of (a) and (c), a polymerization initiator, and a solvent into a reaction vessel, making an oxygen-free atmosphere by substituting oxygen with nitrogen, for example, and heating and keeping warm while stirring. The polymerization initiator and the solvent used here are not particularly limited, and those commonly used in the art can be used. For example, as the polymerization initiator, azo compounds (such as 2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile)) and organic peroxides (such as benzoyl peroxide) can be mentioned. As the solvent, any solvent that can dissolve each monomer may be used, and solvents such as the solvent (K) described later that may be included in the curable composition of the present invention can be mentioned.

[0115] In addition, the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used. In particular, by using the solvent (K) described later as the solvent during this polymerization, the reaction solution can be used as it is for the preparation of the curable composition of the present invention, so the manufacturing process of the curable composition of the present invention can be simplified.

[0116] Resin [f2] can be produced by obtaining a copolymer of (a) and (c) and adding the cyclic ether having 2 to 4 carbon atoms of (b) to the carboxylic acid and / or carboxylic anhydride derived from (a). First, a copolymer of (a) and (c) is produced in the same manner as the method described as the production method of resin [f1]. In this case, the ratio of the structural units derived from each is preferably the same as those mentioned for resin [f1].

[0117] Next, an addition reaction of the cyclic ether having 2 to 4 carbon atoms of (b) is carried out on a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the copolymer. Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst for the reaction between a carboxylic acid or carboxylic anhydride and a cyclic ether (such as tris(dimethylaminomethyl)phenol), a polymerization inhibitor (such as hydroquinone), etc. are put into the flask, and reacted at, for example, 60 to 130 °C for 1 to 10 hours to produce resin [f2].

[0118] The amount of (b) used is preferably 5 mol or more and 80 mol or less, more preferably 10 mol or more and 75 mol or less, per 100 mol of (a). By setting it within this range, the storage stability of the curable composition, the developability when forming a cured pattern, and the balance of solvent resistance, heat resistance, mechanical strength, and sensitivity of the obtained cured pattern tend to be good.

[0119] The amount of the reaction catalyst used is preferably 0.001 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the total amount of (a), (b), and (c). The amount of the polymerization inhibitor used is preferably 0.001 part by mass or more and 5 parts by mass or less based on 100 parts by mass of the total amount of (a), (b), and (c).

[0120] Reaction conditions such as the charging method, reaction temperature, and time can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc. Similar to the polymerization conditions, the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the heat generation amount due to polymerization, etc.

[0121] As the first step, resin [f3] is obtained as a copolymer of (b) and (c) in the same manner as the production method of resin [f1] described above. Similar to the above, the obtained copolymer may be used as the reaction solution as it is, or a concentrated or diluted solution may be used, or a solid (powder) taken out by a method such as reprecipitation may be used.

[0122] The ratio of the structural units derived from (b) and (c) is preferably such that, based on the total number of moles of all the structural units constituting the copolymer, the structural units derived from (b) are 5 mol% or more and 95 mol% or less, and the structural units derived from (c) are 5 mol% or more and 95 mol% or less. More preferably, the structural units derived from (b) are 10 mol% or more and 90 mol% or less, and the structural units derived from (c) are 10 mol% or more and 90 mol% or less.

[0123] Furthermore, under the same conditions as in the method for producing resin [f2], a resin [f3] can be obtained by subjecting the cyclic ether derived from (b) in the copolymer of (b) and (c) to an addition reaction with the carboxylic acid or carboxylic anhydride that (a) has. The amount of (a) used for reaction with the copolymer is preferably 5 mol or more and 80 mol or less per 100 mol of (b).

[0124] Resin [f4] is a resin obtained by further reacting resin [f3] with a carboxylic anhydride. The carboxylic anhydride is subjected to an addition reaction with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride. Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride, and the like. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol per 1 mol of the amount of (a) used.

[0125] As the resin (F), specifically, resins [f1] such as benzyl (meth)acrylate / (meth)acrylic acid copolymer, styrene / (meth)acrylic acid copolymer; resins [f2] such as resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer; resins [f3] such as resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate; resins [f4] such as resins obtained by further reacting tetrahydrophthalic anhydride with a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate can be mentioned.

[0126] As a further example of the resin (F), a resin [f5] containing a structural unit containing a tetrahydropyran ring in the main chain can be mentioned. By the resin (F) containing a resin [f5] containing a structural unit containing a tetrahydropyran ring in the main chain, excellent luminescence intensity and heat resistance can be obtained in the cured film. The structural unit containing a tetrahydropyran ring is represented by the following general formula (I): [Chemical formula] [In the formula, R 1f and R 2f are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. This hydrocarbon group may have a substituent.] It may be a structural unit represented by. The content of the structural unit represented by the general formula (I) in the resin [f5] may be, for example, 0.5% by mass or more and 50% by mass or less based on the total amount of the resin [f5], preferably 1% by mass or more and 40% by mass or less from the viewpoints of luminous intensity and heat resistance, and more preferably 5% by mass or more and 30% by mass or less.

[0127] R 1f and R 2f Examples of the hydrocarbon group having 1 to 25 carbon atoms in R 1f and R 2f include, for example, a linear or branched alkyl group, an aryl group, an alicyclic group, an alkyl group substituted with an alkoxy group, an alkyl group substituted with an aryl group, etc. exemplified in JP-A-2013-61599

[0037] . R

[0128] In addition to the structural unit represented by the general formula (I), the resin [f5] can further contain a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III). [Chemical formula] [In the formula, R 3f represents a hydrogen atom or a methyl group.] [Chemical formula] [In the formula, R 4f represents a hydrogen atom or a methyl group. R 5f represents a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 20 carbon atoms. This hydrocarbon group may have a substituent.]

[0129] R 3f is preferably a methyl group. R 4f is preferably a methyl group. R 5fis preferably a saturated or unsaturated linear, branched or cyclic hydrocarbon group having 1 to 16 carbon atoms, more preferably a saturated linear or cyclic hydrocarbon group having 1 to 10 carbon atoms, and particularly preferably a methyl group or a cyclohexyl group. R 5f The hydrocarbon group in R 5f may have a substituent, but preferably has no substituent. Examples of the substituent include a hydroxyl group and the like. R 5f The hydrocarbon group in R 5f may have an ether group.

[0130] The resin [f5] may further contain a structural unit derived from a compound having a functional group capable of bonding to an acid group described later and a polymerizable double bond (hereinafter also referred to as compound (X)). When the resin [f5] further contains a structural unit derived from the compound (X), the resin [f5] can further contain a structural unit derived from a carboxylic anhydride described later.

[0131] When the resin [f5] contains a structural unit represented by the general formula (II), the content of the structural unit represented by the general formula (II) may be, for example, 0.5% by mass or more and 50% by mass or less based on the total amount of the resin [f5], preferably 2% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 45% by mass or less from the viewpoints of light emission intensity and heat resistance.

[0132] When the resin [f5] contains a structural unit represented by the general formula (III), the content of the structural unit represented by the general formula (III) may be, for example, 10% by mass or more and 90% by mass or less based on the total amount of the resin [f5], preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 75% by mass or less from the viewpoints of light emission intensity and heat resistance.

[0133] The resin [f5] is preferably a polymer containing the structural units represented by the general formulas (I) to (III) in the main chain, and more preferably a polymer whose main chain is composed of the structural units represented by the general formulas (I) to (III).

[0134] When the resin [f5] further contains a structural unit represented by the general formula (II) and a structural unit represented by the general formula (III), the resin [f5] contains 0.5% by mass or more and 50% by mass or less of the structural unit represented by the general formula (I), 9.5% by mass or more and 40% by mass or less of the structural unit represented by the general formula (II), and 10% by mass or more and 90% by mass or less of the structural unit represented by the general formula (III) based on the total amount of the polymer.

[0135] The weight average molecular weight of the resin [f5] may be, for example, 1000 or more and 200,000 or less. From the viewpoints of luminescence intensity and heat resistance, the weight average molecular weight of the resin [f5] is preferably 3000 or more, more preferably 4000 or more, still more preferably 5000 or more, and even more preferably 6000 or more. Also, from the viewpoints of luminescence intensity and heat resistance, the weight average molecular weight of the resin [f5] is preferably 30,000 or less, more preferably 20,000 or less, still more preferably 15,000 or less, and even more preferably 10,000 or less. In this specification, the weight average molecular weight can be determined by the method described in the examples below.

[0136] The resin [f5] may have a double bond equivalent of, for example, 200 or more and 2000 or less. The resin [f5] is a polymer containing a double bond (i.e., an ethylenically unsaturated group) in the side chain, and the double bond equivalent thereof can be 200 or more and 2000 or less. The double bond equivalent is preferably 300 or more, more preferably 400 or more, still more preferably 450 or more, and particularly preferably 490 or more. Also, it is preferably 1900 or less. Note that a polymer having no double bond in the side chain has no double bond equivalent.

[0137] The double bond equivalent is a measure of the amount of double bonds contained in the molecule and means the molecular weight per double bond of the polymer. For compounds having the same molecular weight, the larger the numerical value of the double bond equivalent, the smaller the amount of double bonds introduced. The double bond equivalent can be calculated from the charged amount of the raw materials and can be determined by dividing the mass (g) of the polymer solid content by the amount (mol) of double bonds in the polymer. It can also be measured using various analyses such as titration, elemental analysis, NMR, IR, etc., and differential scanning calorimetry.

[0138] The resin [f5] may have an acid value of, for example, 20 mgKOH / g or more and 300 mgKOH / g or less. The acid value of the resin [f5] is preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more, still more preferably 80 mgKOH / g or more. Also, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, still more preferably 120 mgKOH / g or less.

[0139] [Production of resin [f5]] The resin [f5] is preferably obtained by reacting a polymer (also referred to as a base polymer) obtained by polymerizing a monomer component containing a monomer (5a) represented by the following general formula (i), an acid group-containing monomer (5b), and a monomer (5c) represented by the following general formula (iii) with a compound (X) having a functional group capable of bonding to an acid group and a polymerizable double bond. Each reaction raw material can be used singly or in combination of two or more.

[0140] [Monomer (5a)] The monomer (5a) is a monomer represented by the following general formula (i). The symbols in the formula are the same as those in formula (I). When the monomer (5a) is used in the polymerization reaction, it is presumed that the monomer (5a) undergoes a cyclization reaction during polymerization, and a tetrahydropyran ring structure is formed in the constituent unit of the polymer.

[0141] [Chemical formula]

[0142] In general formula (i), R 1f and R 2f are subject to the definitions and preferred ranges in the above formula (I).

[0143] Examples of the monomer (5a) include dimethyl-2,2’-[oxybis(methylene)]bis-2-propenoate, diethyl-2,2’-[oxybis(methylene)]bis-2-propenoate, di(n-propyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(isopropyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(n-butyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(isobutyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(t-butyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(t-amyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(stearyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(lauryl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(2-ethylhexyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(1-methoxyethyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(1-ethoxyethyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, dibenzyl-2,2’-[oxybis(methylene)]bis-2-propenoate, diphenyl-2,2’-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl-2,2’-[oxybis(methylene)]bis-2-propenoate, di(t-butylcyclohexyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(dicyclopentadienyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(tricyclodecanyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, di(isobornyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, diadamantyl-2,2’-[oxybis(methylene)]bis-2-propenoate, di(2-methyl-2-adamantyl)-2,2’-[oxybis(methylene)]bis-2-propenoate, and the like.

[0144] Among these, dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, diethyl 2,2'-[oxybis(methylene)]bis-2-propenoate, dicyclohexyl 2,2'-[oxybis(methylene)]bis-2-propenoate, and dibenzyl 2,2'-[oxybis(methylene)]bis-2-propenoate are preferable. From the viewpoints of less coloring, dispersibility, and ease of industrial availability, etc., more preferably, it is dimethyl 2,2'-[oxybis(methylene)]bis-2-propenoate.

[0145] The content ratio of the above monomer (5a) may be, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, more preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of the monomer components that give the base polymer.

[0146] [Monomer (5b)] Monomer (5b) is an acid group-containing monomer. The acid group is not particularly limited and may be, for example, a carboxyl group or a carboxylic anhydride group, preferably a carboxyl group, and more preferably a (meth)acrylic acid group.

[0147] Examples of the monomer (5b) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, cinnamic acid, and vinylbenzoic acid; unsaturated polycarboxylic acids such as maleic acid, fumaric acid, itaconic acid, citraconic acid, and mesaconic acid; unsaturated monocarboxylic acids in which the chain is extended between an unsaturated group and a carboxyl group, such as succinic acid mono(2-acryloyloxyethyl) and succinic acid mono(2-methacryloyloxyethyl); unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; and phosphate group-containing unsaturated compounds such as Light Ester P-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among these, from the viewpoints of versatility, availability, etc., carboxylic acid-based monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, unsaturated acid anhydrides) are preferred. More preferably, from the viewpoints of reactivity, alkali solubility, etc., they are unsaturated monocarboxylic acids, and even more preferably (meth)acrylic acid. Here, (meth)acrylic acid means acrylic acid and / or methacrylic acid.

