WO2024185878A1

WO2024185878A1 - Composition, laminate, and display device

Info

Publication number: WO2024185878A1
Application number: PCT/JP2024/008980
Authority: WO
Inventors: 真芳 ▲徳▼田; 崇夫土谷; 崇弘石原; 直優北川
Original assignee: 住友化学株式会社
Priority date: 2023-03-08
Filing date: 2024-03-08
Publication date: 2024-09-12

Abstract

Provided is a composition capable of forming a protective layer for a wavelength conversion layer , the protective layer reducing film loss during development and providing an excellent remaining film percentage. The present invention is a composition containing neither semiconductor particles (A) nor colorant (I), wherein the composition contains a photostabilizer (F) as well as a resin (C), and the resin (C) contains a resin (C-1) having a weight average molecular weight Mw of 10,000 or less. The resin (C-1) preferably has an acid value of 110 mg KOH/g or less.

Description

Composition, laminate and display device

The present invention relates to a composition, a laminate, and a display device including the laminate.

Patent Document 1 describes a curable resin composition containing quantum dots, and a wavelength conversion film formed using the curable resin composition.

JP 2016-065178 A

In some cases, a protective layer is formed in a pattern on a wavelength conversion layer that contains luminescent inorganic semiconductor particles such as quantum dots, but the remaining film rate of the protective layer during the development process is sometimes insufficient.

One object of the present invention is to provide a composition capable of forming a protective layer for a wavelength conversion layer, which reduces film loss during development and has an excellent film remaining rate. Another object of the present invention is to provide a laminate including a wavelength conversion layer, a protective layer for the wavelength conversion layer having an excellent film remaining rate, and further a light absorbing layer, and a display device including the laminate.

The present invention which achieves the above object is as follows.
[1] A composition containing neither semiconductor particles (A) nor a colorant (I),
The composition contains a resin (C) and a light stabilizer (F),
The resin (C) is a composition containing a resin (C-1) having a weight average molecular weight Mw of 10,000 or less.
[2] The composition according to [1], wherein the acid value of the resin (C-1) is 110 mg KOH / g or less.
[3] The composition further comprises a polymerizable compound (D),
The composition according to [1] or [2], wherein a mass ratio of the resin (C-1) to the polymerizable compound (D) (resin (C-1)/polymerizable compound (D)) is 1.8 or less.
[4] The composition according to any one of [1] to [3], which is used for forming a protective layer to be placed on a wavelength conversion layer containing semiconductor particles (A).
[5] A wavelength conversion layer having semiconductor particles (A);
and a protective layer formed from the composition according to any one of [1] to [4] and disposed on the wavelength conversion layer.
[6] A laminate including a wavelength conversion layer having semiconductor particles (A), a protective layer, and a light absorbing layer,
The protective layer is a laminate which is a layer formed from a composition which does not contain any of semiconductor particles (A) and colorant (I), and which contains a resin (C) and further contains a light stabilizer (F), the resin (C) containing a resin (C-1) having a weight average molecular weight Mw of 10,000 or less.
[7] A display device comprising the laminate according to [5] or [6].

The composition of the present invention contains a resin (C-1) with a weight-average molecular weight Mw of 10,000 or less, and therefore can form a protective layer with excellent film remaining rate during development. The laminate of the present invention also has the above-mentioned effect of the protective layer, that is, excellent film remaining rate during development. Furthermore, the composition and laminate of the present invention contain a light stabilizer, and therefore can suppress the decrease in luminescence intensity of the wavelength conversion layer due to heat.

FIG. 1 is a schematic cross-sectional view showing an example of a laminate according to the present invention. FIG. 2 is a schematic cross-sectional view showing another example of the laminate according to the present invention. FIG. 4 is a schematic cross-sectional view showing still another example of the laminate according to the present invention. FIG. 4 is a schematic cross-sectional view showing still another example of the laminate according to the present invention. 1 is a schematic cross-sectional view showing an example of a display device according to the present invention.

The wavelength conversion layer in a display device is a layer that absorbs primary light from a primary light source and emits wavelength-converted (color-converted) light. The composition of the present invention can be used to form a protective layer to be placed on the wavelength conversion layer, and has an excellent film remaining rate during development. The composition of the present invention can also suppress deterioration of the wavelength conversion layer due to heat. In a display device including a wavelength conversion layer, in order to solve the problem that a portion of the primary light irradiated to the wavelength conversion layer passes through the wavelength conversion layer and leaks to the viewing side, preventing the display device from having a wide color gamut, it is preferable to place a light absorbing layer on the wavelength conversion layer that absorbs the primary light that has passed through the wavelength conversion layer.

In this document, the composition used to form the wavelength conversion layer is referred to as "composition I," the composition of the present invention that is preferably used to form a protective layer to be placed on the wavelength conversion layer is referred to as "composition II," and the composition capable of forming a light absorbing layer is referred to as "composition III."

Composition II of the present invention is a composition containing neither semiconductor particles (A) nor colorant (I) and is preferably used for a protective layer to be placed on a wavelength converting layer. The protective layer can be formed by applying composition II onto the wavelength converting layer and curing it.
Composition II contains a resin (C), and further contains a resin (C-1) having a weight average molecular weight Mw of not more than 10,000. By containing such a resin (C-1), the residual film rate of a layer formed from composition II during development can be improved.
The composition II contains a light stabilizer (F). The present inventors have found that by incorporating the light stabilizer (F) in the composition II capable of forming a protective layer, rather than in the composition I that forms the wavelength conversion layer itself, the deterioration of the luminescence characteristics of the wavelength conversion layer due to heat can be suppressed.

The phrase "Composition II does not contain semiconductor particles (A) and colorant (I)" means that the content of semiconductor particles (A) or colorant (I) is preferably 1 mass % or less, more preferably 0.5 mass % or less, even more preferably 0.1 mass % or less, and particularly preferably 0 mass %, respectively, relative to the total amount of solids in Composition II.

In this specification, the content or percentage of each component means the total content or percentage of the components when two or more types of the component are included. Furthermore, the total amount of solids in the composition means the total of the components contained in the composition excluding the solvent (J). The content in the solids of the composition can be measured by known analytical means such as liquid chromatography or gas chromatography. The content of each component in the solids of the composition may be calculated from the blending when the composition is prepared.

The composition II contains a light stabilizer (F), which can suppress deterioration of the wavelength conversion layer due to heat. The composition II preferably contains at least one light stabilizer (F), and more preferably contains at least one of the antioxidant (Fb) and ultraviolet absorber (Fc) described below among the light stabilizers (F). When the composition II contains at least one of the antioxidant (Fb) and ultraviolet absorber (Fc), only one of them may be contained, or both the antioxidant (Fb) and the ultraviolet absorber (Fc) may be contained. From the viewpoint of suppressing deterioration of the luminescence intensity of the wavelength conversion layer, it is preferable to contain both the antioxidant (Fb) and the ultraviolet absorber (Fc). In a preferred embodiment, the total content of the antioxidant (Fb) and the ultraviolet absorber (Fc) is preferably 0.5% by mass or more, more preferably 0.9% by mass or more, even more preferably 2% by mass or more, particularly preferably 4% by mass or more, and may be 10% by mass or less, or may be 8% by mass or less, based on the total amount of solids in the composition II. The content of the antioxidant (Fb) is preferably 0.5% by mass or more, more preferably 0.9% by mass or more, even more preferably 2% by mass or more, particularly preferably 4% by mass or more, and may be 8% by mass or less or 6.5% by mass or less, based on the total amount of solids in the composition II. The content of the ultraviolet absorber (Fc) is preferably 0.5% by mass or more, more preferably 0.9% by mass or more, and may be 3% by mass or less or 2% by mass or less, based on the total amount of solids in the composition II.

In composition II, the antioxidant (Fb) is preferably a phosphorus/phenol complex type antioxidant and/or a phenol-based antioxidant, more preferably a phosphorus/phenol complex type antioxidant, and the ultraviolet absorber (Fc) is preferably a benzotriazole-based compound.

Composition II preferably does not contain an organic ligand (G). When composition II "does not contain an organic ligand (G)," this means that the content of organic ligand (G) relative to the total amount of solids in composition II is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, and particularly preferably 0 mass%.

The resin (C) in composition II contains a resin (C-1) having a weight average molecular weight Mw of 10,000 or less. The content of the resin (C-1) in the resin (C) in composition II is preferably 80 mass% or more, more preferably 90 mass% or more, and most preferably 100 mass%. The weight average molecular weight Mw of the resin (C-1) is more preferably 9,500 or less, even more preferably 9,000 or less, and the lower limit is not particularly limited, but may be, for example, 4,000 or 6,500.

The acid value of resin (C-1) is preferably 110 mgKOH/g or less, which can improve the residual film rate during development for the cured film of composition II, and preferably can further improve both the residual film rate and the development speed. In addition, the acid value of resin (C-1) is preferably 30 mgKOH/g or more, more preferably 40 mgKOH/g or more, and even more preferably 50 mgKOH/g or more.

The double bond equivalent of resin (C-1) is preferably 300 g/eq or more and 1500 g/eq or less, and more preferably 330 g/eq or more and 1000 g/eq or less. The double bond equivalent can be calculated by dividing the total mass of the resin by the number of moles of radically polymerizable double bonds introduced into the resin.

Furthermore,
The composition II may contain a polymerizable compound (D).
Composition II may contain a polymerization initiator (E).
Composition II may contain a polymerization initiation aid (Eα).
Composition II may contain a solvent (J).
Composition II may contain a leveling agent (H).
Composition II preferably does not contain an organic ligand (G).

The mass ratio of resin (C-1) to polymerizable compound (D) (resin (C-1)/polymerizable compound (D)) is preferably 1.8 or less, more preferably 1.7 or less, and also preferably 0.5 or more, more preferably more than 1.0. By adjusting the mass ratio in this way, the residual film rate at the time of development of the cured film of composition II can be further improved, and preferably both the residual film rate and the development speed can be further improved.

The polymerizable compound (D) preferably has a functional group number of 2 or more, more preferably 3 or more, and the upper limit may be 6. The functional group is preferably an ethylenically unsaturated bond.

In composition II, resin (C) contains resin (C-1), and by adjusting the acid value of resin (C-1) and the mass ratio of resin (C-1) to polymerizable compound (D) within the above range, the residual film rate at the time of development of the cured film of composition II can be further improved, and preferably both the residual film rate and the development speed can be further improved.

In composition II, the mass ratio of the polymerizable compound (D) to the polymerization initiator (E) (polymerizable compound (D)/polymerization initiator (E)) is preferably 40 or more, more preferably 60 or more, and even more preferably 80 or more. The mass ratio of the polymerizable compound (D) to the polymerization initiator (E) (polymerizable compound (D)/polymerization initiator (E)) is preferably 140 or less, more preferably 120 or less, and even more preferably 100 or less.

The development speed of the cured film of Composition II can be 0.04 μm/sec or more, preferably 0.05 μm/sec or more, and more preferably 0.06 μm/sec or more, with no particular upper limit, but which may be 0.15 μm/sec. Furthermore, the remaining film rate when the cured film of Composition II is developed can be 70% or more, preferably 80% or more, with no particular upper limit, with 100% being ideal, but 99% or less being acceptable. The development speed and remaining film rate can be measured according to the measurement methods described in the Examples section below.

Composition I is a composition containing semiconductor particles (A) and is suitably used for forming a wavelength conversion layer.
Composition I may contain an organic ligand (G).
Composition I may also contain a white colorant (Iw).
The composition I may contain a resin (C).
The composition I may contain a polymerizable compound (D).
The composition I may contain a polymerization initiator (E).
Composition I may contain a polymerization initiation aid (Eα).
Composition I may contain a light stabilizer (F).
Composition I may contain a solvent (J).
Composition I may contain a leveling agent (H).

Composition III is a composition containing a colorant (I) (particularly a chromatic colorant (Ic)), and is suitably used for forming a light absorbing layer.
Composition III may contain a resin (C).
Composition III may contain a polymerizable compound (D).
Composition III may contain a polymerization initiator (E).
Composition III may contain a polymerization initiator coagent (Eα).
Composition III may also contain a light stabilizer (F).
Composition III may contain a solvent (J).
Composition III may contain a leveling agent (H).

The following explanation of each component can be applied to any of Composition I, Composition II, and Composition III, except where the explanation is limited to a specific composition.

<Semiconductor particles (A)>
The semiconductor particles (A) are preferably luminescent inorganic semiconductor particles that absorb primary light and emit light of a wavelength different from the primary light, and it is more preferable that the luminescent inorganic semiconductor particles absorb the primary light and emit green or red light, and it is even more preferable that the wavelength of the blue light, which is the primary light, is converted to the wavelength of red light or the wavelength of green light.

In this specification, "blue" refers to all light that is perceived as blue (all light having intensity in the blue wavelength range, e.g., 380 nm to 495 nm), and is not limited to light of a single wavelength. "Green" refers to all light that is perceived as green (all light having intensity in the green wavelength range, e.g., 495 nm to 585 nm), and is not limited to light of a single wavelength. "Red" refers to all light that is perceived as red (all light having intensity in the red wavelength range, e.g., 585 nm to 780 nm), and is not limited to light of a single wavelength. "Yellow" refers to all light that is perceived as yellow (all light having intensity in the yellow wavelength range, e.g., 560 nm to 610 nm), and is not limited to light of a single wavelength.

The emission spectrum of the green-emitting semiconductor particles (A) preferably includes a peak having a maximum value in the wavelength range of 500 nm to 560 nm, more preferably includes a peak having a maximum value in the wavelength range of 520 nm to 545 nm, and even more preferably includes a peak having a maximum value in the wavelength range of 525 nm to 535 nm. This can further improve the emission intensity of green light from the display device. The peak preferably has a full width at half maximum of 15 nm to 80 nm, more preferably 15 nm to 60 nm, even more preferably 15 nm to 50 nm, and particularly preferably 15 nm to 45 nm. This can further improve the emission intensity of green light from the display device.

The emission spectrum of the semiconductor particles (A) emitting red light preferably includes a peak having a maximum value in a wavelength range of 610 nm to 750 nm, more preferably includes a peak having a maximum value in a wavelength range of 620 nm to 650 nm, and even more preferably includes a peak having a maximum value in a wavelength range of 625 nm to 645 nm. This can further improve the emission intensity of red light from the display device. The peak preferably has a full width at half maximum of 15 nm to 80 nm, more preferably 15 nm to 60 nm, even more preferably 15 nm to 50 nm, and particularly preferably 15 nm to 45 nm. This can further improve the emission intensity of red light from the display device.
The emission spectrum of the semiconductor particles (A) is measured according to the method described in the Examples section below.

The semiconductor particles (A) include quantum dots and particles composed of a compound having a perovskite crystal structure (hereinafter also referred to as a "perovskite compound"), with quantum dots being preferred. Quantum dots are luminescent semiconductor particles with a particle diameter of 1 nm to 100 nm, which utilize the band gap of the semiconductor to absorb ultraviolet light or visible light (e.g., blue light) and emit light.

Quantum dots include, for example, CdS, CdSe, CdTe, ZnS, ZnSe, ZnTe, HgS, HgSe, HgTe, CdHgTe, CdSeS, CdSeTe, CdSTe, ZnSeS, ZnSeTe, ZnSTe, HgSeS, HgSeTe, HgSTe, CdZnS, CdZnSe, CdZnTe, CdHgS, CdHgSe, CdHgTe, HgZnS, HgZnSe, HgZnTe, CdZnSeS, CdZnSeTe, CdZnSTe, CdHgSeS, CdHgSeTe, CdHgSTe, HgZnSeS, HgZ Compounds of Group 12 elements and Group 16 elements such as nSeTe and HgZnSTe; compounds of Group 13 elements and Group 15 elements such as GaN, GaP, GaAs, AlN, AlP, AlAs, InN, InP, InAs, GaNP, GaNAs, GaPAs, AlNP, AlNAs, AlPAs, InNP, InNAs, InPAs, GaAlNP, GaAlNAs, GaAlPAs, GaInNP, GaInNAs, GaInPAs, InAlNP, InAlNAs, InAlPAs; compounds of Group 14 elements and Group 16 elements such as PdS and PbSe.

When the quantum dots contain S or Se, quantum dots whose surface is modified with a metal oxide or an organic substance may be used. By using surface-modified quantum dots, it is possible to prevent S or Se from being extracted by reactive components that are or may be contained in composition I.

The quantum dots may also be formed into a core-shell structure by combining the above compounds. Examples of such combinations include particles with a CdSe core and a ZnS shell, and particles with an InP core and a ZnSeS shell.

Since the energy state of quantum dots depends on their size, it is possible to freely select the emission wavelength by changing the particle diameter. In addition, the light emitted from quantum dots has a narrow spectral width, which is advantageous for widening the color gamut of display devices. Furthermore, quantum dots have high responsiveness, which is also advantageous in terms of the efficiency of using primary light.

The perovskite compound is a compound that has a perovskite crystal structure and is composed of A, B, and X.

A is a monovalent cation that is located at each vertex of a hexahedron with B at the center in the perovskite crystal structure.

X represents a component located at each vertex of an octahedron with B at the center in the perovskite crystal structure, and is at least one type of ion selected from the group consisting of halide ions and thiocyanate ions.

B is a component located at the center of a hexahedron with A at its vertex and an octahedron with X at its vertex in the perovskite crystal structure, and is a metal ion.

The perovskite compound having components A, B, and X is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a pseudo-two-dimensional structure.

In the case of a three-dimensional structure, the perovskite compound is represented as ABX _(3+δ) .

In the case of a two-dimensional structure, the perovskite compound is represented by A ₂ BX _(4+δ) .

Here, δ is a number that can be changed as appropriate depending on the charge balance of B, and is between -0.7 and 0.7.

Preferable specific examples of perovskite compounds having a three-dimensional perovskite-type crystal structure represented by ABX _(3+δ) include:
CH ₃ NH ₃ PbBr ₃ , CH ₃ NH ₃ PbCl ₃ , CH ₃ NH ₃ PbI ₃ , CH ₃ NH ₃ PbBr _(3-y) I _y (0<y<3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0<y<3), (H ₂ N =CH-NH ₂ )PbBr ₃ , (H ₂ N=CH-NH ₂ )PbCl ₃ , (H ₂ N=CH-NH ₂ )PbI ₃ ,
CH ₃ NH ₃ Pb _(1-a) Ca _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Sr _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) La _a Br _(3+δ) (0<a≦0.7, 0<δ ≦0.7), CH ₃ NH ₃ Pb _(1-a) Ba _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Dy _a Br _(3+δ) (0<a≦0.7, 0<δ≦0.7),
CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0),
CsPb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), CsPb _(1-a) Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0),
CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) I _y (0<a≦0.7, -0.7≦δ<0 ,0<y<3), CH ₃ NH ₃ Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Li _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<3),
(H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Li _a Br _(3+δ) (0<a≦0.7, -0.7≦δ<0), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<3), (H ₂ N=CH-NH ₂ )Pb _(1-a) Na _a Br _(3+δ-y) Cl _y (0<a≦0.7, -0.7 ≦δ<0, 0<y<3),
CsPbBr ₃ , CsPbCl ₃ , CsPbI ₃ , CsPbBr _(3-y) I _y (0<y<3), CsPbBr _(3-y) Cl _y (0<y<3), CH ₃ NH ₃ PbBr _(3-y) Cl _y (0<y<3),
CH ₃ NH ₃ Pb _(1-a) Zn _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0≦δ≦0.7), CH ₃ NH ₃ Pb _(1-a) Co _a Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) _Mna Br ₃ (0<a≦0.7), CH ₃ NH ₃ Pb _(1-a) _Mga Br ₃ (0<a≦0.7),
CsPb _(1-a) Zn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Al _a Br _(3+δ) (0<a≦0.7, 0<δ≦0.7), CsPb _(1-a) Co _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mn _a Br ₃ (0<a≦0.7), CsPb _(1-a) Mg _a Br ₃ (0<a≦0.7),
CH ₃ NH ₃ Pb _(1-a) Zna _Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) I _y (0<a≦0.7, 0<δ≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mg _a B r _(3-y) I _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) _Zna Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Al _a Br _(3+δ-y) Cl _y (0<a≦0. 7,0<δ≦0.7,0<y<3), CH ₃ NH ₃ Pb _(1-a) Co _a Br _(3+δ-y) Cl _y (0<a≦0.7, 0<y<3), CH ₃ NH ₃ Pb _(1-a) Mn _a Br _(3-y) Cl _y (0<a≦0.7 _, 0<y< 3), _CH3NH3Pb _(1-a) Mg _a Br _(3-y) Cl _y (0<a≦0.7, 0<y<3),
(H ₂ N=CH-NH ₂ )Zna _Br ₃ (0<a≦0.7), (H ₂ N=CH-NH ₂ ) _Mga Br ₃ (0<a≦0.7), (H ₂ N=CH-NH ₂ )Pb _(1-a) Zna _Br _(3-y) I _y (0<a ≦0.7, 0<y<3), (H ₂ N=CH—NH ₂ )Pb _(1-a) _Zna Br _(3-y) Cl _y (0<a≦0.7, 0<y<3), and the like.

