Display device

Abstract

A display device is provided with a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C). 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. The display device satisfies 0.7 < = X1 and 0.7 < = X2.

Description

[0001] This application is a divisional application of patent application 202080090083.1 (international application date: December 23, 2020, name of invention: display device). Technical Field

[0002] The present invention relates to a display device having 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

[0003] Patent Document 1 proposes a display device including a light conversion unit including quantum dots and a color filter.

[0004] Patent Document 2 proposes a light-emitting element using a cured film-forming composition containing a binder polymer, a polymerizable compound, semiconductor quantum dots, and a dispersant. Patent Document 3 proposes a color filter produced using a photosensitive resin composition containing a quantum dot dispersion.

[0005] Prior art literature

[0006] Patent Literature

[0007] Patent Document 1: International Publication No. 2015 / 045735

[0008] Patent Document 2: Japanese Patent Application Publication No. 2017-025165

[0009] Patent Document 3: Japanese Patent Application Publication No. 2017-21322 Summary of the invention

[0010] In a display device having a wavelength conversion layer and a light absorption layer including quantum dots that has been proposed in the past, a wide color gamut and excellent energy efficiency may not be obtained simultaneously.

[0011] The object of the present invention is to provide a display device that can achieve both a wide color gamut and excellent energy efficiency, the display device comprising: 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.

[0012] 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.

[0013] 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.

[0014] The present invention provides the following display device and film.

[0015] [1] A display device comprising a blue light source (A), a wavelength conversion layer (B) and a light absorption layer (C), wherein:

[0016] The wavelength conversion layer (B) comprises a first wavelength conversion layer (B1) and a second wavelength conversion layer (B2), wherein the first wavelength conversion layer (B1) contains a compound (Q1) that absorbs blue and emits red light, and the second wavelength conversion layer (B2) contains a compound (Q2) that absorbs blue and emits green light.

[0017] The above-mentioned display device satisfies the following conditions (1) and (2).

[0018] (1) 0.7 ≤ X1

[0019] (2) 0.7 ≤ X2

[0020] [in,

[0021] 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],

[0022] 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.]

[0023] [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.

[0024] [3] The display device according to [1] or [2], wherein the compound (Q1) comprises at least one selected from an indium compound and a cadmium compound.

[0025] [4] The display device according to any one of [1] to [3], wherein the compound (Q2) comprises at least one selected from an indium compound and a cadmium compound.

[0026] [5] The display device according to any one of [1] to [4], wherein the first wavelength conversion layer (B1) further comprises a light scattering agent (S) and satisfies the following condition (3).

[0027] (3)X3≤1.6

[0028] [in,

[0029] 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 [mass %] of the light scattering agent (S) in the first wavelength conversion layer (B1) by 100 [X3=(T1×W3) / 100.]

[0030] [6] The display device according to any one of [1] to [5], wherein the second wavelength conversion layer (B2) further comprises a light scattering agent (S) and satisfies the following condition (4).

[0031] (4)X4≤1.6

[0032] [in,

[0033] 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 [mass %] of the light scattering agent (S) in the second wavelength conversion layer (B2) by 100 [X4=(T2×W4) / 100].]

[0034] [7] A display device as described in any one of [1] to [6], wherein the light absorbing layer (C) comprises a first light absorbing layer (C1) and a second light absorbing layer (C2), the first light absorbing layer (C1) being arranged on the first wavelength conversion layer (B1), and the second light absorbing layer (C2) being arranged on the second wavelength conversion layer (B2).

[0035] [8] A film comprising a compound (Q1) that absorbs blue light and emits red light and satisfies the following condition (5).

[0036] (5)0.7≤X5

[0037] [in,

[0038] 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].]

[0039] [9] A film comprising a compound (Q2) that absorbs blue light and emits green light and satisfies the following condition (6).

[0040] (6)0.7≤X6

[0041] [in,

[0042] 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].

[0043] According to the present invention, a wide color gamut and excellent energy efficiency can be achieved in a display device having: a blue light source; a wavelength conversion layer having a first wavelength conversion layer emitting green light and a second wavelength conversion layer emitting red light; and a light absorbing layer.

[0044] According to another aspect of the present invention, a film can be provided 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.

[0045] According to another aspect of the present invention, there can be provided 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

[0046] Figure 1 It is a schematic cross-sectional view showing a display device according to one embodiment of the present invention.

[0047] Figure 2 It is a schematic cross-sectional view showing a display device according to one embodiment of the present invention.

[0048] Figure 3 It is a schematic cross-sectional view showing a display according to one embodiment of the present invention.

[0049] Explanation of symbols

[0050] 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. DETAILED DESCRIPTION

[0051] <Display device>

[0052] The display device comprises a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C). The display device is a device that emits light from the blue light source (A) to the wavelength conversion layer (B), and extracts the emitted light through the light absorption layer (C).

[0053] The wavelength conversion layer (B) is composed of a first wavelength conversion layer (B1) and a second wavelength conversion layer (B2), wherein the first wavelength conversion layer (B1) contains a compound (Q1) that absorbs blue and emits red light (hereinafter also referred to as the luminescent compound (Q1)), and the second wavelength conversion layer (B2) contains a compound (Q2) that absorbs blue and emits green light (hereinafter also referred to as the luminescent compound (Q2)).

[0054] The so-called "luminescence" refers to the property of emitting light. The luminescence is preferably the property of emitting light by excitation of electrons, and more preferably the property of emitting light by excitation of electrons using excitation light. The peak wavelength of the excitation light may be, for example, 200 nm to 800 nm, 250 nm to 750 nm, 300 nm to 700 nm, or 300 nm to 600 nm.

[0055] “Blue” refers to all light recognized as blue (all light having intensity in a blue wavelength region, for example, 380 nm to 495 nm), and is not limited to light of a single wavelength.

[0056] “Green” refers to all light that is 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.

[0057] “Red” refers to all light that is 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.

[0058] “Yellow” refers to all light that is 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.

[0059] The display device may also include layers such as a light guide plate, a reflective film, a diffusion film, a brightness enhancement portion, a prism sheet, and a dielectric material layer between components, which will be described later.

[0060] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) can be directly arranged on the blue light source (A), or can also be arranged on a light guide plate, and the above-mentioned light guide plate is arranged 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).

[0061] The display device may have a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C) in this order in the optical path of light from the blue light source (A).

[0062] The display device can exhibit a wide color gamut and excellent energy efficiency when conditions (1) and (2) are met. In a display device having a blue light source, a wavelength conversion layer containing a luminescent compound, and a light absorbing layer, a portion of the light from the blue light source leaks out of the wavelength conversion layer, thereby reducing the peak intensity of the light emitted from the wavelength conversion layer, and sometimes the target chromaticity and luminous intensity cannot be obtained. In order to suppress such leakage of light from the blue light source, it is considered to increase the thickness of the wavelength conversion layer, but when the thickness is too large, there is a tendency for the wavelength conversion layer to be difficult to form. The results of the study found that when the product of the thickness of the wavelength conversion layer and the content of the luminescent compound in the wavelength conversion layer is set to a fixed value or more, it is easy to suppress a portion of the light from the blue light source from leaking out of the wavelength conversion layer within the thickness range in which the wavelength conversion layer can be formed, thereby obtaining a wide color gamut and excellent energy efficiency.

[0063] <Condition (1)>

[0064] The value X1 obtained by dividing the product of the thickness T1 [μm] of the first wavelength conversion layer (B1) and the content W1 [mass %] of the above-mentioned luminescent compound (Q1) in the first wavelength conversion layer (B1) by 100 [X1 = (T1×W1) / 100] (hereinafter, also referred to as X1) is 0.7 or more. In the first wavelength conversion layer (B1), from the viewpoint of color gamut and energy efficiency, it is preferably 1.0≤X1, more preferably 1.5≤X1, and further preferably 2.0≤X1. In the first wavelength conversion layer (B1), X1≤4.0 is usually satisfied, and from the viewpoint of easy manufacturing, it is preferably X1≤3.5.

[0065] <Condition (2)>

[0066] The value X2 [X2 = (T2 × W2) / 100] (hereinafter, also referred to as X2) obtained by dividing the product of the thickness T2 [μm] of the second wavelength conversion layer (B2) and the content W2 [mass %] of the above-mentioned luminescent compound (Q2) in the second wavelength conversion layer (B2) by 100 is 0.7 or more. In the first wavelength conversion layer (B2), from the viewpoint of color gamut and energy efficiency, it is preferably 1.0≤X2, more preferably 1.5≤X2, and further preferably 2.0≤X2. In the first wavelength conversion layer (B1), X2≤4.0 is usually set, and from the viewpoint of easy manufacturing, it is preferably X2≤3.5.

[0067] The thickness T1 of the first wavelength conversion layer (B1) can be, for example, 1 μm to 20 μm, preferably 1.5 μm to 15 μm, and more preferably 2 μm to 10 μm from the viewpoint of easy production. The thickness T1 [μm] of the first wavelength conversion layer (B1) can be measured by the method described in the Examples section below.

[0068] The thickness T2 of the second wavelength conversion layer (B2) can be, for example, 1 μm to 20 μm, preferably 1.5 μm to 15 μm, and more preferably 2 μm to 10 μm from the viewpoint of easy production. The thickness T2 [μm] of the second wavelength conversion layer (B2) can be measured by the method described in the Example column below.

[0069] 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.

[0070] The content W1 of the luminescent compound (Q1) in the first wavelength conversion layer (B1) may be, for example, 10% to 80% by mass, preferably 15% to 60% by mass, and more preferably 15% to 40% by mass from the viewpoint of color gamut and energy efficiency. The content W1 of the luminescent compound (Q1) in the first wavelength conversion layer (B1) is obtained as the mass ratio of the mass of the luminescent compound (Q1) to the solid content of the curable resin composition (Q1) described later forming the first wavelength conversion layer (B1).

[0071] The content W2 of the luminescent compound (Q2) in the second wavelength conversion layer (B2) can be, for example, 10% to 80% by mass, preferably 15% to 60% by mass, and more preferably 15% to 40% by mass from the viewpoint of color gamut and energy efficiency. The content W2 of the luminescent compound (Q2) in the second wavelength conversion layer (B2) is obtained as the mass ratio of the mass of the luminescent compound (Q2) to the solid content of the curable resin composition (Q2) described later that forms the second wavelength conversion layer (B2).

[0072] In order to satisfy conditions (1) and (2), for example, there may be mentioned a method of adjusting the type, average particle size and content of the luminescent compound (Q1) and the luminescent compound (Q2) in the curable resin composition (Q) described later, the type and content of the polymer, and a method of adjusting the thickness of the wavelength conversion layer.

[0073] <Blue light source>

[0074] The blue light source (A) can be a light source that can emit at least blue light by causing the luminescent compound (Q1) in the first wavelength conversion layer (B1) and the luminescent compound (Q2) in the second wavelength conversion layer (B2) to emit light. As the blue light source (A), for example, a known light source such as a light emitting diode (LED), a laser, an EL, etc., such as a blue light emitting diode, can be used. From the viewpoint of color gamut and energy efficiency, the blue light source (A) is preferably a light source that emits light having a peak below 600nm. The peak of the light emitted from the blue light source (A) is measured according to the method described in the Example column described later.

[0075] The blue light source (A) can be used as a backlight in combination with the wavelength conversion layer (B). The backlight may also include a light guide plate.

[0076] <Wavelength conversion layer>

[0077] The wavelength conversion layer (B) is composed of a first wavelength conversion layer (B1) and a second wavelength conversion layer (B2). Preferably, the first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) are 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, respectively.

[0078] The first wavelength conversion layer (B1) can absorb a portion of the light from the blue light source (A) and emit red light. The first wavelength conversion layer (B1) can also transmit another portion of the light from the blue light source (A), but preferably the amount of light transmitted from the blue light source (A) is small.

[0079] The light emitted from the first wavelength conversion layer (B1) has a peak in the wavelength range of 620nm to 650nm, and the full width at half maximum of the peak is 15nm to 80nm, more preferably has a peak in the wavelength range of 625nm to 645nm, and the full width at half maximum of the peak is 15nm to 45nm. The wavelength range and full width at half maximum of the peak are measured by the method described in the Example column described later.

[0080] The second wavelength conversion layer (B2) can absorb a portion of the light from the blue light source (A) and emit green light. The second wavelength conversion layer (B2) can also transmit another portion of the light from the blue light source (A), but preferably the amount of light transmitted from the blue light source (A) is small.

[0081] The light emitted from the second wavelength conversion layer (B2) has a peak in the wavelength range of 520nm to 545nm, and the half-maximum width of the peak is 15nm to 80nm, more preferably has a peak in the wavelength range of 525nm to 535nm, and the half-maximum width of the peak is 15nm to 45nm.

[0082] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) may be a layer comprising a cured product of a curable resin composition containing a light-emitting compound (Q1) (hereinafter also referred to as a curable resin composition (D1)), and a layer comprising a cured product of a curable resin composition containing a light-emitting compound (Q2) (hereinafter also referred to as a curable resin composition (D2)). Hereinafter, the curable resin composition (D1) and the curable resin composition (D2) are collectively referred to as the curable resin composition (D).

[0083] The first wavelength conversion layer (B1) and the second wavelength conversion layer (B2) may each be a single-layer structure or a multilayer structure consisting of a plurality of layers. When the first wavelength conversion layer (B1) is a multilayer structure consisting of a plurality of layers, the first wavelength conversion layer (B1) may have two or more layers containing a cured product of the curable resin composition (D1).

[0084] The light transmittance (450nm) of the first wavelength conversion layer (B1) can be, for example, 85% or less. From the viewpoint of color gamut and energy efficiency, it is preferably 60% or less, more preferably 40% or less, further preferably 30% or less, particularly preferably 20% or less, and further preferably 10% or less.

[0085] The light transmittance (450nm) of the second wavelength conversion layer (B2) can be, for example, 90% or less. From the viewpoint of color gamut and energy efficiency, it is preferably 75% or less, more preferably 60% or less, further preferably 40% or less, particularly preferably 30% or less, and further preferably 20% or less.

[0086] [Luminescent Compounds]

[0087] The luminescent spectrum (peak) of the red light emitted by the luminescent compound (Q1) preferably has a maximum value in the range of wavelengths of 610nm to 750nm. When the range of wavelengths of 610nm to 750nm has a maximum value, the color purity of the red light corresponding to the peak is particularly high, so the brightness of the red light of the display device can be further improved. The above-mentioned maximum value is more preferably present in the range of wavelengths of 620nm to 650nm. The luminescent spectrum of the luminescent compound (Q1) can be measured according to the method described in the Example column described later.

[0088] The half-maximum full width of the luminescent spectrum of the luminescent compound (Q1) is preferably 20nm to 80nm. If the above-mentioned half-maximum full width is less than 80nm, the color purity of the red light in the light emitted from the first wavelength conversion layer (B1) becomes higher, so the brightness of the red light of the display device can be further improved. On the other hand, if the above-mentioned half-maximum full width is more than 20nm, the transmittance of the red light can be further increased, so the brightness of the red light can be further improved. The half-maximum full width of the luminescent spectrum of the above-mentioned red light is more preferably 20nm to 60nm, and more preferably 20nm to 50nm.