[0148] The content ratio of the monomer (5b) is preferably set so that the acid value is within the above-described preferred range. For example, it may be 0.5% by mass or more and 50% by mass or less, preferably 2% by mass or more and 50% by mass or less, and more preferably 5% by mass or more and 45% by mass or less, based on 100% by mass of the total amount of the monomer components that give the base polymer.

[0149] When (meth)acrylic acid is used as the monomer (5b), the resulting resin [f5] has a structural unit represented by the general formula (II).

[0150] [Monomer (5c)] The monomer (5c) is a monomer represented by the following general formula (iii). The symbols in the formula are the same as those in the general formula (III). A structural unit represented by the general formula (III) is formed from the monomer (5c).

[0151] [Chemical formula]

[0152] In the general formula (iii), R 4f and R 5f are subject to the definitions and preferred ranges in the above formula (I).

[0153] Examples of the monomer (5c) include linear hydrocarbon group-containing (meth)acrylate compounds such as methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, n-butyl (meth)acrylate, hexyl (meth)acrylate, octyl (meth)acrylate, lauryl (meth)acrylate, and stearyl (meth)acrylate; branched-chain hydrocarbon group-containing (meth)acrylate compounds such as isopropyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, amyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, isodecyl (meth)acrylate, tridecyl (meth)acrylate, and isooctyl (meth)acrylate; cyclic hydrocarbon group-containing (meth)acrylate compounds such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decan-8-yl (meth)acrylate (which is commonly referred to as "dicyclopentanyl (meth)acrylate" in the art. It may also be referred to as "tricyclodecyl (meth)acrylate."), tricyclo[5.2.1.02,6]decen-8-yl (meth)acrylate (which is commonly referred to as "dicyclopentenyl (meth)acrylate" in the art.), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate; unsaturated hydrocarbon group-containing (meth)acrylate compounds such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate; Hydroxyl group-containing (meth)acrylate compounds such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, 4-hydroxybutyl (meth)acrylate; Ether group-containing (meth)acrylate compounds such as 2-ethoxyethyl (meth)acrylate; etc. are mentioned. Among them, from the viewpoint of improving solvent resistance, alkyl (meth)acrylate compounds are preferred.

[0154] The content ratio of the monomer (5c) may be, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, more preferably 30% by mass or more and 75% by mass or less, based on 100% by mass of the total amount of the monomer components that give the base polymer.

[0155] [Monomer (5d)] The resin [f5] may also contain one or more constitutional units derived from other monomers copolymerizable with the above-mentioned monomers (5a), (5b) and / or (5c) (also referred to as monomer (5d)). That is, the monomer component that gives the above base polymer may further contain monomer (5d).

[0156] Examples of the monomer (5d) include aromatic vinyl compounds such as styrene, vinyltoluene, α-methylstyrene; ethylene or substituted ethylene compounds such as ethylene, propylene, vinyl chloride, acrylonitrile; vinyl esters such as vinyl acetate; Dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, diethyl itaconate; Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene and other bicyclic unsaturated compounds; N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, N-(9-acridinyl)maleimide and other dicarbonylimide derivatives; Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene Examples thereof include the above. Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene are preferable.

[0157] The content ratio of the above monomer (5d) is not particularly limited. For example, it may be 50% by mass or less, preferably 25% by mass or less, more preferably 10% by mass or less, based on 100% by mass of the total amount of the monomer components that give the base polymer. Also, the content ratio of the monomer (5d) may be, for example, more than 0% by mass, and may be 0.001% by mass or more or 0.01% by mass or more.

[0158] As a method for polymerizing the above monomer components, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and they can be appropriately selected according to the purpose and application. Among them, solution polymerization is suitable because it is industrially advantageous and the structural adjustment such as molecular weight is easy. Also, as the polymerization mechanism of the above monomer components, polymerization methods based on mechanisms such as radical polymerization, anionic polymerization, cationic polymerization, and coordination polymerization can be used, but a polymerization method based on a radical polymerization mechanism is preferable because it is also industrially advantageous. The preferred form of the polymerization reaction is as described in JP-A-2016-29151

[0062] to

[0072] .

[0159] As described above, it is preferable that the resin [f5] is obtained by reacting the above base polymer with a compound (X) having a functional group capable of bonding to an acid group and a polymerizable double bond.

[0160] Examples of the polymerizable double bond of the above compound (X) include (meth)acryloyl group, vinyl group, allyl group, methallyl group, etc., and those having one or more of these as the compound are suitable. From the viewpoint of reactivity, (meth)acryloyl group is preferably used. Examples of the functional group capable of bonding to the acid group include hydroxy group, epoxy group, oxetanyl group, isocyanate group, etc., and those having one or more of these as the compound are suitable. Among them, epoxy group (including glycidyl group) is preferably used.

[0161] Examples of the above compound (X) include glycidyl (meth)acrylate, β-methylglycidyl (meth)acrylate, β-ethylglycidyl (meth)acrylate, vinylbenzyl glycidyl ether, allyl glycidyl ether, (3,4-epoxycyclohexyl)methyl (meth)acrylate, vinylcyclohexene oxide, etc. Among them, a compound (monomer) having an epoxy group and a (meth)acryloyl group is preferably used. Particularly, from the viewpoints of high reactivity, easy control of the reaction, easy availability, and the ability to introduce not only a radically polymerizable double bond but also a hydroxyl group at the same time, glycidyl (meth)acrylate and / or (3,4-epoxycyclohexyl)methyl (meth)acrylate are more preferably used.

[0162] The addition amount of the above compound (X) is not particularly limited as long as the double bond equivalent of the resin [f5] is within the above-mentioned range. For example, it may be 2 parts by mass or more and 60 parts by mass or less, preferably 10 parts by mass or more and 55 parts by mass or less, more preferably 10 parts by mass or more and 50 parts by mass or less, and still more preferably 10 parts by mass or more and 45 parts by mass or less, based on 100 parts by mass of the total amount of the monomer components giving the base polymer.

[0163] The method of reacting the compound (X) with the acid group (part of it) in the base polymer may adopt a known addition method or the like and is not particularly limited. The reaction temperature is preferably, for example, 60°C to 140°C. Further, it is preferable to use known catalysts such as amine compounds such as triethylamine and dimethylbenzylamine; ammonium salts such as tetraethylammonium chloride; phosphonium salts such as tetraphenylphosphonium bromide, and amide compounds such as dimethylformamide.

[0164] The resin [f5] can also be obtained by reacting the compound (X) with the base polymer and further reacting with a carboxylic anhydride. In this case, the carboxylic anhydride is reacted with the hydroxy group generated by the reaction of the cyclic ether with the carboxylic acid or carboxylic anhydride. Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride and the like. The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol with respect to 1 mol of the amount of the monomer (5b) used.

[0165] Among them, the resin (F) preferably contains at least one selected from the group consisting of the resin [f2], the resin [f3], the resin [f4] and the resin [f5].

[0166] The weight average molecular weight of the resin (F) in terms of polystyrene is preferably 3,000 or more and 100,000 or less, more preferably 5,000 or more and 50,000 or less, and still more preferably 5,000 or more and 30,000 or less. When the molecular weight is within the above range, the hardness of the cured film is improved, the residual film rate of the cured pattern is high, the solubility of the unexposed portion in the composition layer in the developer is good, and the resolution of the cured pattern tends to be improved. The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (F) is preferably 1.1 or more and 6 or less, more preferably 1.2 or more and 4 or less.

[0167] The acid value of the resin (F) is preferably 50 to 170 mg-KOH / g, more preferably 60 to 150 mg-KOH / g, and still more preferably 70 to 135 mg-KOH / g. Here, the acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin, and can be determined, for example, by titration using an aqueous potassium hydroxide solution.

[0168] The content of the resin (F) in the curable resin composition (D) is, for example, 5% by mass or more and 99% by mass or less, preferably 10% by mass or more and 90% by mass or less, more preferably 20% by mass or more and 80% by mass or less, still more preferably 30% by mass or more and 70% by mass or less, and particularly preferably 30% by mass or more and 60% by mass or less, based on the total amount of the solid content of the curable resin composition (D). When the content of the resin (F) is within the above range, the mechanical properties and optical properties of the cured product of the curable resin composition (D) tend to be good.

[0169] [Polymerizable compound] The polymerizable compound (G) is a compound that can be polymerized by active radicals, acids, etc. generated from a polymerization initiator (H) described later. Examples of such compounds include compounds having an ethylenically unsaturated bond, and preferably (meth)acrylate compounds. In the present specification, “(meth)acrylic acid” represents at least one selected from the group consisting of acrylic acid and methacrylic acid. Notations such as “(meth)acryloyl” and “(meth)acrylate” also have the same meaning.

[0170] Among them, the polymerizable compound (G) is preferably a polymerizable compound having three or more ethylenically unsaturated bonds. Examples of such polymerizable compounds include trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl) isocyanurate, ethylene glycol-modified pentaerythritol tetra(meth)acrylate, ethylene glycol-modified dipentaerythritol hexa(meth)acrylate, propylene glycol-modified pentaerythritol tetra(meth)acrylate, propylene glycol-modified dipentaerythritol hexa(meth)acrylate, caprolactone-modified pentaerythritol tetra(meth)acrylate, caprolactone-modified dipentaerythritol hexa(meth)acrylate, and the like. The polymerizable compound can be used alone or in combination of two or more. The weight average molecular weight of the polymerizable compound (G) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less.

[0171] The content of the polymerizable compound (G) in the curable resin composition (D) is preferably 1% by mass to 50% by mass, more preferably 5% by mass or more and 40% by mass or less, still more preferably 10% by mass or more and 30% by mass or less, and particularly preferably 10% by mass or more and 20% by mass or less, based on the total amount of the solid content of the curable resin composition (D). When the content of the polymerizable compound (G) is within the above range, the residual film ratio of the cured pattern and the chemical resistance of the cured pattern tend to be further improved. The solid content of the curable resin composition (D) means the total of the components excluding the solvent among all the components contained in the curable resin composition (D).

[0172] [Polymerization initiator] The polymerization initiator (H) is a compound that can generate active radicals, acids, etc. under the action of light or heat and initiate a polymerization reaction, and contains at least one selected from the group consisting of oxime compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds. Among them, it is preferably included an oxime compound. When using these polymerization initiators, the residual film ratio of the cured pattern becomes high. In addition, the above-mentioned oxime compounds, biimidazole compounds, triazine compounds and acylphosphine compounds preferably are compounds having at least two aromatic rings in the molecule because the degree of polymerization tends to be higher when producing a cured film. Examples of the aromatic ring include 5-membered rings such as furan ring, pyrrole ring, imidazole ring, thiophene ring and thiazole ring, 6-membered rings such as benzene ring, pyridine ring, pyrimidine ring and triazine ring, and condensed rings thereof.

[0173] The oxime compound is preferably an O-acyl oxime compound and is a compound having a partial structure represented by formula (d1). Hereinafter, * represents a bond.

Chemical formula

[0174] Examples of the oxime compound include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxacyclopentanylmethyloxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in JP-A-2011-132215, WO2008 / 78678, WO2008 / 78686, WO2012 / 132558, etc. Commercially available products such as Irgacure OXE01, OXE02 (manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used. Among them, the oxime compound is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropane-1-one-2-imine, and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, and more preferably N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and / or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine.

[0175] As the oxime compound, an oxime compound having a first molecular structure represented by the following formula (1) can also be used. Hereinafter, this oxime compound is also referred to as "oxime compound (1)".

Chemical formula

[0176] When the polymerization initiator (H) contains the oxime compound (1), it tends to be advantageous from the viewpoint of increasing the emission intensity. One of the reasons why the curable resin composition according to the present invention can exhibit such an effect is that due to the specific molecular structure of the oxime compound (1), when the oxime compound (1) initiates photopolymerization, the absorption wavelength of the oxime compound (1) before and after cleavage (decomposition) of the oxime compound (1) required for this changes greatly. Therefore, it is presumed that the oxime compound (1) has a high ability to initiate photoradical polymerization.

[0177] In formula (1), R 1 represents R 11 , OR 11 , COR 11 , SR 11 , CONR 12 R 13 or CN. R 11 , R 12 and R 13 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 11 , R 12 or R 13 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 Ra 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21)-R 22 、-C(=N-OCOR 21 )-R 22 、CN, a halogen atom, or COOR 21 may be substituted. R 21 、R 22 and R 23 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group, or a carboxy group. R 11 、R 12 、R 13 、R 21 、R 22 or R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO-. R 24 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 11 、R 12 、R 13 、R 21 、R 22 or R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched, cyclic, and R 12 and R 13 and R 22 and R 23 may together form a ring. * represents a bond with a second molecular structure, which is a molecular structure other than the first molecular structure possessed by the oxime compound (1).