Preferable specific examples of the perovskite compound having a two-dimensional perovskite-type crystal structure represented by A ₂ BX _(4+δ) include:
( _C4H9NH3 )2PbBr4, (C4H9NH3) _{2PbCl4, (C4H9NH3)2PbI4, (C7H15NH3)2PbBr4, (C7H15NH3)2 PbCl 4 , (C 7 H 15} _{NH 3} ₎ ₂ _PbI ₄ _, ₍ _C ₄ _H ₉ _NH ₃ ₎ ₂ _Pb ₍ ₁ _- _a ₎ _Li _a _Br ₍ _4+δ) (0 _< _a ≦0.7, -0.7 _≦ _δ < ₀ _{), (C 4} _H ₉ _NH ₃ ) ₂ Pb _(1- _a ₎ _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ) (0<a≦0.7, -0.7≦δ<0), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) r _(4+δ) (0<a≦0.7, -0.7≦δ<0),
(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) I _y (0<a ≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) I _y (0<a≦0.7, -0.7≦δ<0, 0<y<4),
(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Na _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Li _a Br _(4+δ-y) Cl _y (0<a ≦0.7, -0.7≦δ<0, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Rb _a Br _(4+δ-y) Cl _y (0<a≦0.7, -0.7≦δ<0, 0<y<4),
(C ₄ H ₉ NH ₃ ) ₂ PbBr ₄ , (C ₇ H ₁₅ NH ₃ ) ₂ PbBr ₄ ,
(C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) Cl _y (0<y<4), (C ₄ H ₉ NH ₃ ) ₂ PbBr _(4-y) I _y (0<y<4),
(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) _Zna Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) C _{o a} Br ₄ (0<a≦0.7), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) _Mna Br ₄ (0<a≦0.7),
(C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) _Zna Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) Mg _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _{(1-a )} Co _a Br ₄ (0<a≦0.7), (C ₇ H ₁₅ NH ₃ ) ₂ Pb _(1-a) _Mna Br ₄ (0<a≦0.7),
(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zna _Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), ( C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) I _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) I _y (0<a≦0.7, 0<y<4),
(C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Zna _Br _(4-y) Cl _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mg _a Br _(4-y) Cl _y (0<a≦0.7, 0<y<4) , (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Co _a Br _(4-y) Cl _y (0<a≦0.7, 0<y<4), (C ₄ H ₉ NH ₃ ) ₂ Pb _(1-a) Mn _a Br _(4-y) Cl _y (0<a≦0.7, 0<y<4), etc. Can be mentioned.

The semiconductor particles (A) that absorb primary light and emit green light can be used alone or in combination of two or more kinds. The semiconductor particles (A) that absorb primary light and emit red light can be used alone or in combination of two or more kinds.

As described above, composition II does not contain semiconductor particles (A). Composition III also does not substantially contain semiconductor particles (A), and the content of semiconductor particles (A) relative to the total amount of solids in composition III is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, and particularly preferably 0 mass%.

The content of semiconductor particles (A) in composition I is, for example, 1% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, more preferably 15% by mass or more and 50% by mass or less, even more preferably 20% by mass or more and 50% by mass or less, and even more preferably 25% by mass or more and 45% by mass or less, based on the total amount of solids in composition I.

<Organic ligand (G)>
The semiconductor particles (A) may be present in the composition in a state where the organic ligand (G) is coordinated to the semiconductor particles (A). The organic ligand (G) can be coordinated to the surface of the semiconductor particle (A), for example. The composition contains one or more organic ligands. It may contain a ligand (G).

It is preferable that at least some of the molecules of the organic ligand (G) are coordinated to the semiconductor particles (A), and all or almost all of the molecules may be coordinated to the semiconductor particles (A). The inclusion of organic ligand (G) coordinated to the semiconductor particles (A) can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer.

The polar group of the organic ligand (G) is, for example, at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH ₂ ). A polar group selected from this group can be advantageous in increasing the coordination ability to the semiconductor particles (A). High coordination ability can contribute to improving the stability and dispersibility of the semiconductor particles (A) in the composition, as well as improving the luminescence intensity of the wavelength conversion layer. Among them, it is more preferable that the polar group is at least one group selected from the group consisting of a thiol group and a carboxy group. The organic ligand (G) can have one or more polar groups.

The organic ligand (G) is, for example, a compound represented by the following formula (x):
XA- ^RX ⁽ x)
In the formula, X ^{1 A} is the polar group described above, and R ^{1 X} is a monovalent hydrocarbon group which may contain a heteroatom (N, O, S, a halogen atom, etc.). The hydrocarbon group may have one or more unsaturated bonds such as a carbon-carbon double bond. The hydrocarbon group may have a linear, branched, or cyclic structure. The number of carbon atoms in the hydrocarbon group is, for example, 1 to 40, and may be 1 to 30. The methylene group contained in the hydrocarbon group may be substituted with -O-, -S-, -C(═O)-, -C(═O)-O-, -O-C(═O)-, -C(═O)-NH-, -NH-, etc.

The group R 1 ^X may contain a polar group, specific examples of which are given in the above description of the polar group X 1 ^A.

Specific examples of organic ligands having a carboxyl group as the polar group ^XA include formic acid, acetic acid, and propionic acid, as well as saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, pentanoic acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecylic acid, palmitic acid, margaric acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, icosenoic acid, erucic acid, and nervonic acid; and polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, stearic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenic acid (docosatetraenoic acid).

Specific examples of the organic ligand having a thiol group or an amino group as the polar group ^XA include organic ligands in which the carboxy group of the organic ligand having a carboxy group as the polar group ^XA exemplified above is replaced with a thiol group or an amino group.

In addition to the above, examples of organic ligands represented by the above formula (x) include compound (G-1) and compound (G-2).

[Compound (G-1)]
The compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxy group (-COOH), and the second functional group is a carboxy group or a thiol group (-SH The compound (G-1) has a carboxy group and/or a thiol group, and therefore can serve as a ligand that coordinates with the semiconductor particles (A). ) may be contained alone or in combination with one or more of them.

An example of compound (G-1) is a compound represented by the following formula (G-1a). Compound (G-1) may be an acid anhydride of the compound represented by formula (G-1a).

[In the formula, R 3 ^B represents a divalent hydrocarbon group. When a plurality of R 3 ^B are present, they may be the same or different. The hydrocarbon group may have one or more substituents. When a plurality of substituents are present, they may be the same or different and may be bonded to each other to form a ring together with the atom to which they are bonded. -CH ₂ - contained in the hydrocarbon group may be replaced by at least one of -O-, -S-, -SO ₂ -, -CO- and -NH-.

p represents an integer of 1 to 10.
Examples of the divalent hydrocarbon group represented by R 3 ^B include chain hydrocarbon groups, alicyclic hydrocarbon groups, aromatic hydrocarbon groups, and groups formed by combining these groups.

Examples of chain hydrocarbon groups include linear or branched alkanediyl groups, which usually have 1 to 50 carbon atoms, preferably 1 to 20, and more preferably 1 to 10. Examples of alicyclic hydrocarbon groups include monocyclic or polycyclic cycloalkanediyl groups, which usually have 3 to 50 carbon atoms, preferably 3 to 20, and more preferably 3 to 10. Examples of aromatic hydrocarbon groups include monocyclic or polycyclic arenediyl groups, which usually have 6 to 20 carbon atoms.

Examples of the substituents that the above-mentioned hydrocarbon group may have include an alkyl group having 1 to 50 carbon atoms, a cycloalkyl group having 3 to 50 carbon atoms, an aryl group having 6 to 20 carbon atoms, a carboxy group, an amino group, a halogen atom, etc. The substituents that the above-mentioned hydrocarbon group may have are preferably a carboxy group, an amino group, or a halogen atom.

When —CH ₂ — contained in the above hydrocarbon group is replaced by at least one of —O—, —CO— and —NH—, it is preferable that —CH ₂ — is replaced by at least one of —CO— and —NH—, more preferably by —NH—.

Examples of the compound represented by formula (G-1a) include compounds represented by the following formulas (1-1) to (1-9).

Specific examples of compounds represented by formula (G-1a) by chemical name include mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutanoic acid, 4-mercaptobutanoic acid, mercaptosuccinic acid, mercaptostearic acid, mercaptooctanoic acid, 4-mercaptobenzoic acid, 2,3,5,6-tetrafluoro-4-mercaptobenzoic acid, L-cysteine, N-acetyl-L-cysteine, 3-methoxybutyl 3-mercaptopropionate, and 3-mercapto-2-methylpropionic acid. Of these, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

Another example of compound (G-1) is a polyvalent carboxylic acid compound, preferably a compound (G-1b) represented by the above formula (G-1a) in which -SH in formula (G-1a) is replaced with a carboxy group (-COOH).

Examples of compound (G-1b) include the following compounds:

Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecafluorosuberic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecafluorosebacic acid, acetylenedicarboxylic acid, trans-aconitic acid, 1,3-adamantanedicarboxylic acid, bicyclo[2.2.2]octane-1,4-dicarboxylic acid, cis-4-cyclohexene-1,2-dicarboxylic acid, 1,1-cyclopropanedicarboxylic acid, 1,1-cyclobutanedicarboxylic acid, cis- or trans-1,3-cyclohexanedicarbo acid, cis- or trans-1,4-cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, decahydro-1,4-naphthalenedicarboxylic acid, 2,3-norbornanedicarboxylic acid, 5-norbornene-2,3-dicarboxylic acid, phthalic acid, 3-fluorophthalic acid, isophthalic acid, tetrafluoroisophthalic acid, terephthalic acid, tetrafluoroterephthalic acid, 2,5-dimethylterephthalic acid, 2,6-naphthalenedicarboxylic acid, 2,3-naphthalenedicarboxylic acid, 1,4-naphthalenedicarboxylic acid, 1,1'-ferrocenedicarboxylic acid, 2,2'-biphenyldicarboxylic acid, 4,4'-biphenyldicarboxylic acid, 2,5-furandicarboxylic acid, benzophenone- 2,4'-dicarboxylic acid monohydrate, benzophenone-4,4'-dicarboxylic acid, 2,3-pyrazinedicarboxylic acid, 2,3-pyridinedicarboxylic acid, 2,4-pyridinedicarboxylic acid, 3,5-pyridinedicarboxylic acid, 2,5-pyridinedicarboxylic acid, 2,6-pyridinedicarboxylic acid, 3,4-pyridinedicarboxylic acid, pyrazole-3,5-dicarboxylic acid monohydrate, 4,4'-stilbene dicarboxylic acid, anthraquinone-2,3-dicarboxylic acid, 4-(carboxymethyl)benzoic acid, chelidonic acid monohydrate, azobenzene-4,4'-dicarboxylic acid, azobenzene-3,3'-dicarboxylic acid, chlorendic acid, 1H-imidazole-4,5-dicarboxylic acid, 2,2-bis(4-carboxyphenyl)hexafluoropropane, 1,1 0-bis(4-carboxyphenoxy)decane, dipropylmalonic acid, dithiodiglycolic acid, 3,3'-dithiodipropionic acid, 4,4'-dithiodibutanoic acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl)ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropylidenediphenoxyacetic acid, 1,3-acetonedicarboxylic acid, methylenedisalicylic acid, 5,5'-thiodisalicylic acid, tris(2-carboxyethyl)isocyanurate, tetrafluorosuccinic acid, α,α,α',α'-tetramethyl-1,3-benzenedipropionic acid, 1,3,5-benzenetricarboxylic acid, etc.

From the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer, the molecular weight of the compound (G-1) is preferably 3000 or less, more preferably 2500 or less, even more preferably 2000 or less, still more preferably 1000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of the compound (G-1) is usually 100 or more.

The above molecular weight may be a number average molecular weight or a weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight, respectively, calculated in terms of standard polystyrene as measured by gel permeation chromatography (GPC).

When composition I contains compound (G-1), the content ratio of compound (G-1) to semiconductor particles (A) in composition I is preferably 0.001 to 1, more preferably 0.01 to 0.5, and even more preferably 0.02 to 0.45, in mass ratio. Having the content ratio within this range can be advantageous from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer.

When composition I contains compound (G-1), the content of compound (G-1) in composition I is, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer, preferably from 0.1 mass% to 20 mass%, more preferably from 0.2 mass% to 20 mass%, even more preferably from 0.2 mass% to 10 mass%, still more preferably from 0.5 mass% to 10 mass%, and particularly preferably from 0.5 mass% to 8 mass%, based on the total amount of solids in composition I.

[Compound (G-2)]
Compound (G-2) is a compound different from compound (G-1), and is a compound that contains a polyalkylene glycol structure and has a polar group at the molecular end. 2) It is preferable that the carbon atom is the end of the longest carbon chain (the carbon atom in the carbon chain may be replaced by another atom such as an oxygen atom).

The composition may contain only one type of compound (G-2), or may contain two or more types. The composition may contain compound (G-1) or compound (G-2), or may contain compound (G-1) and compound (G-2).

Compounds that contain a polyalkylene glycol structure and have the first and second functional groups are considered to belong to compound (G-1).

The polyalkylene glycol structure is the following formula:

(n is an integer of 2 or more) In the formula, R ^{3 C} is an alkylene group, for example, an ethylene group, a propylene group, etc.

A specific example of compound (G-2) is a polyalkylene glycol compound represented by the following formula (G-2a):

In formula (G-2a), X is a polar group, Y is a monovalent group, Z 1 ^C is a divalent or trivalent group, n is an integer of 2 or more, m is 1 or 2, and R 1 ^C is an alkylene group.

The polar group X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH ₂ ). A polar group selected from this group can be advantageous in terms of enhancing coordination to the semiconductor particles (A). Among these, from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer, it is more preferable that the polar group X is at least one group selected from the group consisting of a thiol group and a carboxy group.

The group Y is a monovalent group. The group Y is not particularly limited, and examples thereof include monovalent hydrocarbon groups which may have a substituent (N, O, S, a halogen atom, etc.). The -CH ₂ - contained in the hydrocarbon group may be substituted with -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the hydrocarbon group is, for example, 1 or more and 12 or less. The hydrocarbon group may have an unsaturated bond.

Examples of the group Y include an alkyl group having a linear, branched or cyclic structure and a carbon number of 1 to 12; and an alkoxy group having a linear, branched or cyclic structure and a carbon number of 1 to 12. The number of carbon atoms in the alkyl group and alkoxy group is preferably 1 to 8, more preferably 1 to 6, and even more preferably 1 to 4. The -CH ₂ - contained in the alkyl group and alkoxy group may be substituted with -O-, -S-, -C(═O)-, -C(═O)-O-, -O-C(═O)-, -C(═O)-NH-, -NH-, or the like. Among these, the group Y is preferably a linear or branched alkoxy group having a carbon number of 1 to 4, and more preferably a linear alkoxy group having a carbon number of 1 to 4.

The group Y may contain a polar group. The polar group may be at least one group selected from the group consisting of a thiol group (-SH), a carboxy group (-COOH), and an amino group (-NH ₂ ). However, as described above, a compound containing a polyalkylene glycol structure and having the first functional group and the second functional group is considered to belong to the compound (G-1). The polar group is preferably located at the terminal of the group Y.

The group Z 1 ^C is a divalent or trivalent group. The group Z 1 ^C is not particularly limited, and may be a divalent or trivalent hydrocarbon group which may contain a heteroatom (N, O, S, halogen atom, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond.

Examples of the divalent group Z 3 ^C include an alkylene group having 1 to 24 carbon atoms and a linear, branched or cyclic structure; an alkenylene group having 1 to 24 carbon atoms and a linear, branched or cyclic structure. The number of carbon atoms in the alkyl group and the alkenylene group is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The -CH ₂ - contained in the alkyl group and the alkenylene group may be substituted with -O-, -S-, -C(═O)-, -C(═O)-O-, -O-C(═O)-, -C(═O)-NH-, -NH-, or the like. Examples of the trivalent group Z 3 ^C include a group obtained by removing one hydrogen atom from the divalent group Z 3 ^C.

The group Z 1 ^C may have a branched structure. The group Z ^{1 C} having a branched structure may have a polyalkylene glycol structure other than the polyalkylene glycol structure shown in the above formula (G-2a) in a branched chain other than the branched chain containing the polyalkylene glycol structure shown in the above formula (G-2a).

Among these, the group Z 1 ^C is preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

R ^{3 C} is an alkylene group, preferably a linear or branched alkylene group having 1 to 6 carbon atoms, and more preferably a linear alkylene group having 1 to 4 carbon atoms.

In formula (G-2a), n is an integer of 2 or more, preferably 2 or more and 540 or less, more preferably 2 or more and 120 or less, and even more preferably 2 or more and 60 or less.

The molecular weight of compound (G-2) may be, for example, about 150 or more and 10,000 or less, but from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer, it is preferably 150 or more and 5,000 or less, and more preferably 150 or more and 4,000 or less. The molecular weight may be a number average molecular weight or a weight average molecular weight. In this case, the number average molecular weight and the weight average molecular weight are the number average molecular weight and the weight average molecular weight, respectively, in terms of standard polystyrene measured by GPC.

When composition I contains compound (G-2), the content ratio of compound (G-2) to semiconductor particles (A) in composition I is, in mass ratio, preferably 0.001 to 2, more preferably 0.01 to 1.5, and even more preferably 0.1 to 1. A content ratio within this range can be advantageous from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer.

When composition I contains compound (G-2), the content of compound (G-2) in composition I is preferably 0.1% by mass or more and 40% by mass or less, more preferably 0.1% by mass or more and 20% by mass or less, even more preferably 1% by mass or more and 15% by mass or less, and even more preferably 2% by mass or more and 12% by mass or less, based on the total amount of solids in composition I, from the viewpoint of improving the stability and dispersibility of semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer.

When composition I contains an organic ligand (G), the ratio of the content of the organic ligand (G) to the semiconductor particles (A) in composition I is, in mass ratio, preferably 0.001 to 1, more preferably 0.01 to 0.8, and even more preferably 0.02 to 0.5. Having the content ratio within this range can be advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer. The content of the organic ligand (G) here refers to the total content of all organic ligands contained in composition I.

The total content of the semiconductor particles (A) and the organic ligands (G) in composition I is preferably 10% by mass or more and 75% by mass or less, more preferably 12% by mass or more and 70% by mass or less, based on the total amount of solids in composition I, from the viewpoint of improving the stability and dispersibility of the semiconductor particles (A) and the luminescence intensity of the wavelength conversion layer.

It is preferable that Composition II and Composition III are substantially free of organic ligand (G). "Substantially free of organic ligand (G)" means that the content of organic ligand (G) relative to the total amount of solids in Composition II or Composition III is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, and particularly preferably 0 mass%.

<Resin (C)>
Examples of the resin (C) include the following resins [K1] to [K6].

Resin [K1]: a copolymer having a structural unit derived from at least one type (a) (hereinafter also referred to as "(a)") selected from the group consisting of unsaturated carboxylic acids and unsaturated carboxylic anhydrides, and a structural unit derived from a monomer (c) (however different from (a)) (hereinafter also referred to as "(c)") copolymerizable with (a);
Resin [K2]: a copolymer having a structural unit derived from the (a), a structural unit derived from the (c), and a structural unit derived from a monomer (b) (hereinafter also referred to as "(b)") having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond;
Resin [K3]: a copolymer having a structural unit derived from the (a) and a structural unit derived from the (b) by addition, and a structural unit derived from the (c);
Resin [K4]: A copolymer having a structural unit obtained by adding the (b) to a structural unit derived from the (a) and further ester-bonding a carboxylic acid anhydride, and a structural unit derived from the (c).
Resin [K5]: a copolymer having a structural unit derived from the (b) to which the (a) has been added, and a structural unit derived from the (c);
Resin [K6]: A copolymer having a structural unit obtained by adding the (a) to a structural unit derived from the (b) and further ester-bonding a carboxylic acid anhydride, and a structural unit derived from the (c).

Examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;
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, and 1,4-cyclohexenedicarboxylic acid;
Bicyclounsaturated compounds containing a carboxy group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene, and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;
Unsaturated dicarboxylic acid 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;
Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polyvalent carboxylic acids, such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;
Examples of such an unsaturated (meth)acrylate include those containing a hydroxy group and a carboxy group in the same molecule, such as α-(hydroxymethyl)(meth)acrylic acid.

Of these, (meth)acrylic acid, mono[2-(meth)acryloyloxyethyl] succinate, maleic anhydride, etc. are preferred from the standpoint of copolymerization reactivity, etc.

In this specification, (meth)acrylic acid means acrylic acid and/or methacrylic acid. The same applies to "(meth)acryloyl" and "(meth)acrylate", etc.

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

Examples of (b) include a monomer (b1) having an oxiranyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b1)"), a monomer (b2) having an oxetanyl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b2)"), and a monomer (b3) having a tetrahydrofuryl group and an ethylenically unsaturated bond (hereinafter sometimes referred to as "(b3)"), etc.

Examples of (b1) include monomer (b1-1) (hereinafter sometimes referred to as "(b1-1)") having a structure in which a linear or branched aliphatic unsaturated hydrocarbon is epoxidized, and monomer (b1-2) (hereinafter sometimes referred to as "(b1-2)") having a structure in which an alicyclic unsaturated hydrocarbon is epoxidized.