[0089] The luminescent spectrum (peak) of the green light emitted by the luminescent compound (Q2) preferably has a maximum value in the range of wavelengths of 500nm to 560nm. When the range of wavelengths of 500nm to 560nm has a maximum value, the color purity of the green light corresponding to the peak is particularly high, so the brightness of the green light of the display device can be further improved. The above-mentioned maximum value is more preferably present in the range of wavelengths of 500nm to 560nm. The luminescent spectrum of the luminescent compound (Q2) can be measured according to the method described in the Example column described later.

[0090] The half-maximum full width of the luminescent spectrum of the luminescent compound (Q2) is preferably 20nm to 80nm. If the above-mentioned half-maximum full width is less than 80nm, the color purity of the green light in the light emitted from the second wavelength conversion layer (B2) becomes higher, so the brightness of the green light of the display device can be further improved. On the other hand, if the above-mentioned half-maximum full width is more than 20nm, the transmittance of the green light can be further increased, so the brightness of the green light can be further improved. The half-maximum full width of the luminescent spectrum of the green light is preferably 20nm to 60nm, and more preferably 20nm to 50nm.

[0091] The light-emitting compound (Q1) and the light-emitting compound (Q2) are preferably quantum dots. Examples of quantum dots include particles of light-emitting indium compounds and particles of light-emitting cadmium compounds.

[0092] Examples of the indium compound include Group III-V indium compounds, Group III-VI indium compounds, and Group I-III-VI indium compounds. Group III-V indium compounds are preferred, and Group V indium compounds containing phosphorus are more preferred.

[0093] Examples of the cadmium compound include Group II-VI cadmium compounds and Group II-V cadmium compounds.

[0094] Indium compounds do not contain cadmium, and cadmium compounds do not contain indium.

[0095] [III-V Group Indium Compounds]

[0096] The III-V group indium compound is a compound containing a group III element and a group V element, and is a compound containing at least the indium element. Here, group III refers to group 13 of the periodic table, and group V refers to group 15 of the periodic table (the same below). It should be noted that in this specification, the "periodic table" refers to a long-period type periodic table.

[0097] The III-V group indium compound may be a binary system, a ternary system, or a quaternary system.

[0098] The binary III-V group indium compound may be any compound containing an indium element (first element) and a group V element (second element), and examples thereof include InN, InP, InAs, and InSb.

[0099] The ternary III-V group indium compound can be a compound containing two elements, indium element (first element) and an element selected from group V (second element), or a compound containing two elements selected from group III (first element) with one element being set as indium element and one element selected from group V (second element).

[0100] Examples of the ternary III-V group indium compound include InPN, InPAs, InPSb, and InGaP.

[0101] The quaternary III-V group indium compound is a compound containing two elements selected from group III (first element), one of which is an indium element, and two elements selected from group V (second element).

[0102] Examples of the quaternary III-V group indium compound include InGaPN, InGaPAs, and InGaPSb.

[0103] The semiconductor containing the Group III-V indium compound may contain elements other than Group 13 and Group 15 of the periodic table (except cadmium) as a doping element.

[0104] [III-VI Group Indium Compounds]

[0105] The III-VI group indium compound is a compound containing a group III element and a group VI element, and is a compound containing at least indium element. Here, group VI refers to group 16 of the periodic table (the same applies hereinafter).

[0106] The III-VI group indium compound may be a binary system, a ternary system, or a quaternary system.

[0107] The binary III-VI group indium compound may be any compound containing an indium element (first element) and a group VI element (second element), and examples thereof include In2S3, In2Se3, and In2Te3.

[0108] The ternary III-VI group indium compound can be a compound containing two elements, indium element (first element) and an element selected from group VI (second element), or it can be a compound containing two elements selected from group III (first element) with one element being set as indium element and one element selected from group VI (second element).

[0109] Examples of ternary III-VI group indium compounds include InGaS3, InGaSe3, InGaTe3, In2SSe2, and In2TeSe2.

[0110] The quaternary III-VI group indium compound is a compound containing two elements selected from group III (first element), one of which is an indium element, and two elements selected from group VI (second element).

[0111] Examples of quaternary III-VI group indium compounds include InGaSSe2, InGaSeTe2, and InGaSTe2.

[0112] The semiconductor containing the Group III-VI indium compound may contain elements other than Group 13 and Group 16 of the periodic table (except cadmium) as a doping element.

[0113] [Group I-III-VI Indium Compounds]

[0114] The I-III-VI group indium compound is a compound containing a group I element, a group III element, and a group VI element, and is a compound containing at least indium element. Here, group I refers to group 11 of the periodic table (the same applies hereinafter).

[0115] The Group I-III-VI indium compound may be a ternary system or a quaternary system.

[0116] The ternary Group I-III-VI indium compound is a compound containing an element selected from Group I (first element), indium element (second element), and an element selected from Group VI (third element).

[0117] As a ternary I-III-VI group indium compound, CuInS2 can be cited, for example.

[0118] The semiconductor containing the Group I-III-VI indium compound may contain elements other than Group 11, Group 13, and Group 16 of the periodic table (except cadmium) as a doping element.

[0119] From the viewpoint of obtaining sufficient luminous intensity, the indium compound is preferably InP, CuInS 2 , InNP, and GaInNP, and more preferably InP and CuInS 2 .

[0120] [II-VI Cadmium Compounds]

[0121] The II-VI group cadmium compound is a compound containing a group II element and a group VI element, and is a compound containing at least a cadmium element. Here, group II refers to group 2 or group 12 of the periodic table (the same applies hereinafter).

[0122] The II-VI group cadmium compound may be a binary system, a ternary system, or a quaternary system.

[0123] The binary II-VI Group cadmium compound may be any compound containing a cadmium element (first element) and a Group 16 element (second element), and examples thereof include CdS, CdSe, and CdTe.

[0124] The ternary II-VI Group cadmium compound can be a compound containing two elements, a cadmium element (the first element) and an element selected from Group VI (the second element), or a compound containing two elements selected from Group II (the first element), one of which is a cadmium element, and one element selected from Group VI (the second element).

[0125] Examples of the ternary II-VI Group cadmium compound include CdSeS, CdSeTe, CdSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, and CdHgTe.

[0126] The quaternary II-VI Group cadmium compound is a compound containing two elements selected from Group II (first element), one of which is a cadmium element, and two elements selected from Group VI (second element).

[0127] Examples of the quaternary II-VI Group cadmium compound include CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, and CdHgSTe.

[0128] The semiconductor containing the II-VI Group cadmium compound may contain elements other than Group 2, Group 12, and Group 16 of the periodic table (except indium) as a doping element.

[0129] [II-V Group Cadmium Compounds]

[0130] The Group 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.

[0131] The II-V group cadmium compound may be a binary system, a ternary system, or a quaternary system.

[0132] The binary II-V group cadmium compound may be any compound containing a cadmium element (first element) and a group V element (second element), and examples thereof include Cd 3 P 2 , Cd 3 AS 2 , and Cd 3 N 2 .

[0133] The ternary II-V group cadmium compound can be a compound containing two elements, a cadmium element (the first element) and an element selected from group V (the second element), or a compound containing two elements selected from group II (the first element), one of which is a cadmium element, and one element selected from group V (the second element).

[0134] Examples of ternary II-V Group cadmium compounds include Cd3PN, Cd3PAs, Cd3AsN, Cd2ZnP2, Cd2ZnAS2, and Cd2ZnN2.

[0135] The quaternary II-V Group cadmium compound is a compound containing two elements selected from Group II (first element), one of which is a cadmium element, and two elements selected from Group V (second element).

[0136] Examples of the quaternary II-V Group cadmium compound include CdZnPN, CdZnPAs, and Cd2ZnAsN.

[0137] The semiconductor containing the II-V group cadmium compound may contain elements other than Group 2, Group 12, and Group 15 of the periodic table (except indium) as a doping element.

[0138] 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, further preferably CdS, CdSe, ZnCdS, ZnCdSSe, and CdZnSeS, and particularly preferably CdSe and CdZnSeS.

[0139] From the viewpoint of luminous intensity and durability, the particles of the indium compound and the particles of the cadmium compound may have an inorganic protective layer on the particle surface. The inorganic protective layer may be more than two layers or one layer. As inorganic materials that can form the inorganic protective layer, for example, semiconductors having a band gap greater than that of the indium compound and / or the cadmium compound can be cited, but are not limited thereto. The inorganic protective layer is formed of, for example, known inorganic materials such as ZnS, ZnSe and CdS.

[0140] Indium compound particles and cadmium compound particles can be synthesized by wet chemical process, metal organic chemical vapor deposition process or molecular beam epitaxy process. The wet chemical process is a method of adding precursor substances to organic solvents to grow particles. During crystal growth, the organic solvent naturally coordinates on the surface of the quantum dot crystals and acts as a dispersant to regulate the growth of the crystals. Therefore, compared with vapor phase evaporation methods such as metal organic chemical vapor deposition (MOCVD) or molecular beam epitaxy (MBE), it is easier to control the growth of nanoparticles using inexpensive processes.

[0141] [Light scattering agent]

[0142] From the viewpoint of efficiently absorbing incident light, the first wavelength conversion layer (B1) and / or the second wavelength conversion layer (B2) may further include a light scattering agent (S). The light scattering agent (S) is not particularly limited, but from the viewpoint of extracting emitted light, it is preferably a light scattering agent having light transmittance, for example, light scattering particles such as inorganic oxide particles, etc. Examples of the inorganic oxide particles include titanium oxide particles, etc.

[0143] [Condition (3)]

[0144] When the first wavelength conversion layer (B1) further comprises a light scattering agent (S), from the viewpoint of color gamut and energy efficiency, the first wavelength conversion layer (B1) preferably satisfies the following condition (condition 3): the value X3 obtained by dividing the product of the thickness T1 of the first wavelength conversion layer (B1) and the content W3 of the light scattering agent (S) in the first wavelength conversion layer (B1) by 100 [X3 = (T1 × W3) / 100] (hereinafter also referred to as X3) is 1.6 or less (condition (3)), more preferably X3 ≤ 1.2, and even more preferably X3 ≤ 1.0. When the first wavelength conversion layer (B1) further comprises a light scattering agent (S), it is usually 0.1 ≤ X3, and from the viewpoint of color gamut and energy efficiency, it is preferably 0.5 ≤ X3.

[0145] When the first wavelength conversion layer (B1) further includes a light scattering agent (S), the content of the light scattering agent (S) in the first wavelength conversion layer (B1) can be, for example, 1 mass % to 20 mass %, and is preferably 3 mass % to 15 mass % from the viewpoint of color gamut and energy efficiency.

[0146] [Condition (4)]

[0147] When the second wavelength conversion layer (B2) further comprises a light scattering agent (S), from the viewpoint of color gamut and energy efficiency, the second wavelength conversion layer (B2) preferably satisfies the following condition (condition 4): the value X4 obtained by dividing the product of the thickness T2 of the second wavelength conversion layer (B2) and the content W4 of the light scattering agent (S) in the second wavelength conversion layer (B2) by 100 [X4 = (T2 × W4) / 100] (hereinafter also referred to as X4) is 1.6 or less, more preferably X4 ≤ 1.2, and even more preferably X4 ≤ 1.0. When the second wavelength conversion layer (B2) further comprises a light scattering agent (S), it is usually 0.1 ≤ X4, and from the viewpoint of color gamut and energy efficiency, it is preferably 0.3 ≤ X4.

[0148] When the second wavelength conversion layer (B2) further includes a light scattering agent (S), the content of the light scattering agent (S) in the second wavelength conversion layer (B2) can be, for example, 1 mass % to 20 mass %, and is preferably 3 mass % to 15 mass % from the viewpoint of color gamut and energy efficiency.

[0149] The wavelength conversion layer (B) can be used by laminating it to a substrate, a barrier layer, a light scattering layer, etc.

[0150] [Substrate]

[0151] From the viewpoint of extracting light during luminescence, the substrate preferably has light transmittance. 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.

[0152] [Barrier layer]

[0153] 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 attached. The barrier layer is not particularly limited, and a known barrier layer can be applied.

[0154] [Light scattering layer]

[0155] From the viewpoint of efficiently absorbing incident light, a light scattering layer may be bonded. The light scattering layer is not particularly limited, but from the viewpoint of extracting emitted light, a light scattering layer having light transmittance is preferably used, and for example, a known light scattering layer such as an amplified diffusion film may be used.

[0156] [Method for producing wavelength conversion layer]

[0157] As the method for producing the wavelength conversion layer (B), for example, there can be mentioned: a method for producing a film containing a cured product of the curable resin composition (D), a step of applying the curable resin composition (D) on a substrate, and a step of removing the solvent; a method for producing a film containing a cured product of the curable resin composition (D), and a step of bonding the obtained film to a substrate; a method for producing a curable resin composition (D), a step of applying the curable resin composition (D) on a substrate, and a step of polymerizing a polymerizable compound, etc.

[0158] As a method for applying the curable resin composition (D) on a substrate, for example, a known coating method such as a gravure coating method, a bar coating method, a printing method, a spray method, a spin coating method, a dipping method, a die coating method, etc. can be used.

[0159] In the step of bonding the film containing the cured product of the curable resin composition (D) to the 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.

[0160] The method for producing the wavelength conversion layer (B) may also be a method for producing a further step of laminating an arbitrary film. As the arbitrary film to be laminarized, for example, a barrier film, a light scattering film, a reflective film, a diffusion film, etc. may be cited. In the step of laminating an arbitrary film, any adhesive may 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 may be used.

[0161] [Curable resin composition]

[0162] The wavelength conversion layer (B) may be formed from a curable resin composition (D). In addition to the luminescent compound (Q1) or the luminescent compound (Q2), the curable resin composition (D) may further contain at least one selected from an organic ligand (L), a light scattering agent (S), a solvent (K), a polymerizable compound (G), and a polymerization initiator (H).

[0163] The content of the luminescent compound (Q1) in the curable composition (D1) can be, for example, 10% by mass to 80% by mass, and from the viewpoint of color gamut and energy efficiency, it is preferably 15% by mass to 60% by mass, and more preferably 15% by mass to 40% by mass, relative to the total amount of solid components of the curable composition (D1).

[0164] The content of the luminescent compound (Q2) in the curable composition (D2) can be, for example, 10% by mass to 80% by mass relative to the total amount of solid components of the curable composition (D2). From the viewpoint of color gamut and energy efficiency, it is preferably 15% by mass to 60% by mass, and more preferably 15% by mass to 40% by mass.

[0165] 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) can be, for example, 1% by mass to 20% by mass, and is preferably 3% by mass to 15% by mass from the viewpoint of color gamut and energy efficiency, relative to the total amount of solid content of the curable resin composition (D1).

[0166] 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) can be, for example, 1% by mass to 20% by mass, and is preferably 3% by mass to 15% by mass from the viewpoint of color gamut and energy efficiency, relative to the total amount of the solid content of the curable resin composition (D2).

[0167] [Organic ligand]

[0168] The organic ligand (L) may be any of a non-polar organic ligand and a polar organic ligand. Examples of the non-polar organic ligand include a linear or branched saturated or unsaturated aliphatic acid, aliphatic amine, and aliphatic thiol 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 per molecule. The polar groups are preferably thiol groups and carboxyl groups.

[0169] 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 a molecular terminal.

[0170]

[0171] In the formula, R 1L The alkylene group includes, for example, an ethylene group and a propylene group.

[0172] Specific examples of the compound (La) include the following formula (La-1):

[0173]

[0174] [In formula (La-1), X is a polar group, Y is a monovalent group, and Z is a divalent or trivalent group. n is an integer greater than 2. m is 1 or 2. R 1L Same definition as above.]