[0178] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the alkyl group having 1 to 20 carbon atoms represented by R, R, R, R, R, R, R, and R include methyl group, ethyl group, propyl group, isopropyl group, butyl group, isobutyl group, sec-butyl group, tert-butyl group, pentyl group, isopentyl group, tert-pentyl group, hexyl group, heptyl group, octyl group, isooctyl group, 2-ethylhexyl group, tert-octyl group, nonyl group, isononyl group, decyl group, isodecyl group, undecyl group, dodecyl group, tetradecyl group, hexadecyl group, octadecyl group, icosyl group, cyclopentyl group, cyclohexyl group, cyclohexylmethyl, cyclohexylethyl group, etc.

[0179] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms represented by R, R, R, R, R, R, R, and R include phenyl group, tolyl group, xylyl group, ethylphenyl group, naphthyl group, anthryl group, phenanthryl group, phenyl group substituted with one or more of the above alkyl groups, biphenylyl group, naphthyl group, anthryl group, etc.

[0180] R in formula (1) 11 R 12 R 13 R 21 R 22 R 23 and R 24 Examples of the aralkyl group having 7 to 30 carbon atoms represented by R, R, R, R, R, R, R, and R include benzyl group, α-methylbenzyl group, α,α-dimethylbenzyl group, phenylethyl group, etc.

[0181] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the heterocyclic group having 2 to 20 carbon atoms represented by include a pyridyl group, a pyrimidyl group, a furyl group, a thienyl group, a tetrahydrofuryl group, a dioxolanyl group, a benzoxazol-2-yl group, a tetrahydropyranyl group, a pyrrolidyl group, an imidazolidyl group, a pyrazolidyl group, a thiazolidyl group, an isothiazolidyl group, an oxazolidyl group, an isoxazolidyl group, a piperidyl group, a piperazinyl group, a morpholinyl group, etc., and preferably a 5- to 7-membered heterocycle.

[0182] R in formula (1) 12 and R 13 and R 22 and R 23 each may combine together to form a ring, which means that R 12 and R 13 and R 22 and R 23 each may combine together with the connecting nitrogen atom, carbon atom or oxygen atom to form a ring. Ra in formula (1) 12 and Ra 13 and Ra 22 and Ra 23 Examples of the ring that can be formed by combining together include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, a lactam ring, etc., and preferably a 5- to 7-membered ring.

[0183] R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of the halogen atom that R

[0184] in formula (1) may have as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom. 1is preferably R 11 and more preferably an alkyl group having 1 to 20 carbon atoms, still more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

[0185] An example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (2). The second molecular structure means another molecular structure part other than the above first molecular structure that the oxime compound (1) has. In formula (2), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is a structure represented by formula (2), the benzene ring having "-*" in formula (2) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0186]

Chemical formula

[0187] In formula (2), R 2 and R 3 each independently represents R 11 , OR 11 , SR 11 , COR 11 , CONR 12 R 13 , NR 12 COR 11 , OCOR 11 , COOR 11 , SCOR 11 , OCSR 11 , COSR 11 , CSOR 11 , CN or a halogen atom. When there are a plurality of Rs 2 , they may be the same or different. When there are a plurality of Rs 3 , they may be the same or different. R 11 , R 12 and R 13 represent the same meaning as above. s and t each independently represent an integer from 0 to 4. L is a sulfur atom, CR 31 R 32 , CO or NR 33 represents. R 31 , R 32 and R 33 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. R 31 , R 32 or R 33 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 31 , R 32 and R 33 may each independently form a ring together with either adjacent benzene ring. R 4 is a hydroxy group, a carboxy group or the following formula (2-1)

[0188] [Chemical formula] (In formula (2-1), L 1 is -O-, -S-, -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-. R 22 represents the same meaning as above. L 2 represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms. L 2 When the group represented by has an alkylene moiety, the alkylene moiety is -O-, -S-, -COO-, -OCO-, -NR 22 (-), -NR 22 COO-, -OCONR22 - may be interrupted 1 to 5 times by -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic. R 4a is OR 41 , SR 41 , CONR 42 R 43 , NR 42 COR 43 , OCOR 41 , COOR 41 , SCOR 41 , OCSR 41 , COSR 41 , CSOR 41 , CN or a halogen atom. R 4a When there are a plurality of them, they may be the same or different. R 41 , R 42 and R 43 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms. When the group represented by R 41 , R 42 and R 43 has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 42 and R 43 may together form a ring. v represents an integer of 1 to 3.) represents a group represented by. * represents a bond with the first molecular structure of the oxime compound (1).

[0189] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 and R 33 , and R in the above formula (2-1) 22 , R 41 , R 42and R 43 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, and aralkyl group having 7 to 30 carbon atoms represented by are the same as the examples for R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 are the same as the examples for R in formula (1).

[0190] Examples of the heterocyclic group having 2 to 20 carbon atoms represented by R in formula (2), R, R, R, R, R, R, R, and R in the above formula (2-1) are the same as the examples for R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 R 24 and R in the above formula (2-1) 22 are the same as the examples for R in formula (1). 11 R 12 R 13 R 21 R 22 R 23 and R 24 are the same as the examples for R in formula (1).

[0191] R in formula (2), R 31 R 32 and R 33 each independently may form a ring together with either adjacent benzene ring, which means that R, R 31 R 32 and R 33 each independently may form a ring together with either adjacent benzene ring and the connecting nitrogen atom. Examples of the ring that R in formula (2), R 31 R 32 and R 33 may form together with either adjacent benzene ring are the same as the examples of the ring that Ra 12 and Ra 13 and Ra 22 and Ra 23 may form together.

[0192] L in the above formula (2-1)2 represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0193] Examples of the group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, when v = 1, methylene group, ethylene group, propylene group, methylethylene group, butylene group, 1-methylpropylene group, 2-methylpropylene group, 1,2-dimethylpropylene group, 1,3-dimethylpropylene group, 1-methylbutylene group, 2-methylbutylene group, 3-methylbutylene group, 4-methylbutylene group, 2,4-dimethylbutylene group, 1,3-dimethylbutylene group, pentylene group, hexylene group, heptylene group, octylene group, nonylene group, decylene group, dodecylene group, tridecylene group, tetradecylene group, pentadecylene group, ethane-1,1-diyl group, propane-2,2-diyl group, and other alkylene groups.

[0194] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v = 1, 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group, 2,5-dimethyl-1,4-phenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, diphenylsulfide-4,4'-diyl group, diphenylsulfone-4,4'-diyl group, and other arylene groups.

[0195] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, when v = 1, the group represented by the following formula (a) and the group represented by the following formula (b).

[0196]

Chemical formula

[0197] Examples of the alkylene group having 1 to 10 carbon atoms include a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,2-dimethylpropylene group, a 1,3-dimethylpropylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 4-methylbutylene group, a 2,4-dimethylbutylene group, a 1,3-dimethylbutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, and the like.

[0198] Examples of the group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms include, when v is 1, divalent heterocyclic groups such as a 2,5-pyridinediyl group, a 2,6-pyridinediyl group, a 2,5-pyrimidinediyl group, a 2,5-thiophenediyl group, a 3,4-tetrahydrofuranediyl group, a 2,5-tetrahydrofuranediyl group, a 2,5-furandiyl group, a 3,4-thiazolediy group, a 2,5-benzofurandiyl group, a 2,5-benzothiophenediyl group, an N-methylindole-2,5-diyl group, a 2,5-benzothiazolediy group, a 2,5-benzoxazolediy group, and the like.

[0199] R in formula (2) 2 and R 3 and R in the above formula (2-1) 4a Examples of the halogen atom represented by include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0200] From the viewpoints of solubility in the solvent (K) and / or the development rate of the cured film, a preferred example of the structure represented by formula (2) is the structure represented by the following formula (2a).

[0201]

Chemical formula

[0202] From the same viewpoint as above, another preferred example of the structure represented by formula (2) is the structure represented by the following formula (2b).

[0203]

Chemical formula

[0204]

Chemical formula

[0205] R 44 is preferably a group represented by formula (2-2). In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (K) and the development rate of the cured film.

[0206] L 12 The number of carbon atoms of the alkylene group represented by is preferably 1 to 10, more preferably 1 to 4. R 44a is preferably a hydroxy group or a carboxy group, more preferably a hydroxy group.

[0207] The production method of the oxime compound (1) having the second molecular structure represented by the formula (2) is not particularly limited, and for example, it can be produced by the method described in JP-A-2011-132215.

[0208] Another example of the second molecular structure linked to the first molecular structure represented by the formula (1) is the structure represented by the following formula (3). In the formula (3), the bond represented by "*" is directly bonded to the bond represented by "*" in the formula (1). That is, when the second molecular structure is the structure represented by the formula (3), the benzene ring having "-*" in the formula (3) and the carbonyl group having "-*" in the formula (1) are directly bonded.

[0209]

Chemical formula

[0210] In the formula (3), R 5 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 5 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic. R 5 The hydrogen atom of the group represented by is R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , -C(=N-OR 21 )-R 22, -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21 may be substituted. R 21 , R 22 and R 23 have the same meaning as described above. R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group. R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-. R 24 has the same meaning as described above. R 21 , R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may combine together to form a ring. R 6 , R 7 , R 8 and R 9 are each independently R 61 , OR 61 , SR 61 , COR 62 , CONR 63 R 64 , NR 65 , COR 61 , OCOR 61, COOR 62 , SCOR 61 , OCSR 61 , COSR 62 , CSOR 61 , represents a hydroxyl group, nitro group, CN or halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 Ra 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atom, or COOR 21 may be substituted. R 6 and R 7 , R 7 and R 8 and R 8 and R 9 may together form a ring. * represents a bond with the first molecular structure of the oxime compound (1).

[0211] R 5 , R 21 , R 22 , R 23 , R 24 , R 61 , R62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 is the same as the examples for.

[0212] R in formula (3) 22 and R 23 may combine to form a ring means that R 22 and R 23 may combine to form a ring together with the connecting nitrogen atom, carbon atom or oxygen atom. R in formula (3) 22 and R 23 Examples of the ring that can be formed by combining are the same as the examples for Ra 12 and Ra 13 and Ra 22 and Ra 23 is the same as the examples for the ring that can be formed by combining.

[0213] R in formula (3) 6 , R 7 , R 8 and R 9 Examples of the halogen atom represented by, R 5 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that may substitute the hydrogen atom of include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom.

[0214] From the viewpoints of solubility in the solvent (K) and / or the development rate of the cured film, in one preferred form, R 5is a group represented by the following formula (3-1).

[0215] [Chemical formula] [In formula (3-1), Z represents a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group obtained by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms. When the group represented by Z has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene moiety may be branched or cyclic. R 21 、R 22 and R 24 represent the same meaning as described above.]

[0216] From the same viewpoint as above, in formula (3-1), Z is preferably a methylene group, ethylene or phenylene group. In formula (3-1), R 21 and R 22 are preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms from the same viewpoint as above, and more preferably a methyl group, an ethyl group or a phenyl group.

[0217] From the same viewpoint as above, in another preferred embodiment, R 7 is a nitro group.

[0218] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and for example, it can be produced by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0219] Still another example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (4). In formula (4), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (4), the benzene ring having "-*" in formula (4) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0220]

Chemical formula

[0221] In formula (4), R 71 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 71 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic. R 71 The hydrogen atom of the group represented by is R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR 21May be replaced. R 21 、R 22 and R 23 represent the same meaning as described above. R 21 、R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group. R 21 、R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-. R 24 represents the same meaning as described above. R 21 、R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may combine together to form a ring. R 72 、R 73 and three R 74 each independently represent R 61 、OR 61 、SR 61 、COR 62 、CONR 63 R 64 、NR 65 COR 61 、OCOR 61 、COOR 62 、SCOR 61 、OCSR 61 、COSR 62 、CSOR 61 、a hydroxy group, a nitro group, CN or a halogen atom. R 61 、R 62 、R63 and R 64 and R 65 each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 and R 62 and R 63 and R 64 or R 65 The hydrogen atom of the group represented by is OR 21 COR 21 SR 21 NR 22 Ra 23 CONR 22 R 23 -NR 22 -OR 23 -N(COR 22 )-OCOR 23 -C(=N-OR 21 )-R 22 -C(=N-OCOR 21 )-R 22 CN, a halogen atom, or COOR 21 may be substituted. R 72 and R 73 and two R 74 may together form a ring. * represents a bond with the first molecular structure possessed by the oxime compound (1).

