Composition, film, and display device

Abstract

Provided is a composition containing particles, the particles containing first particles (A-1) having an average particle diameter d of 100 * 10-7 cm or more, the composition further containing at least one substance selected from the group consisting of resins (C) and polymerizable compounds (D), and the settling velocity v represented by formula (i) of the composition being 400 * 10-9 cm / s or less.

Description

Technical Field

[0001] The present invention relates to a composition containing particles, a film formed from the composition, and a display device including the film. Background Art

[0002] Patent Document 1 describes a photosensitive resin composition containing particles for forming a color filter.

[0003] Prior art literature

[0004] Patent Literature

[0005] Patent Document 1: International Publication No. 2014 / 157296 Summary of the invention

[0006] A film exhibiting desired properties such as optical properties can be produced by film formation of a composition containing particles that exhibit the desired properties.

[0007] The present invention provides a composition containing particles exhibiting desired characteristics and capable of forming a film exhibiting the desired characteristics. Another object of the present invention is to provide a film formed from the composition and a display device including the film.

[0008] The present invention provides the composition, film, and display device shown below.

[0009] [1] A composition comprising particles,

[0010] The particles have an average particle size d of 100×10 －7 The first particle (A-1) with a diameter of cm or more,

[0011] The above composition further contains at least one selected from the group consisting of a resin (C) and a polymerizable compound (D),

[0012] The sedimentation velocity v represented by formula (i) of the above composition is 400×10 －9 cm / s or less.

[0013]

[0014] [In formula (i), g represents the acceleration due to gravity (cm / s 2 〕, ρ s represents the density of the first particle (A-1) [g / cm 3 〕, ρ represents the density of the same composition as the above composition except that the above particles are not contained〔g / cm 3 〕, μ represents the viscosity of the above composition at 25°C〔g / (cm·s)〕. ]

[0015] [2] The composition according to [1], wherein the first particles (A-1) are light scattering particles.

[0016] [3] The composition according to [1] or [2], wherein the first particles (A-1) are inorganic particles.

[0017] [4] The composition according to any one of [1] to [3], wherein the particles further comprise －7 The second particle (A-2) is smaller than cm.

[0018] [5] The composition according to [4], wherein the second particles (A-2) are luminescent particles.

[0019] [6] The composition according to any one of [1] to [5], wherein the resin (C) is a resin having a polar group, and the polymerizable compound (D) is a polymerizable compound having a polar group.

[0020] [7] The composition according to [6], wherein the polar group is at least one group selected from the group consisting of a carboxyl group, a thiol group, and an amino group.

[0021] [8] The composition according to any one of [1] to [7], which is a composition for forming an optical functional film.

[0022] [9] A film formed from the composition according to any one of [1] to [8].

[0023]

[10] A display device comprising the film described in [9].

[0024] A composition containing particles exhibiting desired characteristics and capable of forming a film exhibiting the desired characteristics in a satisfactory manner, a film formed from the composition, and a display device including the film can be provided. DETAILED DESCRIPTION

[0025] <Composition>

[0026] The composition of the present invention (hereinafter, also referred to as "composition") is a composition containing particles. The particles contain particles having an average particle size d of 100×10 －7 The first particle (A-1) has a diameter of at least cm (100 nm). In addition to the first particle (A-1), the particle may also include a second particle (A-2) which is a particle different from the first particle (A-1). The composition further includes at least one binder component selected from a resin (C) and a polymerizable compound (D). The components contained or may be contained in the composition are described below.

[0027] In addition, the compounds exemplified as the components contained or may be contained in the composition in the present specification may be used alone or in combination of two or more, unless otherwise specified.

[0028] [1] First particle (A-1)

[0029] The first particle (A-1) is usually a solid particle that can exhibit specific characteristics (functions). The specific characteristics are preferably optical characteristics. The film obtained by forming a composition containing the first particle (A-1) can exhibit the above-mentioned specific characteristics (functions), for example, it can become an optical functional film (a film that exhibits optical functions). The composition can contain one or more first particles (A-1).

[0030] The average particle size d of the first particles (A-1) is 100×10 －7 cm (100nm) or more. When a film is formed from a composition containing particles having such a large particle size, it is easy to cause the problem that the properties exhibited by the particles cannot be well exerted in the film. As a result, according to the present invention, this problem can be solved and a film that well exhibits the properties of the particles can be formed. The average particle size d of the first particle (A-1) can be 150×10 －7 cm or more, 180×10 －7 cm or more or 200×10 －7 The average particle size d of the first particles (A-1) is usually 5000×10 －7 cm or less, or 1000×10 －7 cm or less, 800×10 －7 cm or less, 500×10 －7 cm or less or 300×10 －7 cm or less.

[0031] The first particle (A-1) is not particularly limited, and light scattering particles may be cited. Light scattering particles have the function of scattering incident light. A film containing light scattering particles can be used as a light scattering film (light diffusion film). As described later, the composition and the film may further contain luminescent particles as the second particle (A-2). In this case, the light scattering particles can have the function of increasing the luminescence intensity by scattering the light emitted from the luminescent particles. When the composition further contains luminescent particles as the second particle (A-2), the sedimentation velocity ν represented by the formula (i) described in detail later is 400×10 －9 cm / s or less, the luminescence intensity of a film formed from the composition can be increased.

[0032] As light scattering particles, inorganic particles such as particles of metal or metal oxide, glass particles can be enumerated. As metal oxides, TiO2, SiO2, BaTiO3, ZnO etc. can be enumerated, because light is effectively scattered, therefore preferably TiO2 particles. The light scattering particles can be inorganic particles, can also be organic particles, preferably inorganic particles. In addition, preferably the refractive index of the light scattering particles is high.

[0033] The refractive index of the first particle (A-1) is preferably 1.5 or more, more preferably 2.0 or more. As the refractive index, values ​​described in known literature and catalogs or general physical property tables can be used.

[0034] The density of the first particle (A-1) is s Usually 6g / cm 3 Below, usually 2.5g / cm 3 The first particle (A-1) may have a density of s Larger particles. If the composition is left to stand, particles with high density tend to settle, but according to the present invention, a composition that is less likely to cause particle sedimentation, i.e., has an improved pot life, can be provided. Thus, a film that well exhibits the characteristics of the first particle (A-1) can be formed.

[0035] The density of the first particle (A-1) is s This can be adjusted by selecting the material that constitutes the particle. s The density can be adjusted by a known method such as making the particles hollow or forming a core-shell structure having a surface layer made of a material with a low density.

[0036] The content of the first particles (A-1) in the composition is, for example, 0.001% by mass to 50% by mass relative to the total amount of the solid components of the composition. From the viewpoint of improving the properties of the film based on the first particles (A-1), it is preferably 0.01% by mass or more, more preferably 0.1% by mass or more, further preferably 1% by mass or more, further preferably 2% by mass or more, particularly preferably 5% by mass or more, and is preferably 30% by mass or less, more preferably 15% by mass or less, further preferably 10% by mass or less.

[0037] The total amount of solid content in this specification refers to the total amount of components obtained by removing the solvent (H) from the components contained in the composition. The content of the solid content of the composition can be measured by a known analytical method such as liquid chromatography or gas chromatography. The content of each component in the solid content of the composition can be calculated based on the formulation when the composition is prepared.

[0038] [2] Second particle (A-2)

[0039] The composition may contain second particles (A-2) which are different from the first particles (A-1). The second particles (A-2) are particles having a smaller particle size than the first particles (A-1), for example, an average particle size of 50×10 －7 cm or less. The composition may contain one or more second particles (A-2). The second particles (A-2) are generally solid particles that can exhibit specific characteristics (functions). The specific characteristics are preferably optical characteristics. The film obtained by forming a composition containing the second particles (A-2) can exhibit the above-mentioned specific characteristics (functions). The second particles (A-2) are not particularly limited, and luminescent particles may be mentioned. As luminescent particles, luminescent (fluorescent) semiconductor particles (hereinafter, also referred to as "semiconductor particles") and the like may be mentioned.

[0040] Semiconductor particles can be, for example, red light-emitting semiconductor particles that emit light with a luminescence peak wavelength in a wavelength region of 605nm to 665nm, green light-emitting semiconductor particles that emit light with a luminescence peak wavelength in a wavelength region of 500nm to 560nm, or blue light-emitting semiconductor particles that emit light with a luminescence peak wavelength in a wavelength region of 420nm to 480nm. Semiconductor particles are preferably red light-emitting semiconductor particles and / or green light-emitting semiconductor particles. The luminescence peak wavelength of semiconductor particles can be confirmed, for example, in a luminescence spectrum measured using an ultraviolet-visible spectrophotometer.

[0041] The half-peak width of the luminescence spectrum of semiconductor particles is preferably below 60nm, more preferably below 55nm, further preferably below 50nm, and particularly preferably below 45nm. Thus, light with higher color purity can be emitted. The lower limit of the half-peak width of the luminescence spectrum of semiconductor particles is not particularly limited, and can be above 5nm, or above 15nm.

[0042] The semiconductor particles are particles composed of semiconductor crystals, preferably nanoparticles composed of semiconductor crystals. Preferred examples of semiconductor particles include semiconductor quantum dots (hereinafter, also referred to as "quantum dots") and particles of compounds having a perovskite crystal structure (hereinafter, also referred to as "perovskite compounds"), more preferably quantum dots.

[0043] The average particle size of quantum dots is, for example, 0.5×10 －7 cm~20×10 －7 cm, preferably 1×10 －7 cm~15×10 －7 cm (e.g. 2×10 －7 cm~15×10 －7cm). The energy state of a quantum dot depends on its size, so the emission wavelength can be freely selected by changing the particle size. For example, in the case of a quantum dot composed only of CdSe, the particle size is 2.3×10 － 7 cm, 3.0×10 －7 cm、3.8×10 －7 cm, 4.6×10 －7 The peak wavelengths of the emission spectrum at cm are 528nm, 570nm, 592nm, and 637nm respectively.

[0044] For example, quantum dots can be composed of semiconductor materials containing one or more elements selected from Group IIA elements, Group IB elements, Group IIB elements, Group IIIA elements, Group IVA elements, Group VA elements and Group VIA elements of the periodic table.

[0045] Specific examples of semiconductor materials that can constitute quantum dots include:

[0046] Compounds of Group IVA elements and Group VIA elements such as SnS2, SnS, SnSe, SnTe, PbS, PbSe, PbTe;

[0047] Compounds of Group IIIA elements and Group VA elements such as GaN, GaP, GaAs, GaSb, InN, InP, InAs, InSb, InGaN, InGaP;

[0048] Compounds of Group IIIA elements and Group VIA elements such as Ga2O3, Ga2S3, Ga2Se3, Ga2Te3, In2O3, In2S3, In2Se3, In2Te3;

[0049] Compounds of Group IIB elements and Group VIA elements such as ZnO, ZnS, ZnSe, ZnTe, CdO, CdS, CdSe, CdTe, HgO, HgS, HgSe, HgTe, ZnSTe, ZnSeS, ZnSeTe, CdSTe, CdSeTe, HgSTe, HgSeS, HgSeTe;

[0050] Compounds of Group VA elements and Group VIA elements such as As2O3, As2S3, As2Se3, As2Te3, Sb2O3, Sb2S3, Sb2Se3, Sb2Te3, Bi2O3, Bi2S3, Bi2Se3, Bi2Te3;

[0051] Compounds of Group IIA elements and Group VIA elements such as MgS, MgSe, MgTe, CaS, CaSe, CaTe, SrS, SrSe, SrTe, BaS, BaSe, BaTe;

[0052] A single substance of a Group IVA element, a Group VA element, or a Group VIA element such as Si or Ge.

[0053] Quantum dots can be a single-layer structure composed of a single semiconductor material, or a core-shell structure in which the surface of a core particle (core layer) composed of a single semiconductor material is coated with a coating layer (shell layer) composed of one or more semiconductor materials different from it. In the latter case, as the semiconductor material constituting the shell layer, a material with a larger band gap energy than the semiconductor material constituting the core layer is generally used. Quantum dots can have more than two shell layers. The shape of quantum dots is not particularly limited, for example, it can be spherical or roughly spherical, rod-shaped, disc-shaped, etc.

[0054] The perovskite compound is a compound having A, B, and X as components and having a perovskite-type crystal structure.

[0055] A is a component located at each vertex of a hexahedron with B at the center in the perovskite crystal structure and is a monovalent cation.

[0056] X represents a component located at each vertex of an octahedron centered at B in a perovskite crystal structure, and is at least one ion selected from a halide ion and a thiocyanate ion.

[0057] B is a component located at the center of a hexahedron having A at its vertices and an octahedron having X at its vertices in the perovskite crystal structure, and is a metal ion.

[0058] From the viewpoint of maintaining a good crystal structure, the average particle size of the semiconductor particles composed of the perovskite compound is preferably 3×10 －7 cm or more, more preferably 4×10 －7 cm or more, more preferably 5×10 －7 cm or more, and usually 50×10 －7 cm or less.

[0059] The perovskite compound having A, B, and X as components is not particularly limited, and may be a compound having any of a three-dimensional structure, a two-dimensional structure, and a quasi-two-dimensional structure.

[0060] For the three-dimensional structure, the perovskite compound is composed of ABX (3+δ) express.

[0061] In the case of a two-dimensional structure, the perovskite compound is composed of A2BX (4+δ) express.

[0062] Here, δ is a number that can be appropriately changed according to the charge balance of B, and is in the range of −0.7 to 0.7.

[0063] As a perovskite compound and composed of ABX (3+δ) Preferred specific examples of the compound having a three-dimensional perovskite-type crystal structure represented by include:

[0064] CH3NH3PbBr3, CH3NH3PbCl3, CH3NH3PbI3, CH3NH3PbBr (3－y) I y (0<y<3), CH3NH3PbBr (3－y) Cl y (0<y<3), (H2N=CH-NH2)PbBr3, (H2N=CH-NH2)PbCl3, (H2N=CH-NH2)PbI3,

[0065] CH3NH3Pb (1－a) Ca a Br3(0<a≤0.7), CH3NH3Pb (1－a) Sr a Br3(0<a≤0.7), CH3NH3Pb (1－a) La a Br (3+δ) (0<a≤0.7, 0<δ≤0.7), CH3NH3Pb (1－a) Ba a Br3(0<a≤0.7), CH3NH3Pb (1－a) Dy a Br (3+δ) (0<a≤0.7, 0<δ≤0.7),

[0066] CH3NH3Pb (1－a) Na a Br (3+δ) (0<a≤0.7,-0.7≤δ<0), CH3NH3Pb (1－a) Li a Br (3+δ) (0<a≤0.7, -0.7≤δ<0),

[0067] Cb (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), <h2 style=";text-align:left;direction:ltr">

[0068] <h2 style=";text-align:left;direction:ltr"> CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0069] <h2 style=";text-align:left;direction:ltr"> (H2N=CH-NH2)Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0)、(H2N=CH-NH2)Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Li<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ) <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0)、(H2N=CH-NH2)Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、(H2N=CH-NH2)Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Na<h2 style=";text-align:left;direction:ltr"> a <h2 style=";text-align:left;direction:ltr"> Br<h2 style=";text-align:left;direction:ltr"> (3+δ－y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<a≤0.7,-0.7≤δ<0,0<y<3)、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0070] <h2 style=";text-align:left;direction:ltr"> CsPbBr3、CsPbCl3、CsPbI3、CsPbBr<h2 style=";text-align:left;direction:ltr"> (3－y) <h2 style=";text-align:left;direction:ltr"> I<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<y<3)、CsPbBr<h2 style=";text-align:left;direction:ltr"> (3－y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<y<3)、CH3NH3PbBr<h2 style=";text-align:left;direction:ltr"> (3－y) <h2 style=";text-align:left;direction:ltr"> Cl<h2 style=";text-align:left;direction:ltr"> y <h2 style=";text-align:left;direction:ltr"> (0<y<3)、<h2 style=";text-align:left;direction:ltr"> <h2 style=";text-align:left;direction:ltr">

[0071] <h2 style=";text-align:left;direction:ltr"> CH3NH3Pb<h2 style=";text-align:left;direction:ltr"> (1－a) <h2 style=";text-align:left;direction:ltr"> Zn<h2 style=";text-align:left;direction:ltr"> aBr3(0<a≤0.7)、CH3NH3Pb (1－a) Al a Br (3+δ) (0<a≤0.7,0≤δ≤0.7)、CH3NH3Pb (1－a) CO a Br3(0<a≤0.7)、CH3NH3Pb (1－a) Mn a Br3(0<a≤0.7)、CH3NH3Pb (1－a) Mg a Br3(0<a≤0.7)、

[0072] CsPb (1－a) Zn a Br3(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 Br3(0<a≤0.7)、CsPb (1－a) Mn a Br3(0<a≤0.7)、CsPb (1－a) Mg a Br3(0<a≤0.7)、

[0073] CH3NH3Pb (1－a) Zn a Br (3－y) I y (0<a≤0.7,0<y<3)、CH3NH3Pb (1－a) Al a Br (3+δ－y) I y (0<a≤0.7,0<δ≤0.7,0<y<3)、CH3NH3Pb (1－a) CO a Br (3－y) I y (0<a≤0.7,0<y<3)、CH3NH3Pb (1－a) Mn a Br (3－y) I y (0<a≤0.7,0<y<3)、CH3NH3Pb (1－a) Mg a Br (3－y) I y (0<a≤0.7,0<y<3)、CH3NH3Pb (1－a) Zn a Br (3－y) Cly (0<a≤0.7, 0<y<3), CH3NH3Pb (1－a) Al a Br (3+δ－y) Cl y (0<a≤0.7, 0<δ≤0.7, 0<y<3), CH3NH3Pb (1－a) CO a Br (3+δ－y) Cl y (0<a≤0.7, 0<y<3), CH3NH3Pb (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),

[0074] (H2N=CH-NH2)Zn a Br3(0<a≤0.7), (H2N=CH-NH2)Mg a Br3(0<a≤0.7), (H2N=CH-NH2)Pb (1－a) Zn a Br (3－y) I y (0<a≤0.7, 0<y<3), (H2N=CH-NH2)Pb (1－a) Zn a Br (3－y) Cl y (0<a≤0.7, 0<y<3), etc.