[0175] The polyalkylene glycol compound represented by

[0176] Examples of the polar group include a carboxyl group, a thiol group and an amino group, and a carboxyl group and a thiol group are preferred.

[0177] Y may be, for example, a monovalent hydrocarbon group which may have a substituent (N, O, S, a halogen atom, etc.), preferably an alkyl group having 1 to 12 carbon atoms and having a linear, branched or cyclic structure, or an alkoxy group having 1 to 12 carbon atoms and having a linear, branched or cyclic structure.

[0178] Z can be, for example, a divalent or trivalent hydrocarbon group which may contain a heteroatom (N, O, S, halogen atom, etc.), preferably an alkylene group having 1 to 24 carbon atoms and a linear, branched or cyclic structure, and an alkenylene group having 1 to 24 carbon atoms and a linear, branched or cyclic structure.

[0179] The molecular weight of the compound (B) is preferably 100 to 2,000.

[0180] The curable resin composition may contain only one compound (B) or two or more compounds (B). The molecular weight is preferably 100 to 2,000.

[0181] [Resin]

[0182] The resin (F) is preferably an alkali-soluble resin. Examples of the resin (F) include the following resins [f1] to [f4].

[0183] Resin [f1]: a resin obtained by copolymerizing at least one (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter sometimes referred to as "(a)") and a monomer (c) copolymerizable with (a) (which is different from (a); hereinafter sometimes referred to as "(c)");

[0184] Resin [f2]: a resin obtained by reacting a copolymer of (a) and (c) with a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b)");

[0185] Resin [f3]: a resin obtained by reacting a copolymer of (b) and (c) with (a);

[0186] Resin [f4]: A resin obtained by reacting a copolymer of (b) and (c) with (a), and further reacting with a carboxylic anhydride.

[0187] Examples of (a) include unsaturated monocarboxylic acids such as acrylic acid, methacrylic acid, crotonic acid, and o-, m-, and p-vinylbenzoic acid;

[0188] 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.;

[0189] Bicyclic unsaturated compounds containing a carboxyl 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, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0190] Unsaturated dicarboxylic anhydrides 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;

[0191] Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;

[0192] For example, unsaturated acrylic acid esters containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl)acrylic acid.

[0193] Among them, acrylic acid, methacrylic acid, maleic anhydride and the like are preferred from the viewpoint of copolymerization reactivity and solubility of the resulting resin in an aqueous alkali solution.

[0194] (b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (e.g., at least one selected from 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 having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0195] Examples of (b) include glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinyl benzyl glycidyl ether, m-vinyl benzyl glycidyl ether, p-vinyl benzyl glycidyl ether, α-methyl-o-vinyl benzyl glycidyl ether, α-methyl-m-vinyl benzyl glycidyl ether, α-methyl-p-vinyl benzyl 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 - Monomers having an oxirane ring and an ethylenically unsaturated bond, such as tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 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, and 3-ethyl-3-acryloyloxyethyloxetane; Tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate and other monomers having a tetrahydrofuran ring and an ethylenically unsaturated bond.

[0196] (b) is preferably a monomer having an ethylene oxide ring and an ethylenically unsaturated bond, because (b) has high reactivity when producing the resins [f2] to [f4] and unreacted (b) is less likely to remain.

[0197] Examples of (c) 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](meth)acrylate. 2,6 ] decane-8-yl ester (common name in the technical field: dicyclopentyl (meth)acrylate or tricyclodecyl (meth)acrylate), tricyclo[5.2.1.0 2,6] (Meth)acrylates such as decen-8-yl ester (common name in the art: dicyclopentenyl (meth)acrylate), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, benzyl (meth)acrylate, etc.;

[0198] (Meth)acrylates containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0199] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0200] 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as bicyclo[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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0201] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0202] 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, etc.

[0203] Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance.

[0204] In resin [f1], the ratio of the structural units derived from each monomer is preferably 2 mol% to 70 mol% of the structural units derived from (a), and 30 mol% to 98 mol% of the structural units derived from (c), based on the total structural units constituting resin [f1]. In addition, it is more preferred that the structural units derived from (a) are 10 mol% to 70 mol%, and the structural units derived from (c) are 30 mol% to 90 mol%.

[0205] When the ratio of the structural unit 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.

[0206] Resin [f1] can be produced, for example, by referring to the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, Chemical Dojin Publishing Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the comparative documents described in the document.

[0207] Specifically, the following method can be cited: respectively placing a specified amount of (a) and (c), a polymerization initiator, and a solvent into a reaction vessel, for example, replacing oxygen with nitrogen, thereby forming a deoxygenated environment, and heating and keeping warm while stirring. It should be noted that the polymerization initiator and solvent used here are not particularly limited, and polymerization initiators and solvents commonly used in this field can be used. For example, as a polymerization initiator, it can be cited: azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.), organic peroxides (benzoyl peroxide, etc.). As a solvent, as long as it is a solvent that dissolves each monomer, it can be cited as a solvent (K) that can be present in the curable composition of the present invention and the solvent described later.

[0208] It should be noted that the obtained copolymer may be used directly as a solution after the reaction, or as a concentrated or diluted solution, or as a solution extracted in the form of a solid (powder) by a method such as reprecipitation. In particular, as a solvent during the above-mentioned polymerization, a solvent (K) described later is used, whereby the solution after the reaction can be directly used for the preparation of the curable composition of the present invention, thereby simplifying the manufacturing process of the curable composition of the present invention.

[0209] The resin [f2] can be produced by obtaining a copolymer of (a) and (c), and adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and / or carboxylic anhydride derived from (a).

[0210] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing the resin [f1]. In this case, the ratio of the structural units derived from each is preferably the same as the ratio listed for the resin [f1].

[0211] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is subjected to an addition reaction with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0212] After producing the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and (b), a reaction catalyst (e.g., tris(dimethylaminomethyl)phenol, etc.) and an inhibitor (e.g., hydroquinone) for the reaction between carboxylic acid or carboxylic anhydride and cyclic ether are placed in the flask, and the reaction is carried out at, for example, 60°C to 130°C for 1 hour to 10 hours, thereby producing resin [f2].

[0213] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). By setting it within this range, there is a tendency that the storage stability of the curable composition, the developability when forming a cured pattern, and the balance of the solvent resistance, heat resistance, mechanical strength and sensitivity of the obtained cured pattern become better.

[0214] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c). The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass relative to 100 parts by mass of the total amount of (a), (b) and (c).

[0215] The reaction conditions such as the addition method, reaction temperature and time can be appropriately adjusted in consideration of the production apparatus, the heat generated by polymerization, etc. It should be noted that the addition method and reaction temperature can be appropriately adjusted in consideration of the production apparatus, the heat generated by polymerization, etc., similarly to the polymerization conditions.

[0216] As for resin [f3], as the first stage, a copolymer of (b) and (c) is obtained in the same manner as the method for producing resin [f1]. The copolymer obtained may be used directly as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solution extracted in the form of a solid (powder) by a method such as reprecipitation.

[0217] The ratio of the structural units derived from (b) and (c) to the total molar number of all structural units constituting the above copolymer is preferably 5 mol% to 95 mol% for the structural units derived from (b), and 5 mol% to 95 mol% for the structural units derived from (c). It is more preferred that the structural units derived from (b) are 10 mol% to 90 mol%, and the structural units derived from (c) are 10 mol% to 90 mol%.

[0218] Furthermore, resin [f3] can be obtained by addition reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as the method for producing resin [f2].

[0219] The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol relative to 100 mol of (b).

[0220] The resin [f4] is a resin obtained by further reacting the resin [f3] with a carboxylic acid anhydride. The carboxylic acid anhydride is subjected to an addition reaction with a hydroxyl group generated by a reaction between a cyclic ether and a carboxylic acid or a carboxylic acid anhydride.

[0221] 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, etc. The amount of the carboxylic anhydride used is preferably 0.5 mol to 1 mol relative to 1 mol of the amount of (a) used.

[0222] Specific examples of the resin (F) include: resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymers and styrene / (meth)acrylic acid copolymers [f1]; resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymers, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymers, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymers, Resins such as resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate [f2]; resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, and resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [f3]; resins obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate and further reacting with tetrahydrophthalic anhydride, and the like [f4].

[0223] As a further example of resin (F), resin [f5] having a structural unit containing a tetrahydropyran ring in the main chain can be cited. When resin (F) contains resin [f5] containing a structural unit containing a tetrahydropyran ring in the main chain, excellent luminous intensity and heat resistance can be obtained in the cured film. The structural unit constituting the tetrahydropyran ring can be the following general formula (I):

[0224]

[0225] [Where R 1f and R 2f may be the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. The hydrocarbon group may have a substituent.]

[0226] The content of the structural unit represented by the general formula (I) in the resin [f5] can be, for example, 0.5% to 50% by mass based on the total amount of the resin [f5]. From the viewpoint of luminous intensity and heat resistance, it is preferably 1% to 40% by mass, and more preferably 5% to 30% by mass.

[0227] As R 1f and R 2f The hydrocarbon group having 1 to 25 carbon atoms in R includes, for example, the linear or branched alkyl groups listed in JP-A-2013-61599

[0037] ; aryl groups; alicyclic groups; alkyl groups substituted with alkoxy groups; alkyl groups substituted with aryl groups, and the like. 1f and R 2fFrom the viewpoint of the light emission intensity and heat resistance of the device, a hydrocarbon group having a primary or secondary carbon that is difficult to be released by acid or heat is preferred, and examples thereof include a methyl group, an ethyl group, a cyclohexyl group, and a benzyl group.

[0228] The resin [f5] may further contain a structural unit represented by the following general formula (II) and a structural unit represented by the following general formula (III) in addition to the structural unit represented by the general formula (I).

[0229]

[0230] [Where R 3f represents a hydrogen atom or a methyl group.]

[0231]

[0232] [Where R 4f represents a hydrogen atom or a methyl group. 5f It represents a saturated or unsaturated linear, branched, or cyclic hydrocarbon group having 1 to 20 carbon atoms. The hydrocarbon group may have a substituent.]

[0233] R 3f Preferably it is methyl. 4f Preferably it is methyl. 5f It is 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. 5f The hydrocarbon group in R may have a substituent, but preferably has no substituent. Examples of the substituent include a hydroxyl group and the like. 5f The hydrocarbon group in may have an ether group.

[0234] The resin [f5] may further contain structural units derived from a compound having a functional group capable of bonding to an acid group and a polymerizable double bond (hereinafter also referred to as compound (X)) described later. In the case where the resin [f5] further contains structural units derived from compound (X), the resin [f5] may further contain structural units derived from a carboxylic anhydride described later.

[0235] When the resin [f5] has a structural unit represented by the general formula (II), the content of the structural unit represented by the general formula (II) can be, for example, 0.5% by mass to 50% by mass based on the total amount of the resin [f5]. From the viewpoint of luminous intensity and heat resistance, it is preferably 2% by mass to 50% by mass, and more preferably 5% by mass to 45% by mass.

[0236] When the resin [f5] has a structural unit represented by the general formula (III), the content of the structural unit represented by the general formula (III) can be, for example, 10% by mass to 90% by mass based on the total amount of the resin [f5]. From the viewpoint of luminous intensity and heat resistance, it is preferably 20% by mass to 80% by mass, and more preferably 30% by mass to 75% by mass.

[0237] The resin [f5] is preferably a polymer containing a structural unit represented by the general formula (I) to (III) in the main chain, and more preferably a polymer having a main chain composed of structural units represented by the general formula (I) to (III).

[0238] When resin [f5] further contains structural units represented by general formula (II) and structural units represented by general formula (III), resin [f5] may contain 0.5% to 50% by mass of structural units represented by general formula (I), 9.5% to 40% by mass of structural units represented by general formula (II), and 10% to 90% by mass of structural units represented by general formula (III), based on the total amount of the polymer.

[0239] The weight average molecular weight of resin [f5] can be, for example, 1000 to 200,000. From the viewpoint of luminous intensity and heat resistance, the weight average molecular weight of resin [f5] is preferably 3000 or more, more preferably 4000 or more, further preferably 5000 or more, and further more preferably 6000 or more. In addition, from the viewpoint of luminous intensity and heat resistance, the weight average molecular weight of resin [f5] is preferably 30,000 or less, more preferably 20,000 or less, further preferably 15,000 or less, and further preferably 10,000 or less. In this specification, the weight average molecular weight can be obtained by the method described in the examples described later.

[0240] The double bond equivalent of resin [f5] may be, for example, 200 to 2000. Resin [f5] is a polymer having a double bond (i.e., an ethylenically unsaturated group) in a side chain, and its double bond equivalent may be 200 to 2000. The double bond equivalent is preferably 300 or more, more preferably 400 or more, further preferably 450 or more, and particularly preferably 490 or more. In addition, it is preferably 1900 or less. It should be noted that a polymer having no double bond in a side chain does not have a double bond equivalent.

[0241] Double bond equivalent is a measure of the amount of double bonds contained in a molecule, and refers to the molecular weight of each double bond of a polymer. If the compound has the same molecular weight, the greater the value of the double bond equivalent, the less the amount of double bonds introduced. The double bond equivalent can be calculated based on the amount of raw materials added, and can be obtained by dividing the mass (g) of the polymer solid component by the amount of double bonds (mol) of the polymer. In addition, various analyses such as titration and elemental analysis, NMR, IR, or differential scanning calorimetry can also be used for determination.

[0242] The acid value of the resin [f5] may be, for example, 20 mgKOH / g to 300 mgKOH / g. The acid value of the resin [f5] is preferably 40 mgKOH / g or more, more preferably 60 mgKOH / g or more, and even more preferably 80 mgKOH / g or more. In addition, it is preferably 200 mgKOH / g or less, more preferably 150 mgKOH / g or less, and even more preferably 120 mgKOH / g or less.

[0243] [Manufacture of resin [f5]]

[0244] Resin [f5] is preferably obtained by reacting a compound (X) having a functional group and a polymerizable double bond that can bond to an acid group with a polymer (also referred to as a base polymer), wherein the polymer is obtained by polymerizing monomer components of a monomer (5a) represented by the following general formula (i), a monomer (5b) containing an acid group, and a monomer (5c) represented by the following general formula (iii). Each reaction raw material can be used in one or more kinds.

[0245] [Monomer (5a)]

[0246] 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). It is speculated that when monomer (5a) is used for polymerization, during polymerization, the monomer (5a) undergoes a cyclization reaction to form a tetrahydropyran ring structure in the structural unit of the polymer.

[0247]

[0248] In the general formula (i), R 1f and R 2f The above definitions and preferred ranges for formula (I) apply.

[0249] Examples of the monomer (5a) include dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-propyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isopropyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(n-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isobutyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, -[oxybis(methylene)]bis-2-acrylate, di(tert-butyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tert-amyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(stearyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(lauryl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-ethylhexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Bis(1-methoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Bis(1-ethoxyethyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, Dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate, Diphenyl-2,2'-[oxybis(methylene)]bis-2-acrylate, Dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, Di(tert-butylcyclohexyl)-2,2'-[oxybis(methylene)]bis-2-acrylate ]bis-2-acrylate, di(dicyclopentadienyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(tricyclodecyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, di(isobornyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, diadamantyl-2,2'-[oxybis(methylene)]bis-2-acrylate, di(2-methyl-2-adamantyl)-2,2'-[oxybis(methylene)]bis-2-acrylate, etc.