[0222] In formula (4), R 71 and R 21 and R 22 and R 23 and R 24 and R 61 and R 62 and R 63 and R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are R 11 and R 12 and R 13 and R 21 and R 22 and R23 and R 24 is the same as the example for

[0223] R in formula (4) 22 and R 23 may combine together to form a ring, which means that R 22 and R 23 may combine together to form a ring with the connecting nitrogen atom, carbon atom or oxygen atom. R in formula (4) 22 and R 23 Examples of rings that R and R can form together are the same as the examples of rings that Ra and Ra 12 and Ra 13 and Ra 22 and Ra 23 can form together.

[0224] R in formula (4) 72 , R 73 and R 74 represent halogen atoms, R 71 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of halogen atoms that may substitute the hydrogen atoms of are fluorine atom, chlorine atom, bromine atom and iodine atom.

[0225] The production method of the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0226] Still another example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (5). In formula (5), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (5), the pyrrole ring having "-*" in formula (5) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0227]

Chemical formula

[0228] In formula (5), R 81 represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 81 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic. R 81 The hydrogen atom of the group represented by is R 21 , OR 21 , COR 21 , SR 21 , NR 22 R 23 , CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 , NR 22 COR 21 , OCOR 21 , COOR 21 , -C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , SCOR 21 , OCSR 21 , COSR 21 , CSOR 21 , a hydroxyl group, a nitro group, CN, a halogen atom, or may be substituted with COOR 21 . R 21 , R 22 and R 23represents the same meaning as described above. R 21 , R 22 or R 23 The hydrogen atom of the group represented by may be substituted with CN, a halogen atom, a hydroxy group or a carboxy group. R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-, -NR 24 COO-, -OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO-. R 24 represents the same meaning as described above. R 21 , R 22 and R 23 When the group represented by has an alkyl moiety, the alkyl moiety may be branched or cyclic, and R 22 and R 23 may combine together to form a ring. R 82 , R 83 , R 84 , R 85 and R 86 each independently represents R 61 , OR 61 , SR 61 , COR 62 , CONR 63 R 64 , NR 65 COR 61 , OCOR 61 , COOR 62 , SCOR 61 , OCSR 61 , COSR 62 , CSOR 61 , a hydroxy group, a nitro group, CN or a halogen atom. R 61 , R 62 , R 63 , R 64 and R 65Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms. R 61 、R 62 、R 63 、R 64 or R 65 The hydrogen atom of the group represented by is OR 21 、COR 21 、SR 21 、NR 22 Ra 23 、CONR 22 R 23 、-NR 22 -OR 23 、-N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 、-C(=N-OCOR 21 )-R 22 、CN, a halogen atom, or COOR 21 and may be substituted. R 83 and R 84 、R 84 and R 85 and R 85 and R 86 may each combine together to form a ring. * represents a bond with the first molecular structure possessed by the oxime compound (1).

[0229] R in formula (5) 81 、R 21 、R 22 、R 23 、R 24 、R 61 、R 62 、R 63 、R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by are R in formula (1) 11 、R 12 、R 13 、R 21 、R 22 、R23 and R 24 is the same as the example for

[0230] R in formula (5) 22 and R 23 may combine to form a ring, which means that R 22 and R 23 may combine to form a ring together with the connecting nitrogen atom, carbon atom or oxygen atom. R in formula (5) 22 and R 23 Examples of rings that can be formed by combining R and R together are the same as the examples of rings that can be formed by combining Ra and Ra 12 and Ra 13 and Ra 22 and Ra 23 together.

[0231] R in formula (5) 82 , R 83 , R 84 , R 85 and R 86 Examples of halogen atoms represented by, R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of halogen atoms that may substitute the hydrogen atoms of include fluorine atom, chlorine atom, bromine atom and iodine atom.

[0232] The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0233] Still another example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (6). In formula (6), the bond represented by "*" is directly bonded to the bond represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (6), the benzene ring having "-*" in formula (6) and the carbonyl group having "-*" in formula (1) are directly bonded.

[0234]

Chemical formula

[0235] In formula (6), the four Rs 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 each independently represent R 61 , OR 61 , SR 61 , COR 62 , CONR 63 R 64 , NR 65 , COR 61 , OCOR 61 , COOR 62 , SCOR 61 , OCSR 61 , COSR 62 , CSOR 61 , a hydroxyl group, a nitro group, CN or a halogen atom. R 61 , R 62 , R 63 , R 64 and R 65 each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms. R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atom of the group represented by is OR 21 , COR 21 , SR 21 , NR 22 Ra 23 , CONR22 R 23 、 -NR 22 -OR 23 、 -N(COR 22 )-OCOR 23 、 -C(=N-OR 21 )-R 22 、 -C(=N-OCOR 21 )-R 22 、 CN, a halogen atom, or COOR 21 may be substituted. R 21 、 R 22 and R 23 have the same meaning as described above. R 92 and R 93 、 R 94 and R 95 、 R 95 and R 96 and R 96 and R 97 may together form a ring. * represents a bond with the first molecular structure of the oxime compound (1).

[0236] R in formula (6) 21 、 R 22 、 R 23 、 R 61 、 R 62 、 R 63 、 R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, aryl group having 6 to 30 carbon atoms, aralkyl group having 7 to 30 carbon atoms, and heterocyclic group having 2 to 20 carbon atoms represented by are the same as the examples for R 11 、 R 12 、 R 13 、 R 21 、 R 22 and R 23 in formula (1).

[0237] R in formula (6) 22 and R 23 may together form a ring means that R 22 and R 23 may together form a ring with the connecting nitrogen atom, carbon atom or oxygen atom. R in formula (6) 22 and R 23 Examples of rings that can be formed together are Ra in formula (1) 12 and Ra 13 and Ra 22 and Ra 23 are the same as the examples of rings that can be formed together.

[0238] R in formula (6) 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 represented by the halogen atoms, R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of halogen atoms that may substitute the hydrogen atoms of are fluorine atom, chlorine atom, bromine atom and iodine atom.

[0239] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, and for example, it can be produced by the methods described in International Publication No. 2017 / 051680 and International Publication No. 2020 / 004601.

[0240] The biimidazole compound is, for example, a compound represented by formula (d5).

Chemical formula

[0241] Examples of aryl groups having 6 to 10 carbon atoms include phenyl group, toluyl group, xylyl group, ethylphenyl group and naphthyl group, etc., and preferably phenyl group. Examples of the substituent include a halogen atom, an alkoxy group having 1 to 4 carbon atoms, etc. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc., and a chlorine atom is preferable. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, a butoxy group, etc., and a methoxy group is preferable.

[0242] Examples of the biimidazole compound include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenyl-1,2'-biimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole, an imidazole compound in which the phenyl groups at the 4,4',5,5'-positions are substituted by a carboxyalkoxy group, etc. These compounds are described in, for example, JP-A-06-75372, JP-A-06-75373, JP-B-48-38403, JP-A-62-174204, JP-A-7-10913, etc. Among them, a compound represented by the following formula or a mixture thereof is preferable. [Chemical formula]

[0243] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferable.

[0244] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide, (2,4,6-trimethylbenzoyl)diphenylphosphine oxide, etc.

[0245] The above polymerization initiator (H) may be used alone or in combination of two or more. When two or more polymerization initiators (H) are used in combination, it may be combined with a known polymerization initiator (H) other than the above oxime compound, biimidazole compound, triazine compound, and acylphosphine compound.

[0246] As the combination of two or more polymerization initiators (H), compounds of the same type with different structures may be combined, or different types of compounds may be combined. When combining compounds of the same type, a combination of oxime compounds is preferred, and a combination of O-acyl oxime compounds having a partial structure represented by the formula (d1) is more preferred. Examples of such combinations include a combination of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine. In this case, the mixing ratio of N-benzoyloxy-1-(4-phenylsulfanylphenyl)octane-1-one-2-imine and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine is preferably from 10:90 to 90:10, more preferably from 30:70 to 70:30, and even more preferably from 30:70 to 50:50.

[0247] Examples of combinations of different types of compounds include combinations of an oxime compound and a biimidazole compound, an oxime compound and a triazine compound, an oxime compound and an acylphosphine compound, a biimidazole compound and a triazine compound, a biimidazole compound and an acylphosphine compound, and a triazine compound and an acylphosphine compound.

[0248] Examples of the known polymerization initiator (H) include benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, titanocene compounds, and the like.

[0249] The content of the polymerization initiator (H) is preferably 0.1 part by mass or more and 300 parts by mass or less, more preferably 0.1 part by mass or more and 200 parts by mass or less, based on 100 parts by mass of the polymerizable compound (G). When the curable resin composition (D) contains the resin described below, the content of the polymerization initiator (H) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, based on 100 parts by mass of the total amount of the resin (F) and the polymerizable compound (G) described below. When the content of the polymerization initiator (H) is within the above range, the sensitivity is increased and the exposure time tends to be shortened, so that the productivity of the cured film is improved.

[0250] [Polymerization Initiation Auxiliary Agent] If necessary, a polymerization initiation auxiliary agent may be used in combination. The polymerization initiation auxiliary agent is a compound or a sensitizer used to accelerate the polymerization of the polymerizable compound (G) whose polymerization has been initiated by the polymerization initiator (H). When the polymerization initiation auxiliary agent is included, it is usually used in combination with the polymerization initiator (H). Examples of the polymerization initiation auxiliary agent include amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0251] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethylparatoluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, 4,4'-bis(ethylmethylamino)benzophenone, etc. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Co., Ltd.) may also be used.

[0252] Examples of the alkoxyanthracene compound include 9,10-dimethoxyanthracene, 2-ethyl-9,10-dimethoxyanthracene, 9,10-diethoxyanthracene, 2-ethyl-9,10-diethoxyanthracene, 9,10-dibutoxyanthracene, 2-ethyl-9,10-dibutoxyanthracene, etc.

[0253] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, 1-chloro-4-propoxythioxanthone, etc.

[0254] Examples of the carboxylic acid compound include phenylsulfanyl acetic acid, methylphenylsulfanyl acetic acid, ethylphenylsulfanyl acetic acid, methylethylphenylsulfanyl acetic acid, dimethylphenylsulfanyl acetic acid, methoxyphenylsulfanyl acetic acid, dimethoxyphenylsulfanyl acetic acid, chlorophenylsulfanyl acetic acid, dichlorophenylsulfanyl acetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

[0255] When a polymerization initiation aid is included, the content of the polymerization initiation aid is preferably 0.1 part by mass or more and 300 parts by mass or less, more preferably 0.1 part by mass or more and 200 parts by mass or less, with respect to 100 parts by mass of the polymerizable compound (G). When the curable resin composition (D) contains the resin described later, the content of the polymerization initiator (H) is preferably 0.1 part by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, with respect to 100 parts by mass of the total amount of the curable resin composition (D). When the amount of the polymerization initiation aid is within this range, there is a tendency to form a cured film with higher sensitivity.

[0256] [Solvent] The colored curable resin composition can contain a solvent (K). The solvent (K) is not particularly limited, and solvents commonly used in the art can be used. Examples of the solvent (K) include ester solvents (solvents containing -CO-O- in the molecule and not containing -O-), ether solvents (solvents containing -O- in the molecule and not containing -CO-O-), ether ester solvents (solvents containing -CO-O- and -O- in the molecule), ketone solvents (solvents containing -CO- in the molecule and not containing -CO-O-), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and -CO-O-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide, etc.

[0257] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, pentyl formate, isopentyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone, etc.

[0258] Examples of ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether (PGME), propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, methyl anisole, and the like.

[0259] Examples of ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, propylene glycol monoethyl ether acetate (PGMEA), propylene glycol monopropyl ether acetate, ethylene glycol monomethyl ether acetate, ethylene glycol monoethyl ether acetate, diethylene glycol monoethyl ether acetate, diethylene glycol monobutyl ether acetate, and dipropylene glycol methyl ether acetate, and the like.

[0260] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0261] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0262] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0263] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0264] These solvents may be used in combination of two or more.

[0265] Among the above solvents, from the viewpoints of coatability and drying property, an organic solvent having a boiling point at 1 atm of 120°C or higher and 180°C or lower is preferable. Preferred solvents include propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and N,N-dimethylformamide, and more preferred solvents include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.

[0266] When the curable resin composition (D) contains a solvent (K), the content of the solvent (K) in the curable resin composition (D) may be, for example, 30% by mass or more and 99.99% by mass or less, preferably 40% by mass or more and 90% by mass or less, and more preferably 45% by mass or more and 85% by mass or less. From the viewpoints of storage stability of the liquid and thick film coating, it is preferable that the content of the solvent (K) is within the above range.

[0267] When the curable resin composition (D) contains a solvent (K), a part of the solvent (K) can be mixed with the luminescent compound (Q) to prepare a luminescent compound dispersion (Qh), and then the luminescent compound dispersion (Qh) and other components can be mixed to prepare the curable resin composition (D).

[0268] [Other components] The curable resin composition (D) may contain, as other components, additives known in the art, such as an antioxidant (I), a leveling agent (J), a stabilizer, a chain transfer agent, etc. The content ratio of the other components is preferably 10% by mass or less, more preferably 5% by mass or less, and even more preferably 1% by mass or less based on the total amount of the curable resin composition (D).