[0075] As a perovskite compound and composed of A2BX (4+δ) Preferred specific examples of the compound having a two-dimensional perovskite-type crystal structure represented by include:

[0076] (C4H9NH3)2PbBr4, (C4H9NH3)2PbCl4, (C4H9NH3)2PbI4, (C7H 15 NH3)2PbBr4、(C7H 15 NH3)2PbCl4、(C7H 15 NH3)2PbI4, (C4H9NH3)2Pb (1－a) Li a Br (4+δ) (0<a≤0.7,-0.7≤δ<0), (C4H9NH3)2Pb (1－a) Naa Br (4+δ) (0<a≤0.7,-0.7≤δ<0)、(C4H9NH3)2Pb (1－a) Rb a Br (4+δ) (0<a≤0.7,-0.7≤δ<0)、

[0077] (C7H 15 NH3)2Pb (1－a) Na a Br (4+δ) (0<a≤0.7,-0.7≤δ<0)、(C7H 15 NH3)2Pb (1－a) Li a Br (4+δ) (0<a≤0.7,-0.7≤δ<0)、(C7H 15 NH3)2Pb (1－a) RbaBr (4+δ) (0<a≤0.7,-0.7≤δ<0)、

[0078] (C4H9NH3)2Pb (1－a) Na a Br (4+δ－y) I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb (1－a) Li a Br (4+δ－y) I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb (1－a) Rb a Br (4+δ－y) I y (0<a≤0.7,-0.7≤δ<0,0<y<4)、

[0079] (C4H9NH3)2Pb (1－a) Na a Br (4+δ－y) Cl y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb (1－a) Li a Br (4+δ－y) Cl y (0<a≤0.7,-0.7≤δ<0,0<y<4)、(C4H9NH3)2Pb (1－a) Rb a Br (4+δ－y) Cl y(0<a≤0.7,-0.7≤δ<0,0<y<4)、

[0080] (C4H9NH3)2PbBr4、(C7H 15 NH3)2PbBr4、

[0081] (C4H9NH3)2PbBr (4－y) Cl y (0<y<4)、(C4H9NH3)2PbBr (4－y) I y (0<y<4)、

[0082] (C4H9NH3)2Pb (1－a) Zn a Br4(0<a≤0.7)、(C4H9NH3)2Pb (1－a) Mg a Br4(0<a≤0.7)、(C4H9NH3)2Pb (1－a) CO a Br4(0<a≤0.7)、(C4H9NH3)2Pb (1－a) Mn a Br4(0<a≤0.7)、

[0083] (C7H 15 NH3)2Pb (1－a) Zn a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb (1－a) Mg a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb (1－a) CO a Br4(0<a≤0.7)、(C7H 15 NH3)2Pb (1－a) Mn a Br4(0<a≤0.7)、

[0084] (C4H9NH3)2Pb (1－a) Zn a Br (4－y) I y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb (1－a) Mg a Br (4－y) I y (0<a≤0.7,0<y<4)、(C4H9NH3)2Pb (1－a) CO a Br (4－y) Iy (0<a≤0.7, 0<y<4), (C4H9NH3)2Pb (1－a) Mn a Br (4－y) I y (0<a≤0.7, 0<y<4),

[0085] (C4H9NH3)2Pb (1－a) Zn a Br (4－y) Cl y (0<a≤0.7, 0<y<4), (C4H9NH3)2Pb (1－a) Mg a Br (4－y) Cl y (0<a≤0.7, 0<y<4), (C4H9NH3)2Pb (1－a) CO a Br (4－y) Cl y (0<a≤0.7, 0<y<4), (C4H9NH3)2Pb (1－a) Mn a Br (4－y) Cl y (0<a≤0.7, 0<y<4), etc.

[0086] The semiconductor particles may be ligand-containing semiconductor particles containing organic ligands (G) coordinated to the semiconductor particles. The organic ligands (G) may be, for example, organic compounds having polar groups that exhibit coordination ability to the semiconductor particles. The organic ligands (G) may be coordinated to, for example, the surface of the semiconductor particles.

[0087] Organic ligand (G) can be one kind of ligand, or can be more than two kinds of ligands.In the case where organic ligand (G) is an organic compound with a polar group, organic ligand (G) is usually coordinated to semiconductor particles via the polar group. Organic ligand (G) can be evenly dispersed in a dispersion medium suitable for organic ligand (G) by semiconductor particles to confirm that organic ligand (G) has been coordinated. From the viewpoint of improving the stability and dispersibility of semiconductor particles and luminous intensity, it is advantageous to use semiconductor particles containing ligands as semiconductor particles.

[0088] The polar group of the organic ligand (G) is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2). The polar group selected from this group is advantageous in that the coordination with the semiconductor particles can be improved. Among them, from the viewpoint of improving the luminous intensity, the polar group is more preferably at least one group selected from a thiol group and a carboxyl group. The organic ligand (G) may have one or more polar groups.

[0089] The organic ligand (G) may be, for example, an organic compound represented by the following formula (x).

[0090] X A -R X (x)

[0091] Where, X A is the above polar group, R X It is a monovalent hydrocarbon group that may contain heteroatoms (N, O, S, halogen atoms, etc.). The hydrocarbon group may have one or more unsaturated bonds such as carbon-carbon double bonds. 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, or 1 to 30. The methylene group contained in the hydrocarbon group may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc.

[0092] Group R X A polar group may be contained. Specific examples of the polar group include polar group X A The above records.

[0093] As having carboxyl group as polar group X A Specific examples of organic ligands include, in addition to formic acid, acetic acid, and propionic acid, saturated or unsaturated fatty acids. Specific examples of saturated or unsaturated fatty acids include saturated fatty acids such as butyric acid, valeric acid, caproic acid, caprylic acid, capric acid, lauric acid, myristic acid, pentadecanoic acid, palmitic acid, heptadecanoic acid, stearic acid, arachidic acid, behenic acid, and lignoceric acid; monounsaturated fatty acids such as myristoleic acid, palmitoleic acid, oleic acid, eicosenoic acid, erucic acid, and nervonic acid; polyunsaturated fatty acids such as linoleic acid, α-linolenic acid, γ-linolenic acid, linolenic acid, dihomo-γ-linolenic acid, arachidonic acid, eicosatetraenoic acid, docosadienoic acid, and adrenic acid (docosatetraenoic acid).

[0094] Having a thiol group or an amino group as the polar group X A Specific examples of the organic ligand include the above-exemplified organic ligands having a carboxyl group as a polar group X A An organic ligand obtained by replacing the carboxyl group of an organic ligand with a thiol group or an amino group.

[0095] In addition to the above, examples of the organic ligand represented by the above formula (x) include compound (G-1) and compound (G-2).

[0096] [Compound (G-1)]

[0097] Compound (G-1) is a compound having a first functional group and a second functional group. The first functional group is a carboxyl group (-COOH), and the second functional group is a carboxyl group or a thiol group (-SH). Since compound (G-1) has a carboxyl group and / or a thiol group, it can become a ligand coordinated to semiconductor particles. Semiconductor particles may contain only one compound (G-1) or two or more compounds.

[0098] One example of the compound (G-1) is a compound represented by the following formula (G-1a). The compound (G-1) may be an acid anhydride of the compound represented by the formula (G-1a).

[0099]

[0100] [Where R B Represents a divalent hydrocarbon group. B When , they may be the same or different. The above hydrocarbon group may have one or more substituents. When there are multiple substituents, they may be the same or different, and they may be bonded to each other and form a ring together with the atoms to which they are bonded. The -CH2- contained in the above hydrocarbon group may be substituted with at least one of -O-, -S-, -SO2-, -CO- and -NH-.

[0101] p represents an integer from 1 to 10.]

[0102] As R B Examples of the divalent hydrocarbon group represented by include a chain hydrocarbon group, an alicyclic hydrocarbon group, and an aromatic hydrocarbon group.

[0103] Examples of the chain hydrocarbon group include linear or branched alkanediyl groups, which usually have 1 to 50 carbon atoms, preferably 1 to 20 carbon atoms, and more preferably 1 to 10 carbon atoms. Examples of the alicyclic hydrocarbon group include monocyclic or polycyclic cycloalkanediyl groups, which usually have 3 to 50 carbon atoms, preferably 3 to 20 carbon atoms, and more preferably 3 to 10 carbon atoms. Examples of the aromatic hydrocarbon group include monocyclic or polycyclic aromatic diyl groups, which usually have 6 to 20 carbon atoms.

[0104] Examples of the substituent that the 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 carboxyl group, an amino group, a halogen atom, etc. The substituent that the hydrocarbon group may have is preferably a carboxyl group, an amino group or a halogen atom.

[0105] When -CH2- contained in the above hydrocarbon group is substituted with at least one of -O-, -CO- and -NH-, the group replacing -CH2- is preferably at least one of -CO- and -NH-, more preferably -NH-. p is preferably 1 or 2.

[0106] Examples of the compound represented by formula (G-1a) include compounds represented by the following formulae (1-1) to (1-9).

[0107]

[0108] If specific examples of the compound represented by formula (G-1a) are represented by chemical names, for example, mercaptoacetic acid, 2-mercaptopropionic acid, 3-mercaptopropionic acid, 3-mercaptobutyric acid, 4-mercaptobutyric 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, 3-mercapto-2-methylpropionic acid, etc. Among them, 3-mercaptopropionic acid and mercaptosuccinic acid are preferred.

[0109] Another example of the compound (G-1) is a polycarboxylic acid compound, and preferably a compound (G-1b) in which -SH in the formula (G-1a) is substituted with a carboxyl group (-COOH) in the compound represented by the above formula (G-1a).

[0110] Examples of the compound (G-1b) include the following compounds.

[0111] Succinic acid, glutaric acid, adipic acid, octafluoroadipic acid, azelaic acid, dodecanedioic acid, tetradecanedioic acid, hexadecanedioic acid, heptadecanedioic acid, octadecanedioic acid, nonadecanedioic acid, dodecanedioic acid, 3-ethyl-3-methylglutaric acid, hexafluoroglutaric acid, trans-3-hexenedioic acid, sebacic acid, hexadecanoic acid, acetylene dicarboxylic 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-cyclohexanedicarboxylic acid, cis- or trans-1 ,4-cyclohexanedicarboxylic acid, 1,1-cyclopentanediacetic acid, 1,2,3,4-cyclopentanetetracarboxylic acid, decahydro-1,4-naphthalene dicarboxylic acid, 2,3-norbornene dicarboxylic 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-naphthalene dicarboxylic acid, 2,3-naphthalene dicarboxylic acid, 1,4-naphthalene dicarboxylic acid, 1,1'-ferrocene dicarboxylic acid, 2,2'-biphenyl dicarboxylic acid, 4,4'-biphenyl dicarboxylic acid, 2,5-furan dicarboxylic acid, benzophenone-2,4'-dimethyl 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'-dithiodibutyric acid, 4,4'-dicarboxydiphenyl ether, 4,4'-dicarboxydiphenyl sulfone, ethylene glycol bis(4-carboxyphenyl) ether, 3,4-ethylenedioxythiophene-2,5-dicarboxylic acid, 4,4'-isopropyldiphenoxyacetic 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.

[0112] From the viewpoint of improving the stability and dispersibility of semiconductor particles and the luminescence intensity, the molecular weight of compound (G-1) is preferably 3000 or less, more preferably 2500 or less, further preferably 2000 or less, further preferably 1000 or less, particularly preferably 800 or less, and most preferably 500 or less. The molecular weight of compound (G-1) is usually 100 or more.

[0113] 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 respectively the number average molecular weight and the weight average molecular weight in terms of standard polystyrene measured by gel permeation chromatography (GPC).

[0114] When the ligand-containing semiconductor particles contain compound (G-1), the content ratio of compound (G-1) to the semiconductor particles is preferably 0.001 to 1, more preferably 0.01 to 0.5, and further preferably 0.02 to 0.45 in terms of mass ratio. When the content ratio is within this range, it is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles and the luminescence intensity.

[0115] [Compound (G-2)]

[0116] Compound (G-2) is a compound different from compound (G-1), and is a compound containing a polyalkylene glycol structure and having a polar group at the molecular end. The molecular end is preferably the end of the longest carbon chain (the carbon atoms in the carbon chain may be substituted with other atoms such as oxygen atoms) in compound (G-2).

[0117] The semiconductor particles may contain only one compound (G-2) or two or more compounds. The semiconductor particles may contain the compound (G-1) or the compound (G-2) or the compound (G-1) and the compound (G-2).

[0118] In addition, the compound which contains a polyalkylene glycol structure and has the said 1st functional group and 2nd functional group belongs to compound (G-1).

[0119] The polyalkylene glycol structure refers to a structure represented by the following formula (n is an integer of 2 or more).

[0120]

[0121] In the formula, R C The alkylene group includes, for example, an ethylene group and a propylene group.

[0122] Specific examples of the compound (G-2) include polyalkylene glycol compounds represented by the following formula (G-2a).

[0123]

[0124] In formula (G-2a), X is a polar group, Y is a monovalent group, and Z C is a divalent or trivalent group. n is an integer greater than 2. m is 1 or 2. C It is an alkylene group.

[0125] The polar group X is preferably at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2). The polar group selected from this group is advantageous in that it can improve the coordination with the semiconductor particles. Among them, from the viewpoint of improving the stability and dispersibility of the semiconductor particles and the luminous intensity, the polar group X is more preferably at least one group selected from the group consisting of a thiol group and a carboxyl group.

[0126] The group Y is a monovalent group. There are no particular limitations on the group Y, and examples include monovalent hydrocarbon groups that may have substituents (N, O, S, halogen atoms, etc.). The -CH2- contained in the hydrocarbon group may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. The number of carbon atoms in the above hydrocarbon group is, for example, 1 to 12. The hydrocarbon group may have an unsaturated bond.

[0127] As the group Y, there can be mentioned an alkyl group having 1 to 12 carbon atoms and having a straight chain, branched chain or cyclic structure; an alkoxy group having 1 to 12 carbon atoms and having a straight chain, branched chain or cyclic structure. The number of carbon atoms of the alkyl group and the alkoxy group is preferably 1 to 8, more preferably 1 to 6, and further preferably 1 to 4. The -CH2- contained in the alkyl group and the alkoxy group can be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. Among them, the group Y is preferably a straight chain or branched chain alkoxy group having 1 to 4 carbon atoms, and more preferably a straight chain alkoxy group having 1 to 4 carbon atoms.

[0128] The group Y may contain a polar group. As the polar group, at least one group selected from the group consisting of a thiol group (-SH), a carboxyl group (-COOH) and an amino group (-NH2) may be cited. Among them, as described above, a compound containing a polyalkylene glycol structure and having the first functional group and the second functional group belongs to compound (G-1). The polar group is preferably disposed at the end of the group Y.

[0129] Group Z C is a divalent or trivalent group. C There are no particular limitations, and examples include divalent or trivalent hydrocarbon groups that may contain heteroatoms (N, O, S, halogen atoms, etc.). The number of carbon atoms in the hydrocarbon group is, for example, 1 to 24. The hydrocarbon group may have an unsaturated bond.

[0130] For the group Z as a divalent group C , examples include alkylene groups having 1 to 24 carbon atoms and having a linear, branched or cyclic structure; alkenylene groups having 1 to 24 carbon atoms and having a linear, branched or cyclic structure. The number of carbon atoms in the alkyl and alkenylene groups is preferably 1 to 12, more preferably 1 to 8, and even more preferably 1 to 4. The -CH2- contained in the alkyl and alkenylene groups may be substituted by -O-, -S-, -C(=O)-, -C(=O)-O-, -O-C(=O)-, -C(=O)-NH-, -NH-, etc. For the group Z as a trivalent group C Examples of the group Z include the group Z as the above divalent group. C A radical obtained by removing one hydrogen atom from a.

[0131] Group Z C It may have a branched structure. Group Z having a branched structure C A branch chain different from the branch chain including the polyalkylene glycol structure represented by the above formula (G-2a) may have a polyalkylene glycol structure different from the polyalkylene glycol structure represented by the above formula (G-2a).

[0132] Among them, group Z C It 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.

[0133] R C It 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.

[0134] In the formula (G-2a), n is an integer of 2 or more, preferably 2-540, more preferably 2-120, and even more preferably 2-60.

[0135] The molecular weight of compound (G-2) can be, for example, about 150 to 10,000, preferably 150 to 5,000, and more preferably 150 to 4,000 from the viewpoint of improving the stability and dispersibility of semiconductor particles and the luminous intensity. The molecular weight can 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 measured by GPC and calculated on the basis of standard polystyrene.