[0250] Among them, dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, diethyl-2,2'-[oxybis(methylene)]bis-2-acrylate, dicyclohexyl-2,2'-[oxybis(methylene)]bis-2-acrylate, and dibenzyl-2,2'-[oxybis(methylene)]bis-2-acrylate are preferred. Dimethyl-2,2'-[oxybis(methylene)]bis-2-acrylate is more preferred from the viewpoints of less coloration, dispersibility, and ease of industrial acquisition.

[0251] The content of the monomer (5a) may be, for example, 0.5 to 50% by mass, preferably 1 to 40% by mass, and more preferably 5 to 30% by mass, based on 100% by mass of the total amount of monomer components that provide the base polymer.

[0252] [Monomer (5b)]

[0253] The 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.

[0254] 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 such as succinic acid mono(2-acryloyloxyethyl) and succinic acid mono(2-methacryloyloxyethyl) having an extended chain between an unsaturated group and a carboxyl group; unsaturated acid anhydrides such as maleic anhydride and itaconic anhydride; unsaturated compounds containing a phosphoric acid group such as LIGHT ESTERP-1M (manufactured by Kyoeisha Chemical Co., Ltd.). Among them, carboxylic acid monomers (unsaturated monocarboxylic acids, unsaturated polycarboxylic acids, and unsaturated acid anhydrides) are preferred from the viewpoints of versatility and availability. Unsaturated monocarboxylic acids are more preferred from the viewpoints of reactivity and alkali solubility, and (meth)acrylic acid is further preferred. Here, (meth)acrylic acid refers to acrylic acid and / or methacrylic acid.

[0255] The content of the monomer (5b) is preferably set so that the acid value is within the above-mentioned preferred range. For example, it can be 0.5% to 50% by mass, preferably 2% to 50% by mass, and more preferably 5% to 45% by mass, relative to 100% by mass of the total amount of the monomer components providing the base polymer.

[0256] When (meth)acrylic acid is used as the monomer (5b), the obtained resin [f5] has a structural unit represented by the general formula (II).

[0257] [Monomer (5c)]

[0258] 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 above general formula (III). The monomer (5c) is derived to form a structural unit represented by the general formula (III).

[0259]

[0260] In the general formula (iii), R 4f and R 5f The above definitions and preferred ranges for formula (I) apply.

[0261] Examples of the monomer (5c) include (meth)acrylate compounds containing a linear hydrocarbon group 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;

[0262] (Meth)acrylate compounds containing a branched hydrocarbon group, 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;

[0263] (meth)acrylate compounds containing a cyclic hydrocarbon group, such as cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.02,6]decane-8-yl (meth)acrylate (in the technical field, it is commonly referred to as "dicyclopentyl (meth)acrylate". It is also sometimes referred to as "tricyclodecyl (meth)acrylate".), tricyclo[5.2.1.02,6]decen-8-yl (meth)acrylate (in the technical field, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, and adamantyl (meth)acrylate; (meth)acrylate compounds containing an unsaturated hydrocarbon group, such as allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0264] (meth)acrylate compounds containing hydroxyl groups, such as 2-hydroxyethyl (meth)acrylate, 2-hydroxypropyl (meth)acrylate, 2-hydroxybutyl (meth)acrylate, 3-hydroxybutyl (meth)acrylate, and 4-hydroxybutyl (meth)acrylate;

[0265] Ether group-containing (meth)acrylate compounds such as 2-ethoxyethyl (meth)acrylate, etc. Among them, alkyl (meth)acrylate compounds are preferred from the viewpoint of improving solvent resistance.

[0266] The content of the monomer (5c) may be, for example, 10 to 90% by mass, preferably 20 to 80% by mass, and more preferably 30 to 75% by mass, based on 100% by mass of the total amount of monomer components that provide the base polymer.

[0267] [Monomer (5d)]

[0268] The resin [f5] may also contain one or more structural units derived from other monomers (also referred to as monomers (5d)) copolymerizable with the above-mentioned monomers (5a), (5b) and / or (5c). That is, the above-mentioned monomer component providing the base polymer may further contain monomers (5d).

[0269] Examples of the monomer (5d) include aromatic vinyl compounds such as styrene, vinyltoluene, and α-methylstyrene; ethylene or substituted vinyl compounds such as ethylene, propylene, vinyl chloride, and acrylonitrile; vinyl esters such as vinyl acetate;

[0270] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0271] 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-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept-2-ene Bicyclic unsaturated compounds such as bicyclo[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, and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0272] N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide,

[0273] Dicarbonyl imide derivatives such as N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0274] 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, etc.

[0275] Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, and bicyclo[2.2.1]hept-2-ene are preferred.

[0276] The content of the monomer (5d) is not particularly limited, and may be, for example, 50% by mass or less, preferably 25% by mass or less, and more preferably 10% by mass or less, relative to 100% by mass of the total amount of the monomer components providing the base polymer. In addition, the content of the monomer (5d) may be, for example, more than 0% by mass, or may be 0.001% by mass or more, or 0.01% by mass or more.

[0277] As a method for polymerizing the above-mentioned monomer components, commonly used methods such as bulk polymerization, solution polymerization, and emulsion polymerization can be used, and can be appropriately selected according to the purpose and use. Among them, solution polymerization is industrially advantageous, and the structural adjustment of molecular weight and the like is also easy, so it is preferred. In addition, the polymerization mechanism of the above-mentioned monomer components can use a polymerization method based on a mechanism such as free radical polymerization, anionic polymerization, cationic polymerization, coordination polymerization, etc., but a polymerization method based on a free radical polymerization mechanism is also industrially advantageous, so it is preferred. The preferred method of the polymerization reaction is as described in Japanese Patent Publication No. 2016-29151

[0062] -

[0072] .

[0278] As described above, the resin [f5] is preferably obtained by reacting the above-mentioned base polymer with a compound (X) having a functional group capable of bonding to an acid group and a polymerizable double bond.

[0279] As the polymerizable double bond possessed by the above-mentioned compound (X), for example, (meth)acryloyl, vinyl, allyl, methallyl, etc. can be cited, and as the compound, it is preferably a compound having one or more of them. From the point of view of reactivity, it is preferably a (meth)acryloyl. In addition, as the functional group capable of bonding with the acid group, for example, a hydroxyl, epoxy, oxetanyl, isocyanate, etc. can be cited, and as the compound, it is preferably a compound having one or more of them. Among them, epoxy (including glycidyl) is preferred.

[0280] As the above-mentioned compound (X), for example, glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, vinyl benzyl glycidyl ether, allyl glycidyl ether, (meth)acrylate (3,4-epoxycyclohexyl)methyl ester, vinyl cyclohexene oxide, etc. can be mentioned. Among them, a compound (monomer) having an epoxy group and a (meth)acryloyl group is preferred. In particular, from the viewpoint of high reactivity, easy control of the reaction, and easy availability, not only free radical polymerizable double bonds can be introduced, but also hydroxyl groups can be introduced at the same time, glycidyl (meth)acrylate and / or (meth)acrylate (3,4-epoxycyclohexyl)methyl ester is more preferred.

[0281] As long as the double bond equivalent of the resin [f5] is within the above range, the addition amount of the above compound (X) is not particularly limited. For example, it can be 2 to 60 parts by mass, preferably 10 to 55 parts by mass, more preferably 10 to 50 parts by mass, and further preferably 10 to 45 parts by mass, relative to 100 parts by mass of the total amount of monomer components providing the base polymer.

[0282] The method for reacting (a part of) the acid groups in the above-mentioned base polymer with the compound (X) is not particularly limited as long as a known addition method is used. The reaction temperature is preferably 60°C to 140°C, for example. In addition, it is preferred to use an amine compound such as triethylamine or dimethylbenzylamine; an ammonium salt such as tetraethylammonium chloride; tetraphenylammonium bromide; wait A known catalyst may be used, for example, a catalytic converter such as a catalytic converter comprising: ...

[0283] Resin [f5] can also react the above-mentioned base polymer with compound (X) and then react with carboxylic anhydride. In this case, the carboxylic anhydride and the hydroxyl group generated by the reaction of the cyclic ether with the carboxylic acid or the carboxylic anhydride are reacted. As carboxylic anhydride, 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. are mentioned. The amount of carboxylic anhydride used is preferably 0.5 mol to 1 mol relative to 1 mol of the monomer (5b).

[0284] Among them, the resin (F) is preferably at least one selected from the group consisting of resin [f2], resin [f3], resin [f4] and resin [f5].

[0285] The weight average molecular weight of the resin (F) in terms of polystyrene is preferably 3000 to 100000, more preferably 5000 to 50000, and still more preferably 5000 to 30000. 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 is improved.

[0286] The molecular weight distribution [weight average molecular weight (Mw) / number average molecular weight (Mn)] of the resin (F) is preferably 1.1-6, more preferably 1.2-4.

[0287] The acid value of the resin (F) is preferably 50 mg-KOH / g to 170 mg-KOH / g, more preferably 60 mg-KOH / g to 150 mg-KOH / g, and further preferably 70 mg-KOH / g 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 a potassium hydroxide aqueous solution.

[0288] The content of the resin (F) in the curable resin composition (D) is, for example, 5% to 99% by mass, preferably 10% to 90% by mass, more preferably 20% to 80% by mass, further preferably 30% to 70% by mass, and particularly preferably 30% to 60% by mass, relative to the total amount of the solid content of the curable resin composition (D). If the content of the resin (F) is within the above range, the mechanical properties and optical properties of the cured film of the curable resin composition (D) tend to be good.

[0289] [Polymerizable compound]

[0290] The polymerizable compound (G) is a compound that can be polymerized by active radicals generated from the polymerization initiator (H) described below, acid, etc. Examples of such a compound include compounds having an ethylenically unsaturated bond, and a (meth)acrylate compound is preferred.

[0291] In addition, in this specification, "(meth)acrylic acid" means at least one selected from acrylic acid and methacrylic acid. Expressions such as "(meth)acryloyl" and "(meth)acrylate" also have the same meaning.

[0292] 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, and caprolactone-modified dipentaerythritol hexa(meth)acrylate. The polymerizable compound can be used alone or in combination of two or more.

[0293] The weight average molecular weight of the polymerizable compound (G) is preferably 150 to 2,900, more preferably 250 to 1,500.

[0294] The content of the polymerizable compound (G) in the curable resin composition (D) is preferably 1% to 50% by mass, more preferably 5% to 40% by mass, further preferably 10% to 30% by mass, and particularly preferably 10% to 20% by mass, relative to the total amount of the solid content of the curable resin composition (D). If the content of the polymerizable compound (G) is within the above range, there is a tendency for the residual film rate of the cured pattern and the chemical resistance of the cured pattern to be further improved. The solid content of the curable resin composition (D) refers to the total of the components excluding the solvent from all the components contained in the curable resin composition (D).

[0295] [Polymerization initiator]

[0296] The polymerization initiator (H) is a compound that can generate active free radicals, acids, etc. by the action of light or heat to start the polymerization reaction, and has at least one selected from oxime compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds. Among them, it is preferred to contain oxime compounds. If these polymerization initiators are used, the residual film rate of the cured pattern becomes high.

[0297] In addition, the oxime compound, the biimidazole compound, the triazine compound, and the acylphosphine compound are preferably compounds having at least two aromatic rings in the molecule because the degree of polymerization during the production of a cured film tends to be higher.

[0298] 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.

[0299] The oxime compound is preferably an O-acyl oxime compound, and is a compound having a partial structure represented by formula (d1).

[0300]

[0301] Examples of the oxime compound include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-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-dioxolanylmethyloxy]-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine,

[0063] N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]-3-cyclopentylpropane-2-imine; compounds described in Japanese Patent Application Publication No. 2011-132215, International Publication No. 2008 / 78678, International Publication No. 2008 / 78686, and International Publication No. 2012 / 132558, etc. Commercially available products such as Irgacure OXE01, OXE02 (all manufactured by BASF), and N-1919 (manufactured by ADEKA) can also be used.

[0302] Among them, the oxime compound is preferably at least one selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine, and more preferably N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and / or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine.

[0303] As the oxime compound, an oxime compound having a first molecular structure represented by the following formula (1) may be used. Hereinafter, this oxime compound is also referred to as "oxime compound (1)".

[0304]

[0305] When an oxime compound (1) is contained as a polymerization initiator (H), it tends to be advantageous from the viewpoint of increasing the luminescence intensity. It is speculated that one reason why the curable resin composition of the present invention can achieve such an effect is that due to the unique molecular structure of the oxime compound (1), the absorption wavelength of the oxime compound (1) changes significantly before and after the oxime compound (1) is cleaved (decomposed) which is necessary for the oxime compound (1) to start photopolymerization, so the oxime compound (1) has a high ability to initiate photoradical polymerization.

[0306] In formula (1), R 1 Represents R 11 , OR 11 , COR 11 , SR 11 ,CONR 12 R 13 or CN.

[0307] R 11 , R 12 and R 13 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 aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0308] R 11 , R 12 and R 13 The hydrogen atoms of the group represented can be 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 replace.

[0309] R 21 , R22 and R 23 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 aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0310] R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0311] In 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 -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times.

[0312] R 24 It 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.

[0313] In R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 12 With R 13 and R 22 With R 23 They may also be formed into a ring together.

[0314] * represents a bonding site to the second molecular structure which is another molecular structure other than the first molecular structure of the oxime compound (1).

[0315] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24Examples of the alkyl group having 1 to 20 carbon atoms include methyl, ethyl, propyl, isopropyl, butyl, isobutyl, sec-butyl, tert-butyl, pentyl, isopentyl, t-pentyl, hexyl, heptyl, octyl, isooctyl, 2-ethylhexyl, t-octyl, nonyl, isononyl, decyl, isodecyl, undecyl, dodecyl, tetradecyl, hexadecyl, octadecyl, eicosyl, cyclopentyl, cyclohexyl, cyclohexylmethyl, and cyclohexylethyl.

[0316] As 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 include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0317] As 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 include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0318] As 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 include pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzo oxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, tetrahydrothiazolyl, isotetrahydrothiazolyl, Azolidinyl, iso The oxazolidinyl, piperidinyl, piperazinyl, morpholinyl and the like are preferably 5- to 7-membered heterocyclic rings.

[0319] R in formula (1) 12 With R 13 and R 22 With R 23 can form a ring together, R 12 With R 13 and R 22 With R23 They can form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

[0320] As Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 Examples of the ring that can be formed 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 and the like, and a 5- to 7-membered ring is preferred.

[0321] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of the halogen atom which may be a substituent in the molecule include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0322] R in formula (1) 1 Preferably R 11 , more preferably an alkyl group having 1 to 20 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, and still further preferably an alkyl group having 1 to 6 carbon atoms.

[0323] 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 refers to another molecular structure portion of the oxime compound (1) other than the first molecular structure.

[0324] The bonding site represented by "*" in formula (2) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring having [-*] in formula (2) is directly bonded to the carbonyl group having [-*] in formula (1).

[0325]

[0326] In formula (2), R 2 and R 3 R 11 , OR 11 , SR 11 , COR 11 ,CONR 12 R 13 NR 12 COR 11 ,OCOR 11 、COOR 11 SCOR 11 , OCSR11 、COSR 11 ,CSOR 11 , CN or halogen atom.

[0327] In the presence of multiple R 2 They can be the same or different.

[0328] In the presence of multiple R 3 They can be the same or different.

[0329] R 11 , R 12 and R 13 Means the same as above.

[0330] s and t each independently represent an integer of 0 to 4.