(b1-1) may, for example, be glycidyl (meth)acrylate, β-methyl glycidyl (meth)acrylate, β-ethyl glycidyl (meth)acrylate, glycidyl vinyl ether, o-vinylbenzyl glycidyl ether, m-vinylbenzyl glycidyl ether, p-vinylbenzyl glycidyl ether, α-methyl-o-vinylbenzyl glycidyl ether, α-methyl-m-vinylbenzyl glycidyl ether, α-methyl-p-vinylbenzyl glycidyl ether, 2,3-bis(glycidyl Examples include 2,4-bis(glycidyloxymethyl)styrene, 2,5-bis(glycidyloxymethyl)styrene, 2,6-bis(glycidyloxymethyl)styrene, 2,3,4-tris(glycidyloxymethyl)styrene, 2,3,5-tris(glycidyloxymethyl)styrene, 2,3,6-tris(glycidyloxymethyl)styrene, 3,4,5-tris(glycidyloxymethyl)styrene, and 2,4,6-tris(glycidyloxymethyl)styrene.

(b1-2) includes vinylcyclohexene monoxide, 1,2-epoxy-4-vinylcyclohexane (e.g., Celloxide 2000; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer A400; manufactured by Daicel Corporation), 3,4-epoxycyclohexylmethyl (meth)acrylate (e.g., Cyclomer M100; manufactured by Daicel Corporation), compounds represented by formula (BI) and compounds represented by formula (BII).

In formula (BI) and formula (BII), R ^e and R ^f represent a hydrogen atom or an alkyl group having 1 to 4 carbon atoms, and the hydrogen atom contained in the alkyl group may be substituted with a hydroxy group.
X ^e and X ^f each represent a single bond, *-R ^g -, *-R ^g -O-, *-R ^g -S- or *-R ^g -NH-.
R ^g represents an alkanediyl group having 1 to 6 carbon atoms.
* represents a bond to O.

Examples of the alkyl group having 1 to 4 carbon atoms include a methyl group, an ethyl group, an n-propyl group, an isopropyl group, an n-butyl group, a sec-butyl group, and a tert-butyl group.
Examples of the alkyl group in which a hydrogen atom is substituted with a hydroxy group include a hydroxymethyl group, a 1-hydroxyethyl group, a 2-hydroxyethyl group, a 1-hydroxypropyl group, a 2-hydroxypropyl group, a 3-hydroxypropyl group, a 1-hydroxy-1-methylethyl group, a 2-hydroxy-1-methylethyl group, a 1-hydroxybutyl group, a 2-hydroxybutyl group, a 3-hydroxybutyl group, and a 4-hydroxybutyl group.
R ^e and R ^f are preferably a hydrogen atom, a methyl group, a hydroxymethyl group, a 1-hydroxyethyl group, or a 2-hydroxyethyl group, and more preferably a hydrogen atom or a methyl group.

Examples of the alkanediyl group include a methylene group, an ethylene group, a propane-1,2-diyl group, a propane-1,3-diyl group, a butane-1,4-diyl group, a pentane-1,5-diyl group, and a hexane-1,6-diyl group.
X ^e and X ^f are preferably a single bond, a methylene group, an ethylene group, *-CH ₂ -O-, and *-CH ₂ CH ₂ -O-, and more preferably a single bond or *-CH ₂ CH ₂ -O- (* represents a bond to O).

The compound represented by formula (BI) includes compounds represented by any of formulas (BI-1) to (BI-15). Among them, compounds represented by formulas (BI-1), (BI-3), (BII-5), (BI-7), (BI-9) or (BI-11) to (BI-15) are preferred, and compounds represented by formulas (BI-1), (BI-7), (BI-9) or (BI-15) are more preferred.

The compound represented by formula (BII) includes compounds represented by any of formulas (BII-1) to (BII-15). Among them, compounds represented by formulas (BII-1), (BII-3), (BII-5), (BII-7), (BII-9) or (BII-11) to (BII-15) are preferred, and compounds represented by formulas (BII-1), (BII-7), (BII-9) or (BII-15) are more preferred.

The compound represented by formula (BI) and the compound represented by formula (BII) may be used alone or in combination of two or more kinds. When the compound represented by formula (BI) and the compound represented by formula (BII) are used in combination, the content ratio thereof [compound represented by formula (BI): compound represented by formula (BII)] is preferably 5:95 to 95:5, more preferably 20:80 to 80:20 on a molar basis.

More preferably, (b2) is a monomer having an oxetanyl group and a (meth)acryloyloxy group. Examples of (b2) include 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, 3-ethyl-3-acryloyloxyethyloxetane, and the like.

As (b3), a monomer having a tetrahydrofuryl group and a (meth)acryloyloxy group is more preferable. Specific examples of (b3) include tetrahydrofurfuryl acrylate (e.g., Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.), tetrahydrofurfuryl methacrylate, etc.

As for (b), (b1) is preferable since it can improve reliability in terms of heat resistance, chemical resistance, etc.

Since the reactivity of resins [K3] to [K6] during production is high and unreacted (b) is unlikely to remain, a monomer having an oxirane ring and an ethylenically unsaturated bond is preferred as (b).

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 ^2,6 ^] decan-8-yl (meth)acrylate (commonly known in the art as "dicyclopentanyl (meth)acrylate" and sometimes referred to as "tricyclodecyl (meth)acrylate"). ](meth)acrylic acid esters such as decene-8-yl (meth)acrylate (commonly known in the art as "dicyclopentenyl (meth)acrylate"), dicyclopentanyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;
Hydroxy group-containing (meth)acrylic acid esters such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;
dicarboxylic acid diesters such as diethyl maleate, diethyl fumarate, and diethyl itaconate;
Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, Cyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-di(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-di(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxybicyclo[2.2.1]hept 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, 5,6-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 bicyclo unsaturated compounds such as 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;
Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidocaproate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;
Examples of the copolymer include styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene isoprene, and 2,3-dimethyl-1,3-butadiene.

Of the above, from the viewpoints of copolymerization reactivity and heat resistance of resin (C), methyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dicyclopentanyl (meth)acrylate, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene, etc. are preferred.

In the resin [K1], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K1] is as follows:
The structural units derived from (a) are preferably from 2 mol % to 60 mol %. The structural units derived from (c) are preferably from 40 mol % to 98 mol %.
More preferably, the structural units derived from (a) are from 10 mol % to 50 mol % and the structural units derived from (c) are from 50 mol % to 90 mol %.

When the ratio of structural units in resin [K1] is within the above range, it tends to have excellent storage stability and solvent resistance.

Resin [K1] can be produced, for example, by referring to the method described in the literature "Experimental Methods for Polymer Synthesis" (written by Otsu Takayuki, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published March 1, 1972) and the references cited in said literature.

Specific examples include a method in which predetermined amounts of (a) and (c), a polymerization initiator, a solvent, and the like are placed in a reaction vessel, and the atmosphere is deoxygenated, for example by replacing oxygen with nitrogen, and the mixture is heated and kept warm while being stirred.

The polymerization initiator and solvent used are not particularly limited, and those commonly used in the relevant field can be used. For example, polymerization initiators include azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile), etc.) and organic peroxides (benzoyl peroxide, etc.), and the solvent may be any that dissolves each monomer, such as the solvent (J) described below.

The resulting copolymer may be used as is in the solution after the reaction, or after being concentrated or diluted, or after being extracted as a solid (powder) by a method such as reprecipitation. If a solvent (J) described below is used as the solvent during polymerization, the solution after the reaction can be used as is in the preparation of the composition, simplifying the process of producing the composition.

In the resin [K2], the ratio of the structural units derived from each of them to all the structural units constituting the resin [K2] is as follows:
Structural units derived from (a): 2 to 45 mol%
Structural units derived from (b): 2 to 95 mol%
Structural units derived from (c): 1 to 65 mol%
It is preferred that
Structural units derived from (a): 5 to 40 mol%
Structural units derived from (b): 5 to 80 mol%
Structural units derived from (c): 5 to 60 mol%
It is more preferable that:

When the ratio of structural units in resin [K2] is within the above range, compositions I to III tend to have excellent storage stability and developability when forming colored patterns.

Resin [K2] can be produced, for example, in the same manner as described above for producing resin [K1].

Resin [K3] can be produced by adding the cyclic ether having 2 to 4 carbon atoms contained in (b) to the carboxylic acid and/or carboxylic anhydride contained in (a) to a copolymer of (a) and (c).

First, a copolymer of (a) and (c) is produced in the same manner as described for the production method of resin [K1]. In this case, it is preferable that the ratio of the structural units derived from each is the same as that described for resin [K1].

Next, a portion of the carboxylic acid and/or carboxylic acid anhydride derived from (a) in the copolymer is reacted with a cyclic ether having 2 to 4 carbon atoms contained in (b).

Following the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced with air instead of nitrogen, and (b) the carboxylic acid or carboxylic anhydride is reacted with the cyclic ether in the presence of a reaction catalyst (e.g., an organic phosphorus compound, a metal complex, an amine compound, etc.) and a polymerization inhibitor (e.g., hydroquinone, etc.) at a temperature of 60°C or higher and 130°C or lower for 1 hour to 10 hours, to produce resin [K3].

The amount of (b) used is preferably 5 to 80 moles, more preferably 10 to 75 moles, per 100 moles of (a). By keeping it within this range, the storage stability of the composition and the balance of the solvent resistance, heat resistance, and mechanical strength of each layer tend to be good.

An example of an organic phosphorus compound that can be used as a reaction catalyst is triphenylphosphine. An example of an amine compound that can be used as a reaction catalyst is an aliphatic tertiary amine compound or an aliphatic quaternary ammonium salt compound, and specific examples of such compounds include tris(dimethylaminomethyl)phenol, triethylamine, tetrabutylammonium bromide, and tetrabutylammonium chloride. The reaction catalyst is preferably an organic phosphorus compound.

The amount of the reaction catalyst used is preferably 0.001 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total amount of (a), (b), and (c).

The amount of the polymerization inhibitor used is preferably 0.001 parts by mass or more and 5 parts by mass or less per 100 parts by mass of the total amount of (a), (b), and (c).

The reaction conditions such as the charging method, reaction temperature and time can be adjusted as appropriate, taking into consideration the production equipment, the amount of heat generated by polymerization, etc. As with the polymerization conditions, the charging method and reaction temperature can be adjusted as appropriate, taking into consideration the production equipment, the amount of heat generated by polymerization, etc.

Resin [K4] is a resin obtained by further reacting resin [K3] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether is reacted with the carboxylic acid anhydride.
Examples of carboxylic acid anhydrides include succinic 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.
The amount of the carboxylic acid anhydride used is preferably 0.5 moles or more and 1 mole or less per mole of the amount of (b) used.

In the first step, resin [K5] is produced by obtaining a copolymer of (b) and (c) in the same manner as in the production method of resin [K1] described above. As in the above, the resulting copolymer may be used as it is in the form of a solution after the reaction, or a concentrated or diluted solution, or it may be extracted as a solid (powder) by a method such as reprecipitation.

The ratios of the structural units derived from (b) and (c) to the total number of moles of all structural units constituting the copolymer are, respectively,
The structural units derived from (b) are preferably from 5 mol % to 95 mol %. The structural units derived from (c) are preferably from 5 mol % to 95 mol %.
The structural units derived from (b) are more preferably from 10 mol % to 90 mol %. The structural units derived from (c) are more preferably from 10 mol % to 90 mol %.

Resin [K5] can be obtained by reacting a cyclic ether derived from (b) contained in a copolymer of (b) and (c) with a carboxylic acid or carboxylic anhydride contained in (a) under the same conditions as in the manufacturing method of resin [K3].

The amount of (a) used to react with the copolymer is preferably 5 to 80 moles per 100 moles of (b).

Resin [K6] is a resin obtained by further reacting resin [K5] with a carboxylic acid anhydride. The hydroxyl group generated by the reaction of a cyclic ether with a carboxylic acid or a carboxylic acid anhydride is reacted with the carboxylic acid anhydride.

Examples of carboxylic acid anhydrides include succinic 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, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

The amount of carboxylic acid anhydride used is preferably 0.5 to 1 mole per mole of (a).

Examples of the resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6] include resin [K1] such as benzyl (meth)acrylate/(meth)acrylic acid copolymer, styrene/(meth)acrylic acid copolymer, (meth)acrylic acid/mono[2-(meth)acryloyloxyethyl] succinate/dicyclopentanyl (meth)acrylate/methyl (meth)acrylate copolymer;
Resins [K2] such as glycidyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, glycidyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/methyl (meth)acrylate copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/N-cyclohexylmaleimide copolymer, 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decyl acrylate/(meth)acrylic acid/benzyl (meth)acrylate copolymer;
Resins [K3] such as a resin obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/styrene/(meth)acrylic acid copolymer, a resin obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer, and a resin obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate/methyl (meth)acrylate/(meth)acrylic acid copolymer;
Resins obtained by adding glycidyl (meth)acrylate to a benzyl (meth)acrylate/(meth)acrylic acid copolymer and further bonding with tetrahydrophthalic anhydride or succinic anhydride via ester bonds; resins obtained by adding glycidyl (meth)acrylate to a tricyclodecyl (meth)acrylate/benzyl (meth)acrylate/(meth)acrylic acid copolymer and further bonding with tetrahydrophthalic anhydride or succinic anhydride via ester bonds; resins obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate/methyl (meth)acrylate/(meth)acrylic acid copolymer and further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to the resin; and resins obtained by adding glycidyl (meth)acrylate to a dicyclopentanyl (meth)acrylate/2-ethylhexyl (meth)acrylate/(meth)acrylic acid copolymer and further ester-bonding tetrahydrophthalic anhydride or succinic anhydride to the resin [K4];
Resins [K5] such as a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate/styrene/glycidyl (meth)acrylate;
Examples of the resin include a resin obtained by adding (meth)acrylic acid to a copolymer of tricyclodecyl (meth)acrylate/glycidyl (meth)acrylate, and further bonding with tetrahydrophthalic anhydride or succinic anhydride via an ester bond; and a resin obtained by adding (meth)acrylic acid to a copolymer of dicyclopentanyl (meth)acrylate/2-ethylhexyl (meth)acrylate/glycidyl (meth)acrylate, and further bonding with tetrahydrophthalic anhydride or succinic anhydride via an ester bond [K6].

The resin (C) contained in the composition I preferably contains at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6], more preferably contains at least one selected from the group consisting of resin [K1] and resin [K2], and even more preferably contains resin [K1].
The resin (C) contained in composition II preferably contains at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6], more preferably contains at least one selected from the group consisting of resin [K4] and resin [K6], and even more preferably contains resin [K6]. In particular, a resin in which glycidyl (meth)acrylate is added to a dicyclopentanyl (meth)acrylate/methyl (meth)acrylate/(meth)acrylic acid copolymer and tetrahydrophthalic anhydride is further ester-bonded to the resin, or a resin in which (meth)acrylic acid is added to a dicyclopentanyl (meth)acrylate/2-ethylhexyl (meth)acrylate/glycidyl (meth)acrylate copolymer and succinic anhydride is further ester-bonded to the resin, is preferred, and a resin in which succinic anhydride is further ester-bonded to the resin in which (meth)acrylic acid is added to a dicyclopentanyl (meth)acrylate/2-ethylhexyl (meth)acrylate/glycidyl (meth)acrylate copolymer and succinic anhydride is further ester-bonded to the resin is more preferred.
The resin (C) contained in composition III preferably contains at least one selected from the group consisting of resin [K1], resin [K2], resin [K3], resin [K4], resin [K5] and resin [K6], more preferably contains at least one selected from the group consisting of resin [K1] and resin [K2], and even more preferably contains resin [K1] and resin [K2].

Another example of resin (C) is the resin described in JP 2018-123274 A. Such a resin is a polymer (hereinafter also referred to as "resin (Ca)") that has a double bond in the side chain, contains a structural unit (α) represented by the following formula (I) in the main chain, and contains a structural unit (β) represented by the following formula (II), and further contains an acid group.

The acid group can be introduced into the resin (Ca) by, for example, including a structural unit (γ) derived from an acid group-containing monomer (e.g., (meth)acrylic acid, etc.). The resin (Ca) preferably includes structural units (α), (β), and (γ) in the main chain skeleton.

[In the formula, R ^A and R ^B are the same or different and each represents a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. n represents the average number of repeating units of the structural unit represented by formula (I) and is a number of 1 or more.]

[In the formula, R ^C may be the same or different and represent a hydrogen atom or a methyl group. R ^D may be the same or different and represent a linear or branched hydrocarbon group having 4 to 20 carbon atoms. m represents the average number of repeating units of the structural unit represented by formula (II) and is a number of 1 or more.]
In the resin (Ca), the content of the structural unit (α) is, for example, 0.5% by mass or more and 50% by mass or less, preferably 1% by mass or more and 40% by mass or less, and more preferably 5% by mass or more and 30% by mass or less, based on 100% by mass of the total amount of all monomer units that provide the main chain skeleton of the resin (Ca), from the viewpoint of the heat resistance and storage stability of the resin (Ca). n in the formula (I) represents the average number of repeating units of the structural unit (α) in the resin (Ca), and n can be set so that the content of the structural unit (α) falls within the above range.

The content of the structural unit (β) is, from the viewpoint of the solvent resistance of each layer, for example, 10% by mass or more and 90% by mass or less, preferably 20% by mass or more and 80% by mass or less, and more preferably 30% by mass or more and 75% by mass or less, relative to 100% by mass of the total amount of all monomer units that provide the main chain skeleton of the resin (Ca). m in formula (II) represents the average number of repeating units of the structural unit (β) in the resin (Ca), and m can be set so that the content of the structural unit (β) falls within the above-mentioned range.

The content of the structural unit (γ) is, for example, from 0.5% by mass to 50% by mass, preferably from 2% by mass to 50% by mass, and more preferably from 5% by mass to 45% by mass, relative to 100% by mass of the total amount of all monomer units that provide the main chain structure of the resin (Ca), from the viewpoint of the solubility of the resin (Ca) in the solvent (J).

The weight average molecular weight Mw of resin (C) (other than resin (C-1)) measured by GPC in terms of standard polystyrene is, for example, 1000 or more and 100,000 or less, and from the viewpoint of the developability and luminescence intensity of the composition, is preferably 2000 or more and 50,000 or less, and more preferably 3000 or more and 20,000 or less. The Mw of resin (C) can be adjusted by appropriately combining reaction conditions such as the selection of raw materials used, the charging method, and the reaction temperature and time. The Mw of resin (C) can be measured according to the measurement method described in the Examples section below. Alternatively, the Mw of resin (C) contained in the composition may be measured using GPC.

The molecular weight distribution [weight average molecular weight (Mw)/number average molecular weight (Mn)] of the resin (C) measured by GPC is, for example, 1.0 or more and 6.0 or less, and from the viewpoint of improving the emission intensity, is preferably 1.2 or more and 4.0 or less.

The acid value of resin (C) (other than resin (C-1)) is, from the viewpoint of the developability of the composition and the solvent resistance of each layer, for example, 30 mgKOH/g or more, preferably 90 mgKOH/g to 150 mgKOH/g, more preferably 95 mgKOH/g to 140 mgKOH/g, and even more preferably 100 mgKOH/g to 130 mgKOH/g. The acid value of resin (C) can be adjusted by the content of a monomer component having an acid group (e.g., (a) above) and the content of a carboxylic acid anhydride to be reacted with a hydroxy group generated by the reaction of a carboxylic acid or a carboxylic acid anhydride with a cyclic ether.

The acid value of resin (C) is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of resin (C), and can be determined, for example, by titration with an aqueous potassium hydroxide solution. Specifically, it can be measured according to the measurement method described in the Examples section below. Alternatively, the acid value can be determined, for example, by performing a structural analysis of resin (C) contained in the composition.

From the viewpoint of improving the luminescence intensity, the resin (C) preferably contains a resin having a double bond equivalent of 300 g/eq or more and 2000 g/eq or less, and more preferably contains a resin having a double bond equivalent of 500 g/eq or more and 1500 g/eq or less. An example of a resin having a double bond equivalent of 300 g/eq or more and 2000 g/eq or less is a (meth)acrylic resin. The resin (C) is preferably made of a (meth)acrylic resin.

The content of resin (C) in composition I is, for example, 5% by mass or more and 80% by mass or less, preferably 10% by mass or more and 70% by mass or less, more preferably 13% by mass or more and 60% by mass or less, and even more preferably 17% by mass or more and 55% by mass or less, relative to the total amount of solids in composition I. When the content of resin (C) is within the above range, the semiconductor particles (A) tend to be easily dispersed, and the luminescence intensity of the wavelength conversion layer tends to be high.

The content of resin (C) in composition II is, for example, 0.00001% by mass or more and 99.99999% by mass or less, preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 97% by mass or less, even more preferably 1% by mass or more and 95% by mass or less, still more preferably 3% by mass or more and 90% by mass or less, particularly preferably 5% by mass or more and 80% by mass or less, particularly preferably 10% by mass or more and 70% by mass or less, and most preferably 35% by mass or more and 65% by mass or less, based on the total amount of solids in composition II.

The content of resin (C) in composition III is, for example, 0.00001% by mass or more and 99.99999% by mass or less, preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 97% by mass or less, even more preferably 1% by mass or more and 95% by mass or less, still more preferably 3% by mass or more and 90% by mass or less, particularly preferably 5% by mass or more and 80% by mass or less, and most preferably 10% by mass or more and 70% by mass or less, based on the total amount of solids in composition III.