[0136] When the ligand-containing semiconductor particles contain compound (G-2), the content ratio of compound (G-2) to the semiconductor particles is preferably 0.001 to 2, more preferably 0.01 to 1.5, and further preferably 0.1 to 1. When the content ratio is within this range, it is advantageous from the viewpoint of improving the stability and dispersibility of the semiconductor particles and the luminescence intensity.

[0137] When the semiconductor particles are semiconductor particles containing ligands, the ratio of the content of the organic ligand to the semiconductor particles is preferably 0.001 to 1, more preferably 0.01 to 0.8, and further preferably 0.02 to 0.5 in terms of mass ratio. When the content ratio is within this range, it is advantageous from the perspective of improving the stability and dispersibility of the semiconductor particles and the luminous intensity. The content of the organic ligands mentioned here refers to the total content of all organic ligands.

[0138] The composition may contain light scattering particles as the first particles (A-1) and luminescent semiconductor particles as the second particles (A-2). By containing both light scattering particles and luminescent semiconductor particles, the light scattering particles can be present near the semiconductor particles, which is advantageous in improving the luminescent intensity.

[0139] When the composition contains the second particles (A-2), the content of the second particles (A-2) in the composition (however, in the case of ligand-containing semiconductor particles containing an organic ligand (G), the organic ligand (G) is not included) is, for example, 1 mass % to 70 mass % relative to the total amount of the solid content of the composition. From the viewpoint of improving the properties of the film (for example, light-emitting properties) based on the second particles (A-2), it is preferably 2 mass % or more, more preferably 5 mass % or more, further preferably 8 mass % or more, and further preferably 10 mass % or more. In addition, from the viewpoint of the developability of the composition, it is preferably 65 mass % or less, more preferably 60 mass % or less, further preferably 55 mass % or less, further preferably 50 mass % or less, and particularly preferably 48 mass % or less.

[0140] [3] Dispersant (B)

[0141] The composition may contain one or more dispersants (B). By containing a dispersant (B), the dispersibility of the first particle (A-1) in the composition can be improved. For example, the dispersion obtained by pre-dispersing the first particle (A-1) in a part or all of the solvent (H) using the dispersant (B) can be used to prepare the composition. It should be noted that the above-mentioned organic ligand (G), the resin (Cb) that can improve the dispersibility of the particles described later, and the polymerizable compound (Da) that can improve the dispersibility of the particles described later are not included in the dispersant (B).

[0142] As the dispersant (B), a commercially available product can be used. Examples of commercially available products include:

[0143] BYK-Chemie Japan's DISPERBYK-101, 102, 103, 106, 107, 108, 109, 110, 111, 116, 118, 130, 140, 154, 161, 162, 163, 164, 165, 166, 170, 171, 174, 180, 181, 182, 183, 184, 185, 190, 192, 2000, 2001, 2020, 2025, 2050, 2070, 2095, 2150, 2155; ANTI-TERRA-U, U100, 203, 204, 250,; BYK -P104, P104S, P105, 220S, 6919; BYK-LPN6919, 21116; LACTIMON, LACTIMON-WS; Bykumen, etc.;

[0144] 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 Japan Lubrizol;

[0145] EFKA-46, 47, 48, 452, 4008, 4009, 4010, 4015, 4020, 4047, 4050, 4055, 4060, 4080, 4400, 4401, 4402, 4403, 4406, 4408, 4300, 4310, 4320, 4330, 4340, 450, 451, 453, 4540, 4550, 4560, 4800, 5010, 5065, 5066, 5070, 7500, 7554, 1101, 120, 150, 1501, 1502, 1503, etc. manufactured by BASF;

[0146] Ajisper PA111, PB711, PB821, PB822, PB824, etc. manufactured by Ajinomoto Precision Technology Co., Ltd.

[0147] The content of the dispersant (B) in the composition is, for example, 0.001% by mass to 5% by mass relative to the total amount of the solid content of the composition. From the viewpoint of improving the properties of the film and the developability of the film based on the first particles (A-1) and from the viewpoint of making the sedimentation velocity ν represented by the formula (i) described in detail below 400×10 －9 From the viewpoint of cm / s or less, the content is preferably 0.05% by mass to 2% by mass, and more preferably 0.1% by mass to 1% by mass.

[0148] [4] Resin (C)

[0149] The composition contains at least one binder component selected from a resin (C) and a polymerizable compound (D). When the composition contains a resin (C), it may contain one or more resins. Examples of the resin (C) include the following resins [K1] to [K4].

[0150] Resin [K1]: a copolymer of at least one (a) selected from unsaturated carboxylic acids and unsaturated carboxylic anhydrides (hereinafter also referred to as “(a)”) and a monomer (c) copolymerizable with (a) (which is different from (a)) (hereinafter also referred to as “(c)”);

[0151] Resin [K2]: a resin having a structure derived from (a), (c) and (b) obtained by reacting a monomer (b) having a cyclic ether structure having 2 to 4 carbon atoms and an ethylenically unsaturated bond (hereinafter also referred to as "(b)") with a copolymer of (a) and (c);

[0152] Resin [K3]: a resin having a structure derived from (b), (c) and (a) obtained by reacting (a) with a copolymer of (b) and (c);

[0153] Resin [K4]: A resin having a structure derived from (b), (c), (a) and carboxylic anhydride, which can be obtained by reacting a copolymer of (a), (b) and (c), and further reacting with a carboxylic anhydride.

[0154] Examples of (a) include unsaturated monocarboxylic acids such as (meth)acrylic acid, crotonic acid, o-, m-, and p-vinylbenzoic acid;

[0155] 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;

[0156] Bicyclic unsaturated compounds containing a carboxyl group, such as methyl-5-norbornene-2,3-dicarboxylic acid, 5-carboxybicyclo[2.2.1]hept-2-ene, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene, 5-carboxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-carboxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-carboxy-6-methylbicyclo[2.2.1]hept-2-ene and 5-carboxy-6-ethylbicyclo[2.2.1]hept-2-ene;

[0157] Unsaturated dicarboxylic anhydrides such as maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride;

[0158] Unsaturated mono[(meth)acryloyloxyalkyl] esters of divalent or higher polycarboxylic acids such as mono[2-(meth)acryloyloxyethyl] succinate and mono[2-(meth)acryloyloxyethyl] phthalate;

[0159] Unsaturated (meth)acrylates containing a hydroxyl group and a carboxyl group in the same molecule such as α-(hydroxymethyl) (meth)acrylic acid, and the like.

[0160] Among them, (meth)acrylic acid, maleic anhydride, and the like are preferred from the viewpoint of copolymerization reactivity and the like.

[0161] In this specification, (meth)acrylic acid means acrylic acid and / or methacrylic acid. The same applies to "(meth)acryloyl", "(meth)acrylate" and the like.

[0162] (b) is, for example, a monomer having a cyclic ether structure having 2 to 4 carbon atoms (for example, at least one selected from an oxirane ring, an oxetane ring, and a tetrahydrofuran ring) and an ethylenically unsaturated bond. (b) is preferably a monomer having a cyclic ether structure having 2 to 4 carbon atoms and a (meth)acryloyloxy group.

[0163] Examples of (b) include 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(glycidyloxymethyl)styrene, Monomers having an oxirane ring and an ethylenically unsaturated bond, such as 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;

[0164] Monomers having an oxetane ring and an ethylenically unsaturated bond, such as 3-methyl-3-methacryloyloxymethyloxetane, 3-methyl-3-acryloyloxymethyloxetane, 3-ethyl-3-methacryloyloxymethyloxetane, 3-ethyl-3-acryloyloxymethyloxetane, 3-methyl-3-methacryloyloxyethyloxetane, 3-methyl-3-acryloyloxyethyloxetane, 3-ethyl-3-methacryloyloxyethyloxetane, and 3-ethyl-3-acryloyloxyethyloxetane;

[0165] Monomers having a tetrahydrofuran ring and an ethylenically unsaturated bond, such as tetrahydrofurfuryl acrylate (for example, Viscoat V#150, manufactured by Osaka Organic Chemical Industry Co., Ltd.) and tetrahydrofurfuryl methacrylate, etc.

[0166] As (b), a monomer having an oxirane ring and an ethylenically unsaturated bond is preferred because the reactivity during the production of the resins [K2] to [K4] is high and unreacted (b) is less likely to remain.

[0167] Examples of (c) include methyl (meth)acrylate, ethyl (meth)acrylate, n-butyl (meth)acrylate, sec-butyl (meth)acrylate, tert-butyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, dodecyl (meth)acrylate, lauryl (meth)acrylate, stearyl (meth)acrylate, cyclopentyl (meth)acrylate, cyclohexyl (meth)acrylate, 2-methylcyclohexyl (meth)acrylate, tricyclo[5.2.1.0](meth)acrylate, 2,6] decane-8-yl ester (in the technical field, it is commonly known as "dicyclopentyl (meth)acrylate". It is also sometimes referred to as "tricyclodecyl (meth)acrylate"), tricyclo[5.2.1.0 2,6 ] (Meth)acrylates such as decen-8-yl ester (in the technical field, it is commonly referred to as "dicyclopentenyl (meth)acrylate"), dicyclopentyloxyethyl (meth)acrylate, isobornyl (meth)acrylate, adamantyl (meth)acrylate, allyl (meth)acrylate, propargyl (meth)acrylate, phenyl (meth)acrylate, naphthyl (meth)acrylate, and benzyl (meth)acrylate;

[0168] (Meth)acrylates containing a hydroxyl group, such as 2-hydroxyethyl (meth)acrylate and 2-hydroxypropyl (meth)acrylate;

[0169] Diethyl maleate, diethyl fumarate, diethyl itaconate and other dicarboxylic acid diesters;

[0170] Bicyclo[2.2.1]hept-2-ene, 5-methylbicyclo[2.2.1]hept-2-ene, 5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxybicyclo[2.2.1]hept-2-ene, 5-hydroxymethylbicyclo[2.2.1]hept-2-ene, 5-(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5-methoxybicyclo[2.2.1]hept-2-ene, 5-ethoxybicyclo[2.2.1]hept-2-ene, 5,6-dihydroxybicyclo[2.2.1]hept-2-ene, 5,6-bis(hydroxymethyl)bicyclo[2.2.1]hept-2-ene, 5,6-bis(2'-hydroxyethyl)bicyclo[2.2.1]hept-2-ene, 5,6-dimethoxy Bicyclic unsaturated compounds such as bicyclo[2.2.1]hept-2-ene, 5,6-diethoxybicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-methylbicyclo[2.2.1]hept-2-ene, 5-hydroxy-5-ethylbicyclo[2.2.1]hept-2-ene, 5-hydroxymethyl-5-methylbicyclo[2.2.1]hept-2-ene, 5-tert-butoxycarbonylbicyclo[2.2.1]hept-2-ene, 5-cyclohexyloxycarbonylbicyclo[2.2.1]hept-2-ene, 5-phenoxycarbonylbicyclo[2.2.1]hept-2-ene, 5,6-bis(tert-butoxycarbonyl)bicyclo[2.2.1]hept-2-ene and 5,6-bis(cyclohexyloxycarbonyl)bicyclo[2.2.1]hept-2-ene;

[0171] Dicarbonyl imide derivatives such as N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, N-succinimidyl-3-maleimidobenzoate, N-succinimidyl-4-maleimidobutyrate, N-succinimidyl-6-maleimidohexanoate, N-succinimidyl-3-maleimidopropionate, and N-(9-acridinyl)maleimide;

[0172] Styrene, α-methylstyrene, m-methylstyrene, p-methylstyrene, vinyltoluene, p-methoxystyrene, acrylonitrile, methacrylonitrile, vinyl chloride, vinylidene chloride, acrylamide, methacrylamide, vinyl acetate, 1,3-butadiene, isoprene, 2,3-dimethyl-1,3-butadiene, etc.

[0173] Among them, styrene, vinyltoluene, N-phenylmaleimide, N-cyclohexylmaleimide, N-benzylmaleimide, bicyclo[2.2.1]hept-2-ene and the like are preferred from the viewpoint of copolymerization reactivity and heat resistance of the resin (C).

[0174] In resin [K1], the ratio of the constituent units derived from each unit is preferably 2 mol% to 60 mol% for the constituent units derived from (a), and 40 mol% to 98 mol% for the constituent units derived from (c), among all the constituent units constituting resin [K1]. It is more preferred that the constituent units derived from (a) are 10 mol% to 50 mol% and the constituent units derived from (c) are 50 mol% to 90 mol%.

[0175] When the ratio of the structural unit of the resin [K1] is within the above range, there is a tendency for the storage stability of the composition and the solvent resistance of the film to be excellent.

[0176] It should be noted that when the resin (B) contains a constituent unit derived from (a), it may contain two or more constituent units derived from (a), in which case the ratio (molar content) of the constituent unit derived from (a) is the sum of the ratios of the constituent units. The same applies to constituent units derived from other monomers such as (b) and (c).

[0177] Resin [K1] can be produced, for example, by the method described in the document "Experimental Methods for Polymer Synthesis" (written by Takayuki Otsu, published by Kagaku Dojin Co., Ltd., 1st edition, 1st printing, published on March 1, 1972) and the cited documents described in the document as reference.

[0178] Specifically, a method is exemplified in which predetermined amounts of (a) and (c), a polymerization initiator, a solvent, etc. are placed in a reaction vessel, oxygen is replaced with nitrogen to create a deoxygenated atmosphere, and heating and heat preservation are performed while stirring.

[0179] The polymerization initiator and solvent used are not particularly limited, and those commonly used in the field can be used. For example, as the polymerization initiator, there can be mentioned azo compounds (2,2'-azobisisobutyronitrile, 2,2'-azobis(2,4-dimethylvaleronitrile) etc.), organic peroxides (benzoyl peroxide etc.), and as the solvent, it is sufficient as long as each monomer is dissolved, and the solvent (H) that can be contained in the composition and described later can be mentioned.

[0180] The obtained copolymer may be used directly as a solution after the reaction, or as a solution after concentration or dilution, or as a solid (powder) obtained by reprecipitation or the like. If a solvent (H) described later is used as a solvent during polymerization, the solution after the reaction can be used directly for the preparation of the composition, thereby simplifying the production process of the composition.

[0181] The resin [K2] can be produced by adding a cyclic ether having 2 to 4 carbon atoms contained in (b) and a carboxylic acid and / or a carboxylic anhydride contained in (a) to a copolymer of (a) and (c).

[0182] First, a copolymer of (a) and (c) is produced in the same manner as described as the method for producing resin [K1]. In this case, the ratio of the constituent units derived from each unit is preferably the same as the ratio described for resin [K1].

[0183] Next, the cyclic ether having 2 to 4 carbon atoms contained in (b) is reacted with a part of the carboxylic acid and / or carboxylic anhydride derived from (a) in the above copolymer.

[0184] After the production of the copolymer of (a) and (c), the atmosphere in the flask is replaced from nitrogen to air, and the reaction is carried out in the presence of (b), a reaction catalyst (e.g., an organic phosphorus compound, a metal complex, an amine compound, etc.) of a carboxylic acid or a carboxylic anhydride and a cyclic ether, and a polymerization inhibitor (e.g., hydroquinone, etc.), for example, at 60°C to 130°C for 1 to 10 hours, thereby producing resin [K2].

[0185] The amount of (b) used is preferably 5 to 80 mol, more preferably 10 to 75 mol, relative to 100 mol of (a). Within this range, the storage stability of the composition and the balance of the solvent resistance, heat resistance and mechanical strength of the film tend to be improved.

[0186] For the organic phosphorus compound as a reaction catalyst, for example, triphenylphosphine etc. can be cited. For the amine compound as a reaction catalyst, for example, aliphatic tertiary amine compounds or aliphatic quaternary ammonium salt compounds etc. can be used, and as its specific example, for example, tris (dimethylaminomethyl) phenol, triethylamine, tetrabutylammonium bromide, tetrabutylammonium chloride etc. can be cited. From the viewpoint of the luminous intensity of the film, the reaction catalyst is preferably an organic phosphorus compound.

[0187] The amount of the reaction catalyst used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).

[0188] The amount of the polymerization inhibitor used is preferably 0.001 to 5 parts by mass based on 100 parts by mass of the total amount of (a), (b), and (c).

[0189] The reaction conditions such as the charging method, reaction temperature and time can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc. It should be noted that the charging method and reaction temperature can be appropriately adjusted in consideration of the production equipment, the calorific value based on the polymerization, etc., similarly to the polymerization conditions.

[0190] As for resin [K3], as the first stage, a copolymer of (b) and (c) is obtained in the same manner as in the production method of resin [K1]. As in the above, the obtained copolymer may be used directly as a solution after the reaction, or may be used as a concentrated or diluted solution, or may be used as a solid (powder) obtained by a method such as reprecipitation.

[0191] The ratio of the constituent units derived from (b) and (c) to the total molar number of all constituent units constituting the above-mentioned copolymer is preferably 5 mol% to 95 mol% for the constituent units derived from (b) and 5 mol% to 95 mol% for the constituent units derived from (c), and more preferably 10 mol% to 90 mol% for the constituent units derived from (b) and 10 mol% to 90 mol% for the constituent units derived from (c).

[0192] Resin [K3] can be obtained by reacting the carboxylic acid or carboxylic anhydride contained in (a) with the cyclic ether derived from (b) contained in the copolymer of (b) and (c) under the same conditions as the method for producing resin [K2].

[0193] The amount of (a) to be reacted with the copolymer is preferably 5 to 80 mol relative to 100 mol of (b).