[0331] L represents a sulfur atom, CR 31 R 32 , CO or NR 33 .

[0332] R 31 , R 32 and R 33 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.

[0333] In R 31 , R 32 or R 33 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 31 , R 32 and R 33 Each of them may independently form a ring together with any adjacent benzene ring.

[0334] R 4 represents a hydroxyl group, a carboxyl group or the following formula (2-1)

[0335] (R 4a ) v -L 2 -L 1 - (2-1)

[0336] (In formula (2-1), L 1 Indicates -O-, -S-, -NR 22 -、-NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0337] R 22 Means the same as above.

[0338] L 2 It 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.

[0339] In L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 22 -、-NR 22 COO-、-OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted 1 to 5 times, and the alkylene part may be branched or cyclic.

[0340] R 4a Represents 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 halogen atom.

[0341] In the presence of multiple R 4a They can be the same or different.

[0342] 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, and in R 41 , R 42 and R 43 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 42 With R 43 Can form a ring together.

[0343] v represents an integer from 1 to 3. )

[0344] The group represented.

[0345] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0346] 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 42 and R 43 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the aralkyl group having 7 to 30 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Same as the example.

[0347] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R in the above formula (2-1) 22 Examples of heterocyclic groups having 2 to 20 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Same as the example.

[0348] R in formula (2) 31 , R 32 and R 33 Each of the two rings can independently form a ring with any adjacent benzene ring. 31 , R 32 and R 33 Each of them can independently form a ring together with any adjacent benzene ring and the nitrogen atom to which it is connected.

[0349] R in formula (2) 31 , R 32 and R 33Examples of the ring that can be formed together with any adjacent benzene ring and Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The examples of rings that can be formed together are the same.

[0350] In the above formula (2-1), L 2 It 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.

[0351] Examples of the group formed by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, 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, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, an ethane-1,1-diyl group, a propane-2,2-diyl group and the like.

[0352] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v is 1, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenylsulfide-4,4'-diyl, and diphenylsulfone-4,4'-diyl.

[0353] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, when v is 1, a group represented by the following formula (a) and a group represented by the following formula (b).

[0354]

[0355] [In formula (a) and formula (b), L 3 and L 5 represents an alkylene group having 1 to 10 carbon atoms, L 4 and L 6 represents a single bond or an alkylene group having 1 to 10 carbon atoms.]

[0356] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0357] Examples of the group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms include, for example, 2,5-pyridinediyl, 2,6-pyridinediyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazolediyl, 2,5-benzofurandiyl, 2,5-benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazolediyl, 2,5-benzo A divalent heterocyclic group such as oxadiyl.

[0358] As 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.

[0359] From the viewpoint of solubility in the solvent (K) and / or the development speed of the cured film, a preferred example of the structure represented by the formula (2) is a structure represented by the following formula (2a).

[0360]

[0361] [In formula (2a), L' represents a sulfur atom or NR 50 , R 50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R 2 , R 3 , R 4 , s and t have the same meanings as above.]

[0362] From the same viewpoint as above, another preferred example of the structure represented by formula (2) is a structure represented by the following formula (2b).

[0363]

[0364] [In formula (2b), R 44 represents a hydroxyl group, a carboxyl group or the following formula (2-2)

[0365] R 44a -L12 -L 11 - (2-2)

[0366] (In formula (2-2), L 11 Indicates -O- or *-OCO-, * indicates the same as L 12 The bonding site, L 12 represents an alkylene group having 1 to 20 carbon atoms, which may be interrupted by 1 to 3 -O- groups, R 44 a means OR 55 or COOR 55 , R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )

[0367] The group represented.]

[0368] R 44 Preferred is a group represented by formula (2-2). Such a case is advantageous from the viewpoint of the solubility of the oxime compound (1) in the solvent (K) and the development speed of the cured film.

[0369] L 12 The alkylene group represented has preferably 1 to 10 carbon atoms, more preferably 1 to 4 carbon atoms.

[0370] R 44 a is preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group.

[0371] The method for producing the oxime compound (1) having the second molecular structure represented by formula (2) is not particularly limited, and it can be produced, for example, according to the method described in JP-A-2011-132215.

[0372] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (3).

[0373] The bonding site represented by "*" in formula (3) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring having [-*] in formula (3) is directly bonded to the carbonyl group having [-*] in formula (1).

[0374]

[0375] In formula (3), R 5 It 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.

[0376] In R 5When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic.

[0377] R 5 The hydrogen atoms of the group represented by 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 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0378] R 21 , R 22 and R 23 Means the same as above.

[0379] R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0380] In R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times.

[0381] R 24 Means the same as above.

[0382] In R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0383] R 6 , R 7 , R 8 and R 9 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 , hydroxyl, nitro, CN or halogen atom.

[0384] 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.

[0385] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented can be 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-OCOR21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0386] R 6 With R 7 , R 7 With R 8 and R 8 With R 9 They can each form a ring together.

[0387] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0388] R in formula (3) 5 , 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 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Same as the example.

[0389] R in formula (3) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0390] R in formula (3) 22 With R 23 Examples of the ring that can be formed together and Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The examples of rings that can be formed together are the same.

[0391] As R in formula (3) 6 , R 7 , R 8 and R 9 The halogen atom represented by R 5 , R 21 , R22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0392] In view of solubility in the solvent (K) and / or development speed of the cured film, in a preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0393]

[0394] [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 arylalkyl 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.

[0395] In the case where the group represented by Z has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times, and the alkylene part may be branched or cyclic, R 21 , R 22 and R 24 Means the same as above.]

[0396] From the same viewpoint as described above, Z in formula (3-1) is preferably a methylene group, an ethylene group or a phenylene group.

[0397] From the same viewpoint as above, R in formula (3-1) 21 and R 22 It is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably a methyl group, an ethyl group or a phenyl group.

[0398] From the same viewpoint as above, in another preferred embodiment, R 7 For nitro.

[0399] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and it can be produced, for example, according to the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0400] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (4).

[0401] The bonding site represented by "*" in formula (4) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having [-*] in formula (1).

[0402]

[0403] In formula (4), R 71 It 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.

[0404] In R 71 When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic.

[0405] R 71 The hydrogen atoms of the group represented by 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 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0406] R 21 , R 22 and R 23 Means the same as above.

[0407] R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0408] In R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times.

[0409] R 24 Means the same as above.

[0410] In R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0411] R 72 , R 73 and 3 Rs 74 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 , hydroxyl, nitro, CN or halogen atom.

[0412] 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.

[0413] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented can be 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 atoms, or COOR 21 replace.

[0414] R 72 With R 73 and 2 R 74 They can each form a ring together.

[0415] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0416] R in formula (4) 71 , 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 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Same as the example.

[0417] R in formula (4) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0418] R in formula (4) 22 With R 23 Examples of the ring that can be formed together and Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The examples of rings that can be formed together are the same.

[0419] As R in formula (4) 72 , R 73 and R 74 The halogen atom represented by R 71 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0420] The method for producing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, and can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0421] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (5).

[0422] The bonding site represented by "*" in formula (5) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having [-*] in formula (1).

[0423]

[0424] In formula (5), R 81 It 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.

[0425] In R81 When the group represented has an alkyl portion, the alkyl portion may be branched or cyclic.

[0426] R 81 The hydrogen atoms of the group represented by 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 , hydroxyl, nitro, CN, halogen atom or COOR 21 replace.

[0427] R 21 , R 22 and R 23 Means the same as above.

[0428] R 21 , R 22 or R 23 The hydrogen atoms of the represented groups may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0429] In R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 24 -、-NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times.

[0430] R 24Means the same as above.

[0431] In R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0432] R 82 , R 83 , R 84 , R 85 and R 86 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 , hydroxyl, nitro, CN or halogen atom.

[0433] 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.

[0434] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented can be 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 )-R22 、-C(=N-OCOR 21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0435] R 83 With R 84 , R 84 With R 85 and R 85 With R 86 They can each form a ring together.

[0436] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0437] 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 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Same as the example.

[0438] R in formula (5) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0439] R in formula (5) 22 With R 23 Examples of the ring that can be formed together and Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The examples of rings that can be formed together are the same.

[0440] As R in formula (5) 82 , R 83 , R 84 , R 85 and R 86The halogen atom represented by R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0441] The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, and can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0442] Another example of the second molecular structure linked to the first molecular structure represented by formula (1) is a structure represented by the following formula (6).

[0443] The bonding site represented by "*" in formula (6) is directly bonded to the bonding site 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) is directly bonded to the carbonyl group having [-*] in formula (1).

[0444]

[0445] In formula (6), the four R 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 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 , hydroxyl, nitro, CN or halogen atom.

[0446] R 61 , R 62 , R 63 , R 64and 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.

[0447] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented can be 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 atoms, or COOR 21 replace.

[0448] R 21 , R 22 and R 23 Means the same as above.

[0449] R 92 With R 93 , R 94 With R 95 , R 95 With R 96 and R 96 With R 97 They can each form a ring together.

[0450] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0451] 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, 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 11 , R12 , R 13 , R 21 , R 22 and R 23 Same as the example.

[0452] R in formula (6) 22 With R 23 Can form a ring together means R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0453] R in formula (6) 22 With R 23 Examples of the ring that can be formed together and Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 The examples of rings that can be formed together are the same.

[0454] As R in formula (6) 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 The halogen atom represented by R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom that replaces the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0455] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, and can be produced, for example, according to the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0456] The biimidazole compound is, for example, a compound represented by formula (d5).

[0457]

[0458] [In formula (d5), R 51 ~R 56 represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

[0459] Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluoyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and a phenyl group is preferred.

[0460] Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, an iodine atom, etc. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and a methoxy group is preferred.

[0461] 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, Phenyl biimidazole, 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, imidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with alkoxycarbonyl groups, etc. These compounds are described in, for example, Japanese Patent Laid-Open No. 06-75372, Japanese Patent Laid-Open No. 06-75373, Japanese Patent Publication No. 48-38403, Japanese Patent Laid-Open No. 62-174204, Japanese Patent Laid-Open No. 7-10913, etc. Among them, compounds represented by the following formula or mixtures thereof are preferred.

[0462]

[0463] 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-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine. [2-(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferred.

[0464] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)-phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

[0465] The above-mentioned polymerization initiator (H) may be used alone or in combination of two or more polymerization initiators (H). When two or more polymerization initiators (H) are used in combination, they may be combined with a known polymerization initiator (H) other than the above-mentioned oxime compound, biimidazole compound, triazine compound and acylphosphine compound.

[0466] As a combination of two or more polymerization initiators (H), compounds of the same type with different structures can be combined, or compounds of different types can be combined. In the case of combining compounds of the same type, it is preferably a combination of oxime compounds, and more preferably a combination of compounds having a partial structure represented by formula (d1) as an O-acyl oxime compound. As an example of such a combination, a combination of N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazole-3-yl]ethane-1-imine can be cited. In such a case, the mixing ratio of N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine is preferably 10:90 to 90:10, more preferably 30:70 to 70:30, and further preferably 30:70 to 50:50.

[0467] Examples of the combination of different types of compounds include combinations of oxime compounds and biimidazole compounds, oxime compounds and triazine compounds, oxime compounds and acylphosphine compounds, biimidazole compounds and triazine compounds, biimidazole compounds and acylphosphine compounds, and triazine compounds and acylphosphine compounds.

[0468] 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'-tetrakis(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, benzil, methyl phenylglyoxylate, titanocene compounds, and the like.

[0469] The content of the polymerization initiator (H) is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 200 parts by mass, relative to 100 parts by mass of the polymerizable compound (G). When the curable resin composition (D) has a resin described later, the content of the polymerization initiator (H) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the resin (F) and the polymerizable compound (G) described later. If the content of the polymerization initiator (H) is within the above range, there is a tendency to shorten the exposure time due to high sensitivity, and therefore, the productivity of the cured film is improved.

[0470] [Polymerization initiator aid]

[0471] A polymerization initiation aid may also be used in combination as needed. A polymerization initiation aid is a compound or sensitizer used to promote the polymerization of a polymerizable compound (G) that has been polymerized by a polymerization initiator (H). In the case of a polymerization initiation aid, it can usually be used in combination with a polymerization initiator (H). Examples of the polymerization initiation aid include amine compounds, alkoxy anthracene compounds, thioxanthone compounds, and carboxylic acid compounds.

[0472] Examples of the amine compound include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isopentyl 4-dimethylaminobenzoate, 2-dimethylaminoethyl benzoate, 2-ethylhexyl 4-dimethylaminobenzoate, N,N-dimethyl-p-toluidine, 4,4'-bis(dimethylamino)benzophenone (commonly known as Michler's ketone), 4,4'-bis(diethylamino)benzophenone, and 4,4'-bis(ethylmethylamino)benzophenone. Among them, 4,4'-bis(diethylamino)benzophenone is preferred. Commercially available products such as EAB-F (manufactured by Hodogaya Chemical Industry Co., Ltd.) may also be used.

[0473] 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, and 2-ethyl-9,10-dibutoxyanthracene.

[0474] Examples of the thioxanthone compound include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

[0475] Examples of the carboxylic acid compound include phenylthioacetic acid, methylphenylthioacetic acid, ethylphenylthioacetic acid, methylethylphenylthioacetic acid, dimethylphenylthioacetic acid, methoxyphenylthioacetic acid, dimethoxyphenylthioacetic acid, chlorophenylthioacetic acid, dichlorophenylthioacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, and naphthoxyacetic acid.

[0476] In the case of a polymerization initiator aid, the content of the polymerization initiator aid is preferably 0.1 to 300 parts by mass, more preferably 0.1 to 200 parts by mass, relative to 100 parts by mass of the polymerizable compound (G). In the case where the curable resin composition (D) contains a resin described later, the content of the polymerization initiator (H) is preferably 0.1 to 30 parts by mass, more preferably 1 to 20 parts by mass, relative to 100 parts by mass of the total amount of the curable resin composition (D). If the amount of the polymerization initiator aid is within this range, there is a tendency to form a cured film with higher sensitivity.

[0477] [Solvent]

[0478] The colored curable resin composition may contain a solvent (K). The solvent (K) is not particularly limited, and a solvent commonly used in the field can be used.

[0479] Examples of the solvent (K) include ester solvents (solvents containing -CO-O- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -CO-O- in the molecule), ether ester solvents (solvents containing -CO-O- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -CO-O- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO- and -CO-O-), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like.

[0480] Examples of the ester solvent include methyl lactate, ethyl lactate, butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, amyl formate, isoamyl acetate, butyl propionate, isopropyl butyrate, ethyl butyrate, butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0481] Examples of the ether solvent 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-dihydrofu ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0482] Examples of the ether ester solvent 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 (PGMEA), propylene glycol monoethyl ether acetate, 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.

[0483] 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.

[0484] Examples of the alcohol solvent include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

[0485] Examples of the aromatic hydrocarbon solvent include benzene, toluene, xylene, and mesitylene.

[0486] Examples of the amide solvent include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0487] These solvents may be used in combination of two or more.

[0488] Among the above solvents, an organic solvent having a boiling point of 120° C. to 180° C. at 1 atm is preferred from the viewpoint of coating properties and drying properties. Preferred examples of the solvent 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. More preferred examples include propylene glycol monomethyl ether acetate, propylene glycol monomethyl ether, ethyl lactate, ethyl 3-ethoxypropionate, and 4-hydroxy-4-methyl-2-pentanone.