[0269] [Antioxidant] The colored curable resin composition may contain an antioxidant (I). From the viewpoint of improving the heat resistance and light resistance of the colorant, it is preferable to use an antioxidant alone or in combination of two or more. The antioxidant is not particularly limited as long as it is an industrially commonly used antioxidant, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. can be used.

[0270] Examples of phenolic antioxidants include Irganox 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1076 (Irganox 1076: octadecyl 3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF), Irganox 1330 (Irganox 1330: 3,3’,3’’,5,5’,5’’-hexa-tert-butyl-a,a’,a’’-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF), Irganox 3790 (Irganox 3790: 1,3,5-tris((4-tert-butyl-3-hydroxy-2,6-xylyl)methyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF), Irganox 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1135 (Irganox1135: benzenepropanoic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 branched alkyl ester, manufactured by BASF), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF), Irganox 3125 (Irganox 3125, manufactured by BASF), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy 3’,5’-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF), Adeka Stab AO-80 (Adeka Stab AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro(5,5) Examples include undecane (manufactured by ADEKA Corporation), Sumilizer BHT (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (manufactured by Cytec Industries Inc.), and vitamin E (manufactured by Eisai Co., Ltd.).,

[0271] Examples of phosphorus-based antioxidants include Irgafos 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl) phosphite, manufactured by BASF), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF), Irgafos 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl) ethyl ester phosphorous acid, manufactured by BASF), Adeka Stab 329K (manufactured by ADEKA Corporation), Adeka Stab PEP36 (manufactured by ADEKA Corporation), Adeka Stab PEP-8 (manufactured by ADEKA Corporation), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (Weston618, manufactured by GE), Weston 619G (Weston 619G, manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (Sumilizer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

[0272] Examples of sulfur-based antioxidants include dialkyl thiodipropionate compounds such as dilauryl, dimyristyl, or distearyl thiodipropionate, and polyol β-alkyl mercaptopropionate ester compounds such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0273] [Leveling agent] Examples of the leveling agent (J) include silicone surfactants, fluorine surfactants, and silicone surfactants having fluorine atoms. These may have a polymerizable group in the side chain. Examples of the silicone surfactant include surfactants having a siloxane bond in the molecule. Specifically, Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, SH8400 (trade name: manufactured by Toray Dow Corning Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan LLC) and the like can be mentioned. Examples of the fluorine surfactant include surfactants having a fluorocarbon chain in the molecule. Specifically, Fluorad (registered trademark) FC430, FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, F575, R30, RS-718-K (manufactured by DIC Corporation), F-Top (registered trademark) EF301, EF303, EF351, EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surfron (registered trademark) S381, S382, SC101, SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemical Research Institute Co., Ltd.) and the like can be mentioned. Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule. Specifically, Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation) and the like can be mentioned.

[0274] When the curable resin composition (D) contains at least one compound selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions thereof, the content of the at least one compound selected from the group consisting of ammonia, amines, and carboxylic acids, and salts or ions thereof in the curable resin composition (D) may be, for example, 0.01% by mass or more and 10% by mass or less, preferably 1% by mass or more and 5% by mass or less.

[0275] The wavelength conversion layer (B) can be disposed in a display device in a form sealed in a glass tube or the like, or in a form sealed by sandwiching it as a sheet between two barrier films.

[0276] <Light absorption layer (C)> The light absorption layer (C) can have wavelength selectivity to transmit light in a specific wavelength range and absorb light in other wavelength ranges. The light emitted from the wavelength conversion layer (B) is emitted from the display device as blue light, green light, and red light by passing through the light absorption layer (C). When the display device has the light absorption layer (C), it tends to easily exhibit a wide color gamut.

[0277] The light absorption layer (C) can be disposed on the first wavelength conversion layer (B1) and the second wavelength conversion layer (B2).

[0278] The light absorption layer (C) may be a layer that transmits yellow light but absorbs light other than yellow light (hereinafter also referred to as the light absorption layer (CY)).

[0279] The light absorption layer (C) can also be composed of a first light absorption layer (C1) and a second light absorption layer (C2). When the light absorption layer (C) is composed of the first light absorption layer (C1) and the second light absorption layer (C2), the first light absorption layer (C1) is disposed on the first wavelength conversion layer (B1), and the second light absorption layer (C2) is disposed on the second wavelength conversion layer (B2). The first light absorption layer (C1) may be a layer that transmits red light but absorbs light other than red light. The second light absorption layer (C2) may be a layer that transmits green light but absorbs light other than green light.

[0280] The light absorption layer (C) may be composed of the above-described first light absorption layer (C1), second light absorption layer (C2), and third light absorption layer (C3). The third light absorption layer (C3) may be disposed on the blue light source (A), or may be disposed on the light guide plate when the display device has the above-described light guide plate. The third light absorption layer (C3) can transmit blue light but can absorb light other than blue light.

[0281] The light absorption layer (C) usually contains a colorant (P). The colorant (P) may be a dye or a pigment. As the dye, known dyes can be used, for example, known dyes described in the Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (published by Shikisen Co., Ltd.). Also, according to the chemical structure, azo dyes, cyanine dyes, triphenylmethane dyes, xanthene dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, azomethine dyes, squarylium dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, etc. can be mentioned. These dyes may be used alone or in combination of two or more.

[0282] Specifically, dyes with the following Color Index (C.I.) numbers can be mentioned. C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189; C.I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247; C.I. Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99; C.I. Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60; C.I. Solvent Blue 4, 5, 14, 18, 35, 36, 37, 38, 44, 45, 58, 59, 59:1, 63, 67, 68, 69, 70, 78, 79, 83, 90, 94, 97, 98, 100, 101, 102, 104, 105, 111, 112, 122, 128, 132, 136, 139; C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35 and other C.I. Solvent Dyes, C.I. Acid Yellow 1, 3, 7, 9, 11, 17, 23, 25, 29, 34, 36, 38, 40, 42, 54, 65, 72, 73, 76, 79, 98, 99, 111, 112, 113, 114, 116, 119, 123, 128, 134, 135, 138, 139, 140, 144, 150, 155, 157, 160, 161, 163, 168, 169, 172, 177, 178, 179, 184, 190, 193, 196, 197, 199, 202, 203, 204, 205, 207, 212, 214, 220, 221, 228, 230, 232, 235, 238, 240, 242, 243, 251; C.I. Acid Red 1, 4, 8, 14, 17, 18, 26, 27, 29, 31, 33, 34, 35, 37, 40, 42, 44, 50, 51, 52, 57, 66, 73, 76, 80, 87, 88, 91, 92, 94, 95, 97, 98, 103, 106, 111, 114, 129, 133, 134, 138, 143, 145, 150, 151, 155, 158, 160, 172, 176, 182, 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426; C.I. Acid Orange 6, 7, 8, 10, 12, 26, 50, 51, 52, 56, 62, 63, 64, 74, 75, 94, 95, 107, 108, 149, 162, 169, 173; C.I. Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102; C.I. Acid Blue 1, 3, 5, 7, 9, 11, 13, 15, 17, 18, 22, 23, 24, 25, 26, 27, 29, 34, 38, 40, 41, 42, 43, 45, 48, 51, 54, 59, 60, 62, 70, 72, 74, 75, 78, 80, 82, 83, 86, 87, 88, 90, 90:1, 91, 92, 93, 93:1, 96, 99, 100, 102, 103, 104, 108, 109, 110, 112, 113, 117, 119, 120, 123, 126, 127, 129, 130, 131, 138, 140, 142, 143, 147, 150, 151, 154, 158, 161, 166, 167, 168, 170, 171, 175, 182, 183, 184, 187, 192, 199, 203, 204, 205, 210, 213, 229, 234, 236, 242, 243, 249, 256, 259, 267, 269, 278, 280, 285, 290, 296, 315, 324:1, 335, 340; C.I. Acid Green 1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109 and other C.I. acid dyes, C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141; C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250; C.I. Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107; C.I. Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104; C.I. Direct Blue 1, 2, 3, 6, 8, 15, 22, 25, 28, 29, 40, 41, 42, 47, 52, 55, 57, 71, 76, 77, 78, 80, 81, 84, 85, 86, 87, 90, 93, 94, 95, 97, 98, 99, 100, 101, 106, 107, 108, 109, 113, 114, 115, 117, 119, 120, 137, 149, 150, 153, 155, 156, 158, 159, 160, 161, 162, 163, 164, 165, 166, 167, 168, 170, 171, 172, 173, 188, 189, 190, 192, 193, 194, 195, 196, 198, 199, 200, 201, 202, 203, 207, 209, 210, 212, 213, 214, 222, 225, 226, 228, 229, 236, 237, 238, 242, 243, 244, 245, 246, 247, 248, 249, 250, 251, 252, 256, 257, 259, 260, 268, 274, 275, 293; C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82 and other C.I. Direct dyes, C.I. Disperse Yellow 51, 54, 76; C.I. Disperse Violet 26, 27; C.I. Disperse Blue 1, 14, 56, 60 and other C.I. Disperse dyes, C.I. Basic Red 1, 10; C.I. Basic Blue 1, 3, 5, 7, 9, 19, 21, 22, 24, 25, 26, 28, 29, 40, 41, 45, 47, 54, 58, 59, 60, 64, 65, 66, 67, 68, 81, 83, 88, 89; C.I. Basic Violet 2; C.I. Basic Red 9; C.I. Basic Green 1; C.I. basic dyes such as this, C.I. Reactive Yellow 2, 76, 116; C.I. Reactive Orange 16; C.I. Reactive Red 36; C.I. reactive dyes such as this, C.I. Mordant Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65; C.I. Mordant Red 1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95; C.I. Mordant Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48; C.I. Mordant Violet 1, 1:1, 2, 3, 4, 5, 6, 7, 8, 10, 11, 14, 15, 16, 17, 18, 19, 21, 22, 23, 24, 27, 28, 30, 31, 32, 33, 36, 37, 39, 40, 41, 44, 45, 47, 48, 49, 53, 58; C.I. Mordant Blue 1, 2, 3, 7, 8, 9, 12, 13, 15, 16, 19, 20, 21, 22, 23, 24, 26, 30, 31, 32, 39, 40, 41, 43, 44, 48, 49, 53, 61, 74, 77, 83, 84; C.I. Mordant Green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other C.I. mordant dyes, C.I. Vat Green 1 and other C.I. vat dyes, etc.

[0283] Furthermore, there are products of BASF such as Lumogen®. Examples include Lumogen® F Yellow 083 (manufactured by BASF), Lumogen® F Yellow 170 (manufactured by BASF), Lumogen® F Orange 240 (manufactured by BASF), and Lumogen® F Red 305 (manufactured by BASF).

[0284] As the pigment, known pigments can be used. For example, pigments classified as pigments in the Color Index (published by The Society of Dyers and Colourists) can be mentioned. These can be used alone or in combination of two or more. Specifically, yellow pigments such as C.I. Pigment Yellow 1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, 231, etc.; orange pigments such as C.I. Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73, etc.; red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, 273, etc.; blue pigments such as C.I. Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60, etc.; violet pigments such as C.I. Pigment Violet 1, 19, 23, 29, 32, 36, 38, etc.; green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, 63, etc.; brown pigments such as C.I. Pigment Brown 23, 25, etc.; black pigments such as C.I. Pigment Black 1, 7, 31, 32, etc. are mentioned.

[0285] Examples of colorants include, in terms of chemical structure, perylene yellow dyes, quinophthalone yellow pigments, metal-containing yellow pigments, isoindoline yellow pigments, perylene orange dyes, perylene orange pigments, perylene red dyes, perylene red pigments, phthalocyanine pigments, copper halide phthalocyanine pigments, zinc halide phthalocyanine pigments, aluminum zinc halide phthalocyanine pigments, brominated diketopyrrolopyrrole pigments, and the like.

[0286] The light absorption layer (CY) can contain at least one dye and pigment classified as yellow in hue among the above colorants. The colorant contained in the light absorption layer (CY) is preferably at least one selected from the group consisting of C.I. Pigment Yellow 185 and 150.

[0287] The first light absorption layer (C1) can contain at least one dye and pigment classified as red in hue among the above colorants. The colorant contained in the first light absorption layer (C1) is preferably a red pigment, more preferably C.I. Pigment Red 177, 254, brominated diketopyrrolopyrrole pigments, and the like.

[0288] The second light absorption layer (C2) can contain at least one dye and pigment classified as green in hue among the above colorants. The colorant contained in the second light absorption layer (C2) is preferably a combination of a green pigment and a yellow pigment, more preferably a combination of at least one selected from the group consisting of C.I. Pigment Green 7, 36, 58 and C.I. Pigment Yellow 150.