In composition I, the mass ratio (solid content ratio) of the resin (C) to the polymerizable compound (D) is, for example, 1 or more, and from the viewpoints of the developability of composition I and the luminous intensity of the wavelength conversion layer, is preferably 1.5 or more, more preferably 2 or more, and is preferably 5 or less, more preferably 4 or less.

In composition II, the mass ratio (solid content ratio) of the resin (C) to the polymerizable compound (D) is, for example, 1 or more, and from the viewpoint of the developability of composition II, is preferably 1 or more, more preferably 1.5 or more, and is preferably 5 or less, more preferably 4 or less.

In composition III, the mass ratio (solid content ratio) of the resin (C) to the polymerizable compound (D) is, for example, 0.5 or more, and from the viewpoint of the developability of composition III, is preferably 0.8 or more, more preferably 1.2 or more, and is preferably 5 or less, more preferably 4 or less.

<Polymerizable compound (D)>
The polymerizable compound (D) is a compound that can be polymerized by an active radical, an acid, or the like generated from a polymerization initiator (E) described later. Examples of the polymerizable compound (D) include a compound having an ethylenically unsaturated bond, etc. Examples of the polymerizable compound (D) include photopolymerizable compounds such as (meth)acrylic acid ester compounds. Another example of the polymerizable compound (D) is a thermally polymerizable compound. Two or more types may be included.

The polymerizable compound (D) is preferably a photopolymerizable compound having two or more ethylenically unsaturated bonds in the molecule, more preferably a photopolymerizable compound having three or more ethylenically unsaturated bonds in the molecule, and the number of ethylenically unsaturated bonds in the molecule is preferably six or less. The ethylenically unsaturated bonds are preferably (meth)acryloyloxy groups. The weight average molecular weight of the polymerizable compound (D) is preferably 150 or more and 2900 or less, more preferably 250 or more and 1500 or less.

In composition II, from the viewpoint of suppressing a decrease in the luminescence intensity of the wavelength conversion layer due to heat and from the viewpoint of patterning properties when forming a patterned protective layer, it is preferable that the polymerizable compound (D) has three or more ethylenically unsaturated bonds in the molecule, and more preferably has three or more (meth)acryloyloxy groups. In addition, in composition II, from the viewpoint of suppressing a decrease in the luminescence intensity of the wavelength conversion layer due to heat, it is preferable that the polymerizable compound (D) does not contain a silicon atom in the molecule.

Photopolymerizable compounds having two ethylenically unsaturated bonds in the molecule include bifunctional (meth)acrylic compounds, such as alkylene glycol di(meth)acrylates, polyoxyalkylene glycol di(meth)acrylates, halogen-substituted alkylene glycol di(meth)acrylates, di(meth)acrylates of aliphatic polyols, di(meth)acrylates of hydrogenated dicyclopentadiene or tricyclodecane dialkanol, di(meth)acrylates of dioxane glycol or dioxane dialkanol, di(meth)acrylates of alkylene oxide adducts of bisphenol A or bisphenol F, and epoxy di(meth)acrylates of bisphenol A or bisphenol F.

Specific examples of the bifunctional (meth)acrylic compounds include ethylene glycol di(meth)acrylate, 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, trimethylolpropane di(meth)acrylate, pentaerythritol di(meth)acrylate, ditrimethylolpropane di(meth)acrylate, diethylene glycol di(meth)acrylate, triethylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, polytetramethylene glycol di(meth)acrylate, and di(meth)acrylate of neopentyl glycol ester of hydroxypivalic acid. acrylate, 2,2-bis[4-(meth)acryloyloxyethoxyethoxyphenyl]propane, 2,2-bis[4-(meth)acryloyloxyethoxyethoxycyclohexyl]propane, hydrogenated dicyclopentadienyl di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, 1,3-dioxane-2,5-diyl di(meth)acrylate [also known as dioxane glycol di(meth)acrylate], acrylate of hydroxypivalaldehyde and trimethylolpropane These include di(meth)acrylate of cetal compound (chemical name: 2-(2-hydroxy-1,1-dimethylethyl)-5-ethyl-5-hydroxymethyl-1,3-dioxane), tris(hydroxyethyl)isocyanurate di(meth)acrylate, di(meth)acrylate of ethoxylated bisphenol A, di(meth)acrylate of propoxylated bisphenol A, di(meth)acrylate of ethoxylated bisphenol F, and di(meth)acrylate of propoxylated bisphenol F.

The polymerizable compound (D) may be a compound (Da) having three or more (meth)acryloyloxy groups in the molecule and having an acidic functional group, or a compound (Db) having three or more (meth)acryloyloxy groups in the molecule and having no acidic functional group. The photopolymerizable compound preferably contains at least one of the compounds (Da) and (Db), and may contain two or more compounds (Da), two or more compounds (Db), or at least one compound (Da) and at least one compound (Db). Examples of the acidic functional group include a carboxy group, a sulfonic acid group, and a phosphate group. Of these, the acidic functional group is preferably a carboxy group.

When the polymerizable compound (D) in composition I contains the compound (Da), the dispersibility of the semiconductor particles (A) can be improved, and the luminescence intensity of the wavelength conversion layer can be improved. Furthermore, when the polymerizable compound (D) contains the compound (Da), the curability and heat resistance of the composition can be improved.

The number of (meth)acryloyloxy groups in one molecule of compound (Da) is, for example, 3 or more and 6 or less, preferably 3 or more and 5 or less, and more preferably 3. The number of acidic functional groups in one molecule of compound (Da) is 1 or more, and preferably 1. When compound (Da) has two or more acidic functional groups, the acidic functional groups may be different or the same, but it is preferable that compound (Da) has at least one carboxy group.

Examples of the compound (Da) include compounds obtained by esterifying a compound having three or more (meth)acryloyloxy groups and hydroxyl groups, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, with a dicarboxylic acid. Examples of the compound include a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid, a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with succinic acid, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with maleic acid, and a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid. Among these, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

Commercially available products of compound (Da) include, for example, "Aronix M-510" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate as the main component, and "Aronix M-520D" manufactured by Toagosei Co., Ltd., which contains a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate as the main component. These commercially available products have a carboxy group as the acidic functional group.

The ethylenically unsaturated bond in compound (Db) is preferably a (meth)acryloyloxy group. The number of ethylenically unsaturated bonds in one molecule of compound (Db) is preferably 3 to 6.

Examples of the compound (Db) include glycerin tri(meth)acrylate, alkoxylated glycerin tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, ditrimethylolpropane tri(meth)acrylate, ditrimethylolpropane tetra(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, and tripentaerythritol hepta(meth)acrylate. acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, tris(2-(meth)acryloyloxyethyl)isocyanurate, ethylene glycol modified pentaerythritol tetra(meth)acrylate, ethylene glycol modified dipentaerythritol hexa(meth)acrylate, propylene glycol modified pentaerythritol tetra(meth)acrylate, propylene glycol modified dipentaerythritol hexa(meth)acrylate, caprolactone modified pentaerythritol tetra(meth)acrylate, caprolactone modified dipentaerythritol hexa(meth)acrylate, etc. Among these, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, etc. are preferred.

An example of a commercially available product of compound (Db) is dipentaerythritol polyacrylate, "A-9550" manufactured by Shin-Nakamura Chemical Co., Ltd.

The polymerizable compound (D) in composition II is preferably a compound (Da) since it can more effectively suppress the decrease in the luminescence intensity of the wavelength conversion layer due to heat, and is preferably a compound (Db) since it can improve the residual rate of the film after development. The polymerizable compound (D) in composition II may contain only one of the compounds (Da) and (Db), or may contain both. From the viewpoint of improving the residual rate of the film, the content of the compound (Db) relative to the total amount of the compounds (Da) and (Db) is preferably 50% by mass or more, more preferably 80% by mass or more, even more preferably 90% by mass or more, and is also preferably 100% by mass (i.e., not including the compound (Da)).

From the viewpoint of improving the developability of the composition, it is preferable that composition I contains compound (Da). Compound (Da) is contained in an amount of preferably 50 mass% or more, more preferably 70 mass% or more, based on 100 mass% of polymerizable compound (D) contained in composition I. On the other hand, from the viewpoint of improving the curability, it is preferable that composition III contains compound (Db). Compound (Db) is contained in an amount of preferably 50 mass% or more, more preferably 70 mass% or more, based on 100 mass% of polymerizable compound (D) contained in composition III.

The content of the polymerizable compound (D) in composition I is preferably 7% by mass or more and 60% by mass or less, more preferably 10% by mass or more and 45% by mass or less, and even more preferably 13% by mass or more and 30% by mass or less, based on the total amount of solids in composition I. When the content of the polymerizable compound (D) is within the above range, the developability of composition I and the solvent resistance of the wavelength converting layer tend to be improved.

The content of the polymerizable compound (D) in composition II is from 7% by mass to 60% by mass, more preferably from 10% by mass to 55% by mass, and even more preferably from 15% by mass to 50% by mass, based on the total amount of solids in composition II. If the content is within the above range, it is advantageous in suppressing the decrease in the luminescence intensity of the wavelength conversion layer due to heat.

The content of the polymerizable compound (D) in composition III is, for example, 0.00001% by mass or more and 99.99999% by mass or less, preferably 1% by mass or more and 99% by mass or less, more preferably 1% by mass or more and 97% by mass or less, even more preferably 1% by mass or more and 95% by mass or less, still more preferably 1% by mass or more and 90% by mass or less, particularly preferably 2% by mass or more and 80% by mass or less, and most preferably 3% by mass or more and 70% by mass or less, based on the total amount of solids in composition III.

<Polymerization initiator (E)>
The polymerization initiator (E) is a compound that generates an active radical, an acid, or the like by the action of light or heat and can initiate polymerization of the polymerizable compound (D). The composition can contain one or more polymerization initiators (E).

Examples of the polymerization initiator (E) include photopolymerization initiators such as oxime compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds, and thermal polymerization initiators such as azo compounds and organic peroxides.

An example of an oxime compound is an oxime compound having a first molecular structure represented by the following formula (1). Hereinafter, this oxime compound is also referred to as "oxime compound (1)."

Including oxime compound (1) as polymerization initiator (E) can be advantageous in terms of improving the luminescence intensity. One of the reasons for this effect is presumably that the unique molecular structure of oxime compound (1) causes a large change in the absorption wavelength of oxime compound (1) before and after cleavage (decomposition) of oxime compound (1), which is necessary for oxime compound (1) to initiate photopolymerization, and therefore oxime compound (1) has a high photoradical polymerization initiation ability.

In formula (1), R ¹ represents R ¹¹ , OR ¹¹ , COR ¹¹ , SR ¹¹ , CONR ¹² R ¹³ or CN.

R ¹¹ , R ¹² and R ¹³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

The hydrogen atoms of the groups represented by R ¹¹ , R ¹² or R ¹³ may be substituted by OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -N(COR ²² )-OCOR ²³ , -C(═N-OR ²¹ )-R ²² , -C(═N-OCOR ²¹ )-R ²² , CN, a halogen atom or COOR ²¹ .

R ²¹ , R ²² and R ²³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

The hydrogen atom of the group represented by R ²¹ , R ²² or R ²³ may be substituted by CN, a halogen atom, a hydroxy group or a carboxy group.

When the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² or R ²³ has an alkylene portion, the alkylene portion may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ CO-, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-.

R ²⁴ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

When the group represented by R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² or R ²³ has an alkyl portion, the alkyl portion may be branched or cyclic, and R ¹² and R ¹³ , and R ²² and R ²³ may be joined together to form a ring.

* represents a bond to the second molecular structure, which is a molecular structure other than the first molecular structure that the oxime compound (1) has.

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

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

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

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

In formula (1), R ¹² and R ¹³ , and R ²² and R ²³ may each be joined together to form a ring, which means that R ¹² and R ¹³ , and R ²² and R ²³ may each be joined together to form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

Examples of the ring that can be formed by combining R ¹² and R ¹³ , and R ²² and R ²³ in formula (1) include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, and a lactam ring, and are preferably 5- to 7-membered rings.

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

R ¹ in formula (1) is preferably R ¹¹ , more preferably an alkyl group having 1 to 20 carbon atoms, even more preferably an alkyl group having 1 to 10 carbon atoms, and even more preferably an alkyl group having 1 to 6 carbon atoms.

An example of the second molecular structure linked to the first molecular structure represented by formula (1) is the structure represented by the following formula (2). The second molecular structure means a molecular structure portion other than the first molecular structure that the oxime compound (1) has.

The bond represented by "*" in formula (2) is directly bonded to the bond represented by "*" in formula (1). In other words, when the second molecular structure is the structure represented by formula (2), the benzene ring having "-*" in formula (2) and the carbonyl group having "-*" in formula (1) are directly bonded.

In formula (2), ^R2 and ^R3 each independently represent ^R11 ^, ^OR11 , ^SR11 , ^COR11 , ^CONR12R13 , ^NR12COR11 , ^OCOR11 , ^COOR11 , ^SCOR11 , ^OCSR11 , ^COSR11 , ^CSOR11 , CN or ^a halogen atom.

When multiple ^R2s are present, they may be the same or different.

When multiple ^R3 's are present, they may be the same or different.

R ¹¹ , R ¹² and R ¹³ have the same meanings as above.

s and t each independently represent an integer from 0 to 4.

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

R ³¹ , R ³² and R ³³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms or an aralkyl group having 7 to 30 carbon atoms.

When the group represented by R ³¹ , R ³² or R ³³ has an alkyl portion, the alkyl portion may be branched or cyclic, and R ³¹ , R ³² and R ³³ may each independently form a ring together with either of the adjacent benzene rings.

R ⁴ is a hydroxy group, a carboxy group, or a group represented by the following formula (2-1):

In formula (2-1), L ¹ represents —O—, —S—, —NR ²² —, —NR ²² CO—, —SO ₂ —, —CS—, —OCO— or —COO—.

^R22 has the same meaning as above.

^L2 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.

When the group represented by ^L2 has an alkylene portion, the alkylene portion may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR ²² -, -NR ²² COO-, -OCONR ²² -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene portion may be branched or cyclic.

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 a halogen atom.

When a plurality of R ^4a are present, they may be the same or different.

R ⁴¹ , R ⁴² and R ⁴³ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms. When the groups represented by R ⁴¹ , R ⁴² and R ⁴³ have an alkyl portion, the alkyl portion may be branched or cyclic, and R ⁴² and R ⁴³ may together form a ring.

v represents an integer of 1 to 3.
It represents a group represented by the following formula:

* represents the bond to the first molecular structure of the oxime compound (1).

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 R 11 , R 12 , R 13} ^, ^{R 21 , R 22 , R 23 , R 24 , R 31} ^, ^R ³² ^and ^R ³³ ⁱⁿ ^formula ⁽ 2), and R 22 , R ⁴¹ , R 42 and R ⁴³ in formula (2-1) above, are the same as the examples for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in formula (1).

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

In formula (2), R ³¹ , R ³² and R ³³ may each independently form a ring together with either of the adjacent benzene rings, which means that R ³¹ , R ³² and R ³³ may each independently form a ring together with either of the adjacent benzene rings and the nitrogen atom to which they are connected.

Examples of the ring that R ³¹ , R ³² and R ³³ in formula (2) may form together with either adjacent benzene ring are the same as the examples of the ring that R ¹² and R ¹³ , and R ² and R ²³ in formula (1) may form together.

^L2 in the above formula (2-1) represents a group in which v hydrogen atoms have been removed 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.

　Examples of groups obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, when v is 1, include alkylene groups such as 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, decylene, dodecylene, tridecylene, tetradecylene, pentadecylene, ethane-1,1-diyl, and propane-2,2-diyl.

　Examples of groups in which v hydrogen atoms have been removed from an aryl group having 6 to 30 carbon atoms, when v is 1, include arylene groups such as 1,2-phenylene group, 1,3-phenylene group, 1,4-phenylene group, 2,6-naphthylene group, 1,4-naphthylene group, 2,5-dimethyl-1,4-phenylene group, diphenylmethane-4,4'-diyl group, 2,2-diphenylpropane-4,4'-diyl group, diphenylsulfide-4,4'-diyl group, and diphenylsulfone-4,4'-diyl group.

　Examples of groups in which v hydrogen atoms have been removed from an aralkyl group having 7 to 30 carbon atoms, when v is 1, include groups represented by the following formula (a) and groups represented by the following formula (b).

[In formulas (a) and (b), ^L3 and ^L5 represent an alkylene group having 1 to 10 carbon atoms, and ^L4 and ^L6 represent a single bond or an alkylene group having 1 to 10 carbon atoms.]
Examples of alkylene groups 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.

　Examples of groups in which v hydrogen atoms have been removed from a heterocyclic group having 2 to 20 carbon atoms, when v is 1, include divalent heterocyclic groups such as 2,5-pyridinediyl group, 2,6-pyridinediyl group, 2,5-pyrimidinediyl group, 2,5-thiophenediyl group, 3,4-tetrahydrofurandiyl group, 2,5-tetrahydrofurandiyl group, 2,5-furandiyl group, 3,4-thiazolediyl group, 2,5-benzofurandiyl group, 2,5-benzothiophenediyl group, N-methylindole-2,5-diyl group, 2,5-benzothiazolediyl group, and 2,5-benzoxazolediyl group.

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

From the viewpoint of solubility in the solvent (J) and/or developability of the composition, a preferred example of the structure represented by formula (2) is the structure represented by the following formula (2a):

[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, and R ² , R ³ , R ⁴ , s and t are the same as defined above.]
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).

[In formula (2b), R ⁴⁴ represents a hydroxy group, a carboxy group, or a group represented by the following formula (2-2):

(In formula (2-2), L ¹¹ represents *-O- or *-OCO-, * represents a bond to L ¹² , L ¹² represents an alkylene group having 1 to 20 carbon atoms which may be interrupted by 1 to 3 -O-, R ^44a represents OR ⁵⁵ or COOR ⁵⁵ , and R ⁵⁵ represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms.)
It represents a group represented by the following formula:
R ⁴⁴ is preferably a group represented by formula (2-2), which is advantageous in terms of the solubility of the oxime compound (1) in the solvent (J) and the developability of the composition.

The alkylene group represented by L ¹² preferably has 1 to 10 carbon atoms, and more preferably 1 to 4 carbon atoms.

R ^44a is preferably a hydroxy group or a carboxy group, and more preferably a hydroxy group.

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

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

The bond represented by "*" in formula (3) is directly bonded to the bond represented by "*" in formula (1). In other words, when the second molecular structure is the structure represented by formula (3), the benzene ring having "-*" in formula (3) and the carbonyl group having "-*" in formula (1) are directly bonded.

In formula (3), R ⁵ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

When the group represented by ^R5 has an alkyl moiety, the alkyl moiety may be branched or cyclic.

The hydrogen atoms in the group represented by ^R5 may be substituted ^by ^R21 , ^OR21 , COR21, ^SR21 , ^NR22R23 , ^CONR22R23 , ^-NR22 ^- ^OR23 , -N( ^COR22 )-OCOR23 ^, NR22COR21, ^OCOR21 , ^COOR21 , -C(= ^N - ^OR21 ) ^-R22 , -C ⁽ =N- ^OCOR21 ) ^-R22 , ^SCOR21 , ^OCSR21 , ^COSR21 , ^CSOR21 , a hydroxyl ^group , a nitro group, CN, a halogen atom, or ^COOR21 .

R ²¹ , R ²² and R ²³ have the same meanings as above.

When the groups represented by R ²¹ , R ²² and R ²³ have an alkylene portion, the alkylene portion may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ^{24 CO-, -NR 24} ^COO- , -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-.

R ²⁴ has the same meaning as above.

When the groups represented by R ²¹ , R ²² and R ²³ have an alkyl portion, the alkyl portion may be branched or cyclic, and R ²² and R ²³ may be joined together to form a ring.

R ⁶ , R ⁷ , R ⁸ and R ⁹ each independently represent R ⁶¹ , OR ⁶¹ , SR ⁶¹ , COR ⁶² , CONR ⁶³ R ⁶⁴ , NR ⁶⁵ COR ⁶¹ , OCOR ⁶¹ , ^COOR ⁶² , SCOR ^{61 , OCSR 61} , COSR ⁶² , CSOR ⁶¹ , a hydroxyl group, a nitro group, CN or a halogen atom.

R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ each independently represent a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an arylalkyl group having 7 to 30 carbon atoms or a heterocyclic group having 2 to 20 carbon atoms.

The hydrogen atoms of the groups represented by R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ or R ⁶⁵ may be substituted by OR ²¹ , COR ²¹ , SR ²¹ , NR ²² R ²³ , CONR ²² R ²³ , -NR ²² -OR ²³ , -N(COR ²² )-OCOR ²³ , -C(═N-OR ²¹ )-R ²² , -C(═N-OCOR ²¹ )-R ²² , CN, a halogen atom, or COOR ²¹ .

R ⁶ and R ⁷ , R ⁷ and R ⁸ , and R ⁸ and R ⁹ may each be joined together to form a ring.

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 R ⁵ , R ²¹ , R ²² , R ²³ , R ²⁴ , R 61 , R 62 , R 63 , R 64 and R ⁶⁵ in formula (3) are the same as the examples for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in formula (1).

In formula (3), R ²² and R ²³ may be taken together to form a ring, which means that R ²² and R ²³ may be taken together to form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

Examples of the ring which may be formed by R ²² and R ²³ together in formula (3) are the same as the examples of the ring which may be formed by R ¹² and R ¹³ , and R ²² and R ²³ together in formula (1).