[0194] The resin [K4] is a resin obtained by further reacting the resin [K3] with a carboxylic acid anhydride. The carboxylic acid anhydride is reacted with a hydroxyl group generated by the reaction of the cyclic ether and the carboxylic acid or the carboxylic acid anhydride.

[0195] Examples of the carboxylic anhydride include maleic anhydride, citraconic anhydride, itaconic anhydride, 3-vinylphthalic anhydride, 4-vinylphthalic anhydride, 3,4,5,6-tetrahydrophthalic anhydride, 1,2,3,6-tetrahydrophthalic anhydride, dimethyltetrahydrophthalic anhydride, and 5,6-dicarboxybicyclo[2.2.1]hept-2-ene anhydride.

[0196] The amount of the carboxylic anhydride used is preferably 0.5 to 1 mol relative to 1 mol of the amount of (a) used.

[0197] Examples of the resin [K1], the resin [K2], the resin [K3], and the resin [K4] include:

[0198] Resins such as benzyl (meth)acrylate / (meth)acrylic acid copolymer and styrene / (meth)acrylic acid copolymer [K1];

[0199] Resins obtained by adding glycidyl (meth)acrylate to benzyl (meth)acrylate / (meth)acrylic acid copolymer, resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / styrene / (meth)acrylic acid copolymer, and resins obtained by adding glycidyl (meth)acrylate to tricyclodecyl (meth)acrylate / benzyl (meth)acrylate / (meth)acrylic acid copolymer [K2];

[0200] Resins such as a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate, and a resin obtained by reacting (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / styrene / glycidyl (meth)acrylate [K3];

[0201] Resins [K4] and the like, such as a resin obtained by reacting a (meth)acrylic acid with a copolymer of tricyclodecyl (meth)acrylate / glycidyl (meth)acrylate and further reacting with tetrahydrophthalic anhydride.

[0202] As another example of resin (C), the resin described in Japanese Patent Publication No. 2018-123274 can be cited. As such resin, a polymer having a double bond in the side chain and a main chain containing a constituent unit (α) represented by the following formula (I) and a constituent unit (β) represented by the following formula (II) and further containing an acid group (hereinafter also referred to as "resin (Ca)").

[0203] The acid group can be introduced into the resin by, for example, including a structural unit (γ) derived from an acid group-containing monomer (eg, (meth)acrylic acid). The resin (Ca) preferably includes structural units (α), (β), and (γ) in the main chain skeleton.

[0204]

[0205] [Where R A and R B are the same or different and represent a hydrogen atom or a hydrocarbon group having 1 to 25 carbon atoms. n represents the average number of repeating units of the constituent unit represented by formula (I), and is a number greater than 1.]

[0206]

[0207] [Where R C The same or different, represents a hydrogen atom or a methyl group. D are 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 constituent unit represented by formula (II) and is a number greater than 1.]

[0208] In the resin (Ca), from the viewpoint of heat resistance and storage stability of the resin (Ca), the content ratio of the constituent unit (α) is, for example, 0.5% to 50% by mass, preferably 1% to 40% by mass, and more preferably 5% to 30% by mass, relative to the total amount of all monomer units providing the main chain skeleton of the resin (Ca) (100% by mass). The n in the formula (I) represents the average number of repeating units of the constituent unit (α) in the resin (Ca), and n can be set so that the content ratio of the constituent unit (α) is within the above range.

[0209] From the viewpoint of solvent resistance of the film, the content ratio of the constituent unit (β) is, for example, 10% to 90% by mass, preferably 20% to 80% by mass, and more preferably 30% to 75% by mass, relative to the total amount of all monomer units providing the main chain skeleton of the resin (Ca) (100% by mass). m in formula (II) represents the average number of repeating units of the constituent unit (β) in the resin (Ca), and m can be set so that the content ratio of the constituent unit (β) is within the above range.

[0210] From the viewpoint of the solubility of the resin (Ca) in the solvent (H), the content ratio of the constituent unit (γ) is, for example, 0.5% by mass to 50% by mass, preferably 2% by mass to 50% by mass, and more preferably 5% by mass to 45% by mass, relative to 100% by mass of the total amount of all monomer units providing the main chain skeleton of the resin (Ca).

[0211] Another example of the resin (C) is a polyalkylene glycol compound. Examples of the polyalkylene glycol compound include polyethylene glycol and polypropylene glycol.

[0212] The weight average molecular weight (Mw) of the resin (C) measured by gel permeation chromatography (GPC) in terms of standard polystyrene is preferably 9000 or less. The resin (C) has the above Mw, which tends to improve the optical properties such as the luminous intensity of the film. The Mw of the resin (C) in terms of standard polystyrene is, for example, 1000 to 9000, and is preferably 2000 to 8500, and more preferably 3000 to 8500, from the viewpoint of optical properties such as the strength of the film.

[0213] In order to adjust the Mw of the resin (C) to the above range, the reaction conditions such as the selection of the raw materials used, the charging method, the reaction temperature and time can be appropriately combined and adjusted.

[0214] 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 to 6.0, and preferably 1.2 to 4.0 from the viewpoint of improving the optical properties of the film.

[0215] From the viewpoint of improving the optical properties and solvent resistance of the film, the acid value of the resin (C) is preferably 90 mgKOH / g to 150 mgKOH / g, more preferably 95 mgKOH / g to 140 mgKOH / g, and further preferably 100 mgKOH / g to 130 mgKOH / g. The acid value is a value measured as the amount (mg) of potassium hydroxide required to neutralize 1 g of the resin (C), and can be determined, for example, by titration using a potassium hydroxide aqueous solution.

[0216] From the viewpoint of improving the optical properties of the film, the resin (C) preferably contains a resin having a double bond equivalent of 300 g / eq to 2000 g / eq, and more preferably contains a resin having a double bond equivalent of 500 g / eq to 1500 g / eq. As a resin having a double bond equivalent of 300 g / eq to 2000 g / eq, a (meth) acrylic resin can be cited. The resin (C) is preferably composed of a (meth) acrylic resin.

[0217] The resin (C) preferably contains a resin (Cb) capable of improving the dispersibility of the particles, and more preferably resin (Cb). As the resin (Cb), for example, a resin having a polar group can be cited. The polar group can be adsorbed on the first particle (A-1) and the second particle (A-2). Therefore, it is advantageous for the resin (C) to contain the resin (Cb) in reducing the sedimentation velocity ν represented by formula (i). As the polar group, at least one group selected from a carboxyl group (-COOH), a thiol group (-SH) and an amino group (-NH2) can be cited, preferably a carboxyl group. The resin (Cb) can have two or more polar groups.

[0218] When the composition contains resin (C), the content of the resin (C) in the composition is, for example, 5% by mass or more, preferably 10% by mass or more, more preferably 15% by mass or more, further preferably 20% by mass or more, particularly preferably 25% by mass or more, for example, 90% by mass or less, preferably 85% by mass or less, more preferably 80% by mass or less, relative to the total amount of the solid content of the composition. When the content of the resin (C) is within the above range, there is a tendency that the optical properties of the film are easily improved.

[0219] [5] Polymerizable compound (D)

[0220] The composition may contain a polymerizable compound (D). The polymerizable compound (D) is a compound that can be polymerized under the action of an active free radical, an acid, etc. generated by a polymerization initiator (E) described later. The composition may contain two or more polymerizable compounds (D). When the composition contains a resin (C), the composition may contain a polymerizable compound (D) or may not contain a polymerizable compound (D). When the composition does not contain a resin (C), the composition contains a polymerizable compound (D).

[0221] As the polymerizable compound (D), there can be mentioned photopolymerizable compounds that cure under the irradiation of light and thermal polymerizable compounds that cure under the action of heat. As the photopolymerizable compound, there can be mentioned photoradical polymerizable compounds that cure by free radical polymerization reaction under the irradiation of light, and photocationic polymerizable compounds that cure by cationic polymerization reaction under the irradiation of light. The photopolymerizable compound is preferably a photoradical polymerizable compound.

[0222] The weight average molecular weight of the photopolymerizable compound is, for example, 150 to 3000, preferably 150 to 2900, and more preferably 250 to 1500.

[0223] Examples of the photo-radical polymerizable compound include compounds having polymerizable ethylenically unsaturated bonds, and among these, (meth)acrylate compounds are preferred. Examples of the (meth)acrylate compound include a monofunctional (meth)acrylate monomer having one (meth)acryloyloxy group in the molecule (hereinafter, also referred to as "compound (D-1)"), a bifunctional (meth)acrylate monomer having two (meth)acryloyloxy groups in the molecule (hereinafter, also referred to as "compound (D-2)"), and a polyfunctional (meth)acrylate monomer having three or more (meth)acryloyloxy groups in the molecule (hereinafter, also referred to as "compound (D-3)").

[0224] Examples of the compound (D-1) include methyl (meth)acrylate, ethyl (meth)acrylate, propyl (meth)acrylate, butyl (meth)acrylate, pentyl (meth)acrylate, hexyl (meth)acrylate, 2-ethylhexyl (meth)acrylate, octyl (meth)acrylate, nonyl (meth)acrylate, dodecyl (meth)acrylate (lauryl (meth)acrylate), hexadecyl (meth)acrylate, octadecyl (meth)acrylate, cyclohexyl (meth)acrylate, methoxyethyl (meth)acrylate, butoxyethyl (meth)acrylate, phenoxyethyl (meth)acrylate, nonylphenoxyethyl (meth)acrylate, glycidyl (meth)acrylate, dimethylaminoethyl (meth)acrylate, diethylaminoethyl (meth)acrylate, and (meth)acrylate. isobornyl (meth)acrylate, dicyclopentyl (meth)acrylate, dicyclopentenyl (meth)acrylate, dicyclopentenyloxyethyl (meth)acrylate, 2-hydroxy-3-phenoxypropyl (meth)acrylate, tetrahydrofurfuryl (meth)acrylate, 2-hydroxyethyl (meth)acrylate, benzyl (meth)acrylate, phenyl (meth)acrylate, mono(2-acryloyloxyethyl) succinate, N-[2-(acryloyloxy)ethyl]phthalimide, N-[2-(acryloyloxy)ethyl]tetrahydrophthalimide, 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, ω-carboxy-polycaprolactone monoacrylate, ethyl carbitol (meth)acrylate (ethoxyethoxyethyl (meth)acrylate), 3,3,5-trimethylcyclohexyl (meth)acrylate, and the like.

[0225] Examples of the compound (D-2) include 1,3-butanediol di(meth)acrylate, 1,4-butanediol di(meth)acrylate, 1,5-pentanediol di(meth)acrylate, 3-methyl-1,5-pentanediol di(meth)acrylate, 1,6-hexanediol di(meth)acrylate, neopentyl glycol di(meth)acrylate, 1,8-octanediol di(meth)acrylate, 1,9-nonanediol di(meth)acrylate, tricyclodecane dimethanol di(meth)acrylate, ethylene glycol di(meth)acrylate, polyethylene glycol di(meth)acrylate, propylene glycol di(meth)acrylate, dipropylene glycol di(meth)acrylate, tripropylene glycol di(meth)acrylate, polypropylene glycol di(meth)acrylate, neopentyl glycol hydroxypivalate di(meth)acrylate, tri(2 di(meth)acrylate in which the two hydroxyl groups of (meth)acryloyloxy groups are replaced by (meth)acryloyloxy groups, di(meth)acrylate in which the two hydroxyl groups of (meth)acryloyloxy groups are replaced by (meth)acryloyloxy groups, di(meth)acrylate in which the two hydroxyl groups of (meth)acryloyloxy groups are replaced by (meth)acryloyloxy groups, and the like are preferably used.

[0226] Examples of the compound (D-3) include glycerol tri(meth)acrylate, trimethylolpropane tri(meth)acrylate, pentaerythritol tri(meth)acrylate, pentaerythritol tetra(meth)acrylate, dipentaerythritol penta(meth)acrylate, dipentaerythritol hexa(meth)acrylate, tripentaerythritol octa(meth)acrylate, tripentaerythritol hepta(meth)acrylate, tetrapentaerythritol deca(meth)acrylate, tetrapentaerythritol nona(meth)acrylate, and 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, pentaerythritol triacrylate succinic acid monoester, dipentaerythritol pentaacrylate succinic acid monoester, pentaerythritol triacrylate maleic acid monoester, dipentaerythritol pentaacrylate maleic acid monoester, etc.

[0227] Examples of photocationically polymerizable compounds include compounds having at least one oxetane ring (four-membered cyclic ether) in the molecule (hereinafter also referred to as “oxetane compounds”), compounds having at least one oxirane ring (three-membered cyclic ether) in the molecule (hereinafter also referred to as “epoxy compounds”), and vinyl ether compounds.

[0228] Examples of the oxetane compound include 3-ethyl-3-hydroxymethyloxetane, 1,4-bis[(3-ethyl-3-oxetanyl)methoxymethyl]benzene, 3-ethyl-3-(phenoxymethyl)oxetane, di[(3-ethyl-3-oxetanyl)methyl]ether, 3-ethyl-3-(2-ethylhexyloxymethyl)oxetane, and phenol novolac oxetane. These oxetane compounds are easily commercially available, and examples of commercially available products include trade names such as "Aron Oxetane (registered trademark) OXT-101", "Aron Oxetane (registered trademark) OXT-121", "Aron Oxetane (registered trademark) OXT-211", "Aron Oxetane (registered trademark) OXT-221", and "Aron Oxetane (registered trademark) OXT-212", all of which are sold by Toagosei Co., Ltd.

[0229] Examples of the epoxy compound include aromatic epoxy compounds, glycidyl ethers of polyols having an alicyclic ring, aliphatic epoxy compounds, and alicyclic epoxy compounds.

[0230] Examples of the aromatic epoxy compound include bisphenol-type epoxy resins such as diglycidyl ether of bisphenol A, diglycidyl ether of bisphenol F, and diglycidyl ether of bisphenol S; novolac-type epoxy resins such as phenol novolac epoxy resin, cresol novolac epoxy resin, and hydroxybenzaldehyde phenol novolac epoxy resin; and multifunctional epoxy resins such as glycidyl ether of tetrahydroxyphenylmethane, glycidyl ether of tetrahydroxybenzophenone, and epoxidized polyethylene phenol.

[0231] As the glycidyl ether of the polyol having an alicyclic ring, there can be mentioned the glycidyl ether obtained by glycidyl etherifying the core hydrogenated polyhydroxy compound obtained by subjecting the aromatic ring of the aromatic polyol to selective hydrogenation reaction under pressure in the presence of a catalyst. As the aromatic polyol, there can be mentioned bisphenol-type compounds such as bisphenol A, bisphenol F, and bisphenol S; novolac-type resins such as phenol novolac resin, cresol novolac resin, and hydroxybenzaldehyde phenol novolac resin; polyfunctional compounds such as tetrahydroxydiphenylmethane, tetrahydroxybenzophenone, and polyvinylphenol. Glycidyl ethers can be prepared by reacting epichlorohydrin with the alicyclic polyol obtained by hydrogenating the aromatic ring of these aromatic polyols. As a preferred example of the glycidyl ether of the polyol having an alicyclic ring, diglycidyl ether of hydrogenated bisphenol A can be mentioned.

[0232] Examples of the aliphatic epoxy compound include polyglycidyl ethers of aliphatic polyols or alkylene oxide adducts thereof. Specifically, examples include diglycidyl ether of 1,4-butanediol; diglycidyl ether of 1,6-hexanediol; triglycidyl ether of glycerol; triglycidyl ether of trimethylolpropane; diglycidyl ether of polyethylene glycol; diglycidyl ether of propylene glycol; diglycidyl ether of neopentyl glycol; polyglycidyl ethers of polyether polyols obtained by adding one or more alkylene oxides (ethylene oxide, propylene oxide) to an aliphatic polyol such as ethylene glycol, propylene glycol or glycerol.

[0233] The alicyclic epoxy compound is a compound having at least one structure in the molecule that forms an oxirane ring together with carbon atoms of an alicyclic ring, and "Celloxide" series and "Cyclomer" (both manufactured by Daicel Corporation), "Cyracure UVR" series (manufactured by The Dow Chemical Company), etc. can be used.

[0234] Examples of the vinyl ether compound include 2-hydroxyethyl vinyl ether, triethylene glycol vinyl monoether, tetraethylene glycol divinyl ether, and trimethylolpropane trivinyl ether.

[0235] The photopolymerizable compound preferably includes a multifunctional (meth)acrylate monomer having three or more (meth)acryloyloxy groups in the molecule (compound (D-3)). By including compound (D-3) in the composition, the heat resistance and mechanical strength of the film can be improved, and further, it is also advantageous in improving optical properties such as luminous intensity. In addition, by including compound (D-3) in the composition, the curability of the composition can be improved.

[0236] As compound (D-3), there can be mentioned a compound (D-3a) having three or more (meth)acryloyloxy groups in the molecule and having an acidic functional group, and a compound (D-3b) 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 compound (D-3a) and compound (D-3b), and may contain two or more compounds (D-3a), two or more compounds (D-3b), or at least one of compound (D-3a) and at least one of compound (D-3b). As the above-mentioned acidic functional group, for example, there can be mentioned a carboxyl group, a sulfonic acid group, a phosphoric acid group, etc. Among them, the acidic functional group is preferably a carboxyl group.