[0289] The third light absorption layer (C3) can contain at least one dye and pigment classified as blue in hue among the above colorants. The colorant contained in the third light absorption layer (C3) is preferably a blue pigment, more preferably C.I. Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60, and even more preferably C.I. Pigment Blue 15:6.

[0290] The film thickness (T7) of the first light absorption layer (C1), the film thickness (T8) of the second light absorption layer (C2), and the film thickness (T8) of the third light absorption layer (C3) are not particularly limited and can be appropriately adjusted according to the purpose, application, etc. For example, they are 0.1 μm or more and 30 μm or less, preferably 0.1 μm or more and 20 μm or less, and more preferably 0.5 μm or more and 6 μm or less.

[0291] The colorant content rate (W7) in the first light absorption layer (C1), the colorant content rate (W8) in the second light absorption layer (C2), and the colorant content rate (W9) in the third light absorption layer (C3) are not particularly limited and can be appropriately adjusted according to the purpose, application, etc. For example, they may be 0.01 mass% or more and 99.99 mass% or less, preferably 0.1 mass% or more and 99.9 mass% or less, more preferably 1 mass% or more and 99 mass% or less, still more preferably 10 mass% or more and 90 mass% or less, and particularly preferably 15 mass% or more and 70 mass% or less. The colorant content rate is determined as the mass ratio of the colorant (P) to the total amount of the solid content of the color-curable resin composition (E) described later.

[0292] The product (X7) (hereinafter also simply referred to as X7) of the colorant content rate (W7) [mass%] and the film thickness (T7) [μm] of the first light absorption layer (C1) may be, for example, 0.1 or more and 3 or less, or 0.2 or more and 2 or less.

[0293] The product (X8) (hereinafter also simply referred to as X8) of the colorant content rate (W8) [mass%] and the film thickness (T8) [μm] of the second light absorption layer (C2) may be, for example, 0.1 or more and 3 or less, or 0.2 or more and 2 or less.

[0294] The product (X9) (hereinafter also simply referred to as X9) of the colorant content rate (W9) [mass%] and the film thickness (T9) [μm] of the third light absorption layer (C3) may be, for example, 0.1 or more and 3 or less, or 0.2 or more and 2 or less.

[0295] [Method for manufacturing the light absorption layer (C)] The light absorption layer (C) can be manufactured as a yellow light absorption layer (CY), a first light absorption layer (C1), a second light absorption layer (C2), and a third light absorption layer (C3) by forming yellow patterns, red patterns, green patterns, and blue patterns (hereinafter collectively referred to as colored patterns) on a substrate from, for example, a yellow curable resin composition (E-y), a red curable resin composition (E-r), a green curable resin composition (E-g), and a blue curable resin composition (E-b) (hereinafter collectively referred to as a colored curable resin composition (E)), respectively.

[0296] Examples of the method for forming a colored pattern from the colored curable resin composition (E) include a photolithography method, an inkjet method, a printing method, etc., and preferably the photolithography method. The photolithography method is a method of applying the colored curable resin composition (E) to a substrate, drying it to form a colored curable resin composition layer, exposing the colored curable resin composition layer through a photomask, and developing it. In the photolithography method, a colored coating film that is a cured product of the colored curable resin composition layer can be formed by not using a photomask and / or not developing during exposure. The colored pattern and the colored coating film formed from the colored curable resin composition (E) are the light absorption layer (C) of the present invention.

[0297] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, and soda lime glass with a silica-coated surface, a resin plate such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate, silicon, or a substrate with an aluminum, silver, silver / copper / palladium alloy thin film, etc. formed thereon is used. Another light absorption layer, resin layer, transistor, circuit, etc. may be formed on these substrates. The substrate may be included in the light absorption layer (C).

[0298] The formation of each color by the photolithography method can be carried out using known or tolerated devices and conditions. For example, it can be manufactured as follows. First, the color-curable resin composition (E) is applied onto a substrate, and volatile components such as solvents are removed by heating and drying (pre-baking) and / or drying under reduced pressure to obtain a smooth color-curable resin composition layer. Examples of the coating method include spin coating method, slit coating method, slit and spin coating method, etc. When performing heating and drying, the temperature is preferably 30 to 120°C, more preferably 50 to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When performing drying under reduced pressure, it is preferably performed in a temperature range of 20 to 25°C under a pressure of 50 to 150 Pa. The film thickness of the color-curable resin composition layer is not particularly limited and may be appropriately selected according to the film thickness of the target light absorption layer.

[0299] Next, the color-curable resin composition layer is exposed through a photomask for forming a target color pattern. The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application is used. As the light source used for exposure, a light source that generates light with a wavelength of 250 to 450 nm is preferable. For example, light with a wavelength of less than 350 nm can be cut using a filter that cuts this wavelength range, or light near 436 nm, near 408 nm, or near 365 nm can be selectively extracted using a band-pass filter that extracts these wavelength ranges. Specific examples of the light source include mercury lamps, light-emitting diodes, metal halide lamps, and halogen lamps. Since it is possible to irradiate the entire exposure surface with parallel light rays uniformly and to perform accurate alignment between the photomask and the substrate on which the color-curable resin composition layer is formed, it is preferable to use an exposure apparatus such as a mask aligner and a stepper.

[0300] By bringing the exposed color-curable resin composition layer into contact with a developer and developing it, a color pattern is formed on the substrate. By development, the unexposed portion of the color-curable resin composition layer is dissolved and removed by the developer. As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, and tetramethylammonium hydroxide is preferred. The concentration of the alkaline compound is preferably 0.01 to 10% by mass, more preferably 0.02 to 5% by mass. The developer may contain a surfactant. The development method may be any of the paddle method, dipping method, spray method, etc. Further, the substrate may be tilted at an arbitrary angle during development. The substrate after development is preferably washed with water. Furthermore, it is preferable to perform post-baking on the obtained colored pattern. The post-baking temperature is preferably 150 to 250°C, more preferably 160 to 235°C. The post-baking time is preferably 1 to 120 minutes, more preferably 10 to 60 minutes. The light absorption layer, which is the colored pattern or colored coating film thus obtained, may be further subjected to a surface coating treatment in order to impart various properties.

[0301] [Coloring curable resin composition] The coloring curable resin composition (E) contains, in addition to the above-described colorant (hereinafter also referred to as colorant (P)), a resin (F), a polymerizable compound (G), and a polymerization initiator (H). Examples of the resin (F), the polymerizable compound (G), and the polymerization initiator (H) are applicable to the examples described in the explanation of the curable resin composition (D) above. The coloring curable resin composition (E) may further contain at least one selected from the group consisting of a solvent (K), a leveling agent (J), and an antioxidant (I).

[0302] The content rate of the solid content in the colored curable resin composition (E) is 100% by mass or less, preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less, still more preferably 0.1% by mass or more and 99% by mass or less, particularly preferably 1% by mass or more and 90% by mass or less, still more preferably 1% by mass or more and 80% or less, particularly preferably 1% by mass or more and 70% or less, extremely preferably 1% by mass or more and 60% or less, and most preferably 1% by mass or more and 50% by mass or less. In this specification, the solid content in the colored curable resin composition (E) refers to the total amount of the components excluding the solvent (K) from the colored curable resin composition (E). The total amount of the solid content and the content rate of each component with respect to this can be measured by known analysis means such as liquid chromatography or gas chromatography.

[0303] The content rate of the colorant (P) in the colored curable resin composition may be, for example, 0.01% by mass or more and 99.99% by mass or less in the total amount of the solid content, preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 99% by mass or less, still more preferably 10% by mass or more and 90% by mass or less, and particularly preferably 15% by mass or more and 70% by mass or less.

[0304] In the colored curable resin composition (E), the content rate of the resin (F) is less than 100% by mass with respect to the total amount of the solid content, preferably 0.00001% by mass or more and 99.99999% by mass or less, more preferably 1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 97% by mass or less, particularly preferably 1% by mass or more and 95% by mass or less, still more preferably 3% by mass or more and 90% by mass or less, particularly preferably 5% by mass or more and 80% by mass or less, extremely preferably 10% by mass or more and 70% by mass or less.

[0305] In the colored curable resin composition (E), the content of the polymerizable compound (G) is less than 100% by mass with respect to the total amount of the solid content, preferably 0.00001% by mass or more and 99.99999% or less, more preferably 1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 97% by mass or less, particularly preferably 1% by mass or more and 95% by mass or less, even more preferably 1% by mass or more and 90% by mass or less, particularly preferably 2% by mass or more and 80% by mass or less, and extremely preferably 3% by mass or more and 70% by mass or less.

[0306] In the colored curable resin composition (E), the content of the polymerization initiator (H) is preferably 0.001% by mass or more and 60% by mass or less, more preferably 0.01% by mass or more and 50% by mass or less, with respect to the total amount of the resin (F) and the polymerizable compound (G).

[0307] When using these polymerization initiation aids, in the colored curable resin composition (E), the content of the polymerization initiation aid is preferably 0.00001% by mass or more and 60% by mass or less, more preferably 0.0001% by mass or more and 50% by mass or less, with respect to the total amount of the resin (F) and the polymerizable compound (G).

[0308] [Preparation of Colorant-containing Liquid] When the colored curable resin composition (E) contains the solvent (K), a colorant-containing liquid (Ph) containing the colorant (P) and the solvent (K) may be prepared in advance, and then the colored curable resin composition (E) may be prepared using the colorant-containing liquid (Ph). When the colorant (A) is not soluble in the solvent (K), the colorant-containing liquid (Ph) can be prepared by dispersing and mixing the colorant (A) in the solvent (K). The colorant-containing liquid (Ph) may contain part or all of the solvent (K) contained in the colored curable resin composition (E).

[0309] The solid content ratio in the colorant-containing liquid (Ph) is less than 100% by mass with respect to the total amount of the colorant-containing liquid (Ph), preferably 0.01% by mass or more and 99.99% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less, still more preferably 0.1% by mass or more and 99% by mass or less, particularly preferably 1% by mass or more and 90% by mass or less, even more preferably 1% by mass or more and 80% by mass or less, especially preferably 1% by mass or more and 70% by mass or less, extremely preferably 1% by mass or more and 60% by mass or less, and most preferably 1% by mass or more and 50% by mass or less.

[0310] The content ratio of the colorant (P) in the colorant-containing liquid (Ph) is 100% by mass or less in the total solid content in the colorant-containing liquid (Ph), preferably 0.0001% by mass or more and 99.9999% by mass or less, more preferably 0.0001% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 99% by mass or less, particularly preferably 3% by mass or more and 99% by mass or less, and even more preferably 5% by mass or more and 99% by mass or less.

[0311] The colorant (P) may, if necessary, be subjected to surface treatment using a rosin treatment, a colorant (P) derivative having an acidic group or a basic group introduced, graft treatment of the surface of the colorant (P) with a polymer compound, etc., atomization treatment by a sulfuric acid atomization method, etc., cleaning treatment with an organic solvent, water, etc. for removing impurities, removal treatment by an ion exchange method for ionic impurities, etc. The particle size of the colorant (P) is preferably substantially uniform.

[0312] The colorant (P) can be made to be in a state of being uniformly dispersed in the colorant-containing liquid (Ph) by performing a dispersion treatment by containing a dispersant. The colorant (P) may be subjected to a dispersion treatment alone or a plurality of types may be mixed and subjected to a dispersion treatment.

[0313] Examples of the dispersant include surfactants, and any of cationic, anionic, nonionic, and amphoteric surfactants may be used. Specifically, surfactants such as polyester-based, polyamine-based, and acrylic-based surfactants can be mentioned. These dispersants may be used alone or in combination of two or more. Examples of the dispersant represented by the trade name include KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Floren (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca Ltd.), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno Co., Inc.), DISPERBYK (registered trademark) (manufactured by BYK-Chemie Japan Co., Ltd.), and BYK (registered trademark) (manufactured by BYK-Chemie Japan Co., Ltd.). Among them, solvent-based pigment dispersants are preferred. Representative commercially available products thereof include DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250,; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc., manufactured by BYK-Chemie Japan Co., Ltd. SOLSPERSE-3000, 9000, 13000, 13240, 13650, 13940, 16000, 17000, 18000, 20000, 21000, 24000, 26000, 27000, 28000, 31845, 32000, 32500, 32550, 33500, 32600, 34750, 35100, 36600, 38500, 41000, 41090, 53095, 55000, 76500, etc., manufactured by Lubrizol Japan Ltd. EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF; Ajisper PA111, PB711, PB821, PB822, PB824 manufactured by Ajinomoto Fine-Techno Co., Inc. etc. are mentioned.