Examples of the halogen atoms which may replace the hydrogen atoms of the halogen atoms represented by R ⁶ , R ⁷ , R ⁸ and R ⁹ , and R ^{5 , R 21} ^, R ²² , R ²³ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ in formula (3) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

In terms of solubility in the solvent (J) and/or developability of the composition, in one preferred embodiment, R ⁵ is a group represented by the following formula (3-1).

[In formula (3-1), Z represents a group in which one hydrogen atom has been removed from an alkyl group having 1 to 20 carbon atoms, a group in which one hydrogen atom has been removed from an aryl group having 6 to 30 carbon atoms, a group in which one hydrogen atom has been removed from an aralkyl group having 7 to 30 carbon atoms, or a group in which one hydrogen atom has been removed from a heterocyclic group having 2 to 20 carbon atoms,
When the group represented by Z has an alkylene portion, the alkylene portion may be interrupted 1 to 5 times by -O-, -S-, -COO-, -OCO-, -NR ²⁴ -, -NR ²⁴ COO-, -OCONR ²⁴ -, -SCO-, -COS-, -OCS- or -CSO-, and the alkylene portion may be branched or cyclic.
R ²¹ , R ²² and R ²⁴ have the same meanings as defined above.
From the same viewpoint as above, Z in formula (3-1) is preferably a methylene group, an ethylene group or a phenylene group.

From the same viewpoint as above, R ²¹ and R ²² in formula (3-1) are 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.

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

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

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

The bond represented by "*" in formula (4) is directly bonded to the bond represented by "*" in formula (1). In other words, when the second molecular structure is the structure represented by formula (4), the benzene ring having "-*" in formula (4) and the carbonyl group having "-*" in formula (1) are directly bonded.

In formula (4), R ⁷¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

When the group represented by R ⁷¹ has an alkyl moiety, the alkyl moiety may be branched or cyclic.

The hydrogen atom of the group represented by R ⁷¹ may be substituted 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 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR ²¹ .

R ²¹ , R ²² and R ²³ have the same meanings as defined above.

R ²⁴ has the same meaning as above.

R ⁷² , R ⁷³ and the three R ^74s each independently represent R ⁶¹ , OR ⁶¹ , SR 61 , COR ⁶² , CONR ⁶³ R ⁶⁴ , NR ⁶⁵ COR ⁶¹ , OCOR ⁶¹ , ^COOR ⁶² , SCOR ⁶¹ , OCSR ⁶¹ , COSR ⁶² , CSOR ⁶¹ , a hydroxyl group, a nitro group, CN or a halogen atom.

R ⁷² and R ⁷³ , and two R ^74s may be joined together to form a ring.

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 R ⁷¹ , R ²¹ , R ²² , R ²³ , R ²⁴ , R 61 , R 62 , R 63 , R 64 and R ⁶⁵ in formula (4) are the same as the examples for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in formula (1).

In formula (4), R ²² and R ²³ may be taken together to form a ring, which means that R ²² and R ²³ may be taken together to form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

Examples of the ring that can be formed by R ²² and R ²³ together in formula (4) are the same as the examples of the ring that can be formed by R ¹² and R ¹³ , and R ²² and R ²³ together in formula (1).

Examples of the halogen atoms which may replace the hydrogen atoms of the halogen atoms represented by R ⁷² , R ⁷³ and R ⁷⁴ , and R ⁷¹ , R ²¹ , R ²² , R ²³ , R ⁶¹ , R ⁶² , R ⁶³ , R ⁶⁴ and R ⁶⁵ in formula (4) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The method for producing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, but it can be produced, for example, by the methods described in WO 2017/051680 and WO 2020/004601.

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

The bond represented by "*" in formula (5) is directly bonded to the bond represented by "*" in formula (1). In other words, when the second molecular structure is a structure represented by formula (5), the pyrrole ring having "-*" in formula (5) and the carbonyl group having "-*" in formula (1) are directly bonded.

In formula (5), R ⁸¹ represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

When the group represented by R ⁸¹ has an alkyl moiety, the alkyl moiety may be branched or cyclic.

The hydrogen atoms in the group represented by R ⁸¹ may be substituted 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 , a hydroxyl group, a nitro group, CN, a halogen atom, or COOR ²¹ .

R ²¹ , R ²² and R ²³ have the same meanings as above.

R ²⁴ has the same meaning as above.

^R82 , ^R83 , ^R84 , ^R85 and ^R86 each independently ^represent ^R61 , ^OR61 , SR61, ^COR62 , CONR63R64 ^, ^NR65COR61 , ^OCOR61 , ^COOR62 , ^SCOR61 , ^OCSR61 , ^COSR62 ^, ^CSOR61 , a hydroxyl ^group , a nitro group, CN or a halogen atom.

R ⁸³ and R ⁸⁴ , R ⁸⁴ and R ⁸⁵ , and R ⁸⁵ and R ⁸⁶ may be joined together to form a ring.

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 R ⁸¹ , R ²¹ , R ²² , R ²³ , R ²⁴ , R 61 , R 62 , R 63 , R 64 and R ⁶⁵ in formula (5) are the same as the examples for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² , R ²³ and R ²⁴ in formula (1).

In formula (5), R ²² and R ²³ may be taken together to form a ring, which means that R ²² and R ²³ may be taken together to form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

Examples of the ring that can be formed by R ²² and R ²³ together in formula (5) are the same as the examples of the ring that can be formed by R ¹² and R ¹³ , and R ²² and R ²³ together in formula (1).

Examples of the halogen atoms which may replace the hydrogen atoms of the halogen atoms represented by ^R82 , ^R83 , ^R84 , ^R85 and ^R86 , and ^R81 , ^R21 , ^R22 , ^R23 , ^R61 , ^R62 , ^R63 , ^R64 and ^R65 in formula (5) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, but it can be produced, for example, by the methods described in WO 2017/051680 and WO 2020/004601.

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

The bond represented by "*" in formula (6) is directly bonded to the bond represented by "*" in formula (1). In other words, when the second molecular structure is a structure represented by formula (6), the benzene ring having "-*" in formula (6) and the carbonyl group having "-*" in formula (1) are directly bonded.

In formula (6), the four R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ⁹⁷ each independently represent R ⁶¹ , OR ⁶¹ , SR ⁶¹ , COR ⁶² , CONR 63 R ⁶⁴ , NR ⁶⁵ COR ⁶¹ , OCOR ⁶¹ , COOR ⁶² , SCOR ⁶¹ , OCSR ⁶¹ , COSR ⁶² , CSOR ⁶¹ , a hydroxyl group, ^a nitro group, CN or a halogen atom.

R ²¹ , R ²² and R ²³ have the same meanings as above.

R ⁹² and R ⁹³ , R ⁹⁴ and R ⁹⁵ , R ⁹⁵ and R ⁹⁶ , and R ⁹⁶ and R ⁹⁷ may each be joined together to form a ring.

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 R 21 , R 22} ^, ^R ²³ , R 61 , R 62 , R ⁶³ , R 64 and R ⁶⁵ in formula (6) are the same as the examples for R ¹¹ , R ¹² , R ¹³ , R ²¹ , R ²² and R ²³ in formula (1).

In formula (6), R ²² and R ²³ may be taken together to form a ring, which means that R ²² and R ²³ may be taken together to form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected.

Examples of the ring which R ²² and R ²³ in formula (6) may form together are the same as the examples of the ring which R ¹² and R ¹³ , and R ²² and R ²³ in formula (1) may form together.

Examples of the halogen atoms which may replace the hydrogen atoms of the halogen atoms represented by R ⁹¹ , R ⁹² , R ⁹³ , R ⁹⁴ , R ⁹⁵ , R ⁹⁶ and R ^97, and R ²¹ , R ²² , R ²³ , R ^{61 , R 62} ^, R ⁶³ , R ⁶⁴ and R ⁶⁵ in formula (6) include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, but it can be produced, for example, by the methods described in WO 2017/051680 and WO 2020/004601.

Another example of an oxime compound (excluding oxime compound (1)) is a compound represented by formula (EA).

[Wherein,
R ^ea1 represents a branched hydrocarbon group having 3 to 20 carbon atoms which may have a substituent.
R ^ea2 to R ^ea5 each independently represent a hydrocarbon group having 1 to 20 carbon atoms which may have a substituent.
n represents an integer of 0 to 4.
The —CH ₂ — contained in the hydrocarbon group may be replaced by —O—, —S—, —CO— or —OCO—.]

Examples of the branched hydrocarbon group having 3 to 20 carbon atoms represented by R ^ea1 include branched saturated hydrocarbon groups having 3 to 20 carbon atoms and branched unsaturated hydrocarbon groups having 3 to 20 carbon atoms.

Examples of the branched saturated hydrocarbon group having 3 to 20 carbon atoms represented by R ^ea1 include a 1-methylethyl group (isopropyl group), a 1-methylpropyl group (sec-butyl group), a 2-methylpropyl group (isobutyl group), a 1,1-dimethylethyl group (tert-butyl group), a 1,1-dimethylpropyl group, a 2,2-dimethylpropyl group, a 1,2-dimethylpropyl group, a 1-ethylpropyl group, a 1-methylbutyl group, a 2-methylbutyl group, a 3-methylbutyl group, a 1,1-dimethylbutyl group, a 2,2-dimethylbutyl group, a 3,3-dimethylbutyl group, a 1,2-dimethylbutyl group, a 1,3-dimethylbutyl group, a 2,3-dimethylbutyl group, a Dimethylbutyl group, 1-ethylbutyl group, 2-ethylbutyl group, 1-methylpentyl group, 2-methylpentyl group, 3-methylpentyl group, 4-methylpentyl group, 1,1-dimethylpentyl group, 2,2-dimethylpentyl group, 3,3-dimethylpentyl group, 1,2-dimethylpentyl group, 1,3-dimethylpentyl group, 2,3-dimethylpentyl group, 1-ethylpentyl group, 2-ethylpentyl group, 3-ethylpentyl group, 1-methylhexyl group, 2-methylhexyl group, 3-methylhexyl group, 4-methylhexyl group, 1,1-dimethylhexyl group, 2,2-dimethylhexyl group, 3,3-dimethylhexyl group xyl group, 1,2-dimethylhexyl group, 1,3-dimethylhexyl group, 2,3-dimethylhexyl group, 1-ethylhexyl group, 2-ethylhexyl group, 3-ethylhexyl group, 1-methylheptyl group, 2-methylheptyl group, 3-methylheptyl group, 4-methylheptyl group, 1,1-dimethylheptyl group, 2,2-dimethylheptyl group, 3,3-dimethylheptyl group, 1,2-dimethylheptyl group, 1,3-dimethylheptyl group, 2,3-dimethylheptyl group, 1-ethylheptyl group, 2-ethylheptyl group, 3-ethylheptyl group, 1-methyloctyl group, 2-methyloctyl group, 3-methyloctyl group branched-chain alkyl groups such as 1-methylnonyl group, 2-methylnonyl group, 3-methylnonyl group, 4-methylnonyl group, dimethylnonyl group, ethylnonyl group, methyldecyl group, dimethyldecyl group, ethyldecyl group, methylundecyl group, dimethylundecyl group, ethylundecyl group, methyldodecyl group, and the like;
The branched alkyl group represented by R ^ea1 may be any of a primary branched alkyl group, a secondary branched alkyl group, or a tertiary branched alkyl group.
The branched saturated hydrocarbon group represented by R ^ea1 preferably has 4 or more, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

Examples of the branched unsaturated hydrocarbon group represented by R ^ea1 include groups in which at least one or more carbon-carbon single bonds contained in the branched saturated hydrocarbon group represented by R ^ea1 are replaced with a carbon-carbon double bond or a carbon-carbon triple bond.
Examples of the branched unsaturated hydrocarbon group represented by R ^ea1 include alkenyl groups such as an isopropenyl group, an isobutenyl group, an isopentenyl group, an isohexenyl group, an isoheptenyl group, an isooctenyl group, an isononyl group, and an isodecenyl group; and alkynyl groups such as an isopropynyl group, an isobutynyl group, an isopentynyl group, an isohexynyl group, an isoheptynyl group, an isooctynyl group, an isononynyl group, and an isodecynyl group.
The branched unsaturated hydrocarbon group represented by R ^ea1 preferably has 4 or more, more preferably 5 or more, and preferably 16 or less, more preferably 12 or less, and further preferably 10 or less.

Examples of the hydrocarbon group having 1 to 20 carbon atoms represented by R ^ea2 , R ^ea3 , R ^ea4 and R ^ea5 include a saturated hydrocarbon group having 1 to 20 carbon atoms, an unsaturated hydrocarbon group having 2 to 20 carbon atoms, and an aromatic hydrocarbon group having 6 to 20 carbon atoms. The hydrocarbon groups represented by R ^ea2 , R ^ea3 , R ^ea4 and R ^ea5 may be the same or different.

The saturated hydrocarbon group having 1 to 20 carbon atoms includes, for example, linear alkyl groups such as methyl, ethyl, propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, dodecyl, hexadecyl, and icosyl; branched alkyl groups such as isopropyl, isobutyl, isopentyl, neopentyl, and 2-ethylhexyl; and alicyclic saturated hydrocarbon groups having 3 to 20 carbon atoms such as cyclopropyl, cyclopentyl, cyclohexyl, cycloheptyl, cyclooctyl, and tricyclodecyl. The number of carbon atoms in the saturated hydrocarbon group is preferably 1 to 18, more preferably 1 to 15, even more preferably 1 to 10, and even more preferably 1 to 8.

The unsaturated hydrocarbon group having 2 to 20 carbon atoms includes alkenyl groups such as vinyl, allyl, butenyl, pentenyl, hexenyl, heptenyl, octenyl, nonenyl, decenyl, undecenyl, dodecenyl, hexadecenyl, octadecenyl, and icosenyl; alkynyl groups such as ethynyl, propynyl, hexynyl, decynyl, and icosenyl; cycloalkenyl groups such as cyclopentenyl, cyclohexenyl, and cycloheptenyl; and the like. The number of carbon atoms in the unsaturated hydrocarbon group is preferably 2 to 18, more preferably 2 to 15, and even more preferably 2 to 10.

The aromatic hydrocarbon group having 6 to 20 carbon atoms includes a phenyl group, a xylyl group, a trimethylphenyl group, a dipropylphenyl group, a di(2,2-dimethylpropyl)phenyl group, a naphthyl group, a benzyl group, a phenylethyl group, a phenylbutyl group, etc. The number of carbon atoms in the aromatic hydrocarbon group is preferably 6 to 18, more preferably 6 to 15, and even more preferably 6 to 12.

Examples of the substituent that the hydrocarbon group represented by R ^ea1 , R ^ea2 , R ^ea3 , R ^ea4 and R ^ea5 may have include a halogen atom, a cyano group and a nitro group. The halogen atom is preferably a fluorine atom, a bromine atom, a chlorine atom or an iodine atom.

The --CH ₂ -- contained in the hydrocarbon group may be replaced by --O--, --S--, --CO-- or --OCO--, provided that adjacent --CH ₂ -- are not simultaneously replaced by the same type of group, and the terminal --CH ₂ -- is not replaced.

n represents an integer from 0 to 4, preferably an integer from 0 to 3, more preferably an integer from 0 to 2, even more preferably an integer of 0 or 1, and even more preferably 0.

The bonding position of the *-OCO-R ^ea4 group (* represents a bond to the phenyl group) may be any of the 2-position, 3-position or 4-position of the phenyl group to which the *-OCO-R ^ea4 group is bonded, but is preferably the 3-position or 4-position, and more preferably the 4-position.

The branched hydrocarbon group having 3 to 20 carbon atoms represented by R ^ea1 is
A branched saturated hydrocarbon group having 3 to 20 carbon atoms is preferred,
A branched alkyl group having 3 to 20 carbon atoms is more preferred.
More preferably, the branched alkyl group has 3 to 10 carbon atoms.
It is preferable that the alkyl group is one or more selected from the group consisting of a 1-methylpentyl group, a 2-methylpentyl group, a 3-methylpentyl group, a 1-ethylpentyl group, a 2-ethylpentyl group, a 3-ethylpentyl group, a 1-methylhexyl group, a 2-methylhexyl group, a 3-methylhexyl group, a 1-ethylhexyl group, a 2-ethylhexyl group, a 3-ethylhexyl group, a 1-methylheptyl group, a 2-methylheptyl group, a 3-methylheptyl group, a 1-ethylheptyl group, a 2-ethylheptyl group, and a 3-ethylheptyl group.

The hydrocarbon group having 1 to 20 carbon atoms represented by R ^ea2 , R ^ea3 , R ^ea4 and R ^ea5 is
A saturated hydrocarbon group having 1 to 20 carbon atoms and an unsaturated hydrocarbon group having 2 to 20 carbon atoms are preferred.
A saturated hydrocarbon group having 1 to 20 carbon atoms is more preferable.
A linear saturated hydrocarbon group having 1 to 10 carbon atoms is more preferable.
A chain alkyl group having 1 to 8 carbon atoms is even more preferred.
R ^ea2 is preferably a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 6 carbon atoms.
R ^ea3 is preferably a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 3 carbon atoms.
R ^ea4 is preferably a chain alkyl group having 1 to 8 carbon atoms, and more preferably a chain alkyl group having 1 to 3 carbon atoms.
R ^ea5 is preferably a linear or branched alkyl group having 1 to 8 carbon atoms, and more preferably a linear or branched alkyl group having 1 to 6 carbon atoms.

Other examples of photopolymerization initiators include photopolymerization initiators other than the oxime compound (1) and the compound represented by formula (EA). Other photopolymerization initiators include oxime compounds other than the oxime compound (1) and the compound represented by formula (EA), biimidazole compounds, triazine compounds, and acylphosphine compounds.

Oxime compounds other than oxime compound (1) and the compound represented by formula (EA) include oxime compounds having a partial structure represented by the following formula (d1). * represents a bond.

Examples of oxime compounds having a partial structure represented by formula (d1) include N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-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 N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropan-1-one-2-imine; and compounds described in JP2011-132215A, WO2008/78678, WO2008/78686, and WO2012/132558. Commercially available products such as Irgacure OXE01 (N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine), OXE02 (N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine) (all manufactured by BASF), and N-1919 (manufactured by ADEKA) may also be used.

Among them, the oxime compound having the partial structure represented by formula (d1) is preferably at least one selected from the group consisting of N-benzoyloxy-1-(4-phenylsulfanylphenyl)butan-1-one-2-imine, N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine and N-benzoyloxy-1-(4-phenylsulfanylphenyl)-3-cyclopentylpropan-1-one-2-imine, and more preferably N-benzoyloxy-1-(4-phenylsulfanylphenyl)octan-1-one-2-imine or N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethan-1-imine.

An example of a biimidazole compound is a compound represented by formula (d5).

[In formula (d5), R ^E to R ^J each represent an aryl group having 6 to 10 carbon atoms which may have a substituent.]
Examples of the aryl group having 6 to 10 carbon atoms include a phenyl group, a toluyl group, a xylyl group, an ethylphenyl group, and a naphthyl group, and the like, with a phenyl group being preferred.

Examples of the substituent include halogen atoms and alkoxy groups having 1 to 4 carbon atoms. Examples of the halogen atom include fluorine, chlorine, bromine, and iodine atoms, with chlorine atoms being preferred. Examples of the alkoxy group having 1 to 4 carbon atoms include methoxy, ethoxy, propoxy, and butoxy groups, with methoxy being preferred.

Examples of biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2,3-dichlorophenyl)-4,4',5,5'-tetraphenylbiimidazole (see, for example, JP-A-06-75372 and JP-A-06-75373, etc.), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(alkoxyphenyl) Examples of suitable biimidazole compounds include 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(dialkoxyphenyl)biimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetra(trialkoxyphenyl)biimidazole (see, for example, JP-B-48-38403 and JP-A-62-174204), and biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carboalkoxy groups (see, for example, JP-A-7-10913). Among these, compounds represented by the following formula or mixtures thereof are preferred.

Examples of triazine compounds include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxystyryl)-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6- Examples of such compounds include [2-(5-methylfuran-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)ethenyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)ethenyl]-1,3,5-triazine, and 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)ethenyl]-1,3,5-triazine. Among these, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferred.

Examples of acylphosphine compounds include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide.

Other examples of photopolymerization initiators other than the oxime compound (1) and the compound represented by formula (EA) include, for example, benzoin compounds such as benzoin, benzoin methyl ether, benzoin ethyl ether, benzoin isopropyl ether, and benzoin isobutyl ether; benzophenone compounds such as benzophenone, o-benzoyl methyl benzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetra(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzyl, methyl phenylglyoxylate, and titanocene compounds.

The content of the polymerization initiator (E) in the composition I is preferably 0.1 parts by mass or more and 300 parts by mass or less, more preferably 0.1 parts by mass or more and 200 parts by mass or less, relative to 100 parts by mass of the polymerizable compound (D). The content of the polymerization initiator (E) in the composition I is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 0.5 parts by mass or more and 20 parts by mass or less, relative to 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiator (E) is within the above range, the sensitivity of the composition I tends to be increased and the exposure time tends to be shortened, so that the productivity of the wavelength conversion layer tends to be improved.