[0489] 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% to 99.99% by mass, preferably 40% to 90% by mass, and more preferably 45% to 85% by mass. From the viewpoint of storage stability of the solution and thick film coating, the content of the solvent (K) is preferably within the above range.

[0490] When the curable resin composition (D) contains a solvent (K), a portion of the solvent (K) can be mixed with the light-emitting compound (Q) to prepare a light-emitting compound dispersion (Qh), and then the light-emitting compound dispersion (Qh) can be mixed with other components to prepare the curable resin composition (D).

[0491] [Other ingredients]

[0492] The curable resin composition (D) may also contain additives known in the art such as antioxidants (I), leveling agents (J), stabilizers, chain transfer agents, etc. as other components. The content of other components is preferably 10% by mass or less, more preferably 5% by mass or less, and further preferably 1% by mass or less relative to the total amount of the curable resin composition (D).

[0493] [Antioxidant]

[0494] The colored curable resin composition may contain an antioxidant (I).

[0495] From the viewpoint of improving the heat resistance and optical resistance of the colorant, it is preferred that an antioxidant be used alone or in combination of two or more. As the antioxidant, there is no particular limitation as long as it is an antioxidant commonly used in industry, and phenolic antioxidants, phosphorus antioxidants, sulfur antioxidants, etc. can be used.

[0496] Examples of the phenolic antioxidant 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), and Irganox 1340 (Irganox 1340: 3,3',3",5,5',5"-hexa-tert-butyl-a,a',a"-(mesitylene-2,4,6-triyl)tri-p-cresol, manufactured by BASF). 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: diethylene sulfide bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF), Irganox 1135 (Ilganox 1135: phenylpropionic acid, 3,5-bis(1,1-dimethylethyl)-4-hydroxy, C7-C9 side chain alkyl ester, manufactured by BASF), Irganox 1520L (Ilganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF), Irganox 3125 (Ilganox 3125, manufactured by BASF), Irganox 565 (Ilganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy 3',5'-di-tert-butylphenylamino)-1,3,5-triazine, manufactured by BASF), Adekastab AO-80 (Adekastab 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)undecane, manufactured by ADEKA), Sumilizer BHT (Sumilizer BHT, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GA-80 (Sumilizer GA-80, manufactured by Sumitomo Chemical Co., Ltd.), Sumilizer GS (Sumilizer GS, manufactured by Sumitomo Chemical Co., Ltd.), Cyanox 1790 (Cytec Co., Ltd.), and vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0497] Examples of the phosphorus antioxidant 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), and Irgafos 168. 38 (Ilugafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF), Adekastab 329K (manufactured by ADEKA), Adekastab PEP36 (manufactured by ADEKA), Adekastab PEP-8 (manufactured by ADEKA), Sandstab P-EPQ (manufactured by Clariant), Weston 618 (manufactured by GE), Weston 619G (manufactured by GE), Ultranox 626 (manufactured by GE), and Sumilizer GP (Sumilyzer GP: 6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphine) (manufactured by Sumitomo Chemical Co., Ltd.) and the like.

[0498] Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate; and β-alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0499] [Leveling agent]

[0500] As the leveling agent (J), there can be mentioned silicone-based surfactants, fluorine-based surfactants, silicone-based surfactants having fluorine atoms, etc. These may have a polymerizable group in the side chain.

[0501] As the silicone surfactant, there can be mentioned surfactants having a siloxane bond in the molecule, etc. Specifically, there can be mentioned Toray Silicone DC3PA, Toray Silicone SH7PA, Toray Silicone DC11PA, Toray Silicone SH21PA, Toray Silicone SH28PA, Toray Silicone SH29PA, Toray Silicone SH30PA, Toray Silicone SH8400 (trade name: manufactured by Toray Dow Corning Corporation), 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 Co., Ltd.), etc.

[0502] Examples of fluorine-based surfactants include surfactants having a fluorine-carbon chain in the molecule, and the like. Specifically, examples include Fluorad (registered trademark) FC430, Fluorad FC431 (manufactured by Sumitomo 3M Co., Ltd.), Megafac (registered trademark) F142D, Megafac F171, Megafac F172, Megafac F173, Megafac F177, Megafac F183, Megafac F554, Megafac F575, Megafac R30, Megafac RS-718-K (manufactured by DIC Corporation), Eftop (registered trademark) EF301, EftoPEF303, EftoPEF351, EftoPEF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, Surflon S382, Surflon SC101, Surflon SC105 (manufactured by Asahi Glass Co., Ltd.) and E5844 (manufactured by Daik In Fine Chemical Research Institute), etc.

[0503] Examples of the silicone surfactant having a fluorine atom include surfactants having a siloxane bond and a fluorocarbon chain in the molecule, and specifically include Megafac (registered trademark) R08, Megafac BL20, Megafac F475, Megafac F477, and Megafac F443 (manufactured by DIC Corporation).

[0504] When the curable resin composition (D) contains at least one compound selected from ammonia, amines, carboxylic acids, and salts or ions thereof, the content of at least one compound selected from ammonia, amines, carboxylic acids, and salts or ions thereof in the curable resin composition (D) can be, for example, 0.01% by mass to 10% by mass, preferably 1% by mass to 5% by mass.

[0505] The wavelength conversion layer (B) can be arranged in the display device in a sealed manner by being placed in a glass tube or the like, or in a sheet-like form by being sandwiched and sealed between two barrier films.

[0506] <Light absorbing layer (C)>

[0507] The light absorbing layer (C) may have wavelength selectivity, which means that it transmits light in a specific wavelength range and absorbs light in other wavelength ranges. The light emitted from the wavelength conversion layer (B) transmits the light absorbing layer (C), and is emitted from the display device in the form of blue light, green light, and red light. The display device has a light absorbing layer (C), so there is a tendency to easily display a wide color gamut.

[0508] The light absorbing layer (C) may be disposed on the first wavelength conversion layer (B1) and the second wavelength conversion layer (B2).

[0509] The light-absorbing layer (C) may be a layer that transmits yellow light but absorbs light other than yellow light (hereinafter also referred to as a light-absorbing layer (CY)).

[0510] The light absorbing layer (C) may also include a first light absorbing layer (C1) and a second light absorbing layer (C2). When the light absorbing layer (C) includes the first light absorbing layer (C1) and the second light absorbing layer (C2), the first light absorbing layer (C1) is disposed on the first wavelength conversion layer (B1), and the second light absorbing layer (C2) is disposed on the second wavelength conversion layer (B2). The first light absorbing layer (C1) may be a layer that transmits red light but absorbs light other than red light. The second light absorbing layer (C2) may be a layer that transmits green light but absorbs light other than green light.

[0511] The light absorbing layer (C) may also include the first light absorbing layer (C1), the second light absorbing layer (C2), and the third light absorbing layer (C3). The third light absorbing layer (C3) may be disposed on the blue light source (A), or, when the display device includes the light guide plate, may be disposed on the light guide plate. The third light absorbing layer (C3) may transmit blue light but absorb light other than blue light.

[0512] The light absorbing layer (C) usually has a colorant (P). The colorant (P) can be a dye or a pigment. As a dye, a known dye can be used, for example, the known dyes recorded in the Color Index (published by The Society of DyerSand Colourists) and the Dyeing Notes (Color Dyeing Company) can be cited. In addition, according to the chemical structure, it can be cited: azo dyes, cyanine dyes, triphenylmethane dyes, xanthone dyes, anthraquinone dyes, naphthoquinone dyes, quinoneimine dyes, methine dyes, methine azo dyes, square acid cyanine dyes, acridine dyes, styryl dyes, coumarin dyes, quinoline dyes, nitro dyes, phthalocyanine dyes, perylene dyes, etc. These dyes can be used alone, or two or more can be used in combination.

[0513] Specifically, dyes having the following color index (CI) numbers are mentioned.

[0514] CI 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;

[0515] CI Solvent Red 24, 45, 49, 90, 91111, 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;

[0516] CI Solvent Orange 2, 7, 11, 15, 26, 41, 54, 56, 77, 86, 99;

[0517] CI Solvent Violet 11, 13, 14, 26, 31, 36, 37, 38, 45, 47, 48, 51, 59, 60;

[0518] CI 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;

[0519] CI solvent dyes such as CI solvent green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35, etc.

[0520] CI 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, 156 7, 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;

[0521] CI 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;

[0522] CI 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;

[0523] CI Acid Violet 6B, 7, 9, 15, 16, 17, 19, 21, 23, 24, 25, 30, 34, 38, 49, 72, 102;

[0524] CI 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, 1 26, 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;

[0525] CI 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 CI acid dyes,

[0526] CI 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;

[0527] CI 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;

[0528] CI Direct Orange 26, 34, 39, 41, 46, 50, 52, 56, 57, 61, 64, 65, 68, 70, 96, 97, 106, 107;

[0529] CI Direct Violet 47, 52, 54, 59, 60, 65, 66, 79, 80, 81, 82, 84, 89, 90, 93, 95, 96, 103, 104;

[0530] CI 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, 1 67, 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;

[0531] CI direct green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82 and other CI direct dyes,

[0532] CI Disperse Yellow 51, 54, 76;

[0533] CI Disperse Violet 26, 27;

[0534] CI disperse blue 1, 14, 56, 60 and other CI disperse dyes,

[0535] CI Basic Red 1, 10;

[0536] CI 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;

[0537] CI Basic Violet 2;

[0538] CI Basic Red 9;

[0539] CI basic green 1; etc. CI basic dyes,

[0540] CI Reactive Yellow 2, 76, 116;

[0541] CI Reactive Orange 16;

[0542] CI Reactive Red 36; etc. CI Reactive Dyes,

[0543] CI Medium Yellow 5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

[0544] CI Medium 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;

[0545] CI Medium Orange 3, 4, 5, 8, 12, 13, 14, 20, 21, 23, 24, 28, 29, 32, 34, 35, 36, 37, 42, 43, 47, 48;

[0546] CI medium 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;

[0547] CI Medium 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;

[0548] CI mordant green 1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53 and other CI mordant dyes,

[0549] CI vat green 1 and other CI vat dyes, etc.

[0550] Furthermore, Lumogen (registered trademark), a product of BASF, can be mentioned, including Lumogen (registered trademark) F Yellow 083 (manufactured by BASF), Lumogen (registered trademark) F Yellow 170 (manufactured by BASF), Lumogen (registered trademark) F Orange 240 (manufactured by BASF), and Lumogen (registered trademark) F Red 305 (manufactured by BASF).

[0551] As the pigment, a known pigment can be used, and examples thereof include pigments classified as pigments in the Color Index (published by The Society of Dyer Sand Colourists). These can be used alone or in combination of two or more.

[0552] Specifically, yellow pigments such as CI 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, and 231 are mentioned;

[0553] CI Pigment Orange 13, 31, 36, 38, 40, 42, 43, 51, 55, 59, 61, 64, 65, 71, 73 and other orange pigments;

[0554] CI 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 and other red pigments;

[0555] CI Pigment Blue 15, 15:1, 15:2, 15:3, 15:4, 15:6, 16, 60 and other blue pigments;

[0556] CI Pigment Violet 1, 19, 23, 29, 32, 36, 38 and other purple pigments;

[0557] CI Pigment Green 7, 36, 58, 59, 62, 63 and other green pigments;

[0558] CI Pigment Brown 23, 25 and other brown pigments;

[0559] CI Pigment Black 1, 7, 31, 32 and other black pigments.

[0560] As colorants, there can be mentioned, based on their 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 phthalocyanine halide pigments, zinc phthalocyanine halide pigments, aluminum zinc phthalocyanine halide pigments, and diketopyrrolopyrrole bromide pigments.

[0561] The light absorbing layer (CY) may contain at least one dye or pigment classified as yellow among the above colorants. The colorant contained in the light absorbing layer (CY) is preferably at least one selected from CI Pigment Yellow 185 and 150.

[0562] The first light absorbing layer (C1) may contain at least one dye or pigment of the above colorants classified as red. The colorant contained in the first light absorbing layer (C1) is preferably a red pigment, more preferably CI Pigment Red 177, 254, brominated diketopyrrolopyrrole pigment, etc.

[0563] The second light absorbing layer (C2) may contain at least one dye or pigment of the above coloring agent whose hue is classified as green. The coloring agent contained in the second light absorbing layer (C2) is preferably a combination of a green pigment and a yellow pigment, and more preferably a combination of at least one selected from CI Pigment Green 7, 36, and 58 and CI Pigment Yellow 150.

[0564] The third light absorbing layer (C3) may contain at least one dye or pigment of the above coloring agent whose hue is classified as blue. The coloring agent contained in the third light absorbing layer (C3) is preferably a blue pigment, more preferably CI Pigment Blue 15, 15:3, 15:4, 15:6, 16, 60, and even more preferably CI Pigment Blue 15:6.

[0565] The film thickness (T7) of the first light absorbing layer (C1), the film thickness (T8) of the second light absorbing layer (C2), and the film thickness (T8) of the third light absorbing layer (C3) are not particularly limited and can be appropriately adjusted according to the purpose or use, for example, 0.1 μm to 30 μm, preferably 0.1 μm to 20 μm, and more preferably 0.5 μm to 6 μm.

[0566] The colorant content (W7) in the first light absorbing layer (C1), the colorant content (W8) in the second light absorbing layer (C2), and the colorant content (W9) in the third light absorbing layer (C3) are not particularly limited and can be appropriately adjusted according to the purpose or use, and can be, for example, 0.01% by mass to 99.99% by mass, preferably 0.1% by mass to 99.9% by mass, more preferably 1% by mass to 99% by mass, further preferably 10% by mass to 90% by mass, and particularly preferably 15% by mass to 70% by mass. The colorant content is determined as the mass ratio of the colorant (P) to the total amount of the solid content of the colored curable resin composition (E) described later.

[0567] The product (X7) of the colorant content (W7) [mass %] and the film thickness (T7) [μm] of the first light absorbing layer (C1) (hereinafter also referred to as X7) may be, for example, 0.1 to 3 or 0.2 to 2.

[0568] The product (X8) of the colorant content (W8) [mass %] and the film thickness (T8) [μm] of the second light absorbing layer (C2) (hereinafter also referred to as X8) may be, for example, 0.1 to 3 or 0.2 to 2.

[0569] The product (X9) of the colorant content (W9) [mass %] and the film thickness (T9) [μm] of the third light absorbing layer (C3) (hereinafter also referred to as X9) may be, for example, 0.1 to 3 or 0.2 to 2.

[0570] [Method for producing light absorbing layer (C)]

[0571] The light absorbing layer (C) is, for example, a yellow curable resin composition (Ey), a red curable resin composition (Er), a green curable resin composition (Eg) and a blue curable resin composition (Eb) (hereinafter, also collectively referred to as a colored curable resin composition (E)) to form a yellow pattern, a red pattern, a green pattern and a blue pattern (hereinafter, also collectively referred to as a colored pattern) on a substrate, respectively, thereby manufacturing a light absorbing layer (CY), a first light absorbing layer (C1), a second light absorbing layer (C2), and a third light absorbing layer (C3).

[0572] As a method for forming a colored pattern from a colored curable resin composition (E), there can be mentioned: photolithography, inkjet method, printing method, etc., and preferably photolithography. Photolithography is a method in which a colored curable resin composition (E) is applied to a substrate, dried to form a colored curable resin composition layer, and the colored curable resin composition layer is exposed and developed via a photomask. In the photolithography method, a colored coating film as a cured product of the colored curable resin composition layer can be formed by not using a photomask during exposure and / or not developing. The colored pattern or colored coating film formed by the colored curable resin composition (E) is the light absorbing layer (C) of the present invention.