[0237] The number of (meth)acryloyloxy groups contained in one molecule of the compound (D-3) is, for example, 3 to 6, preferably 3 to 5, and more preferably 3. The number of acidic functional groups contained in one molecule of the compound (D-3a) is 1 or more, preferably 1. When the compound has two or more acidic functional groups, the acidic functional groups may be the same or different, and the compound preferably has at least one carboxyl group.

[0238] As compound (D-3a), compounds obtained by esterifying a compound having three or more (meth)acryloyloxy groups and hydroxyl groups with dicarboxylic acid, such as pentaerythritol tri(meth)acrylate or dipentaerythritol penta(meth)acrylate, can be cited. As such compound, for example, 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, a compound obtained by monoesterifying dipentaerythritol penta(meth)acrylate with maleic acid, etc. can be cited. Among them, a compound obtained by monoesterifying pentaerythritol tri(meth)acrylate with succinic acid is preferred.

[0239] Examples of commercially available products of compound (D-3a) include "Aronix M-510" manufactured by Toagosei Co., Ltd., which has a dibasic acid anhydride adduct of pentaerythritol tri(meth)acrylate as a main component, and "Aronix M-520D" manufactured by Toagosei Co., Ltd., which has a dibasic acid anhydride adduct of dipentaerythritol penta(meth)acrylate as a main component. These commercial products have a carboxyl group as an acidic functional group.

[0240] The polymerizable compound (D) preferably contains a polymerizable compound (Da) that can improve the dispersibility of the particles, and more preferably a polymerizable compound (Da). As the polymerizable compound (Da), for example, a polymerizable compound having a polar group can be mentioned. The polar group can be adsorbed on the first particle (A-1) and the second particle (A-2). Therefore, it is advantageous for the polymerizable compound (D) to contain a polymerizable compound (Da) in reducing the sedimentation velocity ν represented by formula (i). As the polar group, at least one group selected from a carboxyl group (-COOH), a thiol group (-SH) and an amino group (-NH2) can be mentioned, preferably a carboxyl group. The polymerizable compound (Da) can have two or more polar groups. As the polymerizable compound (Da), the above-mentioned compound (D-3a) can be mentioned.

[0241] When the photopolymerizable compound contains compound (D-3), from the viewpoint of improving the curability of the composition, the heat resistance of the film, and the optical properties such as the luminous intensity, the content of compound (D-3) relative to the total amount of the photopolymerizable compound is preferably 5% by mass or more, more preferably 10% by mass or more, further preferably 20% by mass or more, and may also be 30% by mass or more, 50% by mass or more, 70% by mass or more, 90% by mass or more, or 100% by mass.

[0242] When the photopolymerizable compound contains compound (D-3), from the viewpoint of improving the curability of the composition, the heat resistance of the film, and the optical properties such as luminous intensity, the content of compound (D-3) relative to the total amount of the solid content of the composition is preferably 0.5% by mass to 50% by mass, more preferably 1% by mass to 40% by mass, further preferably 2% by mass to 30% by mass, and further preferably 2% by mass to 25% by mass.

[0243] The photopolymerizable compound may include a (meth)acrylate monomer having a vinyl ether group and a (meth)acryloyl group (preferably a (meth)acryloyloxy group) in the same molecule (hereinafter also referred to as "compound (D-4)"). If the composition contains compound (D-4), it may be advantageous in improving the optical properties such as the luminous intensity of the film. Compound (D-4) may be any compound belonging to compound (D-1) to compound (D-3).

[0244] The number of vinyl ether groups in compound (D-4) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1. The number of (meth)acryloyl groups in compound (D-4) is preferably 1 to 4, more preferably 1 to 2, and particularly preferably 1.

[0245] Examples of the compound (D-4) include 2-vinyloxyethyl (meth)acrylate, 3-vinyloxypropyl (meth)acrylate, 2-vinyloxypropyl (meth)acrylate, 1-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxyethyl (meth)acrylate, 4-vinyloxybutyl (meth)acrylate, 3-vinyloxybutyl (meth)acrylate, 2-vinyloxybutyl (meth)acrylate, 1-methyl-3-vinyloxypropyl (meth)acrylate, 2-methyl-3-vinyloxypropyl (meth)acrylate, 1-methyl-2-vinyloxypropyl (meth)acrylate, 1,1-dimethyl-2-vinyloxyethyl ester, 6-vinyloxyhexyl (meth)acrylate, 4-vinyloxycyclohexyl (meth)acrylate, (4-vinyloxymethylcyclohexyl) methyl (meth)acrylate, (3-vinyloxymethylcyclohexyl) methyl (meth)acrylate, (2-vinyloxymethylcyclohexyl) methyl (meth)acrylate, (4-vinyloxymethylphenyl) methyl (meth)acrylate, (3-vinyloxymethylphenyl) methyl (meth)acrylate, 2-vinyloxymethylphenyl methyl (meth)acrylate, 2-(2-vinyloxymethyl)methacrylate 2-(2-vinyloxyethoxy)ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)propyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)propyl (meth)acrylate, 2-(2-vinyloxyethoxy)isopropyl (meth)acrylate, 2-(2-vinyloxyisopropoxy)isopropyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}ethyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)isopropyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}ethyl (meth)acrylate, 2-(2-vinyloxyethoxy)isopropyl (meth)acrylate 2-{2-(2-vinyloxyisopropoxy)isopropoxy}ethyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)isopropoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)isopropoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyethoxy)ethoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)isopropoxy}propyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}isopropyl (meth)acrylate, 2-{2-(2-vinyloxyisopropoxy)ethoxy}isopropyl (meth)acrylate, 2-[2-{2-(2-vinyloxyethoxy)ethoxy}ethoxy]ethyl (meth)acrylate, 2-[2-{2-(2-vinyloxyisopropoxy)ethoxy}ethoxy]ethyl (meth)acrylate, 2-(2-[2-{2-(2-vinyloxyethoxy)ethoxy}ethoxy]ethoxy)ethyl (meth)acrylate, etc.

[0246] As compound (D-4), vinyl (meth)acrylate C 1－6 Alkyl ester or (meth) acrylic acid (vinyloxy C 1－4 Alkoxy)C 1－4 Alkyl esters, more preferably (meth) acrylic acid (ethyleneoxy C 1－4 Alkoxy)C 1－4 The alkyl ester is particularly preferably 2-(2-vinyloxyethoxy)ethyl (meth)acrylate.

[0247] When the photopolymerizable compound includes compound (D-4), from the viewpoint of improving optical properties such as the luminous intensity of the film, the content of compound (D-4) relative to the total amount of the photopolymerizable compound is preferably 5 mass % or more, more preferably 10 mass % or more, further preferably 20 mass % or more, further preferably 25 mass % or more, and is preferably 85 mass % or less, more preferably 75 mass % or less, further preferably 65 mass % or less, further preferably 60 mass % or less, and particularly preferably 55 mass % or less.

[0248] When the photopolymerizable compound includes compound (D-4), from the viewpoint of improving optical properties such as the luminous intensity of the film, the content of compound (D-4) relative to the total amount of solid components of the composition is preferably 3% to 50% by mass, more preferably 5% to 45% by mass, further preferably 10% to 40% by mass, and further preferably 15% to 35% by mass.

[0249] When the photopolymerizable compound contains compound (D-1), the content of compound (D-1) is preferably 5 mass% or more, more preferably 10 mass% or more, further preferably 15 mass% or more, further preferably 20 mass% or more, particularly preferably 25 mass% or more, and is preferably 75 mass% or less, more preferably 65 mass% or less, further preferably 60 mass% or less, further preferably 55 mass% or less, and particularly preferably 50 mass% or less, relative to the total amount of the photopolymerizable compound.

[0250] When the photopolymerizable compound contains compound (D-1), the content of compound (D-1) is preferably 5% by mass to 50% by mass, more preferably 8% by mass to 45% by mass, further preferably 10% by mass to 40% by mass, and further preferably 15% by mass to 35% by mass, relative to the total amount of the solid content of the composition.

[0251] When the composition contains a polymerizable compound (D), the content of the polymerizable compound (D) in the composition is preferably 0.5% by mass to 90% by mass, more preferably 1% by mass to 80% by mass, further preferably 2% by mass to 75% by mass, and further preferably 2% by mass to 70% by mass, relative to the total amount of the solid content of the composition.

[0252] [6]Polymerization initiator (E)

[0253] When the composition contains a polymerizable compound (D), it preferably further contains a polymerization initiator (E). The polymerization initiator (E) is a compound that can generate active free radicals, acids, etc. under the action of light or heat and initiate polymerization of the polymerizable compound (D). The composition may contain one or more polymerization initiators (E).

[0254] Examples of the polymerization initiator (E) include photopolymerization initiators such as oxime compounds, alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds; and thermal polymerization initiators such as azo compounds and organic peroxides.

[0255] One example of the 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)".

[0256]

[0257] Containing an oxime compound (1) as a polymerization initiator (E) is advantageous from the viewpoint of improving optical properties such as the luminescence intensity of the film. It is speculated that one factor that can produce such an effect is that due to the unique molecular structure of the oxime compound (1), the absorption wavelength of the oxime compound (1) before and after the cleavage (decomposition) of the oxime compound (1) required for the oxime compound (1) to initiate photopolymerization changes greatly, so the oxime compound (1) has a high ability to initiate photoradical polymerization.

[0258] In formula (1), R 1 Represents R 11 , OR 11 , COR 11 , SR 11 ,CONR 12 R 13 or CN.

[0259] R 11 , R 12 and R 13 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0260] R 11 , R 12 or R 13 The hydrogen atoms of the group represented by OR 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 , -NR 22 -OR23 , -N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0261] R 21 , R 22 and R 23 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0262] R 21 , R 22 or R 23 The hydrogen atom of the group represented may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0263] R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be represented by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupts 1 to 5 times.

[0264] R 24 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0265] R 11 , R 12 , R 13 , R 21 , R 22 or R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 12 With R 13 and R 22 With R 23 They can each form a ring together.

[0266] * represents a bonding site to a second molecular structure which is a molecular structure other than the first molecular structure of the oxime compound (1).

[0267] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The alkyl group having 1 to 20 carbon atoms represented by is, for example, 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 eicosyl group, a cyclopentyl group, a cyclohexyl group, a cyclohexylmethyl group, a cyclohexylethyl group, and the like.

[0268] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aryl group having 6 to 30 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl, naphthyl, anthracenyl, phenanthryl, phenyl substituted with one or more of the above alkyl groups, biphenyl, naphthyl, anthracenyl, and the like.

[0269] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 Examples of the aralkyl group having 7 to 30 carbon atoms represented by alkyl include benzyl, α-methylbenzyl, α,α-dimethylbenzyl, and phenylethyl.

[0270] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The heterocyclic group having 2 to 20 carbon atoms represented by the present invention includes, for example, pyridyl, pyrimidinyl, furanyl, thienyl, tetrahydrofuranyl, dioxolanyl, benzo Oxazol-2-yl, tetrahydropyranyl, pyrrolidinyl, imidazolidinyl, pyrazolidinyl, thiazolidinyl, isothiazolidinyl, Oxazolidinyl, isocyanate The rings include oxazolidinyl, piperidinyl, piperazinyl and morpholinyl, and preferably are 5- to 7-membered heterocyclic rings.

[0271] R in formula (1) 12 With R 13 and R 22 With R 23 can form a ring together respectively refers to R 12 With R 13 and R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are connected, respectively.

[0272] As Ra in formula (1) 12 With Ra 13 and Ra 22 With Ra 23 Examples of the ring that can be formed together include a cyclopentane ring, a cyclohexane ring, a cyclopentene ring, a benzene ring, a piperidine ring, a morpholine ring, a lactone ring, a lactam ring and the like, and a five- to seven-membered ring is preferred.

[0273] As R in formula (1) 11 , R 12 , R 13 , R 21 , R 22 and R 23 Examples of the halogen atom which may be present as a substituent include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0274] R in formula (1) 1 Preferably R 11 , more preferably an alkyl group having 1 to 20 carbon atoms, further preferably an alkyl group having 1 to 10 carbon atoms, and further preferably an alkyl group having 1 to 6 carbon atoms.

[0275] An example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (2): The second molecular structure refers to a molecular structure other than the first molecular structure of the oxime compound (1).

[0276] The bonding site represented by "*" in formula (2) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (2), the benzene ring having "-*" in formula (2) is directly bonded to the carbonyl group having "-*" in formula (1).

[0277]

[0278] In formula (2), R 2 and R 3 Each independently represents R 11, OR 11 , SR 11 , COR 11 ,CONR 12 R 13 NR 12 COR 11 ,OCOR 11 、COOR 11 SCOR 11 , OCSR 11 、COSR 11 ,CSOR 11 , CN or halogen atom.

[0279] R 2 When there are multiple ones, they may be the same or different.

[0280] R 3 When there are multiple ones, they may be the same or different.

[0281] R 11 , R 12 and R 13 Means the same as above.

[0282] s and t each independently represent an integer of 0-4.

[0283] L represents a sulfur atom, CR 31 R 32 , CO or NR 33 .

[0284] R 31 , R 32 and R 33 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms.

[0285] R 31 , R 32 or R 33 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 31 , R 32 and R 33 Each of them can independently form a ring together with an adjacent benzene ring.

[0286] R 4 It represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-1).

[0287] (R 4a ) v -L 2 -L 1 - (2-1)

[0288] (In formula (2-1), L 1 Indicates -O-, -S-, -NR 22 -, -NR 22 CO-, -SO2-, -CS-, -OCO- or -COO-.

[0289] R 22 Means the same as above.

[0290] L 2 It represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms, a group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms.

[0291] L 2 When the group represented by has an alkylene moiety, the alkylene moiety may be represented by -O-, -S-, -COO-, -OCO-, -NR 22 -, -NR 22 COO-、-OCONR 22 -, -SCO-, -COS-, -OCS- or -CSO- is interrupted 1 to 5 times, and the alkylene part may be branched or cyclic.

[0292] R 4a Represents OR 41 , SR 41 ,CONR 42 R 43 NR 42 COR 43 ,OCOR 41 、COOR 41 SCOR 41 , OCSR 41 、COSR 41 ,CSOR 41 , CN or halogen atom.

[0293] R 4a When there are multiple ones, they may be the same or different.

[0294] R 41 , R 42 and R 43 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, or an aralkyl group having 7 to 30 carbon atoms, and R 41 , R 42 and R 43When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 42 With R 43 Can form a ring together.

[0295] v represents an integer from 1 to 3. )

[0296] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0297] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , R 31 , R 32 and R 33 , and R in the above formula (2-1) 22 , R 41 , R 42 and R 43 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, and the aralkyl group having 7 to 30 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0298] R in formula (2) 11 , R 12 , R 13 , R 21 , R 22 , R 23 , R 24 , and R in the above formula (2-1) 22 Examples of heterocyclic groups having 2 to 20 carbon atoms are the same as those for R in formula (1). 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0299] R in formula (2) 31 , R 32 and R 33 Each of the two rings can independently form a ring with an adjacent benzene ring. 31 , R 32and R 33 Each of them can independently form a ring together with an adjacent benzene ring and the nitrogen atom to which it is connected.

[0300] R in formula (2) 31 , R 32 and R 33 Examples of rings that can be formed together with an adjacent benzene ring are similar to those for Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same is true for the examples of rings that can be formed together.

[0301] In the above formula (2-1), L 2 It represents a group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0302] Examples of the group obtained by removing v hydrogen atoms from an alkyl group having 1 to 20 carbon atoms include, for example, a methylene group, an ethylene group, a propylene group, a methylethylene group, a butylene group, a 1-methylpropylene group, a 2-methylpropylene group, a 1,2-dimethylpropylene group, a 1,3-dimethylpropylene group, a 1-methylbutylene group, a 2-methylbutylene group, a 3-methylbutylene group, a 4-methylbutylene group, a 2,4-dimethylbutylene group, a 1,3-dimethylbutylene group, a pentylene group, a hexylene group, a heptylene group, an octylene group, a nonylene group, a decylene group, a dodecylene group, a tridecylene group, a tetradecylene group, a pentadecylene group, an ethane-1,1-diyl group, and a propane-2,2-diyl group.

[0303] Examples of the group obtained by removing v hydrogen atoms from an aryl group having 6 to 30 carbon atoms include, when v is 1, 1,2-phenylene, 1,3-phenylene, 1,4-phenylene, 2,6-naphthylene, 1,4-naphthylene, 2,5-dimethyl-1,4-phenylene, diphenylmethane-4,4'-diyl, 2,2-diphenylpropane-4,4'-diyl, diphenylsulfide-4,4'-diyl, and diphenylsulfone-4,4'-diyl.

[0304] Examples of the group obtained by removing v hydrogen atoms from an aralkyl group having 7 to 30 carbon atoms include, when v is 1, a group represented by the following formula (a) and a group represented by the following formula (b).

[0305]

[0306] [In formulas (a) and (b), L 3 and L 5 represents an alkylene group having 1 to 10 carbon atoms, L4 and L 6 represents a single bond or an alkylene group having 1 to 10 carbon atoms.]

[0307] Examples of the alkylene group having 1 to 10 carbon atoms include methylene, ethylene, propylene, methylethylene, butylene, 1-methylpropylene, 2-methylpropylene, 1,2-dimethylpropylene, 1,3-dimethylpropylene, 1-methylbutylene, 2-methylbutylene, 3-methylbutylene, 4-methylbutylene, 2,4-dimethylbutylene, 1,3-dimethylbutylene, pentylene, hexylene, heptylene, octylene, nonylene, and decylene.