[0314] When the colorant-containing liquid (P) contains a dispersant, the amount of the dispersant (solid content) used is, for example, 0.01 part by mass or more and 10,000 parts by mass or less, preferably 0.01 part by mass or more and 5,000 parts by mass or less, more preferably 0.01 part by mass or more and 1,000 parts by mass or less, still more preferably 0.1 part by mass or more and 500 parts by mass or less, particularly preferably 0.1 part by mass or more and 300 parts by mass or less, even more preferably 1 part by mass or more and 300 parts by mass or less, and most preferably 5 parts by mass or more and 260 parts by mass or less, per 100 parts by mass of the colorant (P). When the amount of the dispersant used is within the above range, a colorant (A)-containing liquid with a more uniform dispersion state tends to be obtained.

[0315] When a colorant-containing liquid (Ph) containing a colorant (P) and a solvent (K) is prepared in advance and then the colorant-containing liquid (Ph) is used to prepare a color-curable resin composition (E), the colorant-containing liquid (Ph) may contain in advance a part or all, preferably a part, of the resin (F) contained in the color-curable resin composition (E). By pre-containing the resin (F), the dispersion stability of the colorant-containing liquid (Ph) can be further improved.

[0316] When the coloring agent-containing liquid (Ph) contains the resin (F), the content of the resin (F) is, for example, 0.01 part by mass or more and 10,000 parts by mass or less, preferably 0.01 part by mass or more and 5,000 parts by mass or less, more preferably 0.01 part by mass or more and 1,000 parts by mass or less, still more preferably 0.1 part by mass or more and 500 parts by mass or less, and particularly preferably 0.1 part by mass or more and 300 parts by mass or less, based on 100 parts by mass of the coloring agent (P).

[0317] The colored curable resin composition may further contain, if necessary, a leveling agent (J), an antioxidant (I), a filler, other polymer compounds, an adhesion promoter, a light stabilizer, a chain transfer agent, and other additives known in the art. Examples of the leveling agent (J) and the antioxidant (I) are applicable to those exemplified in the description of the above-mentioned curable resin composition (D).

[0318] [Method for producing the colored curable resin composition] The colored curable resin composition (E) can be prepared, for example, by mixing a coloring agent (P), a resin (F), a polymerizable compound (G), a polymerization initiator (H), and, if necessary, a solvent (K), a leveling agent (J), an antioxidant (I), and other components. The mixing can be carried out by known or conventional devices and conditions. The coloring agent (P) is preferably used in the form of a dispersion liquid of the coloring agent (P) which is previously mixed with a part or all of the solvent (K) and dispersed using a bead mill or the like until the average particle diameter of the coloring agent (P) becomes about 0.2 μm or less. At this time, if necessary, a part or all of the dispersant and the resin (F) may be blended. The coloring agent (P) is preferably dissolved in a part or all of the solvent (E) in advance to prepare a solution. Further, it is preferable to filter the solution through a filter having a pore size of about 0.01 μm or more and 1 μm or less. It is preferable to filter the colored curable resin composition (E) after mixing through a filter having a pore size of about 0.01 μm or more and 10 μm.

[0319] [Reflective film] The display device can include, although not particularly limited, a light reflection member for irradiating the light from the light source toward the mixture or the laminate structure. The reflective film can include any suitable known material, although not particularly limited, such as a mirror, a film of reflective particles, a reflective metal film, or a reflector.

[0320] <Diffusion film> The display device can include, although not particularly limited, a diffusion film for diffusing the light from the light source or the light emitted from the mixture. The diffusion film may include any diffusion film known in the art, such as an amplified diffusion film.

[0321] <Brightness enhancement unit> The display device according to the present invention can include, although not particularly limited, a brightness enhancement unit that reflects and returns a part of the light in the direction in which the light is transmitted.

[0322] <Prism sheet> The prism sheet typically has a base material portion and a prism portion. Note that the base material portion may be omitted depending on the adjacent member. The prism sheet can be bonded to an adjacent member via any suitable adhesive layer (e.g., an adhesive layer, a pressure-sensitive adhesive layer). The prism sheet is configured by arranging a plurality of unit prisms that protrude on the side opposite to the viewing side (back side) in parallel. By arranging the convex portion of the prism sheet toward the back side, the light transmitted through the prism sheet is likely to be condensed. Also, if the convex portion of the prism sheet is arranged toward the back side, compared with the case where the convex portion is arranged toward the viewing side, the light that is reflected without entering the prism sheet is less, and a display with high brightness can be obtained.

[0323] <Light guide plate> As the light guide plate, any suitable light guide plate can be used. For example, a light guide plate having a lens pattern formed on the back side so that the light from the lateral direction can be deflected in the thickness direction, or a light guide plate having a prism shape or the like formed on the back side and / or the viewing side is used.

[0324] <Inter-element medium material layer> The display device according to the present invention may include, although not particularly limited, a layer composed of one or more medium materials on the optical path between adjacent elements (layers). Examples of the one or more medium materials include, but are not limited to, vacuum, air, gas, optical materials, adhesives, optical adhesives, glass, polymers, solids, liquids, gels, cured materials, optical coupling materials, refractive index matching or refractive index mismatching materials, refractive index gradient materials, cladding or anti-cladding materials, spacers, silica gel, luminance enhancement materials, scattering or diffusing materials, reflective or anti-reflective materials, wavelength selective materials, wavelength selective anti-reflective materials, or other suitable media known in the art, and any suitable materials may be included.

[0325] Specific examples of the display device include, for example, those provided with a wavelength conversion material for an EL display or a liquid crystal display. Specifically, a wavelength conversion layer (B) is arranged between a blue light source (A) and a light guide plate along the end face (side face) of the light guide plate to form a backlight (an on-edge type backlight) that emits white light, and a light absorption layer (C) is arranged on the light guide plate side; a wavelength conversion layer (B) is installed on the light guide plate to form a backlight (a surface mounting type backlight) that emits the light irradiated from a blue light source (A) placed on the end face (side face) of the light guide plate through the light guide plate to the wavelength conversion layer (B) as white light, and a light absorption layer (C) is arranged on the wavelength conversion layer (B); a quantum dot composition is installed near the light emitting part of a blue light source (A) as a wavelength conversion layer (B) to form a backlight (an on-chip type backlight) that emits the irradiated light as white light, and a light absorption layer (C) is arranged on the wavelength conversion layer (B); and the like.

[0326] Preferably, in the optical path of the light from the blue light source (A), the blue light source (A), the wavelength conversion layer (B), and the light absorption layer (C) are arranged and / or laminated in this order.

[0327] FIG. 1 is a schematic cross-sectional view of a display device according to an embodiment of the present invention. The display device 100 shown in FIG. 1 includes a blue light source (A) 110, a wavelength conversion layer (B) 120, and a light absorption layer (C) 130. The wavelength conversion layer (B) 120 has a first wavelength conversion layer (B1) 121 and a second wavelength conversion layer (B2) 122. The light absorption layer (C) 130 has a first light absorption layer (C1) 131 and a second light absorption layer (C2) 132.

[0328] FIG. 2 is a schematic cross-sectional view of a display device according to another embodiment of the present invention. The display device 200 shown in FIG. 2 includes a blue light source (A) 210, a wavelength conversion layer (B) 220, and a light absorption layer (C) 230. The wavelength conversion layer (B) 220 has a first wavelength conversion layer (B1) 221 and a second wavelength conversion layer (B2) 222. The light absorption layer (C) 230 can be the above-described light absorption layer (CY).

[0329] <Film> Another aspect of the present invention is a film containing a compound that absorbs blue and emits green light and satisfies condition (5). As the compound that absorbs blue and emits green light, the examples and preferred ranges of the above-described luminescent compound Q1 are applicable. The preferred ranges of the thickness T5, the content W5, and the X5 in condition (5) are the preferred ranges of T1 and W1 in the above-described condition (1). When the film satisfying condition (5) is used as the wavelength conversion layer that emits green light in the display device, it is possible to achieve both a wide color gamut and excellent energy efficiency, and thus it is suitable as the wavelength conversion layer of the display device.

[0330] Still another aspect of the present invention is a film containing a compound that absorbs blue and emits red light and satisfies condition (6). As the compound that absorbs blue and emits red light, the examples and preferred ranges of the above-described luminescent compound Q2 are applicable. The preferred ranges of the thickness T6, the content W6, and the X6 in condition (6) are the preferred ranges of T2 and W2 in the above-described condition (2). When the film satisfying condition (6) is used as the wavelength conversion layer that emits red light in the display device, it is possible to achieve both a wide color gamut and excellent energy efficiency, and thus it is suitable as the wavelength conversion layer of the display device.

[0331] <Display> As shown in FIG. 3, the display 300 of the present embodiment includes a liquid crystal panel 301 and the above-described display device 100 in this order from the viewing side. The liquid crystal panel 301 typically includes a liquid crystal cell, a viewing-side polarizing plate disposed on the viewing side of the liquid crystal cell, and a back-side polarizing plate disposed on the back side of the liquid crystal cell. The display may further include any other suitable members.

[0332] <Liquid crystal panel> The above liquid crystal panel typically includes a liquid crystal cell, a viewing-side polarizing plate disposed on the viewing side of the liquid crystal cell, and a back-side polarizing plate disposed on the back side of the liquid crystal cell. The viewing-side polarizing plate and the back-side polarizing plate can be arranged such that their absorption axes are substantially orthogonal or parallel to each other.

[0333] [Liquid crystal cell] The liquid crystal cell has a pair of substrates and a liquid crystal layer as a display medium sandwiched between the substrates. In a general configuration, a light absorption layer and a black matrix are provided on one of the substrates, and a switching element for controlling the electro-optical characteristics of the liquid crystal, a scanning line for supplying a gate signal to the switching element, a signal line for supplying a source signal, a pixel electrode, and a counter electrode are provided on the other substrate. The interval (cell gap) between the above substrates can be controlled by a spacer or the like. On the side of the above substrates in contact with the liquid crystal layer, an alignment film made of, for example, polyimide can be provided.

[0334] [Polarizing plate] The polarizing plate typically has a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorption-type polarizer. As the above polarizer, any appropriate polarizer can be used. For example, a hydrophilic polymer film such as a polyvinyl alcohol-based film, a partially formalized polyvinyl alcohol-based film, or an ethylene-vinyl acetate copolymer-based partially saponified film, to which a dichroic substance such as iodine or a dichroic dye is adsorbed and uniaxially stretched; a polyene-based oriented film such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among these, a polarizer obtained by adsorbing a dichroic substance such as iodine on a polyvinyl alcohol-based film and uniaxially stretching it has a high polarization dichroism ratio and is particularly preferable.

Example

[0335] Hereinafter, the present invention will be described in more detail with reference to examples. In the examples, “%” and “parts” are mass % and parts by mass, respectively, unless otherwise specified.

[0336] <Measurement of display device> Regarding the light emitted from the display devices of the examples and comparative examples, through an optical fiber, using a microscope equipped with a spectroscope spectrometer Spectrum meter (manufactured by Ocean Optics), with the focus on the film surface, the chromaticity (x, y) and emission spectrum at the front (0°) with respect to the light source were measured. The chromaticity (x, y) is the xy chromaticity coordinates (x, y) in the CIE XYZ color system.

[0337] <Measurement of peak wavelength of light source> The emission spectrum of the light source was measured using the measuring device used for the measurement of the above display device, and the peak wavelength of the light source was read from the measured emission spectrum.

[0338] <Measurement of transmittance (450 nm) of wavelength conversion layer> An ultraviolet-visible-near-infrared spectrophotometer (UV-3600; manufactured by Shimadzu Corporation) equipped with an integrating sphere was used. As the measurement substrate, a cured film of the curable resin composition used in the examples and comparative examples was directly formed on a glass substrate in the same manner as the method for forming the wavelength conversion layer in Example 1 described below, except that it was exposed without passing through a photomask. The background was obtained using a glass substrate.

[0339] <Measurement of the thickness of the wavelength conversion layer> It was measured with a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technologies Co., Ltd.).

[0340] <Measurement of the emission spectrum of the luminescent compound> Using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics, product name C9920-02, excitation light 450 nm, room temperature, under atmosphere), the emission spectrum of the quantum dot solution diluted so that the Abs value became 0.4 was measured. The maximum wavelength (λmax) and the full width at half maximum were determined from the obtained emission spectrum.

[0341] <Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)> The measurement of the polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) of resin (F) was carried out under the following conditions by the GPC method. Device: HLC-8120GPC (manufactured by Tosoh Corporation) Column: TSK-GEL G2000HXL Column temperature: 40 °C Solvent: Tetrahydrofuran Flow rate: 1.0 mL / min Solid content concentration of the analysis sample: 0.001 - 0.01 mass% Injection volume: 50 μL Detector: RI Standard substance for calibration: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation) The ratio (Mw / Mn) of the polystyrene-reduced weight average molecular weight (Mw) and number average molecular weight (Mn) obtained above was defined as the dispersity.