The content of the polymerization initiator (E) in the composition II is preferably 0.001% by mass or more and 60% by mass or less, more preferably 0.01% by mass or more and 50% by mass or less, even more preferably 0.05% by mass or more and 30% by mass or less, and even more preferably 0.1% by mass or more and 10% by mass or less, based on the total amount of the resin (C) and the polymerizable compound (D).

In composition II, the polymerization initiator (E) is an oxime compound in which a first molecular structure represented by the formula (1) is bonded to a second molecular structure represented by the formula (2), and in particular, an oxime compound in which the structure represented by the formula (2) is a structure represented by the formula (2b) and/or a compound represented by the formula (EA) is preferred, and an oxime compound in which a first molecular structure represented by the formula (1) is bonded to a second molecular structure represented by the formula (2), and in particular, an oxime compound in which the structure represented by the formula (2) is a structure represented by the formula (2b) is more preferred.

The content of the polymerization initiator (E) in the composition III is preferably 0.001% by mass or more and 60% by mass or less, more preferably 0.01% by mass or more and 50% by mass or less, based on the total amount of the resin (C) and the polymerizable compound (D).

From the viewpoint of improving the emission intensity, the content of the oxime compound (1) in the polymerization initiator (E) is preferably 30% by mass or more and 100% by mass or less, more preferably 50% by mass or more and 100% by mass or less, even more preferably 80% by mass or more and 100% by mass or less, still more preferably 90% by mass or more and 100% by mass or less, particularly preferably 95% by mass or more and 100% by mass or less, and most preferably 100% by mass, based on the total amount of the polymerization initiator (E).

<Polymerization initiator aid (Eα)>
The composition may further contain a polymerization initiation aid (Eα) together with the polymerization initiator (E). The polymerization initiation aid (Eα) is a compound used to promote the polymerization of the polymerizable compound (D) initiated by the polymerization initiator (E), or a sensitizer. Examples of the polymerization initiation aid (Eα) include photopolymerization initiation aids such as amine compounds, alkoxyanthracene compounds, thioxanthone compounds, and carboxylic acid compounds, as well as thermal polymerization initiation aids. The composition may contain two or more polymerization initiation aids (Eα).

Examples of amine compounds include triethanolamine, methyldiethanolamine, triisopropanolamine, methyl 4-dimethylaminobenzoate, ethyl 4-dimethylaminobenzoate, isoamyl 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.

Examples of alkoxyanthracene compounds 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.

Examples of thioxanthone compounds include 2-isopropylthioxanthone, 4-isopropylthioxanthone, 2,4-diethylthioxanthone, 2,4-dichlorothioxanthone, and 1-chloro-4-propoxythioxanthone.

Examples of carboxylic acid compounds include phenylsulfanylacetic acid, methylphenylsulfanylacetic acid, ethylphenylsulfanylacetic acid, methylethylphenylsulfanylacetic acid, dimethylphenylsulfanylacetic acid, methoxyphenylsulfanylacetic acid, dimethoxyphenylsulfanylacetic acid, chlorophenylsulfanylacetic acid, dichlorophenylsulfanylacetic acid, N-phenylglycine, phenoxyacetic acid, naphthylthioacetic acid, N-naphthylglycine, naphthoxyacetic acid, etc.

When composition I contains a polymerization initiation aid (Eα), the content of the polymerization initiation aid (Eα) in composition I is preferably 0.1 parts by mass or more and 300 parts by mass or less, more preferably 0.1 parts by mass or more and 200 parts by mass or less, per 100 parts by mass of the polymerizable compound (D). In addition, the content of the polymerization initiation aid (Eα) in composition I is preferably 0.1 parts by mass or more and 30 parts by mass or less, more preferably 1 part by mass or more and 20 parts by mass or less, per 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D). When the content of the polymerization initiation aid (Eα) is within the above range, the sensitivity of composition I can be further increased.

When a polymerization initiation aid (Eα) is used, the content of the polymerization initiation aid (Eα) in composition II is preferably 0.001 parts by mass or more and 60 parts by mass or less, more preferably 0.01 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D).

When a polymerization initiation aid (Eα) is used, the content of the polymerization initiation aid (Eα) in composition III is preferably 0.00001 parts by mass or more and 60 parts by mass or less, more preferably 0.0001 parts by mass or more and 50 parts by mass or less, per 100 parts by mass of the total amount of the resin (C) and the polymerizable compound (D).

<Light stabilizer (F)>
The light stabilizer (F) includes known light stabilizers (Fa) and may be any additive having the effect of stabilizing components against light. The light stabilizer (F) of the present invention also includes an antioxidant (Fb) and an ultraviolet absorber (Fc) that absorbs light and renders it harmless.

<Light stabilizer (Fa)>
Examples of the light stabilizer (Fa) include hindered amine-based light stabilizers, acrylate-based light stabilizers, nickel-based light stabilizers, and oxamide-based light stabilizers.

<Antioxidant (Fb)>
The antioxidant (Fb) is not particularly limited as long as it is an antioxidant generally used industrially, and examples of the antioxidant that can be used include phenol-based antioxidants, phosphorus-based antioxidants, phosphorus/phenol complex antioxidants, sulfur-based antioxidants, etc. The composition may contain two or more types of antioxidants (Fb).

The phosphorus/phenol complex type antioxidant is, for example, a compound having one or more phosphorus atoms and one or more phenol structures in the molecule. Among these, from the viewpoint of the developability and luminescence intensity of the composition, it is preferable that the antioxidant (Fb) contains a phosphorus/phenol complex type antioxidant.

Examples of phenol-based antioxidants include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis [3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate], manufactured by BASF Corporation), Irganox 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), 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 Co., Ltd.), Irganox 3114 (Irganox 3114: 1,3,5-tris(3,5-di-tert-butyl-4-hydroxybenzyl)-1,3,5-triazine-2,4,6(1H,3H,5H)-trione, manufactured by BASF Co., Ltd.), 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 Co., Ltd.), Irganox 1035 (Irganox 1035: thiodiethylenebis[3-(3,5-di-tert t-butyl-4-hydroxyphenyl)propionate, manufactured by BASF Corporation), Irganox 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of benzenepropanoic acid, manufactured by BASF Corporation), Irganox 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butyl a Nilino)-1,3,5-triazine, manufactured by BASF Co., Ltd.), Adekastab (registered trademark) 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 Co., Ltd.), Sumilizer (registered trademark) BHT, Sumilizer GA-80, Sumilizer GS (all manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by Cytec Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

Examples of phosphorus-based antioxidants include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphine-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), and Irgafos 38 (I rgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl ester phosphorous acid, manufactured by BASF Corporation; Adekastab (registered trademark) 329K, Adekastab PEP36, Adekastab PEP-8 (all manufactured by ADEKA Corporation); Sandstab P-EPQ (manufactured by Clariant); Weston (registered trademark) 618, Adekastab 619G (all manufactured by GE); Ultranox 626 (manufactured by GE); etc.

Examples of phosphorus/phenol complex antioxidants include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenz[d,f][1.3.2]dioxaphosphepine) (manufactured by Sumitomo Chemical Co., Ltd.).

Sulfur-based antioxidants include, for example, dialkyl thiodipropionate compounds such as dilauryl, dimyristyl, or distearyl thiodipropionate, and β-alkyl mercaptopropionate compounds of polyols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

The content of the antioxidant (Fb) in composition I is, for example, 1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of resin (C), and from the viewpoint of luminescence intensity and heat resistance, is preferably 5 parts by mass or more and 40 parts by mass or less, and more preferably 7 parts by mass or more and 30 parts by mass or less.

The content of the antioxidant (F) in composition III is, for example, 1 part by mass or more and 50 parts by mass or less relative to 100 parts by mass of the resin (C), and from the viewpoint of luminescence intensity and heat resistance, is preferably 5 parts by mass or more and 40 parts by mass or less, and more preferably 7 parts by mass or more and 30 parts by mass or less.

<Ultraviolet absorber (Fc)>
Examples of the ultraviolet absorber (Fc) include benzotriazole-based compounds such as 2-(2-hydroxy-3-tert-butyl-5-methylphenyl)-5-chlorobenzotriazole and (2-(2,4-dihydroxyphenyl)-2H-benzotriazole; benzophenone-based compounds such as 2-hydroxy-4-octyloxybenzophenone; benzoate-based compounds such as 2,4-di-tert-butylphenyl-3,5-di-tert-butyl-4-hydroxybenzoate; and triazine-based compounds such as 2-(4,6-diphenyl-1,3,5-triazin-2-yl)-5-hexyloxyphenol.

Composition I preferably contains a light stabilizer (F), particularly an antioxidant (Fb).

<Solvent (J)>
The solvent (J) is preferably one that dissolves the resin (C), the polymerizable compound (D), and the polymerization initiator (E). Examples of the solvent (J) include ester solvents (solvents containing -COO- and not containing -O- in the molecule), ether solvents (solvents containing -O- and not containing -COO- in the molecule), ether ester solvents (solvents containing -COO- and -O- in the molecule), ketone solvents (solvents containing -CO- and not containing -COO- in the molecule), alcohol solvents (solvents containing OH in the molecule and not containing -O-, -CO-, and COO-), aromatic hydrocarbon solvents, amide solvents, and dimethyl sulfoxide.

Ester solvents include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutanoate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-pentyl formate, isopentyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexyl acetate, and gamma-butyrolactone.

Ether solvents include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dioxane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenetole, and methylanisole.

Ether ester solvents include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methyl ...ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxy Examples include ethyl 2-methoxypropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, 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, and diethylene glycol monobutyl ether acetate.

Ketone solvents include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

Alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerin.

Aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene.

Amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

The solvent (J) preferably contains one or more solvents selected from the group consisting of propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, and aromatic hydrocarbon solvents.

The solvent (J) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, cyclohexyl acetate, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone, toluene, or a mixture of two or more of these.

The solvent (J) is a component other than the solid content, and includes, for example, the solvent contained in the dispersion of semiconductor particles (A) or the solution of resin (C).

The content of solvent (J) in composition I is the ratio of the total mass of all solvents contained in the composition to the total amount of composition I, and is, for example, from 40% by mass to 95% by mass, and preferably from 55% by mass to 90% by mass, relative to the total amount of composition I. In other words, the solid content of composition I is, for example, from 5% by mass to 60% by mass, and preferably from 10% by mass to 45% by mass. When the content of solvent (J) is within the above range, the flatness of the composition layer during application is improved, and a wavelength conversion layer of appropriate thickness tends to be formed more easily.

The solid content of Composition II is preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less, even more preferably 0.1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 90% by mass or less, even more preferably 1% by mass or more and 80% by mass or less, particularly preferably 1% by mass or more and 70% by mass or less, extremely preferably 1% by mass or more and 60% by mass or less, and most preferably 1% by mass or more and 50% by mass or less, based on the total amount of Composition II.

The solid content of Composition III is preferably 0.01% by mass or more and 100% by mass or less, more preferably 0.1% by mass or more and 99.9% by mass or less, even more preferably 0.1% by mass or more and 99% by mass or less, still more preferably 1% by mass or more and 90% by mass or less, even more preferably 1% by mass or more and 80% by mass or less, particularly preferably 1% by mass or more and 70% by mass or less, extremely preferably 1% by mass or more and 60% by mass or less, and most preferably 1% by mass or more and 50% by mass or less, based on the total amount of Composition III.

In composition II, it is particularly preferred that the solvent (J) contains an ether ester solvent.

<Leveling Agent (H)>
The leveling agent (H) may be a silicone surfactant, a fluorine surfactant, or a silicone surfactant having a fluorine atom. These may have a polymerizable group in the side chain. From the viewpoint of the developability and luminescence intensity of the composition, the leveling agent (H) is preferably a fluorine surfactant. The composition may contain two or more kinds of leveling agents (H).

Examples of silicone surfactants include surfactants having a siloxane bond in the molecule. Specific examples include Toray Silicone DC3PA, SH7PA, DC11PA, SH21PA, SH28PA, SH29PA, SH30PA, and SH8400 (product names: manufactured by Dow Corning Toray Co., Ltd.), KP321, KP322, KP323, KP324, KP326, KP340, and KP341 (manufactured by Shin-Etsu Chemical Co., Ltd.), TSF400, TSF401, TSF410, TSF4300, TSF4440, TSF4445, TSF4446, TSF4452, and TSF4460 (manufactured by Momentive Performance Materials Japan, LLC).

Fluorosurfactants include surfactants having a fluorocarbon chain in the molecule. Specific examples include Fluorad (registered trademark) FC430 and FC431 (manufactured by Sumitomo 3M Limited), Megafac (registered trademark) F142D, F171, F172, F173, F177, F183, F554, F575, R30, and RS-718-K (manufactured by DIC Corporation), F-top (registered trademark) EF301, EF303, EF351, and EF352 (manufactured by Mitsubishi Materials Electronic Chemicals Co., Ltd.), Surflon (registered trademark) S381, S382, SC101, and SC105 (manufactured by Asahi Glass Co., Ltd.), and E5844 (manufactured by Daikin Fine Chemicals Research Institute, Ltd.).

Examples of silicone surfactants containing fluorine atoms include surfactants that have siloxane bonds and fluorocarbon chains in the molecule. Specific examples include Megafac (registered trademark) R08, BL20, F475, F477, and F443 (manufactured by DIC Corporation).

When composition I contains a leveling agent (H), the content of the leveling agent (H) in composition I is, for example, 0.001 mass% or more and 1.0 mass% or less, preferably 0.005 mass% or more and 0.75 mass% or less, and more preferably 0.01 mass% or more and 0.5 mass% or less, relative to the total amount of composition I. When the content of the leveling agent (H) is within the above range, the flatness of the wavelength conversion layer can be improved.

When composition II contains a leveling agent (H), the content of the leveling agent (H) in composition II is, for example, 0.001 mass% or more and 1.0 mass% or less, preferably 0.005 mass% or more and 0.75 mass% or less, and more preferably 0.01 mass% or more and 0.5 mass% or less, relative to the total amount of composition II.

When composition III contains a leveling agent (H), the content of the leveling agent (H) in composition III is, for example, 0.001 mass% or more and 1.0 mass% or less, preferably 0.005 mass% or more and 0.75 mass% or less, and more preferably 0.01 mass% or more and 0.5 mass% or less, relative to the total amount of composition III.

<Colorant (I)>
The colorant (I) includes a white colorant (Iw) and a chromatic colorant (Ic).

<White Colorant (Iw)>
Examples of the white colorant (Iw) include inorganic particles such as metal or metal oxide particles and glass particles. Examples of metal oxides include TiO ₂ , SiO ₂ , BaTiO ₃ , and ZnO, and TiO ₂ particles are preferred because they efficiently scatter light. The particle diameter of the white colorant (Iw) is, for example, about 0.03 μm or more and 20 μm or less, preferably 0.05 μm or more and 1 μm or less, and more preferably 0.05 μm or more and 0.5 μm or less.

The white colorant (Iw) may be a colorant in which a light scattering agent is dispersed in advance in a part or the whole of the solvent (J) using a dispersant. Commercially available dispersants can be used. Examples of commercially available dispersants include:
DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 20 manufactured by BYK Japan Co., Ltd. 00, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250; BYK-P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen et al.
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;
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 and the like manufactured by BASF Corporation;
Examples of such polyimide resins include Ajisper PA111, PB711, PB821, PB822, and PB824 manufactured by Ajinomoto Fine-Techno Co., Ltd.

The content of the white colorant (Iw) in composition I is, for example, 0.001% by mass or more and 50% by mass or less, based on the total amount of solids in composition I, and from the viewpoint of improving the light scattering ability and luminous intensity of the wavelength conversion layer, is preferably 1% by mass or more and 30% by mass or less, more preferably 2% by mass or more and 20% by mass or less, even more preferably 2% by mass or more and 15% by mass or less, and even more preferably 3% by mass or more and 10% by mass or less.

It is preferable that composition III is substantially free of a white colorant (Iw). "Substantially free of a white colorant (Iw)" means that the content of the white colorant (Iw) relative to the total amount of solids in composition III is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, and particularly preferably 0 mass%.

<Chromatic Colorant (Ic)>
The chromatic colorant (Ic) may be a pigment or a dye. As the pigment, a known pigment may be used, for example, a pigment classified as a pigment in the Color Index (published by The Society of Dyers and Colourists). The pigment may be used alone or in combination of two or more kinds. As the dye, a known dye may be used, for example, a dye described in the Color Index (published by The Society of Dyers and Colourists) and Dyeing Notes (Shikisensha). The dye may be used alone or in combination of two or more kinds.

The chromatic colorant (Ic) is preferably a pigment, and preferably contains at least one selected from the group consisting of a yellow colorant, a green colorant, and a red colorant.

Examples of yellow colorants include yellow pigments such as C.I.

Pigment Yellow

1, 3, 12, 13, 14, 15, 16, 17, 20, 24, 31, 53, 83, 86, 93, 94, 109, 110, 117, 125, 128, 129, 137, 138, 139, 147, 148, 150, 153, 154, 166, 173, 185, 194, 214, and 231. Other examples of yellow colorants are the following dyes.
C.I. Solvent dyes such as C.I. Solvent Yellow 4, 14, 15, 23, 24, 25, 38, 62, 63, 68, 79, 81, 82, 83, 89, 94, 98, 99, 117, 162, 163, 167, 189;
C.I.

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, 15 C.I. Acid dyes such as 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;
C.I. Direct dyes such as C.I. Direct Yellow 2, 4, 28, 33, 34, 35, 38, 39, 43, 44, 47, 50, 54, 58, 68, 69, 70, 71, 86, 93, 94, 95, 98, 102, 108, 109, 129, 132, 136, 138, 141;
C.I. Disperse dyes such as C.I. Disperse Yellow 51, 54, 76;
C.I. Reactive dyes such as C.I. Reactive Yellow 2, 76, 116;
C. I. Mordant dyes such as C. I.

Mordant Yellow

5, 8, 10, 16, 20, 26, 30, 31, 33, 42, 43, 45, 56, 61, 62, 65;

Examples of green colorants include green pigments such as C.I. Pigment Green 7, 36, 58, 59, 62, and 63. Other examples of green colorants are the following dyes.
C.I. Solvent dyes such as C.I. Solvent Green 1, 3, 4, 5, 7, 28, 29, 32, 33, 34, 35;
C.I. Acid dyes such as C.I.

Acid Green

1, 3, 5, 6, 7, 8, 9, 11, 13, 14, 15, 16, 22, 25, 27, 28, 41, 50, 50:1, 58, 63, 65, 80, 104, 105, 106, 109;
C.I. Direct dyes such as C.I. Direct Green 25, 27, 31, 32, 34, 37, 63, 65, 66, 67, 68, 69, 72, 79, 82;
C.I. Basic dyes such as C.I. Basic Green 1;
C.I. Mordant dyes such as C.I.

Mordant Green

1, 3, 4, 5, 10, 13, 15, 19, 21, 23, 26, 29, 31, 33, 34, 35, 41, 43, 53;
C.I. Vat dyes such as C.I. Vat Green 1, etc.

Examples of red colorants include red pigments such as C.I. Pigment Red 9, 97, 105, 122, 123, 144, 149, 166, 168, 176, 177, 178, 179, 180, 190, 192, 209, 215, 216, 224, 242, 254, 255, 264, 265, 266, 268, 269, and 273. Other examples of red colorants are the following dyes.
C.I. Solvent dyes such as C.I. Solvent Red 24, 45, 49, 90, 91, 111, 118, 119, 122, 124, 125, 127, 130, 132, 143, 145, 146, 150, 151, 155, 160, 168, 169, 172, 175, 181, 207, 218, 222, 227, 230, 245, 247;
C.I. 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, C.I. Acid dyes such as 183, 195, 198, 206, 211, 215, 216, 217, 227, 228, 249, 252, 257, 258, 260, 261, 266, 268, 270, 274, 277, 280, 281, 289, 308, 312, 315, 316, 339, 341, 345, 346, 349, 382, 383, 388, 394, 401, 412, 417, 418, 422, 426;
C.I. Direct dyes such as C.I. Direct Red 79, 82, 83, 84, 91, 92, 96, 97, 98, 99, 105, 106, 107, 172, 173, 176, 177, 179, 181, 182, 184, 204, 207, 211, 213, 218, 220, 221, 222, 232, 233, 234, 241, 243, 246, 250;
C.I. Basic dyes such as C.I. Basic Red 1, 9, 10;
C.I. Mordant dyes such as C.I.

Mordant Red

1, 2, 3, 4, 9, 11, 12, 14, 17, 18, 19, 22, 23, 24, 25, 26, 27, 29, 30, 32, 33, 36, 37, 38, 39, 41, 42, 43, 45, 46, 48, 52, 53, 56, 62, 63, 71, 74, 76, 78, 85, 86, 88, 90, 94, 95, etc.

The chromatic colorant (Ic) preferably contains a yellow colorant, more preferably contains a yellow pigment, and even more preferably contains at least one selected from the group consisting of C.I. Pigment Yellow 138, 150, and 231.

The chromatic colorant (Ic) may be subjected to, as necessary, a rosin treatment, a surface treatment using a colorant derivative having an acidic or basic group introduced therein, a grafting treatment to the colorant surface using a polymer compound, a micronization treatment using a sulfuric acid micronization method, a washing treatment using an organic solvent or water to remove impurities, a removal treatment using an ion exchange method for ionic impurities, etc. It is preferable that the particle size of the colorant (I) is approximately uniform.