[0308] Examples of the group obtained by removing v hydrogen atoms from a heterocyclic group having 2 to 20 carbon atoms include, for example, 2,5-pyridinediyl, 2,6-pyridinediyl, 2,5-pyrimidinediyl, 2,5-thiophenediyl, 3,4-tetrahydrofurandiyl, 2,5-tetrahydrofurandiyl, 2,5-furandiyl, 3,4-thiazoldiyl, 2,5-benzofurandiyl, 2,5-benzothiophenediyl, N-methylindole-2,5-diyl, 2,5-benzothiazoldiyl, 2,5-benzo A divalent heterocyclic group such as oxadiyl.

[0309] As R in formula (2) 2 and R 3 , and R in the above formula (2-1) 4 Examples of the halogen atom represented by a include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0310] From the viewpoint of solubility in the solvent (H) and developability of the composition, a preferred example of the structure represented by formula (2) is a structure represented by the following formula (2a).

[0311]

[0312] [In formula (2a), L' represents a sulfur atom or NR 50 , R 50 represents a linear, branched or cyclic alkyl group having 1 to 20 carbon atoms, R 2 , R 3 , R 4 , s and t have the same meanings as above.]

[0313] 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).

[0314]

[0315] [In formula (2b), R 44represents a hydroxyl group, a carboxyl group or a group represented by the following formula (2-2)

[0316] R 44a -L 12 -L 11 - (2-2)

[0317] (In formula (2-2), L 11 Indicates -O- or *-OCO-, * indicates L 12 The bonding site, L 12 represents an alkylene group having 1 to 20 carbon atoms, which may be interrupted by 1 to 3 -O- groups, R 44 a means OR 55 or COOR 55 , R 55 represents a hydrogen atom or an alkyl group having 1 to 6 carbon atoms. )]

[0318] R 44 The group represented by the formula (2-2) is preferred. In this case, it is advantageous in terms of the solubility of the oxime compound (1) in the solvent (H) and the developability of the composition.

[0319] L 12 The alkylene group represented by is preferably 1-10, more preferably 1-4.

[0320] R 44 a is preferably a hydroxyl group or a carboxyl group, more preferably a hydroxyl group.

[0321] The method for producing the oxime compound (1) having the second molecular structure represented by the formula (2) is not particularly limited, and for example, it can be produced by the method described in JP-A-2011-132215.

[0322] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (3).

[0323] The bonding site represented by "*" in formula (3) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (3), the benzene ring having "-*" in formula (3) is directly bonded to the carbonyl group having "-*" in formula (1).

[0324]

[0325] In formula (3), R 5 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0326] R 5When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0327] R 5 The hydrogen atoms of the group represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atoms, or COOR 21 replace.

[0328] R 21 , R 22 and R 23 Means the same as above.

[0329] R 21 , R 22 or R 23 The hydrogen atom of the group represented may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0330] R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be represented by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupts 1 to 5 times.

[0331] R 24 Means the same as above.

[0332] R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0333] R 6 , R 7 , R 8 and R 9 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0334] R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0335] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented by OR 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21)-R 22 , CN, halogen atoms, or COOR 21 replace.

[0336] R 6 With R 7 , R 7 With R 8 and R 8 With R 9 They can each form a ring together.

[0337] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0338] R in formula (3) 5 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0339] R in formula (3) 22 With R 23 Can form a ring together refers to R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0340] R in formula (3) 22 With R 23 Examples of rings that can be formed together are similar to those for Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same is true for the examples of rings that can be formed together.

[0341] As R in formula (3) 6 , R 7 , R 8 and R 9 The halogen atom represented by R 5 , R 21 , R22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom replacing the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0342] From the viewpoint of solubility in the solvent (H) and developability of the composition, in one preferred embodiment, R 5 It is a group represented by the following formula (3-1).

[0343]

[0344] [In the formula (3-1), Z represents a group obtained by removing one hydrogen atom from an alkyl group having 1 to 20 carbon atoms, a group obtained by removing one hydrogen atom from an aryl group having 6 to 30 carbon atoms, a group obtained by removing one hydrogen atom from an aralkyl group having 7 to 30 carbon atoms, or a group obtained by removing one hydrogen atom from a heterocyclic group having 2 to 20 carbon atoms,

[0345] When the group represented by Z has an alkylene moiety, the alkylene moiety may be -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS- or -CSO- are interrupted 1 to 5 times, and the alkylene part may be branched or cyclic.

[0346] R 21 , R 22 and R 24 Means the same as above.]

[0347] From the same viewpoint as described above, Z in formula (3-1) is preferably a methylene group, an ethylene group or a phenylene group.

[0348] From the same viewpoint as above, R in formula (3-1) 21 and R 22 It is preferably an alkyl group having 1 to 20 carbon atoms or an aryl group having 6 to 30 carbon atoms, and more preferably a methyl group, an ethyl group or a phenyl group.

[0349] From the same viewpoint as above, in another preferred embodiment, R 7 For nitro.

[0350] The method for producing the oxime compound (1) having the second molecular structure represented by formula (3) is not particularly limited, and it can be produced, for example, by the methods described in JP-A-2000-80068 and JP-A-2011-178776.

[0351] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (4).

[0352] The bonding site represented by "*" in formula (4) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (4), the benzene ring having "-*" in formula (4) is directly bonded to the carbonyl group having "-*" in formula (1).

[0353]

[0354] In formula (4), R 71 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0355] R 71 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0356] R 71 The hydrogen atoms of the group represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atoms, or COOR 21 replace.

[0357] R 21 , R 22 and R 23 Means the same as above.

[0358] R 21 , R 22 or R 23 The hydrogen atom of the group represented may be substituted by CN, a halogen atom, a hydroxyl group or a carboxyl group.

[0359] R 21 , R 22 and R 23 When the group represented by has an alkylene moiety, the alkylene moiety may be represented by -O-, -S-, -COO-, -OCO-, -NR 24 -, -NR 24 CO-、-NR 24 COO-、-OCONR 24 -, -SCO-, -COS-, -OCS-, or -CSO- interrupts 1 to 5 times.

[0360] R 24 Means the same as above.

[0361] R 21 , R 22 and R 23 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic. 22 With R 23 Can form a ring together.

[0362] R 72 , R 73 and 3 Rs 74 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0363] R 61 , R 62 , R 63 , R64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0364] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented by OR 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0365] R 72 With R 73 and 2 R 74 They can each form a ring together.

[0366] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0367] R in formula (4) 71 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0368] R in formula (4) 22 With R 23 Can form a ring together refers to R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0369] R in formula (4) 22 With R 23 Examples of rings that can be formed together are similar to those for Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same is true for the examples of rings that can be formed together.

[0370] As R in formula (4) 72 , R 73 and R 74 The halogen atom represented by R 71 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom replacing the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0371] The method for producing the oxime compound (1) having the second molecular structure represented by formula (4) is not particularly limited, and for example, it can be produced by the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0372] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (5).

[0373] The bonding site represented by "*" in formula (5) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (5), the pyrrole ring having "-*" in formula (5) is directly bonded to the carbonyl group having "-*" in formula (1).

[0374]

[0375] In formula (5), R 81 It represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0376] R81 When the group represented by has an alkyl portion, the alkyl portion may be branched or cyclic.

[0377] R 81 The hydrogen atoms of the group represented by R 21 , OR 21 , COR 21 , SR 21 NR 22 R 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 NR 22 COR 21 ,OCOR 21 、COOR 21 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 SCOR 21 , OCSR 21 、COSR 21 ,CSOR 21 , hydroxyl, nitro, CN, halogen atoms, or COOR 21 replace.

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

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

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

[0381] R 24Means the same as above.

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

[0383] R 82 , R 83 , R 84 , R 85 and R 86 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0384] R 61 , R 62 , R 63 , R 64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0385] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented by OR 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0386] R 83 With R 84 , R 84 With R 85 and R 85 With R 86 They can each form a ring together.

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

[0388] R in formula (5) 81 , R 21 , R 22 , R 23 , R 24 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by 11 , R 12 , R 13 , R 21 , R 22 , R 23 and R 24 The same example.

[0389] R in formula (5) 22 With R 23 Can form a ring together refers to R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0390] R in formula (5) 22 With R 23 Examples of rings that can be formed together are similar to those for Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same is true for the examples of rings that can be formed together.

[0391] As R in formula (5) 82 , R 83 , R 84 , R 85 and R86 The halogen atom represented by R 81 , R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom including the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0392] The method for producing the oxime compound (1) having the second molecular structure represented by formula (5) is not particularly limited, and can be produced, for example, by the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0393] Another example of the second molecular structure connected to the first molecular structure represented by formula (1) is a structure represented by the following formula (6).

[0394] The bonding site represented by "*" in formula (6) is directly bonded to the bonding site represented by "*" in formula (1). That is, when the second molecular structure is the structure represented by formula (6), the benzene ring having "-*" in formula (6) is directly bonded to the carbonyl group having "-*" in formula (1).

[0395]

[0396] In formula (6), the four R 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 Each independently represents R 61 , OR 61 , SR 61 , COR 62 ,CONR 63 R 64 NR 65 COR 61 ,OCOR 61 、COOR 62 SCOR 61 , OCSR 61 、COSR 62 ,CSOR 61 , hydroxyl, nitro, CN or halogen atom.

[0397] R 61 , R 62 , R 63 , R64 and R 65 Each independently represents a hydrogen atom, an alkyl group having 1 to 20 carbon atoms, an aryl group having 6 to 30 carbon atoms, an aralkyl group having 7 to 30 carbon atoms, or a heterocyclic group having 2 to 20 carbon atoms.

[0398] R 61 , R 62 , R 63 , R 64 or R 65 The hydrogen atoms of the group represented by OR 21 , COR 21 , SR 21 NR 22 Ra 23 ,CONR 22 R 23 , -NR 22 -OR 23 , -N(COR 22 )-OCOR 23 、-C(=N-OR 21 )-R 22 , -C(=N-OCOR 21 )-R 22 , CN, halogen atoms, or COOR 21 replace.

[0399] R 21 , R 22 and R 23 Means the same as above.

[0400] R 92 With R 93 , R 94 With R 95 , R 95 With R 96 and R 96 With R 97 They can each form a ring together.

[0401] * represents a bonding site to the first molecular structure of the oxime compound (1).

[0402] R in formula (6) 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the alkyl group having 1 to 20 carbon atoms, the aryl group having 6 to 30 carbon atoms, the aralkyl group having 7 to 30 carbon atoms, and the heterocyclic group having 2 to 20 carbon atoms represented by11 , R 12 , R 13 , R 21 , R 22 and R 23 The same example.

[0403] R in formula (6) 22 With R 23 Can form a ring together refers to R 22 With R 23 They may form a ring together with the nitrogen atom, carbon atom or oxygen atom to which they are attached.

[0404] R in formula (6) 22 With R 23 Examples of rings that can be formed together are similar to those for Ra in formula (1). 12 With Ra 13 and Ra 22 With Ra 23 The same is true for the examples of rings that can be formed together.

[0405] As R in formula (6) 91 , R 92 , R 93 , R 94 , R 95 , R 96 and R 97 The halogen atom represented by R 21 , R 22 , R 23 , R 61 , R 62 , R 63 , R 64 and R 65 Examples of the halogen atom replacing the hydrogen atom include a fluorine atom, a chlorine atom, a bromine atom and an iodine atom.

[0406] The method for producing the oxime compound (1) having the second molecular structure represented by formula (6) is not particularly limited, and can be produced, for example, by the methods described in International Publication Nos. 2017 / 051680 and 2020 / 004601.

[0407] Other examples of the photopolymerization initiator are photopolymerization initiators other than the oxime compound (1). Examples of the photopolymerization initiator include oxime compounds other than the oxime compound (1), alkylphenone compounds, biimidazole compounds, triazine compounds, and acylphosphine compounds.

[0408] Examples of oxime compounds other than the oxime compound (1) include oxime compounds having a partial structure represented by the following formula (d1): * represents a bonding site.

[0409]

[0410] Examples of the oxime compound having a partial structure represented by formula (d1) include N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-{2-methyl-4-(3,3-dimethyl-2,4-dioxy)propane-1-imine, heterocyclopentylmethoxy)benzoyl}-9H-carbazol-3-yl]ethane-1-imine, N-acetoxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-imine, N-benzoyloxy-1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl]-3-cyclopentylpropane-1-one-2-imine; compounds described in JP-A-2011-132215, WO-2008 / 78678, WO-2008 / 78686, and WO-2012 / 132558, etc. Commercially available products such as Irgacure (registered trademark) OXE01, Irgacure OXE02, Irgacure OXE03 (all manufactured by BASF), N-1919, NCI-930, and NCI-831 (all manufactured by ADEKA) may also be used.

[0411] Among them, the oxime compound having a partial structure represented by formula (d1) is preferably at least one selected from N-benzoyloxy-1-(4-phenylthiophenyl)butane-1-one-2-imine, N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine and N-benzoyloxy-1-(4-phenylthiophenyl)-3-cyclopentylpropane-1-one-2-imine, and N-benzoyloxy-1-(4-phenylthiophenyl)octane-1-one-2-imine is more preferred.

[0412] The alkylphenone compound is a compound having a partial structure represented by the following formula (d2) or a partial structure represented by the following formula (d3). In these partial structures, the benzene ring may have a substituent.

[0413]

[0414] Examples of the compound having a structure represented by formula (d2) include 2-methyl-2-morpholino-1-(4-methylthiophenyl)propane-1-one, 2-dimethylamino-1-(4-morpholinophenyl)-2-benzylbutane-1-one, 2-(dimethylamino)-2-[(4-methylphenyl)methyl]-1-[4-(4-morpholinyl)phenyl]butane-1-one, etc. Commercially available products such as OMNIRAD (registered trademark) 369, OMNIRAD 907, and OMNIRAD 379 (all manufactured by IGM Resins) can also be used.

[0415] Examples of the compound having a structure represented by formula (d3) include 2-hydroxy-2-methyl-1-phenylpropane-1-one, 2-hydroxy-2-methyl-1-[4-(2-hydroxyethoxy)phenyl]propane-1-one, 1-hydroxycyclohexyl phenyl ketone, oligomers of 2-hydroxy-2-methyl-1-(4-isopropenylphenyl)propane-1-one, α,α-diethoxyacetophenone, and benzil dimethyl ketal.

[0416] In terms of sensitivity, the alkylphenone compound is preferably a compound having a structure represented by formula (d2).

[0417] Examples of the biimidazole compound include compounds represented by formula (d5).

[0418]

[0419] [In formula (d5), R E ~R J represents an aryl group having 6 to 10 carbon atoms which may have a substituent.]

[0420] Examples of the aryl group having 6 to 10 carbon atoms include phenyl, tolyl, xylyl, ethylphenyl and naphthyl, and preferably phenyl.

[0421] Examples of the substituent include a halogen atom and an alkoxy group having 1 to 4 carbon atoms. Examples of the halogen atom include a fluorine atom, a chlorine atom, a bromine atom, and an iodine atom, and preferably a chlorine atom. Examples of the alkoxy group having 1 to 4 carbon atoms include a methoxy group, an ethoxy group, a propoxy group, and a butoxy group, and preferably a methoxy group.

[0422] Examples of the biimidazole compound 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, Japanese Patent Application Laid-Open Nos. 6-75372 and 6-75373), 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, 2,2'-bis(2-chlorophenyl)-4,4',5,5'-tetraphenylbiimidazole, Biimidazole compounds in which the phenyl groups at the 4,4',5,5'-positions are substituted with carbonyl alkoxy groups (for example, see Japanese Patent Publication No. 7-10913). Among them, compounds represented by the following formula or mixtures thereof are preferred.

[0423]

[0424] Examples of the triazine compound include 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxynaphthyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-(4-methoxyphenyl)-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2 -(5-methylfuran-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(furan-2-yl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(4-diethylamino-2-methylphenyl)vinyl]-1,3,5-triazine, 2,4-bis(trichloromethyl)-6-[2-(3,4-dimethoxyphenyl)vinyl]-1,3,5-triazine, etc. Among them, 2,4-bis(trichloromethyl)-6-piperonyl-1,3,5-triazine is preferred.

[0425] Examples of the acylphosphine compound include bis(2,4,6-trimethylbenzoyl)phenylphosphine oxide and (2,4,6-trimethylbenzoyl)diphenylphosphine oxide. Commercially available products such as OMNIRAD (registered trademark) 819 (manufactured by IGM Resins Co., Ltd.) may also be used.

[0426] Other examples of photopolymerization initiators other than the oxime compound (1) 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, methyl o-benzoylbenzoate, 4-phenylbenzophenone, 4-benzoyl-4'-methyldiphenyl sulfide, 3,3',4,4'-tetrakis(tert-butylperoxycarbonyl)benzophenone, 2,4,6-trimethylbenzophenone, and 4,4'-bis(diethylamino)benzophenone; quinone compounds such as 9,10-phenanthrenequinone, 2-ethylanthraquinone, and camphorquinone; 10-butyl-2-chloroacridone, benzil, methyl benzoylformate, and titanocene compounds.

[0427] When the composition contains a polymerization initiator (E), the content of the polymerization initiator (E) in the composition is, for example, 0.01% by mass to 20% by mass relative to the total amount of the solid content of the composition. From the viewpoint of improving the sensitivity of the composition and the viewpoint of improving the luminous intensity and heat resistance of the film, it is preferably 0.1% by mass to 15% by mass, more preferably 0.15% by mass to 10% by mass, further preferably 0.2% by mass to 8% by mass, and may also be 5% by mass or less or 3% by mass or less.