[0573] As the substrate, a glass plate such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass coated with silicon dioxide on the surface, a resin plate such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, or a substrate having an aluminum, silver, silver / copper / palladium alloy thin film formed thereon can be used. Other light absorbing layers, resin layers, transistors, circuits, etc. can also be formed on these substrates. The substrate can also be included in the light absorbing layer (C).

[0574] Each color and its formation by photolithography can be performed by a known or permitted device and condition. For example, it can be produced as follows.

[0575] First, the colored curable resin composition (E) is applied onto a substrate, and volatile components such as a solvent are removed by heating and drying (prebaking) and / or drying under reduced pressure, and then dried to obtain a smooth colored curable resin composition layer.

[0576] Examples of the coating method include spin coating, slit coating, and slit spin coating.

[0577] The temperature for heating and drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. In addition, the heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. In the case of reduced pressure drying, it is preferably carried out under a pressure of 50Pa to 150Pa and a temperature range of 20°C to 25°C. The film thickness of the colored curable resin composition layer is not particularly limited, and can be appropriately selected according to the film thickness of the target light absorbing layer.

[0578] Next, the colored curable resin composition layer is exposed through a photomask for forming a target colored pattern.

[0579] The pattern on the photomask is not particularly limited, and a pattern corresponding to the target application can be used. As the light source used for exposure, a light source that generates light with a wavelength of 250nm to 450nm is preferred. For example, a filter that cuts off this wavelength range can be used to cut off light less than 350nm, or a bandpass filter that extracts light in the wavelength range near 436nm, 408nm, and 365nm can be used to selectively extract these wavelength ranges. Specific examples of light sources include mercury lamps, light emitting diodes, metal halide lamps, and halogen lamps.

[0580] In order to uniformly irradiate the entire exposure surface with parallel light or accurately align the photomask and the substrate on which the colored curable resin composition layer is formed, it is preferable to use an exposure device such as a mask aligner and a stepper.

[0581] The exposed colored curable resin composition layer is brought into contact with a developer and developed to form a colored pattern on the substrate. By developing, the unexposed portion of the colored curable resin composition layer is dissolved in the developer and removed.

[0582] As the developer, for example, an aqueous solution of an alkaline compound such as potassium hydroxide, sodium hydrogen carbonate, sodium carbonate, or tetramethylammonium hydroxide is preferable.

[0583] The concentration of the basic compound is preferably 0.01% by mass to 10% by mass, and more preferably 0.02% by mass to 5% by mass. The developer may contain a surfactant.

[0584] The developing method may be any of a liquid coating method, an immersion method, a spray method, etc. Furthermore, during the development, the substrate may be tilted at any angle.

[0585] The developed substrate is preferably washed with water.

[0586] Furthermore, it is preferable to post-bake the obtained colored pattern.

[0587] The post-baking temperature is preferably 150° C. to 250° C., more preferably 160° C. to 235° C. The post-baking time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes. In order to impart various properties to the coloring pattern and coloring coating film, i.e., the light absorbing layer obtained in this way, a surface coating treatment may be further applied.

[0588] [Colored curable resin composition]

[0589] The colored curable resin composition (E) contains a resin (F), a polymerizable compound (G) and a polymerization initiator (H) in addition to the above-mentioned colorant (hereinafter also referred to as a colorant (P)). The examples of the resin (F), the polymerizable compound (G) and the polymerization initiator (H) are the same as those in the description of the curable resin composition (D). The colored curable resin composition (E) may further contain at least one selected from a solvent (K), a leveling agent (J) and an antioxidant (I).

[0590] The content of the solid content in the colored curable resin composition (E) is 100% by mass or less relative to the total amount of the colored curable resin composition (E), preferably 0.01% by mass to 100% by mass, more preferably 0.1% by mass to 99.9% by mass, further preferably 0.1% by mass to 99% by mass, further preferably 1% by mass to 90% by mass, further preferably 1% by mass to 80% by mass, particularly preferably 1% by mass to 70% by mass, extremely preferably 1% by mass to 60% by mass, and most preferably 1% by mass to 50% by mass. In this specification, the solid content in the colored curable resin composition (E) refers to the total amount of the components after removing the solvent (K) from the colored curable resin composition (E). The total amount of the solid content and the content of each component relative thereto can be measured using known analytical means such as liquid chromatography or gas chromatography.

[0591] The content of the colorant (P) in the colored curable resin composition can be, for example, 0.01% by mass to 99.99% by mass, preferably 0.1% by mass to 99.9% by mass, more preferably 1% by mass to 99% by mass, further preferably 10% by mass to 90% by mass, and particularly preferably 15% by mass to 70% by mass, based on the total amount of the solid content.

[0592] In the colored curable resin composition (E), the content of the resin (F) is less than 100% by mass, preferably 0.00001% by mass to 99.99999% by mass, more preferably 1% by mass to 99% by mass, further preferably 1% by mass to 97% by mass, further preferably 1% by mass to 95% by mass, further preferably 3% by mass to 90% by mass, particularly preferably 5% by mass to 80% by mass, and extremely preferably 10% by mass to 70% by mass, relative to the total amount of the solid content.

[0593] In the colored curable resin composition (E), the content of the polymerizable compound (G) is less than 100% by mass, preferably 0.00001% by mass to 99.99999% by mass, more preferably 1% by mass to 99% by mass, further preferably 1% by mass to 97% by mass, further preferably 1% by mass to 95% by mass, further preferably 1% by mass to 90% by mass, particularly preferably 2% by mass to 80% by mass, and extremely preferably 3% by mass to 70% by mass, relative to the total amount of the solid content.

[0594] In the colored curable resin composition (E), the content of the polymerization initiator (H) is preferably 0.001 to 60% by mass, more preferably 0.01 to 50% by mass, based on the total amount of the resin (F) and the polymerizable compound (G).

[0595] When using these polymerization initiator aids, the content of the polymerization initiator aids in the colored curable resin composition (E) is preferably 0.00001% by mass to 60% by mass, more preferably 0.0001% by mass to 50% by mass, based on the total amount of the resin (F) and the polymerizable compound (G).

[0596] [Preparation of colorant-containing solution]

[0597] When the colored curable resin composition (E) contains a solvent (K), a colorant-containing solution (Ph) containing a colorant (P) and a solvent (K) may be prepared in advance, and the colored curable resin composition (E) may be prepared using the colorant-containing solution (Ph). When the colorant (A) is insoluble in the solvent (K), the colorant-containing solution (Ph) may be prepared by dispersing the colorant (A) in the solvent (K) and mixing them. The colorant-containing solution (Ph) may contain a part or all of the solvent (K) contained in the colored curable resin composition (E).

[0598] The content of the solid component in the colorant-containing solution (Ph) is less than 100 mass % relative to the total amount of the colorant-containing solution (Ph), preferably 0.01 mass % to 99.99 mass %, more preferably 0.1 mass % to 99.9 mass %, further preferably 0.1 mass % to 99 mass %, further preferably 1 mass % to 90 mass %, further preferably 1 mass % to 80 mass %, particularly preferably 1 mass % to 70 mass %, extremely preferably 1 mass % to 60 mass %, and most preferably 1 mass % to 50 mass %.

[0599] The content of the colorant (P) in the colorant-containing solution (Ph) is 100% by mass or less, preferably 0.0001% by mass to 99.9999% by mass, more preferably 0.0001% by mass to 99% by mass, further preferably 1% by mass to 99% by mass, further preferably 3% by mass to 99% by mass, and further preferably 5% by mass to 99% by mass, based on the total amount of solid components in the colorant-containing solution (Ph).

[0600] The colorant (P) may be subjected to rosin treatment, surface treatment using a colorant (P) derivative having an acidic group or a basic group introduced therein, grafting treatment on the surface of the colorant (P) using a polymer compound, micronization treatment using a sulfuric acid micronization method, etc., washing treatment using an organic solvent or water to remove impurities, removal treatment of ionic impurities using an ion exchange method, etc. The particle size of the colorant (P) is preferably substantially uniform.

[0601] The colorant (P) can be made uniformly dispersed in the colorant-containing solution (Ph) by containing a dispersant and performing a dispersion treatment. The colorant (P) can be dispersed individually or in combination of multiple types.

[0602] As dispersants, surfactants and the like can be mentioned, which can be any of cationic, anionic, nonionic and amphoteric surfactants. Specifically, surfactants such as polyester, polyamine and acrylic acid can be mentioned. These dispersants can be used alone or in combination of two or more. As dispersants, if represented by trade names, they can be mentioned: KP (manufactured by Shin-Etsu Chemical Co., Ltd.), Flowlen (manufactured by Kyoeisha Chemical Co., Ltd.), Solsperse (registered trademark) (manufactured by Zeneca), EFKA (registered trademark) (manufactured by BASF), Ajisper (registered trademark) (manufactured by Ajinomoto Fine-Techno), DISPERBYK (registered trademark) (manufactured by BYK-Chemie), and BYK (registered trademark) (manufactured by BYK-Chemie), etc. Among them, solvent-based pigment dispersants are preferred. As representative commercial products thereof, they can be mentioned:

[0603] BYK-ChemieJapan manufactured 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,; B YK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.;

[0604] 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;

[0605] 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;

[0606] Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Fine-Techno.

[0607] When the colorant-containing solution (P) contains a dispersant, the amount of the dispersant (solid content) used is, for example, 0.01 to 10,000 parts by mass, preferably 0.01 to 5,000 parts by mass, more preferably 0.01 to 1,000 parts by mass, further preferably 0.1 to 500 parts by mass, further preferably 0.1 to 300 parts by mass, still further preferably 1 to 300 parts by mass, and particularly preferably 5 to 260 parts by mass, relative to 100 parts by mass of the colorant (P). When the amount of the dispersant used is within the above range, a colorant-containing solution (A) in a more uniform dispersed state tends to be obtained.

[0608] When a colorant-containing solution (Ph) having a colorant (P) and a solvent (K) is prepared in advance and the colorant-containing solution (Ph) is used to prepare a colored curable resin composition (E), the colorant-containing solution (Ph) may contain a part or all, preferably a part, of the resin (F) contained in the colored curable resin composition (E). By containing the resin (F) in advance, the dispersion stability of the colorant-containing solution (Ph) can be further improved.

[0609] When the colorant-containing solution (Ph) contains a resin (F), the content of the resin (F) is, for example, 0.01 to 10,000 parts by mass, preferably 0.01 to 5,000 parts by mass, more preferably 0.01 to 1,000 parts by mass, further preferably 0.1 to 500 parts by mass, and further preferably 0.1 to 300 parts by mass, relative to 100 parts by mass of the colorant (P).

[0610] The colored curable resin composition may further contain additives known in the art such as a leveling agent (J) and an antioxidant (I), a filler, other polymer compounds, a close contact promoter, a light stabilizer, and a chain transfer agent as needed. The examples of the leveling agent (J) and the antioxidant (I) are the same as those in the description of the curable resin composition (D).

[0611] [Method for producing colored curable resin composition]

[0612] The colored curable resin composition (E) can be prepared by mixing, for example, a colorant (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.

[0613] The mixing can be performed by known or customary means or conditions.

[0614] The colorant (P) is preferably used in the form of a colorant (P) dispersion obtained by mixing the colorant (P) with a part or all of the solvent (K) in advance and dispersing the colorant (P) using a bead mill or the like until the average particle size of the colorant (P) is about 0.2 μm or less. In this case, a part or all of the dispersant and the resin (F) may be mixed as needed.

[0615] The colorant (P) is preferably dissolved in part or all of the solvent (E) to prepare a solution, and the solution is preferably filtered through a filter having a pore size of about 0.01 μm to 1 μm or less.

[0616] It is preferable to filter the mixed colored curable resin composition (E) through a filter having a pore size of about 0.01 μm to 10 μm or less.

[0617] <Reflective film>

[0618] The display device is not particularly limited, and may include a light reflecting member for irradiating light from a light source toward the mixture or the stacked structure.

[0619] The reflective film is not particularly limited, and may include any preferred known material such as a reflective mirror, a film of reflective particles, a reflective metal film, or a reflector.

[0620] <Diffusion film>

[0621] The display device is not particularly limited, and may include a diffusion film for diffusing the light from the light source or the light emitted from the mixture. The diffusion film may be any diffusion film known in the above technical field, such as an amplifying diffusion film.

[0622] <Brightness enhancement section>

[0623] The display device of the present invention is not particularly limited, and may include a brightness enhancement unit that reflects a portion of light in the direction of the transmitted light and returns it.

[0624] <Prism Sheet>

[0625] The prism sheet typically has a substrate portion and a prism portion. It should be noted that the substrate portion can be omitted depending on the adjacent components. The prism sheet can be bonded to the adjacent components via any appropriate bonding layer (for example, an adhesive layer, a bonding agent layer). The prism sheet is composed of a plurality of unit prisms protruding to the opposite side (back side) of the recognition side in parallel. By arranging the convex portion of the prism sheet toward the back side, light passing through the prism sheet becomes easier to focus. In addition, 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 recognition side, light will not be incident on the prism sheet, less light is reflected, and a high-brightness display can be obtained.

[0626] <Light guide plate>

[0627] Any appropriate light guide plate may be used as the light guide plate, for example, a light guide plate having a lens pattern formed on the back side, a light guide plate having a prism shape formed on the back side and / or the recognition side, etc., in order to deflect the light from the lateral direction in the thickness direction.

[0628] <Dielectric material layer between components>

[0629] The display device of the present invention is not particularly limited, but may also include a layer composed of one or more dielectric materials in the optical path between adjacent components (layers). As one or more dielectric materials, for example, it may include vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, curing material, optical bonding material, refractive index matching or refractive index mismatching material, refractive index gradient material, coating or anti-coating material, gasket, silica gel, brightness enhancement material, scattering or diffusion material, reflection or anti-reflection material, wavelength selective material, wavelength selective anti-reflection material or other preferred media known in the above technical field, but it is not limited to these, and it may also have any preferred material.

[0630] Specific examples of display devices include devices including an EL display or a wavelength conversion material for a liquid crystal display. Specifically, the following can be mentioned: a display device in which a wavelength conversion layer (B) is arranged between a blue light source (A) and a light guide plate along an end face (side face) of the light guide plate as a backlight source that emits white light (on-edge backlight source), and a light absorption layer (C) is arranged on the light guide plate side; a display device in which a wavelength conversion layer (B) is arranged on a light guide plate as a backlight source that emits light irradiated from a blue light source (A) placed on the end face (side face) of the light guide plate to the wavelength conversion layer (B) via the light guide plate in the form of white light (surface mounted backlight source), and a light absorption layer (C) is arranged on the wavelength conversion layer (B); a display device in which a quantum dot composition is arranged near the light-emitting portion of a blue light source (A) to form a wavelength conversion layer (B), and the wavelength conversion layer (B) is used as a backlight source that emits the irradiated light in the form of white light (on-chip backlight source), and a light absorption layer (C) is arranged on the wavelength conversion layer (B), etc.

[0631] The display device preferably has a blue light source (A), a wavelength conversion layer (B), and a light absorption layer (C) arranged / laminated in this order in the optical path of light from the blue light source (A).

[0632] Figure 1 is a schematic cross-sectional view of a display device according to an embodiment of the present invention. Figure 1The display device 100 shown 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) 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.