When composition III contains a green colorant and/or a red colorant, the chromatic colorant (Ic) contained in composition III is preferably a green colorant when the wavelength conversion layer is a layer that emits green light, and is preferably a red colorant when the wavelength conversion layer is a layer that emits red light. The green colorant and the red colorant may each be used alone or in combination of two or more kinds.

The content of the chromatic colorant (Ic) in composition III is, for example, 0.01% by mass or more and 99.99% by mass or less, preferably 0.1% by mass or more and 99.9% by mass or less, more preferably 1% by mass or more and 99% by mass or less, even more preferably 10% by mass or more and 90% by mass or less, and even more preferably 15% by mass or more and 70% by mass or less, based on the total amount of solids in composition III.

It is preferable that composition I is substantially free of a chromatic colorant (Ic). "Substantially free of a chromatic colorant (Ic)" means that the content of the chromatic colorant (Ic) relative to the total amount of solids in composition I is preferably 1 mass% or less, more preferably 0.5 mass% or less, even more preferably 0.1 mass% or less, and particularly preferably 0 mass%.

<Other ingredients>
Compositions I, II and III may optionally further contain additives known in the art, such as polymerization inhibitors, fillers, other polymeric compounds, adhesion promoters, chain transfer agents and the like.

<Production method of composition>
Compositions I, II, and III can be produced by a method including a step of mixing the prescribed components and other components used as necessary. The method for producing compositions I, II, and III can further include a step of preparing resin (C).

When using a chromatic colorant (Ic), it is preferable to use the chromatic colorant (Ic) in the form of a colorant dispersion liquid in which the chromatic colorant (Ic) is mixed in advance with part or all of the solvent (J) and dispersed using a bead mill or the like until the average particle size of the chromatic colorant (Ic) is approximately 0.2 μm or less. At this time, a dispersant and part or all of the resin (C) may be added as necessary. As for the dispersant, the description of the dispersant mentioned in the section on the white colorant (Iw) is cited.

<Structure of laminate and manufacturing method>
The laminate according to the present invention (hereinafter, simply referred to as "laminate") is a laminate including a wavelength conversion layer having semiconductor particles (A) and a protective layer formed from the above-mentioned composition II, and a laminate including a wavelength conversion layer having semiconductor particles (A), a protective layer formed from composition II, and a light absorbing layer. Fig. 1 is a schematic cross-sectional view showing an example of the laminate according to the present invention, Fig. 2 is a schematic cross-sectional view showing another example of the laminate according to the present invention, and Fig. 3 is a schematic cross-sectional view showing yet another example of the laminate according to the present invention.

The laminate shown in Figs. 1 to 3 includes a wavelength conversion layer 10 and a protective layer 20 disposed thereon. As in the laminate shown in Figs. 1 and 2, the protective layer 20 may be directly laminated on the wavelength conversion layer 10, and the protective layer 20 and the wavelength conversion layer 10 may be in contact with each other. Alternatively, as in the laminate shown in Fig. 3, another layer may be interposed between the wavelength conversion layer 10 and the protective layer 20. An example of the other layer is a light absorbing layer 30. If another layer is interposed, heat may be applied to the wavelength conversion layer in the process of forming the other layer, which may reduce the luminescence intensity of the wavelength conversion layer. In consideration of this point, as in the laminate shown in Fig. 2, it is preferable that a protective layer is provided between the wavelength conversion layer and the light absorbing layer, and as in the laminate shown in Figs. 1 and 2, it is preferable that the protective layer 20 is directly laminated on the wavelength conversion layer 10 (i.e., the protective layer 20 and the wavelength conversion layer 10 are laminated without any other layer therebetween).

FIG. 4 is a schematic cross-sectional view showing yet another example of a laminate according to the present invention. As shown in FIG. 4, the laminate includes a first wavelength conversion layer 11 that emits red light, a first protective layer 21 disposed thereon, a second wavelength conversion layer 12 that emits green light, and a second protective layer 22 disposed thereon. The first protective layer 21 and the second protective layer 22 are both protective layers formed from the composition II according to the present invention. Instead of providing the first protective layer 21 and the second protective layer 22, respectively, one (integral) protective layer may be provided on the first wavelength conversion layer 11 and the second wavelength conversion layer 12. In addition, the laminate shown in FIG. 4 may be provided with a light absorbing layer 30, as in the laminates of FIG. 2 and FIG. 3.

When providing the light absorbing layer 30 in the laminate shown in FIG. 4, the first light absorbing layer can be provided on the first wavelength conversion layer 11 or the first protective layer 21, and the second light absorbing layer can be provided on the second wavelength conversion layer 12 or the second protective layer 22. Alternatively, one (integral) light absorbing layer can be provided on the first wavelength conversion layer 11 and the second wavelength conversion layer 12, or on the first protective layer 21 and the second protective layer 22.

The laminate can be suitably used as a color conversion member disposed on the primary light source (blue light source) of a display device. The laminate according to the present invention can suppress the decrease in luminescence intensity caused by heat of the wavelength conversion layer.

The luminescence intensity maintenance rate of the laminate according to the present invention is preferably 80% or more, more preferably 85% or more, and even more preferably 90% or more. There is no particular upper limit, and 100% is ideal, but 99% or less is also acceptable. The luminescence intensity maintenance rate of the laminate can be achieved by providing a protective layer on the wavelength conversion layer. The luminescence intensity maintenance rate can be measured according to the measurement method described in the Examples section below.

1. Wavelength conversion layer (composition I) and its manufacturing method The thickness of the wavelength conversion layer is, for example, 1 μm to 20 μm, preferably 1.5 μm to 18 μm, more preferably 1.8 μm to 14 μm, even more preferably 2 μm to 12 μm, and even more preferably 2 μm to 10 μm. If the thickness of the wavelength conversion layer is excessively small, when the wavelength conversion layer is irradiated with primary light, a proportion of the primary light that is not sufficiently absorbed or scattered by the wavelength conversion layer and transmits through the wavelength conversion layer tends to be large.
The shape and dimensions of the patterned wavelength-converting layer are not particularly limited. For example, the patterned wavelength-converting layer has a rectangular shape in plan view.

The wavelength conversion layer may be, for example,
Method a comprising a step of applying composition I to a substrate and then drying the applied composition I; or Method b comprising producing a wavelength-converting layer by a step of applying composition I to a support and then drying the support, peeling the wavelength-converting layer from the support, and attaching the layer to a substrate via an adhesive layer.
The conductive layer can be provided on the substrate by the above-mentioned methods.

In one embodiment, the composition I is a resin composition R1 further containing a resin (C). The wavelength conversion layer (resin film) formed from the resin composition R1 can be formed by applying the composition I to a substrate or support and then drying it.
In another embodiment, the composition I is a curable composition R2 further comprising a polymerizable compound (D) and a polymerization initiator (E). The curable composition R2 may further comprise a resin (C). The wavelength conversion layer formed from the curable composition R2 is a cured film. The cured film can be obtained by applying the curable composition R2 to a substrate or support, drying the composition, and curing the composition by the action of light and/or heat.
One embodiment of the curable composition R2 is a photocurable composition R3 containing a photopolymerizable compound and a photopolymerization initiator. The photocurable composition R3 may further contain a resin (C).

2. Protective layer (composition II) and its manufacturing method The protective layer is formed on the wavelength conversion layer. The protective layer is disposed on the wavelength conversion layer, meaning that the protective layer is disposed on at least a part of the surface of the wavelength conversion layer directly or via another layer. The surface may be the main surface or side surface of the wavelength conversion layer. The main surface is preferably the main surface of the wavelength conversion layer in the light extraction direction. The protective layer may be disposed so as to cover the entire main surface of the wavelength conversion layer, or may be disposed so as to cover a part of the main surface. The protective layer is preferably disposed so as to cover the entire main surface of the wavelength conversion layer in the light extraction direction. The protective layer may be disposed so as to cover the entire surface of the wavelength conversion layer.

The thickness of the protective layer is, for example, 0.1 μm or more and 20 μm or less, and from the viewpoint of suppressing warping or wrinkles that may occur during curing and suppressing a decrease in the luminescence intensity of the wavelength conversion layer due to heat, is preferably 0.1 μm or more and 15 μm or less, more preferably 0.5 μm or more and 10 μm or less, even more preferably 0.5 μm or more and 6 μm or less, and even more preferably 0.5 μm or more and 4.5 μm or less.

Composition II is resin composition R4 containing resin (C). The protective layer (resin film) formed from resin composition R4 can be formed by applying composition II to a substrate and then drying it.
In a preferred embodiment, the composition II is a curable composition R5 that further includes a resin (C), a polymerizable compound (D), and a polymerization initiator (E). The overcoat layer formed from the curable composition R5 is a cured film. The cured film can be obtained by applying the curable composition R5 to a substrate, drying the composition, and curing the composition by the action of light and/or heat.
One embodiment of the curable composition R5 is a photocurable composition R6 that contains the resin (C) and further a photopolymerizable compound and a photopolymerization initiator.

3. Light absorbing layer (composition III) and its manufacturing method By providing a light absorbing layer formed from composition III on the wavelength conversion layer, it is possible to suppress leakage of primary light (e.g., blue light) to the viewing side of the light absorbing layer, and to suppress the decrease in luminous intensity when the light absorbing layer is arranged on the wavelength conversion layer, as compared with the case where the light absorbing layer is not arranged. Although it is desirable that the amount of primary light transmitted through the wavelength conversion layer is small, by arranging a light absorbing layer formed from composition III containing a chromatic colorant (Ic) on the wavelength conversion layer, it is possible to suppress leakage of primary light to the viewing side and suppress the decrease in luminous intensity even when a part of the primary light transmits through the wavelength conversion layer. From this viewpoint, the wavelength conversion layer may have a light transmittance at a wavelength of 450 nm of 10% or more, further 15% or more, and even 20% or more.

The wavelength range of light transmitted through the light absorbing layer is preferably a green or red wavelength range. The green wavelength range is, for example, a wavelength range from 495 nm to 585 nm. The red wavelength range is, for example, a wavelength range from 585 nm to 780 nm. The wavelength range of light absorbed by the light absorbing layer is preferably a blue wavelength range, more preferably a wavelength range including 450 nm, for example, a wavelength range from 380 nm to less than 495 nm.
In one embodiment, the composition III and the light absorbing layer have an average light transmittance of 98% or more in the wavelength range of 520 nm to 780 nm. The average light transmittance of 98% or more can further increase the emission intensity. The average light transmittance can be determined based on an absorption spectrum measured using an ultraviolet-visible-near infrared spectrophotometer equipped with an integrating sphere.

The thickness of the light absorbing layer is, for example, 0.1 μm or more and 30 μm or less, and from the viewpoint of effectively suppressing leakage of primary light (blue light) to the viewing side of the light absorbing layer, is preferably 0.1 μm or more and 20 μm or less, more preferably 0.5 μm or more and 10 μm or less, and even more preferably 0.5 μm or more and 6 μm or less.

In one embodiment, the composition III is a resin composition R7 further containing a resin (C). The light absorbing layer (resin film) formed from the resin composition R7 can be formed by applying the composition II to a substrate and then drying it.
In another embodiment, the composition III is a curable composition R8 further comprising a polymerizable compound (D) and a polymerization initiator (E). The curable composition R8 may further comprise a resin (C). The light absorbing layer formed from the curable composition R8 is a cured film. The cured film can be obtained by applying the curable composition R8 to a substrate, drying the composition, and curing the composition by the action of light and/or heat.
One embodiment of the curable composition R8 is a photocurable composition R9 containing a photopolymerizable compound and a photopolymerization initiator. The photocurable composition R9 may further contain a resin (C).

4. Substrate Examples of the substrate on which the wavelength conversion layer is formed include glass plates such as quartz glass, borosilicate glass, alumina silicate glass, and soda lime glass with a silica-coated surface; resin plates such as polycarbonate, polymethyl methacrylate, and polyethylene terephthalate; silicon; aluminum, silver, and silver/copper/palladium alloy thin films formed on these substrates; and components that are or may be included in the display device. Examples of components that are or may be included in the display device include a primary light source (e.g., a blue light source), a light guide plate, a diffusion film (diffusion layer), a light reflecting member (such as a reflection film), a brightness enhancing member, a prism sheet, and a barrier layer.

The substrate on which the protective layer is formed is the wavelength conversion layer or another layer formed on the wavelength conversion layer (however, a layer different from the wavelength conversion layer, the protective layer, and the light absorbing layer).

The substrate on which the light absorbing layer is formed is the protective layer or another layer formed on the protective layer (however, a layer different from the wavelength conversion layer, the protective layer, and the light absorbing layer).

The wavelength conversion layer, protective layer, and light absorbing layer may be provided on the entire surface of each substrate, or may be provided in a pattern on a part of the substrate. Methods for forming each layer (wavelength conversion layer, protective layer, or light absorbing layer) in a pattern on the substrate include photolithography, inkjet, and printing. Printing methods include stencil printing, screen printing, and printing and coating using an applicator.

5. Manufacturing method of laminate The patterned resin film (wavelength conversion layer) formed from the resin composition R1, the patterned resin film (protective layer) formed from the resin composition R4, and the patterned resin film (light absorbing layer) formed from the resin composition R7 can be formed on the substrate corresponding to each of the above-mentioned layers, for example, as follows. First, the resin composition R1, R4, or R7 is applied to the substrate corresponding to each of the above-mentioned layers through a mask to form a patterned composition layer. Examples of the method for applying the resin composition include spin coating, slit coating, and slit and spin coating.

Then, the composition layer is dried (volatile components such as the solvent are removed) to obtain a resin film (wavelength conversion layer, protective layer, or light absorption layer). Drying methods include heat drying, reduced pressure drying, and a combination of these. The temperature when heat drying is performed is preferably 30°C or higher and 250°C or lower, more preferably 50°C or higher and 235°C or lower. The heating time is preferably 10 seconds or higher and 180 minutes or lower, more preferably 30 seconds or higher and 90 minutes or lower. When reduced pressure drying is performed, it is preferably performed under a pressure of 50 Pa or higher and 150 Pa or lower. Drying of the composition layer may be performed in multiple stages, for example by performing multiple drying steps with different drying temperatures.

The patterned cured film (wavelength conversion layer) formed from photocurable composition R3, the patterned cured film (protective layer) formed from photocurable composition R6, and the patterned cured film (light absorption layer) formed from photocurable composition R9 can each be formed on a substrate corresponding to each of the layers described above, for example, by a method using photolithography as follows. First, photocurable composition R3, R6, or R9 is applied onto a substrate corresponding to each of the layers described above, and volatile components such as the solvent are removed by heating and drying (pre-baking) and/or drying under reduced pressure to obtain a composition layer. Examples of application methods include the same methods as those described above.

When drying by heating, the temperature is preferably 30°C or higher and 120°C or lower, and more preferably 50°C or higher and 110°C or lower. The heating time is preferably 10 seconds or higher and 60 minutes or lower, and more preferably 30 seconds or higher and 30 minutes or lower. When drying under reduced pressure, it is preferably performed under a pressure of 50 Pa or higher and 150 Pa or lower, and at a temperature range of 20°C or higher and 25°C or lower.

The composition layer is then exposed through a photomask to form the desired pattern shape. The light source used for exposure is preferably a light source that generates light with a wavelength of 250 nm or more and 450 nm or less. For example, from the light with this wavelength, light with a wavelength of around 436 nm, around 408 nm, or around 365 nm may be selectively extracted using a bandpass filter depending on the absorption wavelength of the photopolymerization initiator. Specific examples of light sources include mercury lamps, light-emitting diodes, metal halide lamps, halogen lamps, etc.

It is preferable to use an exposure device such as a mask aligner or stepper, since this allows for uniform irradiation of the entire exposure surface with parallel light and allows for accurate alignment of the photomask with the substrate on which the composition layer is formed. The exposed composition layer hardens as the photopolymerizable compound contained in the composition layer polymerizes.

By contacting the exposed composition layer with a developer and developing it, the unexposed portions of the composition layer are dissolved and removed in the developer, resulting in a patterned cured film (wavelength conversion layer, protective layer, or light absorbing layer). Examples of the developer include aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents. The concentration of the alkaline compound in the aqueous solution is preferably 0.01% by mass or more and 10% by mass or less, and more preferably 0.03% by mass or more and 5% by mass or less. Examples of the organic solvent include the same as the solvent (J) described above. The developer may contain a surfactant.

The development method may be any of the puddle method, dipping method, spray method, etc. Furthermore, the substrate may be tilted at any angle during development.

It is preferable to further heat (post-bake) the patterned film obtained by development. The heating temperature is preferably 150°C or higher and 250°C or lower, and more preferably 160°C or higher and 235°C or lower. The heating time is preferably 1 minute or higher and 120 minutes or lower, and more preferably 10 minutes or higher and 60 minutes or lower. By heating after development, the polymerization of unreacted photopolymerizable compounds contained in the film can be promoted, and a cured film with better chemical resistance can be obtained. Even if development is not performed, it is preferable to further heat (post-bake) the exposed composition layer.

On the other hand, a method for forming a cured film (wavelength conversion layer, protective layer, or light absorbing layer) on the entire surface of a substrate includes a method in which a curable composition is applied to a substrate corresponding to each of the above-mentioned layers, dried as necessary to form a composition layer, and the composition layer is heated and/or the entire surface of the composition layer is exposed to light.

The cured films formed from the curable compositions R2, R5, and R7 contain a cured reaction product of the polymerizable compound and polymerization initiator contained in the curable compositions R2, R5, and R7. The cured reaction product is a substance containing a structure resulting from the structure of the polymerizable compound and polymerization initiator. The structure resulting from the structure of the polymerizable compound and polymerization initiator is, for example, a skeletal structure or a part thereof other than the curing reaction site of the polymerizable compound and polymerization initiator.

The shapes and dimensions of the patterned wavelength conversion layer, protective layer, and light absorbing layer are not particularly limited. For example, the patterned wavelength conversion layer, protective layer, and light absorbing layer have a rectangular shape in plan view.

The wavelength conversion layer according to one embodiment is a layer that absorbs primary light from a primary light source and emits green light, and is preferably a layer that converts the wavelength of the primary light, that is, blue light, into the wavelength of green light. The green light emitted by the wavelength conversion layer preferably includes a peak having a maximum value in a wavelength range of 500 nm to 560 nm inclusive, more preferably includes a peak having a maximum value in a wavelength range of 520 nm to 555 nm inclusive, and even more preferably includes a peak having a maximum value in a wavelength range of 525 nm to 550 nm inclusive. The peak preferably has a full width at half maximum of 15 nm to 80 nm inclusive, more preferably 15 nm to 60 nm inclusive, even more preferably 15 nm to 50 nm inclusive, and particularly preferably 15 nm to 45 nm inclusive.

The wavelength conversion layer according to another embodiment is a layer that absorbs primary light from a primary light source and emits red light, and is preferably a layer that converts the wavelength of the primary light, that is, blue light, into the wavelength of red light. The red light emitted by the wavelength conversion layer preferably includes a peak having a maximum value in the wavelength range of 610 nm to 750 nm inclusive, more preferably includes a peak having a maximum value in the wavelength range of 620 nm to 650 nm inclusive, and even more preferably includes a peak having a maximum value in the wavelength range of 625 nm to 645 nm inclusive. The peak preferably has a full width at half maximum of 15 nm to 80 nm inclusive, more preferably 15 nm to 60 nm inclusive, even more preferably 15 nm to 50 nm inclusive, and particularly preferably 15 nm to 45 nm inclusive.

The laminate and display device described below can include both a wavelength conversion layer that emits green light and a wavelength conversion layer that emits red light.

The wavelength conversion layer may be a layer that absorbs a part of the primary light and transmits the remaining part of the primary light. From the viewpoint of widening the color gamut and energy efficiency of the display device, the wavelength conversion layer preferably has a light transmittance of 90% or less at a wavelength of 450 nm, more preferably 85% or less, even more preferably 75% or less, even more preferably 60% or less, particularly preferably 40% or less, even more particularly preferably 30% or less, and most preferably 20% or less. It is desirable that the amount of primary light that transmits through the wavelength conversion layer is small, but according to the present invention that includes a light absorbing layer, even if a part of the primary light transmits through the wavelength conversion layer, leakage of the primary light to the viewing side can be suppressed, and the provision of the light absorbing layer can suppress a decrease in the emission intensity. From this viewpoint, the wavelength conversion layer may have a light transmittance of 10% or more, even 15% or more, and even 20% or more at a wavelength of 450 nm.

<Display Device>
A display device according to the present invention (hereinafter, also simply referred to as a "display device") includes a primary light source and the laminate according to the present invention. The display device is a device that irradiates a wavelength conversion layer with primary light from the primary light source to cause the wavelength conversion layer to emit light, and extracts the emitted light via a light absorbing layer.

5 is a schematic cross-sectional view showing an example of a display device according to the present invention. The display device shown in FIG. 5 includes the laminate shown in FIG. 4, and includes a blue light source 40 as a primary light source having a first region, a second region, and a third region that are different from each other, a first wavelength conversion layer 11 arranged on the first region of the blue light source 40 and emitting, for example, red light, a first protective layer 21 arranged thereon, a second wavelength conversion layer 12 arranged on the second region of the blue light source 40 and emitting, for example, green light, and a second protective layer 22 arranged thereon. The display device has a red light emission region (i.e., the first region), a green light emission region (i.e., the second region), and a blue light emission region (i.e., the third region). In this way, the display device has a blue light source, a wavelength conversion layer, and a protective layer in this order in the optical path of light from the blue light source 40.