[0428] [7] Antioxidants (F)

[0429] The composition may contain an antioxidant (F). As the antioxidant (F), there is no particular limitation as long as it is an antioxidant generally used in industry, and phenolic antioxidants, phosphorus antioxidants, phosphorus / phenol composite antioxidants, sulfur antioxidants, etc. can be used. Two or more antioxidants (F) can be used in combination.

[0430] The phosphorus / phenol complex antioxidant may be a compound having one or more phosphorus atoms and a phenol structure in each molecule. From the viewpoint of optical properties such as the luminescence intensity of the film, the antioxidant (F) preferably contains a phosphorus / phenol complex antioxidant.

[0431] Examples of the phenolic antioxidant include Irganox (registered trademark) 1010 (Irganox 1010: pentaerythritol tetrakis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Irganox (registered trademark) 1076 (Irganox 1076: octadecyl-3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate, manufactured by BASF Corporation), Irganox (registered trademark) 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 Corporation), and Irganox (registered trademark) 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 Corporation), Irganox (registered trademark) 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 Corporation), Irganox (registered trademark) 1035 (Irganox 1035: thiodiethylene bis[3-(3,5-di-tert-butyl-4-hydroxyphenyl) propionate], manufactured by BASF Corporation), Irganox (registered trademark) 1135 (Irganox 1135: 3,5-bis(1,1-dimethylethyl)-4-hydroxy-C7-C9 side chain alkyl ester of phenylpropionic acid, manufactured by BASF Corporation), Irganox (registered trademark) 1520L (Irganox 1520L: 4,6-bis(octylthiomethyl)-o-cresol, manufactured by BASF Corporation), Irganox (registered trademark) 3125 (Irganox 3125, manufactured by BASF Corporation), Irganox (registered trademark) 565 (Irganox 565: 2,4-bis(n-octylthio)-6-(4-hydroxy-3',5'-di-tert-butylanilino)-1,3,5-triazine, manufactured by BASF Corporation), ADK STAB (registered trademark) AO-80 (ADK STAB AO-80: 3,9-bis(2-(3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propionyloxy)-1,1-dimethylethyl)-2,4,8,10-tetraoxaspiro[5,5] Undecane (manufactured by ADEKA Co., Ltd.), Sumilizer (registered trademark) BHT, Sumilizer (registered trademark) GA-80, Sumilizer (registered trademark) GS (all of the above are manufactured by Sumitomo Chemical Co., Ltd.), Cyanox (registered trademark) 1790 (Cyanox 1790, manufactured by Sitech Co., Ltd.), Vitamin E (manufactured by Eisai Co., Ltd.), etc.

[0432] Examples of the phosphorus-based antioxidant include Irgafos (registered trademark) 168 (Irgafos 168: tris(2,4-di-tert-butylphenyl)phosphite, manufactured by BASF Corporation), Irgafos (registered trademark) 12 (Irgafos 12: tris[2-[[2,4,8,10-tetra-tert-butyldibenzo[d,f][1,3,2]dioxaphosphin-6-yl]oxy]ethyl]amine, manufactured by BASF Corporation), Irgafos (registered trademark) 38 (Irgafos 38: bis(2,4-bis(1,1-dimethylethyl)-6-methylphenyl)ethyl phosphite, manufactured by BASF Corporation), ADK STAB (registered trademark) 329K, ADK STAB (registered trademark) PEP36, and ADK STAB (registered trademark) PEP-8 (all manufactured by ADEKA Corporation), and Sandstab P-EPQ (manufactured by Clariant AG), Weston (registered trademark) 618, Weston (registered trademark) 619G (all manufactured by GE), Ultranox 626 (manufactured by GE), etc.

[0433] Examples of the phosphorus / phenol composite antioxidant include Sumilizer (registered trademark) GP (6-[3-(3-tert-butyl-4-hydroxy-5-methylphenyl)propoxy]-2,4,8,10-tetra-tert-butyldibenzo[d,f][1.3.2]dioxaphosphophepane) (manufactured by Sumitomo Chemical Co., Ltd.).

[0434] Examples of the sulfur-based antioxidant include dialkyl thiodipropionate compounds such as dilauryl thiodipropionate, dimyristyl thiodipropionate, and distearyl thiodipropionate, and β-alkylmercaptopropionate compounds of polyhydric alcohols such as tetrakis[methylene(3-dodecylthio)propionate]methane.

[0435] When the composition contains an antioxidant (F), the content of the antioxidant (F) in the composition is, for example, 0.1% by mass to 20% by mass, preferably 0.5% by mass to 15% by mass, more preferably 1% by mass to 10% by mass, and further preferably 1% by mass to 5% by mass, relative to the total amount of the solid content of the composition.

[0436] [8]Solvent (H)

[0437] The resin composition may contain a solvent (H). Examples of the solvent (H) 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 and not containing -O-, -CO- and -COO- in the molecule), aromatic hydrocarbon solvents, amide solvents, dimethyl sulfoxide, and the like. Two or more solvents (H) may be used in combination.

[0438] Examples of the ester solvent include methyl lactate, ethyl lactate, n-butyl lactate, methyl 2-hydroxyisobutyrate, ethyl acetate, n-butyl acetate, isobutyl acetate, n-amyl formate, isoamyl acetate, n-butyl propionate, isopropyl butyrate, ethyl butyrate, n-butyl butyrate, methyl pyruvate, ethyl pyruvate, propyl pyruvate, methyl acetoacetate, ethyl acetoacetate, cyclohexanol acetate, and γ-butyrolactone.

[0439] Examples of the ether solvent include ethylene glycol monomethyl ether, ethylene glycol monoethyl ether, ethylene glycol monopropyl ether, ethylene glycol monobutyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, diethylene glycol monobutyl ether, propylene glycol monomethyl ether, propylene glycol monoethyl ether, propylene glycol monopropyl ether, propylene glycol monobutyl ether, 3-methoxy-1-butanol, 3-methoxy-3-methylbutanol, tetrahydrofuran, tetrahydropyran, 1,4-dihydrofu ... Alkane, diethylene glycol dimethyl ether, diethylene glycol diethyl ether, diethylene glycol methyl ethyl ether, diethylene glycol dipropyl ether, diethylene glycol dibutyl ether, anisole, phenethyl ether and methyl anisole, etc.

[0440] Examples of the ether ester solvent include methyl methoxyacetate, ethyl methoxyacetate, butyl methoxyacetate, methyl ethoxyacetate, ethyl ethoxyacetate, methyl 3-methoxypropionate, ethyl 3-methoxypropionate, methyl 3-ethoxypropionate, ethyl 3-ethoxypropionate, methyl 2-methoxypropionate, ethyl 2-methoxypropionate, propyl 2-methoxypropionate, methyl 2-ethoxypropionate, ethyl 2-ethoxypropionate, methyl 2-methoxy-2-methylpropionate, ethyl 2-ethoxy-2-methylpropionate, 3-methoxybutyl acetate, 3-methyl-3-methoxybutyl acetate, propylene glycol monomethyl ether acetate, 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.

[0441] Examples of the ketone solvent include 4-hydroxy-4-methyl-2-pentanone, acetone, 2-butanone, 2-heptanone, 3-heptanone, 4-heptanone, 4-methyl-2-pentanone, cyclopentanone, cyclohexanone, and isophorone.

[0442] Examples of alcohol solvents include methanol, ethanol, propanol, butanol, hexanol, cyclohexanol, ethylene glycol, propylene glycol, and glycerol. Examples of aromatic hydrocarbon solvents include benzene, toluene, xylene, and mesitylene. Examples of amide solvents include N,N-dimethylformamide, N,N-dimethylacetamide, and N-methylpyrrolidone.

[0443] The solvent (H) is preferably propylene glycol monomethyl ether acetate, ethyl lactate, propylene glycol monomethyl ether, ethyl 3-ethoxypropionate, ethylene glycol monomethyl ether, diethylene glycol monomethyl ether, diethylene glycol monoethyl ether, 4-hydroxy-4-methyl-2-pentanone or toluene, or a mixture of two or more thereof.

[0444] [9] Other ingredients

[0445] The composition may further contain additives known in the technical field such as a polymerization inhibitor, a filler, other polymer compounds, an adhesion promoter, a light stabilizer, a chain transfer agent, a polymerization initiation aid, and a leveling agent, as required.

[0446]

[10] Sedimentation velocity of the composition v

[0447] The sedimentation velocity ν represented by the formula (i) of the composition is 400×10 －9 cm / s or less.

[0448]

[0449] Formula (i) is Stokes' law. In the formula, g is the acceleration due to gravity, which is 980.665 cm / s 2 ρ s is the density of the first particle (A-1) [g / cm 3 ] ρ is the density of a composition having the same structure as the composition except that the particles (first particles and second particles) contained in the composition are not contained (hereinafter also referred to as "fluid") 〔g / cm 3 〕, hereinafter, its density is also referred to as "fluid density". μ is the viscosity of the composition at 25°C [g / (cm·s)]. The unit of the average particle size d of the first particle (A-1) is cm. When the composition contains two or more first particles (A-1) having different average particle sizes, in order to form a film that well exhibits the properties of these particles, the two or more first particles (A-1) preferably have a sedimentation velocity ν represented by formula (i) of 400×10 －9 cm / s or less.

[0450] The sedimentation velocity v of the composition is 400×10 －9 cm / s or less, even if the first particle (A-1) having a larger average particle size d is contained, a film that well exhibits the characteristics of the particle can be formed. At least part of the reason is that the first particle (A-1) is not easy to settle in the composition. According to the present invention, for example, when a film made from a freshly prepared composition is compared with a film made from a composition that has been left to stand for 10 days after preparation, the deviation of the characteristics (optical characteristics, etc.) is small, and both can be films with excellent characteristics.

[0451] When the composition further contains luminescent particles as the second particles (A-2), the sedimentation velocity ν represented by the formula (i) is 400×10 －9 cm / s or less, the luminescence intensity of a film formed from the composition can be increased.

[0452] The sedimentation velocity v of the composition is preferably 300×10 －9 cm / s or less, more preferably 250×10 －9 cm / s or less, more preferably 200×10 －9 cm / s or less, and more preferably 150×10 －9 cm / s or less, particularly preferably 100×10 －9 cm / s or less, and most preferably 70×10 －9 cm / s or less. The sedimentation velocity ν is usually 1×10 －9 cm / s or more, preferably 5×10 －9 cm / s or more, more preferably 10×10 －9 cm / s or more.

[0453] The sedimentation velocity v of the composition can be adjusted by adjusting the average particle size d and density ρ of the first particles (A-1). s , the solid content (solvent content) and viscosity of the composition.

[0454] The viscosity μ of the composition at 25° C. is, for example, 0.1 g / (cm·s) to 300 g / (cm·s), preferably 0.2 g / (cm·s) to 300 g / (cm·s), more preferably 0.35 g / (cm·s) to 250 g / (cm·s), further preferably 0.5 g / (cm·s) to 200 g / (cm·s), further preferably 1 g / (cm·s) to 150 g / (cm·s), and particularly preferably 4 g / (cm·s) to 100 g / (cm·s). The viscosity μ of the composition can be measured using a Brookfield rotational viscometer.

[0455] The density of the first particle (A-1) iss The average particle size d and the average particle size d can be measured before preparing the composition, or the first particle (A-1) can be taken out from the composition and measured. The average particle size of the second particle (A-2) is the same, and the fluid density ρ is the same. For example, by separating the particles from the composition by centrifugal separation, the physical properties related to the particles (density ρ of the first particle (A-1) and the average particle size d) can be measured. s and the average particle size d, and the average particle size of the second particle (A-2). At this time, the dispersant adsorbed on the separated particles can be regarded as a part of the particles to measure the physical properties related to the particles. In addition, the remaining part after the particles are separated by the above separation can be regarded as a fluid to measure the fluid density ρ.

[0456] When the particles are separated from the composition for measurement, if the composition contains the first particle (A-1) and the second particle (A-2), when the first particle (A-1) and the second particle (A-2) can be separated independently by centrifugal separation, etc., the density and average particle size of each particle can be measured by separating them independently using this method. Alternatively, when the composition contains the first particle (A-1) and the second particle (A-2), another method for obtaining the average particle size of these particles is as follows: a mixture of the first particle (A-1) and the second particle (A-2) is taken out from the composition, the particle size distribution of the mixture is measured, and the particle size distribution is separated into the particle size distribution of the first particle (A-1) and the particle size distribution of the second particle (A-2), thereby obtaining the average particle size of each.

[0457] <Method for producing composition>

[0458] The composition can be produced by a method including a step of mixing a predetermined component and other components used as necessary. The method for producing the composition may further include a step of preparing the resin (C).

[0459] The composition of the first embodiment (hereinafter also referred to as "composition M") contains the first particle (A-1) and the resin (C). The composition M may contain the first particle (A-1), the dispersant (B) and the resin (C). The composition M may further contain a polymerizable compound (D), in which case it is preferred to further contain a polymerization initiator (E). In order to improve the coating properties of the composition and the flatness of the composition layer during coating, the composition M preferably contains a solvent (H).

[0460] When the composition M contains a polymerizable compound (D), the content of the polymerizable compound (D) in the composition M is, for example, 0.5% to 50% by mass, preferably 1% to 40% by mass, more preferably 2% to 30% by mass, and further preferably 2% to 25% by mass, relative to the total amount of the solid content of the composition.

[0461] The content of the solvent (H) in the composition M is, for example, 40% to 95% by mass, preferably 45% to 90% by mass, and more preferably 50% to 80% by mass, relative to the total amount of the composition M. In other words, the solid content concentration of the composition is, for example, 5% to 60% by mass, preferably 10% to 55% by mass, and more preferably 20% to 50% by mass. Among them, the solid content concentration of the composition is preferably 30% by mass or more, more preferably 34% by mass or more, and further preferably 36% by mass or more. When the solid content concentration is within this range, it is advantageous to suppress pinholes that may be generated in the film.

[0462] The composition of the second embodiment (hereinafter also referred to as "composition N") does not contain the resin (C). The composition N contains the first particle (A-1) and the polymerizable compound (D), and preferably further contains a polymerization initiator (E). The composition N may contain the first particle (A-1), a dispersant (B) and a polymerizable compound (D). The composition N may contain a solvent (H), but preferably does not contain the solvent (H) or contains a small amount of the solvent (H).

[0463] The content of the polymerizable compound (D) in the composition N is, for example, 10 to 90 mass %, preferably 20 to 80 mass %, more preferably 30 to 75 mass %, further preferably 40 to 70 mass %, and even more preferably 50 to 70 mass %, relative to the total amount of solid components of the composition.

[0464] The content of the solvent (H) in the composition N is preferably 10% by mass or less, more preferably 5% by mass or less, further preferably 3% by mass or less, further preferably 2% by mass or less, particularly preferably 1% by mass or less, and may be 0% by mass or more. By reducing the content of the solvent (H), the film thickness control when forming the cured film becomes easy, and the manufacturing cost and the load on the earth environment and the working environment caused by the solvent can be reduced. The composition N can be suitably used as an inkjet printer ink for making a film.

[0465] <Resin film and method for producing the same>

[0466] The film of the present invention is a film formed from the composition of the present invention. The film production method includes the following steps, for example.

[0467] a step of forming a composition layer by applying the composition to a substrate or spraying the composition onto a region of a substrate having a bank formed thereon and partitioned by the bank, and

[0468] A step of heat-treating the composition layer.

[0469] The film may be formed on the entire surface of the substrate, or may be formed on a portion of the surface of the substrate (for example, in a pattern).

[0470] The film production method may include other steps in addition to the above steps. Examples of the other steps include an exposure step of irradiating the composition layer with light, and a development step of the composition layer after the exposure step.

[0471] In the step of forming the composition layer, as a method of applying the composition to the substrate, spin coating, slit coating, slit and spin coating, etc. can be cited. The step of forming the composition layer by ejecting the composition can be a step of selectively ejecting the composition by, for example, an inkjet method and attaching it to the area divided by the bank. A patterned composition layer can also be formed by a stencil printing method, a screen printing method, or a printing coating based on an applicator.

[0472] Examples of the substrate include glass plates such as quartz glass, borosilicate glass, aluminosilicate glass, soda-lime glass with a surface coated with silicon dioxide, resin plates such as polycarbonate, polymethyl methacrylate, polyethylene terephthalate, silicon, and substrates having aluminum, silver, silver / copper / palladium alloy thin films formed on the above substrates.

[0473] The patterned film can be formed on the substrate, for example, as follows: First, the composition is applied onto the substrate through a mask or sprayed onto the regions partitioned by the banks to form a patterned composition layer.

[0474] Next, the composition layer is heat-treated to obtain a film. The heat treatment may include a drying step (a step of removing volatile components such as solvents) of the composition layer. Examples of drying methods include heating drying, reduced pressure drying, or a combination thereof. The temperature for heating drying is preferably 30°C to 120°C, more preferably 50°C to 110°C. The heating time is preferably 10 seconds to 60 minutes, more preferably 30 seconds to 30 minutes. When reduced pressure drying is performed, it is preferably performed under a pressure of 50 Pa to 150 Pa. The drying of the composition layer may be performed in multiple steps, for example, by implementing multiple drying steps with different drying temperatures.

[0475] The step of heat treating the composition layer may include the above-mentioned drying step (pre-baking) and a subsequent post-baking step. The heating temperature in the baking step is preferably 150° C. to 250° C., more preferably 160° C. to 235° C. The heating time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes.