[0633] Figure 2 is a schematic cross-sectional view of a display device according to another embodiment of the present invention. Figure 2 The display device 200 shown has 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 may be the above-mentioned light absorption layer (CY).

[0634] <Film>

[0635] Another embodiment of the present invention is a film containing a compound that absorbs blue and emits green light and satisfies condition (5). As a compound that absorbs blue and emits green light, the above-mentioned illustrative and preferred ranges of the luminescent compound Q1 are applicable. The preferred ranges of thickness T5, content W5 and X5 in condition (5) are applicable to the preferred ranges of T1 and W1 in the above-mentioned condition (1). When the film satisfying condition (5) is used as a wavelength conversion layer emitting green light of a display device, it can have both a wide color gamut and excellent energy efficiency, and is therefore suitable as a wavelength conversion layer of a display device.

[0636] Another embodiment 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 above-mentioned illustrative and preferred ranges of the luminescent compound Q2 are applicable. The preferred ranges of thickness T6, content W6 and X6 in condition (6) are applicable to the preferred ranges of T2 and W2 in the above-mentioned condition (2). When the film satisfying condition (6) is used as a wavelength conversion layer for emitting red in a display device, it can have both a wide color gamut and excellent energy efficiency, and is therefore suitable as a wavelength conversion layer for a display device.

[0637] <Display>

[0638] like Figure 3 As shown, the display 300 of this embodiment has a liquid crystal panel 301 and the above-mentioned display device 100 in order from the recognition side. The liquid crystal panel 301 typically has a liquid crystal unit, a recognition side polarizing plate arranged on the recognition side of the above-mentioned liquid crystal unit, and a back side polarizing plate arranged on the back side of the above-mentioned liquid crystal unit. The display may further have any other appropriate parts.

[0639] <LCD Panel>

[0640] The liquid crystal panel typically includes a liquid crystal cell, a viewing side polarizer disposed on the viewing side of the liquid crystal cell, and a back side polarizer disposed on the back side of the liquid crystal cell. The viewing side polarizer and the back side polarizer may be disposed so that their absorption axes are substantially orthogonal or parallel.

[0641] [Liquid crystal unit]

[0642] 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 structure, a light absorbing layer and a black matrix are provided on one of the substrates, and a switching element for controlling the electro-optical properties of the liquid crystal, a scanning line for providing a gate signal to the switching element, a signal line for providing a source signal, a pixel electrode, and a counter electrode are provided on the other substrate. The spacing (cell gap) of the substrates can be controlled by a spacer or the like. An alignment film, for example, formed of polyimide, can be provided on the side of the substrate that is in contact with the liquid crystal layer.

[0643] [Polarizing plate]

[0644] The polarizing plate typically includes a polarizer and protective layers disposed on both sides of the polarizer. The polarizer is typically an absorption-type polarizer.

[0645] As the polarizer, any appropriate polarizer can be used. Examples include: films obtained by uniaxially stretching a hydrophilic polymer film such as a polyvinyl alcohol film, a partially formalized polyvinyl alcohol film, or a partially saponified film of an ethylene-vinyl acetate copolymer by adsorbing a dichroic substance such as iodine or a dichroic dye; and polyolefin-based oriented films such as a dehydrated product of polyvinyl alcohol or a dehydrochlorinated product of polyvinyl chloride. Among them, a polarizer obtained by uniaxially stretching a polyvinyl alcohol film by adsorbing a dichroic substance such as iodine is particularly preferred because of its high polarization dichroism.

[0646] Example

[0647] The present invention will be described in more detail below with reference to Examples. "%" and "parts" in the Examples refer to mass % and mass parts unless otherwise specified.

[0648] <Measurement of display device>

[0649] For the light emitted from the display device of the embodiment and the comparative example, the chromaticity (x, y) and the emission spectrum were measured in the front (0°) direction relative to the light source using a microscope with a spectrometer (manufactured by OceanOptics) via an optical fiber, with the focus placed on the film surface. Chromaticity (x, y) is the xy color coordinate (x, y) in the XYZ color system of CIE.

[0650] <Measurement of peak wavelength of light source>

[0651] The emission spectrum of the light source is measured by the measuring device used in the measurement of the above-mentioned display device, and the peak wavelength of the light source is read from the measured emission spectrum.

[0652] <Measurement of transmittance (450 nm) of wavelength conversion layer>

[0653] An ultraviolet-visible-near-infrared spectrophotometer (UV-3600; manufactured by Shimadzu Corporation) with an integrating sphere was used. The substrate was measured in the same manner as the method for forming a wavelength conversion layer in Example 1 described later, except that the exposure was not performed through a photomask, and a substrate formed by directly forming a cured film of the curable resin composition used in the examples and comparative examples on a glass substrate was used. The background was obtained through a glass substrate.

[0654] <Measurement of the thickness of the wavelength conversion layer>

[0655] The film thickness was measured using a film thickness measuring device (DEKTAK3; manufactured by Nippon Vacuum Technology Co., Ltd.).

[0656] <Measurement of the luminescence spectrum of luminescent compounds>

[0657] The luminescence spectrum of the quantum dot solution diluted to an Abs value of 0.4 was measured using an absolute PL quantum yield measuring device (manufactured by Hamamatsu Photonics Co., Ltd., trade name C9920-02, excitation light 450nm, room temperature, atmospheric air). The maximum wavelength (λmax) and half-maximum full width were obtained from the obtained luminescence spectrum.

[0658] <Measurement of weight average molecular weight (Mw) and number average molecular weight (Mn)>

[0659] The polystyrene-equivalent weight average molecular weight (Mw) and number average molecular weight (Mn) of the resin (F) were measured by a GPC method under the following conditions.

[0660] Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)

[0661] Column: TSK-GELG2000HXL

[0662] Column temperature: 40°C.

[0663] Solvent: Tetrahydrofuran

[0664] Flow rate: 1.0mL / min

[0665] Solid content concentration of analysis sample: 0.001 mass% to 0.01 mass%

[0666] Injection volume: 50 μL

[0667] Detector: RI

[0668] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0669] The ratio (Mw / Mn) of the polystyrene-equivalent weight average molecular weight (Mw) and the number average molecular weight (Mn) obtained above was defined as the degree of dispersion.

[0670] <Color gamut evaluation value (Y)>

[0671] The area of ​​the overlapping portion of the color gamut enclosed by the coordinates calculated from the xy chromaticity coordinates (x, y) measured in the above “Measurement of the display device” and the color gamut enclosed by the coordinates of BT2020 is set to Y1, and the color gamut enclosed by the coordinates of BT2020 is set to Y2. At this time, the following formula is used:

[0672] Y=(Y1 / Y2)×100

[0673] Figure it out.

[0674] <Efficiency evaluation value (Z)>

[0675] From the light emission spectrum measured according to the above-mentioned “Measurement of Display Device”, the spectral intensity of each of the blue pixel, the green pixel, and the red pixel is calculated according to the following formula.

[0676] Z=[(Zr+Zg+Zb) / 3Zb]×100

[0677] Zb: integrated intensity of blue pixels

[0678] Zg: integrated intensity of green pixels

[0679] Zr: integrated intensity of red pixels

[0680] <Characteristic evaluation value>

[0681] Calculate according to the following formula.

[0682] Characteristic evaluation value = (Y×Z) / 100

[0683] Y: Color gamut evaluation value

[0684] Z: Efficiency evaluation value

[0685] 〔Preparation of blue light source〕

[0686] Blue light source (A1): a blue light emitting diode having a maximum peak wavelength at 445 nm.

[0687] Blue light source (A2): A blue light emitting diode having a maximum peak wavelength at 450 nm.

[0688] [Synthesis Example 1] Resin (F1)

[0689] A flask equipped with a reflux cooler, a dropping funnel and a stirrer was circulated with an appropriate amount of nitrogen gas to replace the nitrogen atmosphere, and 80 parts of propylene glycol monomethyl ether acetate was added and 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 1-[2-(methacryloyloxy)ethyl] succinate in 20 parts of propylene glycol monomethyl ether acetate was added dropwise to the flask over a period of 4 hours. On the other hand, a solution obtained 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 a period of 5 hours. After the addition of the initiator solution was completed, it was kept 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 11500.

[0690] [Synthesis Example 2] Resin (F2)

[0691] A flask equipped with a reflux cooler, a dropping funnel, and a stirrer was circulated with an appropriate amount of nitrogen gas to replace the nitrogen atmosphere, and 371 parts of propylene glycol monomethyl ether acetate was placed, and 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 (containing ratio of 50:50 in molar ratio), and 81 parts of vinyltoluene (isomer mixture) in 80 parts of propylene glycol monomethyl ether acetate was added dropwise to 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 addition of the initiator solution was completed, the temperature was maintained 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.

[0692] [Preparation Example 1] Preparation of quantum dot dispersion (Qh)

[0693] Toluene dispersion of InP / ZnSeS quantum dots (Q1) containing oleic acid as an organic ligand (L): Maximum peak wavelength: 625nm, full width at half maximum: 44nm

[0694] Toluene dispersion of InP / ZnSeS quantum dots (Q2) containing oleic acid as an organic ligand (L): Maximum peak wavelength: 530nm, full width at half maximum: 42nm

[0695] The toluene dispersion of the above-mentioned quantum dots is dried by reduced pressure distillation. After removing the toluene, 70 parts of cyclohexyl acetate (K3) are added to a total of 30 parts of quantum dots (Q) and organic ligands (L) to obtain quantum dot dispersions (Qh-1) and (Qh-2) in Table 1.

[0696] [Table 1]

[0697]

[0698] The ratio of quantum dots (Q) to organic ligands (L) was calculated from the residual amount of the mixture after toluene was removed by TG-DTA measurement and heated to 550° C. at a heating rate of 5° C. / min.

[0699] [Preparation Example 2] Curable resin composition (D)

[0700] For the quantum dot dispersion (Qh), the components of Tables 2 and 3 were 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 the components other than the solvent (K) represents the solid content conversion value.

[0701] [Table 2]

[0702]

[0703] [Table 3]

[0704]

[0705] Light scattering agent (S1): 10 parts by mass (in terms of solid content) of the resin (F1) and 30 parts by mass of PGMEA in total were mixed with 60 parts of titanium oxide particles, and the titanium oxide particles were fully dispersed using a bead mill.

[0706] Polymerizable compound (G1): polyacid-modified acrylic oligomer (trade name: M-510, manufactured by Toagosei Co., Ltd.)

[0707] Polymerization initiator (H1): IRGACURE (registered trademark) OXE-02: manufactured by BASF

[0708] Antioxidant (I1): Sumilizer GP: manufactured by Sumitomo Chemical Co., Ltd.

[0709] Leveling agent (J1): Toray Silicone SH8400: Toray manufactured by Dow Corning Corporation

[0710] Solvent (K1): Propylene glycol monomethyl ether acetate (PGMEA)

[0711] [Adjustment Example 3] Pigment dispersion (Ph)

[0712] The components shown in Table 4 were mixed and the pigment was sufficiently dispersed using a bead mill to prepare pigment dispersions (Ph-1) to (Ph-7).

[0713] [Table 4]

[0714]

[0715] Pigment (P1): CI Pigment Red 254

[0716] Pigment (P2): CI Pigment Red 177

[0717] Pigment (P3): CI Pigment Yellow 185

[0718] Pigment (P4): CI Pigment Yellow 150

[0719] Pigment (P5): CI Pigment Green 58

[0720] Pigment (P6): CI Pigment Green 36

[0721] Pigment (P7): CI Pigment Green 7

[0722] Pigment dispersant: solvent-based pigment dispersant

[0723] Resin (F3): Methacrylic acid / benzyl methacrylate copolymer (copolymerization ratio (mass ratio): 30 / 70, M w :1.2×10 4

[0724] Solvent (K2): Propylene glycol 1-monomethyl ether (PGME)

[0725] [Preparation Example 4] Colored curable resin composition (E)

[0726] The components shown in Table 5 were mixed to obtain colored curable resin compositions (Er) and (Eg) for forming a light absorbing layer. In Table 5, the number of parts of the resin indicates a value converted into solid content.

[0727] Table 5

[0728]

[0729] Polymerizable compound (G2): dipentaerythritol hexaacrylate, trade name: KAYARAD (registered trademark) DPHA: manufactured by Nippon Kayaku Co., Ltd.

[0730] Polymerization initiator (H2): N-benzoyloxy 1-(4-phenylthiophenyl) octan-1-one-2-imide, trade name: Irgacure (registered trademark) OXE-01: manufactured by BASF

[0731] Leveling agent (J2): polyether-modified silicone oil, trade name: Toray Silicone SH8400, manufactured by Toray DowCorning Corporation

[0732] <Example 1>

[0733] A colored curable resin composition (E-r1) for forming a light absorbing layer was applied to a 5 cm square glass substrate (Eagle 2000; manufactured by Corning Corporation) by spin coating, and then pre-baked at 100°C for 3 minutes to form a red curable resin composition layer. The substrate on which the red curable resin composition layer was formed was exposed to light at 100 mJ / cm2 in an atmospheric environment using an exposure machine (TME-150RSK; manufactured by Topcon Corporation). 2 The first light absorbing layer (C1) was prepared by irradiating with light at an exposure amount (365 nm reference), developing, and then post-baking at 230°C for 20 minutes to obtain a cured film. The cured film was used as the first light absorbing layer (C1). Similarly, on the substrate having the first light absorbing layer (C1), a second light absorbing layer (C2) was prepared using the colored curable resin composition (E-g1).

[0734] Next, the curable resin composition (D-r2) was used on the substrate and the exposure amount was changed to 500 mJ / cm 2 The first wavelength conversion layer (B1) was prepared on the first light absorbing layer (C1) in the same manner as the above-mentioned method for preparing the first light absorbing layer, except that the post-baking was changed to 180°C for 60 minutes. Similarly, the second wavelength conversion layer (B2) was prepared on the second light absorbing layer (C2) using the curable resin composition (D-g2).

[0735] The display device was manufactured under the display device manufacturing conditions shown in Table 6. The above substrate was arranged on a blue light source (A) in such a manner that the first light absorbing layer (C1) was arranged on the first wavelength conversion layer (B1), and the second light absorbing layer (C2) was arranged on the second wavelength conversion layer (B2). The evaluation results are shown in Table 7.

[0736] <Example 2 to Example 12 and Comparative Example 1 and Comparative Example 2>

[0737] A display device was produced in the same manner as in Example 1 except that the materials and film thicknesses were set as shown in Table 6. Table 7 shows the evaluation results.

[0738]

[0739]

[0740] In the display device produced in the example, full-color display can be performed by independently driving the LED elements of the light source.

Claims

1. A film comprising a compound Q1 that absorbs blue light and emits red light and satisfies the following condition (5): (5)0.7≤X5； in, X5 is the 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, that is, X5=(T5×W5) / 100; Furthermore, it further contains a light scattering agent S and satisfies the following condition (3): (3)X3≤1.6； in, 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, that is, X3=(T1×W3) / 100.

2. The film according to claim 1, wherein The compound Q1 includes at least one selected from the group consisting of indium compounds and cadmium compounds.

3. A film comprising a compound Q2 that absorbs blue and emits green light and satisfies the following condition (6): (6)0.7≤X6； in, X6 is the 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, that is, X6=(T6×W6) / 100; Furthermore, it further contains a light scattering agent S and satisfies the following condition (4): (4)X4≤1.6； in, 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, that is, X4=(T2×W4) / 100.

4. The film according to claim 2, wherein The compound Q2 includes at least one selected from indium compounds and cadmium compounds.

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