The first wavelength conversion layer 11 and the second wavelength conversion layer 12 may be disposed directly on the blue light source 40, or may be disposed on a light guide plate disposed between the blue light source 40 and the first wavelength conversion layer 11 and the second wavelength conversion layer 12 in the optical path of the light from the blue light source 40.

The display device may further include a transparent layer that transmits blue light or a layer that contains a light diffusing agent, which is disposed on the third region of the blue light source 40. The laminate included in the display device may also include a light absorbing layer 30, similar to the laminates in Figures 2 and 3. A third light absorbing layer that transmits blue light and absorbs light other than blue light may be provided on the transparent layer that transmits blue light or the layer that contains a light diffusing agent.

The blue light source 40 may be, for example, a known light source such as a light emitting diode (LED) such as a blue light emitting diode, a laser, or an EL. From the standpoint of color gamut and energy efficiency, the blue light source 40 is preferably a light source that emits light having a peak at 495 nm or less, and more preferably a light source that emits light having a peak at 425 nm or more and 495 nm or less.

The display device may further include, for example, a light guide plate, a diffusion film (diffusion layer), a light reflecting member (such as a reflective film), a brightness enhancing member, a prism sheet, a barrier layer, etc.

Any suitable light guide plate can be used as the light guide plate. For example, a light guide plate having a lens pattern formed on the back side, or a light guide plate having a prism shape or the like formed on the back side and/or the viewing side can be used so that light from the lateral direction can be deflected in the thickness direction.

The diffusion film is a film for diffusing the primary light or the light emitted from the wavelength conversion layer, and may be an amplifying diffusion film, etc. The light reflecting member is a member for reflecting the primary light toward the wavelength conversion layer, and may be, for example, a reflecting mirror, a film of reflective particles, a reflective metal film, or a reflector, etc. The brightness enhancing member is a member for reflecting a portion of the light back in the direction from which the light was transmitted.

A prism sheet typically has a base portion and a prism portion. The base portion may be omitted depending on the adjacent member. The prism sheet can be attached to the adjacent member via any appropriate adhesive layer (e.g., an adhesive layer, a pressure-sensitive adhesive layer). The prism sheet is composed of a number of unit prisms arranged in parallel, each of which is convex on the side opposite the viewing side (the rear side). By arranging the convex portions of the prism sheet facing the rear side, the light passing through the prism sheet is easily concentrated. Furthermore, by arranging the convex portions of the prism sheet facing the rear side, less light is reflected without entering the prism sheet compared to when the convex portions are arranged facing the viewing side, and a display device with high luminous intensity can be obtained.

The barrier layer is a layer for protecting the wavelength conversion layer from water vapor in the outside air and oxygen in the atmosphere. A display device according to one embodiment includes both a protective layer and a barrier layer for protecting the wavelength conversion layer from water vapor in the outside air and oxygen in the atmosphere.

The display device may include a layer of one or more media materials in the optical path between adjacent elements (layers). The one or more media materials may include any suitable material, including, but not limited to, vacuum, air, gas, optical material, adhesive, optical adhesive, glass, polymer, solid, liquid, gel, curable material, optical bonding material, index matching or index mismatching material, index gradient material, cladding or anti-cladding material, spacer, silica gel, brightness enhancing material, scattering or diffusing material, reflective or anti-reflective material, wavelength selective material, wavelength selective anti-reflective material, or other suitable media known in the art.

Specific examples of the display device include those equipped with a wavelength conversion material for an EL display or a liquid crystal display. The display device is not limited to the example shown in FIG. 5, and may be, for example,
A display device in which a wavelength conversion layer is disposed between a blue light source and a light guide plate along an end face (side face) of the light guide plate to form a backlight that emits white light (on-edge type backlight), and a light absorbing layer is disposed on the light guide plate side;
A display device in which a wavelength conversion layer is placed on a light guide plate, a backlight (surface mount type backlight) is formed in which light irradiated from a blue light source placed on an end face (side face) of the light guide plate to the wavelength conversion layer through the light guide plate is emitted as white light, and a light absorbing layer is placed on the wavelength conversion layer;
A display device in which a wavelength conversion layer is disposed near a light emitting portion of a blue light source, and a backlight (on-chip type backlight) is formed to emit irradiated light as white light, and a light absorbing layer is disposed on the wavelength conversion layer;
etc.

The present invention will be explained in more detail below with reference to examples. In the examples, "%" and "parts" are by mass % and parts by mass unless otherwise specified.

<Measurement>
(1) Measurement of Thickness of Wavelength Conversion Layer and Protective Layer The thickness was measured using a film thickness measuring device (DEKTAKXT; manufactured by Bruker Corporation).

(2) Measurement of Emission Intensity Maintenance Rate A light diffusion plate was placed on a backlight using a blue LED lamp with an emission peak wavelength of 450 nm as a point light source to form a backlight unit. The backlight unit was placed with the light diffusion plate facing upward, and a spectroradiometer ("SR-UL1R" manufactured by Topcon Corporation) was installed at a height of 60 cm from the surface of the light diffusion plate. A wavelength conversion layer formed on a glass substrate, and a laminate of the wavelength conversion layer and protective layer formed on a glass substrate were used as measurement samples, and the measurement samples were placed on the surface of the light diffusion plate with the laminate facing upward. In this state, the backlight was turned on, and the spectral radiance spectrum of the light emitted from the laminate was measured using the spectroradiometer, and the emission intensity EI (μW) at the maximum peak wavelength of the green emission peak was calculated from this spectrum.
The maximum peak wavelength of the green emission peak described above was 530 nm, which is the maximum peak wavelength of the green emission peak in the emission spectrum of the semiconductor particles (A) contained in the wavelength conversion layer. The full width at half maximum of the green emission peak was 42 nm.
The emission spectrum of the semiconductor particles (A) was measured using an absolute PL quantum yield measurement device ("C9920-02" manufactured by Hamamatsu Photonics, excitation light of 450 nm, room temperature, under atmospheric air) using a dispersion of semiconductor particles (A) diluted so as to have an absorbance of 0.4 at a wavelength of 450 nm as a measurement sample.
The luminous intensity EI _a of the laminate of the wavelength conversion layer and the protective layer formed on the glass substrate was measured, and the luminous intensity of the wavelength conversion layer formed on the glass substrate was designated as EI _b . The maintenance rate of the luminous intensity EI before and after the lamination of the protective layer was calculated according to the following formula.
Maintenance rate of luminescence intensity EI (%) = [EI _a /EI _b ] × 100

(3) Measurement of Weight Average Molecular Weight (Mw) of Resin The polystyrene-equivalent weight average molecular weight (Mw) of Resin (C) was measured by GPC under the following conditions.
Apparatus: HLC-8120GPC (manufactured by Tosoh Corporation)
Column: TSK-GELG2000HXL
Column temperature: 40°C
Solvent: tetrahydrofuran Flow rate: 1.0 mL/min Solids concentration of analytical sample: 0.001 to 0.01% by mass
Injection volume: 50 μL
Detector: RI
Calibration standard material: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

(4) Acid Value of Resin (C) 3 g of resin (C) solution was precisely weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. Using a 0.1 N KOH aqueous solution as a titrant, the acid value of the resin (C) solution was measured with an automatic titrator (manufactured by Hiranuma Sangyo Co., Ltd., product name: COM-555). The acid value per 1 g of solid content (mg KOH/g) was calculated from the acid value of the solution and the solid content of the solution.

(5) Measurement of development rate In the examples described later, the laminate obtained by applying the compositions II-1 to II-11 onto the wavelength conversion layer and pre-baking was immersed in a developer (a 0.02 wt % aqueous TMAH solution) for development. The time (seconds) until the protective layer was completely removed was measured to evaluate the development rate (μm/second).

(6) Evaluation of film remaining rate In the examples described later, compositions II-1 to II-11 were applied onto the wavelength conversion layer, prebaked and exposed, and developed by immersing in a 0.02 wt % aqueous TMAH solution at 25° C. for 30 seconds, followed by post-baking at 180° C. for 60 minutes. The film thickness in the exposed area after pre-baking and exposure, and the film thickness of the laminate sample further developed and post-baked after exposure were measured by measuring the step of the scratches made on the surface of the film using a stylus-type step gauge (DektakXT, manufactured by Bluker). The film remaining rate calculated by the following formula was evaluated as ◎ when it was 80% or more, ○ when it was less than 80% or 70% or more, and × when it was less than 70%.
Residual film ratio (%)=100×(film thickness after post-baking)/(film thickness after exposure)

<Synthesis Example 1: Synthesis of Resin (C1)>
A suitable amount of nitrogen was flowed into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 80 parts of propylene glycol monomethyl ether acetate (PGMEA) was added, and the mixture was heated to 85°C while stirring. Next, a mixed solution prepared by dissolving 6 parts of methacrylic acid, 25 parts of dicyclopentanyl methacrylate, 40 parts of methyl methacrylate, and 29 parts of 1-[2-(methacryloyloxy)ethyl] succinate in 20 parts of PGMEA was dropped into the flask over 4 hours. Meanwhile, a solution prepared by dissolving 9 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 40 parts of PGMEA was dropped over 5 hours. After the drop of the initiator solution was completed, the mixture was kept at 85°C for 4 hours and then cooled to room temperature to obtain a copolymer (resin (C1)) solution. The solid content of the resin (C1) solution was 40%, and the weight average molecular weight Mw was 11,500.

<Synthesis Example 2: Synthesis of Resin (C2)>
Into a flask equipped with a stirrer, a reflux condenser with a thermometer, a dropping funnel, and a nitrogen inlet tube, 110 parts of PGMEA were put, and then the mixture was stirred while replacing with nitrogen, and the temperature was raised to 80° C. A solution obtained by dissolving 25 parts of dicyclopentanyl methacrylate, 23 parts of methyl methacrylate, 19 parts of methacrylic acid, and 10 parts of 2,2′-azobis(2,4-dimethylvaleronitrile) in 110 parts of PGMEA was dropped from the dropping funnel into the flask, and then the mixture was stirred at 80° C. for 3 hours.
Next, 16 parts of glycidyl methacrylate, 0.4 parts of 2,2'-methylenebis(4-methyl-6-tert-butylphenol), and 0.8 parts of triphenylphosphine were added to the flask, and the temperature was raised to 110°C. The mixture was stirred for 8 hours to react the carboxylic acid and epoxy group in the polymer, thereby introducing a polymerizable unsaturated bond. Next, 17 parts of 1,2,3,6-tetrahydrophthalic anhydride were added and the reaction was continued for 3 hours to introduce a carboxylic acid group into the side chain. The reaction solution was cooled to room temperature to obtain a resin (C2) solution.
Resin (C2) had a weight average molecular weight Mw of 8,400 in terms of standard polystyrene, a molecular weight distribution of 2.2, and an acid value of 100 mgKOH/g, and the solid content in the resin (C2) solution was 40 mass %.

<Synthesis Example 3: Synthesis of Resin (C3)>
A suitable amount of nitrogen was poured into a flask equipped with a reflux condenser, a dropping funnel and a stirrer to replace the atmosphere with nitrogen, 371 parts of PGMEA was added, and the mixture was heated to 85°C while stirring. Next, a mixed solution prepared by dissolving 54 parts of acrylic acid, 225 parts of a mixture of 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-8-yl acrylate and 3,4-epoxytricyclo[5.2.1.0 ^2,6 ]decan-9-yl acrylate (content ratio is 50:50 in molar ratio), and 81 parts of vinyltoluene (mixture of isomers) in 80 parts of PGMEA was dropped into the flask over 4 hours. Meanwhile, a solution prepared by dissolving 30 parts of polymerization initiator 2,2-azobis(2,4-dimethylvaleronitrile) in 160 parts of PGMEA was dropped over 5 hours. After the dropwise addition of the initiator solution was completed, the mixture was kept at 85° C. for 4 hours and then cooled to room temperature to obtain a copolymer (resin (C3)) solution. The resin (C3) solution had a solid content of 37%, an acid value of 120 mgKOH/g, and a weight average molecular weight Mw of 10,600.

<Synthesis Example 4: Synthesis of Resin (C4)>
Resin (C4) was prepared as follows by adjusting the amount of raw material monomer. Propylene glycol monomethyl ether acetate was placed in a flask equipped with a stirrer, dropping funnel, condenser, thermometer, and gas inlet tube, and the mixture was stirred and heated to 120°C while replacing with nitrogen. Next, a monomer mixture consisting of 2-ethylhexyl acrylate, glycidyl methacrylate, and dicyclopentanyl methacrylate to which t-butylperoxy-2-ethylhexanoate (polymerization initiator) had been added was dropped into the flask from the dropping funnel over a period of 2 hours. After the dropwise addition was completed, the mixture was stirred for an additional 30 minutes at 120°C to carry out a copolymerization reaction, and an addition copolymer was produced.

Then, the atmosphere in the flask was replaced with air, and acrylic acid, triphenylphosphine (catalyst), and methoquinone (polymerization inhibitor) were added to the addition copolymer solution, and the reaction was continued at 110°C for 10 hours, cleaving the epoxy groups by the reaction of the epoxy groups derived from glycidyl methacrylate with acrylic acid, while simultaneously introducing polymerizable unsaturated bonds into the side chains of the polymer. Succinic anhydride was then added to the reaction system, and the reaction was continued at 110°C for 1 hour, introducing carboxyl groups into the side chains by reacting the hydroxyl groups generated by the cleavage of the epoxy groups with succinic anhydride, yielding a polymer (resin (C4)).

Finally, 383.3 g of propylene glycol monomethyl ether acetate was added to the reaction solution to obtain a resin (C4) solution with a polymer solids content of 40%.

The weight average molecular weight Mw of the resulting copolymer was 4,960, the acid value calculated as solids was 37 mg-KOH/g, and the double bond equivalent was 344 g/eq.

<Preparation Example 1: Preparation of semiconductor particle (A1) dispersion>
A toluene dispersion a of semiconductor particles (A1) [green-emitting InP/ZnSeS quantum dots] containing oleic acid as an organic ligand (G1) was prepared. As described above, the maximum peak wavelength of the green emission peak of the quantum dots was 530 nm, and the full width at half maximum of the green emission peak was 42 nm.

After removing the toluene from the toluene dispersion a by vacuum distillation, 70 parts of cyclohexyl acetate (J3) was added to a total of 30 parts of the semiconductor particles (A1) and organic ligand (G1) to obtain semiconductor particle (A1) dispersion b. The composition of semiconductor particle (A1) dispersion b is shown in Table 1.

The composition ratio of the semiconductor particles (A1) and the organic ligand (G1) was determined by measuring the amount of the mixture remaining after removing the toluene and heating it to 550°C at a heating rate of 5°C/min using TG-DTA measurement, and calculating the weight of the organic ligand (G1).

<Preparation Example 2: Preparation of wavelength conversion layer forming composition I>
The semiconductor particle (A1) dispersion b and each component were mixed to prepare a wavelength conversion layer forming composition I having the composition shown in Table 2. In Table 2, the parts of the components other than the solvent (J) are shown as solid content equivalents.

Details of the abbreviations of the ingredients shown in Table 2 are as follows:

Organic ligand (G1): Oleic acid White colorant (Iw1): 60 parts of titanium oxide particles, 10 parts of resin C1 (solid content equivalent), and 30 parts of PGMEA were mixed, and the titanium oxide particles were thoroughly dispersed using a bead mill. The number of parts of light scattering agent (B1) shown in Table 2 is the number of parts of titanium oxide particles.
Polymerizable compound (D1): Carboxy group-containing polyfunctional (meth)acrylate (product name "Aronix (registered trademark) M-510" manufactured by Toagosei Co., Ltd.)
Polymerization initiator (E1): "Irgacure (registered trademark) OXE-02" manufactured by BASF Corporation
Antioxidant (Fb1): Trade name "Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd.
Leveling agent (H1): Polyether modified silicone oil (product name "Toray Silicone SH8400" manufactured by Toray Dow Corning Co., Ltd.)
Solvent (J1): Propylene glycol monomethyl ether acetate Solvent (J3): Cyclohexyl acetate

<Examples 1-1 to 1-10 and Comparative Example 1: Preparation of Composition II>
Compositions II-1 to II-11 were obtained by mixing the components shown in Table 3. In Table 3, the parts of the resin are calculated as solid content.

Details of the abbreviations of the ingredients shown in Table 3 are as follows:

Polymerizable compound (Da): Carboxy group-containing polyfunctional (meth)acrylate (product name "Aronix (registered trademark) M-510" manufactured by Toagosei Co., Ltd.)
Polymerizable compound (Db): A-9550 (photopolymerizable compound, dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Co., Ltd., solid content 100%)
Polymerization initiator (E2): A photopolymerization initiator represented by the following formula, produced by the method described in JP-A-2011-132215 (solid content 100%).

Polymerization initiator (E3): a compound represented by the following formula (EA-1).

Antioxidant (Fb1): Trade name "Sumilizer (registered trademark) GP" manufactured by Sumitomo Chemical Co., Ltd.
Antioxidant (Fb2): Trade name "Sumilizer (registered trademark) GA80" manufactured by Sumitomo Chemical Co., Ltd.
Ultraviolet absorber (Fc1): Trade name "DAINSORB T-0" (2-(2,4-dihydroxyphenyl)-2H-benzotriazole) manufactured by Daiwa Kasei
Solvent (J1): Propylene glycol monomethyl ether acetate (PGMEA)

<Example 2-1>
The composition I for forming a wavelength conversion layer prepared in Preparation Example 2 was applied by spin coating onto a 5 cm square glass substrate ("Eagle XG" manufactured by Corning Incorporated) so that the thickness of the layer after post-baking was 3 μm, and then pre-baked at 100° C. for 3 minutes to form a composition layer. The substrate on which this composition layer was formed was irradiated with light at an exposure dose of 80 mJ/cm ² (based on 365 nm) in an air atmosphere using an exposure machine ("TME-150RSK" manufactured by Topcon Corporation), and after development, post-baked at 180° C. for 30 minutes to form a wavelength conversion layer. The luminescence intensity EI _b of the obtained wavelength conversion layer (luminescence intensity before lamination of the protective layer) was measured.

Next, the composition II-1 prepared in Example 1-1 was applied onto the wavelength conversion layer by spin coating so that the thickness of the layer after post-baking was 1 μm, and then pre-baked at 100 ° C. for 3 minutes to form a composition layer. The substrate on which the composition layer was formed on the wavelength conversion layer was irradiated with light at an exposure dose of 100 mJ / cm ² (based on 365 nm) in an air atmosphere using an exposure machine (Topcon Corporation's "TME-150RSK"), and post-baked at 180 ° C. for 30 minutes to form a laminate of the wavelength conversion layer and the protective layer. The luminescence intensity (luminescence intensity after lamination of the protective layer) EI _a of the obtained laminate was measured, and the luminescence intensity maintenance rate was measured according to the measurement method described above. In addition, the development rate and the residual film rate were measured according to the above "(5) Measurement of development rate" and "(6) Evaluation of residual film rate".

<Examples 2-2 to 2-10 and Comparative Example 2>
Laminates of wavelength conversion layers and protective layers of Examples 2-2 to 2-10 and Comparative Example 2 were formed in the same manner as in Example 2-1, except that compositions II-2 to II-11 were used instead of composition II-1, and the maintenance rates of luminous intensity EI before and after lamination of the protective layer were determined. In addition, the development rate and the film remaining rate were measured according to the above "(5) Measurement of development rate" and "(6) Evaluation of film remaining rate".

Table 4 shows the results of the luminescence intensity maintenance rate, development speed, and film remaining rate for Examples 2-1 to 2-10 and Comparative Example 2.

10 wavelength conversion layer, 11 first wavelength conversion layer, 12 second wavelength conversion layer, 20 protective layer, 21 first protective layer, 22 second protective layer, 30 light absorbing layer, 40 blue light source

Claims

A composition containing neither semiconductor particles (A) nor a colorant (I),
The composition contains a resin (C) and a light stabilizer (F),
The resin (C) is a composition containing a resin (C-1) having a weight average molecular weight Mw of 10,000 or less.
The composition according to claim 1, wherein the acid value of the resin (C-1) is 110 mg KOH/g or less.
The composition further comprises a polymerizable compound (D),
The composition according to claim 1, wherein a mass ratio of the resin (C-1) to the polymerizable compound (D) (resin (C-1)/polymerizable compound (D)) is 1.8 or less.
The composition according to claim 1, which is used to form a protective layer to be placed on a wavelength conversion layer containing semiconductor particles (A).
a wavelength conversion layer having semiconductor particles (A);
and a protective layer formed from the composition of claim 1 and disposed on the wavelength converting layer.
A laminate including a wavelength conversion layer having semiconductor particles (A), a protective layer, and a light absorbing layer,
The protective layer is a laminate which is a layer formed from a composition which does not contain any of semiconductor particles (A) and colorant (I), and which contains a resin (C) and further contains a light stabilizer (F), the resin (C) containing a resin (C-1) having a weight average molecular weight Mw of 10,000 or less.
A display device comprising the laminate according to claim 5 or 6.