[0476] When the composition is curable (including a polymerizable compound (D) and preferably further including a polymerization initiator (E)), the film production method preferably includes the above-mentioned exposure step. For a patterned cured film formed by a photocurable composition, if a method using photolithography is cited as an example, it can be formed on a substrate as follows. First, a composition layer is formed on a substrate, and a drying step of heating drying (prebaking) and / or reduced pressure drying is performed. As a method for forming and drying the composition layer, the same method as described above can be cited.

[0477] Next, the composition layer is exposed through a photomask for forming a target pattern shape. As the light source used in the exposure, a light source that generates light with a wavelength of 250nm to 450nm is preferred. For example, light near 436nm, near 408nm, or near 365nm can be selectively extracted from the light of this wavelength using a bandpass filter according to the absorption wavelength of the photopolymerization initiator. As the light source, specifically, a mercury lamp, a light emitting diode, a metal halide lamp, a halogen lamp, etc. can be cited.

[0478] In order to evenly irradiate the entire exposure surface with parallel light and accurately align the photomask and the substrate on which the composition layer is formed, it is preferred to use an exposure device such as a mask aligner and a stepper. The exposed composition layer is cured by polymerization of the photopolymerizable compound contained in the composition layer.

[0479] The above-mentioned development step is carried out by contacting the exposed composition layer with a developer, so that the unexposed portion of the composition layer is dissolved in the developer and removed to obtain a patterned cured film. As the developer, for example, aqueous solutions of alkaline compounds such as potassium hydroxide, sodium bicarbonate, sodium carbonate, and tetramethylammonium hydroxide, and organic solvents can be cited. The concentration of the alkaline compound in the aqueous solution is preferably 0.01% to 10% by mass, and more preferably 0.03% to 5% by mass. As the organic solvent, the same solvent as the above-mentioned solvent (H) can be cited. The developer may contain a surfactant.

[0480] The developing method may be any of a paddle method, a dipping method, a spray method, etc. Furthermore, the substrate may be tilted at an arbitrary angle during the developing process.

[0481] It is preferred to further heat (post-bake) the patterned film obtained by development. The heating temperature is preferably 150°C to 250°C, more preferably 160°C to 235°C. The heating time is preferably 1 minute to 120 minutes, more preferably 10 minutes to 60 minutes. By heating after development, unreacted polymerizable compounds contained in the film can be polymerized, thereby obtaining a cured film with better chemical resistance. In the case of no development, it is also preferred to further heat (post-bake) the exposed composition layer.

[0482] On the other hand, examples of a method for forming a film on the entire surface of a substrate include a method of forming a composition layer on a substrate, drying the composition layer as necessary, heating the composition layer, and / or exposing the entire surface of the composition layer to light.

[0483] The film thickness is not particularly limited, and can be appropriately selected according to the purpose, for example, 1 μm to 30 μm, preferably 3 μm to 25 μm, more preferably 5 μm to 25 μm, and further preferably 5 μm to 20 μm. The shape and size of the patterned resin film are not particularly limited. The patterned resin film, for example, has a square shape when viewed from above.

[0484] <Display device>

[0485] The display device of the present invention comprises at least a light source and the above-mentioned film. As the display device, for example, a liquid crystal display device, an organic EL display device or an inorganic EL display device can be cited, and specifically, the display devices described in Japanese Patent Publication No. 2006-309219, Japanese Patent Publication No. 2006-310303, Japanese Patent Publication No. 2013-15812, Japanese Patent Publication No. 2009-251129, Japanese Patent Publication No. 2014-2363, etc. can be cited.

[0486] A display device of one embodiment includes a backlight as a blue light source, and a plurality of patterns arranged on the viewing side of the backlight. The plurality of patterns may be a red pattern, a green pattern, and a white (transparent, achromatic) pattern, and at least one of these patterns may be the film of the present invention. The color pattern as a red pattern or a green pattern may be a film having a function of converting the wavelength of incident light and emitting it, and formed by a composition containing a first particle (A-1) and a second particle (A-2). The white (transparent, achromatic) pattern may also be a film formed by a composition containing a first particle (A-1) and not containing a second particle (A-2).

[0487] Example

[0488] Hereinafter, the present invention will be described in more detail with reference to Examples. "%" and "parts" in the Examples are by mass % and by mass parts unless otherwise specified.

[0489] <Measurement and Evaluation>

[0490] (1) Measurement of average particle size d of first particles (A-1)

[0491] The particle size distribution of titanium oxide (TiO2) particles as the first particle (A-1) is measured using the following centrifugal sedimentation type dispersion stability particle size distribution apparatus under the following conditions, using a dispersion of the particles using propylene glycol monomethyl ether acetate (PGMEA) as a solvent as a measurement sample, and the average particle size d [cm] is determined as the volume-based median particle size (D50).

[0492] Device: LUMiSizer 611 manufactured by LUM GmbH

[0493] Speed: 1000rpm

[0494] Set density: Titanium oxide 4.260g / cm 3 , PGMEA 0.9700g / cm 3

[0495] Set refractive index: Titanium oxide 2.720, PGMEA 1.400

[0496] (2) Measurement of average particle size of second particles (A-2)

[0497] Using the scanning transmission electron microscope described below, a dispersion of quantum dots as the second particle (A-2) using PGMEA as a solvent was used as a measurement sample. A particle image was obtained under the following conditions and binarized using the image processing software "ImagePro". The diameters of 600 particles were calculated based on the image and used as their median value to determine the average particle size [cm] of the quantum dots as the second particle (A-2).

[0498] Device: FEI HeliosG4UX

[0499] Mode: STEM BF mode

[0500] Accelerating voltage: 23 kV

[0501] Current value: 50pA

[0502] (3) Density ρ of the first particle (A-1) s Determination of

[0503] The density of the first particle (A-1) was measured using a Gay-Lussac pycnometer at 25°C. s 〔g / cm 3 〕.

[0504] (4) Determination of fluid density ρ

[0505] At 25°C, use a Gay-Lussac type pycnometer to measure the density of the fluid. s 〔g / cm 3The fluid referred to here refers to a composition having the same structure as the composition prepared in Examples and Comparative Examples except that the fluid does not contain particles (first particles and second particles).

[0506] (5) Measurement of viscosity μ (25° C.) of composition

[0507] The viscosity of the compositions prepared in Examples and Comparative Examples was measured using a Brookfield rotational viscometer at a constant temperature of 25°C and a rotation speed of 3 rpm [g / (cm·s)].

[0508] (6) Sedimentation velocity v of the composition

[0509] According to the above formula (i), the sedimentation velocity ν [cm / s] is calculated.

[0510] (7) Weight average molecular weight Mw and number average molecular weight Mn of resin (C)

[0511] The weight average molecular weight Mw and the number average molecular weight Mn of the resin (C) were measured by a GPC method under the following conditions.

[0512] Device: K2479 (manufactured by Shimadzu Corporation)

[0513] Column: SHIMADZU Shim-pack GPC-80M

[0514] Column temperature: 40°C

[0515] Solvent: Tetrahydrofuran

[0516] Flow rate: 1.0mL / min

[0517] Detector: RI

[0518] Calibration standard substances: TSK STANDARD POLYSTYRENE F-40, F-4, F-288, A-2500, A-500 (manufactured by Tosoh Corporation)

[0519] (8) Acid value of resin (C)

[0520] 3 g of the resin (C) solution was accurately weighed and dissolved in a mixed solvent of 90 g of acetone and 10 g of water. A 0.1-equivalent aqueous KOH solution was used as a titrant. The acid value of the resin (C) solution was measured using an automatic titrator (trade name "COM-555" manufactured by Hiranuma Industries Co., Ltd.). The acid value Av (mgKOH / g) per 1 g of solid content was calculated based on the acid value of the solution and the solid content of the solution.

[0521] (9) Solid content of resin (C) solution

[0522] About 1 g of the resin (C) solution was weighed in an aluminum cup, dried at 180° C. for 1 hour, and then the mass was measured. The solid content (mass %) of the resin (C) solution was calculated from the mass loss.

[0523] (10) Evaluation of the rate of change of luminous intensity

[0524] A backlight unit was prepared by placing a light diffusion plate on a backlight using a blue LED lamp with a peak wavelength of 450 nm as a point light source. The backlight unit was placed with the light diffusion plate facing upward, and a spectroradiometer ("SR-UL1R" manufactured by TOPCON Co., Ltd.) was set at a height of 60 cm from the surface of the light diffusion plate.

[0525] Next, a substrate having a film made of the composition S1 just prepared was placed on the surface of the glass substrate. In this state, the backlight was turned on, and the luminous intensity E1 (W·sr) of the light emitted from the film was measured by a cumulative radiation flux meter within the wavelength range of 485nm to 780nm. －1 ·m －2 ·nm －1 The luminous intensity E1 was measured using the above-mentioned spectroradiometer ("SR-UL1R" manufactured by TOPCON Corporation).

[0526] In addition, the luminescence intensity E2 (W·sr) of a film prepared from composition S2 which was left to stand for 10 days at 25°C after preparation was measured in the same manner as above. －1 ·m －2 ·nm －1 〕.

[0527] Based on the above results, the following rate of change X of luminous intensity was calculated.

[0528] Change rate X〔%〕=100×luminous intensity E2 / luminous intensity E1

[0529] <Production Example 1: Preparation of a dispersion of first particles (A1a)>

[0530] In the titanium oxide particles (average particle size d: 219×10 －7 cm, density ρ s :4.260g / cm 3 ) were added with 3 parts of "DISPERBYK21116" (manufactured by BYK-Chemie Japan) as a dispersant (B1) in terms of solid content to 70 parts, and PGMEA was added to make the total amount reach 100 parts, and then stirred with a paint shaker until fully dispersed to obtain a dispersion of the first particle (A1a) (solid content 73%).

[0531] <Production Example 2: Preparation of a dispersion of first particles (A1b)>

[0532] Titanium oxide particles (average particle size d: 192×10 －7 cm, density ρ s :4.260g / cm 3 ) was used instead of the first particles (A1a). In the same manner as in Production Example 1, a dispersion of the first particles (A1b) (solid content: 73%) was obtained.

[0533] <Production Example 3: Preparation of dispersion of second particles (A2a)>

[0534] A toluene dispersion of the second particles (A2a) was prepared. The second particles (A2a) were InP / ZnSeS quantum dots (average particle size: 6.0×10 －7 cm). The toluene dispersion was distilled under reduced pressure to remove toluene. 50 parts of cyclohexyl acetate was added to 50 parts of the solid content to obtain a dispersion of the second particles (A2a) (solid content 50%).

[0535] <Production Example 4: Preparation of dispersion of second particles (A2b)>

[0536] InP / ZnSeS quantum dots (average particle size: 4.6×10 －7 A dispersion of second particles (A2b) (solid content: 50%) was obtained in the same manner as in Production Example 3, except that the second particles (A2a) were replaced with the second particles (A2b).

[0537] <Production Example 5: Preparation of Resin (C1) Solution>

[0538] 110 parts of PGMEA were placed in a flask equipped with a stirrer, a reflux cooling tube with a thermometer, a dropping funnel, and a nitrogen inlet tube, and the mixture was stirred while nitrogen substitution was performed, and the temperature was raised to 80° C. A solution prepared by dissolving 25 parts of dicyclopentanyl methacrylate, 26 parts of methyl methacrylate, 16 parts of methacrylic acid, and 14 parts of 2,2'-azobis(2,4-dimethylvaleronitrile) in 110 parts of PGMEA was dropped into the flask from the dropping funnel, and the mixture was stirred at 80° C. for 3 hours.

[0539] 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 heated to 110°C and stirred for 8 hours to react the carboxylic acid in the polymer with the epoxy group to introduce 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 carboxyl group into the side chain. The reaction solution was cooled to room temperature to obtain a resin (C1) solution.

[0540] The resin (C1) had a standard polystyrene-equivalent weight average molecular weight Mw of 5200, a molecular weight distribution of 2.3, an acid value of 100 mgKOH / g, and a solid content of 50% by mass in the resin (C1) solution.

[0541] <Examples 1 to 9, Comparative Example 1>

[0542] (1) Preparation of composition

[0543] The dispersion of the first particles (A1a) obtained in Production Example 1 or the dispersion of the first particles (A1b) obtained in Production Example 2, the dispersion of the second particles (A2a) obtained in Production Example 3 or the dispersion of the second particles (A2b) obtained in Production Example 4, and the resin (C1) solution obtained in Production Example 5 were mixed with the other components shown in Table 1 in predetermined amounts to prepare a composition.

[0544] The content of each component in the composition obtained from the addition amount is shown in Table 1. In Table 1, the components other than the solvent (H) are the contents converted to solid content (unit: mass parts). The unit of the content of the solvent (H) is mass parts. For example, the first particle is formulated in the form of a dispersion of the first particle in the preparation of the composition, but the content shown in Table 1 is the amount of the first particle itself contained in the dispersion. The solvent (H) in Table 1 includes the solvent contained in the dispersion or solution used in the preparation of the composition.

[0545] The content of the organic ligand (G1) in the composition shown in Table 1 was calculated based on the concentration of the organic ligand (G1) in the dispersion of the second particles obtained in Production Example 2 or 3 measured by the following method. That is, after the dispersion of the second particles was vacuum dried at 150°C to remove the solvent, the weight change of the remaining solid content was measured at 50°C to 550°C at a heating rate of 5°C / min using a thermogravimetric analyzer "TGDTA6200". The weight change from 50°C to 500°C was taken as the weight of the organic ligand (G1), and the concentration of the organic ligand (G1) in the dispersion of the second particles was calculated.

[0546] (2) Film preparation

[0547] The composition was applied to a 5 cm square glass substrate (EAGLE2000; manufactured by CORNING) by spin coating to a film thickness of 6 μm, and then dried at 100° C. for 3 minutes and then at 180° C. for 10 minutes to form a film, thereby obtaining a substrate having a film.

[0548] The sedimentation velocity ν was calculated for each composition of the examples and comparative examples. Also, the rate of change X of emission intensity was determined for the obtained film. The results are shown in Table 1.

[0549] [Table 1]

[0550]

[0551] The detailed information of the abbreviations of the components shown in Table 1 are as follows.

[0552] 〔1〕Organic ligand (G1): oleic acid

[0553] [2] Polymerizable compound (D1): Aronix M-510 (photopolymerizable compound, carboxyl group-containing polyfunctional (meth)acrylate, manufactured by Toagosei Co., Ltd., solid content 100%)

[0554] [3] Polymerizable compound (D2): A-9550 (photopolymerizable compound, dipentaerythritol polyacrylate, manufactured by Shin-Nakamura Chemical Industry Co., Ltd., solid content 100%)

[0555] [4] Polymerization initiator (E1): A photopolymerization initiator represented by the following formula: Produced by the method described in JP-A-2011-132215 (solid content: 100%).

[0556]

[0557] [5] Antioxidant (F1): Sumilizer-GP (phosphorus / phenol composite antioxidant, manufactured by Sumitomo Chemical Co., Ltd., solid content 100%)

[0558] [6] Solvent (H1): PGMEA (propylene glycol monomethyl ether acetate)

[0559] [7] Solvent (H2): Cyclohexyl acetate

[0560] The film formed by the composition of the embodiment showed the same or close luminescence intensity as that of the film formed by the composition just prepared, even when the film was formed by the composition left to stand for 10 days after preparation, and the deviation of the luminescence characteristics was suppressed. In contrast, in the composition of Comparative Example 1, when the film was formed by the composition left to stand for 10 days after preparation, the luminescence intensity was significantly reduced (change rate X = 79%) compared with that of the film formed by the composition just prepared. It is speculated that the reason is that the first particle precipitated due to standing for 10 days, resulting in excessive or strong aggregation.

[0561] In addition, in the examples, the reason why the change rate X may be larger than 100% is that there is a possibility that a part of the first particles aggregate and the apparent particle size increases.

Claims

1. A composition comprising particles, The particles include an average particle size d of 100×10 －7 The first particle (A-1) with a diameter of cm or more, The composition further contains at least one selected from a resin (C) and a polymerizable compound (D), The sedimentation velocity ν represented by formula (i) of the composition is 400×10 －9 cm / s or less, In formula (i), g represents the acceleration due to gravity, and its unit is cm / s 2 , ρ s The density of the first particle (A-1) is expressed in g / cm 3 ρ represents the density of a composition identical to the composition except that the particles are not contained, and its unit is g / cm 3 , μ represents the viscosity of the composition at 25° C., and its unit is g / (cm·s).

2. The composition according to claim 1, wherein The first particles (A-1) are light scattering particles.

3. The composition according to claim 1, wherein The first particles (A-1) are inorganic particles.

4. The composition according to claim 1, wherein The particles further comprise an average particle size of 50×10 －7 The second particle (A-2) is smaller than cm.

5. The composition according to claim 4, wherein The second particles (A-2) are luminescent particles.

6. The composition according to any one of claims 1 to 5, wherein The resin (C) is a resin having a polar group, and the polymerizable compound (D) is a polymerizable compound having a polar group.

7. The composition according to claim 6, wherein The polar group is at least one group selected from the group consisting of a carboxyl group, a thiol group and an amino group. 8 . The composition according to claim 1 , which is a composition for forming an optical functional film.

9. A film formed from the composition according to any one of claims 1 to 5. 10 . A display device comprising the film according to claim 9 .

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