[0342] <Color gamut evaluation value (Y)>

[0343] When the area of the overlapping part of the color gamut surrounded by the coordinates calculated from the xy chromaticity coordinates (x, y) measured according to the above-mentioned "Measurement of the display device" and the color gamut surrounded by the coordinates of BT2020 was defined as Y1, and the color gamut surrounded by the coordinates of BT2020 was defined as Y2, the following formula: Y = (Y1 / Y2) × 100 It was calculated from

[0344] <Efficiency evaluation value (Z)> From the emission spectrum measured according to the above-mentioned "Measurement of Display Device", the spectral intensities of the blue pixel, green pixel, and red pixel were calculated according to the following formula. Z = [(Zr + Zg + Zb) / 3Zb] × 100 Zb: Integrated intensity of blue pixel Zg: Integrated intensity of green pixel Zr: Integrated intensity of red pixel

[0345] <Characteristic evaluation value> It was calculated according to the following formula. Characteristic evaluation value = (Y × Z) / 100 Y: Color gamut evaluation value Z: Efficiency evaluation value

[0346] 〔Preparation of blue light source〕 Blue light source (A1): A blue light-emitting diode having a maximum peak wavelength of 445 nm. Blue light source (A2): A blue light-emitting diode having a maximum peak wavelength of 450 nm.

[0347] 〔Synthesis Example 1〕Resin (F1) An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 80 parts of propylene glycol monomethyl ether acetate was placed, and it was heated to 85 °C while stirring. Next, a mixed solution prepared by dissolving 6 parts of methacrylic acid, 25 parts of dicyclopentanyl methacrylate, 40 parts of methyl methacrylate, and 29 parts of succinic acid 1-[2-(methacryloyloxy)ethyl] in 20 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 4 hours. On the other hand, a solution prepared by dissolving 9 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 40 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the dropping of the initiator solution was completed, it was held at 85 °C for 4 hours and then cooled to room temperature to obtain a copolymer (resin F1) solution. The solid content of the resin F1 solution was 40%, and the weight average molecular weight was 11,500.

[0348] 〔Synthesis Example 2〕Resin (F2) An appropriate amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel, and a stirrer, and the atmosphere was replaced with a nitrogen atmosphere. 371 parts of propylene glycol monomethyl ether acetate was placed, and it was heated to 85 °C while stirring. Next, a mixed solution prepared by dissolving 54 parts of acrylic acid, 225 parts of a mixture of 3,4-epoxytricyclo[5.2.1.02,6]decane-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.02,6]decane-9-yl acrylate (the content ratio was 50:50 in molar ratio), and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate was added dropwise into the flask over 4 hours. On the other hand, a solution prepared by dissolving 30 parts of a polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 160 parts of propylene glycol monomethyl ether acetate was added dropwise over 5 hours. After the dropping of the initiator solution was completed, it was held at 85 °C for 4 hours and then cooled to room temperature to obtain a copolymer (resin F2) solution. The solid content of the resin F2 solution was 37%, and the weight average molecular weight was 10,600.

[0349] 〔Preparation Example 1〕Preparation of quantum dot dispersion (Qh) Toluene dispersion of InP / ZnSeS quantum dots (Q1) containing oleic acid as the organic ligand (L): maximum peak wavelength: 625 nm, full width at half maximum: 44 nm Toluene dispersion of InP / ZnSeS quantum dots (Q2) containing oleic acid as the organic ligand (L): maximum peak wavelength: 530 nm, full width at half maximum: 42 nm

[0350] After drying the toluene dispersion of the above quantum dots by vacuum distillation to remove toluene, 70 parts of cyclohexyl acetate (K3) was added to a total of 30 parts of the quantum dots (Q) and the organic ligand (L) to obtain the quantum dot dispersions (Qh-1) and (Qh-2) in Table 1.

[0351]

Table 1

[0352] The ratio of the quantum dots (Q) to the organic ligand (L) was calculated from the remaining amount after heating to 550 °C at a heating rate of 5 °C / min by TG-DTA measurement of the mixture after removing toluene.

[0353] 〔Preparation Example 2〕Curable resin composition (D) For the quantum dot dispersion (Qh), each component in Tables 2 and 3 was mixed to prepare curable resin compositions (D-r1), (D-r2), (D-r3), (D-g1), (D-g2), and (D-g3) for forming a wavelength conversion layer. In Tables 2 and 3, the number of parts of components other than the solvent (K) represents the value in terms of solid content.

[0354]

Table 2

[0355]

Table 3

[0356] Light scattering agent (S1): A mixture of 60 parts of titanium oxide particles, 10 parts by mass (in terms of solid content) of resin (F1), and a total of 30 parts by mass of PGMEA was used. The titanium oxide particles were sufficiently dispersed using a bead mill. Polymerizable compound (G1): Polybasic acid-modified acrylic oligomer (trade name: M-510, manufactured by Toagosei Co., Ltd.) Polymerization initiator (H1): Irgacure (registered trademark) OXE-02, manufactured by BASF Antioxidant (I1): Sumilizer GP, manufactured by Sumitomo Chemical Co., Ltd. Leveling agent (J1): Toray silicone SH8400, manufactured by Toray Dow Corning Co., Ltd. Solvent (K1): Propylene glycol monomethyl ether acetate (PGMEA)

[0357] 〔Adjustment Example 3〕Pigment dispersion liquid (Ph) The components in Table 4 were mixed, and the pigments were sufficiently dispersed using a bead mill to prepare pigment dispersion liquids (Ph-1) to (Ph-7).

[0358]

Table 4

[0359] Pigment (P1): C.I. Pigment Red 254 Pigment (P2): C.I. Pigment Red 177 Pigment (P3): C.I. Pigment Yellow 185 Pigment (P4): C.I. Pigment Yellow 150 Pigment (P5): C.I. Pigment Green 58 Pigment (P6): C.I. Pigment Green 36 Pigment (P7): C.I. Pigment Green 7 Pigment dispersant: Solvent-based pigment dispersant Resin (F3): Methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio (mass ratio): 30 / 70, Mw: 1.2×10 4 Solvent (K2): Propylene glycol 1 - methyl ether (PGME)

[0360] 〔Adjustment Example 4〕Colored curable resin composition (E) The colored curable resin compositions (E - r) and (E - g) for forming a light absorption layer were obtained by mixing the respective components in Table 5. In Table 5, the number of parts of the resin indicates the value in terms of solid content conversion.

[0361]

Table 5

[0362] Polymerizable compound (G2): Dipentaerythritol hexaacrylate, trade name: KAYARAD (registered trademark) DPHA, manufactured by Nippon Kayaku Co., Ltd. Polymerization initiator (H2): N - benzoyloxy - 1 - (4 - phenylsulfanylphenyl) octane - 1 - one - 2 - imine, trade name: Irgacure (registered trademark) OXE - 01, manufactured by BASF Leveling agent (J2): Polyether - modified silicone oil, trade name: Toray silicone SH8400, manufactured by Toray Dow Corning Co., Ltd.

[0363] <Example 1> On a 5 cm square glass substrate (Eagle 2000; manufactured by Corning), the colored curable resin composition (E - r1) for forming a light absorption layer was applied by spin - coating, and then pre - baked at 100 °C for 3 minutes to form a red curable resin composition layer. With respect to the substrate on which this red curable resin composition layer was formed, using an exposure machine (TME - 150RSK; manufactured by Topcon Corporation), in an air atmosphere, light was irradiated with an exposure amount of 100 mJ / cm 2 (based on 365 nm), and after development, post - baking was performed at 230 °C for 20 minutes to obtain a cured film. This cured film was used as the first light absorption layer (C1). Similarly, on the substrate on which the first light absorption layer (C1) was produced, a second light absorption layer (C2) was produced using the colored curable resin composition (E - g1).

[0364] Next, on the above substrate, using the curable resin composition (D-r2), except that the exposure amount was changed to 500 mJ / cm 2 and the post-baking was changed to 180 °C for 60 minutes, the first wavelength conversion layer (B1) was formed on the first light absorption layer (C1) in the same manner as the production method of the above first light absorption layer. Similarly, using the curable resin composition (D-g2), the second wavelength conversion layer (B2) was formed on the second light absorption layer (C2).

[0365] As shown in the display device production conditions shown in Table 6, the above substrate was placed so that the first light absorption layer (C1) was on the first wavelength conversion layer (B1) and the second light absorption layer (C2) was on the second wavelength conversion layer (B2) on the blue light source (A), and a display device was produced. The evaluation results are shown in Table 7.

[0366] <Examples 2 to 12 and Comparative Examples 1 and 2> A display device was produced in the same manner as in Example 1, except that the materials and film thicknesses shown in Table 6 were used. The evaluation results are shown in Table 7.

[0367]

Table 6

[0368]

Table 7

[0369] In the display device produced in the example, by independently driving the LED elements of the light source, full-color display becomes possible.

Explanation of Signs

[0370] 100, 200 Display device, 110, 210 Blue light source, 120, 220 Wavelength conversion layer, 121, 221 First wavelength conversion layer, 122, 222 Second wavelength conversion layer, 130, 230 Light absorption layer, 131 First light absorption layer, 132 Second light absorption layer, 300 Liquid crystal display, 301 Liquid crystal panel.

Claims

1. A display device having a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C), wherein the wavelength conversion layer (B) has a first wavelength conversion layer (B1) containing a compound (Q1) that absorbs blue light and emits red light, and a second wavelength conversion layer (B2) containing a compound (Q2) that absorbs blue light and emits green light, satisfies the following conditions (1) and (2), the first wavelength conversion layer (B1) further contains a light scattering agent (S) and satisfies the following condition (3), the second wavelength conversion layer (B2) further contains a light scattering agent (S) and satisfies the following condition (4). (1) 0.7 ≤ X1 ≤ 4.0 (2) 0.7 ≤ X2 ≤ 4.0 [However, X1 is a value obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content W1 [% by mass] of the compound (Q1) in the first wavelength conversion layer (B1) by 100 [X1 = (T1 × W1) / 100], and T1 [μm] is 1 μm or more and 20 μm or less, X2 is a value obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content W2 [% by mass] of the compound (Q2) in the second wavelength conversion layer (B2) by 100 [X2 = (T2 × W2) / 100], and T2 [μm] is 1 μm or more and 20 μm or less.]] (3) 0.4 ≤ X3 ≤ 1.6 [However, X3 is a value obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content W3 [% by mass] of the light scattering agent (S) in the first wavelength conversion layer (B1) by 100 [X3 = (T1 × W3) / 100].]] (4) 0.3 ≤ X4 ≤ 1.6 [However, X4 is a value obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content W4 [% by mass] of the light scattering agent (S) in the second wavelength conversion layer (B2) by 100 [X4 = (T2 × W4) / 100].]]

2. The display device according to claim 1, wherein the blue light source (A) emits light having a peak at a wavelength of 600 nm or less.

3. The display device according to claim 1 or 2, wherein the compound (Q1) contains at least one selected from the group consisting of indium compounds and cadmium compounds.

4. The display device according to any one of claims 1 to 3, wherein the compound (Q2) contains at least one selected from the group consisting of indium compounds and cadmium compounds.

5. The light absorption layer (C) has a first light absorption layer (C1) and a second light absorption layer (C2). The first light absorption layer (C1) is disposed on the first wavelength conversion layer (B1), and the second light absorption layer (C2) is disposed on the second wavelength conversion layer (B2). The display device according to any one of claims 1 to 4.

6. A film containing a compound (Q1) that absorbs blue and emits red, further containing a light scattering agent (S), and satisfying the following conditions (3) and (5). (3) 0.4 ≤ X3 ≤ 1.6 [However, X3 is a value obtained by dividing the product of the thickness T1 [μm] of the film and the content W3 [mass%] of the light scattering agent (S) in the film by 100 [X3 = (T1 × W3) / 100], and T1 [μm] is 1 μm or more and 20 μm or less. ] (5) 0.7 ≤ X5 ≤ 4.0 [However, X5 is a value obtained by dividing the product of the thickness T5 [μm] of the film and the content W5 [mass%] of the compound (Q1) in the film by 100 [X5 = (T5 × W5) / 100]. ]

7. A film containing a compound (Q2) that absorbs blue and emits green, further containing a light scattering agent (S), and satisfying the following conditions (4) and (6). (4) 0.3 ≤ X4 ≤ 1.6 [However, X4 is a value obtained by dividing the product of the thickness T2 [μm] of the film and the content W4 [mass%] of the light scattering agent (S) in the film by 100 [X4 = (T2 × W4) / 100], and T2 [μm] is 1 μm or more and 20 μm or less. ] (6) 0.7 ≤ X6 ≤ 4.0 [However, X6 is a value obtained by dividing the product of the thickness T6 [μm] of the film and the content W6 [mass%] of the compound (Q2) in the film by 100 [X6 = (T6 × W6) / 100]. ]

8. The film according to claim 6, wherein the compound (Q1) contains at least one selected from the group consisting of indium compounds and cadmium compounds.

9. The film according to claim 7, wherein the compound (Q2) contains at least one selected from the group consisting of indium compounds and cadmium compounds.

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